CN100410341C - Coating liquid for forming transparent coating film, base with such coating film, and liquid crystal display cell - Google Patents

Coating liquid for forming transparent coating film, base with such coating film, and liquid crystal display cell Download PDF

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CN100410341C
CN100410341C CNB2004800146489A CN200480014648A CN100410341C CN 100410341 C CN100410341 C CN 100410341C CN B2004800146489 A CNB2004800146489 A CN B2004800146489A CN 200480014648 A CN200480014648 A CN 200480014648A CN 100410341 C CN100410341 C CN 100410341C
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coating
transparent coating
liquid crystal
forms
substrate
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CN1795244A (en
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吉田宣昭
中岛昭
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Gc Catalysts And Chemicals Lt
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Catalysts and Chemicals Industries Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on 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; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/133345Insulating layers

Abstract

A coating liquid for forming transparent coating films is disclosed which enables to form a transparent coating film that is excellent in abrasion resistance, acid resistance, alkali resistance, water resistance, insulating property, adhesiveness to an electrode film or a film (an alignment film) made of a resin with high hydrophobicity such as polyimide resin, toughness, and flexibility. The coating liquid for forming transparent coating films wherein a matrix-forming component is dispersed in a mixed solvent composed of water and an organic solvent is characterized in that the matrix-forming component contains an organic silicon compound having two or more hydrolyzable groups or a hydrolysate thereof.

Description

Transparent coating forms with coating fluid, the base material that has this tunicle and liquid crystal display cell
Technical field
The present invention relates to novel transparent coating and form with coating fluid and have and forms the base material that has tunicle of the tunicle that forms with coating fluid and have the liquid crystal display cell that this has the base material of tunicle, relate more specifically to flexibility and transparent coating tenacity excellent and excellent scratch resistance, that can form transparent coating formation coating fluid that transparent coating formation in the past is difficult to obtain with coating fluid by this tunicle.
Background technology
In the past, known will be on the surface of glass substrate successively the oriented film that constitutes of the macromolecular materials such as ELD, polyimide of laminated ITO etc. a pair of to have the substrate of transparency electrode opposed between spacer, make between each ELD opposedly, in the gap that separates appointed interval by this spacer, enclose the liquid crystal display cell of liquid crystal.
In such liquid crystal display cell, cause the oriented film damage owing to sneak into the foreign matter or the spacer of liquid crystal cell inside in the manufacturing process sometimes, and cause conducting between upper/lower electrode thus, produce by the demonstration of this conducting initiation bad.
Therefore, in the liquid crystal display cell as above-mentioned, between the ELD of the substrate that has transparency electrode and oriented film, be formed with transparent insulating film (opening clear 60-260021 communique, Japanese patent laid-open 1-150116 communique, Japanese patent laid-open 2-221923 communique etc. with reference to the Japanese Patent spy).
In addition, above-mentioned oriented film uses the strong resins of hydrophobicity such as polyimide resin mostly.If form the oriented film that is made of the strong resin of such hydrophobicity on insulating film, then the binding property of insulating film and oriented film becomes insufficient, can produce by scratch on liquid crystal display cell and wait the bright spot that causes.Therefore, the applicant as the coating fluid that can form with the insulating film of the binding property excellence of oriented film, has proposed to contain the coating fluid of the mineral compound with specified particle diameter in patent documentation 1 (Japanese patent laid-open 4-247427 communique).
In addition, if form such insulating film between ELD and oriented film, the static that produces in the time of also can rubbing owing to oriented film etc. causes damage or directed bad etc. on oriented film.Therefore, the applicant proposes to form on the transparency electrode surface by electrically conductive microparticle and matrix and constitutes and surface resistivity is 10 in patent documentation 2 (Japanese patent laid-open 5-232459 communique) 9~10 13The protective membrane of Ω/mouth.
Yet, because nowadays to demands such as the slimming of liquid crystal indicator, high-definition, big pictureizations, so need be higher and material that scuff resistance is high with the binding property of oriented film.In addition, in the substrate of plastics etc., need insulating film self to have good flexibility and toughness.
In addition, in recent years, TFT type liquid crystal indicator is widely used.
TFT type liquid crystal indicator uses the liquid crystal display cell that is provided with tft array such as TFT (thin film transistor) element, data electrode on transparency carrier.By being set, planarization film eliminates uneven that this tft array produces, by uneven cause directed disorderly that show electrodes such as ITO make the aperture opening ratio raising of TFT type liquid crystal indicator and eliminate tft array is set thereon.
In addition, in having the liquid crystal indicator of colour filter,, insulativity protection tunicle can be set also in order to make the colour filter planarization or the reliability of liquid crystal indicator to be improved.
The planarization tunicle insulativity protection tunicle that uses in such liquid crystal indicator can use for example organic resin tunicle of formation such as polypropylene-based resin, vibrin, SiO 2, Si 3N 4Etc. the mineral-type tunicle, the compound tunicle of organic-inorganic that the polymkeric substance of alkyl ortho-siliformic acid constitutes etc.
Yet organic resin is not enough by film heat resistance, thus can produce the crack, and then if be placed on the strength degradation that the next meeting of high temperature is emitted gaseous constituent or made tunicle.In addition, in this organic resin tunicle, on tunicle, form etchant resist, also be difficult to many problems such as formation even exist.
In addition, in the mineral-type tunicle, there is hygroscopic problem in tunicle self, also has the many problems such as thickness increase that are difficult to form etchant resist even tunicle self on tunicle.
In addition, in the compound tunicle of organic-inorganic, tunicle is frangible, also has problems such as the easy scuffing in surface, and the aspects such as formation of the etchant resist on this tunicle existing problems.
Patent documentation 1: Japanese patent laid-open 4-247427 communique
Patent documentation 2: Japanese patent laid-open 5-232459 communique
The announcement of invention
The problem that invention will solve
The inventor is based on such situation, carried out conscientious research in order to address the above problem, found that the silicoorganic compound or its hydrolysate that have an ad hoc structure formula by use can obtain good transparent coatings such as water tolerance, water-repellancy, toughness, flexibility, thereby finished the present invention.
The present invention finishes for the problem that solves in the aforesaid prior art, its purpose is to provide and can forms scuff resistance, acid resistance, alkali resistance, water tolerance, insulativity excellence, the binding property of the film (oriented film) that constitutes with electrode film or by the strong resin of hydrophobicitys such as polyimide etc. is also good, and the transparent coating of toughness, flexible excellent transparent coating forms with coating fluid and has base material that has tunicle and liquid crystal display cell by such tunicle.
Solve the method for problem
Main contents of the present invention comprise following item.
[1] transparent coating forms and uses coating fluid, it is that disperse matrix is formed into transparent coating that branch obtains and forms and use coating fluid in the mixed solvent that is made of water and organic solvent, it is characterized in that, contain be selected from the represented silicoorganic compound of a) following formula (I) or its hydrolysate, b) represented silicoorganic compound or its hydrolysate or the c of following formula (II)) their more than a kind of mixture.
R 1-SiR 2 mR 3 (3-m)(I)
(in the formula, R 1-expression R 8(CR 9 2) n-or R 10X-.
R 8Expression hydrolization group, hydroxyl, hydrogen atom or halogen atom.
R 9Represent hydrogen atom or halogen atom respectively independently.
R 10Expression methyl, hydrogen atom or hydrolization group.
N is 3~30 integer.
X is for being selected from-(CH 2) q-,-(Ph)-[wherein, Ph represents phenyl ring] ,-(CH 2) q-(Ph)-,-(CH 2) q-(Ph)-(CH 2) y-,-[(CH 2) q(CF 2) y(CH 2) r]-and-(CH 2) q-(S)-(CH 2) r-divalent group [wherein, q, r and y represent 1~30 integer].
R 2The expression hydrolization group.
R 3The carbonatoms that expression can contain halogen atom is 1~30 organic group.
M represents 1~3 integer.
Wherein, formula (I) has 2~3 hydrolization groups in 1 molecule.〕
R 4 nR 5 3-nSi-(X)-SiR 6 pR 7 (3-p) (II)
(in the formula, R 4And R 6Represent hydrolization group independently.
R 5And R 7The expression carbonatoms that can contain halogen atom is 1~30 any monovalent organic radical group independently.
X is for being selected from-(CH 2) q-,-(Ph)-(wherein, Ph represents phenyl ring) ,-(CH 2) q-(Ph)-,-(CH 2) q-(Ph)-(CH 2) y-,-[(CH 2) q(CF 2) y(CH 2) r]-,-(CH 2) q-(S)-(CH 2) r-and-(S) q-divalent group [wherein, q, r and y represent 1~30 integer].
N represents 0~3 number.
P represents 0~3 number.
Wherein, formula (II) has the hydrolization group more than 2 in 1 molecule.〕
[2] the transparent coating formation coating fluid as being put down in writing in [1], its feature also is, the silicoorganic compound of described formula (I) have the hydrolization group above 2 in 1 molecule, the silicoorganic compound of described formula (II) have the hydrolization group above 2 in 1 molecule.
[3] the transparent coating formation coating fluid as being put down in writing in [1] or [2], its feature also is, described matrix form composition also contain be selected from a) the represented silicoorganic compound b of following formula (III)) acetylacetone chelate, c) metal alkoxides and d) more than a kind of polysilazane.
R tSi(OR′) 4-t (III)
(wherein, R is selected from methyl, ethyl, vinyl or epoxy group(ing).R ' is the alkyl of carbonatoms 1~6.T is 0~4 number.〕
[4] use coating fluid, its feature also to be as each transparent coating of the putting down in writing formation in [1]~[3], described matrix forms composition and also contains inorganic compound particles.
[5] have the base material of transparent coating, it is characterized in that, substrate surface is formed with by each transparent coating put down in writing in above-mentioned [1]~[4] and forms the transparent coating that obtains with the coating fluid coating.
[6] liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively ELD in the surface of the substrate of at least one side, transparent coating and oriented film, make between each ELD opposed, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved
It is characterized in that transparent coating is for forming the tunicle that forms with the coating fluid coating with each transparent coating put down in writing in [1]~[4].
[7] liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively colour filter in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved
It is characterized in that transparent coating is for forming the tunicle that forms with the coating fluid coating with each transparent coating put down in writing in [1]~[4].
[8] liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively tft array in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved
It is characterized in that transparent coating is for forming the tunicle that forms with the coating fluid coating with each transparent coating put down in writing in [1]~[4].
The effect of invention
As mentioned above, transparent coating of the present invention forms and contains the matrix that is made of specific silicoorganic compound with coating fluid and form composition.
The water-repellancy of the transparent coating that therefore, obtains, flexibility, toughness are good.
In addition, if at rough substrate, for example have the substrate of tft array or have on the substrate of colour filter and form such transparent coating, then can make the surface become very smooth.In addition, because can form smooth oriented film, so help suppressing demonstration disorder, the generation that prevents bright spot, the scattering of light when reducing flat pannel display of the liquid crystal that surface shape causes and improve contrast gradient etc. on this transparent coating surface.
The best mode that carries out an invention
Below, transparent coating formation of the present invention is specifically described with coating fluid, the base material that has this film and liquid crystal display cell.
[transparent coating forms and uses coating fluid]
At first, transparent coating formation of the present invention is described with coating fluid.
Transparent coating of the present invention forms with in the coating fluid, and matrix forms composition and is dispersed in the mixed solvent that is made of water and organic solvent.
Matrix forms composition
Matrix form composition contain be selected from the represented silicoorganic compound of a) following formula (I) or its hydrolysate, b) represented silicoorganic compound or its hydrolysate or the c of following formula (II)) their more than a kind of mixture.
R 1-SiR 2 mR 3 (3-m) (I)
(in the formula, R 1-expression R 8(CR 9 2) n-or R 10X-.
R 8Expression hydrolization group, hydroxyl, hydrogen atom or halogen atom.Halogen atom can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.
Wherein, hydrolization group is meant atom or the atomic group that is replaced by hydroxyl by the chemical reaction with water.Hydrolization group can exemplify the alkoxyl group of carbonatoms 1~6, the alkenyloxy of carbonatoms 2~7, the alkoxy aryl of carbonatoms 1~9 and the alkyl-aryloxy of carbonatoms 1~9, better is to be selected from methoxyl group, oxyethyl group.
R 9Represent hydrogen atom or halogen atom respectively independently.R 9Can all be hydrogen atom, also wherein a part be a halogen atom, can also all be halogen atom.Halogen atom can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.
N is 3~30 integer, is preferably 3~20 integer, more preferably 3~12 integer.
So, R 8(CR 9 2) n-exemplary can exemplified by alkyl groups, haloalkyl, particularly perfluoroalkyl.
R 10Be selected from methyl, hydrogen atom or hydrolization group.Hydrolization group can exemplify group as hereinbefore, better is the alkoxyl group that is selected from carbonatoms 1~6.Alkoxyl group better is methoxyl group, oxyethyl group.
X is for being selected from-(CH 2) q-,-(Ph)-[wherein, Ph represents phenyl ring] ,-(CH 2) q-(Ph)-,-(CH 2) q-(Ph)-(CH 2) y-,-[(CH 2) q(CF 2) y(CH 2) r]-and-(CH 2) q-(S)-(CH 2) r-divalent group.
Wherein, q, r and y are separately respectively 1~30 integer, are preferably 1~20 integer, more preferably 2~12 integer.
X in above-mentioned divalent group better is-(CH 2) q-,-(Ph)-.
So, R 10The exemplary of X-can exemplify CH 3O-(CH 2) q-, C 2H 5O-(CH 2) q-, CH 3O-(Ph)-, C 2H 5O-(Ph)-.
R 2The expression hydrolization group.Hydrolization group can exemplify group as hereinbefore, better is the alkoxyl group that is selected from carbonatoms 1~6.Alkoxyl group better is methoxyl group, oxyethyl group.
R 3The carbonatoms that expression can contain halogen atom is 1~30, be preferably 1~20, more preferably 1~12 organic group.This organic group can exemplify the alkyl of carbonatoms 1~20, the aromatic hydrocarbons of carbonatoms 6~20, the alkylaryl of carbonatoms 7~27, the arylalkyl of carbonatoms 7~27, the alkenyl of carbonatoms 2~20 and the haloalkyl of carbonatoms 1~20.The halogen atom of this haloalkyl can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.Haloalkyl can be that all hydrogen atoms are replaced by halogen atom, also can be that the hydrogen atom of part is replaced by halogen atom.
M represents 1~3 integer, is preferably 3.
The silicoorganic compound of formula (I) have 2~3 hydrolization groups in 1 molecule.
The silicoorganic compound of formula (I) better are to have 1 haloalkyl in 1 molecule at least.
The silicoorganic compound of such formula (I) can exemplify 3,3,3-trifluoro propyl Trimethoxy silane, methyl-3,3,3-trifluoro propyl dimethoxy silane, 17 fluorine decyl methyl dimethoxysilanes, n-perfluoro capryl ethyl triethoxysilane, 17 fluorine decyl Trimethoxy silanes etc.〕
R 4 nR 5 3-nSi-(X)-SiR 6 pR 7 (3-p)(II)
(in the formula, R 4And R 6Represent hydrolization group independently.
R 5And R 7The expression carbonatoms that can contain halogen atom is 1~30 any monovalent organic radical group independently.
The object lesson of hydrolization group and organic group, the explanation that preference is relevant with described formula (I) are identical.
The explanation that X is also relevant with described formula (I) is identical, can also for-(S) q-.Wherein, q and aforementioned 1~30 the integer that is similarly are preferably 1~20 integer, more preferably 2~12 integer.
N represents 0~3 number, is preferably 2 or 3.
P represents 0~3 number, is preferably 2 or 3.
Wherein, the silicoorganic compound of formula (II) have the hydrolization group more than 2 in 1 molecule, are preferably to have 3~6 hydrolization groups.〕
The represented silicoorganic compound of formula (II) can exemplify two (trifluoro propyl dimethoxy silylation) hexane, two (Trimethoxy silane base) ethane, two (Trimethoxy silane base) propane, two (Trimethoxy silane base) butane, two (Trimethoxy silane base) pentane, two (Trimethoxy silane base) hexane, two (Trimethoxy silane base) heptane, two (Trimethoxy silane base) octane, two (Trimethoxy silane base) nonane, two (Trimethoxy silane base) decane, two (Trimethoxy silane base) dodecane, two (Trimethoxy silane base) heptadecane, two (Trimethoxy silane base) octadecane, two (triethoxysilicane alkyl) hexane, two (tripropoxy silylation) hexane, two (three n-butoxy silane bases) hexane, two (three i-butoxy silane bases) hexane, two (allyl dimethyl TMOS base) hexane, two (vinyl-dimethyl TMOS base) hexane, two (propenyl dimethoxy silylation) hexane, four sulfurations, two (3-tri-ethoxy silylpropyls), 1,4-two (Trimethoxy silane base ethyl) benzene etc.
Therefore silicoorganic compound or its hydrolysate hydrophobicity height with such ad hoc structure formula, can obtain water tolerance, water-repellancy is good, and toughness, flexible good transparent coating.In addition, it is good to form scuff resistance, acid resistance, alkali resistance, water tolerance, insulativity, the also good tunicle of binding property of the film (oriented film) that constitutes with the strong resin of hydrophobicitys such as electrode film or polyimide resin etc.
Among the present invention, can use the represented silicoorganic compound of formula (II) or its hydrolysate.
The represented silicoorganic compound of formula (II) have-(X)-, X is hydrophobic, if the chain length of X increases, then can also be crooked, and so can improve water-repellancy, flexibility, the toughness of tunicle.In addition, in the represented silicoorganic compound of formula (II), two ends are hydrolization group, so reactive high.
Among the present invention, above-mentioned silicoorganic compound can directly use (that is, not hydrolysis), use after also can making hydrolysate.If make hydrolysate earlier, then can obtain the coating fluid that in the preservation process, do not react, long-term reliability is good, can also form the tunicle of homogeneous simultaneously.
Hydrolysate, can by for example in the water-ethanol mixed solvent of silicoorganic compound in the presence of acid catalyst hydrolysis obtain.Such hydrolysate can be a partial hydrolysate, also can be the polycondensate of hydrolysate.
The said hydrolyzed product is preferably 500~20000 with the number-average molecular weight of polystyrene conversion, and good especially is in 700~10000 scope.If in this scope, then the binding property of film toughness, base material is all high, and is stable in coating fluid, can form the tunicle of homogeneous.
If the number-average molecular weight of the polystyrene conversion of hydrolysate is too small, then in fact have no difference with the material that does not have hydrolysis.If the number-average molecular weight of the polystyrene conversion of hydrolysate is excessive, the bad stability of coating fluid then possibly can't obtain the transparent coating of homogeneous thickness.
Described matrix formation composition is more preferably except being selected from the represented silicoorganic compound of above-mentioned formula (I) or its hydrolysate, represented silicoorganic compound or more than a kind of its hydrolysate or their mixture of above-mentioned formula (II), also containing and is selected from more than a kind of following compositions:
A) silicoorganic compound [except silicoorganic compound] corresponding to described formula (I) and described formula (II),
B) acetylacetone chelate,
C) metal alkoxides and
D) polysilazane.
Below, these compositions are specifically described.
(a) silicoorganic compound
Matrix forms the silicoorganic compound of composition except above-mentioned (I), (II), can also contain other silicoorganic compound (following also note is made silicoorganic compound (a)).Other silicoorganic compound like this can use for example represented silicoorganic compound of following formula (III).
R tSi(OR′) 4-t (III)
(wherein, R is selected from methyl, ethyl, vinyl or epoxy group(ing).
R ' is the alkyl of carbonatoms 1~6.T is 0~4 number.〕
Such silicoorganic compound (a), particularly, better be to use for example tetramethoxy-silicane, tetraethoxysilane, monomethyl Trimethoxy silane, an ethyl triethoxysilane, an ethyl trimethoxy silane, monomethyl triethoxyl silane, vinyltriethoxysilane, epoxy group(ing) triethoxyl silane etc.
These silicoorganic compound (a) can directly use, and also can use after the hydrolysis.Such hydrolysate can for example be mixed with organic silicon compound (a) by the ordinary method that adopted in the past in alcohol such as methyl alcohol or ethanol, add the method that acid and water is hydrolyzed obtains.
If the transparent coating formation of the present invention of adding above-mentioned silicoorganic compound (a) is coated on tunicle drying, the sintering that obtains on the base material with coating fluid, then forms the tunicle of scuff resistance, acid resistance, alkali resistance, water tolerance and insulativity excellence.
(b) acetylacetone chelate
Acetylacetone chelate (b) is with the inner complex of methyl ethyl diketone as dentate, is the represented compound of following formula (IV) or its condenses.
Figure C20048001464800121
(wherein, a+b is 2~4, and a is 0~3, and b is 1~4, and R is-C nH 2n+1(n=3 or 4), X is-CH 3,-OCH 3,-C 2H 5Or-OC 2H 5M is element or the vanadyl (VO) that is selected from the periodic table of elements 2~15 families.Wherein, these elements etc. are as shown in the table with the preferably combination of a, b.〕
Table 1
a 0~1 0~2 0~3
b 1~2 1~3 1~4
a+b 2 3 4
M Co,Cu,Mg, Mn,Pb,Ni, Zn,Sn,Ba, Be,VO、 Al,Cr,Fe, V,Co,In, Ta,Y,B Ti,Zr,Hf, Sb
The object lesson of such compound for example can be enumerated dibutoxy-diacetyl acetone and close zirconium, three butoxy-acetyl acetone zirconium, diacetyl acetone and close that lead, praseodynium close iron, dibutoxy-diacetyl acetone closes hafnium, three butoxy-acetyl acetone hafnium etc.
The transparent coating of such interpolation acetylacetone chelate forms the tunicle that can obtain alkali resistance, acid resistance, salt water resistance corrodibility, water tolerance, anti-solvent corrosion excellence with coating fluid.
(c) metal alkoxides
In addition, metal alkoxides (c) better is
M 2(OR) n (V)
(in the formula, M 2Be atoms metal, R be alkyl or-C mH 2mO 2(m=3~10), n is and M 2The identical integer of valence.) represented compound or its condenses, can use a kind that is selected from these compounds or its condenses, or the combination more than 2 kinds.M in the above-mentioned formula 2So long as metal is not particularly limited, but better be Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, Bi, Ce or Cu.
Such metal alkoxides particularly, better is to use tetrabutyl zirconate, diisopropoxy-two octyloxy titanium, diethoxy lead etc.
If will be added with the transparent coating of the present invention of above-mentioned metal alkoxides forms with coating fluid coating, dry, sintering, then, form the tunicle of scuff resistance, acid resistance, alkali resistance, water tolerance and insulativity excellence by the polymerizing curable of this metal alkoxides.
(d) polysilazane
Figure C20048001464800141
Polysilazane (d) can use the polysilazane with the represented repeating unit of following formula (VI).
(wherein, R 1, R 2And R 3Represent that respectively hydrogen atom or carbonatoms are 1~8 alkyl.〕
Matrix forms composition when using the represented polysilazane of described formula (VI), better is that alkyl is the polysilazane of methyl, ethyl or propyl group.In this case, the alkyl that decomposes when not having heating, during heating the contraction of film few, tail off so fissured situation takes place when being subjected to string stress, can almost do not had fissured transparent coating.
In addition, the polysilazane with the represented repeating unit of following formula (VI) can be straight chain shape or cyclic, can also mix and contain straight catenate polysilazane and cyclic polysilazane.
In addition, the number-average molecular weight of the polystyrene conversion of such polysilazane is preferably 500~10000, is more preferably in 1000~4000 scope.Number-average molecular weight was less than 500 o'clock, and low-molecular-weight polysilazane volatilizees when being heating and curing, and the transparent coating that obtains becomes porous matter easily, in addition, if number-average molecular weight surpasses 10000, the then mobile decline easily of coating fluid.
Mixed solvent
Above-mentioned matrix forms composition and is scattered in the mixed solvent that is made of water and organic solvent.
Organic solvent can use the known organic solvent that is selected from alcohols, ethers, di-alcohols, ketone etc.Such organic solvent can be independent, perhaps mixes more than 2 kinds and use.
The ratio of the water in the mixed solvent is not particularly limited, but is preferably 0.1~10 weight % in the mixed solvent, is more preferably in the scope of 0.1~5 weight %.
Inorganic compound particles
Transparent coating of the present invention forms can also contain inorganic compound particles (ionic adsorption particle) with coating fluid.
Inorganic compound particles can exemplify SiO 2, Al 2O 3, ZrO 2, TiO 2, SnO 2, In 2O 3, Sb 2O 5Deng metal oxide, SiO 2Al 2O 3, SiO 2TiO 2, In 2O 3SnO 2, Sb 2O 5SnO 2, SnO 2In 2O 3Sb 2O 5In complex metal oxides or sosoloid, zeolite (crystallinity aluminosilicate) etc.In addition, preferably use the mixture more than 2 kinds of these compounds.
If contain these inorganic compound particles, then can adsorb any the movable ion in inorganic cation, inorganic anion, organic cation, the organic anion etc. of belonging to that exists in the liquid crystal for example.Therefore, can lower the movable ion concentration in the liquid crystal, so the liquid crystal indicator that obtains, because the high voltage holding ratio characteristic is good, it is few to consume electric power, thereby the power efficiency height, can not show badly, and long-term reliability is good.
The median size of the inorganic compound particles that uses among the present invention better is in the scope of 1nm~10 μ m, is more preferably in the scope of 10nm~2 μ m, and good especially is in the scope of 10nm~0.5 μ m.If the median size of inorganic compound particles less than 1nm, then possibly can't binding property form other film that is made of the strong resin of hydrophobicitys such as polyimide resin on the transparent coating surface well.
In addition, if median size surpasses 10 μ m, then may be in ionic adsorption capacity and the decline of ionic adsorption speed, the transparency of transparent coating also descends.
If the median size of inorganic compound particles is in above-mentioned scope, then can make at rough substrate, the surface that for example has the substrate of tft array or have a transparent coating that forms on the substrate of colour filter becomes smooth, thereby the surface that also makes the oriented film that contacts with liquid crystal layer becomes smooth, thereby helps suppressing demonstration disorder, the generation that prevents bright spot, the scattering of light when reducing flat pannel display of the liquid crystal that surface shape causes and improve contrast gradient etc.
Just when taking in sail ion, can use known in the past ion exchange resin bead.Particularly, Zeo-karb can exemplify ダ イ ヤ イ オ Application SK シ リ one ズ (Mitsubishi chemical Co., Ltd's system), carboxy methyl cellulose, SE Mierocrystalline cellulose, P Mierocrystalline cellulose, セ Off ア デ Star Network ス (above by Off ア Le マ シ ア corporate system) etc.Zeo-karb can exemplify ダ イ ヤ イ オ Application SA シ リ one ズ (Mitsubishi chemical Co., Ltd's system), DEAE Mierocrystalline cellulose, triethylaminoethylcellulose, ECTEOLA Mierocrystalline cellulose, セ Off ア デ Star Network ス (above by Off ア Le マ シ ア corporate system) etc.In addition, can exemplify ダ イ ヤ イ オ Application both sexes exchange resins such as (Mitsubishi chemical Co., Ltd's systems).
Be used for liquid crystal display cell etc. if will contain the transparent coating of such inorganic compound particles or ion exchange resin bead, can remove the ion in the liquid crystal, so can be used as transparent ion adsorbed film.
The ionic adsorption capacity of such inorganic compound particles or ion exchange resin bead better is in the scope of 0.1~6.0mmol/g.
If the ionic adsorption capacity is less than 0.1mmol/g, abundant adsorbed ion then, it is bad or lack long-term reliability to produce demonstration that movable ion causes thus, and is difficult to obtain above the ionic adsorption body of 6.0mmol/g.
Ionic adsorption capacity among the present invention is measured with the following method.
(1) mensuration of inorganic cation loading capacity
In 100g concentration is to add in the NaCl aqueous solution of 1 weight % that 1.5g is dry down at 120 ℃, the mineral ion adsorbents of constant weight, after room temperature (25 ℃) stirs 15 hours down, filter and get filtrate, Na ionic concn in the filtrate is analyzed with atomic absorption spectrometry, by trying to achieve the Na ionic adsorption amount (mmol/g) of mineral ion adsorbent with the concentration difference of the Na ionic concn of the former NaCl aqueous solution.
(2) mensuration of inorganic anion loading capacity
In 100g concentration is to add in the NaCl aqueous solution of 1 weight % that 1.5g is dry down at 120 ℃, the ionic adsorption particulates of constant weight, after room temperature (25 ℃) stirs 15 hours down, filter and get filtrate, Cl ionic concn in the filtrate is analyzed with atomic absorption spectrometry, by trying to achieve the Cl ionic adsorption amount (mmol/g) of ionic adsorption row particulate with the concentration difference of the Cl ionic concn of the former NaCl aqueous solution.
(3) mensuration of organic cation loading capacity
In 100g concentration is the ionic adsorption particulate that adds 1.5g drying, constant weight under 120 ℃ in the 1 weight % tetramethylammonium hydroxide aqueous solution, after room temperature (25 ℃) stirs 15 hours down, filter and get filtrate, tetramethylammonium ionic concn in the filtrate is analyzed with ion chromatography, by trying to achieve the organic cation adsorptive capacity (mmol/g) of ionic adsorption particulate with the concentration difference of the former aqueous solution.
The mensuration of (4) organic anion loading capacity
In 100g concentration is to add in the aqueous acetic acid of 1 weight % that 1.5g is dry down at 120 ℃, the ionic adsorption particulates of constant weight, after room temperature (25 ℃) stirs 15 hours down, filter and get filtrate, acetic acid ion concentration in the filtrate is analyzed with ion chromatography, by trying to achieve the organic anion adsorptive capacity (mmol/g) of ionic adsorption particulate with the concentration difference of the former aqueous solution.
Can various mixing be used according to the ionic kind of stripping in the ionic kind in the liquid crystal, the liquid crystal, their ratio of amount as the inorganic compound particles of ionic adsorption particulate.
In addition, can also use the insulativity beyond these inorganic compound particles or the mineral compound particulate or the resin particle of electroconductibility as required.
Such inorganic compound particles better is to use under the state of the colloidal sol in being scattered in water or organic solvent, if inorganic compound particles can be disperseed or be dispersed in transparent coating near monodispersed state to form with in the coating fluid with single, then also can use the inorganic compound particles that is in non-collosol state.
Coating fluid
Transparent coating forms and is converted into solid component concentration with the formation of the matrix in coating fluid composition better is below 15 weight %.If this value surpasses 15 weight %, then be easy to generate the tendency of the storage stability decline of coating fluid; On the other hand, if its solid component concentration is low excessively,, must carry out coating operation repeatedly repeatedly, more than 0.1 weight % so solid component concentration is practical though obtain required thickness.
The amount that forms with the represented silicoorganic compound (also comprising hydrolysate) of the formula (I) of the total solids composition in the coating fluid (total amounts of matrix formation composition, inorganic compound particles ion-exchange particle etc.) or formula (II) corresponding to transparent coating better is more than 18 weight %, is more preferably more than 40 weight %.In such scope, can realize effect of the present invention, promptly form water-repellancy, toughness, flexible good transparent coating.
The amount of described silicoorganic compound (a), acetylacetone chelate (b), metal alkoxides (c) and polysilazane (d) better is below the 75 weight % in the total solids composition, to be more preferably in the scope of 1~40 weight %.In addition, the amount of inorganic compound particles better is below the 70 weight % in the total solids composition, to be more preferably in the scope of 4.5~50 weight %.
If described silicoorganic compound (a), acetylacetone chelate (b), metal alkoxides (c) and the amount of polysilazane (d) and the amount of inorganic compound particles increase, then described formula (I) or the represented silicoorganic compound of formula (II) tail off, use the effect of these silicoorganic compound, the toughness of the transparent coating that promptly obtains, flexibility, scuff resistance, water-repellancy etc. can be insufficient.
[base material that has tunicle]
Then, the base material that has tunicle of the present invention is specifically described.
The base material that has tunicle of the present invention is characterised in that, is formed with the above-mentioned transparent coating of coating and forms the transparent coating that obtains with coating fluid on substrate surface.
The base material that has tunicle of the present invention, by on substrate surfaces such as glass, plastics, being coated with aforesaid transparent coating formation coating fluid with methods such as dip coating, spin-coating method, spraying method, roller painting, flexible board print processes, then, the tunicle that forms at substrate surface like this is ℃ dry down in normal temperature~80, forming in method such as be heating and curing more than 300 ℃ more than 120 ℃, under some situation as required.
In addition, the tunicle that is formed at this base material can also promote solidification treatment with the following method.
Promote that solidification treatment can exemplify particularly, after above-mentioned application step or drying step or in the drying process, be placed on processing in the gas atmosphere that promotes curing reaction with the tunicle in the uncured stage of electromagnetic wave irradiation shorter or with the tunicle in uncured stage than visible wavelength.
The hertzian wave of the tunicle in the uncured stage before such irradiation heating can exemplify ultraviolet ray, electron rays, X ray, gamma-rays etc. particularly, and good especially is ultraviolet ray.
When carrying out the uviolizing processing, better be for example luminous intensity to be reached maximum value, light intensity at 10mW/cm at about 250nm and 360nm place 2Above high voltage mercury lamp shines 100mJ/cm as ultraviolet source 2More than, be preferably 1000mJ/cm 2The ultraviolet ray of above energy.
In addition, promote the gas of curing reaction can exemplify for example ammonia, ozone etc.In addition, when carrying out such gas processing, better be that to be placed on gas concentration be 100~100000ppm, be preferably under the atmosphere of above-mentioned reactive gas of 1000~10000ppm 1~60 minute for tunicle with the uncured stage.
This gas processing carries out also obtaining same effect after being heating and curing.
If carry out aforesaid promotion solidification treatment, then in promoting transparent coating, in the polycondensation of contained matrix formation composition, compoundization, promote the water remaining in the tunicle and the evaporation of solvent.Therefore, can after heating steps in relax the conditions that are heating and curing such as necessary Heating temperature, heat-up time, improve the manufacturing efficient that has the base material of transparent coating of the present invention.
Adopt above technology can obtain the base material that has transparent coating of the present invention, the tunicle that forms on this base material not only has toughness, flexibility, binding property, the transparency are good the time, weather resistance such as scuff resistance, water tolerance, alkali resistance are also excellent, and under the situation that contains the ionic adsorption inorganic compound particles, can also reduce movable ion in the liquid crystal flat-panel effectively, and the insulation resistance height can be used as the film of insulativity.
[liquid crystal display cell]
Then, liquid crystal display cell of the present invention is specifically described.
Liquid crystal display cell of the present invention uses has the substrate that has transparency electrode that forms the transparent coating that forms with coating fluid with any above-mentioned transparent coating.
The 1st liquid crystal display cell of the present invention is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively ELD in the surface of the substrate of at least one side, transparent coating and oriented film, make between each ELD opposedly, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved.
Except transparent coating uses described coating fluid, can use known substrate, ELD, oriented film, liquid crystal etc. without particular limitation.
Fig. 1 is the cross section mode chart of a kind of sample of the 1st liquid crystal display cell of the present invention.
This liquid crystal display cell 1 following formation, separate specified interval d configuration at the laminated successively ELD 12 in the surface of substrate 11, transparent coating 13 and the oriented film 14 formed a pair of substrates 2 that have transparency electrode by a plurality of spacer particles 5, make between each ELD 12,12 opposedly, enclose liquid crystal in the gap between the ELD 12,12 that separates this appointed interval d.
Substrate can be a glass substrate, also can be plastic base.Plastic base is not particularly limited so long as be made of transparent resin.In addition, resin films such as polyethylene terephthalate, polyethylene, polycarbonate also can be used as substrate, if flexible resin especially can bend to film arbitrary shape and use.
Transparent coating 13 is to form the film that forms with coating fluid by the above-mentioned transparent coating of coating on ELD 12, excellences such as the toughness of this film, flexibility, water-repellancy, the transparency and excellent scratch resistance, the insulation resistance height, the binding property of transparent coating 13 and oriented film 14 is good.
The 1st liquid crystal display cell of the present invention can also be done various distortion, forms SiO as using again between substrate 11 and ELD 12 2The substrate that has transparency electrode of alkali passive films such as film etc.
The 2nd liquid crystal display cell of the present invention is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively colour filter in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposedly, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved.
Fig. 2 is the cross section mode chart of a kind of sample of the 2nd liquid crystal display cell of the present invention.
In this Fig. 2, illustrated the colour LCD device 1 of its characteristic ', possesses liquid crystal display cell 2 ' and be positioned at a pair of Polarizer 3,4 of these liquid crystal display cell both sides, described liquid crystal display cell 2 ' have laminated successively alkali passive film 21b, a plurality of pixel electrode 21c, transparent coating 21d and the formed battery lead plate 21 of oriented film 21e on glass substrate 21a, laminated successively alkali passive film 22b, colour filter 22c, transparent coating 22d, transparency electrode 22e and the formed counter electrode plate 22 of oriented film 22f on glass substrate 22a.Wherein, transparent coating 21d and 22d form the film that forms with the coating fluid coating by aforementioned transparent coating.
Described liquid crystal display cell 2 ' battery lead plate 21 and counter electrode plate 22 outside configuration that lays respectively at glass substrate 21a and 22a, make a plurality of pixel electrode 21c respectively with a plurality of colour filter R, G, B subtend one by one.In addition, enclose liquid crystal in the gap between this battery lead plate 21 and the counter electrode plate 22.
In addition, between a plurality of pixel electrode 21c and transparency electrode 22e, form not shown circuit respectively, this circuit connect colour LCD device 1 ' main body.In addition, the colour filter 22c that forms on the alkali passive film 22b of counter electrode plate 22 is made of R (red color filter), G (green color filter), a plurality of color elements of B (blue color filter), each color elements is arranged regularly in the mode that adjoins each other, thus according to the demonstration signal of sending here from liquid crystal indicator 1 ' main body, the circuit working that forms between specific pixel electrode 21c and the transparency electrode 22e, the Polarizer 4 that can see through the outside that is disposed at counter electrode plate 22 is observed and the coloured image that shows that signal is corresponding.
The 3rd liquid crystal display cell of the present invention is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively tft array in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposedly, enclose the liquid crystal display cell of liquid crystal in the gap of between this is to the substrate that has transparency electrode, being reserved.
Can use known alkali passive film, pixel electrode, oriented film, glass substrate, colour filter, transparency electrode, Polarizer, liquid crystal without particular limitation.
Fig. 3 is the cross section mode chart of a kind of sample of the 3rd liquid crystal display cell of the present invention.
" the subtend substrate 41 that is formed the transparent insulating substrate 31 of the laminated successively transparent coating 33 of tft array 32 and this tft array 32 surfaces, pixel electrode 34 and oriented film 35 and (black matrix) (shielding film) 42, colour filter 43, transparent coating 44, counter electrode 45 and oriented film 46 at the bottom of the laminated successively fast black base in surface by the surface constitutes this liquid crystal display cell 1, oriented film 35 and 46 opposed across liquid crystal layer 51.
Can between oriented film 35 and 46, be situated between as shown in Figure 1 with spacer particle.
Tft array 32 is by formations such as TFT (thin film transistor) element, data electrode, auxiliary capacitors.
At the bottom of can using known pixel electrode, oriented film, fast black base without particular limitation, colour filter, counter electrode, substrate.
In the aforesaid liquid crystal display cell of the present invention, described transparent coating contains the matrix that is made of specific silicoorganic compound and forms composition and constitute excellences such as water tolerance, water-repellancy, toughness, flexibility.
In addition, transparent coating contains under the situation of inorganic compound particles of ionic adsorption, and the movable ion in the liquid crystal (type impurity ion) reduces.Therefore, liquid crystal display cell of the present invention, the high voltage holding ratio characteristic is good, can not produce show bad, long-term reliability excellence, and because to consume electric power few, so can improve effect.
Embodiment
Below, the present invention will be described by embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
Transparent coating forms the preparation with coating fluid (A)
25.6g two (Trimethoxy silane base) hexane (eastern レ ダ ウ コ one ニ Application ダ シ リ コ one Application Co., Ltd. system) is formed composition as matrix to join in 47.0g pure water and the 526.4g ethanol mixed solvent, the nitric acid that adds 1.0g concentration 61 weight % therein, under agitation, make the partial hydrolysate solution (A-1) of two (Trimethoxy silane base) hexane in 60 ℃ of maintenances 24 hours.After being cooled to room temperature, in partial hydrolysate solution (A-1), add 18g both sexes exchange resins (ダ イ ヤ イ オ Application), at room temperature stir 16 hours deionizing after, elimination ion exchange resin.Then, add the 85g hexylene glycol in this solution, by underpressure distillation, obtaining with the hexylene glycol is the hydrolysising product solution (A-2) of solid component concentration 16 weight % of primary solvent composition.
In this hydrolysising product solution of 94.2g (A-2), add the Sb of 42.2g with median size 20nm, Na ionic adsorption capacity 2.4mmol/g 2O 52.7H 2The particulate of O is scattered in the ionic adsorption particulate colloidal sol of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirs 1 hour, then adds the 7.3g tetraethoxysilane and (is converted into SiO 2Be 28.8 weight %), 206.1g hexylene glycol and 2.0g water, stirred 24 hours down at 40 ℃, the transparent coating of preparation solid component concentration 6 weight % forms with coating fluid (A).
The formation of transparent coating (A)
Go up with flexible board print process coating transparent coating at the glass substrate that has the ITO show electrode that forms Butut (Asahi Glass Co., Ltd's system: 30 Ω/below the product) and to form with coating fluid (A), with filming after under 90 ℃ dry 5 minutes of obtaining, adding up light quantity 6000mJ/cm with high voltage mercury lamp 2The condition irradiation ultraviolet radiation of (by the 365nm sensor determination) then 200 ℃ of following sintering 30 minutes, thereby forms transparent coating (A).Measure the thickness of the transparent coating (A) obtain with the contact pin type surface roughometer, the result is 80nm.
In addition, following vertical load test, the scratch hardness mensuration of carrying out, the result is shown in table 2 and table 3.
The vertical load test
The pin that will add the tip with radius-of-curvature 1mm of 12V volts DS between ITO electrode surface and transparent coating upper surface is pressed on the transparent coating surface, when voltage is arrived 3V as electric short circuit, with the load tolerance of this payload values evaluated for film constantly in vertical direction.10 places on the transparent coating are measured the load tolerance.Mean value is shown in table 2 and table 3.
Scratch hardness is measured
With scratch hardness tester (レ ス カ Co., Ltd. system: the CSR-02) scratch hardness of mensuration transparent coating (A).Mean value is shown in table 2 and table 3.
The making of liquid crystal display cell (A)
Then, transparent coating (A) go up with flexible board print process coating polyimide film form with coating (Misao Kusano's system: サ Application エ バ one), at 100 ℃ down after dry 5 minutes, 200 ℃ of heat treated 30 minutes, form polyimide film (oriented film), carry out polished finish then.
Like this, obtain on glass substrate laminated successively transparency electrode, transparent coating (A) and through a pair of substrate that has transparency electrode of the oriented film of polished finish.In a pair of substrate that has a transparency electrode that obtains, scatter spacer (its particle diameter is equivalent to 2 distances between substrate) on the substrate, printing and sealing material on another piece, with two base plate bondings, make transparency electrode opposite each other, inject stn liquid crystal then, then with material for sealing with the inlet sealing, thereby make liquid crystal display cell (A).
The mensuration of movable ion amount
Measure machine (Dongyang テ Network ニ カ Co., Ltd. system: MTR-1), measure the movable ion amount in the liquid crystal display cell (A) that obtains with the condition of impressed voltage 10V, choppy sea frequency 0.1Hz with ion density.Record the peak value that movable ion produces at the nearly 0.8V of impressed voltage place, the movable ion amount is 0.8nC/cm 2
The observation of the bright spot of liquid crystal display cell
In addition, make 30 liquid crystal display cells with aforesaid method, lighting a lamp shows test, carries out visual observations to having or not bright spot.At this moment, investigate the piece number of the flat board that produces bright spot.Mean value is shown in table 2 and table 3.
The evaluation of long-term reliability
Use does not produce the liquid crystal display cell (A) of bright spot with aforesaid method, to 10 (relative humidity 20% under hot environment, 80 ℃ of temperature), to other 10 (relative humidity 95% under hot and humid environment, 80 ℃ of temperature) place after 500 hours, carry out lighting a lamp of liquid crystal display cell and show test, carry out visual observations having or not bright spot.At this moment, investigate the piece number of the flat board that does not produce bright spot.Mean value is shown in table 2 and table 3.
Embodiment 2
Transparent coating forms the preparation with coating fluid (B)
Form as matrix in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 to 94.2g, add the SiO of 42.2g median size 25nm, Na ionic adsorption capacity 0.5mmol/g 2Al 2O 3Particulate is scattered in the ionic adsorption particulate colloidal sol of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirs 1 hour, then adds the 7.5g tetraisopropoxy titanium and (is converted into TiO 2Be 28 weight %), 205.9g hexylene glycol and 2.0g water, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (B).
The formation of transparent coating (B)
Except using transparent coating to form, form transparent coating (B) similarly to Example 1 with the coating fluid (B).Measure the thickness of the transparent coating (B) obtain with the contact pin type surface roughometer, the result is 70nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (B)
Then, except formation of carrying out polyimide film on the transparent coating (B) etc., make liquid crystal display cell (B) similarly to Example 1.The liquid crystal display cell (B) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 3
Transparent coating forms the preparation with coating fluid (C)
Form as matrix in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 to 94.2g, adding 42.2g is scattered in the MgO particulate of median size 45nm, Cl ionic adsorption capacity 0.3mmol/g the ionic adsorption particulate colloidal sol of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirred 1 hour, and then added 15.1g dibutoxy-diacetyl acetone and close zirconium and (be converted into ZrO 2Be 14 weight %), 198.3g hexylene glycol and 2.0g water, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (C).
The formation of transparent coating (C)
Except using transparent coating to form, form transparent coating (C) similarly to Example 1 with the coating fluid (C).Measure the thickness of the transparent coating (C) obtain with the contact pin type surface roughometer, the result is 90nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (C)
Then, except formation of carrying out polyimide film on the transparent coating (C) etc., make liquid crystal display cell (C) similarly to Example 1.The liquid crystal display cell (C) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 4
Transparent coating forms the preparation with coating fluid (D)
Form as matrix in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 to 53.8g, add the 32.1g tetramethoxy-silicane and (be converted into SiO 2Be 39.5 weight %), 264.3g hexylene glycol and 2.0g water, stirred 24 hours down at 40 ℃, the transparent coating of preparation solid component concentration 6 weight % forms with coating fluid (D).
The formation of transparent coating (D)
Except using transparent coating to form, form transparent coating (D) similarly to Example 1 with the coating fluid (D).Measure the thickness of the transparent coating (D) obtain with the contact pin type surface roughometer, the result is 80nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (D)
Then, except formation of carrying out polyimide film on the transparent coating (D) etc., make liquid crystal display cell (D) similarly to Example 1.The liquid crystal display cell (D) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 5
Transparent coating forms the preparation with coating fluid (E)
Form as matrix in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 to 121.1g, add the Sb of 5.3g median size 20nm, Na ionic adsorption capacity 2.4mmol/g 2O 52.7H 2The O particulate is scattered in the ionic adsorption particulate colloidal sol of the solid component concentration 20 weight % that obtain in the propylene glycol as ionic adsorption particulate homogeneous, stirs 1 hour, and the butanol solution that then adds 10.6g three butoxy-acetyl acetone zirconium (is converted into ZrO 2Be 10 weight %) and 0.5g water, stirring 24 hours down at 40 ℃, the transparent coating of making solid component concentration 15.6 weight % forms with coating fluid (E).
The formation of transparent coating (E)
Be formed with on the glass substrate of colour filter, with spin-coating method (spin coating) transparent coating is formed with coating fluid (E) with 1500rpm, 10 seconds condition coating, then after under 50 ℃ dry 120 minutes, under 120 ℃, carried out heat treated 60 minutes, form transparent coating (E), thereby carry out the lining of colour filter pixel.Measure the thickness of the transparent coating (E) obtain with the contact pin type surface roughometer, the result is 2 μ m.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
In addition, go up electrode film at transparent coating (E) with sputtering method formation ITO.
The making of liquid crystal display cell (E)
This ITO electrode film is formed Butut with ordinary method, form show electrode, form polyimide alignment film thereon similarly to Example 1, then carry out polished finish.Thus, obtain on glass substrate laminated successively colour filter, transparent coating (E), transparency electrode and through a pair of substrate that has transparency electrode of the oriented film of polished finish.
Then, the substrate that has identical electrodes of subtend is bonding with sealing material across spacer, inject stn liquid crystal in the gap between substrate, with material for sealing with the inlet sealing, thereby make liquid crystal display cell (E).The liquid crystal display cell (E) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 6
Transparent coating forms the preparation with coating fluid (F)
With 17g CF 3(CF 2) 7(CH 2) 2Si (OCH 3) 3(KCC of SHIN-ETSU HANTOTAI system, KBM7803) forming composition as matrix joins in 47.0g pure water and the 526.4g ethanol mixed solvent, the nitric acid that adds 1.0g concentration 61 weight % therein, under agitation, make the partial hydrolysate solution (F-1) of 17 fluorine decyl Trimethoxy silanes in 60 ℃ of maintenances 24 hours.
After it is cooled to room temperature, in partial hydrolysate solution (F-1), add 18g amphoteric ion-exchange resin (ダ イ ヤ イ オ Application), at room temperature stir 16 hours after, elimination ion exchange resin, deionizing.Then, in this solution, add the 85g hexylene glycol, underpressure distillation again, obtaining with the hexylene glycol is the hydrolysising product solution (F-2) of solid component concentration 16 weight % of primary solvent composition.
In this hydrolysising product solution of 94.2g (F-2), add the Sb of 21.1g with median size 20nm, Na ionic adsorption capacity 2.4mmol/g 2O 52.7H 2The particulate of O is scattered in the ionic adsorption particulate colloidal sol of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirs 1 hour, then adds the 14.6g tetraethoxysilane and (is converted into SiO 2Be 28.8 weight %), 211.6g hexylene glycol and 4.0g water, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (F).
The formation of transparent coating (F)
Except using transparent coating to form, form transparent coating (F) similarly to Example 1 with the coating fluid (F).Measure the thickness of the transparent coating (F) obtain with the contact pin type surface roughometer, the result is 75nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (F)
Then, except formation of carrying out polyimide film on the transparent coating (F) etc., make liquid crystal display cell (F) similarly to Example 1.The liquid crystal display cell (F) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
(comparative example 1)
Transparent coating forms the preparation with coating fluid (G)
The 51.3g tetraethoxysilane (is converted into SiO 2Be 28.8 weight %) join in 9.0g pure water and the 432.2g ethanol mixed solvent as matrix formation composition, the nitric acid that adds 0.2g concentration 61 weight % therein, under agitation, make the partial hydrolysate solution (G-1) of tetraethoxysilane in 60 ℃ of maintenances 24 hours.
After being cooled to room temperature, in partial hydrolysate solution (G-1), add 18g amphoteric ion-exchange resin (ダ イ ヤ イ オ Application), at room temperature stir 16 hours after, elimination ion exchange resin, deionizing.Then, add the 85g hexylene glycol in this solution, by underpressure distillation, obtaining with the hexylene glycol is the hydrolysising product solution (G-2) of solid component concentration 16 weight % of primary solvent composition.
In this hydrolysising product solution of 94.2g (G-2), add the Sb of 16.4g with median size 20nm, Na ionic adsorption capacity 2.4mmol/g 2O 52.7H 2The particulate of O is scattered in ionic adsorption particulate colloidal sol, 161.1g hexylene glycol and the 2.0g water of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (G).
The formation of transparent coating (G)
Except using transparent coating to form, form transparent coating (G) similarly to Example 1 with the coating fluid (G).Measure the thickness of the transparent coating (G) obtain with the contact pin type surface roughometer, the result is 80nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (G)
Then, except formation of carrying out polyimide film on the transparent coating (G) etc., make liquid crystal display cell (G) similarly to Example 1.The liquid crystal display cell (G) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 7
Transparent coating forms the preparation with coating fluid (H)
Form as matrix in this hydrolysising product solution (F-2) composition, preparation similarly to Example 6 to 26.9g, add the SiO of 21.1g median size 25nm, Na ionic adsorption capacity 0.5mmol/g 2-Al 2O 3Particulate be scattered in the ionic adsorption particulate colloidal sol of the solid component concentration 10 weight % that obtain in the hexylene glycol as ionic adsorption particulate homogeneous, stirred 1 hour, then add the 52.8g tetraisopropoxy titanium and (be converted into TiO 2Be 28 weight %), 251.0g hexylene glycol and 3.0g water, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (H).
The formation of transparent coating (H)
Except using transparent coating to form, form transparent coating (H) similarly to Example 1 with the coating fluid (H).Measure the thickness of the transparent coating (H) obtain with the contact pin type surface roughometer, the result is 75nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (H)
Then, except formation of carrying out polyimide film on the transparent coating (H) etc., make liquid crystal display cell (H) similarly to Example 1.The liquid crystal display cell (H) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 8
Transparent coating forms the preparation with coating fluid (I)
Form as matrix in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 to 94.2g, add 155.0g hexylene glycol and 2.0g water, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (I).
The formation of transparent coating (I)
Except using transparent coating to form, form transparent coating (I) similarly to Example 1 with the coating fluid (I).Measure the thickness of the transparent coating (I) obtain with the contact pin type surface roughometer, the result is 80nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (I)
Then, except formation of carrying out polyimide film on the transparent coating (I) etc., make liquid crystal display cell (I) similarly to Example 1.The liquid crystal display cell (I) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Embodiment 9
Transparent coating forms the preparation with coating fluid (J)
Form this hydrolysising product solution (F-2) that adding 47.1g prepares similarly to Example 6 in the hydrolysising product solution (A-2) composition, preparation similarly to Example 1 as matrix to 47.1g, stirred 1 hour, add 155.0g hexylene glycol and 2.0g water again, stirred 24 hours down at 40 ℃, the transparent coating of making solid component concentration 6 weight % forms with coating fluid (J).
The formation of transparent coating (J)
Except using transparent coating to form, form transparent coating (J) similarly to Example 1 with the coating fluid (J).Measure the thickness of the transparent coating (J) obtain with the contact pin type surface roughometer, the result is 80nm.In addition, carry out vertical load test, scratch hardness mensuration.The result is shown in table 2 and table 3.
The making of liquid crystal display cell (J)
Then, except formation of carrying out polyimide film on the transparent coating (J) etc., make liquid crystal display cell (J) similarly to Example 1.The liquid crystal display cell (J) that obtains is carried out the mensuration of movable ion amount, the observation of bright spot, the evaluation of long-term reliability, and the result is shown in table 2 and table 3.
Figure C20048001464800291
Table 3
Figure C20048001464800301
The simple declaration of accompanying drawing
[Fig. 1] Fig. 1 is the cross section mode chart of a kind of sample of the 1st liquid crystal display cell of the present invention.
[Fig. 2] Fig. 2 is the cross section mode chart of a kind of sample of the 2nd liquid crystal display cell of the present invention.
[Fig. 3] Fig. 3 is the cross section mode chart of a kind of sample of the 3rd liquid crystal display cell of the present invention.
Reference numerals among the figure is as follows.
1,1 ', 1 " ... liquid crystal display cell, 2; 2 ' ... liquid crystal display cell, 3; 4 ... Polarizer, 5 ... spacer particle, 6 ... liquid crystal, 11 ... glass substrate, 12 ... ELD, 13 ... transparent ion adsorbed film, 14 ... oriented film, 21 ... battery lead plate, 21a ... glass substrate, 21b ... the alkali passive film, 21c ... a plurality of pixel electrodes, 21d ... transparent coating, 21e ... oriented film, 22 ... the counter electrode plate, 22a ... glass substrate, 22b ... the alkali passive film, 22c ... colour filter, 22d ... transparent coating, 22e ... transparency electrode, 22f ... oriented film, 23 ... liquid crystal, 31 ... the transparent insulating substrate, 32 ... tft array, 33 ... transparent coating, 34 ... pixel electrode, 35 ... oriented film, 36 ... insulating film, 41 ... the subtend substrate, 42 ... at the bottom of the fast black base (shielding film), 43 ... colour filter, 44 ... transparent coating, 45 ... counter electrode, 46 ... oriented film, 51 ... liquid crystal layer

Claims (17)

1. transparent coating forms and uses coating fluid, it is that disperse matrix is formed into transparent coating that branch obtains and forms and use coating fluid in the mixed solvent that is made of water and organic solvent, it is characterized in that this matrix forms composition and contains a) represented silicoorganic compound or its hydrolysate of following formula (I)
R 1-SiR 2 mR 3 (3-m) (I)
In the formula, R 1-expression R 8(CR 9 2) n-,
R 8The expression halogen atom,
R 9Represent hydrogen atom or halogen atom respectively independently,
N is 3~30 integer,
R 2The expression hydrolization group,
R 3The carbonatoms that expression can contain halogen atom is 1~30 organic group,
M represents 1~3 integer,
Wherein, formula (I) has 2~3 hydrolization groups in 1 molecule;
2. transparent coating as claimed in claim 1 forms uses coating fluid, its feature also to be, above-mentioned transparent coating forms and also contains the represented silicoorganic compound of following formula (II) or its hydrolysate with coating fluid,
R 4 nR 5 3-nSi-(X)-SiR 6 pR 7 (3-p) (II)
In the formula, R 4And R 6Represent hydrolization group independently,
R 5And R 7The expression carbonatoms that contains halogen atom is 1~30 any monovalent organic radical group independently,
X is for being selected from-(CH 2) q-,-(Ph)-,-(CH 2) q-(Ph)-,-(CH 2) q-(Ph)-(CH 2) y-,-[(CH 2) q(CF 2) y(CH 2) r]-,-(CH 2) q-(S)-(CH 2) r-and-(S) q-divalent group, wherein, Ph represents phenyl ring, q, r and y represent 1~30 integer,
N represents 0~3 number,
P represents 0~3 number,
Wherein, formula (II) has the hydrolization group more than 2 in 1 molecule.
3. transparent coating as claimed in claim 1 forms uses coating fluid, its feature also to be, the silicoorganic compound of described formula (I) have the hydrolization group above 2 in 1 molecule.
4. transparent coating as claimed in claim 2 forms uses coating fluid, its feature also to be, the silicoorganic compound of the silicoorganic compound of described formula (I) and/or described formula (II) have the hydrolization group above 2 in 1 molecule.
5. the transparent coating described in claim 1 or 2 forms and uses coating fluid, its feature also is, described matrix forms composition and also contains and be selected from a) the represented silicoorganic compound of following formula (IH), b) methyl ethyl diketone chelate, c) metal alkoxides and d) more than a kind of polysilazane
R tSi(OR′) 4-t (III)
In the formula (III), R is selected from methyl, ethyl, vinyl or epoxy group(ing), and R ' is the alkyl of carbonatoms 1~6, and t is 0~4 number.
6. transparent coating as claimed in claim 1 forms uses coating fluid, its feature also to be, described matrix forms composition and also contains inorganic compound particles.
7. transparent coating as claimed in claim 2 forms uses coating fluid, its feature also to be, described matrix forms composition and also contains inorganic compound particles.
8. transparent coating as claimed in claim 5 forms uses coating fluid, its feature also to be, described matrix forms composition and also contains inorganic compound particles.
9. have the base material of transparent coating, it is characterized in that, substrate surface is formed with by the described transparent coating of claim 6 and forms the transparent coating that obtains with the coating fluid coating.
10. have the base material of transparent coating, it is characterized in that, substrate surface is formed with by the described transparent coating of claim 7 and forms the transparent coating that obtains with the coating fluid coating.
11. have the base material of transparent coating, it is characterized in that substrate surface is formed with by the described transparent coating of claim 8 and forms the transparent coating that obtains with the coating fluid coating.
12. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively ELD in the surface of the substrate of at least one side, transparent coating and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 7.
13. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively ELD in the surface of the substrate of at least one side, transparent coating and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 8.
14. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively colour filter in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 7.
15. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively colour filter in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 8.
16. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively tft array in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 7.
17. liquid crystal display cell, it is to separate specified arranged spaced at the formed a pair of substrate that has transparency electrode of the laminated successively tft array in the surface of the substrate of at least one side, transparent coating, ELD and oriented film, make between each ELD opposed, in by this gap of being reserved between to the substrate that has transparency electrode, enclose the liquid crystal display cell of liquid crystal
It is characterized in that transparent coating forms the tunicle that forms with the coating fluid coating for the transparent coating of putting down in writing with claim 8.
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EP1970421B1 (en) * 2005-12-22 2015-04-29 JGC Catalysts and Chemicals Ltd. Coating liquid for forming low dielectric constant amorphous silica coating film and low dielectric constant amorphous silica coating film obtained from such coating liquid
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CN105045451B (en) * 2015-08-14 2019-03-26 昆山国显光电有限公司 Touch-control display panel and its manufacturing method
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