WO2010125964A1 - Élément hydrofuge et verre destiné à être installé à bord d'un véhicule - Google Patents

Élément hydrofuge et verre destiné à être installé à bord d'un véhicule Download PDF

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Publication number
WO2010125964A1
WO2010125964A1 PCT/JP2010/057147 JP2010057147W WO2010125964A1 WO 2010125964 A1 WO2010125964 A1 WO 2010125964A1 JP 2010057147 W JP2010057147 W JP 2010057147W WO 2010125964 A1 WO2010125964 A1 WO 2010125964A1
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Prior art keywords
water
layer
electrode
gas
repellent
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PCT/JP2010/057147
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English (en)
Japanese (ja)
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一良 工藤
義朗 戸田
尚秀 遠山
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コニカミノルタホールディングス株式会社
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Priority to JP2011511379A priority Critical patent/JP5494656B2/ja
Publication of WO2010125964A1 publication Critical patent/WO2010125964A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present invention relates to a water-repellent member and an in-vehicle glass excellent in water repellency and excellent in weather resistance and wear resistance.
  • water repellent members are used for window materials for building materials, in-vehicle (transportation vehicles), and window materials for ships, but it is desirable that the surface of the water repellent members such as water droplets and dirt do not adhere.
  • glass used for in-vehicle and marine window glass is required to have excellent water repellency and weather resistance and wear resistance (resistance to sliding of wipers, etc.) that these characteristics last for a long time. .
  • Patent Document 2 In order to improve this, there is a technique (for example, see Patent Document 2) using a copolymer obtained by polymerizing a silicone to be added in advance and copolymerizing with a fluororesin, but to a level where wear resistance is required. Not reached.
  • Patent Document 8 As a technique related to the smooth water-repellent layer, there is an example described in Patent Document 8.
  • Patent Document 8 when normal glass is wet with rain, a water film is uniformly formed between the wiper and the glass, and this water film acts as a lubricant, whereas water-repellent glass repels water. Therefore, it is difficult to form a water film between the wiper and the glass, and friction unevenness occurs in the part with or without water droplets, and the wiper operation deteriorates, so it was necessary to reduce the friction coefficient on the wiper blade. It is not sufficient by itself, and it is described that the life of the water-repellent coating and the wiper operation are both achieved by smoothing the surface of the water-repellent glass. However, due to the combination of a surface with a high coefficient of friction and a special wiper, the wiping property is low, the wiping property is good, and the life has not been significantly improved.
  • An object of the present invention is to form a highly durable water-repellent member, and to form a water-repellent material that slides well on the surface of the substrate. Further, by smoothing the surface of the water-repellent layer, smooth contact with an object to be slid, such as a wiper blade, can be obtained, and an excellent water-repellent member free from fluctuations in the speed of the wiper blade such as slip and chatter It is to obtain glass for vehicle use.
  • a water-repellent member having at least one subbing layer on at least one surface of a substrate and further having a water-repellent layer thereon, the surface roughness Ra of the water-repellent layer is 100 nm or less,
  • the water repellent layer is formed from a fluoroether polymer Si compound having a reactive silyl group, and the undercoat layer is formed from an organometallic compound having a reactive group, and the undercoat layer is formed in the undercoat layer.
  • a water repellent member comprising at least one of carbon atom, nitrogen atom, chlorine atom or fluorine atom, wherein the total of the atoms contained is 0.3 to 50 at%.
  • a highly durable water-repellent member can be formed, and a water-repellent member excellent in water repellency and having high wear resistance and weather resistance by a wiper blade can be obtained.
  • the present inventor has a water-repellent member having an undercoat layer on a substrate and a water-repellent layer on the substrate, and the undercoat layer is reactive. A part of the reactive group is left in the undercoat layer, and a water repellent layer made of a fluoroether polymer Si compound is formed on the surface.
  • the roughness Ra centerline average roughness: JIS 0601-1976 surface roughness standard
  • the water repellency, sliding property water droplet falling property
  • high durability high wear resistance
  • the undercoat layer of the present invention is formed from an organometallic compound having a reactive group.
  • the reactive group includes a halogen atom, an alkoxy group, an isocyanate group, a silazane group, a carboxyl group, a hydroxyl group, and an azide group. And groups selected from epoxy groups and the like.
  • a reactive group is a halogen atom, a silazane group or an alkoxy group.
  • Examples of the metal atom of the organometallic compound having a reactive group include Si, Ti, Ge, Zr, Sn, Hf, Zn, and Al.
  • organometallic compound having a reactive group used in the present invention in which the metal atom is Si, include tetramethoxysilane, tetraethoxysilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, ⁇ -amino.
  • fluorine-containing silane coupling agents examples include fluorine-containing silane coupling agents, alkylsilane coupling agents, polydimethylsiloxane skeleton compounds, and the like.
  • fluorine-containing silane coupling agent examples include, for example, 3,3,3-trifluoropropyltrichlorosilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trimethyl Fluoropropylsilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, CF 3 CH 2 CH 2 Si (OCH 3) 3, CF 3 (CF 2) 5 CH 2 CH 2 Si (OCH 3) 3, CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3 and the like.
  • Fluorine-containing silane coupling agents include, for example, Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries Co., Ltd. (eg, OPTOOL DSX), and Gelest Inc. In addition to being marketed by Solvay Solexis Co., Ltd., etc. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J. MoI. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No.
  • organometallic compound having a reactive group used in the present invention in which the metal atom is Ti, include tetramethoxy titanium, tetraethoxy titanium, isocyanate propyl trimethoxy titanium, isocyanate propyl triethoxy titanium, ⁇ -amino.
  • organometallic compound having a reactive group used in the present invention and having a metal atom of Zr include tetramethoxy zirconia, tetraethoxy zirconia, isocyanate propyl trimethoxy zirconia, isocyanate propyl triethoxy zirconia, ⁇ -amino.
  • Examples thereof include propyltrimethoxyzirconia, ⁇ -aminopropyltriethoxyzirconia, vinyltrichlorozirconia, vinyltrimethoxyzirconia, vinyltriethoxyzirconia, vinyltris ( ⁇ -methoxyethoxy) zirconia, ⁇ -glycidoxypropyltrimethoxyzirconia and the like.
  • organometallic compound having a reactive group used in the present invention and organometallic compounds such as Sn, Zn, Ge, and Al as other metal atoms can also be used as preferred compounds.
  • a wet coating method such as a spray method, a spin coating method, a dip method, a sputtering method, an ion assist method, a plasma CVD method, an organometallic compound having the reactive group, which will be described later. It can be formed by applying a dry coating method such as a plasma CVD method under atmospheric pressure or near atmospheric pressure.
  • the reactive group is bonded to the water repellent layer formed thereon. Can be strengthened. However, if it remains too much, the undercoat layer becomes brittle and deteriorates over time, which is not preferable.
  • the content (at%) of atoms is measured.
  • the CVD method exposes the introduced thin film forming gas to energy such as plasma, heat, light, etc., regardless of atmospheric pressure and vacuum. Therefore, it is possible to control by adjusting the energy at the time of film formation and adjusting the gas amount, gas flow rate, and substrate temperature of the thin film forming gas to be introduced.
  • the thin film forming component when using the wet coating method, is used as a liquid, but it should be controlled by adjusting the energy (plasma, heat, light, etc.) applied after coating and applying the energy to the coating liquid itself. Can do.
  • the method for measuring the content (at%) of carbon atoms, nitrogen atoms, chlorine atoms or fluorine atoms on the surface of the undercoat layer it can be determined using a known analysis means, but is preferably used in the present invention.
  • the method is calculated by the following XPS method.
  • the method is defined as follows.
  • Carbon atom number concentration% (atomic concentration) number of carbon atoms / number of all atoms ⁇ 100 The same applies to nitrogen atoms, chlorine atoms, and fluorine atoms.
  • the XPS surface analyzer used in the present invention was ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.
  • the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.
  • the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.
  • the obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer.
  • the content value of the element (carbon, oxygen, silicon, titanium, nitrogen, chlorine, fluorine, etc.) of each analysis target is atomic concentration (atomic concentration: at%) As sought.
  • the thickness of the undercoat layer is not particularly limited, but is preferably 1 to 500 nm, and more preferably 10 to 200 nm.
  • any of the above-described methods may be used as a method for forming the undercoat layer, and it is not particularly limited.
  • the surface roughness Ra of the water layer needs to be 100 nm or less
  • the atmospheric pressure plasma method is a film forming method that does not require a decompression chamber or the like, enables high-speed film formation, and has high productivity. It is preferable from the point. The details of the layer forming conditions of the atmospheric pressure plasma method will be described later.
  • Plasma CVD method A plasma CVD method will be described as a method for forming the undercoat layer of the present invention.
  • silicon oxide can be obtained by using Si compound as a raw material compound as an organometallic compound and using oxygen as the decomposition gas, and silicon carbonate is generated by using carbon dioxide as the decomposition gas.
  • Si compound as a raw material compound as an organometallic compound
  • oxygen as the decomposition gas
  • silicon carbonate is generated by using carbon dioxide as the decomposition gas.
  • an inorganic material as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.
  • a solvent an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.
  • silicon carbides, silicon nitrides, silicon oxides, silicon halides, and silicon sulfides can be obtained by appropriately selecting a source gas and a decomposition gas.
  • discharge gases are mixed with a discharge gas that tends to be in a plasma state, and the gas is sent to a plasma discharge generator.
  • a discharge gas nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.
  • the film is formed by mixing the discharge gas and the reactive gas and supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator).
  • a plasma discharge generator plasma generator
  • the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.
  • PECVD method plasma-assisted chemical vapor deposition method
  • various inorganic substances can be coated and adhered even in a three-dimensional shape, and the substrate temperature can be controlled. This is a technique that can form a film without making it too high.
  • the plasma CVD method an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is introduced into the plasma space.
  • the inorganic thin film is formed by spraying on the base material after the decomposition reaction occurs.
  • a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is very high.
  • the organometallic compound that is a raw material of the inorganic film can be decomposed even at a low temperature because it is in contact with an excited state gas such as ions or radicals. Therefore, it is a film forming method that can lower the temperature of a substrate on which an inorganic material is formed, and can sufficiently form a film on a plastic substrate.
  • the plasma CVD method near atmospheric pressure (hereinafter referred to as the atmospheric pressure plasma CVD method or the atmospheric pressure plasma method) that can be suitably used in the present invention is reduced in pressure compared to the plasma CVD method under vacuum. Not only is the productivity high and the plasma density is high, but the film-forming speed is high.In addition, compared with the normal conditions of the CVD method, the gas is not Since the mean free path is very short, a very flat film is obtained, and such a flat film has good optical properties. From the above, in the present invention, it is more preferable to apply the atmospheric pressure plasma CVD method than the plasma CVD method under vacuum.
  • symbol F is a glass substrate or a long film as an example of the substrate.
  • FIG. 1 is a schematic view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
  • the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. 1 (shown in FIG. 2 described later), gas supply means, It is an apparatus having electrode temperature adjusting means.
  • the plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency ⁇ 1 from the first power supply 21 is connected from the first electrode 11 between the counter electrodes. , A first high-frequency electric field of electric field intensity V 1 and current I 1 is formed, and a second high-frequency electric field of frequency ⁇ 2 , electric field intensity V 2 and electric current I 2 from the second power source 22 is formed from the second electrode 12. Is to be formed.
  • the first power source 21 can apply a higher frequency electric field strength (V 1 > V 2 ) than the second power source 22, and the first frequency ⁇ 1 of the first power source 21 is higher than the second frequency ⁇ 2 of the second power source 22. A low frequency can be applied.
  • a first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of a current from the first power source 21 to the first electrode 11, and a current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.
  • a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.
  • a gas G is introduced into the gap (discharge space) 13 between the first electrode 11 and the second electrode 12 from a gas supply means as shown in FIG. 2 to be described later, and the first electrode 11 and the second electrode A processing space created between the lower surface of the counter electrode and the base material F by generating a discharge by applying a high-frequency electric field from 12 and blowing the gas G in a plasma state to the lower side of the counter electrode (the lower side of the paper).
  • a thin film is formed near position 14.
  • 25 and 26 indicate high-frequency voltage probes
  • 27 and 28 indicate oscilloscopes.
  • the high-frequency voltage probes 25 and 26 and the oscilloscopes 27 and 28 can measure the high-frequency electric field strength (applied electric field strength) and the discharge start electric field strength.
  • the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG.
  • the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this.
  • the temperature control medium an insulating material such as distilled water or oil is preferably used.
  • it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur as much as possible.
  • Jet-type atmospheric pressure plasma discharge treatment apparatus can discharge a gas in the same plasma state simultaneously by arranging a plurality of bases in series, so that it can be processed many times and processed at high speed.
  • each apparatus jets gas in a different plasma state, it is possible to form a laminated thin film having different layers, for example, undercoat layers having different compositions.
  • FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a method for treating a substrate between counter electrodes useful for the present invention.
  • An atmospheric pressure plasma discharge treatment apparatus useful for the present invention is an apparatus having at least a plasma discharge treatment apparatus 30, an electric field application means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjustment means 60.
  • FIG. 2 shows a plasma discharge treatment of a film-like substrate F in a counter electrode (discharge space) 32 between a roll rotating electrode (first electrode) 35 and a square tube fixed electrode group (second electrode) 36.
  • a thin film undercoat layer is formed on the surface.
  • one electric field is formed by a pair of rectangular tube type fixed electrode group (second electrode) 36 and roll rotating electrode (first electrode) 35, and one unit, for example, a low carbon atom
  • a number concentration layer is formed.
  • FIG. 2 shows a configuration example in which a total of five units having such a configuration are provided. By each unit, the type of raw material to be supplied, the output voltage, etc. are arbitrarily controlled independently.
  • a laminated transparent gas barrier layer having a carbon atom number concentration structure defined in the present invention can be continuously formed.
  • the roll rotating electrode (first electrode) 35 has a first power source. 41 to the first high-frequency electric field of frequency ⁇ 1 , electric field strength V 1 , current I 1 , and rectangular tube-shaped fixed electrode group (second electrode) 36 from each second power source 42 corresponding to frequency ⁇ 2. A second high frequency electric field of electric field strength V 2 and current I 2 is applied.
  • a first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes current from the first power supply 41 to the first electrode.
  • the current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass.
  • a second filter 44 is provided between the square tube-type fixed electrode group (second electrode) 36 and the second power source 42, and the second filter 44 is connected to the second electrode from the second power source 42. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.
  • the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode.
  • the first power source is connected to the first electrode, and the second power source is connected to the second electrode.
  • the first power supply preferably applies a higher high-frequency electric field strength (V 1 > V 2 ) than the second power supply. Further, the frequency has the ability to satisfy ⁇ 1 ⁇ 2 .
  • the current is preferably I 1 ⁇ I 2 .
  • the current I 1 of the first high-frequency electric field is preferably 0.3 to 20 mA / cm 2 , more preferably 1.0 to 20 mA / cm 2 .
  • the current I 2 of the second high-frequency electric field is preferably 10 to 100 mA / cm 2 , more preferably 20 to 100 mA / cm 2 .
  • the gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge treatment vessel 31 from the air supply port while controlling the flow rate.
  • the base material F is unwound from the original winding (not shown) and is transported or is transported from the previous process, and the air or the like accompanying the base material is blocked by the nip roll 65 via the guide roll 64. Then, while being wound while being in contact with the roll rotating electrode 35, it is transferred between the square tube fixed electrode group 36 and the roll rotating electrode (first electrode) 35 and the square tube fixed electrode group (second electrode) 36. An electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 32.
  • the base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.
  • the base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.
  • the treated exhaust gas G ′ that has been discharged is discharged from the exhaust port 53.
  • a medium whose temperature is adjusted by the electrode temperature adjusting means 60 is used as a liquid feed pump. P is sent to both electrodes through the pipe 61, and the temperature is adjusted from the inside of the electrode.
  • Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.
  • FIG. 3 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 2 and the dielectric material coated thereon.
  • a roll electrode 35a has a conductive metallic base material 35A and a dielectric 35B coated thereon.
  • a temperature adjusting medium water, silicon oil or the like
  • FIG. 4 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube type electrode and a dielectric material coated thereon.
  • a rectangular tube electrode 36a has a coating of a dielectric 36B similar to that of FIG. 3 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.
  • the number of the rectangular tube-shaped fixed electrodes is set in plural along a circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a full square tube type facing the roll rotating electrode 35. It is represented by the sum of the area of the fixed electrode surface.
  • the rectangular tube electrode 36a shown in FIG. 4 may be a cylindrical electrode, but the rectangular tube electrode has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .
  • the roll electrode 35a and the rectangular tube type electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing the inorganic compound. Is subjected to a sealing treatment.
  • the ceramic dielectric may be covered by about 1 mm with a single wall.
  • As the ceramic material used for thermal spraying alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed.
  • the dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.
  • Examples of the conductive metal base materials 35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.
  • the distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes.
  • the dielectric When the dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.
  • the distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing the above, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.
  • the plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes.
  • polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be applied to the metal frame to provide insulation.
  • FIG. 2 it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above material.
  • Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500 A2 Shinko Electric 5kHz SPG5-4500 A3 Kasuga Electric 15kHz AGI-023 A4 Shinko Electric 50kHz SPG50-4500 A5 HEIDEN Laboratory 100kHz * PHF-6k A6 Pearl Industry 200kHz CF-2000-200k A7 Pearl Industry 400kHz CF-2000-400k And the like, and any of them can be used.
  • * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.
  • an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.
  • the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm 2 or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma.
  • the energy is applied to the thin film forming gas to form a thin film.
  • the upper limit value of the power supplied to the second electrode is preferably 50 W / cm 2 , more preferably 20 W / cm 2 .
  • the lower limit is preferably 1.2 W / cm 2 .
  • discharge area (cm ⁇ 2 >) points out the area of the range which discharge occurs in an electrode.
  • the output density is improved while maintaining the uniformity of the second high frequency electric field. be able to.
  • the further uniform high-density plasma can be produced
  • it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the second electrode side second
  • the high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.
  • the film quality when controlled in the present invention, it can also be achieved by controlling the power on the second power source side.
  • An electrode used for such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance.
  • Such an electrode is preferably a metal base material coated with a dielectric.
  • the characteristics match between various metallic base materials and dielectrics.
  • One of the characteristics is linear thermal expansion between the metallic base material and the dielectric.
  • the combination is such that the difference in coefficient is 10 ⁇ 10 ⁇ 6 / ° C. or less. It is preferably 8 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 5 ⁇ 10 ⁇ 6 / ° C. or less, and particularly preferably 2 ⁇ 10 ⁇ 6 / ° C. or less.
  • the linear thermal expansion coefficient is a well-known physical property value of a material.
  • Metal base material is pure titanium or titanium alloy
  • dielectric is ceramic spray coating
  • Metal base material is pure titanium or titanium alloy
  • dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic spray coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above-mentioned item 1 or item 2 and item 5 to 8 are preferable, and item 1 is particularly preferable.
  • titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics.
  • the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.
  • the atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2004-68143, 2003-49272, International Publication No. 02/48428, etc. in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.
  • the fluoroether polymer Si compound according to the present invention is characterized in that a fluorohydrocarbon is ether-bonded and has a reactive silyl group.
  • the weight average molecular weight of the fluorine-containing polymer is preferably 1500 or more, preferably from 1500 to 200,000, more preferably from 2000 to 100,000, particularly preferably from 3000 to 10,000.
  • the molecule preferably has 2 to 50 reactive silyl groups.
  • the fluoroether polymer Si compound having a reactive silyl group can be obtained by, for example, reacting a fluoroether polymer having a hydroxy group with a silane modifier to introduce a reactive silyl group.
  • a fluoroether-based polymer having a hydroxy group is obtained by copolymerizing a fluoroolefin and a hydroxy group-containing monomer such as hydroxyalkyl vinyl ether or allyl alcohol as a main monomer component. In this case, in addition to these components, an alkyl group is used. It may be obtained by copolymerizing a mixture of other monomer components such as vinyl ether, vinyl ester, allyl ether, isopropenyl ether and the like.
  • the fluoroolefin is not particularly limited, and those commonly used as monomers for fluororesins are used, and perfluoroolefin is preferred, and among them, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoroolefin, Fluoropropyl vinyl ether and mixtures thereof are particularly preferred.
  • the reactive silyl group is preferably a reactive silyl group selected from an alkoxy group, a chloro group, an isocyanate group, a silazane group, a carboxyl group, a hydroxyl group and an epoxy group. Of these, an alkoxy group is preferred.
  • fluoroether polymer Si compound having a reactive silyl group that forms the water-repellent layer according to the present invention a compound represented by the following general formula (1) is preferably used.
  • R f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms
  • X is an iodine atom or a hydrogen atom
  • Y is a hydrogen atom or a lower alkyl group
  • Z is a fluorine atom or a trifluoromethyl group
  • R 1 is a hydrolyzable group
  • R 2 is a hydrogen atom or an inert monovalent organic group
  • a, b, c, d are integers of 0 to 200
  • e is 0 or 1
  • f is 0 to 10
  • m and n are integers from 0 to 2
  • p is an integer from 1 to 10.
  • the fluoroether polymer Si compound represented by the general formula (1) preferably used in the present invention can be produced, for example, by the method described in Japanese Patent No. 2874715 and the following: The compound can be obtained as a commercial product.
  • a dipping method or a spray method in which these materials are used as they are or dissolved in a solvent.
  • the excess fluoroether polymer Si compound is removed by treatment with a solvent.
  • the surface roughness Ra of the obtained water repellent layer is required to be 100 nm or less from the viewpoint of high durability and high wear resistance of the water repellent layer, preferably 50 nm or less, more preferably 10 nm or less. It is.
  • the surface roughness of the water repellent layer is controlled by polishing, grinding, blasting, engraving and surface treatment (plasma, heat, light, etc.), flame treatment, and mechanical pressure heating treatment (calendering treatment). I can do it.
  • the surface roughness Ra can be measured by SII Nano Technology Co., Ltd., atomic force microscope (AFM) SPA300, manufactured by Nippon Beco Co., Ltd., a non-contact three-dimensional surface shape measuring instrument, and the like.
  • the substrate applicable to the water-repellent member of the present invention is preferably a substrate excellent in transparency, and is an inorganic transparent substrate such as a transparent glass substrate or an organic transparent resin group such as a plastic substrate. Materials.
  • transparent resin base materials examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate.
  • polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate.
  • Cellulose esters or derivatives thereof polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone, polysulfones, polyether ketone imide , Polyamide, fluororesin, nylon, polymethylmethacrylate DOO, and organic-inorganic hybrid resins such as acrylic or polyarylates, or these resins and silica.
  • the substrate is a transparent glass substrate, and as a final water repellent member, in the visible light region.
  • An average transmittance of 85% or more is preferable from the viewpoint of obtaining excellent transparency when applied to architectural window glass or automotive glass, and most preferably applied to automotive glass. .
  • the average transmittance in the visible light region referred to in the present invention is obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm, and calculating an average value thereof.
  • a conventionally known measuring device can be used for the transmittance at each measurement wavelength.
  • a spectrophotometer UVIDFC-610 manufactured by Shimadzu Corporation a 330 type self-recording spectrophotometer manufactured by Hitachi, Ltd.
  • a U-3210 type self-recording It can be obtained by measuring using a spectrophotometer, a U-3410 type self-recording spectrophotometer, a U-4000 type self-recording spectrophotometer, or the like.
  • glass substrate examples include inorganic glass having a functional group (hydroxyl group, amino group, thiol group, etc.) on the surface, organic glass, alkali-containing glass substrate such as soda lime silicate glass substrate, borosilicate Examples include alkali-free glass substrates such as acid glass substrates.
  • the glass substrate may be laminated glass, tempered glass, or the like.
  • the undercoat layer and the water repellent layer of the present invention are formed on the surface of such a substrate, and the dynamic friction coefficient of the surface is 0.3 or less.
  • the method of controlling the surface dynamic friction coefficient of the water repellent layer within the range specified above can be adjusted by the amount of the water repellent layer attached or bonded to the surface of the undercoat layer.
  • the water repellent layer is formed using a wet coating method
  • the adjustment of the material concentration in the coating liquid, the coating amount, the amount of reactive groups remaining on the surface of the undercoat layer, and the water repellent layer are repeated.
  • the coating method can also be controlled. It can also be controlled by using a water repellent layer material in combination with materials having different or different molecular weights, or adding additives such as surfactants and binders.
  • the water repellent layer constituting material when used as a thin film forming gas by using a dry coating method, it can be controlled by adjusting the amount of gas supplied to the surface of the undercoat layer, the supply time and the like. It can also be controlled by adjusting the surface roughness.
  • the dynamic friction coefficient can be measured according to JIS-K-7125 (1987).
  • Example 1 The top surface of a 3.5 mm thick float glass (clear) substrate was washed with a neutral detergent, water, and alcohol, dried, and used as a substrate 1 for forming a water repellent layer.
  • undercoat layer 1 (Formation of undercoat layer 1) Using the atmospheric pressure plasma discharge processing apparatus shown in FIG. 1 on the top surface of the substrate 1, a substrate A with an undercoat layer having a thickness of 30 nm was obtained under the following gas conditions and power supply conditions.
  • ⁇ Gas conditions> Discharge gas: Nitrogen gas 97.9% by volume Thin film forming gas: tetraethoxysilane (mixed with nitrogen gas and vaporized by a vaporizer manufactured by Lintec Corporation) 0.1% by volume Added gas: Hydrogen gas 2.0% by volume ⁇ Power supply conditions> 1st electrode side Power supply type High frequency power supply made by Applied Electric Company Frequency 80kHz Output density 10W / cm 2 2nd electrode side Power supply type High frequency power supply made by Pearl Industry Co., Ltd. Frequency 13.56MHz Output density 8W / cm 2 About the obtained undercoat layer, the contained element (at%) was measured using ESCALAB-200R manufactured by VG Scientific as an XPS surface analyzer. The same analysis was performed on the obtained undercoat layer. The obtained results are shown in Table 1.
  • repelling is performed in the same manner.
  • Water substrates 2 to 5, 10, and 11 were obtained.
  • the water-repellent substrate 5 was prepared by using Optool AES-2 (manufactured by Daikin Industries) instead of Optool AES-4E (manufactured by Daikin Industries) as the fluoroether polymer Si compound forming the water-repellent layer. It was formed in the same manner as the water repellent substrate 1.
  • the fluoroether polymer Si compound forming the water-repellent layer of the water-repellent substrate 11 was synthesized by the method described in Japanese Patent No. 28747715, and fractionated with an average molecular weight of about 650 was collected by gel permeation chromatography. Compound A was used.
  • the water-repellent substrate 7 is a water-repellent substrate obtained in the same manner except that the glass substrate of the water-repellent substrate 1 is replaced with an acrylic resin substrate having the same thickness.
  • the polishing treatment “present” described in Table 1 means that a cerium oxide is added to water to prepare a 5% mixed solution, and the 5% mixed solution is dipped in gauze to make a 3.5 mm thick float glass ( Clear) The top surface of the substrate was polished and then washed with a neutral detergent, water, and alcohol. As in the case of the water repellent substrate 1, an undercoat layer and a water repellent layer were formed to obtain a water repellent substrate 2. .
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: Nitrogen gas 97.6% by volume Thin film forming gas: Hexamethyldisiloxane 0.1% by volume Additive gas: Hydrogen gas 2.3% by volume, except that OPTOOL AES-6 (made by Daikin Industries) was used instead of OPTOOL AES-4E (made by Daikin Industries) A water repellent substrate 6 was obtained.
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: Nitrogen gas 99.89% by volume Thin film forming gas: n-propyltrichlorosilane 0.1% by volume Added gas: oxygen gas A water-repellent substrate 12 was obtained in the same manner as the water-repellent substrate 1 except that it was changed to 0.01% by volume.
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: Nitrogen gas 99.79% by volume Thin film forming gas: 0.2% by volume of methyltrifluorosilane Added gas: Oxygen gas A water-repellent substrate 13 was obtained in the same manner as the water-repellent substrate 1 except that the volume was changed to 0.01% by volume.
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: Nitrogen gas 99.89% by volume Thin film forming gas: Nonamethyltrisilazane 0.1% by volume Added gas: Oxygen gas A water-repellent substrate 14 was obtained in the same manner as the water-repellent substrate 1 except that the volume was changed to 0.01% by volume.
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: nitrogen gas Thin film forming gas: Titanium tetraisopropoxide 0.1% by volume Added gas: hydrogen gas A water-repellent substrate 8 was obtained in the same manner as the water-repellent substrate 1 except that it was changed to 1.9% by volume.
  • the gas conditions for forming the undercoat layer are as follows: Discharge gas: nitrogen gas Thin film forming gas: zirconium tetranormal propoxide 0.1% by volume Added gas: hydrogen gas A water-repellent substrate 9 was obtained in the same manner as the water-repellent substrate 1 except that the volume was changed to 1.1% by volume.
  • undercoat layer 2 (Formation of undercoat layer 2) While stirring, 75.2 g of isopropyl alcohol was added and 0.1 g of tetraethoxysilane was added to the mixture. After stirring, 5.2 g of 30% HCl aqueous solution was added and the mixture was heated to 40 ° C. and allowed to stand for 2 hours. The undercoat layer coating solution was obtained.
  • the top surface of a 3.5 mm thick float glass (clear) substrate was washed with a neutral detergent, water, and alcohol, and the coating layer for dipping the undercoat layer was dipped onto the dried water-repellent layer forming substrate. After drying, the substrate was kept at 100 ° C. for 1 day to obtain a substrate B with an undercoat layer having a film thickness of 25 nm. Next, a water repellent layer was formed in the same manner as the water repellent substrate 1 to obtain a water repellent substrate 15.
  • Discharge gas Nitrogen gas 97.9% by volume
  • Thin film forming gas tetraethoxysilane 0.05% by volume n-Propyltrichlorosilane 0.1% by volume (Vaporized by mixing with nitrogen gas with a Lintec vaporizer)
  • Addition gas 2.0% by volume of oxygen gas
  • the power supply conditions are the same as those for forming the undercoat layer 1.
  • a water-repellent substrate 16 was obtained in the same manner as the water-repellent substrate 1 except that the substrate C with an undercoat layer was used.
  • Comparative Example 1 was obtained in the same manner as the water-repellent substrate 2 except that the polishing treatment of the water-repellent substrate 2 was repeated three times.
  • Comparative Example 2 was obtained in exactly the same manner except that the additive gas when forming the undercoat layer of the water repellent substrate 1 was changed to oxygen gas.
  • Comparative Example 3 was obtained by changing the gas conditions and the power supply conditions during the formation of the undercoat layer so that C contained in the undercoat layer of the water-repellent substrate 1 was as shown in Table 1.
  • Comparative Example 4 was obtained in exactly the same manner except that the perfluoroether Si compound used for forming the water-repellent layer of the water-repellent substrate 1 was changed to dodecyltriethoxysilane and Novec HFE7100 was changed to isopropyl alcohol.
  • the filter used was CIRA / soda lime.
  • the 10 ⁇ l water contact angle on the surface of the water-repellent layer before radiation was C °
  • the water contact angle after radiation for 6000 hours was D °
  • the D / C ratio was evaluated according to the following rank.
  • the sample of the present invention showed excellent operability even when wiping was performed using a wiper dedicated to water-repellent glass and a general-purpose wiper.

Abstract

L'invention concerne la formation d'un élément hydrofuge d'une grande durabilité et d'une grande résistance aux intempéries. L'invention concerne également une surface hydrofuge rendue lisse, ce qui permet un contact sans heurt avec le balai d'essuie-glace et permet d'obtenir un excellent élément hydrofuge ne provoquant pas de variations de la vitesse du balai d'essuie-glace telles que glissement ou vibrations (accrochage). Cet élément hydrofuge possède au moins une sous-couche sur au moins une surface de sa base ainsi qu'au-dessus, une couche hydrofuge dont la rugosité de surface est égale ou inférieure à 100nm. Ladite couche hydrofuge est formée à partir d'un composé Si polymère de fluoroéther possédant une base de silyle réactif et ladite sous-couche est formée à partir d'un composé organométallique possédant une base réactive. La sous-couche se caractérise en ce qu'elle contient au moins une sorte d'atomes choisie dans le groupe comprenant atomes de carbone, atomes d'azote ou atomes de chlore et en ce que le total d'atomes contenu représente entre 0,3 et 50 % atomique.
PCT/JP2010/057147 2009-04-30 2010-04-22 Élément hydrofuge et verre destiné à être installé à bord d'un véhicule WO2010125964A1 (fr)

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Cited By (6)

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WO2013072622A1 (fr) 2011-11-16 2013-05-23 Saint-Gobain Glass France Vitrage hydrophobe
JP2013170088A (ja) * 2012-02-20 2013-09-02 Asahi Glass Co Ltd 防汚膜付き基体
WO2015118987A1 (fr) * 2014-02-06 2015-08-13 旭硝子株式会社 Procédé de production d'un complexe verre/résine
JP2017524745A (ja) * 2013-12-05 2017-08-31 サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. 樹脂膜及び樹脂膜の製造方法
WO2020066533A1 (fr) 2018-09-28 2020-04-02 ダイキン工業株式会社 Procédé de traitement de surface et article dont la surface a été traitée
CN113448126A (zh) * 2021-06-22 2021-09-28 Tcl华星光电技术有限公司 封框胶及其制备方法、液晶显示面板

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CN117794740A (zh) 2021-08-05 2024-03-29 信越化学工业株式会社 具有拒水拒油表面层的物品
CN117794741A (zh) 2021-08-05 2024-03-29 信越化学工业株式会社 具有拒水拒油表面层的物品

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WO2007018184A1 (fr) * 2005-08-08 2007-02-15 Nippon Sheet Glass Company, Limited Article doté d’un revêtement hydrophobe et procédé de production correspondant
JP2007076940A (ja) * 2005-09-13 2007-03-29 Ishizuka Glass Co Ltd 撥水性ガラス材料及びその製造方法

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JP2002113805A (ja) * 2000-10-10 2002-04-16 Dainippon Printing Co Ltd 撥水性防汚フィルム
WO2007018184A1 (fr) * 2005-08-08 2007-02-15 Nippon Sheet Glass Company, Limited Article doté d’un revêtement hydrophobe et procédé de production correspondant
JP2007076940A (ja) * 2005-09-13 2007-03-29 Ishizuka Glass Co Ltd 撥水性ガラス材料及びその製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013072622A1 (fr) 2011-11-16 2013-05-23 Saint-Gobain Glass France Vitrage hydrophobe
JP2013170088A (ja) * 2012-02-20 2013-09-02 Asahi Glass Co Ltd 防汚膜付き基体
JP2017524745A (ja) * 2013-12-05 2017-08-31 サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. 樹脂膜及び樹脂膜の製造方法
WO2015118987A1 (fr) * 2014-02-06 2015-08-13 旭硝子株式会社 Procédé de production d'un complexe verre/résine
WO2020066533A1 (fr) 2018-09-28 2020-04-02 ダイキン工業株式会社 Procédé de traitement de surface et article dont la surface a été traitée
KR20210022091A (ko) 2018-09-28 2021-03-02 다이킨 고교 가부시키가이샤 표면 처리 방법 및 표면 처리 물품
EP3858496A4 (fr) * 2018-09-28 2022-06-22 Daikin Industries, Ltd. Procédé de traitement de surface et article dont la surface a été traitée
CN113448126A (zh) * 2021-06-22 2021-09-28 Tcl华星光电技术有限公司 封框胶及其制备方法、液晶显示面板
CN113448126B (zh) * 2021-06-22 2022-04-08 Tcl华星光电技术有限公司 封框胶及其制备方法、液晶显示面板

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