JP2005059820A - Glass for vehicle window and its manufacturing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a glass for a vehicle window without nonuniformity of coating without passing a drying process. <P>SOLUTION: A thin-film forming device 1 as a manufacturing device for the glass for the vehicle window forms a thin-film 22 on a glass base material 21 by introducing a discharge gas G at or near the atmospheric pressure into a discharge space area A, holding a thin-film forming gas M including the material by the glass base material 21 and an excitation discharge gas G' so that the excitation discharge gas G' does not come into direct contact with the glass base material 21, bringing the thin-film forming gas M into contact with the excitation discharge gas G' in an area B on the outside of a discharge space to indirectly excite the gas, and exposing the glass base material 21 to an indirectly excited indirect excitation gas N. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a glass for a vehicle window of a vehicle such as an automobile or a train, and an apparatus for manufacturing the same, and particularly to a technique for forming a film on the surface of the glass substrate by exposing the glass substrate to an excited gas.

In recent years, water-repellent glass having excellent water slidability (water repellency) has been developed as glass for car windows of automobiles and trains. Such window glass has greatly improved the ability to repel raindrops, which makes it extremely useful for vehicle drivers as a means of significantly improving visibility and safety during rainy weather driving. Yes. Car window glass having water repellency is usually configured to exhibit its functions sufficiently by various surface treatments on the glass surface. For example, in Patent Document 1, a surface treatment agent such as a lubricant or a water repellent is applied to the glass surface, and the glass surface is coated with the surface treatment agent to give high water repellency to the glass for vehicle windows.
JP 2002-293219 A

However, as described in Patent Document 1, in a car window glass in which a coating is formed on the glass surface by a coating method, a drying process must be provided after the surface treatment agent is applied to the glass surface in the manufacturing process. It is difficult to improve the productivity of glass, and since the surface treatment agent is liquid, it is difficult to make the film thickness of the surface treatment agent to be applied constant on the glass surface. Unevenness occurs.
The objective of this invention is providing the glass for vehicle windows which can be manufactured without passing through a drying process, and there is no coating unevenness, and its manufacturing apparatus.

In order to solve the above problems, the glass for a car window of the invention according to claim 1 is:
The thin film forming gas containing the raw material and the glass substrate are excited so that the excited discharge gas excited by introducing the discharge gas into the discharge space under atmospheric pressure or near atmospheric pressure does not directly contact the glass substrate. The glass substrate is sandwiched between a discharge gas, the thin film forming gas is indirectly excited by bringing it into contact with the excitation discharge gas outside the discharge space, and the glass substrate is exposed to the indirectly excited indirect excitation gas on the glass substrate. A thin film is formed.

The invention according to claim 2 is the glass for vehicle windows according to claim 1,
The discharge space is formed by applying a high frequency voltage between opposing electrodes.

The invention according to claim 3 is the glass for vehicle windows according to claim 1 or 2,
The discharge gas contains nitrogen and / or a rare gas.

Invention of Claim 4 is the glass for vehicle windows as described in any one of Claims 1-3,
The thin film forming gas raw material contains an organometallic compound, a metal halide and / or an organofluorine compound.

The invention according to claim 5 is the glass for vehicle windows according to claim 4,
The raw material of the thin film forming gas is an organometallic compound having an organic group having a fluorine atom.

Invention of Claim 6 is the glass for vehicle windows as described in any one of Claims 1-5,
The surface of the glass substrate contains an inorganic compound.

Invention of Claim 7 is the glass for vehicle windows as described in any one of Claims 1-6,
The main component of the surface of the glass substrate is a metal oxide.

Invention of Claim 8 is the glass for vehicle windows as described in any one of Claims 1-7,
The glass substrate is exposed to the indirect excitation gas after being pretreated by being exposed to the discharge space or the excitation discharge gas.

Invention of Claim 9 is the glass for vehicle windows as described in any one of Claims 1-8,
The specific surface resistance value is 1 × 10 ¹² Ω / □ or less under conditions of 23 ° C. and 55% RH.

Invention of Claim 10 in the glass for vehicle windows as described in any one of Claims 1-9,
The glass substrate is used as a windshield of an automobile.

Invention of Claim 11 in the glass for vehicle windows as described in any one of Claims 1-9,
The glass substrate is used as a side glass of an automobile.

The invention according to claim 12
In the manufacturing apparatus of the glass for vehicle windows which manufactures the glass for vehicle windows as described in any one of Claims 1-11,
Counter electrodes arranged to face each other;
Voltage applying means for applying a high-frequency voltage between the opposing electrodes;
With
Excited discharge gas that is excited by introducing a discharge gas into the discharge space between the counter electrodes to which a high-frequency voltage is applied by the voltage application means at or near atmospheric pressure does not directly contact the glass substrate. The thin film forming gas containing the raw material is sandwiched between the glass substrate and the excited discharge gas, and the thin film forming gas is indirectly excited by contacting the excited discharge gas with the excited discharge gas outside the discharge space. A thin film is formed on the glass substrate by exposure to the indirectly excited gas that has been indirectly excited.

The invention according to claim 13
The vehicle window glass manufacturing apparatus according to claim 12,
At least one of the counter electrodes is covered with a dielectric.

The invention according to claim 14
In the vehicle window glass manufacturing apparatus according to claim 12 or 13,
An excited discharge gas discharge port for discharging the excited discharge gas;
A thin film forming gas discharge port for discharging the thin film forming gas;
A substrate support device for supporting the glass substrate;
With
The thin film forming gas discharge port is closer to the glass substrate supported by the substrate support device than the excited discharge gas discharge port.

Details of the present invention will be described below.
The glass for a car window according to the present invention is a thin film formation containing a raw material so that the excited discharge gas excited by introducing the discharge gas into the discharge space under atmospheric pressure or near atmospheric pressure does not directly contact the glass substrate. Gas is sandwiched between the glass substrate and the excitation discharge gas, the thin film forming gas is indirectly excited by contacting the excitation discharge gas outside the discharge space, and the glass substrate is converted into the indirectly excited gas that has been indirectly excited. A thin film is formed on the glass substrate by exposure. That is, the thin film forming gas and the indirect excitation gas are in direct contact with the glass substrate, and the excited discharge gas is not in direct contact with the glass substrate. Therefore, the main feature is that the glass substrate is less damaged by the excited discharge gas, and a more efficient and uniform thin film is formed.

First, the “discharge gas” and “thin film forming gas” of the present invention will be described.
The gas to be used is basically a discharge gas containing no raw material and a thin film forming gas containing the raw material as constituents, and an auxiliary gas for accelerating or controlling the reactivity may be added.

  “Discharge gas” is a gas that can cause plasma discharge, and is a gas that itself acts as a medium for transferring energy, and is necessary for generating plasma discharge. Examples of the discharge gas include nitrogen, rare gas, air, and the like. These may be used alone as a discharge gas or may be used in combination. Examples of the rare gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and the like. In the present invention, the discharge gas is preferably nitrogen, argon or helium. It is preferable to contain 70-100 volume% of discharge gas amount with respect to the total gas amount supplied in discharge space. In addition, you may mix 0.001 volume%-30 volume% with hydrogen, oxygen, a hydrocarbon, nitrogen oxide, ammonia, or a water | moisture content as auxiliary gas with respect to this discharge gas.

  “Thin film-forming gas” refers to a gas containing a raw material that receives energy from an excited discharge gas (excited discharge gas) and excites itself to become active and chemically forms a thin film on a glass substrate. That is.

  The thin film forming gas may be only the raw material, but preferably contains at least one selected from nitrogen, rare gas, oxygen, hydrogen, hydrocarbon and nitrogen oxide in addition to the raw material. These may be used alone as a thin film forming gas, or may be mixed and used. Examples of the rare gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and the like.

  Examples of the raw material contained in the thin film forming gas useful in the present invention include an organic metal compound, a metal halide, an organic fluorine compound, and the like, which are useful for forming a functional thin film.

  More specifically, when an organometallic compound or a metal halide is added to the raw material, for example, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, A metal selected from Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu can be included. Among them, it contains at least one element selected from Sn, In, Al, Ti, Zn, Si, Sb, Mg, Ba, Mo, V, Nb, P, B, W, Cs, Zr, Ga, and As. It is preferable. In the case of an organometallic compound, those selected from metal alkoxides, alkylated metals, and metal complexes are preferred.

  Various highly functional thin films can be obtained by appropriately selecting the above or other raw materials and forming the thin film. One example is shown below, but the present invention is not limited to this.

Electrode film Au, Al, Ag, Ti, Ti, Pt, Mo, Mo-Si
Dielectric protective film _{SiO 2, SiO, Si 3 N} 4, Al 2 O 3, Al 2 O 3, Y 2 O 3
Transparent conductive film In ₂ O ₃ , SnO ₂ , ZnO
Electrochromic film WO ₃ , IrO ₂ , MoO ₃ , V ₂ O ₅
Fluorescent film ZnS, ZnS + ZnSe, ZnS + CdS
Magnetic recording film Fe-Ni, Fe-Si-Al, γ-Fe ₂ O ₃ , Co, Fe ₃ O ₄ , Cr, SiO ₂ , Al ₂ O ₃
Superconductive film Nb, Nb-Ge, NbN
Solar cell film a-Si, Si
Reflective film Ag, Al, Au, Cu
Selective absorption membrane ZrC-Zr
Selective permeable membrane In ₂ O ₃ , SnO ₂
Antireflection film SiO ₂ , TiO ₂ , SnO ₂ , Ta ₂ O ₅
Shadow mask Cr
Abrasion resistant film Cr, Ta, Pt, TiC, TiN
Corrosion resistant film Al, Zn, Cd, Ta, Ti, Cr
Heat resistant film W, Ta, Ti
Lubricating film MoS ₂
Decorative film Cr, Al, Ag, Au, TiC, Cu
For example, in the formation of the antireflection film, examples of the raw material for forming the low refractive index layer include organic silicon compounds, silicon hydrogen compounds, and silicon halide compounds. Examples of the organic silicon compounds include tetraethylsilane, tetramethyl, and the like. Silane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanediacetacetonate, methyltrimethoxysilane, methyltriethoxysilane, ethyl Examples of the silicon hydride compound such as triethoxysilane include tetrahydrogen silane and hexahydrogen disilane, and examples of the halogenated silicon compound include tetrachlorosilane, methyltrichlorosilane, and diethyldichlorosilane. It can, both can be preferably used in the present invention.

In the formation of the antireflection film, a tin compound is used as a metal compound used as a raw material for forming a medium refractive index layer or a high refractive index layer. Preferred tin compounds include organic tin compounds, tin hydrogen compounds, tin halides, and the like. Examples of the organic tin compound include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, and triisopropylethoxy. Tin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyl Tin diacetacetonate, etc., tin hydride, etc., halogen As tin, tin chloride, it can be mentioned tin tetrachloride, etc., all of which can be used preferably in the present invention. Two or more of these reactive gases may be mixed and used at the same time. In addition, since the tin oxide layer thus formed can reduce the surface specific resistance value to 1 × 10 ¹² Ω / □ or less, it is also useful as an antistatic layer.

  In addition, the titanium compound used as a raw material for the reaction gas for forming the high refractive index layer in the antireflection film includes an organic titanium compound, a titanium hydrogen compound, a titanium halide, etc. Examples of the organic titanium compound include triethyl titanium. , Trimethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyldimethoxy Titanium hydrogen compound such as titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, tetradimethylamino titanium, dimethyl titanium diacetoacetonate, ethyl titanium triacetoacetonate, etc. Mono-titanium hydride, Jichitan hydrogen compound such as titanium halide, titanium trichloro, the titanium tetrachloride and the like. Alternatively, as the high refractive index layer, alkoxy tantalum such as tetraisopropoxy tantalum can be cited as a raw material for forming the tantalum oxide layer, and any of them can be preferably used in the present invention. These raw materials can be used by mixing two or more kinds at the same time, but are not limited thereto.

  Furthermore, a typical example of thin film formation is an article having a highly functional thin film such as an antifouling thin film. In the present invention, a thin film forming gas for producing an antifouling thin film will be described as a representative example.

  As the film forming gas for producing the antifouling thin film of the present invention, an organic fluorine compound or an organic metal compound in which an organic group is directly bonded to a metal is used, and an organic metal compound having an organic group having a fluorine atom is particularly useful. It is.

  As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like can be preferably used. Examples of the fluorocarbon gas include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like. Examples of the fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, and trifluoropropylene. Further, for example, halogenated fluorocarbon compounds such as chlorotrifluoromethane, chlorodifluoromethane, dichlorotetrafluorocyclobutane, fluoroalcohols such as trifluoromethanol and pentafluoroethanol, fluorine such as trifluoroacetic acid and pentafluoropropionic acid Organic fluorine compounds such as fluorinated ketones such as fluorinated fatty acids and hexafluoroacetone can be used, but are not limited thereto. These compounds may have a fluorinated ethylenically unsaturated group in the molecule.

  In the organometallic compound having an organic group used in the present invention, examples of the organic group include an organic group containing an alkyl group, an alkenyl group, an aryl group, etc., and an organometallic compound having an organic group used in the present invention. These organic groups are directly bonded to metal atoms, for example, metals such as silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium, lanthanum, iron, neodymium, copper, gallium, and halfnium. It is an organometallic compound. Of these metals, silicon, titanium, germanium, zirconium, tin and the like are preferable, and silicon and titanium are more preferable. These fluorine-containing organic groups may be bonded to the metal compound in any form. For example, when a compound having a plurality of metal atoms such as siloxane has these organic groups, at least one metal atom is organic. It only needs to have a group, and the position is not limited.

  For example, as the silicon compound having an organic group, methyltrichlorosilane, methyldichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, ethyldichlorosilane, n-propyltrichlorosilane, ethylmethyldichlorosilane, trimethylbromosilane, trimethylchlorosilane, n -Butyltrichlorosilane, i-butyltrichlorosilane, diethyldichlorosilane, methylpropyldichlorosilane, tetramethylsilane, diethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, pentyltrichlorosilane, butylmethyldichlorosilane, trimethyl Methoxysilane, ethyltrimethoxysilane, hexyltrichlorosilane, triethylchlorosilane, dimethyldiethoxysila , Propyltrimethoxysilane, heptyltrichlorosilane, hexamethyldichlorosilane, butyltrimethoxysilane, methyltriethoxysilane, octyltrichlorosilane, heptylmethyldichlorosilane, dibutyldichlorosilane, diethyldiethoxylane, ethyltriethoxysilane, tripropyl Chlorosilane, hexyltrimethoxysilane, propyltriethoxysilane, decyltrichlorosilane, dimethyloctylchlorosilane, pentyltriethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, octyltriethoxysilane, dodecylmethyldiethoxysilane, dodecyltriethoxysilane , Octadecylmethyldiethoxysilane, octadecyltriethoxysilane, 1,1,3,3-tetramethyl Rudisiloxane, 1,1,3,3-tetramethyldisilazane, hexamethyldisiloxane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3- Divinyl-1,1,3,3-tetramethyldisilazane, hexaethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisilazane, hexapropyldisiloxane, 1,1,3 3,5,5-hexamethyltricytoxane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, hexaethylcyclosiloxane, octamethylcyclotetrasiloxane, 1,1,1,3,5 , 7,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane, decamethyltetrasiloxane Any of these can be preferably used in the present invention.

  In the present invention, an organic metal compound containing a fluorine atom in the organic group, that is, having an organic group having a fluorine atom is preferable, and a compound represented by the following general formula (1) can be preferably used. .

In the general formula (1), M represents Si, Ti, Ge, Zr, or Sn. R _{1 to} R ₆ each represent a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is an organic group having a fluorine atom, for example, having a fluorine atom. An organic group containing an alkyl group, an alkenyl group or an aryl group is preferable. Examples of the alkyl group having a fluorine atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and 4,4. , 3, 3, 2, 2, 1, 1-octafluorobutyl group and the like, as the alkenyl group having a fluorine atom, for example, a group such as 3, 3, 3-trifluoro-1-propenyl group In addition, examples of the aryl group having a fluorine atom include groups such as a pentafluorophenyl group. In addition, an alkyl group, an alkenyl group, an alkoxy group formed from an aryl group, an alkenyloxy group, an aryloxy group, or the like can also be used.

  Further, in the alkyl group, alkenyl group, aryl group, etc., any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, but preferably at least one is bonded. . The carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.

Of the groups represented by R _{1 to} R ₆ , other than the organic group having a fluorine atom represents a hydrogen atom or a monovalent group, and examples of the monovalent group include a hydroxy group, an amino group, and an isocyanate group. , Halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, and the like, but are not limited thereto. j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.

  Of the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom. Among the alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, and aryloxy groups that are the monovalent groups, preferred are an alkoxy group, an alkenyloxy group, and an aryloxy group. Preferred is an alkoxy group.

  Of the metal atoms represented by M, Si and Ti are preferable, and Si is more preferable.

  The monovalent group may be further substituted with other groups, and is not particularly limited. Preferred substituents include amino groups, hydroxyl groups, isocyanate groups, fluorine atoms, chlorine atoms, bromine atoms and the like. Atom, alkyl group, cycloalkyl group, aryl group such as alkenyl group, phenyl group, alkoxy group, alkenyloxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, alkaneamide group, arylamide group, alkylcarbamoyl And groups such as an arylcarbamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Further, the organic group having a fluorine atom or other groups represented by these R ₁ to R _6, and ^{is, R 1 R 2 R 3 M-} (M represents the metal atom, R ^1, R ² R ³ represents a monovalent group, and the monovalent group represents an organic group having the fluorine atom or a group other than the organic group having the fluorine atom exemplified as R _{1 to} R ₆ . A structure having a plurality of metal atoms further substituted by the group represented may be used. Examples of these metal atoms include Si and Ti, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Examples of the alkyl group, alkenyl group, and the alkoxy group formed from these, the alkyl group in the alkenyloxy group, and the alkenyl group, which are the groups having fluorine atoms mentioned in R _{1 to} R ₆ , include the following general formula (F) The group represented by these is preferable.

Formula (F)
_{Rf-X- (CH 2) k} -
Here, Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted by a fluorine atom. For example, Rf represents a perfluoro group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, or a heptafluoropropyl group. Groups such as alkyl groups, groups such as 3,3,3-trifluoropropyl groups, 4,4,3,3,2,2,1,1-octafluorobutyl groups, and 1,1,1 -An alkenyl group substituted by a fluorine atom such as trifluoro-2-chloropropenyl group is preferred, among which a group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, a heptafluoropropyl group, 3,3,3-trifluoropropyl group, 4,4,3,3,2,2,1,1-octafluorobutyl group, etc. Alkyl group preferably has at least two or more fluorine atoms.

X is a simple bond or a divalent group. The divalent group is a group such as —O—, —S—, —NR— (R represents a hydrogen atom or an alkyl group), —CO—, and the like. , -CO-O -, - CONH -, - SO 2 NH -, - SO 2 -O -, - OCONH-,

Represents a group such as
k represents an integer of 0 to 50, preferably 0 to 30.

In addition to the fluorine atom, other substituents may be substituted in Rf, and examples of the substitutable group include the same groups as those exemplified as the substituents in R _{1 to} R ₆ . The skeletal carbon atom in Rf is another atom, for example, —O—, —S—, —NR ₀ — (R ₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and the general formula (F Or a group represented by carbonyl group, —NHCO—, —CO—O—, —SO ₂ NH— or the like.

  Of the compounds represented by the general formula (1), a compound represented by the following general formula (2) is preferable.

General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
In general formula (2), M represents the same metal atom as in general formula (1), Rf and X represent the same groups as Rf and X in general formula (F), and k represents the same integer. Represent. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group, or an aryl group, each of which is the same as the group exemplified as the substituent for R _{1 to} R _{6 in} the general formula (1). May be substituted, but preferably represents an unsubstituted alkyl group or alkenyl group. Further, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be linked to form a ring.

  Of the general formula (2), more preferred are compounds represented by the following general formula (3).

General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
Here, Rf, X and k are as defined in the general formula (2). R _{12 is} also synonymous with R ₁₁ in the general formula (2). Further, M is the same as M in the general formula (2), but Si and Ti are particularly preferable, and Si is most preferable.

  In the present invention, another preferred example of the organometallic compound having a fluorine atom includes a compound represented by the following general formula (4).

In the general formula (4), R ₁ to R ₆ have the same meanings as R ₁ to R ₆ in the general formula (1). Also in this case, at least one of R _{1 to} R ₆ is an organic group having the fluorine atom, and a group represented by the general formula (F) is preferable. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. J represents an integer of 0 to 150, preferably 0 to 50, and most preferably j is in the range of 0 to 20.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (5).

General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
In the general formula (5), M represents In, Al, Sb, Y, or La. Rf and X represent the same groups as Rf and X in formula (F), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, and is preferably an integer of 30 or less. R ₉ represents an alkyl group or an alkenyl group, and R ₈ represents an alkyl group, an alkenyl group, or an aryl group, each of which is the same as the group listed as the substituent for R _{1 to} R _{6 in} the general formula (1). May be substituted. Moreover, in General formula (5), it is m + n + p = 3, m is at least 1, n represents 0-2, p represents the integer of 0-2. It is preferable that m + p = 3, that is, n = 0.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (6).

General formula (6)
^{_{R f1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1
-Si- (R ²⁾ ₃
In the general formula (6), R ^f1 represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1 An integer of ˜50, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0.

As for carbon number of the linear or branched perfluoroalkyl group which can be introduce ^| transduced into Rf1, 1-16 are more preferable, and 1-3 are the most preferable. Therefore, the _{^{R f1, -CF 3, -C 2}} F 5, -C 3 F 7 and the like are preferable.

Examples of the hydrolyzable group that can be introduced into R ² include —Cl, —Br, —I, —OR ¹¹ , —OCOR ¹¹ , —CO (R ¹¹ ) C═C (R ¹² ) ₂ , —ON═C (R _{^{11) 2, -ON = CR 13}} , -N (R 12) 2, are preferred, such as -R ¹² NOCR ^11. R ¹¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R ¹² represents a carbon such as a hydrogen atom or an alkyl group. R 1 represents an aliphatic hydrocarbon having 1 to 5 carbon atoms, and R ¹³ represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. Among these hydrolyzable groups, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OCOCH ₃ and —NH ₂ are preferable.

As for m1 in the said General formula (6), it is more preferable that it is 1-30, and 5-20
More preferably. n1 is more preferably 1 or 2, and p1
Is more preferably 1 or 2. Further, q1 is more preferably 1 to 3.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (7).

In the general formula (7), Rf 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 trifluoro A methyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1, m and n represent an integer of 0 to 2, and p represents an integer of 1 to 10.

In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group. It is. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms.

Examples of the hydrolyzable group of R ²¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, R ²³ O group, R ²³ COO group, (R ²⁴ ) ₂ C═C (R ²³ ) CO group, ( R ²³ ) ₂ C═NO group, R ²⁵ C═NO group, (R ²⁴ ) ₂ N group, and R ²³ CONR ²⁴ group are preferred. Here, R ²³ is usually an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group usually having 6 to 20 carbon atoms such as a phenyl group, and R ²⁴ is a hydrogen atom or an alkyl group. Usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ²⁵ is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. More preferred are a chlorine atom, a CH ₃ O group, a C ₂ H ₅ O group, and a C ₃ H ₇ O group.

R ²² is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is 5 × 10 ² to 1 × 10 ⁵ , preferably 1 × 10 ³ to 1 × 10 ⁴ .

Further, as a preferred structure of the silane compound represented by the general formula (7), Rf is C ₃ F ₇ group, a is an integer of 1 to 50, b, c and d is 0 , E is 1, Z is a fluorine atom, and n is 0.

  In the present invention, typical examples of the organometallic compound having an organic group having fluorine, which is preferably used as the silane compound having a fluorine atom, and the compounds represented by the general formulas (1) to (7) are listed below. However, the present invention is not limited to these compounds.

1: (CF ₃ CH ₂ CH ₂ ) ₄ Si
2: (CF ₃ CH ₂ CH ₂ ) ₂ (CH ₃ ) ₂ Si
_{3: (C 8 F 17 CH} 2 CH 2) Si (OC 2 H 5) 3
_{4: CH 2 = CH 2 Si} (CF 3) 3
5: (CH ₂ = CH ₂ COO) Si (CF ₃ ) ₃
6: (CF ₃ CH ₂ CH ₂ ) ₂ SiCl (CH ₃ )
7: C ₈ F ₁₇ CH ₂ CH ₂ Si (Cl) _{3
8: (C 8 F 17 CH} 2 CH 2) 2 Si (OC 2 H 5) 2
9: CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
10: CF ₃ CH ₂ CH ₂ SiCl ₃
11: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCl ₃
12: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃
13: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
14: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
15: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
16: CF ₃ (CF ₂ ) ₈ CH ₂ Si (OC ₂ H ₅ ) ₃
17: CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
18: CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
19: CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃
20: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

21: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
22: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
23: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
24: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OC ₃ H ₇ ) ₂
25: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OC ₃ H ₇
26: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂
27: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₂ H ₅ ) ₂
28: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂
29: (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
30: C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
31: C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
32: C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
33: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
34: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
35: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
36: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂
37: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂
38: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
39: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
40: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂

41: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
42: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
43: CF ₃ (CF ₂ ) ₂ O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) _{3
44: C 7 F 15 CH 2} O (CH 2) 3 Si (OC 2 H 5) 3
45: C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
46: C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃
47: CF ₃ (CF ₂ ) ₅ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) ₃
48: CF ₃ (CF ₂ ) ₃ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) _{3
49: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 CH 2 Si (OCH 3) 3
50: CF ₃ CO—O—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
51: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl
52: CF ₃ CH ₂ CH ₂ (CH ₃ ) Si (OCH ₃ ) _{2
53: CF 3 CO-O-} Si (CH 3) 3
54: CF ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl _{2
55: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OCH 3) 3
_{56: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OC 6 H 5) 3
_{57: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CH 3) 3
_{58: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CF 3 C 2 H 4) (CH 3) 2
_{59: CF 3 (OC 3 F} 6) 24 -O- (CF 2) 2 -CH 2 -O-CH 2 Si (OCH 3) 3
_{60: CF 3 O (CF (} CF 3) CF 2 O) m CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (m = 11~30),

_{61: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCOCF 2 O (CF 2 O) n (CF 2 CF 2 O) p CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (n / p = About 0.5, number average molecular weight = about 3000)
_{62: C 3 F 7 - (} OCF 2 CF 2 CF 2) q-O- (CF 2) 2 - [CH 2 CH {Si- (OCH 3) 3}] 9 -H (q = about 10)
63: F (CF (CF ₃ ) CF ₂ O) ₁₅ CF (CF ₃ ) CONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
64: F (CF ₂ ) ₄ [CH ₂ CH (Si (OCH ₃ ) ₃ )] _2.02 OCH _{3
65: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCO- [CF 2 (OC 2 F 4) 10 (OCF 2) 6 OCF 2] -CONHC 3 H 6 Si (OC 2 H 5) 3
_{66: C 3 F 7 (OC} 3 F 6) 24 O (CF 2) 2 CH 2 OCH 2 Si (OCH 3) 3
67: CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃
68: (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) _{2
69: CF 3 (CF 2)} 3 (C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
70: CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ Si (OC ₂ H ₅ ) ₃
71: CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si (NCO) ₃
72: CF ₃ (CF ₂ ) ₅ C ₂ H ₄ Si (NCO) ₃
73: C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
74: C ₉ F ₁₉ CONH (CH ₂ ) ₃ SiCl ₃
75: C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) _{3
76: C 3 F 7 O (} CF (CF 3) CF 2 O) 2 -CF (CF 3) -CONH (CH 2) Si (OC 2 H 5) 3
77: CF ₃ O (CF (CF ₃ ) CF ₂ O) ₆ CF ₂ CONH (CH ₂ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ (CH ₂ ) ₃ NHCOCF ₂ (OCF ₂ CF (CF ₃ )) ₆ OCF _{Three
78: C 3 F 7 COOCH 2} Si (CH 3) 2 OSi (CH 3) 2 CH 2 OCOC 3 F 7
_{79: CF 3 (CF 2)} 7 CH 2 CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 3 OCH 2 CH 2 (CF 2) 7 CF 3
_{80: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) 2 (OC 2 H 5)

_{81: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) (OC 2 H 5) 2
82: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ O (CH ₂ ) ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (OC ₂ H ₅ )
In addition to the compounds exemplified above, as fluorine-substituted alkoxysilanes,
83: (Perfluoropropyloxy) dimethylsilane 84: Tris (perfluoropropyloxy) methylsilane 85: Dimethylbis (nonafluorobutoxy) silane 86: Methyltris (nonafluorobutoxy) silane 87: Bis (perfluoropropyloxy) diphenylsilane 88: Bis (perfluoropropyloxy) methylvinylsilane 89: Bis (1,1,1,3,3,4,4,4-octafluorobutoxy) dimethylsilane 90: Bis (1,1,1,3,3) , 3-Hexafluoroisopropoxy) dimethylsilane 91: Tris (1,1,1,3,3,3-hexafluoroisopropoxy) methylsilane 92: Tetrakis (1,1,1,3,3,3-hexafluoro Isopropoxy) silane 93: dimethylbis (nonaf) (Luoro-t-butoxy) silane 94: bis (1,1,1,3,3,3-hexafluoroisopropoxy) diphenylsilane 95: tetrakis (1,1,3,3-tetrafluoroisopropoxy) silane 96: Bis [1,1-bis (trifluoromethyl) ethoxy] dimethylsilane 97: Bis (1,1,1,3,3,4,4,4-octafluoro-2-butoxy) dimethylsilane 98: Methyltris [2 , 2,3,3,3-pentafluoro-1,1-bis (trifluoromethyl) propoxy] silane 99: diphenylbis [2,2,2-trifluoro-1- (trifluoromethyl) -1-tolyl Ethoxy] silane and the following compounds,
100: (CF ₃ CH ₂ ) ₃ Si (CH ₂ —NH ₂ )
_{101: (CF 3 CH 2)} 3 Si-N (CH 3) 2

  Furthermore,

Silazanes such as
106: CF ₃ CH ₂ —CH ₂ TiCl ₃
107: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ TiCl ₃
108: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Ti (OCH ₃ ) ₃
109: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ TiCl ₃
110: Ti (OC ₃ F ₇ ) ₄
111: (CF ₃ CH ₂ —CH ₂ O) ₃ TiCl _{3
112: (CF 3 C 2 H} 4) (CH 3) 2 Ti-O-Ti (CH 3) 3
Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organometallic compounds as follows.

113: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ O (CH ₂ ) ₃ GeCl
114: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCH ₂ Ge (OCH ₃ ) ₃
115: (C ₃ F ₇ O) ₂ Ge (OCH ₃ ) ₂
116: [(CF ₃ ) ₂ CHO] ₄ Ge
117: [(CF ₃ ) ₂ CHO] ₄ Zr
_{118: (C 3 F 7 CH} 2 CH 2) 2 Sn (OC 2 H 5) 2
_{119: (C 3 F 7 CH} 2 CH 2) Sn (OC 2 H 5) 3
120: Sn (OC ₃ F ₇ ) ₄
121: CF ₃ CH ₂ CH ₂ In (OCH ₃ ) ₂
122: In (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
123: Al (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
124: Al (OC ₃ F ₇ ) ₃
125: Sb (OC ₃ F ₇ ) ₃
126: Fe (OC ₃ F ₇ ) ₃
127: Cu (OCH ₂ CH ₂ OC ₃ F ₇ ) ₂
128: C ₃ F ₇ (OC ₃ F ₆ ) ₂₄ O (CF ₂ ) ₂ CH ₂ OCH ₂ Si (OCH ₃ ) ₃

  The compounds mentioned in these specific examples are Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries Co., Ltd. (for example, OPTOOL DSX), and Gelest Inc. In addition to being easily marketed, for example, J.A. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J.M. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No. 3,668,233, etc., JP-A 58-122979, JP-A 7-242675, JP-A 9-61605, etc. 11-29585, JP-A Nos. 2000-64348, 2000-144097 and the like, or a synthesis method based on the synthesis method.

  The organic fluorine compound, the organic metal compound having an organic group, and the organic metal compound having an organic group having a fluorine atom may be used alone or in admixture of two or more.

  By using an organic fluorine compound, an organic metal compound having an organic group, or an organic metal compound having an organic group having a fluorine atom, the surface energy of the antifouling layer (the surface of the antifouling layer) is reduced. A thin film having both water repellency and oil repellency can be obtained.

  In the present invention, when the organic fluorine compound, the organic metal compound having an organic group, or the organic metal compound having an organic group having a fluorine atom is a gas at normal temperature and normal pressure, it can be used as it is as a component of the mixed gas. Therefore, a thin film can be formed most easily. However, if the organofluorine compound, the organometallic compound having an organic group, or the organometallic compound having an organic group having a fluorine atom is liquid or solid at normal temperature and normal pressure, it is vaporized by a method such as heating or decompression. What is necessary is just to use it, and you may melt | dissolve in a suitable solvent and use it.

  As described above, the glass for a vehicle window according to the present invention is excited by introducing a discharge gas into a discharge space under atmospheric pressure or a pressure near atmospheric pressure, and exciting discharge with the above-described thin film forming gas containing an organometallic compound. A thin film is formed by bringing the gas into contact with the outside of the discharge space to form an indirectly excited gas, and exposing the indirectly excited gas to the glass substrate.

  When a discharge gas (excited discharge gas) directly exposed to the discharge space is brought into contact with the thin film forming gas outside the discharge space, the thin film forming gas receives energy from the excited discharge gas excited in the discharge space and indirectly Is estimated to be excited. In this invention, what processed the thin film formation gas in this way is called indirect excitation gas.

  Although the principle is not clear, the present inventors have found that an antifouling thin film can be formed at a very high performance and at a high speed as compared with the case where a thin film forming gas is directly exposed to a discharge space. It is.

  In the present invention, the term “discharge space” refers to a space that is sandwiched between electrode pairs arranged to face each other at a predetermined distance, and causes discharge by introducing a discharge gas between the electrode pairs and applying a voltage. It is. “Outside the discharge space” refers to a space that is not the discharge space.

  The form of the discharge space is not particularly limited, and may be, for example, a slit formed by opposing plate electrode pairs or a space formed in a circumferential shape between two cylindrical electrodes. Further, the excitation discharge gas and the thin film forming gas may be supplied so as to be in contact with each other, and the supply direction may be parallel flow, counter flow, or flow so as to intersect diagonally.

  In the present invention, “under atmospheric pressure or a pressure near atmospheric pressure” refers to a pressure of 20 kPa to 110 kPa. In this invention, the more preferable pressure between the electrodes which apply a voltage is 70 kPa-140 kPa.

  In the invention according to claims 1 to 11, a thin film is formed on the glass substrate by contacting the thin film forming gas with the excitation discharge gas to generate an indirect excitation gas, and exposing the glass substrate to the indirect excitation gas. Therefore, it can be manufactured without going through a drying process, and coating unevenness does not occur.

  In the invention according to claims 12 and 13, indirect excitation gas is generated by bringing a thin film forming gas into contact with the excitation discharge gas, and the glass substrate is exposed to the indirect excitation gas to form a thin film on the glass substrate. The window glass without coating unevenness can be produced without going through a drying step.

  In the invention described in claim 14, since the thin film forming gas discharge port is closer to the glass substrate supported by the substrate support device than the excited discharge gas discharge port, the thin film forming gas is located near the glass substrate. The excited discharge gas does not directly contact the glass substrate due to the presence of the thin film forming gas. Therefore, damage to the glass substrate due to the excited discharge gas can be suppressed, and a higher performance and uniform thin film can be formed on the glass substrate.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples. The following description may include assertive expressions for terms and the like, but it shows preferred examples of the present invention and limits the meaning and technical scope of the terms of the present invention. Not what you want.

FIG. 1 is a sectional view of a window glass according to the present invention.
As shown in FIG. 1, the vehicle window glass 20 has a glass substrate 21, and has a structure in which an antifouling thin film 22 is formed on the surface of the glass substrate 21. The glass base material 21 is used as a raw material for glass for car windows of vehicles such as automobiles and trains, and is preferably used as a windshield or side glass (door glass) for automobiles.

  Examples of the glass substrate 21 include inorganic glass and organic glass having functional groups (hydroxyl group, amino group, thiol group, etc.) on the surface. For example, soda lime glass widely used as a plate glass material is made of glass. It can be used as the material 21. The glass substrate 21 may be laminated glass, tempered glass, or the like, and a film (a film other than the thin film 22) may be formed on the surface by various methods such as a vapor deposition method, a sputtering method, and a wet method. The glass substrate 21 preferably has a surface on which the thin film 22 is formed of an inorganic compound, or a main component of the surface on which the thin film 22 is formed of a metal oxide such as silica.

  The surface of the glass substrate 8 may be pretreated before the thin film 22 is formed. Examples of the pretreatment include acid treatment with diluted hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, sodium hydroxide aqueous solution, and the like. There are alkali treatment by, and treatments such as plasma irradiation, corona irradiation and electron beam irradiation. When the surface of the glass substrate 21 is pretreated, the adhesion between the surface of the glass substrate 21 and the thin film 22 can be improved.

  The thin film 22 is a film formed by chemically depositing a film-forming gas (see below). Specifically, the discharge gas G (see FIG. 2) is discharged into the discharge space under a pressure at or near atmospheric pressure. The thin film forming gas M (see FIG. 2) containing the raw material is made of glass so that the excited discharge gas G ′ (see FIG. 2) introduced into the region A (see FIG. 2) and excited does not directly contact the glass substrate 21. The glass substrate 21 is indirectly excited by being sandwiched between the base material 21 and the excitation discharge gas G ′, and the thin film forming gas M is indirectly excited by bringing it into contact with the excitation discharge gas G ′ in the region B outside the discharge space (see FIG. 2). It is formed on the surface of the glass substrate 21 by being exposed to the gas N (see FIG. 2). The thin film 22 is excellent in water slidability, abrasion resistance, UV resistance, and the like, and improves general functions required for glass for vehicle windows.

Next, a vehicle window glass manufacturing apparatus for manufacturing the vehicle window glass 20 will be described.
FIG. 2 is a cross-sectional view showing a vehicle window glass manufacturing apparatus, and more specifically, a cross-sectional view showing a thin film forming apparatus 1 for forming a thin film 22 on a glass substrate 21.

  As shown in FIG. 2, a thin film forming apparatus 1 as a vehicle window glass manufacturing apparatus mainly includes two flat plate electrodes 2 and 3 as opposed electrodes arranged so as to face each other, and flat plate electrodes 2 and 2. 3 includes a high-frequency power source 5 as a voltage applying means for applying a high-frequency electric field between the three, and a base material supply device 6 that supplies the glass base material 21 while supporting it. Discharge gas supply means (not shown) for supplying the region A, thin film formation gas supply means (not shown) for supplying the thin film forming gas M to the region B outside the discharge space, and the temperatures of the plate electrodes 2 and 3 are controlled. Electrode temperature adjusting means (not shown).

  The thin film forming apparatus 1 includes an L-shaped first cylindrical body 10 that forms a flow path for the discharge gas G, and an L-shaped second cylindrical body 11 that forms a flow path for the thin film forming gas M. The first cylinder 10 and the second cylinder 11 extend while being adjacent to each other. In the thin film forming apparatus 1, the first cylinder 10 and the second cylinder 11 are configured to merge at the ends of each other, and the discharge space outside region B is formed at the merged portion.

  A discharge gas inlet 13 for introducing the discharge gas G into the first cylinder 10 is formed above the first cylinder 10, and the excitation discharge gas G ′ is discharged into the discharge space below the first cylinder 10. An excited discharge gas discharge port 16 that discharges to the outer region B is formed. On the other hand, a thin film forming gas inlet 15 for introducing the thin film forming gas M into the second cylindrical body 11 is formed above the second cylindrical body 11, and the thin film forming gas M is formed below the second cylindrical body 11. Is formed into the thin film forming gas discharge port 17 for discharging the gas to the region B outside the discharge space.

  In the thin film forming apparatus 1, the excitation discharge gas discharge port 16 and the thin film formation gas discharge port 17 are located closer to the substrate supply device 6 than the excitation discharge gas discharge port 16. The discharge gas discharge port 16 is arranged at a position farther from the substrate supply device 6 than the thin film forming gas discharge port 17. Therefore, the excited discharge gas G ′ discharged from the excited discharge gas discharge port directly contacts the glass substrate 21 of the substrate supply device 6 only by contacting the thin film forming gas M in the region B outside the discharge space. There is nothing.

  Two plate electrodes 2 and 3 are provided in the middle of the first cylinder 10. As shown in FIG. 2, a region having the dielectric 7 between the plate electrodes 2 and 3 and indicated by hatching on the plate electrodes 2 and 3 is the discharge space region A, and is inside the first cylinder 10. A discharge space region A is formed. In the thin film forming apparatus 1, the discharge gas G is introduced into the discharge space region A in the first cylinder 10 to excite the discharge gas G, and the thin film is formed in the second cylinder 11 in which the plate electrodes 2 and 3 are not installed. A forming gas M is introduced.

  In the thin film forming apparatus 1, when the discharge gas G and the thin film forming gas M are introduced into the cylinders 10 and 11, the excited discharge gas G ′ and the thin film forming gas M that are excited by the discharge gas G are supplied to the plate electrode 2. The indirect excitation gas N is diffused on the surface of the glass substrate 21 as a indirectly excited gas N by contacting in the discharge space outside region B where 3 does not exist, and a thin film 22 is formed on the glass substrate 21. Yes. In the thin film forming apparatus 1, the excitation discharge gas G ′ does not directly contact the glass substrate 21, but the indirect excitation gas N contacts the glass substrate 21. Compared with the case where it does, the damage with respect to the glass base material 21 can be made much smaller.

  The thin film forming apparatus 1 can process not only a sheet-like glass substrate 21 such as a support but also glass substrates 21 having various sizes and shapes. The thin film 22 can also be formed on the glass substrate 21 having a shape with a certain surface.

  The substrate supply device 6 as a substrate support device is disposed in the vicinity of the discharge space outside region B, and supports the glass substrate 21 with the surface of the glass substrate 21 exposed to the discharge space outside region B. ing. In the thin film forming apparatus 1, the glass base material 21 is installed on one side of the rotatable polygonal base material supply apparatus 6 shown in FIG. 2 to form a thin film 22. If another glass substrate 21 is installed on the other side of the substrate supply device 6, the thin film 22 can be continuously formed on each glass substrate 21.

  In the thin film forming apparatus 1, for example, an organometallic compound having an organic group having fluorine atoms is used as a thin film forming raw material of the thin film 22, and the excitation discharge gas G ′ and the thin film forming gas M are brought into contact with each other in the discharge space outside region B. By using the indirect excitation gas N, the thin film 22 having excellent water repellency, oil repellency, abrasion resistance, UV resistance and the like can be formed on the glass substrate 21 even after long-term storage.

  The pair of flat plate electrodes 2 and 3 is composed of a metal base material and a dielectric 7, and the metal base material is lined to cover the dielectric material 7 having an inorganic property, and the metal base material is ceramics. After thermal spraying, a combination of covering the dielectric 7 sealed with a substance having an inorganic property may be used. As the metal base material, metals such as titanium, copper, gold, silver, platinum, stainless steel, aluminum, and iron can be used, but stainless steel or titanium is preferable. Dielectric lining materials include silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Of these, borate glass is preferable because it is easy to process. Moreover, as a ceramic used for thermal spraying of the dielectric 7, alumina is preferable, and it is preferable to perform a sealing treatment with silicon oxide or the like. Further, as the sealing treatment, the alkoxysilane-based sealing material can be made inorganic by a sol-gel reaction.

  In the thin film forming apparatus 1, the high frequency power source 5 is connected to one flat plate electrode 2 of the pair of flat plate electrodes 2 and 3, the other flat plate electrode 3 is grounded by a ground 9, and An electric field can be applied. In the thin film forming apparatus 1, the pair of flat plate electrodes 2 and 3 have a flat plate shape, but one or both of the flat plate electrodes 2 and 3 as the counter electrodes are formed as hollow cylindrical electrodes or prismatic electrodes. A configuration may be adopted in which a voltage is applied between the electrodes.

  The thin film forming apparatus 1 applies a voltage between the plate electrodes 2 and 3 by a high frequency power source 5. The high-frequency power source 5 is not particularly limited, but as the high-frequency power source 5 that can be used for forming the antifouling thin film 22, a high-frequency power source (50 kHz) manufactured by Shinko Electric, a high-frequency power source manufactured by HEIDEN Laboratory (continuous mode use, 100 kHz), Pearl Industrial High Frequency Power Supply (200 kHz), Pearl Industrial High Frequency Power Supply (800 kHz), Pearl Industrial High Frequency Power Supply (2 MHz), JEOL High Frequency Power Supply (13.56 MHz), Pearl Industrial High Frequency Power Supply (27 MHz), manufactured by Pearl Industrial It is preferable to use a high frequency power source (150 MHz) or the like. Further, as the high-frequency power source 5, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.

The frequency of the high-frequency electric field applied between the flat plate electrodes 2 and 3 when forming the antifouling thin film 22 is not particularly limited, but is preferably 0.5 kHz or more and 2.45 GHz or less. The power supplied between the flat plate electrodes 2 and 3 is preferably 0.1 W / cm ² or more, and more preferably 50 W / cm ² or less. However, the voltage application area (cm ² ) in the plate electrodes 2 and 3 refers to the area in which discharge occurs. The high frequency voltage applied between the plate electrodes 2 and 3 may be an intermittent pulse wave or a continuous sine wave.

  In the thin film forming apparatus 1, the discharge space region A may be formed between the flat plate electrodes 2 and 3 by applying an electric field between the flat plate electrodes 2 and 3 by two or more high-frequency power sources 5.

  The distance between the plate electrodes 2 and 3 (see gap 1 in FIG. 1) is determined in consideration of the thickness of the dielectric 7 on the metal base material, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the dielectric 7 and the other electrode when the dielectric 7 is installed on one of the flat electrodes 2 and 3, and the dielectric 7 is installed on both the flat electrodes 2 and 3 In any case, the distance between the dielectrics 7 is preferably 0.1 mm to 20 mm, more preferably 0.2 to 10 mm, from the viewpoint of uniform discharge.

Next, the operation of the thin film forming apparatus 1 and the method for forming the thin film 22 on the glass substrate 21 will be described.
First, the discharge gas supply means introduces the discharge gas G into the first cylinder 10 from the discharge gas introduction port 13, and causes the discharge gas G to exist in the discharge space region A under atmospheric pressure or near atmospheric pressure.

  Thereafter, a high frequency voltage is applied between the flat plate electrodes 2 and 3 by the high frequency power source 5 to excite the discharge gas G present in the discharge space region A, thereby generating an excited discharge gas G '. The excited discharge gas G ′ is pressed by the discharge gas G newly introduced into the first cylinder 10 from the discharge gas supply means, and is discharged from the excited discharge gas discharge port 16 to the region B outside the discharge space.

  At substantially the same time, the thin film forming gas supply means introduces the thin film forming gas M into the second cylinder 11 from the thin film forming gas inlet 15. The introduced thin film forming gas M is pressed by the thin film forming gas M newly introduced from the thin film forming gas supply means, as in the case of the discharge gas G, and is discharged from the thin film forming gas discharge port 17 to the region B outside the discharge space. To be released.

  In the region B outside the discharge space, the excitation discharge gas G 'and the thin film forming gas M come into contact with each other to generate indirect excitation gas N. Here, in the region B outside the discharge space, since the thin film forming gas discharge port 17 is closer to the base material supply device 6 than the excited discharge gas discharge port 16, the thin film forming gas M discharged from the thin film forming gas discharge port 17. Exists in the vicinity of the glass substrate 21 on the substrate supply device 6, and due to the influence of the thin film forming gas M, the excited discharge gas G ′ released from the excitation discharge gas discharge port 17 is converted into the glass on the substrate supply device 6. It does not contact the base material 21. In other words, in the region B outside the discharge space, the thin film forming gas M is divided between the substrate 21 and the excitation discharge gas G ′ on the substrate supply device 6 so that the excitation discharge gas G ′ does not directly contact the glass substrate 21. The indirect excitation gas N is generated by being indirectly excited by being sandwiched and brought into contact with the excitation discharge gas G ′.

  In this state, the thin film forming apparatus 1 operates the base material supply device 6 to expose the glass base material 21 to the indirectly excited gas N generated in the discharge space outside region B, so that the thin film 22 is formed on the surface of the glass base material 21. Form. With such a configuration, the vehicle window glass 20 according to the present invention is manufactured. That is, the vehicle window glass 20 manufactured here is a glass in which a thin film 22 is formed on a glass base material 21, and more specifically, the glass base material 21 is exposed to the indirect excitation gas N and applied to the surface of the glass base material 21. A thin film 22 is formed.

  In the thin film forming apparatus 1 described above, the excited discharge gas G ′, which is excited by introducing the discharge gas G into the discharge space region A under atmospheric pressure or near atmospheric pressure, and the thin film forming gas M are discharged from the discharge space. The glass 20 for vehicle windows is manufactured by forming the thin film 22 on the glass base material 21 by making it contact in the area | region B, making it the indirect excitation gas N, and exposing the glass base material 21 to the indirect excitation gas N. Therefore, in the thin film forming apparatus 1, the vehicle window glass 20 without coating unevenness can be manufactured without going through a drying process.

  Moreover, since the glass substrate 21 manufactured by the thin film forming apparatus 1 is exposed to the indirect excitation gas N, the thin film 22 is formed on the surface of the glass substrate 21 without passing through the drying step. Can be manufactured without causing coating unevenness. The thin film 22 formed on the glass substrate 21 is excellent in water drop sliding resistance, abrasion resistance, UV resistance, etc., and the car window glass 20 can be applied as glass for car windows of vehicles such as automobiles and trains. In particular, it can be suitably used as a windshield or side glass of an automobile.

  In this embodiment, the thin film 22 is formed by exposing the glass substrate 21 to the indirect excitation gas N. However, before the thin film 22 is formed, the glass substrate 21 is moved to the discharge space region A or the excited discharge gas G ′. The glass substrate 21 may be subjected to surface treatment by exposure (see FIGS. 3 and 4. A pretreatment device for the glass substrate 21 will be described later). For example, when the raw material is an alkoxide, a hydrophilic treatment by exposure to the discharge space region A or the excited discharge gas G ′ is preferably used. Further, before the thin film 22 is formed, the surface of the glass substrate 21 may be previously subjected to a charge removal process, and further dust may be removed. Although the static elimination means and the dust removal means after the static elimination treatment are not shown, as the static elimination means, a plurality of positive and negative ion generation static elimination electrodes and the glass substrate 21 are sandwiched in addition to the normal blower type and contact type. You may use the high-density static elimination system (Unexamined-Japanese-Patent No. 7-263173) which provided the static elimination apparatus which made the ion attraction electrode oppose, and the positive / negative DC type static elimination apparatus after that. Examples of the dust removal means after the charge removal treatment include a non-contact type jet-type depressurization type dust removal apparatus (Japanese Patent Laid-Open No. 7-60211) and can be preferably used, but are not limited thereto.

  Next, a pretreatment apparatus that performs pretreatment of the glass substrate 21 will be described with reference to FIGS. 3 and 4. However, in the following, the members described above are denoted by the same reference numerals as those described above, and detailed descriptions of the members are omitted.

FIG. 4 is a schematic diagram illustrating an example of a preprocessing device.
As shown in FIG. 4, the pretreatment device 40 includes two plate electrodes 2 and 3 whose inner surfaces are covered with a dielectric 7, the discharge gas supply means, the electrode temperature adjustment means, and the like. The plate electrode 2 is connected to a high frequency power source 5, the plate electrode 3 is grounded by a ground 9, and a discharge space region A is formed between the plate electrodes 2 and 3.

  A belt 12 is provided below the discharge space region A. The belt 12 constitutes a part of a belt conveyor, and scans so as to reciprocate in only one direction or both directions from the right side to the left side (or from the left side to the right side) in FIG. 3 while supporting the glass substrate 21. It is.

  When the pretreatment of the surface of the glass substrate 21 (surface on which the thin film 22 is formed) is performed using the pretreatment device 40, a high frequency is applied between the flat plate electrodes 2 and 3 while introducing the discharge gas G into the discharge space region A. A voltage is applied by the power source 5 to generate the excited discharge gas G ′. In this state, the belt 12 is operated to expose the discharge gas G ′ to the glass substrate 21 while scanning the glass substrate 21 in the horizontal direction. Thereby, the surface treatment of the glass base material 21 can be performed.

  FIG. 4 is a schematic view showing another example of the pre-processing apparatus.

  As shown in FIG. 5, the pretreatment device 50 includes two flat plate electrodes 2 and 3, the discharge gas supply means, the electrode temperature adjustment means, and the like. The plate electrodes 2 and 3 are supported in a horizontal direction at a predetermined distance from each other, and the inner surface of the plate electrode 2 is covered with a dielectric 7. The plate electrode 2 is connected to a high frequency power source 5, the plate electrode 3 is grounded by a ground 9, and a discharge space region A is formed between the plate electrodes 2 and 3.

  When performing the pretreatment of the surface of the glass substrate 21 (surface on which the thin film 22 is formed) using the pretreatment device 50, first, the glass substrate 21 is placed (set) on the plate electrode 3, Thereafter, the glass substrate 21 is exposed to the discharge space region A by applying a voltage between the plate electrodes 2 and 3 by the high frequency power source 5 while introducing the discharge gas G between the plate electrodes 2 and 3. Thereby, the surface treatment of the glass base material 21 can be performed.

  Hereinafter, the usefulness of the glass for car windows in which a thin film is actually formed on a glass substrate using the thin film forming apparatus described in the above embodiment will be specifically described. However, the scope of the invention is not limited to these.

<< Preparation of thin film (antifouling film) formation sample >>
[Preparation of Sample 1: Present Invention]
(Glass substrate)
Float flat tempered glass (3.5 mm thickness) was used as the glass substrate.

(Thin film formation)
Using a thin film forming apparatus similar to the thin film forming apparatus 1 shown in FIG. 2, an antifouling thin film was formed on the glass substrate. The thin film was formed for 1 minute. The following gas type A was used as the discharge gas introduced from the discharge gas inlet, and the following gas type B was used as the thin film forming gas introduced from the thin film forming gas inlet.

<Gas type A: Discharge gas>
Nitrogen gas 98.5% by volume
Hydrogen gas 1.5% by volume
<Gas type B: Thin film forming gas>
Nitrogen gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in nitrogen gas by a vaporizer manufactured by STEC.)
<Gas species supply ratio and mixing>
A discharge gas and a thin film forming gas are supplied into each cylinder at a gas type A: gas type B = 2: 1 (volume ratio), the excited discharge gas and the thin film forming gas are brought into contact with each other in the region outside the discharge space, and then indirectly excited. Gas was supplied onto the glass substrate.

<Plate electrode>
Stainless steel SUS316 is used as the plate electrode, and further, the surface of the plate electrode is spray-coated with alumina ceramic until the thickness becomes 1 mm, and then a coating solution in which an alkoxysilane monomer is dissolved in an organic solvent is applied to the alumina ceramic coating and dried. After that, a dielectric was formed by heating at 150 ° C. and performing a sealing treatment. A high-frequency power source was connected to the portion of the plate electrode that was not covered with a dielectric, and grounded.

<Gap>
Table 1 shows the gap distance between the excited discharge gas discharge port and the thin film forming gas (see gaps 1 and 2 in FIG. 1).

<High frequency power supply>
A high frequency power source (40 kHz) manufactured by HEIDEN Laboratory was used as the high frequency power source, and a discharge power of 7 W / cm ² was applied between the plate electrodes.

[Preparation of Sample 2: Present Invention]
In the preparation of the sample 1, the gas type A, the gas type B, the gap of the excited discharge gas discharge port and the gap of the gap of the thin film forming gas discharge port were changed as shown in the following and Table 1, Similarly, Sample 2 was produced.

<Gas type A: Discharge gas>
Nitrogen gas 100% by volume
<Gas type B: Thin film forming gas>
Nitrogen gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in nitrogen gas by a vaporizer manufactured by STEC.)

[Preparation of Sample 3: Present Invention]
The preparation of Sample 2 is the same as the preparation of Sample 2 except that the gas type A, the gas type B, the gap of the excited discharge gas discharge port and the gap of the thin film forming gas discharge port are changed as shown in Table 1 and Table 1 below. Thus, Sample 3 was produced.

<Gas type A: Discharge gas>
Argon gas 98.5% by volume
Hydrogen gas 1.5% by volume
<Gas type B: Thin film forming gas>
Argon gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in argon gas by a vaporizer manufactured by STEC.)

A high frequency power source (13.56 MHz) manufactured by Pearl Industry was used as the high frequency power source, and discharge power was applied at 7 W / cm ² .

[Preparation of Sample 4: Present Invention]
Prior to forming the thin film, the glass substrate was subjected to the following pretreatment A using a pretreatment device similar to the pretreatment device 40 shown in FIG. Otherwise, Sample 4 was prepared in the same manner as Sample 1.

Pretreatment A: Before exposing the glass substrate to the indirect excitation gas, nitrogen: oxygen = 99: 1 (volume ratio) is caused to flow into the discharge space region as a discharge gas, and the glass substrate is exposed to the excitation discharge gas for 3 seconds. did. A high frequency power source (frequency: 40 kHz) manufactured by HEIDEN Laboratory was used as the high frequency power source, and the discharge output was set to 10 W / cm ² .

[Preparation of Sample 5: Present Invention]
Prior to forming the thin film, the glass substrate was subjected to the following pretreatment B using a pretreatment device similar to the pretreatment device 50 shown in FIG. Otherwise, Sample 5 was prepared in the same manner as Sample 2.

Pretreatment B: Before exposing the glass substrate to the indirectly excited gas, nitrogen: oxygen = 99: 1 (volume ratio) is allowed to flow into the discharge space region as a discharge gas, and the glass substrate is exposed to the excited discharge gas for 3 seconds. did. A high frequency power source (frequency: 40 kHz) manufactured by HEIDEN Laboratory was used as the high frequency power source, and the discharge output was set to 5 W / cm ² .

[Preparation of Comparative Samples 1-3: Comparative Example]
In the thin film forming apparatus similar to the thin film forming apparatus shown in FIG. 2, two flat plate electrodes as counter electrodes are provided in the second cylinder (the flat electrode is not provided in the first cylinder). A thin film was formed on a glass substrate using a thin film forming apparatus in which the flow paths of the film and the thin film forming gas were switched. The thin film was formed for 1 minute. As shown in Table 1, gas type A was used as the discharge gas, and gas type B was used as the thin film forming gas. The gaps of the gas type A, gas type B, excited discharge gas discharge port, and thin film forming gas discharge port were changed as shown in Table 1, and the other cases were made on the glass substrate in the same manner as in the preparation of Sample 1. A thin film was formed, and comparative samples 1 to 3 were obtained.

  Table 1 shows main characteristics of the thin film forming methods of Samples 1 to 5 and Comparative Samples 1 to 3.

Subsequently, the evaluation shown below was implemented about each produced samples 1-5 and each comparative samples 1-3.
<< Measurement and evaluation of characteristic values of each sample >>
(Measurement of contact angle)
For each sample 1 to 5 and each comparative sample 1 to 3, using a contact angle meter CA-W manufactured by Kyowa Interface Science Co., Ltd., contact angle with water and hexadecane on the surface of the thin film in an environment of 23 ° C. and 55% The corners were measured. The measurement was performed at 10 locations at random and the average value was obtained. Table 2 shows the measurement results of Samples 1 to 5 and Comparative Samples 1 to 3.

[Evaluation of sliding down]
The samples 1 to 5 and the comparative samples 1 to 3 were held horizontally with the surface on which the thin film was formed facing upward, and 5 μl of water droplets were dropped on an arbitrary place on the surface on which the thin film was formed. Thereafter, the samples 1 to 5 and the comparative samples 1 to 3 are slowly tilted, and the tilt angles of the samples 1 to 5 and the comparative samples 1 to 3 when the water droplet starts to move (slide) are determined. As measured. Table 2 shows the measurement results of Samples 1 to 5 and Comparative Samples 1 to 3.
In Table 2, the sliding angles of Samples 1 to 5 and Comparative Samples 1 to 3 are indicated by ◎, ○, and X, respectively, according to the following.
◎: 15 ° or less ○: 15-20 °
×: 30 ° or more

[Evaluation of wear resistance]
For each of Samples 1 to 5 and Comparative Samples 1 to 3, while water is dripped onto the surface on which the thin film is formed, the automobile wiper is slid on the surface 100,000 times (one reciprocation is one time). The contact angle was measured. A load of 105 g was applied to the automobile wiper. Table 2 shows the measurement results of Samples 1 to 5 and Comparative Samples 1 to 3.
In Table 2, the contact angles of Samples 1 to 5 and Comparative Samples 1 to 3 are indicated by ◯, Δ, and X, respectively, according to the following.
○: 100 ° or more Δ: 100-85 °
×: 85 ° or less

[Evaluation of UV resistance]
About each sample 1-5 and each comparative sample 1-3, 60 mW / cm < ² > super UV (Ultra Violet) was irradiated for 2000 hours, and the contact angle after that was measured. Table 2 shows the measurement results of Samples 1 to 5 and Comparative Samples 1 to 3.
In Table 2, the contact angles of Samples 1 to 5 and Comparative Samples 1 to 3 are indicated by ◎, ○, and X, respectively, according to the following.
◎: 110 ° or more ○: 110-100 °
×: 90 ° or less

[Measurement of surface resistivity]
After each sample 1-5 and each comparative sample 1-3 were conditioned for 24 hours in an environment of 23 ° C. and 55% RH, each sample 1-5 and each comparison were compared using a terraohm meter model VE30 manufactured by Kawaguchi Electric Co., Ltd. The surface specific resistance values of Samples 1 to 3 were measured. In the measurement, two electrodes (parts in contact with each of the samples 1 to 5 and the comparative samples 1 to 3 are 1 cm × 5 cm) are arranged at an interval of 1 cm, and each of the samples 1 to 5 and the comparative samples 1 to 3 are arranged on the electrode. Was measured, and the value obtained by multiplying the measured value by 5 was defined as the surface specific resistance value (Ω / □) of each of Samples 1 to 5 and Comparative Samples 1 to 3. As a result, each sample 1 to 5 had a surface specific resistance value of 1 × 10 ¹² Ω / □ or less, and each comparative sample 1 to 3 had a surface specific resistance value higher than 1 × 10 ¹² Ω / □.

  As shown in Table 2, excellent or good measurement results can be obtained from each of the samples 1 to 5 in any of the measurement of the contact angle and the evaluation of sliding property, wear resistance and UV resistance. No good results were obtained from 3. From this measurement result, it was found that Samples 1 to 5 of the present invention were superior in water droplet sliding property, abrasion resistance, and UV resistance as compared with Comparative Samples 1 to 3 as comparative examples. Therefore, if only the indirect excitation gas is brought into contact with the glass substrate so that the excitation discharge gas does not directly contact the glass substrate, the glass substrate can be prevented from being damaged by the excitation discharge gas, and a higher performance and uniform thin film can be obtained. It can be formed on a substrate. And it turned out that it is very useful to use the glass base material which formed the thin film by such a method as glass for vehicle windows.

It is sectional drawing of the glass for vehicle windows. It is sectional drawing of a thin film forming apparatus. It is the schematic which shows an example of the pre-processing apparatus of a glass base material. It is the schematic which shows the other example of the pre-processing apparatus of a glass base material.

Explanation of symbols

1,30 Thin film forming equipment (vehicle window glass manufacturing equipment)
2, 3 Flat plate electrode (counter electrode)
5 High frequency voltage (voltage application means)
20 Car Window Glass 21 Glass Base Material 22 Thin Film 40, 50 Pretreatment Device

Claims (14)

  The thin film forming gas containing the raw material and the glass substrate are excited so that the excited discharge gas excited by introducing the discharge gas into the discharge space under atmospheric pressure or near atmospheric pressure does not directly contact the glass substrate. Sandwiched between the discharge gas, the thin film forming gas is indirectly excited by contacting the excited discharge gas outside the discharge space, and the glass substrate is exposed to the indirectly excited indirect excited gas on the glass substrate. A window glass characterized in that a thin film is formed.   The glass for a car window according to claim 1, wherein the discharge space is formed by applying a high frequency voltage between opposing electrodes.   The window glass according to claim 1 or 2, wherein the discharge gas contains nitrogen and / or a rare gas.   The glass for a car window according to any one of claims 1 to 3, wherein the raw material of the thin film forming gas contains an organometallic compound, a metal halide and / or an organofluorine compound.   The glass for car windows according to claim 4, wherein a raw material of the thin film forming gas is an organometallic compound having an organic group having a fluorine atom.   The glass for vehicle windows according to any one of claims 1 to 5, wherein the surface of the glass substrate contains an inorganic compound.   The glass for vehicle windows according to any one of claims 1 to 6, wherein a main component of the surface of the glass substrate is a metal oxide.   The glass substrate is exposed to the indirect excitation gas after being subjected to pretreatment by being exposed to the discharge space or the excitation discharge gas. Car window glass. The surface specific resistance value is 1 × 10 ¹² Ω / □ or less under conditions of 23 ° C. and 55% RH, and the glass for vehicle windows according to any one of claims 1 to 8.   The window glass according to any one of claims 1 to 9, wherein the glass substrate is used as a windshield of an automobile.   The glass for vehicle windows according to any one of claims 1 to 9, wherein the glass substrate is used as a side glass of an automobile. In the manufacturing apparatus of the glass for vehicle windows which manufactures the glass for vehicle windows as described in any one of Claims 1-11,
Counter electrodes arranged to face each other;
Voltage applying means for applying a high-frequency voltage between the opposing electrodes;
With
Excited discharge gas, which is excited by introducing a discharge gas into the discharge space between the counter electrodes to which a high-frequency voltage is applied by the voltage application means under atmospheric pressure or a pressure near atmospheric pressure, does not directly contact the glass substrate. The thin film forming gas containing the raw material is sandwiched between the glass substrate and the excited discharge gas, and the thin film forming gas is indirectly excited by contacting the excited discharge gas with the excited discharge gas outside the discharge space. An apparatus for producing glass for vehicle windows, wherein a thin film is formed on the glass substrate by exposure to the indirectly excited gas that has been indirectly excited. The vehicle window glass manufacturing apparatus according to claim 12,
An apparatus for manufacturing glass for a car window, wherein at least one of the counter electrodes is covered with a dielectric. In the vehicle window glass manufacturing apparatus according to claim 12 or 13,
An excited discharge gas discharge port for discharging the excited discharge gas;
A thin film forming gas discharge port for discharging the thin film forming gas;
A substrate support device for supporting the glass substrate;
With
The thin film forming gas discharge port is closer to the glass base material supported by the base material support device than the excited discharge gas discharge port.

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