WO2017142174A1 - Composition for window film and flexible window film formed from same - Google Patents

Composition for window film and flexible window film formed from same Download PDF

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Publication number
WO2017142174A1
WO2017142174A1 PCT/KR2016/014146 KR2016014146W WO2017142174A1 WO 2017142174 A1 WO2017142174 A1 WO 2017142174A1 KR 2016014146 W KR2016014146 W KR 2016014146W WO 2017142174 A1 WO2017142174 A1 WO 2017142174A1
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Prior art keywords
group
window film
formula
composition
silicone resin
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PCT/KR2016/014146
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French (fr)
Korean (ko)
Inventor
최진희
한동일
강경구
김주희
우창수
Original Assignee
삼성에스디아이 주식회사
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Priority claimed from KR1020160071345A external-priority patent/KR101963003B1/en
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Publication of WO2017142174A1 publication Critical patent/WO2017142174A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/22Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/302Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements characterised by the form or geometrical disposition of the individual elements

Definitions

  • the present invention relates to a composition for a window film and a flexible window film formed therefrom.
  • a flexible display device having a flexibility to be folded and unfolded while replacing a glass substrate or a high hardness substrate with a film has been developed.
  • Flexible display devices are thin, light, impact-resistant, and foldable. Since the window film is located at the outermost side of the display device, it should have good flexibility and hardness.
  • the window film is prepared by applying a coating solution on a substrate layer, which may not have a good appearance if the coating solution is not uniformly applied, resulting in distortion on the display, and high reflectivity, resulting in an unclear or glare on the display. Can give
  • the problem to be solved by the present invention is to provide a composition for a window film that can implement a window film with excellent appearance and low reflectance.
  • Another object of the present invention is to provide a composition for a window film that can implement a flexible window film with excellent hardness and flexibility.
  • Another object of the present invention is to provide a composition for a window film that can implement a window film having an effect of improving the screen quality.
  • Another problem to be solved by the present invention is to provide a flexible window film having excellent appearance, low reflectance and excellent hardness and flexibility.
  • composition for a window film of the present invention may include a first fluorine-containing silicone resin of Formula 1, a second silicone resin having an epoxy group or an epoxy group-containing functional group, and an initiator:
  • the flexible window film of the present invention includes a base layer and a coating layer formed on the base layer, wherein the flexible window film may have a RIQ of about 85 or more, a pencil hardness of about 4H or more, and a radius of curvature of about 5.0 mm or less. .
  • the present invention provides a composition for a window film that can implement a window film having excellent appearance and low reflectance.
  • the present invention provides a composition for a window film that can implement a flexible window film having excellent hardness and flexibility.
  • the present invention provides a composition for a window film that can implement a window film having an effect of improving screen quality.
  • the present invention provides a flexible window film having excellent appearance, low reflectance and excellent hardness and flexibility.
  • FIG. 1 is a cross-sectional view of a flexible window film according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view according to an exemplary embodiment of the display unit of FIG. 3.
  • FIG. 5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
  • RIQ Reflected Image Quality
  • epoxy group is a glycidyl group, glycidoxy group or epoxidized C4 to C20 cycloalkyl group
  • epoxy group containing functional group is C1 to C20 alkyl group having an epoxy group or C5 to C20 cycloalkyl group having an epoxy group. to be.
  • halogen refers to fluorine, chlorine, bromine or iodine
  • (meth) acryl refers to acrylic and / or methacryl
  • substituted means one or more of the functional groups, unless specifically noted.
  • Hydrogen atom is hydroxyl group, unsubstituted C1 to C10 alkyl group, C1 to C10 alkoxy group, C3 to C10 cycloalkyl group, unsubstituted C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C10 alkyl group It means substituted with a substituted C6 to C20 aryl group, or C1 to C10 alkoxy group substituted with a C1 to C10 alkyl group.
  • Ec is 2- (3,4-epoxycyclohexyl) ethyl group
  • Gp is 3-glycidoxypropyl group
  • Me is methyl group
  • Fd is 1H, 1H, 2H, 2H- Perfluorodecyl group
  • Fo is a 1H, 1H, 2H, 2H- perfluorooctyl group.
  • the composition for a window film according to an embodiment of the present invention may include a first fluorine-containing silicone resin, a second silicone resin, and an initiator.
  • the composition for a window film according to the present embodiment includes the first fluorine-containing silicone resin to improve the appearance of the window film, to reduce diffuse reflection, to increase the transparency of the window film, and to improve the coating property of the composition for the window film. Can be.
  • the composition for a window film according to the present embodiment may implement a flexible window film by improving the hardness and flexibility of the window film by including the first fluorine-containing silicone resin and the second silicon resin.
  • the first fluorine-containing silicone resin and the second silicone resin are different from each other, and may be included in the composition for a window film, alone or in combination of two or more thereof.
  • the first fluorine-containing silicone resin may be represented by Formula 1 below:
  • R is an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
  • X is a substituted or unsubstituted C1 to C30 alkyl group containing at least one fluorine, a substituted or unsubstituted C5 to C20 cycloalkyl group containing at least one fluorine, or a substituted or unsubstituted containing at least one fluorine Substituted C6 to C20 aryl group,
  • a is an integer of 0 to 3
  • b is an integer of 1 to 3
  • x + y 1).
  • R is an epoxy group or an epoxy group-containing functional group, and C1 to C20 alkyl group having a epoxidized C4 to C20 cycloalkyl group, C1 to C20 alkyl group having a glycidoxy group, or C1 to C10 alkyl group, more specifically It may be an epoxycyclohexylethyl group, a glycidoxy propyl group, a methyl group, or an ethyl group.
  • X represents C1 to C10 fluoroalkyl group, C1 to C10 perfluoroalkyl group, C1 to C10 alkyl group having C1 to C10 fluoroalkyl group, or C1 to C10 having C1 to C10 perfluoroalkyl group It may be an alkyl group of C10. More specifically, X is a 1H, 1H, 2H, 2H- perfluorodecyl group, 1H, 1H, 2H, 2H- perfluorooctyl group, or 1H, 1H, 2H, 2H-perfluorohexyl group, etc. Can be.
  • the first fluorine-containing silicone resin may be represented by the following Formula 1-1, Formula 1-2, or Formula 1-3:
  • first fluorine-containing silicone resin may be represented by the following Chemical Formulas 1-1-1 to 1-1-10:
  • the first fluorine-containing silicone resin has a fluorine content of about 0.1% to about 50% by weight, specifically about 0.2% to about 30% by weight, more specifically about 0.5% to about 20% by weight, even more specifically about And from about 1% to about 10% by weight. In the above range, the appearance of the window film may be improved and transparency may be good.
  • the first fluorine-containing silicone resin may have a weight average molecular weight of about 2,000 to about 20,000, specifically about 4,000 to about 10,000, more specifically about 4,500 to about 6,000. It is possible to improve the appearance of the window film in the above range and to increase the transparency.
  • the first fluorine-containing silicone resin has a polydispersity (PDI) of about 1.0 to about 3.0, specifically about 1.5 to about 2.5, epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g To about 0.8 mol / 100 g.
  • PDI polydispersity
  • the first fluorine-containing silicone resin is about 0.1 wt% to about 50 wt%, specifically about 0.2 wt% to about 30 wt%, more specifically about 0.5 wt% of the total of the first fluorine-containing silicone resin and the second silicon resin. To about 20% by weight. In the above range, the appearance of the window film can be improved and the transparency can be good.
  • the second silicone resin is a binder for forming the window film, and may improve the hardness and flexibility of the window film, and may be represented by the following Chemical Formula 2 as a non-fluorine-based silicone resin containing no fluorine:
  • R 1 is an epoxy group or an epoxy group-containing functional group
  • R 2 and R 3 are each independently hydrogen, a crosslinkable functional group, an unsubstituted or substituted C1 to C20 alkyl group, or an unsubstituted or substituted C5 to C20 cycloalkyl group,
  • R 4 , R 5 and R 6 are each independently hydrogen, a crosslinkable functional group, unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 aryl group,
  • R 1 may be a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, or a C1 to C20 alkyl group having a glycidoxy group, more specifically an epoxycyclohexylethyl group, or a glycidoxypropyl group.
  • R 2 and R 3 may each independently be a C1 to C20 alkyl group, a C1 to C10 alkyl group, more particularly an epoxycyclohexylethyl group or a methyl group having a C4 to C20 cycloalkyl group.
  • a crosslinkable functional group refers to an epoxy group, an epoxy group-containing functional group, an oxetanyl group, or an oxetanyl group-containing functional group.
  • the second silicone resins of the following Chemical Formulas 2-1 and 2-2 are more preferable for securing the appearance, hardness and the like of the window film.
  • the second silicone resin may be represented by the following Chemical Formulas 2-1, 2-2:
  • R 1a may be a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group
  • R 1b may be a C1 to C20 having a glycidyl group or a glycidoxy group. It may be an alkyl group.
  • the second silicone resin may be represented by the following Chemical Formula 2-1-1, 2-1-2:
  • the second silicone resin may have a weight average molecular weight of about 2,000 to about 20,000, specifically about 4,000 to about 10,000, more specifically about 4,500 to about 7,000. In the above range may be effective to support the coating layer of the window film in the above range.
  • the second silicone resin has a polydispersity (PDI) of about 1.0 to about 3.0, specifically about 1.5 to about 2.5, epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g to about It may be 0.8 mol / 100 g.
  • PDI polydispersity
  • epoxy equivalent weight epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g to about It may be 0.8 mol / 100 g.
  • the coating property of the composition is good, there may be a stable coating properties.
  • the second silicon resin is about 50% to about 99.9% by weight, specifically about 70% to about 99.8% by weight, more specifically about 80% to about 80% by weight of the sum of the first fluorine-containing silicone resin and the second silicon resin. It may be included in 99.5% by weight. In the above range, there is an effect of improving the flexibility and hardness of the window film, it is possible to see the appearance improvement effect by increasing the RIQ of the window film.
  • the initiator is used to cure the first fluorine-containing silicone resin and the second silicone resin, and one or more of a photocationic initiator and an optical radical initiator may be used, and may be used alone or in combination of two or more thereof.
  • Photocationic initiators can be used that is commonly known to those skilled in the art, may be used onium salt containing a cation and an anion.
  • the cation is diphenyl iodonium, 4-methoxydiphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, (4 Triarylsulfonium and bis [4, such as diaryl iodonium, such as -methylphenyl) [4- (2-methylpropyl) phenyl] iodonium, triphenylsulfonium, and diphenyl-4-thiophenoxyphenylsulfonium; -(Diphenylsulfonio) phenyl] sulfide, and the like, and the anion is hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, or the like, and
  • the initiator may be included in an amount of about 0.1 parts by weight to about 10 parts by weight, specifically about 0.5 parts by weight to about 5 parts by weight, based on 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicon resin. In this range, the silicone resin can be sufficiently cured and the residual amount of initiator remains to prevent the optical properties of the window film (such as transmittance, color and light reliability) from being lowered.
  • composition for a window film according to the present embodiment may further include nanoparticles.
  • Nanoparticles can further increase the hardness of the window film.
  • Nanoparticles may include, but are not limited to, one or more of silica, aluminum oxide, zirconium oxide, titanium oxide. Nanoparticles may be surface treated with some or all of the surface of a silicone compound for mixing with the silicone resin. Nanoparticles are not limited in shape and size. Specifically, the nanoparticles may include particles having a spherical shape, a plate shape, an amorphous shape, and the like. The nanoparticles may have an average particle diameter (D50) of about 1 nm to about 200 nm, specifically about 10 nm to about 50 nm.
  • D50 average particle diameter
  • the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.
  • the nanoparticles may be included in an amount of about 0.1 part by weight to about 60 parts by weight, specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicon resin.
  • the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.
  • the composition for a window film according to the present embodiment may further include an additive.
  • the additive may provide additional functionality to the window film.
  • the additives may include additives that are typically added to the window film.
  • the additive may include, but is not limited to, at least one of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a color adjuster, a stabilizer, an antistatic agent, and an antioxidant.
  • the reaction inhibitor may include ethynylcyclohexane.
  • An adhesion promoter may include a silane compound having an epoxy or alkoxysilyl group.
  • the thixotropic agent may include fumed silica and the like.
  • the conductivity providing agent may include metal powder such as silver and copper aluminum.
  • Dye control agents may include pigments, dyes and the like.
  • the UV absorber can increase the light resistance of the window film. UV absorbers can be used conventional absorbents known to those skilled in the art. Specifically, the UV absorber may include, but is not limited to, one or more UV absorbers of triazine-based, benzimidazole-based, benzophenone-based, and benzotriazole-based.
  • the additive may be included in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.1 parts by weight to about 2.5 parts by weight, based on 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicon resin. In the above range can improve the hardness and flexibility of the window film and implement the additive effect.
  • the composition for a window film according to the present embodiment may further include a solvent in order to facilitate coating, coatability, or processability.
  • the solvent may include one or more of methyl ethyl ketone (MEK, methyl ethyl ketone), methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.
  • composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that the composition further includes a crosslinking agent.
  • the composition further includes a crosslinking agent, the hardness and flexibility of the window film can be improved.
  • the crosslinking agent may be cured with the first fluorine-containing silicone resin and the second silicone resin by containing a crosslinkable functional group to increase the hardness of the window film and improve flexibility.
  • the crosslinking agent may further increase the flexibility of the coating layer by further including at least one of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group.
  • the crosslinking agent may comprise one or more of a chained aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, an oxetane monomer, which may be included alone or in combination.
  • Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, and polyethylene glycol diglycol.
  • the cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like. More specifically, (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy-6-methylcyclohexyl) adipate, 3,4-epoxy-6-methyl Cyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ⁇ -caprolactone modified 3,4-epoxycyclohexylmethyl-3',
  • Aromatic epoxy monomers include, for example, bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinyl phenol.
  • bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like
  • Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac
  • Oxetane monomers include 3-methyloxetane, 2-methyloxetane, 2-ethylhexyl oxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethanethiol, 4- (3-methyl Oxetan-3-yl) benzonitrile, N- (2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3- Oxetanemethaneamine, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl- May comprise one or more of 3-hydroxymethyloxetane, xylenebisoxetane, 3- [ethyl-3 [[(3-e
  • the crosslinking agent may be included in an amount of about 1 part by weight to about 50 parts by weight, specifically about 1 part by weight to about 40 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicon resin. In the above range it can ensure the flexibility and hardness of the coating layer, curl properties, optical properties.
  • composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that the composition further includes a crosslinking agent and a fluorine-based (meth) acrylate resin.
  • the crosslinking agent is as described above.
  • the fluorine-based (meth) acrylate resin can simultaneously improve the hardness and appearance of the window film by compensating for the decrease in hardness of the window film due to the first fluorine-containing silicone resin.
  • the fluorine-based (meth) acrylate resin has a surface energy at 25 ° C. of the coating layer of the window film at about 30 mN / m or less, about 25 mN / m or less, for example, at about 23 mN / m to about 25 mN / m and 25 ° C. May have a water contact angle of about 90 ° or less, for example, about 85 ° to about 89 °. In the above range, there may be a surface quality improvement effect.
  • Fluorine-based (meth) acrylate resins may include commercially available products such as RS-75, KY-1203, and the like.
  • the fluorine-based (meth) acrylate resin is about 1 part by weight to about 20 parts by weight, specifically about 1 part by weight to about 10 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. About 1 to about 5 parts by weight. In the above range, the hardness and appearance of the window film can be improved at the same time.
  • the first fluorine-containing silicone resin may be included in about 0.5% to about 2% by weight, specifically about 0.5% to about 1.5% by weight, based on the sum of the first fluorine-containing silicone resin and the second silicon resin. have. In the above range, the appearance and hardness of the window film can be improved at the same time.
  • FIG. 1 is a cross-sectional view of a flexible window film of one embodiment of the present invention.
  • a flexible window film 100 includes a base layer 110 and a coating layer 120, and the coating layer 120 is a window film according to embodiments of the present invention. It may be formed into a composition for.
  • the base layer 110 may support the flexible window film 100 and the coating layer 120 to increase the mechanical strength of the flexible window film 100.
  • the base layer 110 may be attached onto the display unit, the touch screen panel, or the polarizer by an adhesive layer.
  • the base layer 110 may be formed of an optically transparent and flexible resin.
  • resins include polyester resins including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and the like, polycarbonate resins, polyimide resins, polystyrene resins, polymethylmethacrylates, and the like. It may include one or more of the poly (meth) acrylate resin.
  • the resin may be included in the base layer 110 alone or in combination.
  • the base layer 110 may have a thickness of about 10 ⁇ m to about 200 ⁇ m, specifically about 20 ⁇ m to about 150 ⁇ m, and more specifically about 50 ⁇ m to about 100 ⁇ m. It can be used for the flexible window film in the above range.
  • the coating layer 120 is formed on the base layer 110 to protect the base layer 110 and the display unit, the touch screen panel, or the polarizing plate, improve the appearance, and have a high flexibility and high hardness to be used in a flexible display device. can do.
  • the coating layer 120 may have a thickness of about 5 ⁇ m to about 100 ⁇ m, specifically about 10 ⁇ m to about 80 ⁇ m. It can be used for the flexible window film in the above range.
  • another surface of the coating layer 120 may further include a functional surface layer such as an antireflection layer, an antiglare layer, a hard coating layer, and provide additional functions to the flexible window film.
  • the coating layer 120 may be further formed on the other surface of the substrate layer 110.
  • the flexible window film 100 may have a RIQ of about 85 or more, specifically about 85 to about 98, and an inferior reflectance at a wavelength of 550 nm of about 2% or less, specifically about 1.5% or less, more specifically about 0.8% to About 1.2%. Within this range, the appearance of the window film may be good and the display image may be clear.
  • the flexible window film 100 may have a light transmittance of about 88% or more and specifically about 88% to about 100% in the visible light region, specifically, about 400 nm to about 800 nm. It can be used as a flexible window film in the said range.
  • the flexible window film 100 may have a pencil hardness of about 4H or more and a radius of curvature of about 5.0 mm or less. In the above range, good hardness and flexibility can be used as a flexible window film.
  • the flexible window film 100 may have a pencil hardness of about 4H to about 9H and a radius of curvature of about 0.1 mm to about 5.0 mm.
  • the flexible window film 100 may have a thickness of about 5 ⁇ m to about 300 ⁇ m. It can be used as a flexible window film in the said range.
  • FIG. 2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.
  • the flexible window film 200 is except that the adhesive layer 130 is further formed on the other surface of the base layer 110. It is substantially the same as the flexible window film 100.
  • the adhesive layer 130 is further formed on the other surface of the base layer 110 to facilitate adhesion between the flexible window film and the touch screen panel, the polarizing plate, or the display unit. Except that the adhesive layer is further formed is substantially the same as the flexible window film according to an embodiment of the present invention. Thus, only the adhesive layer 130 will be described below.
  • the adhesive layer 130 may adhere to a polarizing plate, a touch screen panel, or a display unit that may be disposed below the flexible window film 200, and may be formed of a composition for an adhesive layer.
  • the pressure-sensitive adhesive layer 130 may be formed of a pressure-sensitive adhesive layer containing a pressure-sensitive resin, such as (meth) acrylic resin, urethane resin, silicone resin, epoxy resin, curing agent, photoinitiator, silane coupling agent.
  • the (meth) acrylic resin is a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an aromatic group, a carboxylic acid group, an alicyclic group, a heteroalicyclic group, or the like, and may include a conventional (meth) acrylic copolymer.
  • a (meth) acrylic monomer having a C1 to C10 unsubstituted alkyl group a (meth) acrylic monomer having a C1 to C10 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having a C6 to C20 aromatic group , (Meth) acrylic monomer having a carboxylic acid group, (meth) acrylic monomer having a C3 to C20 alicyclic group, C3 to C10 heteroalicyclic having at least one of nitrogen (N), oxygen (O), sulfur (S) It may be formed of a monomer mixture including at least one of the (meth) acrylic monomer having a group.
  • the curing agent is a polyfunctional (meth) acrylate, such as bifunctional (meth) acrylates such as hexanediol diacrylate; Trifunctional (meth) acrylate of trimethylolpropane tri (meth) acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; 6 functional (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, may be included, but is not limited thereto.
  • the photoinitiator may include the photoradical initiator described above as a conventional photoinitiator.
  • the silane coupling agent may include a silane coupling agent having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and the like.
  • the adhesive layer composition may include 100 parts by weight of a (meth) acrylic resin, about 0.1 part by weight to about 30 parts by weight of a curing agent, about 0.1 part by weight to about 10 parts by weight of a photoinitiator, and about 0.1 part by weight to about 20 parts by weight of a silane coupling agent. have.
  • the flexible window film may be attached well on the display unit, the touch screen panel or the polarizing plate.
  • the adhesive layer 130 may have a thickness of about 10 ⁇ m to about 100 ⁇ m.
  • Optical elements such as a flexible window film and a polarizing plate, can fully be stuck in the said range.
  • FIGS. 3 and 4 are cross-sectional views of a flexible display device according to an embodiment of the present invention
  • FIG. 4 is a cross-sectional view of an embodiment of the display unit of FIG. 3.
  • the flexible display device 300 may include a display unit 350a, an adhesive layer 360, a polarizer 370, a touch screen panel 380, and a flexible window film 390.
  • the flexible window film 390 may include a flexible window film according to embodiments of the present invention.
  • the display unit 350a is for driving the flexible display apparatus 300 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate.
  • 4 is a cross-sectional view according to an exemplary embodiment of the display unit of FIG. 3.
  • the display 350a may include a lower substrate 310, a thin film transistor 316, an organic light emitting diode 315, a planarization layer 314, a passivation layer 318, and an insulating layer 317. have.
  • the lower substrate 310 supports the display unit 350a, and the thin film transistor 316 and the organic light emitting diode 315 may be formed on the lower substrate 310.
  • a flexible printed circuit board for driving the touch screen panel 380 may be formed on the lower substrate 310.
  • the flexible printed circuit board may further include a timing controller, a power supply, and the like for driving the organic light emitting diode array.
  • the lower substrate 310 may include a substrate formed of a flexible resin.
  • the lower substrate 310 may include a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, a polyacrylate substrate, but is not limited thereto.
  • a plurality of pixel areas are defined by crossing a plurality of driving wires (not shown) and sensor wires (not shown), and the thin film transistor 316 and the thin film transistor 316 are defined for each pixel area.
  • the organic light emitting diode array including the organic light emitting diode 315 connected to the) may be formed.
  • a gate driver for applying an electrical signal to the driving line may be formed in the form of a gate in panel.
  • the gate-in panel circuit unit may be formed on one side or both sides of the display area.
  • the thin film transistor 316 controls the current flowing through the semiconductor by applying an electric field perpendicular to the current, and may be formed on the lower substrate 310.
  • the thin film transistor 316 may include a gate electrode 310a, a gate insulating layer 311, a semiconductor layer 312, a source electrode 313a, and a drain electrode 313b.
  • the thin film transistor 316 is an oxide thin film transistor using an oxide such as indium gallium zinc oxide (IGZO), ZnO, or TiO as the semiconductor layer 312, an organic thin film transistor using an organic material as the semiconductor layer, and amorphous silicon as the semiconductor layer. It may be an amorphous silicon thin film transistor to be used, or a polycrystalline silicon thin film transistor to use polycrystalline silicon as a semiconductor layer.
  • the planarization layer 314 may cover the thin film transistor 316 and the circuit portion 310b to planarize the top surfaces of the thin film transistor 316 and the circuit portion 310b so that the organic light emitting diode 315 may be formed.
  • the planarization layer 314 may be formed of a spin-on-glass (SOG) film, a polyimide polymer, a polyacrylic polymer, or the like, but is not limited thereto.
  • the organic light emitting diode 315 implements a display by emitting light by itself, and may include a first electrode 315a, an organic light emitting layer 315b, and a second electrode 315c which are sequentially stacked. Adjacent organic light emitting diodes may be distinguished through the insulating layer 317.
  • the organic light emitting diode 315 may include a bottom light emitting structure in which light generated in the organic light emitting layer 315b is emitted through the lower substrate, or a top light emitting structure in which light generated in the organic light emitting layer 315b is emitted upward.
  • the passivation layer 318 may cover the organic light emitting diode 315 to protect the organic light emitting diode 315.
  • the passivation layer 318 may be formed of an inorganic material such as SiOx, SiNx, SiC, SiON, SiONC, and amorphous carbon (aC). It may be formed of an organic material such as meth) acrylate, epoxy polymer, imide polymer and the like.
  • the passivation layer 318 may include an encapsulation layer in which a layer formed of an inorganic material and a layer formed of an organic material are sequentially stacked one or more times.
  • the adhesive layer 360 adheres the display unit 350a and the polarizing plate 370, and is formed of an adhesive composition including a (meth) acrylate-based resin, a curing agent, an initiator, and a silane coupling agent. Can be.
  • the polarizer 370 may implement polarization of internal light or prevent reflection of external light to implement a display or increase a contrast ratio of the display.
  • the polarizing plate may be composed of a polarizer alone.
  • the polarizer may include a polarizer and a protective film formed on one or both sides of the polarizer.
  • the polarizing plate may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer.
  • the polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.
  • the touch screen panel 380 detects a change in capacitance generated when a human body or a conductor such as a stylus touches to generate an electrical signal.
  • the display unit 350a may be driven by the signal.
  • the touch screen panel 380 is formed by patterning a flexible and conductive conductor, and may include a second sensor electrode formed between the first sensor electrode and the first sensor electrode to cross the first sensor electrode. have.
  • the conductor for the touch screen panel 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.
  • the flexible window film 390 may be formed on the outermost side of the flexible display device 300 to protect the display device.
  • an adhesive layer is further formed between the polarizing plate 370 and the touch screen panel 380 and / or between the touch screen panel 380 and the flexible window film 390 to form a polarizing plate, a touch screen panel, and a flexible display panel.
  • the bond between the window films can be strengthened.
  • the adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.
  • a polarizer may be further formed below the display unit 350a to implement polarization of the internal light.
  • FIG. 5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • the flexible display device 400 includes a display 350a, a touch screen panel 380, a polarizer 370, and a flexible window film 390.
  • the window film 390 may include a flexible window film according to embodiments of the present invention.
  • Flexible display according to an embodiment of the present invention except that the touch screen panel 380 is not directly formed on the flexible window film 390, but the touch screen panel 380 is formed below the polarizer 370. It is substantially the same as the device. In this case, the touch screen panel 380 may be formed together with the display 350a.
  • the touch screen panel 380 since the touch screen panel 380 is formed together with the display unit 350a on the display unit 350a, the display panel 350a may be thinner and brighter than the flexible display device according to the exemplary embodiment of the present invention, and thus may have good visibility.
  • the touch screen panel 380 may be formed by deposition, but is not limited thereto.
  • the pressure-sensitive adhesive layer is further formed therein to increase the mechanical strength of the display device.
  • the adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.
  • a polarizing plate is further formed below the display unit 350a to induce polarization of internal light to improve a display image.
  • the flexible display apparatus 500 includes a display unit 350b, an adhesive layer 360, and a flexible window film 390, and a flexible window film 390. May include a flexible window film according to embodiments of the present invention. It is substantially the same as the flexible display device according to the exemplary embodiment of the present invention except that the device may be driven only by the display unit 350b and the polarizer and the touch screen panel are excluded.
  • the display unit 350b may include a substrate and an optical element including an LCD, an OLED, or an LED element formed on the substrate, and the display unit 350b may have a touch screen panel therein.
  • the first fluorine-containing silicone resin of formula 1 is a silicone monomer that provides (R a SiO (4-a) / 2 ) and a silicone monomer that provides (X b SiO (4-b) / 2 ) It may be prepared by the hydrolysis and condensation reaction of the silicone mixture comprising a.
  • the silicone monomers providing (R a SiO (4-a) / 2 ) are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane, and the like, but is not limited thereto.
  • the silicone monomers providing (X b SiO (4-b) / 2 ) are 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorojade.
  • Tyltrimethoxysilane 1H, 1H, 2H, 2H-perfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Octyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane, and the like, but is not limited thereto.
  • the monomer mixture is a (R a SiO (4-a ) / 2) silicone monomer about 0.01mol% to about 99.99mol%, specifically from about 80mol% to about 99.99mol%, and more specifically to provide about 90 mol% to about 99.5 mol%, about 0.01 mol% to about 99.99 mol%, specifically about 0.01 mol% to about 20 mol%, more specifically about about 0.1 mol% of a silicone monomer providing (X b SiO (4-b) / 2 ) 0.5 mol% to about 10 mol%.
  • the appearance of the window film can be improved and less glare.
  • a second silicone resin is silicone monomer to provide a silicon monomer alone, or (R 1 SiO 3/2) to provide (R 1 SiO 3/2) according to the embodiment; And (R 2 R 3 SiO 2/ 2) a silicon monomer, to provide a (R 4 R 5 R 6 SiO 1/2) to provide the silicon monomer, (SiO 4/2) at least one mixture of the silicone monomers to provide for It can be prepared by the hydrolysis and condensation reaction of.
  • (R 1 SiO 3/2) to provide a silicone monomer is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 3- doksi glycidyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be the doksi propyl triethoxysilane, (R 2 R 3 SiO 2 /2) to provide a silicon monomer include dimethyl dimethoxysilane, dimethyl diethoxysilane , Diethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane, and the like, (SiO 4 / 2 ) may be te
  • the monomer mixture (R 1 SiO 3/2) silicone monomer 100mol% which provides, specifically from about 85mol% to about 99mol%, about 1mol% to about 15mol%, about 40mol% to about 95mol%, It may be about 1mol% to about 40mol%, (SiO 4/2 ) silicon monomer from about 0mol%, about 1mol% to about 20mol% to service. In the above range, the hardness and flexibility of the window film can be improved.
  • Hydrolysis and condensation reaction of the monomer mixture can be carried out according to a conventional method for producing a silicone resin.
  • Hydrolysis can include reacting the monomer mixture in water and in a mixture of one or more of the desired acids, bases.
  • the acid may be HCl, HNO 3 , acetic acid and the like
  • the base may be NaOH, KOH and the like.
  • the hydrolysis may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 10 hours
  • the condensation reaction may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 12 hours under the same conditions as the hydrolysis. have. In the above range, the production yield of the silicone resin may be high.
  • the flexible window film 100 may be manufactured by a method of manufacturing a flexible window film including coating and curing a composition for a window film according to embodiments of the present invention on a base layer 110.
  • the method of coating the composition for the window film on the base layer 110 may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating, or the like, but is not limited thereto.
  • the composition for the window film may be coated on the base layer 110 in a thickness of about 5 ⁇ m to about 100 ⁇ m. It is possible to secure the desired coating layer in the above range and may have an excellent effect of hardness and flexibility.
  • Curing is to form a coating layer by curing the composition for a window film, and may include at least one of photocuring and thermal curing. Photocuring may involve irradiation with light intensity of approximately 10mJ / cm 2 to about 1,000mJ / cm 2 at a wavelength of 400nm or less. Thermal curing may include treatment at about 40 ° C.
  • the composition for a window film may be sufficiently cured.
  • it may be thermally cured after photocuring, and as a result, the hardness of the coating layer may be further increased.
  • the method may further include drying the composition for a window film before the composition for a window film is coated on the base layer 110 and then cured. By curing after drying, it is possible to prevent the surface roughness of the coating layer from increasing due to prolonged photocuring and thermal curing. Drying may be performed at about 40 ° C. to about 200 ° C. for about 1 minute to about 30 hours, but is not limited thereto.
  • a first fluorine-containing silicone resin was prepared in the same manner except for changing the type and / or content of the silicone monomer in Preparation Example 1-1 as shown in Table 1 below.
  • the structure of the silicone resin of a manufacture example is as Table 1 below.
  • the coating layer composition was applied to a PI film (polyimide film, SDI, thickness: 80 ⁇ m), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating film having a thickness of 50 ⁇ m. Postcure was carried out in an oven for 24hr to prepare a window film.
  • Example 1 the window film was manufactured in the same manner except for changing the type and content of the first fluorine-containing silicone resin and the second silicone resin, the content of the crosslinking agent, and / or the thickness of the coating layer as shown in Table 2 below. .
  • composition for coating layer on a PI film polyimide film, SDI, thickness: 80 ⁇ m
  • PI film polyimide film, SDI, thickness: 80 ⁇ m
  • Postcure for 24hr in a 100 °C oven to prepare a window film.
  • a window film was manufactured in the same manner as in Example 11, except that the content of the first fluorine-containing silicone resin of Preparation Example 1-1, the second silicone resin of Preparation Example 4, a crosslinking agent, and an initiator were changed as shown in Table 3 below. It was.
  • a window film was manufactured in the same manner except in Example 15, 5g of fluorine acrylate resin RS-75 was used.
  • a composition for a window coating layer 25 g of Epoxy hybrimer (Solip Co., Ltd.) and 20 g of diluent MEK (Daejung Chemical) were mixed to prepare a composition for a window coating layer.
  • the composition for window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 ⁇ m), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating layer having a thickness of 10 ⁇ m. Postcure was performed in the oven for 24hr.
  • RIQ The window coating layer of the window film was measured by Rhopoint IQ of Rhopoint.
  • Pencil hardness It measures by the JIS K5400 method using the pencil hardness meter (Heidon) about the coating layer of a window film. In measuring the pencil hardness, a pencil of 6B to 9H manufactured by Mitsubishi Corporation was used. The load of the pencil on the coating layer was 1 kg, the angle at which the pencil was drawn was 45 °, and the speed at which the pencil was drawn was 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, the five times the five times the maximum pencil hardness value when there is no scratch.
  • Curvature radius The window film (width x length, 1cmx10cm) was evaluated visually whether the crack generate
  • Example 11 12 13 14 15 16 1st fluorine-containing silicone resin (by weight) Preparation Example 1-1 0.5 One 5 10 One One Preparation Example 1-2 - - - - - - Preparation Example 1-3 - - - - - - Preparation Example 1-4 - - - - - - 2nd silicone resin (part by weight) Preparation Example 4 99.5 99 95 90 99 99 Crosslinking agent (parts by weight) 40 40 40 40 40 40 40 40 40 Fluorine (meth) acrylate resin (parts by weight) - - - - 2 5 Initiator (parts by weight) One One One One One One One One One Coating layer thickness ( ⁇ m) 50 50 50 50 50 50 50 50 50 50 50 50 RIQ 88.1 91.3 93.5 94.0 93.6 94.2 Pencil hardness 6H 6H 5H 5H 7H 8H Exterior 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 2nd silicone resin (part by weight) Preparation Example 2 100 - 100 Epoxy hybrimer (parts by weight) - 100 - Crosslinking agent (parts by weight) 25 - 25 Initiator (parts by weight) One - One Fluorine-containing leveling agent (parts by weight) - - 2.5 Coating layer thickness ( ⁇ m) 10 10 10 RIQ 76.6 83.7 79.8 Diffuse reflectance (%, @ 550nm) 2.109 1.361 1.179 Pencil hardness 9H 9H 4H Bending Radius (mm) 0.39 0.38 0.14 Exterior One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One Fluorine-containing leveling agent (parts by weight) - - 2.5 Coating layer thickness ( ⁇ m) 10 10 10 10 RIQ 76.6 83.7 79.8 Diffuse
  • the flexible window film of the present invention had an RIQ of 85 or more and an egg reflectance of 2% or less, which was excellent in appearance and less glare.
  • the flexible window film of the present invention has a pencil hardness of 4H or more, a high hardness, a radius of curvature of 5.0 mm or less, and excellent flexibility, and thus can be used as a flexible window film.
  • the window film containing a fluorine-based acrylate resin was improved hardness compared to the window film containing the same amount of the first fluorine-containing silicone resin, but also improved the appearance of the window film.
  • the comparative example does not include a first fluorine-containing silicone resin, the RIQ was less than 85 was not good appearance.

Abstract

Provided are a composition for a window film and a flexible window film formed from same, the composition comprising: a first fluorine-containing silicone resin; a second silicone resin having an epoxy group or an epoxy-group-containing functional group; and an initiator. The flexible window film has low diffuse reflectance and excellent hardness and flexibility.

Description

윈도우 필름용 조성물 및 이로부터 형성된 플렉시블 윈도우 필름Composition for window film and flexible window film formed therefrom
본 발명은 윈도우 필름용 조성물 및 이로부터 형성된 플렉시블 윈도우 필름 에 관한 것이다.The present invention relates to a composition for a window film and a flexible window film formed therefrom.
디스플레이 장치에서 유리 기판 또는 고경도 기판을 필름으로 대체하면서, 접고 펼 수 있는 유연성을 갖는 플렉시블(flexible) 디스플레이 장치가 개발되고 있다. 플렉시블 디스플레이 장치는 얇고 가볍고 충격에도 강하고, 접고 펼 수 있다. 윈도우 필름은 디스플레이 장치의 최 외곽에 위치되므로 유연성 및 경도가 좋아야 한다. 윈도우 필름은 코팅 용액을 기재층 위에 도포하여 제조되는데, 코팅 용액이 균일하게 도포되지 않을 경우 외관이 좋지 않을 수 있고, 이로 인해 디스플레이 상의 왜곡이 생길 수 있고, 난 반사율이 높아 디스플레이 상이 선명하지 않거나 눈부심을 줄 수 있다.In the display device, a flexible display device having a flexibility to be folded and unfolded while replacing a glass substrate or a high hardness substrate with a film has been developed. Flexible display devices are thin, light, impact-resistant, and foldable. Since the window film is located at the outermost side of the display device, it should have good flexibility and hardness. The window film is prepared by applying a coating solution on a substrate layer, which may not have a good appearance if the coating solution is not uniformly applied, resulting in distortion on the display, and high reflectivity, resulting in an unclear or glare on the display. Can give
본 발명의 배경기술은 일본공개특허 제2007-176542호에 개시되어 있다.Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2007-176542.
본 발명이 해결하고자 하는 과제는 외관이 우수하고 난 반사율이 낮은 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하는 것이다.The problem to be solved by the present invention is to provide a composition for a window film that can implement a window film with excellent appearance and low reflectance.
본 발명이 해결하고자 하는 다른 과제는 경도와 유연성이 우수한 플렉시블 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하는 것이다.Another object of the present invention is to provide a composition for a window film that can implement a flexible window film with excellent hardness and flexibility.
본 발명이 해결하고자 하는 또 다른 과제는 화면 품질 개선 효과가 있는 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하는 것이다.Another object of the present invention is to provide a composition for a window film that can implement a window film having an effect of improving the screen quality.
본 발명이 해결하고자 하는 또 다른 과제는 외관이 우수하고 난 반사율이 낮으며 경도와 유연성이 우수한 플렉시블 윈도우 필름을 제공하는 것이다.Another problem to be solved by the present invention is to provide a flexible window film having excellent appearance, low reflectance and excellent hardness and flexibility.
본 발명의 윈도우 필름용 조성물은 하기 화학식 1의 제1 불소 함유 실리콘 수지, 에폭시기 또는 에폭시기 함유 작용기를 갖는 제2실리콘 수지, 및 개시제를 포함할 수 있다:The composition for a window film of the present invention may include a first fluorine-containing silicone resin of Formula 1, a second silicone resin having an epoxy group or an epoxy group-containing functional group, and an initiator:
<화학식 1><Formula 1>
(RaSiO(4-a)/2)x(XbSiO(4-b)/2)y (R a SiO (4-a) / 2 ) x (X b SiO (4-b) / 2 ) y
(상기 화학식 1에서, R, X, a, b, x 및 y는 하기 발명의 상세한 설명에서 정의한 바와 같다).(In Formula 1, R, X, a, b, x and y are as defined in the detailed description of the invention below).
본 발명의 플렉시블 윈도우 필름은 기재층 및 상기 기재층 상에 형성된 코팅층을 포함하고, 상기 플렉시블 윈도우 필름은 RIQ가 약 85 이상, 연필경도가 약 4H 이상, 곡률반경이 약 5.0mm 이하가 될 수 있다.The flexible window film of the present invention includes a base layer and a coating layer formed on the base layer, wherein the flexible window film may have a RIQ of about 85 or more, a pencil hardness of about 4H or more, and a radius of curvature of about 5.0 mm or less. .
본 발명은 외관이 우수하고 난 반사율이 낮은 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하였다.The present invention provides a composition for a window film that can implement a window film having excellent appearance and low reflectance.
본 발명은 경도와 유연성이 우수한 플렉시블 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하였다.The present invention provides a composition for a window film that can implement a flexible window film having excellent hardness and flexibility.
본 발명은 화면 품질 개선 효과가 있는 윈도우 필름을 구현할 수 있는 윈도우 필름용 조성물을 제공하였다.The present invention provides a composition for a window film that can implement a window film having an effect of improving screen quality.
본 발명은 외관이 우수하고 난 반사율이 낮으며 경도와 유연성이 우수한 플렉시블 윈도우 필름을 제공하였다.The present invention provides a flexible window film having excellent appearance, low reflectance and excellent hardness and flexibility.
도 1은 본 발명의 일 실시예에 따른 플렉시블 윈도우 필름의 단면도이다.1 is a cross-sectional view of a flexible window film according to an embodiment of the present invention.
도 2는 본 발명의 다른 실시예에 따른 플렉시블 윈도우 필름의 단면도이다.2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.
도 3은 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치의 단면도이다.3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention.
도 4는 도 3의 디스플레이부의 일 실시예에 따른 단면도이다.4 is a cross-sectional view according to an exemplary embodiment of the display unit of FIG. 3.
도 5는 본 발명의 다른 실시예에 따른 플렉시블 디스플레이 장치의 단면도이다.5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
도 6은 본 발명의 또 다른 실시예에 따른 플렉시블 디스플레이 장치의 단면도이다.6 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
첨부한 도면을 참고하여 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성 요소에 대해서는 동일한 도면 부호를 붙였다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.
본 명세서에서 "상부"와 "하부"는 도면을 기준으로 정의한 것으로서, 시 관점에 따라 "상부"가 "하부"로 "하부"가 "상부"로 변경될 수 있고, "위(on)" 또는 "상(on)"으로 지칭되는 것은 바로 위뿐만 아니라 중간에 다른 구조를 개재한 경우도 포함할 수 있다. 반면, "직접 위(directly on)" 또는 "바로 위"로 지칭되는 것은 중간에 다른 구조를 개재하지 않은 것을 의미한다.In the present specification, "upper" and "lower" are defined based on the drawings, and according to a viewpoint, "upper" may be changed to "lower" and "lower" to "upper", and "on" or What is referred to as “on” may include not only the above but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly on" means that there is no intervening structure in between.
본 명세서에서 "RIQ(Reflected Image Quality)"는 윈도우 코팅층 표면의 반사된 이미지의 선명도를 측정하는 것이다. RIQ는 Rhopoint社의 Rhopoint IQ로 측정하고, 0부터 100까지의 값이 될 수 있으며, RIQ 값이 클수록, 즉 100에 가까울수록 윈도우 코팅층 표면이 매끄럽고(smooth) 외관이 우수함을 의미한다."Reflected Image Quality (RIQ)" herein refers to measuring the sharpness of the reflected image of the surface of the window coating layer. RIQ is measured by Rhopoint's Rhopoint IQ, and can be a value from 0 to 100. The larger the RIQ value, that is, the closer to 100, the smoother the surface of the window coating layer and the better appearance.
본 명세서에서 "에폭시기"는 글리시딜기, 글리시독시기 또는 에폭시화된 C4 내지 C20의 시클로알킬기이고, "에폭시기 함유 작용기"는 에폭시기를 갖는 C1 내지 C20의 알킬기 또는 에폭시기를 갖는 C5 내지 C20의 시클로알킬기이다.As used herein, "epoxy group" is a glycidyl group, glycidoxy group or epoxidized C4 to C20 cycloalkyl group, and "epoxy group containing functional group" is C1 to C20 alkyl group having an epoxy group or C5 to C20 cycloalkyl group having an epoxy group. to be.
본 명세서에서 "할로겐"은 불소, 염소, 브롬 또는 요오드를 의미하고, "(메트)아크릴"은 아크릴 및/또는 메타아크릴을 의미하고, "치환된"은 특별히 언급되지 않는 한, 작용기 중 하나 이상의 수소 원자가 수산기, 비치환된 C1 내지 C10의 알킬기, C1 내지 C10의 알콕시기, C3 내지 C10의 시클로알킬기, 비치환된 C6 내지 C20의 아릴기, C7 내지 C20의 아릴알킬기, C1 내지 C10의 알킬기로 치환된 C6 내지 C20의 아릴기, 또는 C1 내지 C10의 알콕시기로 치환된 C1 내지 C10의 알킬기로 치환된 것을 의미한다.As used herein, "halogen" refers to fluorine, chlorine, bromine or iodine, "(meth) acryl" refers to acrylic and / or methacryl, and "substituted" means one or more of the functional groups, unless specifically noted. Hydrogen atom is hydroxyl group, unsubstituted C1 to C10 alkyl group, C1 to C10 alkoxy group, C3 to C10 cycloalkyl group, unsubstituted C6 to C20 aryl group, C7 to C20 arylalkyl group, C1 to C10 alkyl group It means substituted with a substituted C6 to C20 aryl group, or C1 to C10 alkoxy group substituted with a C1 to C10 alkyl group.
본 명세서에서 "Ec"는 2-(3,4-에폭시시클로헥실)에틸기, "Gp"는 3-글리시독시프로필기, "Me"는 메틸기, "Fd"는 1H, 1H, 2H, 2H-퍼플루오로데실기, "Fo"는 1H, 1H, 2H, 2H-퍼플루오로옥틸기이다.In the present specification, "Ec" is 2- (3,4-epoxycyclohexyl) ethyl group, "Gp" is 3-glycidoxypropyl group, "Me" is methyl group, "Fd" is 1H, 1H, 2H, 2H- Perfluorodecyl group, "Fo" is a 1H, 1H, 2H, 2H- perfluorooctyl group.
이하, 본 발명의 일 실시예에 따른 윈도우 필름용 조성물을 설명한다.Hereinafter, a composition for a window film according to an embodiment of the present invention will be described.
본 발명의 일 실시예에 따른 윈도우 필름용 조성물은 제1불소 함유 실리콘 수지, 제2실리콘 수지, 및 개시제를 포함할 수 있다. 본 실시예에 따른 윈도우 필름용 조성물은 제1 불소 함유 실리콘 수지를 포함함으로써 윈도우 필름의 외관을 좋게 하고 난 반사율(diffuse reflection)을 낮추며 윈도우 필름의 투명성을 높이고, 윈도우 필름용 조성물의 코팅성을 높일 수 있다. 본 실시예에 따른 윈도우 필름용 조성물은 제1 불소 함유 실리콘 수지와 제2실리콘 수지를 포함함으로써 윈도우 필름의 경도 및 유연성을 좋게 하여 플렉시블 윈도우 필름을 구현할 수 있다. 제1 불소 함유 실리콘 수지와 제2실리콘 수지는 서로 다르며, 각각 단독 또는 2종 이상 혼합하여 윈도우 필름용 조성물에 포함될 수 있다.The composition for a window film according to an embodiment of the present invention may include a first fluorine-containing silicone resin, a second silicone resin, and an initiator. The composition for a window film according to the present embodiment includes the first fluorine-containing silicone resin to improve the appearance of the window film, to reduce diffuse reflection, to increase the transparency of the window film, and to improve the coating property of the composition for the window film. Can be. The composition for a window film according to the present embodiment may implement a flexible window film by improving the hardness and flexibility of the window film by including the first fluorine-containing silicone resin and the second silicon resin. The first fluorine-containing silicone resin and the second silicone resin are different from each other, and may be included in the composition for a window film, alone or in combination of two or more thereof.
제1 불소 함유 실리콘 수지는 하기 화학식 1로 표시될 수 있다:The first fluorine-containing silicone resin may be represented by Formula 1 below:
<화학식 1><Formula 1>
(RaSiO(4-a)/2)x(XbSiO(4-b)/2)y (R a SiO (4-a) / 2 ) x (X b SiO (4-b) / 2 ) y
(상기 화학식 1에서, R은 에폭시기, 에폭시기 함유 작용기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C5 내지 C20의 시클로알킬기, 또는 치환 또는 비치환된 C6 내지 C20의 아릴기,(In Formula 1, R is an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
X는 1개 이상의 불소를 함유하는 치환 또는 비치환된 C1 내지 C30의 알킬기, 1개 이상의 불소를 함유하는 치환 또는 비치환된 C5 내지 C20의 시클로알킬기, 또는 1개 이상의 불소를 함유하는 치환 또는 비치환된 C6 내지 C20의 아릴기,X is a substituted or unsubstituted C1 to C30 alkyl group containing at least one fluorine, a substituted or unsubstituted C5 to C20 cycloalkyl group containing at least one fluorine, or a substituted or unsubstituted containing at least one fluorine Substituted C6 to C20 aryl group,
a는 0 내지 3의 정수, b는 1 내지 3의 정수, 0≤x<1, 0<y≤1, x+y=1).a is an integer of 0 to 3, b is an integer of 1 to 3, 0 ≦ x <1, 0 <y ≦ 1, and x + y = 1).
구체적으로, R은 에폭시기 또는 에폭시기 함유 작용기로서, 에폭시화된 C4 내지 C20의 시클로알킬기를 갖는 C1 내지 C20의 알킬기, 글리시독시기를 갖는 C1 내지 C20의 알킬기, 또는 C1 내지 C10의 알킬기, 더 구체적으로 에폭시시클로헥실에틸기, 글리시독시프로필기, 메틸기 또는 에틸기일 수 있다. 구체적으로, X는 C1 내지 C10의 플루오로알킬기, C1 내지 C10의 퍼플루오로알킬기, C1 내지 C10의 플루오로알킬기를 갖는 C1 내지 C10의 알킬기, 또는 C1 내지 C10의 퍼플루오로알킬기를 갖는 C1 내지 C10의 알킬기가 될 수 있다. 더 구체적으로, X는 1H, 1H, 2H, 2H-퍼플루오로데실기, 1H, 1H, 2H, 2H-퍼플루오로옥틸기, 또는 1H, 1H, 2H, 2H-퍼플루오로헥실기 등이 될 수 있다. 구체적으로, 화학식 1에서, 약 0.0001≤x≤ 약 0.9999, 약 0.0001≤y≤ 약 0.9999, 더 구체적으로 약 0.8000≤x≤ 약 0.9999, 약 0.0001≤y≤ 약 0.2000, 보다 더 구체적으로 약 0.9000≤x≤ 약 0.995, 약 0.005≤y≤ 약 0.1000이 될 수 있다. 상기 범위에서, 윈도우 필름의 외관이 개선되고 투명성이 좋으며 난 반사율이 낮아질 수 있다.Specifically, R is an epoxy group or an epoxy group-containing functional group, and C1 to C20 alkyl group having a epoxidized C4 to C20 cycloalkyl group, C1 to C20 alkyl group having a glycidoxy group, or C1 to C10 alkyl group, more specifically It may be an epoxycyclohexylethyl group, a glycidoxy propyl group, a methyl group, or an ethyl group. Specifically, X represents C1 to C10 fluoroalkyl group, C1 to C10 perfluoroalkyl group, C1 to C10 alkyl group having C1 to C10 fluoroalkyl group, or C1 to C10 having C1 to C10 perfluoroalkyl group It may be an alkyl group of C10. More specifically, X is a 1H, 1H, 2H, 2H- perfluorodecyl group, 1H, 1H, 2H, 2H- perfluorooctyl group, or 1H, 1H, 2H, 2H-perfluorohexyl group, etc. Can be. Specifically, in Formula 1, about 0.0001 ≦ x ≦ about 0.9999, about 0.0001 ≦ y ≦ about 0.9999, more specifically about 0.8000 ≦ x ≦ about 0.9999, about 0.0001 ≦ y ≦ about 0.2000, and more specifically about 0.9000 ≦ x <About 0.995, about 0.005 <y <about 0.1000. In the above range, the appearance of the window film can be improved, the transparency is good and the egg reflectance can be lowered.
일 구체예에서, 제1 불소 함유 실리콘 수지는 하기 화학식 1-1, 화학식 1-2또는 화학식 1-3으로 표시될 수 있다:In one embodiment, the first fluorine-containing silicone resin may be represented by the following Formula 1-1, Formula 1-2, or Formula 1-3:
<화학식 1-1><Formula 1-1>
(RSiO3/2)x(XSiO3/2)y (RSiO 3/2 ) x (XSiO 3/2 ) y
<화학식 1-2><Formula 1-2>
(RSiO3/2)x1(RR'SiO2/2)x2(XSiO3/2)y (RSiO 3/2 ) x1 (RR'SiO 2/2 ) x2 (XSiO 3/2 ) y
<화학식 1-3><Formula 1-3>
(RSiO3/2)x1(R'SiO3/2)x2(XSiO3/2)y (RSiO 3/2 ) x1 (R'SiO 3/2 ) x2 (XSiO 3/2 ) y
(상기 화학식 1-1 내지 1-3에서, R 및 X는 상기 화학식 1에서 정의한 바와 같고, R'은 에폭시기, 에폭시기 함유 작용기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C5 내지 C20의 시클로알킬기, 또는 치환 또는 비치환된 C6 내지 C20의 아릴기, R 및 R'은 서로 다르고, 0<x<1, 0<y<1, x+y=1, 0<x1<1, 0<x2<1, 0<y<1, x1+x2+y=1). 구체적으로, 화학식 1-1 내지 1-3에서, 약 0.0001≤x 또는 x1+x2≤ 약 0.9999, 약 0.0001≤y≤ 약 0.9999, 약 0.8000≤x 또는 x1+x2≤ 약 0.9999, 약 0.0001≤y≤ 약 0.2000, 보다 더 구체적으로 약 0.9000≤x 또는 x1+x2≤ 약 0.995, 약 0.005≤y≤ 약 0.1000가 될 수 있다. 상기 범위에서, 윈도우 필름의 외관이 개선되고 투명성이 좋으며 난 반사율이 낮아질 수 있다.(In Formulas 1-1 to 1-3, R and X are as defined in Formula 1, R 'is an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 To C20 cycloalkyl group, or substituted or unsubstituted C6 to C20 aryl group, R and R 'are different from each other, 0 <x <1, 0 <y <1, x + y = 1, 0 <x1 <1 , 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1). Specifically, in Formulas 1-1 to 1-3, about 0.0001≤x or x1 + x2≤ about 0.9999, about 0.0001≤y≤ about 0.9999, about 0.8000≤x or x1 + x2≤ about 0.9999, about 0.0001≤y≤ About 0.2000, more specifically about 0.9000 ≦ x or x1 + x2 ≦ about 0.995, about 0.005 ≦ y ≦ about 0.1000. In the above range, the appearance of the window film can be improved, the transparency is good and the egg reflectance can be lowered.
더 구체적으로, 제1 불소 함유 실리콘 수지는 하기 화학식 1-1-1 내지 1-1-10으로 표시될 수 있다:More specifically, the first fluorine-containing silicone resin may be represented by the following Chemical Formulas 1-1-1 to 1-1-10:
<화학식 1-1-1><Formula 1-1-1>
(EcSiO3/2)x(FdSiO3/2)y (EcSiO 3/2 ) x (FdSiO 3/2 ) y
<화학식 1-1-2><Formula 1-1-2>
(EcSiO3/2)x(FoSiO3/2)y (EcSiO 3/2 ) x (FoSiO 3/2 ) y
<화학식 1-1-3><Formula 1-1-3>
(GpSiO3/2)x(FdSiO3/2)y (GpSiO 3/2 ) x (FdSiO 3/2 ) y
<화학식 1-1-4><Formula 1-1-4>
(GpSiO3/2)x(FoSiO3/2)y (GpSiO 3/2 ) x (FoSiO 3/2 ) y
<화학식 1-1-5><Formula 1-1-5>
(EcSiO3/2)x1((Me)2SiO2/2)x2(FdSiO3/2)y (EcSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FdSiO 3/2 ) y
<화학식 1-1-6><Formula 1-1-6>
(EcSiO3/2)x1((Me)2SiO2/2)x2(FoSiO3/2)y (EcSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FoSiO 3/2 ) y
<화학식 1-1-7><Formula 1-1-7>
(GpSiO3/2)x1((Me)2SiO2/2)x2(FdSiO3/2)y (GpSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FdSiO 3/2 ) y
<화학식 1-1-8><Formula 1-1-8>
(GpSiO3/2)x1((Me)2SiO2/2)x2(FoSiO3/2)y (GpSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FoSiO 3/2 ) y
<화학식 1-1-9><Formula 1-1-9>
(EcSiO3/2)x1(GpSiO3/2)x2(FdSiO3/2)y (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (FdSiO 3/2 ) y
<화학식 1-1-10><Formula 1-1-10>
(EcSiO3/2)x1(GpSiO3/2)x2(FoSiO3/2)y (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (FoSiO 3/2 ) y
(상기 화학식 1-1-1 내지 화학식 1-1-10에서, 0<x<1, 0<y<1, x+y=1, 0<x1<1, 0<x2<1, 0<y<1, x1+x2+y=1).(In Formulas 1-1-1 to 1-1-10, 0 <x <1, 0 <y <1, x + y = 1, 0 <x1 <1, 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1).
제1 불소 함유 실리콘 수지는 불소 함량이 약 0.1중량% 내지 약 50중량%, 구체적으로 약 0.2중량% 내지 약 30중량%, 보다 구체적으로 약 0.5 중량% 내지 약 20 중량%, 보다 더 구체적으로 약 1중량% 내지 약 10중량%가 될 수 있다. 상기 범위에서 윈도우 필름의 외관이 개선되고 투명성이 좋을 수 있다. 제1 불소 함유 실리콘 수지는 중량평균분자량이 약 2,000 내지 약 20,000, 구체적으로 약 4,000 내지 약 10,000, 더 구체적으로 약 4,500 내지 약 6,000이 될 수 있다. 상기 범위에서 윈도우 필름의 외관을 개선하고, 투명성을 높일 수 있다. 제1 불소 함유 실리콘 수지는 다분산도(PDI)가 약 1.0 내지 약 3.0, 구체적으로 약 1.5 내지 약 2.5, 에폭시 당량이 약 0.1mol/100g 내지 약 1.0mol/100g, 구체적으로 약 0.3mol/100g 내지 약 0.8mol/100g이 될 수 있다. 상기 범위에서, 조성물의 코팅성이 좋고, 코팅 물성이 안정적인 효과가 있을 수 있다. 제1 불소 함유 실리콘 수지는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 중 약 0.1중량% 내지 약 50중량%, 구체적으로 약 0.2중량% 내지 약 30중량%, 더 구체적으로 약 0.5중량% 내지 약 20중량%로 포함될 수 있다. 상기 범위에서, 윈도우 필름의 외관이 개선되고 투명성이 좋을 수 있다.The first fluorine-containing silicone resin has a fluorine content of about 0.1% to about 50% by weight, specifically about 0.2% to about 30% by weight, more specifically about 0.5% to about 20% by weight, even more specifically about And from about 1% to about 10% by weight. In the above range, the appearance of the window film may be improved and transparency may be good. The first fluorine-containing silicone resin may have a weight average molecular weight of about 2,000 to about 20,000, specifically about 4,000 to about 10,000, more specifically about 4,500 to about 6,000. It is possible to improve the appearance of the window film in the above range and to increase the transparency. The first fluorine-containing silicone resin has a polydispersity (PDI) of about 1.0 to about 3.0, specifically about 1.5 to about 2.5, epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g To about 0.8 mol / 100 g. In the above range, the coating property of the composition is good, there may be a stable coating properties. The first fluorine-containing silicone resin is about 0.1 wt% to about 50 wt%, specifically about 0.2 wt% to about 30 wt%, more specifically about 0.5 wt% of the total of the first fluorine-containing silicone resin and the second silicon resin. To about 20% by weight. In the above range, the appearance of the window film can be improved and the transparency can be good.
이하, 제2실리콘 수지에 대해 구체적으로 설명한다.Hereinafter, a 2nd silicone resin is demonstrated concretely.
제2실리콘 수지는 윈도우 필름을 형성하는 바인더로서, 윈도우 필름의 경도와 유연성을 좋게 할 수 있으며, 불소를 함유하지 않는 비-불소계 실리콘 수지로서, 하기 화학식 2로 표시될 수 있다:The second silicone resin is a binder for forming the window film, and may improve the hardness and flexibility of the window film, and may be represented by the following Chemical Formula 2 as a non-fluorine-based silicone resin containing no fluorine:
<화학식 2><Formula 2>
(R1SiO3/2)x(R2R3SiO2/2)y(R4R5R6SiO1/2)z(SiO4/2)w (R 1 SiO 3/2 ) x (R 2 R 3 SiO 2/2 ) y (R 4 R 5 R 6 SiO 1/2 ) z (SiO 4/2 ) w
(상기 화학식 2에서, R1은 에폭시기 또는 에폭시기 함유 작용기,(In Formula 2, R 1 is an epoxy group or an epoxy group-containing functional group,
R2 및 R3은 각각 독립적으로, 수소, 가교성 작용기, 비치환 또는 치환된 C1 내지 C20의 알킬기, 또는 비치환 또는 치환된 C5 내지 C20의 시클로알킬기,R 2 and R 3 are each independently hydrogen, a crosslinkable functional group, an unsubstituted or substituted C1 to C20 alkyl group, or an unsubstituted or substituted C5 to C20 cycloalkyl group,
R4, R5 및 R6은 각각 독립적으로, 수소, 가교성 작용기, 비치환 또는 치환된 C1 내지 C20의 알킬기, 비치환 또는 치환된 C5 내지 C20의 시클로알킬기, 또는 비치환 또는 치환된 C6 내지 C30의 아릴기,R 4 , R 5 and R 6 are each independently hydrogen, a crosslinkable functional group, unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 aryl group,
0<x≤1, 0≤y<1, 0≤z<1, 0≤w<1, x+y+z+w=1).0 <x ≦ 1, 0 ≦ y <1, 0 ≦ z <1, 0 ≦ w <1, x + y + z + w = 1).
구체적으로, R1은 에폭시화된 C4 내지 C20의 시클로알킬기를 갖는 C1 내지 C20의 알킬기, 또는 글리시독시기를 갖는 C1 내지 C20의 알킬기, 더 구체적으로 에폭시시클로헥실에틸기, 또는 글리시독시프로필기일 수 있다. 구체적으로, R2 및 R3은 각각 독립적으로 에폭시화된 C4 내지 C20의 시클로알킬기를 갖는 C1 내지 C20의 알킬기, C1 내지 C10의 알킬기, 더 구체적으로 에폭시시클로헥실에틸기 또는 메틸기가 될 수 있다. 상기 화학식 2에서 가교성 작용기는 에폭시기, 에폭시기 함유 작용기, 옥세탄일기 또는 옥세탄일기 함유 작용기를 의미한다. 이중 하기 화학식 2-1, 2-2의 제2실리콘 수지가 윈도우 필름의 외관, 경도 등을 확보하는데 더 바람직하다.Specifically, R 1 may be a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, or a C1 to C20 alkyl group having a glycidoxy group, more specifically an epoxycyclohexylethyl group, or a glycidoxypropyl group. have. Specifically, R 2 and R 3 may each independently be a C1 to C20 alkyl group, a C1 to C10 alkyl group, more particularly an epoxycyclohexylethyl group or a methyl group having a C4 to C20 cycloalkyl group. In Chemical Formula 2, a crosslinkable functional group refers to an epoxy group, an epoxy group-containing functional group, an oxetanyl group, or an oxetanyl group-containing functional group. Among them, the second silicone resins of the following Chemical Formulas 2-1 and 2-2 are more preferable for securing the appearance, hardness and the like of the window film.
일 구체예에서, 제2실리콘 수지는 하기 화학식 2-1, 2-2로 표시될 수 있다:In one embodiment, the second silicone resin may be represented by the following Chemical Formulas 2-1, 2-2:
<화학식 2-1><Formula 2-1>
(R1aSiO3/2)x1(R1bSiO3/2)x2 (R 1a SiO 3/2 ) x1 (R 1b SiO 3/2 ) x2
(상기 화학식 2-1에서, R1a, R1b는 에폭시기 또는 에폭시기 함유 작용기, 0≤x1≤1, 0≤x2≤1, x1+x2=1, x1+x2≠0, R1a와 R1b는 서로 다르다)(In Formula 2-1, R 1a , R 1b is an epoxy group or an epoxy group-containing functional group, 0 ≦ x1 ≦ 1, 0 ≦ x2 ≦ 1, x1 + x2 = 1, x1 + x2 ≠ 0, R 1a and R 1b are Different from each other)
<화학식 2-2><Formula 2-2>
(R1aSiO3/2)x1(R1bSiO3/2)x2(SiO4/2)w (R 1a SiO 3/2 ) x1 (R 1b SiO 3/2 ) x2 (SiO 4/2 ) w
(상기 화학식 2-2에서, R1a, R1b는 에폭시기 또는 에폭시기 함유 작용기, 0<x1<1, 0<x2<1, 0<w<1, x1+x2+w=1, R1a와 R1b는 서로 다르다). (In Formula 2-2, R 1a , R 1b is an epoxy group or an epoxy group-containing functional group, 0 <x1 <1, 0 <x2 <1, 0 <w <1, x1 + x2 + w = 1, R 1a and R 1b are different).
화학식 2-1에서, 약 0.70≤x1< 약 1, 약 0<x2≤ 약 0.30, 구체적으로 약 0.80≤x1< 약 1, 약 0<x2≤ 약 0.20, 더 구체적으로 약 0.85≤x1≤ 약 0.99, 약 0.01≤x2≤ 약 0.15가 될 수 있다. 또는, 화학식 2-1에서 x1은 1, x2는 0이 될 수 있다. 화학식 2-2에서, 약 0.30≤x1< 약 1.0, 약 0<x2≤ 약 0.50, 약 0<w≤ 약 0.40 더 구체적으로 약 0.40≤x1< 약 1.0, 약 0<x2≤ 약 0.40, 약 0<w≤ 약 0.30, 보다 더 구체적으로 약 0.40≤x1≤ 약 0.95, 약 0.01≤x2≤ 약 0.40, 약 0.01≤w≤ 약 0.20가 될 수 있다. 상기 범위에서, 윈도우 필름의 유연성과 경도 개선 효과가 있을 수 있다. 화학식 2-1, 2-2에서 R1a는 에폭시화된 C4 내지 C20의 시클로알킬기를 갖는 C1 내지 C20의 알킬기가 될 수 있고, R1b는 글리시딜기 또는 글리시독시기를 갖는, C1 내지 C20의 알킬기가 될 수 있다. In Formula 2-1, about 0.70 ≦ x1 <about 1, about 0 <x2 ≦ about 0.30, specifically about 0.80 ≦ x1 <about 1, about 0 <x2 ≦ about 0.20, more specifically about 0.85 ≦ x1 ≦ about 0.99 , About 0.01 ≦ x2 ≦ about 0.15. Alternatively, in Formula 2-1, x1 may be 1 and x2 may be 0. In Formula 2-2, about 0.30 ≦ x1 <about 1.0, about 0 <x2 ≦ about 0.50, about 0 <w ≦ about 0.40 More specifically about 0.40 ≦ x1 <about 1.0, about 0 <x2 ≦ about 0.40, about 0 <w ≦ about 0.30, even more specifically about 0.40 ≦ x1 ≦ about 0.95, about 0.01 ≦ x2 ≦ about 0.40, about 0.01 ≦ w ≦ about 0.20. In the above range, there may be an effect of improving the flexibility and hardness of the window film. In Formulas 2-1 and 2-2, R 1a may be a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, and R 1b may be a C1 to C20 having a glycidyl group or a glycidoxy group. It may be an alkyl group.
더 구체적으로, 제2실리콘 수지는 하기 화학식 2-1-1, 2-1-2으로 표시될 수 있다:More specifically, the second silicone resin may be represented by the following Chemical Formula 2-1-1, 2-1-2:
<화학식 2-1-1><Formula 2-1-1>
(EcSiO3/2)x1(GpSiO3/2)x2 (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2
(상기 화학식 2-1-1에서, 0≤x1≤1, 0≤x2≤1, x1+x2=1, x1+x2≠0).(In Formula 2-1-1, 0 ≦ x1 ≦ 1, 0 ≦ x2 ≦ 1, x1 + x2 = 1, x1 + x2 ≠ 0).
<화학식 2-1-2><Formula 2-1-2>
(EcSiO3/2)x1(GpSiO3/2)x2(SiO4/2)w (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (SiO 4/2 ) w
(상기 화학식 2-1-2에서, 0<x1<1, 0<x2<1, 0<w<1, x1+x2+w=1).(In Formula 2-1-2, 0 <x1 <1, 0 <x2 <1, 0 <w <1, x1 + x2 + w = 1).
제2실리콘 수지는 중량평균분자량이 약 2,000 내지 약 20,000, 구체적으로 약 4,000 내지 약 10,000, 더 구체적으로 약 4,500 내지 약 7,000이 될 수 있다. 상기 범위에서 상기 범위에서 윈도우 필름의 코팅층을 지지하는 효과가 있을 수 있다. 제2실리콘 수지는 다분산도(PDI)가 약 1.0 내지 약 3.0, 구체적으로 약 1.5 내지 약 2.5, 에폭시 당량이 약 0.1mol/100g 내지 약 1.0mol/100g, 구체적으로 약 0.3mol/100g 내지 약 0.8mol/100g이 될 수 있다. 상기 범위에서, 조성물의 코팅성이 좋고, 코팅 물성이 안정적인 효과가 있을 수 있다. 제2실리콘 수지는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 중 약 50중량% 내지 약 99.9중량%, 구체적으로 약 70중량% 내지 약 99.8중량%, 더 구체적으로 약 80중량% 내지 약 99.5중량%로 포함될 수 있다. 상기 범위에서, 윈도우 필름의 유연성과 경도 개선 효과가 있고, 윈도우 필름의 RIQ를 증가시켜 외관 개선 효과를 볼 수 있다.The second silicone resin may have a weight average molecular weight of about 2,000 to about 20,000, specifically about 4,000 to about 10,000, more specifically about 4,500 to about 7,000. In the above range may be effective to support the coating layer of the window film in the above range. The second silicone resin has a polydispersity (PDI) of about 1.0 to about 3.0, specifically about 1.5 to about 2.5, epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g to about It may be 0.8 mol / 100 g. In the above range, the coating property of the composition is good, there may be a stable coating properties. The second silicon resin is about 50% to about 99.9% by weight, specifically about 70% to about 99.8% by weight, more specifically about 80% to about 80% by weight of the sum of the first fluorine-containing silicone resin and the second silicon resin. It may be included in 99.5% by weight. In the above range, there is an effect of improving the flexibility and hardness of the window film, it is possible to see the appearance improvement effect by increasing the RIQ of the window film.
개시제는 제1 불소 함유 실리콘 수지, 제2실리콘 수지를 경화시키는 것으로, 광양이온 개시제, 광라디칼 개시제 중 하나 이상을 사용할 수 있고, 단독 또는 2종 이상 혼합하여 사용될 수 있다. 광양이온 개시제는 당업자에게 통상적으로 알려진 것을 사용할 수 있는데, 양이온과 음이온을 포함하는 오늄염을 사용할 수 있다. 구체적으로, 양이온은 디페닐요오드늄, 4-메톡시디페닐요오드늄, 비스(4-메틸페닐)요오드늄, 비스(4-터트-부틸페닐)요오드늄, 비스(도데실페닐)요오드늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]요오드늄 등의 디아릴요오드늄, 트리페닐술포늄, 디페닐-4-티오페녹시페닐술포늄 등의 트리아릴술포늄, 비스[4-(디페닐술포니오)페닐]술피드 등을 들 수 있고, 음이온은 헥사플루오로포스페이트, 테트라플루오로보레이트, 헥사플루오로안티모네이트, 헥사플루오로아르세네이트, 헥사클로로안티모네이트 등을 들 수 있다. 개시제는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 0.1중량부 내지 약 10중량부, 구체적으로 약 0.5중량부 내지 약 5중량부로 포함될 수 있다. 상기 범위에서 실리콘 수지가 충분히 경화될 수 있고 잔량의 개시제가 남아서 윈도우 필름의 광 특성(투과율, 색상 및 내광신뢰성에 등)이 저하되는 것을 막을 수 있다.The initiator is used to cure the first fluorine-containing silicone resin and the second silicone resin, and one or more of a photocationic initiator and an optical radical initiator may be used, and may be used alone or in combination of two or more thereof. Photocationic initiators can be used that is commonly known to those skilled in the art, may be used onium salt containing a cation and an anion. Specifically, the cation is diphenyl iodonium, 4-methoxydiphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, (4 Triarylsulfonium and bis [4, such as diaryl iodonium, such as -methylphenyl) [4- (2-methylpropyl) phenyl] iodonium, triphenylsulfonium, and diphenyl-4-thiophenoxyphenylsulfonium; -(Diphenylsulfonio) phenyl] sulfide, and the like, and the anion is hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, or the like. Can be mentioned. The initiator may be included in an amount of about 0.1 parts by weight to about 10 parts by weight, specifically about 0.5 parts by weight to about 5 parts by weight, based on 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicon resin. In this range, the silicone resin can be sufficiently cured and the residual amount of initiator remains to prevent the optical properties of the window film (such as transmittance, color and light reliability) from being lowered.
본 실시예에 따른 윈도우 필름용 조성물은 나노입자를 더 포함할 수 있다.The composition for a window film according to the present embodiment may further include nanoparticles.
나노입자는 윈도우 필름의 경도를 더 높일 수 있다. 나노입자는 실리카, 산화알루미늄, 산화지르코늄, 산화티타늄 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다. 나노입자는 실리콘 수지와의 혼합을 위해 실리콘(silicone) 화합물로 표면의 일부 또는 전부가 표면 처리될 수도 있다. 나노입자는 형상, 크기에 제한을 두지 않는다. 구체적으로, 나노입자는 구형, 판상형, 무정형 등의 형상의 입자를 포함할 수 있다. 나노입자는 평균 입경(D50)이 1nm 내지 200nm, 구체적으로 약 10nm 내지 약 50nm가 될 수 있다. 상기 범위에서 윈도우 필름의 표면 조도와 투명성에 영향을 주지 않고 윈도우 필름의 경도를 높일 수 있다. 나노입자는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 0.1중량부 내지 약 60중량부, 구체적으로 약 10중량부 내지 약 50중량부로 포함될 수 있다. 상기 범위에서 윈도우 필름의 표면 조도와 투명성에 영향을 주지 않고 윈도우 필름의 경도를 높일 수 있다.Nanoparticles can further increase the hardness of the window film. Nanoparticles may include, but are not limited to, one or more of silica, aluminum oxide, zirconium oxide, titanium oxide. Nanoparticles may be surface treated with some or all of the surface of a silicone compound for mixing with the silicone resin. Nanoparticles are not limited in shape and size. Specifically, the nanoparticles may include particles having a spherical shape, a plate shape, an amorphous shape, and the like. The nanoparticles may have an average particle diameter (D50) of about 1 nm to about 200 nm, specifically about 10 nm to about 50 nm. In the above range, the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film. The nanoparticles may be included in an amount of about 0.1 part by weight to about 60 parts by weight, specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicon resin. In the above range, the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.
본 실시예에 따른 윈도우 필름용 조성물은 첨가제를 더 포함할 수 있다. 첨가제는 윈도우 필름에 추가적인 기능을 제공할 수 있다. 첨가제는 윈도우 필름에 통상적으로 첨가되는 첨가제를 포함할 수 있다. 구체적으로, 첨가제는 UV 흡수제, 반응 억제제, 접착성 향상제, 요변성 부여제, 도전성 부여제, 색소 조정제, 안정화제, 대전방지제, 산화방지제 중 하나 이상을 포함할 수 있지만, 이에 제한되지 않는다. 반응 억제제는 에티닐시클로헥산을 포함할 수 있다. 접착성 향상제는 에폭시 또는 알콕시실릴기를 갖는 실란 화합물을 포함할 수 있다. 요변성 부여제는 연무상 실리카 등을 포함할 수 있다. 도전성 부여제는 은, 구리 알루미늄 등의 금속 분말을 포함할 수 있다. 색소 조정제는 안료, 염료 등을 포함할 수 있다. UV 흡수제는 윈도우 필름의 내광 신뢰성을 높일 수 있다. UV 흡수제는 당업자에게 알려진 통상의 흡수제를 사용할 수 있다. 구체적으로, UV 흡수제는 트리아진계, 벤즈이미다졸계, 벤조페논계, 벤조트리아졸계 중 하나 이상의 UV 흡수제를 포함할 수 있지만, 이에 제한되지 않는다. 첨가제는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 0.01중량부 내지 약 5중량부, 구체적으로 약 0.1중량부 내지 약 2.5중량부로 포함될 수 있다. 상기 범위에서 윈도우 필름의 경도와 유연성을 좋게 하고 첨가제 효과를 구현할 수 있다.The composition for a window film according to the present embodiment may further include an additive. The additive may provide additional functionality to the window film. The additives may include additives that are typically added to the window film. Specifically, the additive may include, but is not limited to, at least one of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a color adjuster, a stabilizer, an antistatic agent, and an antioxidant. The reaction inhibitor may include ethynylcyclohexane. An adhesion promoter may include a silane compound having an epoxy or alkoxysilyl group. The thixotropic agent may include fumed silica and the like. The conductivity providing agent may include metal powder such as silver and copper aluminum. Dye control agents may include pigments, dyes and the like. The UV absorber can increase the light resistance of the window film. UV absorbers can be used conventional absorbents known to those skilled in the art. Specifically, the UV absorber may include, but is not limited to, one or more UV absorbers of triazine-based, benzimidazole-based, benzophenone-based, and benzotriazole-based. The additive may be included in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.1 parts by weight to about 2.5 parts by weight, based on 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicon resin. In the above range can improve the hardness and flexibility of the window film and implement the additive effect.
본 실시예에 따른 윈도우 필름용 조성물은 코팅성, 도공성 또는 가공성을 용이하게 하기 위해 용제를 더 포함할 수도 있다. 용제는 메틸에틸케톤(MEK, methylethylketone), 메틸이소부틸케톤, 프로필렌글리콜모노메틸에테르아세테이트 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다.The composition for a window film according to the present embodiment may further include a solvent in order to facilitate coating, coatability, or processability. The solvent may include one or more of methyl ethyl ketone (MEK, methyl ethyl ketone), methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.
이하, 본 발명의 다른 실시예에 따른 윈도우 필름용 조성물을 설명한다.Hereinafter, a composition for a window film according to another embodiment of the present invention will be described.
본 실시예에 따른 윈도우 필름용 조성물은 가교제를 더 포함하는 점을 제외하고는 본 발명의 일 실시예에 따른 윈도우 필름용 조성물과 실질적으로 동일하다. 가교제를 더 포함함으로써 윈도우 필름의 경도와 유연성을 더 좋게 할 수 있다.The composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that the composition further includes a crosslinking agent. By further including a crosslinking agent, the hardness and flexibility of the window film can be improved.
가교제는 가교성 작용기를 함유함으로써 제1 불소 함유 실리콘 수지, 제 2실리콘 수지와 경화되어 윈도우 필름의 경도를 높이고 유연성을 좋게 할 수 있다. 가교제는 사슬형 지방족 탄화수소기, 고리형 지방족 탄화수소기, 수소 첨가된 방향족 탄화수소기 중 하나 이상을 더 포함함으로써 코팅층의 유연성을 더 높일 수도 있다. 가교제는 사슬형 지방족 에폭시 모노머, 고리형 지방족 에폭시 모노머, 수소 첨가된 방향족 탄화수소 에폭시 모노머, 옥세탄 모노머 중 하나 이상을 포함할 수 있고, 이들은 단독 또는 혼합하여 포함될 수 있다.The crosslinking agent may be cured with the first fluorine-containing silicone resin and the second silicone resin by containing a crosslinkable functional group to increase the hardness of the window film and improve flexibility. The crosslinking agent may further increase the flexibility of the coating layer by further including at least one of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group. The crosslinking agent may comprise one or more of a chained aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, an oxetane monomer, which may be included alone or in combination.
사슬형 지방족 에폭시 모노머는 1,4-부탄디올디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 글리세린트리글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르; 에틸렌글리콜, 프로필렌글리콜, 글리세린 등의 지방족 다가 알코올에 1종 또는 2종 이상의 알킬렌옥시드를 부가함으로써 얻어지는 폴리에테르폴리올의 폴리글리시딜에테르류; 지방족 장쇄 이염기산의 디글리시딜에스테르류; 지방족 고급 알코올의 모노글리시딜에테르류; 고급 지방산의 글리시딜에테르류; 에폭시화 대두유; 에폭시스테아르산부틸; 에폭시스테아르산옥틸; 에폭시화아마인유; 에폭시화 폴리부타디엔 등을 들 수 있다.Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, and polyethylene glycol diglycol. Cydyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Glycidyl ethers of higher fatty acids; Epoxidized soybean oil; Butyl epoxystearate; Octyl epoxystearate; Epoxidized flax oils; Epoxidized polybutadiene etc. are mentioned.
고리형 지방족 에폭시 모노머는 지환식기에 1개 이상의 에폭시기를 갖는 화합물로서, 구체적으로 지환족 에폭시 카르복실레이트, 지환족 에폭시 (메트)아크릴레이트 등을 포함할 수 있다. 더 구체적으로, (3,4-에폭시시클로헥실)메틸-3',4'-에폭시시클로헥산카르복실레이트, 디글리시딜 1,2-시클로헥산디카르복실레이트, 2-(3,4-에폭시시클로헥실-5,5-스피로-3,4-에폭시)시클로헥산-메타-디옥산, 비스(3,4-에폭시-6-메틸시클로헥실)아디페이트, 3,4-에폭시-6-메틸시클로헥실메틸-3',4'-에폭시-6'-메틸시클로헥산카르복실레이트, ε-카프로락톤 변성 3,4-에폭시시클로헥실메틸-3',4'-에폭시시클로헥산카르복실레이트, 트리메틸카프로락톤 변성 3,4-에폭시시클로헥실메틸-3',4'-에폭시시클로헥산카르복실레이트, β-메틸-δ-발레로락톤 변성 3,4-에폭시시클로헥실메틸-3'4,'-에폭시시클로헥산카르복실레이트, 1,4-시클로헥산디메탄올 비스(3,4-에폭시시클로헥산카르복실레이트), 에틸렌글리콜의 디(3,4-에폭시시클로헥실메틸)에테르, 에틸렌비스(3,4-에폭시시클로헥산카르복실레이트)), 3,4-에폭시시클로헥실메틸(메트)아크릴레이트, 비스(3,4-에폭시시클로헥실메틸)아디페이트, 4-비닐시클로헥센다이옥시드, 비닐시클로헥센모노옥시드 등을 들 수 있다. The cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like. More specifically, (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy-6-methylcyclohexyl) adipate, 3,4-epoxy-6-methyl Cyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethyl Caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3'4,'- Epoxycyclohexanecarboxylate, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohex Acid carboxylate)), 3,4-epoxycyclohexylmethyl (meth) acrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 4-vinylcyclohexenedioxide, vinylcyclohexene monooxide Etc. can be mentioned.
수소 첨가된 방향족 탄화수소 에폭시 모노머는 방향족 에폭시 모노머를 촉매 존재 하에 가압 하에서 선택적으로 수소화 반응을 행하여 얻어지는 화합물을 의미한다. 방향족 에폭시 모노머는 예를 들면, 비스페놀 A의 디글리시딜에테르, 비스페놀 F의 디글리시딜 에테르, 비스페놀 S의 디글리시딜 에테르 등과 같은 비스페놀형 에폭시 수지; 페놀 노볼락 에폭시 수지, 크레졸 노볼락 에폭시 수지, 히드록시벤즈알데히드페놀노볼락에폭시 수지와 같은 노볼락형 에폭시 수지; 테트라히드록시페닐메탄의 글리시딜 에테르, 테트라히드록시벤조페논의 글리시딜 에테르, 에폭시화 폴리비닐 페놀과 같은 다관능형의 에폭시 수지 등을 들 수 있다. Hydrogenated aromatic hydrocarbon epoxy monomer means a compound obtained by selectively hydrogenating an aromatic epoxy monomer under pressure in the presence of a catalyst. Aromatic epoxy monomers include, for example, bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinyl phenol.
옥세탄 모노머는 3-메틸옥세탄, 2-메틸옥세탄, 2-에틸헥실옥세탄, 3-옥세탄올, 2-메틸렌옥세탄, 3,3-옥세탄디메탄티올, 4-(3-메틸옥세탄-3-일)벤조나이트릴, N-(2,2-디메틸프로필)-3-메틸-3-옥세탄메탄아민, N-(1,2-디메틸부틸)-3-메틸-3-옥세탄메탄아민, (3-에틸옥세탄-3-일)메틸(메트)아크릴레이트, 4-[(3-에틸옥세탄-3-일)메톡시]부탄-1-올, 3-에틸-3-히드록시메틸옥세탄, 자일렌비스옥세탄, 3-[에틸-3[[(3-에틸옥세탄-3-일)]메톡시]메틸]옥세탄 중 하나 이상을 포함할 수 있지만, 이에 제한되지 않는다.Oxetane monomers include 3-methyloxetane, 2-methyloxetane, 2-ethylhexyl oxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethanethiol, 4- (3-methyl Oxetan-3-yl) benzonitrile, N- (2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3- Oxetanemethaneamine, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl- May comprise one or more of 3-hydroxymethyloxetane, xylenebisoxetane, 3- [ethyl-3 [[(3-ethyloxetan-3-yl)] methoxy] methyl] oxetane, This is not restrictive.
가교제는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 1중량부 내지 약 50중량부, 구체적으로 약 1중량부 내지 약 40중량부로 포함될 수 있다. 상기 범위에서 코팅층의 유연성과 경도, curl특성, 광 특성을 확보할 수 있다.The crosslinking agent may be included in an amount of about 1 part by weight to about 50 parts by weight, specifically about 1 part by weight to about 40 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicon resin. In the above range it can ensure the flexibility and hardness of the coating layer, curl properties, optical properties.
이하, 본 발명의 또 다른 실시예에 따른 윈도우 필름용 조성물을 설명한다.Hereinafter, a composition for a window film according to another embodiment of the present invention will be described.
본 실시예에 따른 윈도우 필름용 조성물은 가교제 및 불소계 (메트)아크릴레이트 수지를 더 포함하는 점을 제외하고는 본 발명의 일 실시예에 따른 윈도우 필름용 조성물과 실질적으로 동일하다. The composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that the composition further includes a crosslinking agent and a fluorine-based (meth) acrylate resin.
가교제는 상기에서 상술한 바와 같다.The crosslinking agent is as described above.
불소계 (메트)아크릴레이트 수지는 제1불소 함유 실리콘 수지로 인한 윈도우 필름의 경도 저하를 보완하여 윈도우 필름의 경도와 외관을 동시에 개선할 수 있다. 또한, 불소계 (메트)아크릴레이트 수지는 윈도우 필름의 코팅층의 25℃에서의 표면 에너지가 약 30mN/m 이하, 약 25mN/m 이하, 예를 들면 약 23mN/m 내지 약 25mN/m, 25℃에서의 물접촉각이 약 90° 이하 예를 들면 약 85° 내지 약 89°가 되도록 할 수 있다. 상기 범위에서, 면 품질 개선 효과가 있을 수 있다. 불소계 (메트)아크릴레이트 수지는 상업적으로 판매되는 제품 예를 들면 RS-75, KY-1203 등을 포함할 수 있다. 불소계 (메트)아크릴레이트 수지는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 1중량부 내지 약 20중량부, 구체적으로 약 1중량부 내지 약 10중량부 더 구체적으로 약 1중량부 내지 약 5중량부로 포함될 수 있다. 상기 범위에서 윈도우 필름의 경도와 외관을 동시에 개선할 수 있다. 일 구체예에서, 제1 불소 함유 실리콘 수지는 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 중 약 0.5중량% 내지 약 2중량%, 구체적으로 약 0.5중량% 내지 약 1.5중량%로 포함될 수 있다. 상기 범위에서, 윈도우 필름의 외관과 경도가 동시에 개선될 수 있다.The fluorine-based (meth) acrylate resin can simultaneously improve the hardness and appearance of the window film by compensating for the decrease in hardness of the window film due to the first fluorine-containing silicone resin. Further, the fluorine-based (meth) acrylate resin has a surface energy at 25 ° C. of the coating layer of the window film at about 30 mN / m or less, about 25 mN / m or less, for example, at about 23 mN / m to about 25 mN / m and 25 ° C. May have a water contact angle of about 90 ° or less, for example, about 85 ° to about 89 °. In the above range, there may be a surface quality improvement effect. Fluorine-based (meth) acrylate resins may include commercially available products such as RS-75, KY-1203, and the like. The fluorine-based (meth) acrylate resin is about 1 part by weight to about 20 parts by weight, specifically about 1 part by weight to about 10 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. About 1 to about 5 parts by weight. In the above range, the hardness and appearance of the window film can be improved at the same time. In one embodiment, the first fluorine-containing silicone resin may be included in about 0.5% to about 2% by weight, specifically about 0.5% to about 1.5% by weight, based on the sum of the first fluorine-containing silicone resin and the second silicon resin. have. In the above range, the appearance and hardness of the window film can be improved at the same time.
이하, 도 1을 참고하여 본 발명의 일 실시예의 플렉시블 윈도우 필름을 설명한다. 도 1은 본 발명의 일 실시예의 플렉시블 윈도우 필름의 단면도이다.Hereinafter, a flexible window film of an embodiment of the present invention will be described with reference to FIG. 1. 1 is a cross-sectional view of a flexible window film of one embodiment of the present invention.
도 1을 참고하면, 본 발명의 일 실시예에 따른 플렉시블 윈도우 필름 (100)은 기재층(110)과 코팅층(120)을 포함하고, 코팅층(120)은 본 발명의 실시예들에 따른 윈도우 필름용 조성물로 형성될 수 있다.Referring to FIG. 1, a flexible window film 100 according to an embodiment of the present invention includes a base layer 110 and a coating layer 120, and the coating layer 120 is a window film according to embodiments of the present invention. It may be formed into a composition for.
기재층(110)은 플렉시블 윈도우 필름(100)과 코팅층(120)을 지지하여 플렉시블 윈도우 필름(100)의 기계적 강도를 높일 수 있다. 기재층(110)은 점착층 등에 의해 디스플레이부, 터치스크린패널, 또는 편광판 상에 부착될 수 있다. 기재층(110)은 광학적으로 투명하고 플렉시블한 수지로 형성될 수 있다. 예를 들면 수지는 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트, 폴리부틸렌나프탈레이트 등을 포함하는 폴리에스테르 수지, 폴리카보네이트 수지, 폴리이미드 수지, 폴리스티렌 수지, 폴리메틸메타아크릴레이트 등을 포함하는 폴리(메트)아크릴레이트 수지 중 하나 이상을 포함할 수 있다. 수지는 기재층(110)에 단독 또는 혼합하여 포함될 수 있다. 기재층(110)은 두께가 약 10㎛ 내지 약 200㎛, 구체적으로 약 20㎛ 내지 약 150㎛, 더 구체적으로 약 50㎛ 내지 약 100㎛가 될 수 있다. 상기 범위에서 플렉시블 윈도우 필름에 사용될 수 있다.The base layer 110 may support the flexible window film 100 and the coating layer 120 to increase the mechanical strength of the flexible window film 100. The base layer 110 may be attached onto the display unit, the touch screen panel, or the polarizer by an adhesive layer. The base layer 110 may be formed of an optically transparent and flexible resin. For example, resins include polyester resins including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and the like, polycarbonate resins, polyimide resins, polystyrene resins, polymethylmethacrylates, and the like. It may include one or more of the poly (meth) acrylate resin. The resin may be included in the base layer 110 alone or in combination. The base layer 110 may have a thickness of about 10 μm to about 200 μm, specifically about 20 μm to about 150 μm, and more specifically about 50 μm to about 100 μm. It can be used for the flexible window film in the above range.
코팅층(120)은 기재층(110) 상에 형성되어 기재층(110)과 디스플레이부, 터치스크린패널 또는 편광판을 보호하고, 외관을 좋게 하며 고유연성과 고경도를 가져 플렉시블 디스플레이 장치에 사용 가능하게 할 수 있다. 코팅층(120)은 두께가 약 5㎛ 내지 약 100㎛, 구체적으로 약 10㎛ 내지 약 80㎛가 될 수 있다. 상기 범위에서 플렉시블 윈도우 필름에 사용될 수 있다. 도 1에서 도시되지 않았지만, 코팅층(120)의 다른 일면에는 반사 방지층, 방현성층, 하드코팅층 등의 기능성 표면층이 더 형성되어 플렉시블 윈도우 필름에 추가적인 기능을 제공할 수 있다. 또한, 도 1에서 도시되지 않았지만, 기재층(110)의 다른 일면에 코팅층(120)이 더 형성될 수도 있다.The coating layer 120 is formed on the base layer 110 to protect the base layer 110 and the display unit, the touch screen panel, or the polarizing plate, improve the appearance, and have a high flexibility and high hardness to be used in a flexible display device. can do. The coating layer 120 may have a thickness of about 5 μm to about 100 μm, specifically about 10 μm to about 80 μm. It can be used for the flexible window film in the above range. Although not shown in FIG. 1, another surface of the coating layer 120 may further include a functional surface layer such as an antireflection layer, an antiglare layer, a hard coating layer, and provide additional functions to the flexible window film. In addition, although not shown in FIG. 1, the coating layer 120 may be further formed on the other surface of the substrate layer 110.
플렉시블 윈도우 필름(100)은 RIQ가 약 85 이상, 구체적으로 약 85 내지 약 98이 될 수 있고, 파장 550nm에서 난 반사율이 약 2% 이하, 구체적으로 약 1.5% 이하, 더 구체적으로 약 0.8% 내지 약 1.2%가 될 수 있다. 상기 범위에서, 윈도우 필름의 외관이 좋고 디스플레이 상이 선명할 수 있다.The flexible window film 100 may have a RIQ of about 85 or more, specifically about 85 to about 98, and an inferior reflectance at a wavelength of 550 nm of about 2% or less, specifically about 1.5% or less, more specifically about 0.8% to About 1.2%. Within this range, the appearance of the window film may be good and the display image may be clear.
플렉시블 윈도우 필름(100)은 가시광 영역 구체적으로 파장 약 400nm 내지 약 800nm에서 광 투과도가 약 88% 이상 구체적으로 약 88% 내지 약 100%가 될 수 있다. 상기 범위에서 플렉시블 윈도우 필름으로 사용할 수 있다. 플렉시블 윈도우 필름(100)은 연필경도가 약 4H 이상, 곡률반경이 약 5.0mm 이하가 될 수 있다. 상기 범위에서, 경도 및 유연성이 좋아 플렉시블 윈도우 필름으로 사용될 수 있다. 구체적으로, 플렉시블 윈도우 필름(100)은 연필경도가 약 4H 내지 약 9H이고, 곡률반경이 약 0.1mm 내지 약 5.0mm가 될 수 있다. 플렉시블 윈도우 필름(100)은 두께가 약 5㎛ 내지 약 300㎛가 될 수 있다. 상기 범위에서 플렉시블 윈도우 필름으로 사용할 수 있다.The flexible window film 100 may have a light transmittance of about 88% or more and specifically about 88% to about 100% in the visible light region, specifically, about 400 nm to about 800 nm. It can be used as a flexible window film in the said range. The flexible window film 100 may have a pencil hardness of about 4H or more and a radius of curvature of about 5.0 mm or less. In the above range, good hardness and flexibility can be used as a flexible window film. Specifically, the flexible window film 100 may have a pencil hardness of about 4H to about 9H and a radius of curvature of about 0.1 mm to about 5.0 mm. The flexible window film 100 may have a thickness of about 5 μm to about 300 μm. It can be used as a flexible window film in the said range.
이하, 도 2를 참고하여 본 발명의 다른 실시예에 따른 플렉시블 윈도우 필름을 설명한다. 도 2는 본 발명의 다른 실시예에 따른 플렉시블 윈도우 필름의 단면도이다.Hereinafter, a flexible window film according to another embodiment of the present invention will be described with reference to FIG. 2. 2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.
도 2를 참고하면, 본 발명의 다른 실시예에 따른 플렉시블 윈도우 필름(200)은 기재층(110)의 타면에 점착층(130)이 더 형성된 점을 제외하고는 본 발명의 일 실시예에 따른 플렉시블 윈도우 필름(100)과 실질적으로 동일하다. 기재층(110) 타면에 점착층(130)이 더 형성됨으로써 플렉시블 윈도우 필름과 터치스크린패널, 편광판, 또는 디스플레이부 간의 점착을 용이하게 할 수 있다. 점착층이 더 형성된 것을 제외하고는 본 발명의 일 실시예에 따른 플렉시블 윈도우 필름과 실질적으로 동일하다. 이에, 이하에서는 점착층(130)에 대해서만 설명한다.Referring to FIG. 2, the flexible window film 200 according to another exemplary embodiment of the present invention is except that the adhesive layer 130 is further formed on the other surface of the base layer 110. It is substantially the same as the flexible window film 100. The adhesive layer 130 is further formed on the other surface of the base layer 110 to facilitate adhesion between the flexible window film and the touch screen panel, the polarizing plate, or the display unit. Except that the adhesive layer is further formed is substantially the same as the flexible window film according to an embodiment of the present invention. Thus, only the adhesive layer 130 will be described below.
점착층(130)은 플렉시블 윈도우 필름(200)의 하부에 배치될 수 있는 편광판, 터치스크린패널, 또는 디스플레이부를 점착시키는 것으로, 점착층용 조성물로 형성될 수 있다. 구체적으로, 점착층(130)은 (메트)아크릴계 수지, 우레탄 수지, 실리콘 수지, 에폭시 수지 등의 점착성 수지, 경화제, 광개시제, 실란커플링제를 포함하는 점착층용 조성물로 형성될 수 있다. The adhesive layer 130 may adhere to a polarizing plate, a touch screen panel, or a display unit that may be disposed below the flexible window film 200, and may be formed of a composition for an adhesive layer. Specifically, the pressure-sensitive adhesive layer 130 may be formed of a pressure-sensitive adhesive layer containing a pressure-sensitive resin, such as (meth) acrylic resin, urethane resin, silicone resin, epoxy resin, curing agent, photoinitiator, silane coupling agent.
(메트)아크릴계 수지는 알킬기, 수산기, 방향족기, 카르복시산기, 지환족기, 헤테로지환족기 등을 갖는 (메트)아크릴계 공중합체로 통상의 (메트)아크릴계 공중합체를 포함할 수 있다. 구체적으로, C1 내지 C10의 비치환된 알킬기를 갖는 (메트)아크릴계 모노머, 1개 이상의 수산기를 갖는 C1 내지 C10의 알킬기를 갖는 (메트)아크릴계 모노머, C6 내지 C20의 방향족기를 갖는 (메트)아크릴계 모노머, 카르복시산기를 갖는 (메트)아크릴계 모노머, C3 내지 C20의 지환족기를 갖는 (메트)아크릴계 모노머, 질소(N), 산소(O), 황(S) 중 하나 이상을 갖는 C3 내지 C10의 헤테로지환족기를 갖는 (메트)아크릴계 모노머 중 하나 이상을 포함하는 단량체 혼합물로 형성될 수 있다.The (meth) acrylic resin is a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an aromatic group, a carboxylic acid group, an alicyclic group, a heteroalicyclic group, or the like, and may include a conventional (meth) acrylic copolymer. Specifically, a (meth) acrylic monomer having a C1 to C10 unsubstituted alkyl group, a (meth) acrylic monomer having a C1 to C10 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having a C6 to C20 aromatic group , (Meth) acrylic monomer having a carboxylic acid group, (meth) acrylic monomer having a C3 to C20 alicyclic group, C3 to C10 heteroalicyclic having at least one of nitrogen (N), oxygen (O), sulfur (S) It may be formed of a monomer mixture including at least one of the (meth) acrylic monomer having a group.
경화제는 다관능성 (메트)아크릴레이트로서 헥산디올디아크릴레이트 등의 2관능 (메트)아크릴레이트; 트리메틸올프로판트리(메트)아크릴레이트의 3관능 (메트)아크릴레이트; 펜타에리스리톨테트라(메트)아크릴레이트 등의 4관능 (메트)아크릴레이트; 디펜타에리스리톨펜타(메트)아크릴레이트 등의 5관능 (메트)아크릴레이트; 디펜타에리스리톨헥사(메트)아크릴레이트 등의 6관능 (메트)아크릴레이트를 포함할 수 있지만 이에 제한되지 않는다. The curing agent is a polyfunctional (meth) acrylate, such as bifunctional (meth) acrylates such as hexanediol diacrylate; Trifunctional (meth) acrylate of trimethylolpropane tri (meth) acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; 6 functional (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, may be included, but is not limited thereto.
광개시제는 통상의 광개시제로서 상술한 광라디칼 개시제를 포함할 수 있다. The photoinitiator may include the photoradical initiator described above as a conventional photoinitiator.
실란커플링제는 3-글리시독시프로필트리메톡시실란 등의 에폭시기를 갖는 실란 커플링제 등을 포함할 수 있다.The silane coupling agent may include a silane coupling agent having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and the like.
점착층용 조성물은 (메트)아크릴계 수지 100중량부, 경화제 약 0.1중량부 내지 약 30중량부, 광개시제 약 0.1중량부 내지 약 10중량부, 실란커플링제 약 0.1중량부 내지 약 20중량부를 포함할 수 있다. 상기 범위에서, 플렉시블 윈도우 필름이 디스플레이부, 터치스크린패널 또는 편광판 상에 잘 부착될 수 있다.The adhesive layer composition may include 100 parts by weight of a (meth) acrylic resin, about 0.1 part by weight to about 30 parts by weight of a curing agent, about 0.1 part by weight to about 10 parts by weight of a photoinitiator, and about 0.1 part by weight to about 20 parts by weight of a silane coupling agent. have. In the above range, the flexible window film may be attached well on the display unit, the touch screen panel or the polarizing plate.
점착층(130)은 두께가 약 10㎛ 내지 약 100㎛가 될 수 있다. 상기 범위에서 플렉시블 윈도우 필름과 편광판 등의 광학 소자를 충분히 점착시킬 수 있다.The adhesive layer 130 may have a thickness of about 10 μm to about 100 μm. Optical elements, such as a flexible window film and a polarizing plate, can fully be stuck in the said range.
이하, 도 3 및 도 4를 참고하여 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치에 대해 설명한다. 도 3은 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치의 단면도이고, 도 4는 도 3의 디스플레이부의 일 실시예에 따른 단면도이다.Hereinafter, a flexible display device according to an exemplary embodiment of the present invention will be described with reference to FIGS. 3 and 4. 3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention, and FIG. 4 is a cross-sectional view of an embodiment of the display unit of FIG. 3.
도 3을 참조하면, 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치(300)는 디스플레이부(350a), 점착층(360), 편광판(370), 터치스크린패널(380), 플렉시블 윈도우 필름(390)을 포함하고, 플렉시블 윈도우 필름(390)은 본 발명의 실시예들에 따른 플렉시블 윈도우 필름을 포함할 수 있다.Referring to FIG. 3, the flexible display device 300 according to an exemplary embodiment of the present invention may include a display unit 350a, an adhesive layer 360, a polarizer 370, a touch screen panel 380, and a flexible window film 390. ), And the flexible window film 390 may include a flexible window film according to embodiments of the present invention.
디스플레이부(350a)는 플렉시블 디스플레이 장치(300)를 구동시키기 위한 것으로, 기판 및 기판 상에 형성된 OLED, LED 또는 LCD 소자를 포함하는 광학 소자를 포함할 수 있다. 도 4는 도 3의 디스플레이부의 일 실시예에 따른 단면도이다. 도 4를 참조하면, 디스플레이부(350a)는 하부기판(310), 박막 트랜지스터(316), 유기발광다이오드(315), 평탄화층(314), 보호막(318), 절연막(317)을 포함할 수 있다.The display unit 350a is for driving the flexible display apparatus 300 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate. 4 is a cross-sectional view according to an exemplary embodiment of the display unit of FIG. 3. Referring to FIG. 4, the display 350a may include a lower substrate 310, a thin film transistor 316, an organic light emitting diode 315, a planarization layer 314, a passivation layer 318, and an insulating layer 317. have.
하부기판(310)은 디스플레이부(350a)를 지지하는 것으로, 하부기판(310)에는 박막 트랜지스터(316), 유기발광다이오드(315)가 형성되어 있을 수 있다. 하부기판(310)에는 터치스크린패널(380)을 구동하기 위한 연성 인쇄 회로 기판이 형성될 수도 있다. 연성 인쇄 회로 기판에는 유기발광다이오드어레이를 구동하기 위한 타이밍 컨트롤러, 전원 공급부 등이 더 형성되어 있을 수 있다.The lower substrate 310 supports the display unit 350a, and the thin film transistor 316 and the organic light emitting diode 315 may be formed on the lower substrate 310. A flexible printed circuit board for driving the touch screen panel 380 may be formed on the lower substrate 310. The flexible printed circuit board may further include a timing controller, a power supply, and the like for driving the organic light emitting diode array.
하부기판(310)은 플렉시블한 수지로 형성된 기판을 포함할 수 있다. 구체적으로, 하부기판(310)은 실리콘 기판, 폴리이미드 기판, 폴리카보네이트 기판, 폴리아크릴레이트 기판 등의 플렉시블 기판을 포함할 수 있지만, 이에 제한되지 않는다.The lower substrate 310 may include a substrate formed of a flexible resin. Specifically, the lower substrate 310 may include a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, a polyacrylate substrate, but is not limited thereto.
하부기판(310)의 표시영역에는 복수 개의 구동 배선(도시되지 않음)과 센서 배선(도시되지 않음)이 교차하여 복수 개의 화소 영역이 정의되고, 화소 영역마다 박막 트랜지스터(316) 및 박막 트랜지스터(316)와 접속된 유기발광다이오드(315)를 포함하는 유기발광다이오드 어레이가 형성될 수 있다. 하부 기판의 비표시 영역에는 구동 배선에 전기적 신호를 인가하는 게이트 드라이버가 게이트 인 패널(gate in panel) 형태로 형성될 수 있다. 게이트 인 패널 회로부는 표시영역의 일측 또는 양측에 형성될 수 있다.In the display area of the lower substrate 310, a plurality of pixel areas are defined by crossing a plurality of driving wires (not shown) and sensor wires (not shown), and the thin film transistor 316 and the thin film transistor 316 are defined for each pixel area. The organic light emitting diode array including the organic light emitting diode 315 connected to the) may be formed. In the non-display area of the lower substrate, a gate driver for applying an electrical signal to the driving line may be formed in the form of a gate in panel. The gate-in panel circuit unit may be formed on one side or both sides of the display area.
박막 트랜지스터(316)는 반도체에 흐르는 전류를 그와 수직인 전계를 가해서 제어하는 것으로, 하부 기판(310) 상에 형성될 수 있다. 박막 트랜지스터(316)는 게이트 전극(310a), 게이트 절연막(311), 반도체층(312), 소스 전극(313a), 및 드레인 전극(313b)을 포함할 수 있다. 박막 트랜지스터(316)는 반도체층(312)으로 IGZO(indium gallium zinc oxide), ZnO, TiO 등의 산화물을 사용하는 산화물 박막 트랜지스터, 반도체층으로 유기물을 사용하는 유기 박막 트랜지스터, 반도체층으로 비정질 실리콘을 이용하는 비정질 실리콘 박막 트랜지스터, 또는 반도체층으로 다결정 실리콘을 이용하는 다결정 실리콘 박막 트랜지스터일 수 있다.The thin film transistor 316 controls the current flowing through the semiconductor by applying an electric field perpendicular to the current, and may be formed on the lower substrate 310. The thin film transistor 316 may include a gate electrode 310a, a gate insulating layer 311, a semiconductor layer 312, a source electrode 313a, and a drain electrode 313b. The thin film transistor 316 is an oxide thin film transistor using an oxide such as indium gallium zinc oxide (IGZO), ZnO, or TiO as the semiconductor layer 312, an organic thin film transistor using an organic material as the semiconductor layer, and amorphous silicon as the semiconductor layer. It may be an amorphous silicon thin film transistor to be used, or a polycrystalline silicon thin film transistor to use polycrystalline silicon as a semiconductor layer.
평탄화층(314)은 박막 트랜지스터(316) 및 회로부(310b)를 덮어 박막 트랜지스터(316)와 회로부(310b)의 상부면을 평탄화시킴으로써 유기발광다이오드(315)가 형성되도록 할 수 있다. 평탄화층(314)은 SOG(spin-on -glass)막, 폴리이미드계 고분자, 폴리아크릴계 고분자 등으로 형성될 수 있지만 이에 제한되지 않는다.The planarization layer 314 may cover the thin film transistor 316 and the circuit portion 310b to planarize the top surfaces of the thin film transistor 316 and the circuit portion 310b so that the organic light emitting diode 315 may be formed. The planarization layer 314 may be formed of a spin-on-glass (SOG) film, a polyimide polymer, a polyacrylic polymer, or the like, but is not limited thereto.
유기발광다이오드(315)는 자체 발광하여 디스플레이를 구현하는 것으로, 차례로 적층된 제1전극(315a), 유기발광층(315b) 및 제2전극(315c)을 포함할 수 있다. 인접한 유기발광다이오드는 절연막(317)을 통해 구분될 수 있다. 유기발광다이오드(315)는 유기발광층(315b)에서 발생된 광이 하부 기판을 통해 방출되는 배면 발광구조 또는 유기발광층(315b)에서 발생된 광이 상부로 방출되는 전면 발광구조를 포함할 수 있다.The organic light emitting diode 315 implements a display by emitting light by itself, and may include a first electrode 315a, an organic light emitting layer 315b, and a second electrode 315c which are sequentially stacked. Adjacent organic light emitting diodes may be distinguished through the insulating layer 317. The organic light emitting diode 315 may include a bottom light emitting structure in which light generated in the organic light emitting layer 315b is emitted through the lower substrate, or a top light emitting structure in which light generated in the organic light emitting layer 315b is emitted upward.
보호막(318)은 유기발광다이오드(315)를 덮어 유기발광다이오드(315)를 보호할 수 있다 보호막(318)은 SiOx, SiNx, SiC, SiON, SiONC 및 a-C(amorphous Carbon)과 같은 무기 물질과 (메트)아크릴레이트, 에폭시계 폴리머, 이미드계 폴리머 등과 같은 유기 물질로 형성될 수 있다. 구체적으로, 보호막(318)은 무기 물질로 형성된 층과 유기 물질로 형성된 층이 1회 이상 순차로 적층된 봉지층(encapsulation layer)을 포함할 수 있다.The passivation layer 318 may cover the organic light emitting diode 315 to protect the organic light emitting diode 315. The passivation layer 318 may be formed of an inorganic material such as SiOx, SiNx, SiC, SiON, SiONC, and amorphous carbon (aC). It may be formed of an organic material such as meth) acrylate, epoxy polymer, imide polymer and the like. In detail, the passivation layer 318 may include an encapsulation layer in which a layer formed of an inorganic material and a layer formed of an organic material are sequentially stacked one or more times.
다시 도 3을 참조하면, 점착층(360)은 디스플레이부(350a)와 편광판(370)을 점착시키는 것으로, (메트)아크릴레이트계 수지, 경화제, 개시제 및 실란커플링제를 포함하는 점착제 조성물로 형성될 수 있다.Referring to FIG. 3 again, the adhesive layer 360 adheres the display unit 350a and the polarizing plate 370, and is formed of an adhesive composition including a (meth) acrylate-based resin, a curing agent, an initiator, and a silane coupling agent. Can be.
편광판(370)은 내광의 편광을 구현하거나 또는 외광의 반사를 방지하여 디스플레이를 구현하거나 디스플레이의 명암비를 높일 수 있다. 편광판은 편광자 단독으로 구성될 수 있다. 또는 편광판은 편광자 및 편광자의 일면 또는 양면에 형성된 보호필름을 포함할 수 있다. 또는 편광판은 편광자 및 편광자의 일면 또는 양면에 형성된 보호코팅층을 포함할 수 있다. 편광자, 보호필름, 보호코팅층은 당업자에게 알려진 통상의 것을 사용할 수 있다.The polarizer 370 may implement polarization of internal light or prevent reflection of external light to implement a display or increase a contrast ratio of the display. The polarizing plate may be composed of a polarizer alone. Alternatively, the polarizer may include a polarizer and a protective film formed on one or both sides of the polarizer. Alternatively, the polarizing plate may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer. The polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.
터치스크린패널(380)은 인체나 스타일러스(stylus)와 같은 도전체가 터치할 때 발생되는 커패시턴스의 변화를 감지하여 전기적 신호를 발생시키는 것으로, 이러한 신호에 의해 디스플레이부(350a)가 구동될 수 있다. 터치스크린패널(380)은 플렉시블하고 도전성이 있는 도전체를 패턴화하여 형성되는 것으로, 제1센서 전극 및 제1센서 전극 사이에 형성되어 제1센서 전극과 교차하는 제2센서 전극을 포함할 수 있다. 터치스크린패널(380)을 위한 도전체는 금속나노와이어, 전도성 고분자, 탄소나노튜브 등을 포함할 수 있지만 이에 제한되지 않는다.The touch screen panel 380 detects a change in capacitance generated when a human body or a conductor such as a stylus touches to generate an electrical signal. The display unit 350a may be driven by the signal. The touch screen panel 380 is formed by patterning a flexible and conductive conductor, and may include a second sensor electrode formed between the first sensor electrode and the first sensor electrode to cross the first sensor electrode. have. The conductor for the touch screen panel 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.
플렉시블 윈도우 필름(390)은 플렉시블 디스플레이 장치(300)의 최 외곽에 형성되어 디스플레이 장치를 보호할 수 있다.The flexible window film 390 may be formed on the outermost side of the flexible display device 300 to protect the display device.
도 3에서 도시되지 않았지만, 편광판(370)과 터치스크린패널(380) 사이 및/또는 터치스크린패널(380)과 플렉시블 윈도우 필름(390) 사이에는 점착층이 더 형성됨으로써 편광판, 터치스크린패널, 플렉시블 윈도우 필름 간의 결합을 강하게 할 수 있다. 점착층은 (메트)아크릴레이트계 수지, 경화제, 개시제 및 실란커플링제를 포함하는 점착제 조성물로 형성될 수 있다. 또한, 도 3에서 도시되지 않았지만, 디스플레이부(350a)의 하부에는 편광판이 더 형성됨으로써, 내광의 편광을 구현할 수 있다.Although not shown in FIG. 3, an adhesive layer is further formed between the polarizing plate 370 and the touch screen panel 380 and / or between the touch screen panel 380 and the flexible window film 390 to form a polarizing plate, a touch screen panel, and a flexible display panel. The bond between the window films can be strengthened. The adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. In addition, although not shown in FIG. 3, a polarizer may be further formed below the display unit 350a to implement polarization of the internal light.
이하, 도 5를 참조하여 본 발명의 다른 실시예에 따른 플렉시블 디스플레이 장치를 설명한다. 도 5는 본 발명의 다른 실시예에 따른 플렉시블 디스플레이 장치의 단면도이다.Hereinafter, a flexible display device according to another exemplary embodiment of the present invention will be described with reference to FIG. 5. 5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
도 5를 참조하면, 본 발명의 다른 실시예에 따른 플렉시블 디스플레이 장치(400)는 디스플레이부(350a), 터치스크린패널(380), 편광판(370), 플렉시블 윈도우 필름(390)을 포함하고, 플렉시블 윈도우 필름(390)은 본 발명의 실시예들에 따른 플렉시블 윈도우 필름을 포함할 수 있다. 플렉시블 윈도우 필름(390)상에 터치스크린패널(380)이 직접 형성되지 않고 편광판(370)의 하부에 터치스크린패널(380)이 형성된다는 점을 제외하고는 본 발명의 일 실시예에 따른 플렉서블 디스플레이 장치와 실질적으로 동일하다. 또한, 이 때, 디스플레이부(350a)와 함께 터치스크린패널(380)이 형성될 수도 있다. 이 경우 디스플레이부(350a) 상에 디스플레이부(350a)와 함께 터치스크린패널(380)이 형성됨으로써 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치에 비해 두께가 얇고 밝아서 시인성이 좋을 수 있다. 또한, 이 경우 터치스크린패널(380)은 증착 등에 의해 형성될 수 있지만 이에 제한되는 것은 아니다. 도 5에서 도시되지 않았지만, 디스플레이부(350a)와 터치스크린패널(380) 사이 및/또는 터치스크린패널(380)과 편광판(370) 사이 및/또는 편광판(370)과 플렉시블 윈도우 필름(390) 사이에는 점착층이 더 형성됨으로써 디스플레이 장치의 기계적 강도를 높일 수 있다. 점착층은 (메트)아크릴레이트계 수지, 경화제, 개시제 및 실란커플링제를 포함하는 점착제 조성물로 형성될 수 있다. 또한, 도 5에서 도시되지 않았지만, 디스플레이부(350a) 하부에 편광판이 더 형성됨으로써 내광의 편광을 유도하여 디스플레이 화상을 좋게 할 수 있다.Referring to FIG. 5, the flexible display device 400 according to another embodiment of the present invention includes a display 350a, a touch screen panel 380, a polarizer 370, and a flexible window film 390. The window film 390 may include a flexible window film according to embodiments of the present invention. Flexible display according to an embodiment of the present invention except that the touch screen panel 380 is not directly formed on the flexible window film 390, but the touch screen panel 380 is formed below the polarizer 370. It is substantially the same as the device. In this case, the touch screen panel 380 may be formed together with the display 350a. In this case, since the touch screen panel 380 is formed together with the display unit 350a on the display unit 350a, the display panel 350a may be thinner and brighter than the flexible display device according to the exemplary embodiment of the present invention, and thus may have good visibility. In addition, in this case, the touch screen panel 380 may be formed by deposition, but is not limited thereto. Although not shown in FIG. 5, between the display unit 350a and the touch screen panel 380 and / or between the touch screen panel 380 and the polarizer 370 and / or between the polarizer 370 and the flexible window film 390. The pressure-sensitive adhesive layer is further formed therein to increase the mechanical strength of the display device. The adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. In addition, although not shown in FIG. 5, a polarizing plate is further formed below the display unit 350a to induce polarization of internal light to improve a display image.
이하, 도 6을 참조하여 본 발명의 또 다른 실시예에 따른 플렉시블 디스플레이 장치를 설명한다. 도 6은 본 발명의 또 다른 실시예에 따른 플렉시블 디스플레이 장치의 단면도이다. 도 6을 참조하면, 본 발명의 또 다른 실시예에 따른 플렉시블 디스플레이 장치(500)는 디스플레이부(350b), 점착층(360), 플렉시블 윈도우 필름(390)을 포함하고, 플렉시블 윈도우 필름(390)은 본 발명의 실시예들에 따른 플렉시블 윈도우 필름을 포함할 수 있다. 디스플레이부(350b)만으로 장치의 구동이 가능하고 편광판, 터치스크린패널이 제외된 것을 제외하고는 본 발명의 일 실시예에 따른 플렉시블 디스플레이 장치와 실질적으로 동일하다.Hereinafter, a flexible display device according to still another embodiment of the present invention will be described with reference to FIG. 6. 6 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention. Referring to FIG. 6, the flexible display apparatus 500 according to another embodiment of the present invention includes a display unit 350b, an adhesive layer 360, and a flexible window film 390, and a flexible window film 390. May include a flexible window film according to embodiments of the present invention. It is substantially the same as the flexible display device according to the exemplary embodiment of the present invention except that the device may be driven only by the display unit 350b and the polarizer and the touch screen panel are excluded.
디스플레이부(350b)는 기판 및 기판 상에 형성된 LCD, OLED, 또는 LED 소자를 포함하는 광학 소자를 포함할 수 있으며, 디스플레이부(350b)는 내부에 터치스크린패널이 형성될 수 있다.The display unit 350b may include a substrate and an optical element including an LCD, an OLED, or an LED element formed on the substrate, and the display unit 350b may have a touch screen panel therein.
이하, 본 발명의 일 실시예에 따른 제1 불소 함유 실리콘 수지, 제2실리콘 수지의 제조 방법을 설명한다.Hereinafter, a manufacturing method of the first fluorine-containing silicone resin and the second silicone resin according to an embodiment of the present invention will be described.
본 실시예에 따른 화학식 1의 제1 불소 함유 실리콘 수지는 (RaSiO(4-a)/ 2)을 제공하는 실리콘 단량체와 (XbSiO(4-b)/ 2)을 제공하는 실리콘 단량체를 포함하는 실리콘 혼합물의 가수분해 및 축합 반응에 의해 제조될 수 있다. 구체적으로, (RaSiO(4-a)/ 2)을 제공하는 실리콘 단량체는 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 디메틸디메톡시실란, 디메틸디에톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸트리에톡시실란 등이 될 수 있지만, 이에 제한되지 않는다. 구체적으로, (XbSiO(4-b)/ 2)을 제공하는 실리콘 단량체는 1H,1H,2H,2H-퍼플루오로데실트리메톡시실란, 1H,1H,2H,2H-퍼플루오로옥틸트리메톡시실란, 1H,1H,2H,2H-퍼플루오로헥실트리메톡시실란, 1H,1H,2H,2H-퍼플루오로데실트리에톡시실란, 1H,1H,2H,2H-퍼플루오로옥틸트리에톡시실란, 1H,1H,2H,2H-퍼플루오로헥실트리에톡시실란 등이 될 수 있지만, 이에 제한되지 않는다. 일 구체예에서, 단량체 혼합물은 (RaSiO(4-a)/ 2)을 제공하는 실리콘 단량체 약 0.01mol% 내지 약 99.99mol%, 구체적으로 약 80mol% 내지 약 99.99mol%, 더 구체적으로 약 90mol% 내지 약 99.5mol%, (XbSiO(4-b)/ 2)을 제공하는 실리콘 단량체 약 0.01mol% 내지 약 99.99mol%, 구체적으로 약 0.01mol% 내지 약 20mol%, 더 구체적으로 약 0.5mol% 내지 약 10mol%가 될 수 있다. 상기 범위에서, 윈도우 필름의 외관이 개선되고 눈부심이 적을 수 있다.The first fluorine-containing silicone resin of formula 1 according to this embodiment is a silicone monomer that provides (R a SiO (4-a) / 2 ) and a silicone monomer that provides (X b SiO (4-b) / 2 ) It may be prepared by the hydrolysis and condensation reaction of the silicone mixture comprising a. Specifically, the silicone monomers providing (R a SiO (4-a) / 2 ) are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane, and the like, but is not limited thereto. Specifically, the silicone monomers providing (X b SiO (4-b) / 2 ) are 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorojade. Tyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Octyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane, and the like, but is not limited thereto. In one embodiment, the monomer mixture is a (R a SiO (4-a ) / 2) silicone monomer about 0.01mol% to about 99.99mol%, specifically from about 80mol% to about 99.99mol%, and more specifically to provide about 90 mol% to about 99.5 mol%, about 0.01 mol% to about 99.99 mol%, specifically about 0.01 mol% to about 20 mol%, more specifically about about 0.1 mol% of a silicone monomer providing (X b SiO (4-b) / 2 ) 0.5 mol% to about 10 mol%. In this range, the appearance of the window film can be improved and less glare.
본 실시예에 따른 제2실리콘 수지는 (R1SiO3 / 2)을 제공하는 실리콘 단량체 단독, 또는 (R1SiO3 / 2)을 제공하는 실리콘 단량체; 및 (R2R3SiO2 / 2)을 제공하는 실리콘 단량체, (R4R5R6SiO1/2)을 제공하는 실리콘 단량체, (SiO4 / 2)을 제공하는 실리콘 단량체 중 하나 이상의 혼합물의 가수분해 및 축합 반응에 의해 제조될 수 있다. (R1SiO3 / 2)을 제공하는 실리콘 단량체는 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란 등이 될 수 있고, (R2R3SiO2 / 2)을 제공하는 실리콘 단량체는 디메틸디메톡시실란, 디메틸디에톡시실란, 디에틸디에톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸트리에톡시실란 등이 될 수 있고, (SiO4 / 2)을 제공하는 실리콘 단량체는 테트라메톡시실란, 테트라에톡시실란, 테트라프로폭시실란 등이 될 수 있지만, 이에 제한되지 않는다. 일 구체예에서, 단량체 혼합물은 (R1SiO3 / 2)을 제공하는 실리콘 단량체 100mol%, 구체적으로 약 85mol% 내지 약 99mol%, 약 1mol% 내지 약 15mol%, 약 40mol% 내지 약 95mol%, 약 1mol% 내지 약 40mol%, (SiO4 / 2)을 제공하는 실리콘 단량체 약 0mol%, 약 1mol% 내지 약 20mol%가 될 수 있다. 상기 범위에서, 윈도우 필름의 경도와 유연성이 좋아질 수 있다.A second silicone resin is silicone monomer to provide a silicon monomer alone, or (R 1 SiO 3/2) to provide (R 1 SiO 3/2) according to the embodiment; And (R 2 R 3 SiO 2/ 2) a silicon monomer, to provide a (R 4 R 5 R 6 SiO 1/2) to provide the silicon monomer, (SiO 4/2) at least one mixture of the silicone monomers to provide for It can be prepared by the hydrolysis and condensation reaction of. (R 1 SiO 3/2) to provide a silicone monomer is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 3- doksi glycidyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be the doksi propyl triethoxysilane, (R 2 R 3 SiO 2 /2) to provide a silicon monomer include dimethyl dimethoxysilane, dimethyl diethoxysilane , Diethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane, and the like, (SiO 4 / 2 ) may be tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and the like, but is not limited thereto. In one embodiment, the monomer mixture (R 1 SiO 3/2) silicone monomer 100mol% which provides, specifically from about 85mol% to about 99mol%, about 1mol% to about 15mol%, about 40mol% to about 95mol%, It may be about 1mol% to about 40mol%, (SiO 4/2 ) silicon monomer from about 0mol%, about 1mol% to about 20mol% to service. In the above range, the hardness and flexibility of the window film can be improved.
단량체 혼합물의 가수분해 및 축합 반응은 통상의 실리콘 수지의 제조 방법에 따라 수행될 수 있다. 가수분해는 상기 단량체 혼합물을 물 및 소정의 산, 염기 중 하나 이상의 혼합물에서 반응시키는 것을 포함할 수 있다. 구체적으로, 산은 HCl, HNO3, 아세트산 등, 염기는 NaOH, KOH 등이 사용될 수 있다. 가수분해는 약 20℃ 내지 약 100℃에서 약 10분 내지 약 10시간 동안 수행되고, 축합 반응은 가수분해와 동일 조건에서 약 20℃ 내지 약 100℃에서 약 10분 내지 약 12시간 동안 수행될 수 있다. 상기 범위에서 실리콘 수지의 제조 수율이 높을 수 있다.Hydrolysis and condensation reaction of the monomer mixture can be carried out according to a conventional method for producing a silicone resin. Hydrolysis can include reacting the monomer mixture in water and in a mixture of one or more of the desired acids, bases. Specifically, the acid may be HCl, HNO 3 , acetic acid and the like, the base may be NaOH, KOH and the like. The hydrolysis may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 10 hours, and the condensation reaction may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 12 hours under the same conditions as the hydrolysis. have. In the above range, the production yield of the silicone resin may be high.
이하, 본 발명의 일 실시예에 따른 윈도우 필름의 제조 방법을 설명한다.Hereinafter, a method of manufacturing a window film according to an embodiment of the present invention.
플렉시블 윈도우 필름(100)은 기재층(110) 상에 본 발명의 실시예들에 따른 윈도우 필름용 조성물을 코팅하고 경화시키는 단계를 포함하는 플렉시블 윈도우 필름의 제조 방법에 의해 제조될 수 있다.The flexible window film 100 may be manufactured by a method of manufacturing a flexible window film including coating and curing a composition for a window film according to embodiments of the present invention on a base layer 110.
윈도우 필름용 조성물을 기재층(110) 상에 코팅하는 방법은 바코팅, 스핀코팅, 딥코팅, 롤코팅, 플로우코팅, 다이코팅 등이 될 수 있지만 제한되지 않는다. 윈도우 필름용 조성물을 기재층(110) 상에 약 5㎛ 내지 약 100㎛ 두께로 코팅할 수 있다. 상기 범위에서 원하는 코팅층을 확보할 수 있고 경도 및 유연성이 우수한 효과가 있을 수 있다. 경화는 윈도우 필름용 조성물을 경화시켜 코팅층을 형성하는 것으로, 광경화, 열경화 중 하나 이상을 포함할 수 있다. 광경화는 파장 400nm 이하에서 약 10mJ/cm2 내지 약 1,000mJ/cm2의 광량으로 조사하는 것을 포함할 수 있다. 열 경화는 약 40℃ 내지 약 200℃에서 약 1시간 내지 약 30시간 동안 처리하는 것을 포함할 수 있다. 상기 범위에서 윈도우 필름용 조성물이 충분히 경화될 수 있다. 예를 들면, 광경화시킨 후 열경화시킬 수 있는데, 그 결과 코팅층의 경도를 보다 높일 수 있다. 윈도우 필름용 조성물을 기재층(110) 상에 코팅한 후 경화시키기 전에, 윈도우 필름용 조성물을 건조시키는 단계를 더 포함할 수 있다. 건조시킨 후 경화시킴으로써 장시간의 광경화, 열경화로 인해 코팅층의 표면 조도가 높아지는 것을 막을 수 있다. 건조는 약 40℃ 내지 약 200℃에서 약 1분 내지 약 30시간 동안 수행될 수 있지만, 이에 제한되지 않는다.The method of coating the composition for the window film on the base layer 110 may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating, or the like, but is not limited thereto. The composition for the window film may be coated on the base layer 110 in a thickness of about 5 μm to about 100 μm. It is possible to secure the desired coating layer in the above range and may have an excellent effect of hardness and flexibility. Curing is to form a coating layer by curing the composition for a window film, and may include at least one of photocuring and thermal curing. Photocuring may involve irradiation with light intensity of approximately 10mJ / cm 2 to about 1,000mJ / cm 2 at a wavelength of 400nm or less. Thermal curing may include treatment at about 40 ° C. to about 200 ° C. for about 1 hour to about 30 hours. In the above range, the composition for a window film may be sufficiently cured. For example, it may be thermally cured after photocuring, and as a result, the hardness of the coating layer may be further increased. The method may further include drying the composition for a window film before the composition for a window film is coated on the base layer 110 and then cured. By curing after drying, it is possible to prevent the surface roughness of the coating layer from increasing due to prolonged photocuring and thermal curing. Drying may be performed at about 40 ° C. to about 200 ° C. for about 1 minute to about 30 hours, but is not limited thereto.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로, 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
제조예Production Example 1-1: 제1 불소 함유 실리콘 수지  1-1: First Fluorine-Containing Silicone Resin
2-(3,4-에폭시시클로헥실)에틸트리메톡시실란(KBM-303, Shin-Etsu 社) 95mol%, 1H,1H,2H,2H-퍼플루오로데실트리메톡시실란(Aldrich社) 5mol%의 단량체의 혼합물 총 100g을 500mL 3-neck flask에 넣었다. 상기 혼합물에 단량체 혼합물 대비 0.5mol%의 KOH, 1.5mol%의 물을 첨가하고, 70℃에서 2시간 동안 교반하고, 감압 증류 장치로 용매를 제거하여 제1 불소 함유 실리콘 수지(겔투과크로마토그래피(GPC)에 의한 중량평균분자량:5,000) (EcSiO3 / 2)0.95(FdSiO3/2)0 .05를 제조하였다. 메틸에틸케톤을 추가하여 고형분 90중량%를 맞추었다.95 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Etsu), 5 mol of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane (Aldrich) A total of 100 g of a mixture of% monomer was placed in a 500 mL 3-neck flask. 0.5 mol% KOH and 1.5 mol% water were added to the mixture, stirred at 70 ° C. for 2 hours, and the solvent was removed using a vacuum distillation apparatus to obtain a first fluorine-containing silicone resin (gel permeation chromatography ( was prepared in a 5,000) (EcSiO 3/2) 0.95 (FdSiO 3/2) 0 .05: GPC) weight average molecular weight by. Methyl ethyl ketone was added to adjust the solid content by 90% by weight.
제조예Production Example 1-2 내지  1-2 to 제조예Production Example 1-4:  1-4: 제1불소First fluorine 함유 실리콘 수지 Containing silicone resin
제조예 1-1에서 실리콘 단량체의 종류 및/또는 함량을 하기 표 1과 같이 변경한 것을 제외하고는 동일한 방법으로 제1 불소 함유 실리콘 수지를 제조하였다A first fluorine-containing silicone resin was prepared in the same manner except for changing the type and / or content of the silicone monomer in Preparation Example 1-1 as shown in Table 1 below.
제조예 2: 제2실리콘 수지Preparation Example 2 Second Silicone Resin
2-(3,4-에폭시시클로헥실)에틸트리메톡시실란(KBM-303, 신예츠사) 95mol% 및 (3-글리시독시프로필)트리메톡시실란(KBM-403, 신예츠사) 5mol%를 포함하는 실리콘 단량체 혼합물 400g을 1L 3-neck 플라스크에 넣었다. 상기 실리콘 단량체 혼합물 대비 0.1mol%의 KOH와 총 실리콘 단량체 대비 1 당량의 물을 첨가하고, 65℃에서 8시간 동안 교반시킨 후, 톨루엔으로 수세하고 농축시켜, 제2실리콘 수지(GPC에 의한 중량평균분자량: 5,500) (EcSiO3/2)0.95(GpSiO3/2)0.05를 제조하였다.95 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Yestsu) and 5 mol% of (3-glycidoxypropyl) trimethoxysilane (KBM-403, Shin-Yestsu) 400 g of the containing silicone monomer mixture was placed in a 1 L 3-neck flask. 0.1 mol% of KOH and 1 equivalent of water relative to the total silicone monomers were added to the silicone monomer mixture, stirred at 65 ° C. for 8 hours, washed with toluene and concentrated to obtain a second silicone resin (GPC averaged by weight). Molecular weight: 5,500) (EcSiO 3/2 ) 0.95 (GpSiO 3/2 ) 0.05 was prepared.
제조예Production Example 3:  3: 제2실리콘2nd silicon 수지 Suzy
제조예 2에서 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란(KBM-303, 신예츠사) 50mol%, (3-글리시독시프로필)트리메톡시실란(KBM-403, 신예츠사) 30mol% 및 테트라에톡시실란 20mol%를 포함하는 실리콘 단량체 혼합물을 사용한 것을 제외하고는 동일한 방법으로 제2실리콘 수지 (EcSiO3/2)0.50(GpSiO3/2)0.30(SiO4/2)0.20를 제조하였다.50 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Etsu Co.) in Preparation Example 2, (3-glycidoxypropyl) trimethoxysilane (KBM-403, Shin-Yetsu Co., Ltd.) ) Second silicone resin (EcSiO 3/2 ) 0.50 (GpSiO 3/2 ) 0.30 (SiO 4/2 ) 0.20 in the same manner, except that a silicone monomer mixture comprising 30 mol% and 20 mol% tetraethoxysilane was used. Was prepared.
제조예 4: 제2 실리콘 수지Preparation Example 4 Second Silicone Resin
2-(3,4-에폭시시클로헥실)에틸트리메톡시실란(KBM-303, 신예츠사) 50g을 200mL 3-neck 플라스크에 넣었다. 상기 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란 대비 0.5mol%의 KOH와 1.5mol% 물을 첨가하고, 70℃에서 2시간 동안 교반시킨 후, 톨루엔으로 수세하고 농축시켜, 제2실리콘 수지(GPC에 의한 중량평균분자량: 5000) (EcSiO3/2)를 제조하였다.50 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Yestsu) was placed in a 200 mL 3-neck flask. 0.5 mol% KOH and 1.5 mol% water were added to the 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, stirred at 70 ° C for 2 hours, washed with toluene, and concentrated. A 2 silicone resin (weight average molecular weight by GPC: 5000) (EcSiO 3/2 ) was prepared.
제조예의 실리콘 수지의 구성은 하기 표 1과 같다.The structure of the silicone resin of a manufacture example is as Table 1 below.
실리콘 단량체(mol%)Silicone monomer (mol%) 제조예 1-1Preparation Example 1-1 제조예 1-2Preparation Example 1-2 제조예 1-3Preparation Example 1-3 제조예 1-4Preparation Example 1-4 제조예 2Preparation Example 2 제조예 3Preparation Example 3 제조예 4Preparation Example 4
2-(3,4-에폭시시클로헥실) 에틸트리메톡시실란2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 9595 9494 9090 9595 9595 5050 100100
3-글리시독시프로필 트리메톡시실란3-glycidoxypropyl trimethoxysilane -- 55 -- -- 55 3030 --
디메틸디메톡시실란Dimethyldimethoxysilane -- -- 55 -- -- -- --
테트라에톡시실란Tetraethoxysilane -- -- -- -- -- 2020 --
1H,1H,2H,2H-퍼플루오로데실트리메톡시실란1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane 55 1One 55 -- -- -- --
1H,1H,2H,2H-퍼플루오로옥틸트리메톡시실란1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane -- -- -- 55 -- -- --
중량평균분자량Weight average molecular weight 5,0005,000 5,3005,300 4,7004,700 5,1005,100 5,5005,500 5,6005,600 5,0005,000
실시예Example 1 One
제조예 1-1의 제1불소 함유 실리콘 수지 0.5g, 제조예 2의 제2실리콘 수지 99.5g, 가교제 CELLOXIDE 2021P(daicel社) 25g, 희석제 MEK(대정화학) 25g, 개시제 Diphenyliodonium hexafluorophosphate (TCI社) 1g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 코팅층용 조성물을 PI 필름(폴리이미드 필름, SDI社, 두께:80㎛)에 도포 후, 100℃에서 5분간 건조 후 1000mJ의 자외선에 노광하여 두께 50㎛의 코팅 필름을 제조한 후에, 80℃ 오븐에서 24hr동안 postcure를 진행하여 윈도우 필름을 제조하였다.0.5 g of the first fluorine-containing silicone resin of Preparation Example 1-1, 99.5 g of the second silicone resin of Preparation Example 2, 25 g of the crosslinking agent CELLOXIDE 2021P (daicel Co.), 25 g of the diluent MEK (Daejung Chemical Co., Ltd.), initiator Diphenyliodonium hexafluorophosphate (TCI Co.) 1g was mixed to prepare a composition for a window coating layer. The coating layer composition was applied to a PI film (polyimide film, SDI, thickness: 80 μm), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating film having a thickness of 50 μm. Postcure was carried out in an oven for 24hr to prepare a window film.
실시예Example 2 내지  2 to 실시예Example 10 10
실시예 1에서, 제1불소 함유 실리콘 수지, 제2실리콘 수지의 종류 및 함량, 가교제의 함량 및/또는 코팅층의 두께를 하기 표 2와 같이 변경한 것을 제외하고는 동일한 방법으로 윈도우 필름을 제조하였다.In Example 1, the window film was manufactured in the same manner except for changing the type and content of the first fluorine-containing silicone resin and the second silicone resin, the content of the crosslinking agent, and / or the thickness of the coating layer as shown in Table 2 below. .
실시예 11Example 11
제조예 1-1의 제1불소 함유 실리콘 수지 0.5g, 제조예 4의 제2실리콘 수지 99.5g, 가교제 CY-179(Ciba社) 40g, 희석제 MEK(대정화학) 60g, 개시제 Diphenyliodonium hexafluorophosphate (TCI社) 1g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 코팅층용 조성물을 PI 필름(폴리이미드 필름, SDI社, 두께:80㎛)에 도포 후, 80℃에서 5분간 건조 후 1000mJ/cm2의 자외선에 노광하여 두께 50㎛의 코팅 필름을 제조한 후에, 100℃ 오븐에서 24hr동안 postcure를 진행하여 윈도우 필름을 제조하였다.0.5 g of the first fluorine-containing silicone resin of Preparation Example 1-1, 99.5 g of the second silicone resin of Preparation Example 4, 40 g of the crosslinking agent CY-179 (Ciba), 60 g of the diluent MEK (Daejeong Chemical), and initiator diphenyliodonium hexafluorophosphate 1) was mixed to prepare a composition for a window coating layer. After coating the composition for coating layer on a PI film (polyimide film, SDI, thickness: 80㎛), and dried at 80 ℃ for 5 minutes and then exposed to ultraviolet light of 1000mJ / cm 2 to prepare a coating film having a thickness of 50㎛ , Postcure for 24hr in a 100 ℃ oven to prepare a window film.
실시예Example 12 내지  12 to 실시예Example 14 14
실시예 11에서 제조예 1-1의 제1불소 함유 실리콘 수지, 제조예 4의 제2실리콘 수지, 가교제, 개시제의 함량을 하기 표 3과 같이 변경한 것을 제외하고는 동일한 방법으로 윈도우 필름을 제조하였다. A window film was manufactured in the same manner as in Example 11, except that the content of the first fluorine-containing silicone resin of Preparation Example 1-1, the second silicone resin of Preparation Example 4, a crosslinking agent, and an initiator were changed as shown in Table 3 below. It was.
실시예 15Example 15
제조예 1-1의 제1불소 함유 실리콘 수지 1g, 제조예 4의 제2실리콘 수지 99g, 가교제 CY-179(Ciba社) 40g, 불소계 아크릴레이트 수지 RS-75 2g, 희석제 MEK(대정화학) 30g, 개시제 Diphenyliodonium hexafluorophosphate (TCI社) 1g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 코팅층용 조성물을 사용하여 실시예 1과 동일한 방법으로 윈도우 필름을 제조하였다. 1 g of the first fluorine-containing silicone resin of Preparation Example 1-1, 99 g of the second silicone resin of Preparation Example 4, 40 g of the crosslinking agent CY-179 (Ciba), 2 g of the fluorine-based acrylate resin RS-75, and 30 g of the diluent MEK (Tejeong Chemical) , Initiator Diphenyliodonium hexafluorophosphate (TCI) 1g was mixed to prepare a composition for a window coating layer. A window film was manufactured in the same manner as in Example 1 using the composition for a coating layer.
실시예Example 16 16
실시예 15에서 불소계 아크릴레이트 수지 RS-75 5g을 사용한 것을 제외하고는 동일한 방법으로 윈도우 필름을 제조하였다.A window film was manufactured in the same manner except in Example 15, 5g of fluorine acrylate resin RS-75 was used.
비교예Comparative example 1 One
제조예 2의 제2실리콘 수지 20.0g, 가교제 CELLOXIDE 2021P(daicel社) 5.0g, 희석제 MEK(대정화학) 25g, 개시제 Diphenyliodonium hexafluorophosphate (TCI社) 0.2g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 윈도우 코팅층용 조성물을 PI 필름(폴리이미드 필름, SDI社, 두께:80㎛)에 도포 후, 100℃에서 5분간 건조 후 1000mJ의 자외선에 노광하여 두께 10㎛의 코팅층을 제조한 후에, 80℃ 오븐에서 24hr동안 postcure를 진행하였다.20.0 g of the second silicone resin of Preparation Example 2, 5.0 g of the crosslinking agent CELLOXIDE 2021P (daicel Co.), 25 g of the diluent MEK (Daejung Chemical Co.), and 0.2 g of the initiator Diphenyliodonium hexafluorophosphate (TCI Co.) were mixed to prepare a composition for a window coating layer. The composition for window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 μm), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating layer having a thickness of 10 μm. Postcure was performed in the oven for 24hr.
비교예Comparative example 2 2
Epoxy hybrimer(Solip社) 25g, 희석제 MEK(대정화학) 20g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 윈도우 코팅층용 조성물을 PI 필름(폴리이미드 필름, SDI社, 두께:80㎛)에 도포 후, 100℃에서 5분간 건조 후 1000mJ의 자외선에 노광하여 두께 10㎛의 코팅층을 제조한 후에, 80℃ 오븐에서 24hr동안 postcure를 진행하였다.25 g of Epoxy hybrimer (Solip Co., Ltd.) and 20 g of diluent MEK (Daejung Chemical) were mixed to prepare a composition for a window coating layer. The composition for window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 μm), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating layer having a thickness of 10 μm. Postcure was performed in the oven for 24hr.
비교예Comparative example 3  3
제조예 2의 실리콘 수지 20.0g, 가교제 CELLOXIDE 2021P(daicel社) 5.0g, 희석제 MEK(대정화학) 25g, 개시제 Diphenyliodonium hexafluorophosphate (TCI社) 0.2g, 불소 함유 레벨링제 RS75(megaface社) 0.5g을 혼합하여 윈도우 코팅층용 조성물을 제조하였다. 상기 윈도우 코팅층용 조성물을 PI 필름(폴리이미드 필름, SDI社, 두께:80㎛)에 도포 후, 100℃에서 5분간 건조 후 1000mJ의 자외선에 노광하여 두께 10㎛의 코팅층을 제조한 후에, 80℃ 오븐에서 24hr동안 postcure를 진행하였다.20.0 g of the silicone resin of Preparation Example 2, 5.0 g of the crosslinking agent CELLOXIDE 2021P (daicel), 25 g of the diluent MEK (Taejeong Chemical), 0.2 g of the initiator Diphenyliodonium hexafluorophosphate (TCI), and 0.5 g of the fluorine-containing leveling agent RS75 (megaface) were mixed. To prepare a composition for a window coating layer. The composition for window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 μm), dried at 100 ° C. for 5 minutes, and then exposed to 1000 mJ UV light to prepare a coating layer having a thickness of 10 μm. Postcure was performed in the oven for 24hr.
실시예와 비교예에서 제조한 윈도우 필름에 대해 하기 물성 (1) 내지 (5)를 측정하고 하기 표 2, 표 3, 표 4에 나타내었다.The following physical properties (1) to (5) of the window films prepared in Examples and Comparative Examples were measured and shown in Tables 2, 3, and 4 below.
(1)RIQ: 윈도우 필름 중 윈도우 코팅층에 대해 Rhopoint社의 Rhopoint IQ로 측정하였다.(1) RIQ: The window coating layer of the window film was measured by Rhopoint IQ of Rhopoint.
(2)난반사율: 윈도우 필름에 대해 파장 550nm에서 Lambda 1050 UV spectrometer(Perkin Elmer사)를 사용하여 측정하였다.(2) diffuse reflectance: measured using a Lambda 1050 UV spectrometer (Perkin Elmer) at a wavelength of 550nm for the window film.
(3)연필경도: 윈도우 필름의 코팅층에 대해 연필 경도계(Heidon)를 사용하여 JIS K5400 방법에 의해 측정한 것이다. 연필 경도 측정시, 연필은 Mitsubishi 사의 6B 내지 9H의 연필을 사용하였다. 코팅층에 대한 연필의 하중은 1kg, 연필을 긋는 각도는 45°, 연필을 긋는 속도는 60mm/min으로 하였다. 5회 평가하여 1회 이상 스크래치가 발생하면 연필경도 아래 단계의 연필을 이용하여 측정하고, 5회 평가시 5회 모두 스크래치가 없을 때의 최대 연필경도값이다.(3) Pencil hardness: It measures by the JIS K5400 method using the pencil hardness meter (Heidon) about the coating layer of a window film. In measuring the pencil hardness, a pencil of 6B to 9H manufactured by Mitsubishi Corporation was used. The load of the pencil on the coating layer was 1 kg, the angle at which the pencil was drawn was 45 °, and the speed at which the pencil was drawn was 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, the five times the five times the maximum pencil hardness value when there is no scratch.
(4)곡률반경: 윈도우 필름(가로x세로, 1cmx10cm)을 곡률 시험용 버니어 캘리퍼스로 크랙 발생여부를 육안으로 평가하였다. 이때 compression 방향은 코팅층이 굴곡이 지는 방향을 향해 서로 맞닿도록 하고, tensile 방향은 기재층이 굴곡지는 방향을 향해 서로 맞닿도록 하였다. 곡률반경 측정은 compression 방향으로 반지름이 큰 값에서 작은 방향으로 줄여가며 측정하였으며, 크랙이 발생하지 않는 JIG의 최소 반지름을 곡률반경으로 결정하였다.(4) Curvature radius: The window film (width x length, 1cmx10cm) was evaluated visually whether the crack generate | occur | produced with the vernier caliper for curvature test. At this time, the compression direction is in contact with each other toward the direction in which the coating layer is curved, the tensile direction is in contact with each other toward the direction in which the substrate layer is curved. The radius of curvature was measured by decreasing the radius from the larger radius to the smaller direction in the compression direction. The minimum radius of the JIG without cracking was determined as the radius of curvature.
(5)외관: 윈도우 필름 중 코팅 층 표면에 오렌지 필 및 물결 무늬의 패턴이 형성되는지 여부를 육안으로 평가하였다. 물결 무늬의 형성 여부는 A4용지부터 10cm 상부에 코팅층을 위치한 후 표면에 빛을 투과하였을 때 블랙시트 면에 불규칙적인 음영 유무로 판단하였다. 물결 무늬 패턴 및 오렌지 필 형성 없이 외관이 좋으면 '3', 물결 무늬 패턴 및 오렌지 필 둘 중 하나라도 형성 시 '2', 물결 무늬 패턴과 오렌지 필 모두 형성 시 '1'로 평가하였다.(5) Appearance: It was visually evaluated whether an orange peel and a wave pattern were formed on the surface of the coating layer in the window film. Formation of wave pattern was determined by the presence of irregular shadow on the surface of the black sheet when light was transmitted to the surface after placing the coating layer on the top 10cm from A4 paper. If the appearance is good without the formation of the moire pattern and the orange peel, it was evaluated as '3', at least one of the moire pattern and the orange peel, and '1' when forming both the moire pattern and the orange peel.
(6)표면 에너지와 물접촉각: Surface Electro Optics사의 Contact angle analyzer(Phoenix 300)을 사용하여 윈도우 필름의 윈도우 코팅층에 대해 25℃에서 측정하였다. (6) Surface energy and water contact angle: The contact angle analyzer (Phoenix 300) of Surface Electro Optics was used to measure the window coating layer of the window film at 25 ° C.
실시예Example
1One 22 33 44 55 66 77 88 99 1010
제1불소함유실리콘수지(중량부)1st fluorine-containing silicone resin (by weight) 제조예 1-1Preparation Example 1-1 0.50.5 1One 55 1010 55 55 -- -- -- 55
제조예 1-2Preparation Example 1-2 -- -- -- -- -- -- 55 -- -- --
제조예 1-3Preparation Example 1-3 -- -- -- -- -- -- -- 55 -- --
제조예 1-4Preparation Example 1-4 -- -- -- -- -- -- -- -- 55 --
제2실리콘 수지(중량부)2nd silicone resin (part by weight) 제조예 2Preparation Example 2 99.599.5 9999 9595 9090 9595 9595 9595 9595 9595 --
제조예 3Preparation Example 3 -- -- -- -- -- -- -- -- -- 9595
가교제(중량부)Crosslinking agent (parts by weight) 2525 2525 2525 2525 2525 33 2525 2525 2525 2525
개시제(중량부)Initiator (parts by weight) 1One 1One 1One 1One 1One 1One 1One 1One 1One 1One
코팅층 두께(㎛)Coating layer thickness (㎛) 5050 5050 5050 5050 1010 5050 5050 5050 5050 5050
RIQRIQ 88.488.4 91.291.2 92.592.5 91.191.1 91.891.8 8787 91.791.7 90.890.8 90.190.1 89.789.7
난반사율(%, @550nm)Diffuse reflectance (%, @ 550nm) 1.1081.108 0.9900.990 0.9430.943 0.9250.925 0.9840.984 0.9070.907 0.9790.979 0.9840.984 0.990.99 0.9470.947
연필경도 Pencil hardness 8H8H 8H8H 8H8H 8H8H 4H4H 8H8H 8H8H 8H8H 8H8H 8H8H
곡률반경(mm)Bending Radius (mm) 0.380.38 0.420.42 0.360.36 0.420.42 0.240.24 0.440.44 0.670.67 0.410.41 0.570.57 0.510.51
외관Exterior 22 33 33 33 33 22 33 33 33 33
실시예Example
1111 1212 1313 1414 1515 1616
제1불소함유실리콘수지(중량부)1st fluorine-containing silicone resin (by weight) 제조예 1-1Preparation Example 1-1 0.50.5 1One 55 1010 1One 1One
제조예 1-2Preparation Example 1-2 -- -- -- -- -- --
제조예 1-3Preparation Example 1-3 -- -- -- -- -- --
제조예1-4Preparation Example 1-4 -- -- -- -- -- --
제2실리콘 수지(중량부)2nd silicone resin (part by weight) 제조예 4Preparation Example 4 99.599.5 9999 9595 9090 9999 9999
가교제(중량부)Crosslinking agent (parts by weight) 4040 4040 4040 4040 4040 4040
불소계(메트)아크릴레이트 수지(중량부)Fluorine (meth) acrylate resin (parts by weight) -- -- -- -- 22 55
개시제(중량부)Initiator (parts by weight) 1One 1One 1One 1One 1One 1One
코팅층 두께(㎛)Coating layer thickness (㎛) 5050 5050 5050 5050 5050 5050
RIQRIQ 88.188.1 91.391.3 93.593.5 94.094.0 93.693.6 94.294.2
연필경도Pencil hardness 6H6H 6H6H 5H5H 5H5H 7H7H 8H8H
외관Exterior 33 33 33 33 33 33
표면에너지(mN/m, @25℃)Surface energy (mN / m, @ 25 ℃) 28.99928.999 27.15427.154 24.76724.767 23.34023.340 24.29224.292 23.27623.276
물접촉각(°, @25℃)Water contact angle (°, @ 25 ℃) 82.1882.18 84.3084.30 87.1487.14 88.9088.90 87.7287.72 88.9888.98
비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
제2 실리콘 수지 (중량부)2nd silicone resin (part by weight) 제조예 2Preparation Example 2 100100 -- 100100
Epoxy hybrimer(중량부)Epoxy hybrimer (parts by weight) -- 100100 --
가교제(중량부)Crosslinking agent (parts by weight) 2525 -- 2525
개시제(중량부)Initiator (parts by weight) 1One -- 1One
불소 함유 레벨링제(중량부)Fluorine-containing leveling agent (parts by weight) -- -- 2.52.5
코팅층 두께(㎛)Coating layer thickness (㎛) 1010 1010 1010
RIQRIQ 76.676.6 83.783.7 79.879.8
난반사율(%,@550nm)Diffuse reflectance (%, @ 550nm) 2.1092.109 1.3611.361 1.1791.179
연필경도Pencil hardness 9H9H 9H9H 4H4H
곡률반경(mm)Bending Radius (mm) 0.390.39 0.380.38 0.140.14
외관Exterior 1One 1One 1One
상기 표 2, 표 3에서 나타난 바와 같이, 본 발명의 플렉시블 윈도우 필름은 RIQ가 85 이상, 난 반사율이 2% 이하로서 외관이 우수하고 눈부심이 적었다. 또한, 본 발명의 플렉시블 윈도우 필름은 연필경도가 4H 이상으로 경도가 높고, 곡률반경이 5.0mm 이하로 유연성이 좋아서, 플렉시블 윈도우 필름으로 사용할 수 있다. 상기 표 3에서 나타난 바와 같이, 불소계 아크릴레이트 수지를 포함하는 윈도우 필름은 제1불소 함유 실리콘 수지를 동량으로 포함하는 윈도우 필름 대비 경도를 높이되 윈도우 필름의 외관도 개선하였다.As shown in Table 2 and Table 3, the flexible window film of the present invention had an RIQ of 85 or more and an egg reflectance of 2% or less, which was excellent in appearance and less glare. In addition, the flexible window film of the present invention has a pencil hardness of 4H or more, a high hardness, a radius of curvature of 5.0 mm or less, and excellent flexibility, and thus can be used as a flexible window film. As shown in Table 3, the window film containing a fluorine-based acrylate resin was improved hardness compared to the window film containing the same amount of the first fluorine-containing silicone resin, but also improved the appearance of the window film.
그러나, 상기 표 4에서 나타난 바와 같이, 제1불소 함유 실리콘 수지를 포함하지 않는 비교예는 RIQ가 85 미만으로 외관이 좋지 않았다.However, as shown in Table 4, the comparative example does not include a first fluorine-containing silicone resin, the RIQ was less than 85 was not good appearance.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

  1. 하기 화학식 1의 제1 불소 함유 실리콘 수지, 에폭시기 또는 에폭시기 함유 작용기를 갖는 제2실리콘 수지, 및 개시제를 포함하는 윈도우 필름용 조성물:A composition for a window film comprising a first fluorine-containing silicone resin of formula 1, a second silicone resin having an epoxy group or an epoxy group-containing functional group, and an initiator:
    <화학식 1><Formula 1>
    (RaSiO(4-a)/2)x(XbSiO(4-b)/2)y (R a SiO (4-a) / 2 ) x (X b SiO (4-b) / 2 ) y
    (상기 화학식 1에서, R은 에폭시기, 에폭시기 함유 작용기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C5 내지 C20의 시클로알킬기, 또는 치환 또는 비치환된 C6 내지 C20의 아릴기,(In Formula 1, R is an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
    X는 1개 이상의 불소를 함유하는 치환 또는 비치환된 C1 내지 C30의 알킬기, 1개 이상의 불소를 함유하는 치환 또는 비치환된 C5 내지 C20의 시클로알킬기, 또는 1개 이상의 불소를 함유하는 치환 또는 비치환된 C6 내지 C20의 아릴기,X is a substituted or unsubstituted C1 to C30 alkyl group containing at least one fluorine, a substituted or unsubstituted C5 to C20 cycloalkyl group containing at least one fluorine, or a substituted or unsubstituted containing at least one fluorine Substituted C6 to C20 aryl group,
    a는 0 내지 3의 정수, b는 1 내지 3의 정수, 0≤x<1, 0<y≤1, x+y=1).a is an integer of 0 to 3, b is an integer of 1 to 3, 0 ≦ x <1, 0 <y ≦ 1, and x + y = 1).
  2. 제1항에 있어서, 상기 제2실리콘 수지는 하기 화학식 2의 실리콘 수지를 포함하는 것인, 윈도우 필름용 조성물:The composition of claim 1, wherein the second silicone resin comprises a silicone resin of Formula 2 below:
    <화학식 2><Formula 2>
    (R1SiO3/2)x(R2R3SiO2/2)y(R4R5R6SiO1/2)z(SiO4/2)w (R 1 SiO 3/2) x ( R 2 R 3 SiO 2/2) y (R 4 R 5 R 6 SiO 1/2) z (SiO 4/2) w
    (상기 화학식 2에서, R1은 에폭시기 또는 에폭시기 함유 작용기,(In the formula 2, R 1 is an epoxy group or the epoxy group-containing functional groups,
    R2 및 R3은 각각 독립적으로, 수소, 가교성 작용기, 비치환 또는 치환된 C1 내지 C20의 알킬기, 또는 비치환 또는 치환된 C5 내지 C20의 시클로알킬기,R 2 and R 3 are each independently, hydrogen, a crosslinkable functional group, an unsubstituted or alkyl group-substituted C1 to C20, or unsubstituted or substituted cycloalkyl group of C5 to C20,
    R4, R5 및 R6은 각각 독립적으로, 수소, 가교성 작용기, 비치환 또는 치환된 C1 내지 C20의 알킬기, 비치환 또는 치환된 C5 내지 C20의 시클로알킬기, 또는 비치환 또는 치환된 C6 내지 C30의 아릴기,R 4 , R 5 and R 6 are each independently hydrogen, a crosslinkable functional group, unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 aryl group,
    0<x≤1, 0≤y<1, 0≤z<1, 0≤w<1, x+y+z+w=1).0 <x ≦ 1, 0 ≦ y <1, 0 ≦ z <1, 0 ≦ w <1, x + y + z + w = 1).
  3. 제1항에 있어서, 상기 제1 불소 함유 실리콘 수지는 하기 화학식 1-1-1 내지 화학식 1-1-10의 실리콘 수지를 포함하는 것인, 윈도우 필름용 조성물:The composition of claim 1, wherein the first fluorine-containing silicone resin comprises a silicone resin of the following Chemical Formula 1-1-1 to Chemical Formula 1-1-10:
    <화학식 1-1-1><Formula 1-1-1>
    (EcSiO3/2)x(FdSiO3/2)y (EcSiO 3/2 ) x (FdSiO 3/2 ) y
    <화학식 1-1-2><Formula 1-1-2>
    (EcSiO3/2)x(FoSiO3/2)y (EcSiO 3/2 ) x (FoSiO 3/2 ) y
    <화학식 1-1-3><Formula 1-1-3>
    (GpSiO3/2)x(FdSiO3/2)y (GpSiO 3/2 ) x (FdSiO 3/2 ) y
    <화학식 1-1-4><Formula 1-1-4>
    (GpSiO3/2)x(FoSiO3/2)y (GpSiO 3/2 ) x (FoSiO 3/2 ) y
    <화학식 1-1-5><Formula 1-1-5>
    (EcSiO3/2)x1((Me)2SiO2/2)x2(FdSiO3/2)y (EcSiO 3/2) x1 ((Me ) 2 SiO 2/2) x2 (FdSiO 3/2) y
    <화학식 1-1-6><Formula 1-1-6>
    (EcSiO3/2)x1((Me)2SiO2/2)x2(FoSiO3/2)y (EcSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FoSiO 3/2 ) y
    <화학식 1-1-7><Formula 1-1-7>
    (GpSiO3/2)x1((Me)2SiO2/2)x2(FdSiO3/2)y (GpSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FdSiO 3/2 ) y
    <화학식 1-1-8><Formula 1-1-8>
    (GpSiO3/2)x1((Me)2SiO2/2)x2(FoSiO3/2)y (GpSiO 3/2 ) x1 ((Me) 2 SiO 2/2 ) x2 (FoSiO 3/2 ) y
    <화학식 1-1-9><Formula 1-1-9>
    (EcSiO3/2)x1(GpSiO3/2)x2(FdSiO3/2)y (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (FdSiO 3/2 ) y
    <화학식 1-1-10><Formula 1-1-10>
    (EcSiO3/2)x1(GpSiO3/2)x2(FoSiO3/2)y (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (FoSiO 3/2 ) y
    (상기 화학식 1-1-1 내지 화학식 1-1-10에서, Ec는 2-(3,4-에폭시시클로헥실)에틸기, Gp는 3-글리시독시프로필기, Me는 메틸기, Fd는 1H, 1H, 2H, 2H-퍼플루오로데실기, Fo는 1H, 1H, 2H, 2H-퍼플루오로옥틸기, 0<x<1, 0<y<1, x+y=1, 0<x1<1, 0<x2<1, 0<y<1, x1+x2+y=1).(In Formulas 1-1-1 to 1-1-10, Ec is 2- (3,4-epoxycyclohexyl) ethyl group, Gp is 3-glycidoxypropyl group, Me is methyl group, Fd is 1H, 1H, 2H, 2H-perfluorodecyl group, Fo is 1H, 1H, 2H, 2H-perfluorooctyl group, 0 <x <1, 0 <y <1, x + y = 1, 0 <x1 < 1, 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1).
  4. 제1항에 있어서, 상기 제2실리콘 수지는 하기 화학식 2-1-1 또는 2-1-2의 실리콘 수지를 포함하는 것인, 윈도우 필름용 조성물:The composition of claim 1, wherein the second silicone resin comprises a silicone resin of the following Chemical Formula 2-1-1 or 2-1-2:
    <화학식 2-1-1><Formula 2-1-1>
    (EcSiO3/2)x1(GpSiO3/2)x2 (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2
    (상기 화학식 2-1-1에서, Ec는 2-(3,4-에폭시시클로헥실)에틸기, Gp는 3-글리시독시프로필기, 0≤x1≤1, 0≤x2≤1, x1+x2=1, x1+x2≠0).(In Formula 2-1-1, Ec is 2- (3,4-epoxycyclohexyl) ethyl group, Gp is 3-glycidoxypropyl group, 0≤x1≤1, 0≤x2≤1, x1 + x2 = 1, x1 + x2 ≠ 0).
    <화학식 2-1-2><Formula 2-1-2>
    (EcSiO3/2)x1(GpSiO3/2)x2(SiO4/2)w (EcSiO 3/2 ) x1 (GpSiO 3/2 ) x2 (SiO 4/2 ) w
    (상기 화학식 2-2에서, Ec는 2-(3,4-에폭시시클로헥실)에틸기, Gp는 3-글리시독시프로필기, 0<x1<1, 0<x2<1, 0<w<1, x1+x2+w=1).In Formula 2-2, Ec is a 2- (3,4-epoxycyclohexyl) ethyl group, Gp is a 3-glycidoxypropyl group, 0 <x1 <1, 0 <x2 <1, 0 <w <1 , x1 + x2 + w = 1).
  5. 제1항에 있어서, 상기 제1 불소 함유 실리콘 수지는 상기 제1 불소 함유 실리콘 수지와 상기 제2실리콘 수지의 총합 중 약 0.1중량% 내지 약 50중량%로 포함되는 것인, 윈도우 필름용 조성물.The composition of claim 1, wherein the first fluorine-containing silicone resin is included in about 0.1 wt% to about 50 wt% of the total of the first fluorine-containing silicone resin and the second silicon resin.
  6. 제1항에 있어서, 상기 윈도우 필름용 조성물은 가교제를 더 포함하는 것인, 윈도우 필름용 조성물.The composition for a window film according to claim 1, wherein the composition for window film further comprises a crosslinking agent.
  7. 제6항에 있어서, 상기 가교제는 사슬형 지방족 에폭시 모노머, 고리형 지방족 에폭시 모노머, 수소 첨가된 방향족 탄화수소 에폭시 모노머, 옥세탄 모노머 중 하나 이상을 포함하는 것인, 윈도우 필름용 조성물.The composition of claim 6, wherein the crosslinking agent comprises at least one of a chained aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer.
  8. 제6항에 있어서, 상기 윈도우 필름용 조성물은 불소계 (메트)아크릴레이트 수지를 더 포함하는 것인, 윈도우 필름용 조성물.The composition for a window film according to claim 6, wherein the composition for window film further comprises a fluorine-based (meth) acrylate resin.
  9. 제6항에 있어서, 상기 불소계 (메트)아크릴레이트 수지는 상기 제1 불소 함유 실리콘 수지와 제2실리콘 수지의 총합 100중량부에 대해 약 1중량부 내지 약 20중량부로 포함되는 것인, 윈도우 필름용 조성물.The window film of claim 6, wherein the fluorine-based (meth) acrylate resin is included in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicon resin. Composition.
  10. 기재층 및 상기 기재층 상에 형성된 코팅층을 포함하는 플렉시블 윈도우 필름이고, 상기 플렉시블 윈도우 필름은 RIQ가 약 85 이상, 연필경도가 약 4H 이상, 곡률반경이 약 5.0mm 이하인 것인, 플렉시블 윈도우 필름.A flexible window film comprising a substrate layer and a coating layer formed on the substrate layer, wherein the flexible window film has a RIQ of about 85 or more, a pencil hardness of about 4H or more, and a radius of curvature of about 5.0 mm or less.
  11. 제10항에 있어서, 상기 코팅층은 제1항 내지 제9항 중 어느 한 항의 윈도우 필름용 조성물로 형성된 것인, 플렉시블 윈도우 필름.The flexible window film of claim 10, wherein the coating layer is formed of the composition for a window film of claim 1.
  12. 제10항에 있어서, 상기 코팅층은 25℃에서의 표면 에너지가 약 30mN/m 이하인 것인, 플렉시블 윈도우 필름.The flexible window film of claim 10, wherein the coating layer has a surface energy at 25 ° C. of about 30 mN / m or less.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113136149A (en) * 2020-01-17 2021-07-20 欧富莱斯有限公司 Protective film for brightness uniformity of display device and display device comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014090A1 (en) * 2004-07-16 2006-01-19 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus
US20110027702A1 (en) * 2008-03-11 2011-02-03 3M Innovative Properties Company Hardcoat composition
WO2011028075A2 (en) * 2009-09-04 2011-03-10 위더스케미칼 주식회사 Hard coating composition and a production method for the same and a hard coating film formed using the hard coating composition
US20110230594A1 (en) * 2008-12-12 2011-09-22 Jouko Vyorykka Coating composition, a process of producing a coating composition, a coated article, and a method of forming such articles
JP2014176988A (en) * 2013-03-14 2014-09-25 Fujifilm Corp Laminated film and display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014090A1 (en) * 2004-07-16 2006-01-19 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus
US20110027702A1 (en) * 2008-03-11 2011-02-03 3M Innovative Properties Company Hardcoat composition
US20110230594A1 (en) * 2008-12-12 2011-09-22 Jouko Vyorykka Coating composition, a process of producing a coating composition, a coated article, and a method of forming such articles
WO2011028075A2 (en) * 2009-09-04 2011-03-10 위더스케미칼 주식회사 Hard coating composition and a production method for the same and a hard coating film formed using the hard coating composition
JP2014176988A (en) * 2013-03-14 2014-09-25 Fujifilm Corp Laminated film and display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113136149A (en) * 2020-01-17 2021-07-20 欧富莱斯有限公司 Protective film for brightness uniformity of display device and display device comprising same
CN113136149B (en) * 2020-01-17 2023-04-18 欧富莱斯有限公司 Protective film for brightness uniformity of display device and display device comprising same

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