JP2016204217A - Multiple glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multiple glass fitted with a transparent conductive film in which secular deterioration in conductivity is suppressed even in the case of being placed under a high temperature-high moisture environment.SOLUTION: Provided is a multiple glass, in a multiple glass made of two or more glass plates and a resin intermediate film interposed in the joining face between the glass plates each other, in which the joining face of at least one of the glass plates is formed with a transparent conductive film, the resin intermediate film being an intermediate film containing a specified modified block copolymer hydride introduced with an alkoxysilyl group. The block copolymer is made of a block essentially consisting of a structural unit derived from an aromatic vinyl compound and a block essentially consisting of linear conjugated diene compound, and 90% or more of the carbon-carbon unsaturated bonds of the main chain and the side chains and the unsaturated bonds of the aromatic ring is hydrogenated.SELECTED DRAWING: None

Description

  The present invention relates to a multilayer glass having a transparent conductive film, and more particularly to a multilayer glass having a transparent conductive film coated with a specific modified block copolymer hydride and having excellent durability.

Glass having a transparent conductive film formed on its surface (multi-layer glass with a transparent conductive film) is used for liquid crystal displays, organic EL displays, touch panels, plasma displays, solar cells, anti-fogging automotive glass, thermal barrier glass, and the like. For example, in an electric vehicle that is expected to spread in the future from the viewpoint of environmental protection, an anti-fogging function using exhaust heat cannot be added. It is desired. As a thin film for providing a heat generating function, transparent conductive films such as ITO (In ₂ O ₃ (Sn)), SnO _X , ZnO _X , Sb, F-doped SnO _X , and Al-doped ZnO _X are known.
However, in a multi-layer glass using a transparent conductive film, the electrical resistance value of the transparent conductive film changes with time under high temperature and high humidity conditions, which may adversely affect the anti-fogging performance of the multi-layer glass. there were.

As countermeasures against this, Patent Document 1 discloses a change in electrical resistance by forming a layer made of metal, metal oxide, silicon oxide, or the like between a transparent conductive film formed on a glass surface and an intermediate film. A method for reducing the above is disclosed.
However, the method of forming a protective layer on the transparent conductive film is not an advantageous method for industrial production.

  In relation to the present invention, Patent Documents 2 and 3 disclose main and side chains of a block copolymer comprising a polymer block derived from an aromatic vinyl compound and a polymer block derived from a chain conjugated diene compound. The modified block copolymer hydride in which an alkoxysilyl group is introduced into the block copolymer hydride obtained by hydrogenating the carbon-carbon unsaturated bond and the carbon-carbon unsaturated bond of the aromatic ring is made of glass. It is disclosed that it is useful as an adhesive, low hygroscopicity, transparency, solar cell encapsulant, adhesive for multilayer glass, and the like.

JP-A-8-217499 WO2012 / 043708 pamphlet WO2013 / 176258 pamphlet

  This invention is made | formed in view of the prior art mentioned above, and it aims at providing the multilayer glass with a transparent conductive film which suppressed the time-dependent fall of electroconductivity also in a high-temperature, high-humidity environment.

  As a result of intensive studies to solve the above problems, the inventors of the present invention, in the double-layer glass using a glass having a transparent conductive film formed on the surface, the cause of the change in the electrical resistance value in a high temperature and high humidity environment, It was speculated that this was caused by the deterioration of the transparent conductive film due to moisture penetrating through the intermediate film. And based on this assumption, instead of the multilayer glass intermediate film using polyvinyl acetal conventionally used for general purposes, an intermediate using a specific modified block copolymer hydride in which an alkoxysilyl group is introduced By using the film, it was found that the change over time in the electrical resistance value of the transparent conductive film formed on the glass surface in a high temperature and high humidity environment was suppressed, and the present invention was completed.

Thus, according to the present invention, the following multilayer glasses (1) and (2) are provided.
(1) A composite film comprising two or more glass plates and a plastic intermediate film interposed between the bonding surfaces of these glass plates, wherein a transparent conductive film is formed on at least one of the bonding surfaces of these glass plates. In layer glass,
The plastic intermediate film has at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component and at least one heavy component having a structural unit derived from a chain conjugated diene compound as a main component. And the weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the weight fraction of the entire polymer block [B] in the entire block copolymer is The main-chain and side-chain carbon-carbon unsaturated bonds and fragrance of the block copolymer [C] in which the ratio of wA to wB (wA: wB) is 30: 70-60: 40 An intermediate containing a hydrogenated block copolymer [E] obtained by introducing an alkoxysilyl group into a block copolymer hydride [D] in which 90% or more of ring carbon-carbon unsaturated bonds are hydrogenated. Is a membrane Double glazing characterized and.
(2) At least the first glass plate, a transparent conductive film formed on the first glass plate, a resin intermediate film, and a multi-layer glass laminated in the order of the second glass plate,
a. The end of the transparent conductive film laminated on the first glass plate is disposed 2 mm or more apart over the entire circumference with respect to the end of the first glass plate,
b. The resin intermediate film has an area larger than the area of the transparent conductive film,
c. A multi-layer glass, wherein the transparent conductive film is covered with a resin intermediate film, and the end of the resin intermediate film is located 2 mm or more away from the end of the transparent conductive film over the entire periphery.

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it is set | placed on a high temperature, high humidity environment, the multilayer glass with a transparent conductive film by which the temporal change of the electrical resistance value was suppressed is provided.

Hereinafter, the multilayer glass with a transparent conductive film of the present invention will be described in detail.
The multi-layer glass with a transparent conductive film of the present invention comprises two or more glass plates and a plastic intermediate film interposed between the bonding surfaces of these glass plates, and at least one of the bonding surfaces of these glass plates. In the multilayer glass in which a transparent conductive film is formed on
The plastic interlayer is
At least two polymer blocks [A] mainly comprising a structural unit derived from an aromatic vinyl compound, and at least one polymer block [B] mainly comprising a structural unit derived from a chain conjugated diene compound. When the weight fraction of the whole polymer block [A] in the entire block copolymer is wA and the weight fraction of the whole polymer block [B] in the whole block copolymer is wB, The block copolymer [C] in which the ratio of wA to wB (wA: wB) is 30:70 to 60:40, the carbon-carbon unsaturated bond of the main chain and the side chain and the carbon-carbon bond of the aromatic ring Modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into a block copolymer hydride [D] in which 90% or more of the saturated bonds are hydrogenated (hereinafter referred to as “specific modified block copolymer weight”). Combined hydride [E May be referred to ".), Characterized in that an intermediate film containing.

1. Intermediate Film The intermediate film used in the present invention is formed from only the modified block copolymer hydride [E] as long as it contains at least the specific modified block copolymer hydride [E]. Alternatively, it may be molded from a resin composition containing a compounding agent described later in the modified block copolymer hydride [E].

The content of the modified block copolymer hydride [E] in the component constituting the intermediate film is usually 70% by weight or more, preferably 80% by weight or more, more preferably, relative to the total components constituting the intermediate film. 90% by weight or more.
When the content of the modified block copolymer hydride [E] is 70% by weight or more, the interlayer film is excellent in heat resistance, flexibility, low hygroscopicity, transparency, and adhesion to glass.

  The specific modified block copolymer hydride [E] comprises at least two polymer blocks [A] mainly comprising a structural unit derived from an aromatic vinyl compound and a structural unit derived from a chain conjugated diene compound. It is composed of at least one polymer block [B] as a main component, and the weight fraction of the whole polymer block [A] in the entire block copolymer is wA, and the block ratio of all polymer blocks [B] is The main chain and side chain of the block copolymer [C] in which the ratio of wA to wB (wA: wB) is 30:70 to 60:40 when the weight fraction of the whole polymer is wB This is obtained by introducing an alkoxysilyl group into the hydride of block copolymer [D] in which 90% or more of the carbon-carbon unsaturated bond and aromatic carbon-carbon unsaturated bond of hydrogen are hydrogenated.

(Block copolymer [C])
The block copolymer [C], which is a precursor of the modified block copolymer hydride [E], is a polymer containing at least two polymer blocks [A] and at least one polymer block [B]. is there. The number of polymer blocks [A] in the block copolymer [C] is usually 3 or less, preferably 2 in number.

The block form of the block copolymer [C] may be a chain type block or a radial type block, but a chain type block is preferred because of its excellent mechanical strength.
The most preferable form of the block copolymer [C] is [A]-[B]-[A] type triblock copolymer in which the polymer block [A] is bonded to both ends of the polymer block [B]. It is.

The polymer block [A] is mainly composed of a structural unit derived from an aromatic vinyl compound, and the content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 90% by weight. Above, preferably 95% by weight or more, more preferably 99% by weight or more.
When there are too few structural units derived from the aromatic vinyl compound in the polymer block [A], the heat resistance of the multilayer glass may be lowered.
The plurality of polymer blocks [A] may be the same as or different from each other as long as the above range is satisfied.

  Specific examples of the aromatic vinyl compound include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4- Styrenes having an alkyl group as a substituent such as t-butylstyrene and 5-t-butyl-2-methylstyrene; alkoxy groups as a substituent such as 3-methoxystyrene and 2-methoxy-4-isopropoxystyrene Styrenes; styrenes having a halogen atom as a substituent such as 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene; styrenes having an aryl group as a substituent such as 4-phenylstyrene; Among these, from the viewpoint of hygroscopicity, those that do not contain a polar group (styrene, styrenes having an alkyl group as a substituent, and styrenes having an aryl group as a substituent) are preferable, and are easy to obtain industrially. Styrene is particularly preferred.

Moreover, polymer block [A] can contain the structural unit derived from a chain conjugated diene and / or the structural unit derived from another vinyl compound as components other than the structural unit derived from an aromatic vinyl compound. The content is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less.
Examples of the chain conjugated diene and other vinyl compounds include those similar to the chain conjugated diene and other vinyl compounds that are structural units of the polymer block [B] described later.

The polymer block [B] has a structural unit derived from a chain conjugated diene compound as a main component, and the content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 80. % By weight or more, preferably 90% by weight or more, more preferably 95% by weight or more.
When the structural unit derived from the chain conjugated diene compound is in the above range, the thermal shock resistance and low-temperature adhesiveness of the multilayer glass of the present invention are excellent.

Moreover, as a component other than the structural unit derived from the chain conjugated diene compound in the polymer block [B], a structural unit derived from an aromatic vinyl compound and / or a structural unit derived from another vinyl compound can be included. The content is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less. When the content of the structural unit derived from the aromatic vinyl compound in the polymer block [B] increases, the flexibility of the adhesive resin layer at a low temperature decreases, and the thermal shock resistance of the multilayer glass may decrease.
When the block copolymer [C] has a plurality of polymer blocks [B], the polymer blocks [B] may be the same or different from each other as long as they satisfy the above range. May be.

  As the chain conjugated diene compound, a chain conjugated diene compound not containing a polar group is preferable from the viewpoint of hygroscopicity. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like. Among these, 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability.

  Examples of other vinyl compounds include chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, and unsaturated imide compounds. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen atom. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, C2-C20 chain olefins such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; C5-C20 cyclic olefins such as vinylcyclohexane and norbornene; 1,3-cyclohexadiene And those containing no polar group such as cyclic diene compounds such as norbornadiene;

In the block copolymer [C], the weight fraction of the total amount of the polymer block [A] in the block copolymer [C] is wA, and the total amount of the polymer block [B] is the block copolymer [C]. ], The ratio of wA to wB (wA: wB) is usually 30: 70-60: 40, preferably 35: 65-55: 45, more preferably 40: 60-50: 50.
When wA is too much, the heat resistance of the modified block copolymer hydride [E] is high, but the flexibility is low, and the adhesiveness to glass or metal is weak, and the glass of the thermal resin composition according to the present invention. There is a possibility that adhesion to metal and metal may be impaired.

  The molecular weight of the block copolymer [C] is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and usually 40,000 to 200. , Preferably 45,000 to 150,000, more preferably 50,000 to 100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the modified block copolymer hydride [E] has good heat resistance and mechanical strength, and the heat resistance and mechanical strength of the multilayer glass according to the present invention. Will not drop.

  The manufacturing method of block copolymer [C] is not specifically limited, A well-known method is employable. For example, a method of alternately polymerizing a monomer mixture containing an aromatic vinyl compound as a main component and a monomer mixture containing a chain conjugated diene compound as a main component by a method such as living anion polymerization; By sequentially polymerizing a monomer mixture containing as a main component and a monomer mixture containing a chain conjugated diene compound as a main component, and then coupling the ends of the polymer block [B] with a coupling agent, etc. Can get.

(Block copolymer hydride [D])
The block copolymer hydride [D] is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain of the block copolymer [C] and the carbon-carbon unsaturated bond of the aromatic ring. Is a molecule.
The hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance and durability of the modified block copolymer hydride [E], and the lower the heat resistance and durability of the multilayer glass according to the present invention.
The hydrogenation rate of the block copolymer hydride [D] can be determined by measuring ¹ H-NMR of the block copolymer hydride [D].

  There are no particular restrictions on the hydrogenation method or reaction mode of the unsaturated bond, and it may be carried out according to a known method, but a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction is preferred. Examples of such hydrogenation methods include the methods described in WO2011 / 096389 pamphlet, WO2012 / 043708 pamphlet and the like.

  After completion of the hydrogenation reaction, after removing the hydrogenation catalyst or the hydrogenation catalyst and the polymerization catalyst from the reaction solution, the block copolymer hydride [D] can be recovered from the resulting solution. Although the form of the recovered block copolymer hydride [D] is not limited, it can usually be formed into a pellet shape and used for the subsequent introduction reaction of alkoxysilyl groups.

  The molecular weight of the block copolymer hydride [D] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 50,000 to 150. , 000, more preferably 60,000 to 100,000. The molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the modified block copolymer hydride [E] has good heat resistance and mechanical strength, and the heat resistance and mechanical strength of the multilayer glass according to the present invention. Is preferable without lowering.

(Modified block copolymer hydride [E])
The modified block copolymer hydride [E], which is a main component constituting the interlayer film used in the multilayer glass of the present invention, is converted into the block copolymer hydride [D] in the presence of an organic peroxide. An alkoxysilyl group is introduced by reacting an ethylenically unsaturated silane compound. By introducing an alkoxysilyl group into the block copolymer hydride [D], it is possible to impart strong adhesion to glass or metal.

  Examples of the alkoxysilyl group include tri (C1-C6 alkoxy) silyl groups such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group Group, propyldimethoxysilyl group, propyldiethoxysilyl group, (C1-C20 alkyl) di (C1-C6 alkoxy) silyl group; phenyldimethoxysilyl group, phenyldiethoxysilyl group, (aryl ) Di (C1-C6 alkoxy) silyl group; and the like. The alkoxysilyl group is bonded to the block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. You may do it.

The amount of the alkoxysilyl group introduced into the block copolymer hydride [D] is usually 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [D]. 5 parts by weight, more preferably 0.5 to 3 parts by weight. When the introduction amount of the alkoxysilyl group is too large, the resulting modified block copolymer hydride [E] undergoes cross-linking between the alkoxysilyl groups decomposed with a small amount of moisture during storage, gelling, or melt molding There is a risk that the fluidity at the time is lowered, the temperature at which the intermediate film can be melt-extruded and molded becomes high, or the surface of the molded intermediate film becomes rough. Moreover, when there is too little introduction amount of an alkoxy silyl group, there exists a possibility that the adhesiveness with respect to the glass or metal of the intermediate film shape | molded may fall.
The introduction of the alkoxysilyl group can be confirmed by IR spectrum. Further, the amount introduced can be calculated by ¹ H-NMR spectrum.

  The ethylenically unsaturated silane compound to be used is not particularly limited as long as it is graft-polymerized with the block copolymer hydride [D] and introduces an alkoxysilyl group into the block copolymer hydride [D]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Loxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysila, 3-acryloxypropyltrimethoxy Silane and the like are preferably used. These ethylenically unsaturated silane compounds may be used alone or in combination of two or more.

  The amount of the ethylenically unsaturated silane compound used is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0 to 100 parts by weight of the block copolymer hydride [D]. 0.5 to 3 parts by weight.

As the peroxide, those having a one-minute half-life temperature of 170 to 190 ° C. are preferably used. For example, t-butyl cumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, Di (2-t-butylperoxyisopropyl) benzene or the like is preferably used. These peroxides may be used alone or in combination of two or more.
The amount of the peroxide used is generally 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [D]. 0.5 weight.

The method for reacting the block copolymer hydride [D] with the ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited. For example, an alkoxysilyl group can be introduced into the block copolymer hydride [D] by kneading at a desired temperature for a desired time in a biaxial kneader.
The kneading temperature by the biaxial kneader is usually 180 to 220 ° C, preferably 185 to 210 ° C, more preferably 190 to 200 ° C.
The heat kneading time is usually about 0.1 to 10 minutes, preferably about 0.2 to 5 minutes, and more preferably about 0.3 to 2 minutes.
What is necessary is just to knead | mix and extrude continuously so that temperature and residence time may become the said range. Although the form of the obtained modified block copolymer hydride [E] is not limited, it can usually be formed into a pellet shape and used for subsequent blending of additives.

  The molecular weight of the modified block copolymer hydride [E] is substantially the same as the molecular weight of the block copolymer hydride [D] used as a raw material because the amount of the introduced alkoxysilyl group is small. On the other hand, in order to react with the ethylenically unsaturated silane compound in the presence of peroxide, the cross-linking reaction and cleavage reaction of the polymer occur simultaneously, and the molecular weight distribution of the modified block copolymer hydride [E] is large. Become.

  The molecular weight of the modified block copolymer hydride [E] is a polystyrene-reduced weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 50,000 to 150,000, more preferably 60,000 to 100,000. The molecular weight distribution (Mw / Mn) is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. When Mw and Mw / Mn are within the above ranges, the heat resistance and mechanical strength of the modified block copolymer hydride [E] are maintained.

(Combination agent)
As a component constituting the interlayer film used in the double-layer glass of the present invention, various additives can be blended in addition to the main component, the modified block copolymer hydride [E].
Preferred additives include filling aids for adjusting fillability, lowering of bonding temperature, and adhesion to glass, ultraviolet absorbers for shielding ultraviolet rays, and antioxidants for improving processability, etc. And anti-blocking agents, light stabilizers for enhancing durability, and the like.

  As a filling aid for filling the intermediate film without gaps in the fine structure of the surface of the object to which the intermediate film is bonded, the block copolymer hydride [D] and / or the modified block copolymer hydride [E] are used. Those that can be dissolved or dispersed uniformly are preferred, and hydrocarbon polymers having a number average molecular weight of 300 to 5,000 are preferred.

  Specific examples of the hydrocarbon polymer include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, low molecular weight compounds such as ethylene / α-olefin copolymer and hydrides thereof; polyisoprene, Examples thereof include low molecular weight substances such as polyisoprene-butadiene copolymers and hydrides thereof. Filling aids can be used alone or in combination of two or more. Among these, a low molecular weight polyisobutylene hydride and a low molecular weight polyisoprene hydride are particularly preferable in terms of maintaining transparency and light resistance and being excellent in filling properties.

  The blending amount of the low molecular weight hydrocarbon polymer is usually 20 parts by weight or less, preferably 10 parts by weight or less with respect to 100 parts by weight of the modified block copolymer hydride [E]. When the amount of the low molecular weight hydrocarbon polymer is increased, the filling property is improved in the case of an interlayer film for a double-glazed glass, but the heat resistance tends to decrease or the effluent tends to increase. is there.

  The ultraviolet absorbers, antioxidants, antiblocking agents, light stabilizers and the like blended in the modified block copolymer hydride [E] can be used singly or in combination of two or more. . The compounding amount of these additives is usually 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less with respect to 100 parts by weight of the modified block copolymer hydride [E].

As the ultraviolet absorber, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, triazine compounds, and the like can be used.
As the antioxidant, phosphorus antioxidants, phenol antioxidants, sulfur antioxidants and the like can be used.
As the light stabilizer, a hindered amine light stabilizer or the like can be used.

  As a method of blending various additives into the modified block copolymer hydride [E], known methods that are generally used can be applied. For example, modified block copolymer hydride [E] pellets and compounding ingredients are mixed evenly using a mixer such as a tumbler, ribbon blender, Henschel type mixer, etc., and then continuously melted using a twin screw extruder or the like. A method of melt-mixing with a kneader and extruding into pellets, a modified block copolymer hydride [E], while continuously adding compounding agents from the side feeder with a twin-screw extruder equipped with a side feeder The modified block copolymer hydride [E] in which the compounding agent is uniformly dispersed can be produced by melt kneading, extruding, pelletizing, or the like.

(Interlayer film)
The intermediate film used in the present invention is used for the purpose of forming a modified block copolymer hydride [E] into a sheet and bonding at least two glass plates.

The method for forming the interlayer film is not particularly limited, and a known melt extrusion molding method, inflation molding method, calendar molding method, or the like can be applied.
The intermediate film formed from the modified block copolymer hydride [E] does not require the blending of an organic peroxide or a crosslinking aid for imparting thermal crosslinkability, and therefore has a wide range of melt molding temperature selection. . For example, when the intermediate film is formed by a melt extrusion molding method, the resin temperature is appropriately selected within the range of usually 170 to 250 ° C, preferably 180 to 240 ° C, more preferably 190 to 230 ° C. If the resin temperature is too low, the fluidity deteriorates, and the resulting intermediate film is liable to cause defects such as the skin and die line, and the extrusion speed of the intermediate film cannot be increased, which may be industrially disadvantageous. is there. If the resin temperature is too high, the adhesion of the interlayer film to the glass will be poor, or the storage stability of the interlayer film will be reduced, and the interlayer film will adhere to the glass after being stored for a long time in a normal temperature and humidity environment. May deteriorate.

  The thickness of the interlayer film is not particularly limited, but is usually in the range of 0.05 to 5 mm, preferably 0.1 to 4 mm, more preferably 0.2 to 3 mm. When the thickness of the intermediate film is smaller than 0.05 mm, the handleability of the intermediate film is inferior when laminated with glass, and workability may be reduced. In addition, when the thickness of the interlayer film is larger than 5 mm, the light transmittance in the entire multilayer glass is lowered, or the amount of the modified block copolymer hydride [E] used is increased and the economic efficiency is lowered. There is a fear.

  The layer structure of the interlayer film may be a single-layer sheet comprising a composition obtained by blending the modified block copolymer hydride [E] with the above-mentioned compounding agent as necessary, or a block copolymer hydride. Even if it is a multilayer sheet by which the layer which consists of a modified block copolymer hydride [E] is laminated | stacked on the single side | surface or both surfaces of the sheet which consists of a composition which mix | blended the said compounding agent with [D] as needed. good.

  When the interlayer film is a multilayer sheet, the multilayer sheet can be formed by, for example, a two-layer / three-layer coextrusion molding method; a block copolymer hydrogenation [D] on one side or both sides of a sheet. And a method of laminating a sheet comprising the polymer hydride [E] by thermocompression bonding.

  When the interlayer film is a multilayer sheet, the thickness of the layer made of the modified block copolymer hydride [E] is usually 0.005 mm or more, preferably 0.01 mm or more, more preferably 0.015 mm or more. If the thickness of the layer composed of the modified block copolymer hydride [E] is smaller than 0.005 mm, sufficient adhesion to the glass plate may not be obtained.

  The surface of the intermediate film can be flat or embossed. In addition, in order to prevent blocking of the interlayer films, a release film can be stacked and stored on one side of the interlayer film.

2. Glass plate In the multilayer glass of the present invention, the glass plate used is not particularly limited in thickness, material and the like. The thickness of the glass plate used is usually about 0.5 to 10 mm. An ultrathin glass plate having a thickness of about 0.05 to 0.4 mm can also be used. For example, a different thickness such as a 3.2 mm thick glass plate (first glass plate) / resin intermediate film / 1.0 mm thick glass plate (second glass plate) on which a transparent conductive film is formed. It is also possible to use a glass plate.

  The modified block copolymer hydride [E] is bonded with glass plates having different thermal expansion coefficients in order to maintain flexibility in a wide temperature range from a low temperature range of about −50 ° C. to a high temperature range of about + 120 ° C. It is also possible to reduce the glass breakage by a sudden temperature change.

  The material of the glass plate to be used is not particularly limited. For example, aluminosilicate glass, aluminoborosilicate glass, uranium glass, potash glass, silicate glass, crystallized glass, germanium glass, quartz glass, soda glass, white plate glass, lead glass, barium silicate glass, silicate glass, etc. Can be mentioned.

3. Transparent conductive film The transparent conductive film used in the present invention has a light transmittance at a wavelength of 550 nm of 60% or more, preferably 70% or more, more preferably 75% or more when directly formed on the surface of a glass plate.

  Specifically, the transparent conductive film used in the present invention is formed and laminated on glass using an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic sulfide, or a metal. The film thickness of the transparent conductive film can be appropriately selected within the range of 5 to 400 nm according to the purpose such as energization, heat generation, electromagnetic wave shielding or light reflection.

  Examples of inorganic substances include zinc oxide, Al-doped zinc oxide, Ga-doped zinc oxide, In-doped zinc oxide, F-doped zinc oxide, indium oxide, Sn-doped indium oxide, F-doped indium oxide, gallium oxide, tin oxide, and Sb-doped. Tin oxide, F-doped tin oxide, aluminum oxide, silicon oxide, titanium oxide, tungsten oxide, aluminum nitride, silicon nitride, titanium nitride, cadmium sulfide, zinc sulfide, zinc selenide, etc .; as metals, Ag, Pd, Al, Zn or the like can be used, and it can be used as a single layer film or a multilayer film.

  As a method for forming the transparent conductive film, a vacuum film forming method, for example, a film forming method such as a sputtering method, a vapor deposition method, or a CVD method can be used. The transparent conductive film may be formed directly on the surface of the glass plate, or may be formed on another thin film such as a solar cell element or a display element formed on the glass surface.

4). Multi-layer glass The multi-layer glass of the present invention comprises two or more glass plates and a resin intermediate film interposed between the bonding surfaces of these glass plates, and at least one of the bonding surfaces of these glass plates. Is a double-glazed glass on which a transparent conductive film is formed, and the resin intermediate film is formed from the above-mentioned specific modified block copolymer hydride [E] into which the alkoxysilyl group is introduced.
That is, the multilayer glass of the present invention has a structure in which at least the first glass plate / transparent conductive film / resin intermediate film / second glass plate are laminated in this order. A transparent conductive film may also be formed on the surface of the second glass plate.

In the multilayer glass of the present invention, the end of the transparent conductive film is preferably covered with a resin intermediate film, and more preferably in the states a to c.
a. The end of the transparent conductive film laminated on the first glass plate is disposed 2 mm or more apart over the entire circumference with respect to the end of the first glass plate,
b. The resin intermediate film has an area larger than the area of the transparent conductive film,
c. The transparent conductive film is covered with a resin intermediate film, and the end of the resin intermediate film is disposed 2 mm or more away from the end of the transparent conductive film over the entire periphery.

  The resin intermediate film used in the present invention uses a modified block copolymer hydride [E] that has low hygroscopicity and moisture permeability, and excellent adhesion to glass. By covering with a film, even when used in a high temperature and high humidity environment, the occurrence of problems such as an increase in resistance and loss of conductivity can be reduced.

In order to produce a multilayer glass, at least the first glass plate / transparent conductive film is formed and the resin interlayer / second glass plate is stacked in this order so as to contact the surface on which the transparent conductive film is formed, A method of adhering under reduced pressure by heating using a vacuum laminator, a method of adhering under reduced pressure by using an autoclave after putting in a heat-resistant rubber bag capable of reducing pressure, and the like can be applied.

  As the layer constitution of the multilayer glass of the present invention, a first glass plate / first resin intermediate film / display element / second resin intermediate film / second glass plate on which a transparent conductive film is formed, a transparent conductive film 1st glass plate / first resin intermediate film / light control element / second resin intermediate film / second glass plate, first glass plate / first resin intermediate formed with transparent conductive film Film / solar cell element / second resin intermediate film / second glass plate, and the like.

  Display elements, EL elements, dimming elements, solar cell elements, etc. are composed of organic EL elements, liquid crystal elements, thermochromic elements, photochromic elements, electrochromic elements, semiconductor elements, and the like. Many of them are easily deteriorated by moisture or oxygen entering from the end.

  Therefore, the same structure as the multilayer glass of the present invention, that is, the end of the display element, the light control element, the solar cell element, etc. is 2 mm over the entire circumference with respect to the ends of the first and second resin intermediate films. First glass plate / first resin intermediate film / display element / second resin intermediate film / second glass plate, first glass plate / first resin intermediate film / tone, which are arranged apart from each other Optical element / second resin intermediate film / second glass plate, first glass plate / first resin intermediate film / solar cell element / second resin intermediate film / second glass plate, etc. It is also effective for preventing deterioration of an organic EL display element, a liquid crystal display element, a light control element, a solar cell element and the like in a high temperature and high humidity environment.

  The double-glazed glass of the present invention includes anti-fogging glass, building window glass, roof glass, room heat shield wall material, automotive side glass and sunroof glass, electric vehicle windshield, railcar and ship windows. Useful as glass, display substrate, etc.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.

Evaluation in this example is performed by the following method.
(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The molecular weights of the block copolymer and the hydride of the block copolymer were measured at 38 ° C. as standard polystyrene equivalent values by GPC using THF as an eluent.
As a measuring apparatus, HLC8020GPC manufactured by Tosoh Corporation was used.
(2) Hydrogenation rate The hydrogenation rate of the main chain, side chain, and aromatic ring of the block copolymer hydride [D] was calculated by measuring a ¹ H-NMR spectrum.
(3) Durability of transparent conductive film Two conductive wires are fixed on a transparent conductive film formed on one glass plate and bonded to another glass plate through a resin intermediate film to form a single piece. The multilayer glass used as a body was used as a test piece.
This test piece is put in a constant temperature and humidity chamber and exposed to an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, and the electrical resistance value (R) between the two conductors of the multilayer glass test piece is initially ( R ₀ ) and measurement over time, and the conductivity of the transparent conductive film was evaluated.
The evaluation of durability was such that the ratio (R ₁₅₀₀ / R ₀ 0) of the resistance value (R ₁₅₀₀ ) after 1500 hours to the initial value (R ₀ ) of the electrical resistance value (R) between the two conductors was 10. The following cases were judged as good (◯) and those exceeding 10 were judged as bad (×).

[Production Example 1] Production of resin interlayer [G-1] (modified block copolymer hydride "E-1")
400 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.475 part of di-n-butyl ether were placed in a reactor equipped with a stirrer that was sufficiently purged with nitrogen. While stirring the whole volume at 60 ° C., 0.88 part of a 15% cyclohexane solution of n-butyllithium was added to initiate polymerization, and the reaction was carried out at 60 ° C. for 60 minutes while stirring. At this time, the reaction solution was analyzed by gas chromatography (GC), and as a result, the polymerization conversion was 99.5%.

Subsequently, 50.0 parts of dehydrated isoprene was added to the reaction solution, and stirring was continued at 60 ° C. for 30 minutes. At this time, as a result of analyzing the reaction solution by GC, the polymerization conversion rate was 99.5%.
Thereafter, 25.0 parts of dehydrated styrene was further added to the reaction solution, followed by stirring at 60 ° C. for 60 minutes. At this point, the reaction solution was analyzed by GC. As a result, the polymerization conversion rate was almost 100%.
Here, 0.5 part of isopropyl alcohol was added to stop the reaction to obtain a polymer solution.
The weight average molecular weight (Mw) of the block copolymer [C-1] contained in the polymer solution was 47,200, the molecular weight distribution (Mw / Mn) was 1.04, and wA: wB = 50: 50.

Next, the above polymer solution is transferred to a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “E22U”, nickel supported amount 60%, manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a hydrogenation catalyst. 8.0 parts and 100 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
The weight average molecular weight (Mw) of the block copolymer hydride [D-1] contained in the reaction solution obtained by the hydrogenation reaction was 49,900, and the molecular weight distribution (Mw / Mn) was 1.06.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate] (product name “Songnox 1010”, manufactured by Matsubara Sangyo Co., Ltd.) 2.0 parts of xylene solution in which 0.1 part was dissolved was added and dissolved.
Next, the above solution was filtered through a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less.
The molten polymer was extruded into a strand shape from a die, and after cooling, 95 parts of pellets of the block copolymer hydride [D-1] were produced by a pelletizer.
The resulting block-like block copolymer hydride [D-1] had a weight average molecular weight (Mw) of 49,500, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%. It was.

  2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane with respect to 100 parts of pellets of the obtained block copolymer hydride [D-1] (Product name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) was added in an amount of 0.2 parts. This mixture is kneaded using a twin screw extruder at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds, extruded into a strand, air cooled, cut with a pelletizer, and modified block copolymer having an alkoxysilyl group. 96 parts of pellets of the combined hydride [E-1] were obtained.

After dissolving 10 parts of pellets of the obtained modified block copolymer hydride [E-1] in 100 parts of cyclohexane, it was poured into 400 parts of dehydrated methanol, and the modified block copolymer hydride [E-1] was added. The solution was solidified, and the solidified product was collected by filtration. The filtrate was vacuum-dried at 25 degreeC, and 9.0 parts of crumbs of the modified block copolymer hydride [E-1] were isolated.
When the FT-IR spectrum of the modified block copolymer hydride [E-1] was measured, it was newly derived from Si—OCH ₃ groups at 1090 cm ⁻¹ and Si—CH ₂ groups at 825 cm ⁻¹ and 739 cm ^−1. Absorption bands were observed at different positions from absorption bands (1075 cm ⁻¹ , 808 cm ⁻¹ and 766 cm ⁻¹ ) derived from the Si—OCH ₃ group and Si—CH ₂ group of vinyltrimethoxysilane.
Further, when the ¹ H-NMR spectrum (in deuterated chloroform) of the modified block copolymer hydride [E-1] was measured, a peak based on a proton of a methoxy group was observed at 3.6 ppm. It was confirmed that 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of copolymer hydride [D-1].

(Intermediate film [G-1])
The modified block copolymer hydride [E-1] pellets obtained above were converted into a T-die film melt extrusion molding machine (T-die width 300 mm) having a twin-screw kneader equipped with a 37 mmφ screw, a cast roll ( Using an extrusion sheet molding machine equipped with a rubber nip roll and a sheet take-up device, and extrusion molding under molding conditions of a molten resin temperature of 200 ° C., a T-die temperature of 200 ° C., and a cast roll temperature of 80 ° C. Then, an intermediate film [G-1] (thickness: 760 μm, width: 230 mm) made of the modified block copolymer hydride [E-1] was molded to obtain an intermediate film [G-1].
The intermediate film [G-1] transferred the embossed pattern by pressing one side of the extruded sheet against the embossed roll with a nip roll. The obtained interlayer film [G-1] was wound up and collected on a roll.

[Production Example 2]
Production of interlayer film [G-2] (modified block copolymer hydride “E-2”)
In Production Example 1, 20.0 parts of styrene, 60.0 parts of isoprene, and 20.0 parts of styrene were added in three portions each in this order, and n-butyllithium (15% cyclohexane solution) was added to 0.80 parts. Except for changing, the polymerization reaction and the reaction termination operation were performed in the same manner as in Production Example 1.
The resulting block copolymer [C-2] had a weight average molecular weight (Mw) of 51,200, a molecular weight distribution (Mw / Mn) of 1.04, and wA: wB = 40: 60.

  Next, the above polymer solution was subjected to a hydrogenation reaction in the same manner as in Production Example 1. The weight average molecular weight (Mw) of the block copolymer hydride [D-2] after the hydrogenation reaction was 54,200, and the molecular weight distribution (Mw / Mn) was 1.06.

  After completion of the hydrogenation reaction, an antioxidant was added in the same manner as in Production Example 1, followed by concentration and drying to obtain 92 parts of a block copolymer hydride [D-2] pellet. The resulting block-like block copolymer hydride [D-2] had a weight average molecular weight (Mw) of 53,700, a molecular weight distribution (Mw / Mn) of 1.11 and a hydrogenation rate of almost 100%. It was.

Using the obtained block copolymer hydride [D-2] pellets, 95 parts of a modified block copolymer hydride [E-2] pellet having an alkoxysilyl group was obtained in the same manner as in Production Example 1. It was.
The obtained modified block copolymer hydride [E-2] was analyzed in the same manner as in Production Example 1, and vinyltrimethoxysilane 1.D was added to 100 parts of the block copolymer hydride [D-2]. It was confirmed that 8 parts were combined.

(Intermediate film [G-2])
A pellet of the modified block copolymer hydride [E-2] was formed into a sheet in the same manner as in Production Example 1, and an intermediate film [G-2] (thickness made of the modified block copolymer hydride [E-2]) was formed. 760 μm, width 230 mm).
Similarly to Production Example 1, the intermediate film [G-2] was provided with an embossed pattern, collected on a roll.

[Production Example 3]
Production of intermediate film [G-3] (intermediate film [G-3] comprising ethylene / vinyl acetate copolymer as a main component)
Ethylene / vinyl acetate copolymer (hereinafter abbreviated as “EVA”) (product name “Evaflex (registered trademark) EV150”, vinyl acetate content 33 wt%, melting point 61 ° C., manufactured by Mitsui DuPont Polychemical Co., Ltd.) ), 7 parts by weight of triallyl isocyanurate, 0.5 part by weight of 3-methacryloxypropyltrimethoxysilane (trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.), dicumyl peroxide ( 1.0 part by weight of trade name “Park Mill D” (manufactured by NOF Corporation) and 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 4 parts were added and mixed.

  Using this mixture, a T-die type film melt extrusion molding machine having the same biaxial kneader as used in Production Example 1 and an extrusion sheet molding machine equipped with a cast roll, a rubber nip roll and a sheet take-up device were used. Under the molding conditions of molten resin temperature 90 ° C., T die temperature 90 ° C., embossing roll temperature 40 ° C., one side of the extruded sheet is pressed against the embossing roll with a nip roll to give an embossed shape, and an intermediate film made of EVA [ G-3] (thickness: 760 μm, width: 230 mm). The obtained intermediate film [G-3] was wound up and collected on a roll. The interlayer [G-3] was sealed in a polyethylene bag and stored in a refrigerator (temperature 5 ° C.).

[Example 1]
On a blue plate glass (length 80 mm, width 80 mm, thickness 2 mm), an Al-doped zinc oxide (AZO) film (film thickness 650 nm, sheet resistance 10 Ω / □ cm, light transmittance 85.0 at a wavelength of 550 nm) as a transparent conductive film %, Manufactured by Geomatec). Two tab lines (width 1.6 mm, thickness 0.20 mm) spaced 2 cm apart on the AZO film, one end is 2 cm away from the glass edge and the other end is a glass plate And extended to the outside of the AZO film, and fixed with silver paste over a length of 6 cm on the AZO film.
The resin intermediate film [G-1] obtained in Production Example 1 is placed on the AZO film surface on which the tab wire is fixed so as to cover the entire surface, and another blue plate glass (80 mm long, 80 mm wide, 80 mm thick) 2 mm). This laminate is put into a 75 μm-thick resin bag having a layer structure of nylon / adhesive layer / polypropylene, and the inside of the bag is deaerated using a sealed pack device (BH-951, manufactured by Panasonic Corporation). The opening was heat sealed while the laminate was hermetically packaged.
After that, the laminated package sealed was put in an autoclave and treated at a temperature of 140 ° C. and a pressure of 0.8 MPa for 30 minutes to form a glass sheet / transparent conductive film / resin intermediate film / glass plate layered glass test. Piece [H-1] was produced. In the appearance of the multilayer glass test piece [H-1], defects such as bubbles, poor filling, and peeling were not observed.

As a result of evaluating the durability of the transparent conductive film of the multilayer glass test piece [H-1], the initial electrical resistance between the tab wires was exposed to an environment of R ₀ = 5.1Ω, 85 ° C., 85% RH for 1500 hours. After that, the electric resistance value was R ₁₅₀₀ = 22.4Ω, R ₁₅₀₀ / R ₀ = 4.4, and the evaluation was good.

[Example 2]
A multilayer glass test piece [H-2] was produced in the same manner as in Example 1 except that the resin interlayer “G-2” was used instead of the resin interlayer [G-1].
As a result of evaluating the durability of the transparent conductive film of the multilayer glass test piece [H-2], the initial value was an electric resistance value after exposure to an environment of R ₀ = 5.0Ω, 85 ° C., 85% RH for 1500 hours. R ₁₅₀₀ = 19.7Ω, R ₁₅₀₀ / R ₀ = 3.9, and the evaluation was good.

[Comparative Example 1]
A multilayer glass test piece [H-3] was produced in the same manner as in Example 1 except that the resin intermediate film “G-3” was used instead of the resin intermediate film [G-1].
As a result of evaluating the durability of the transparent conductive film of the multilayer glass test piece [H-3], the initial value was an electrical resistance value after exposure to an environment of R ₀ = 5.4Ω, 85 ° C., 85% RH for 1500 hours. Was R ₁₅₀₀ = 2725.5Ω, R ₁₅₀₀ / R ₀ = 504, and the evaluation was x.

[Comparative Example 2]
An intermediate film (product name: Saflex (registered trademark) RF41, thickness: 760 μm, manufactured by Solusia) using a polyvinyl butyral resin (hereinafter sometimes referred to as “PVB resin”) instead of the resin intermediate film [G-1]. A multilayer glass test piece [H-4] was produced in the same manner as in Example 1 except that it was used.
As a result of evaluating the durability of the transparent conductive film of the multilayer glass test piece [H-4], the initial value was an electrical resistance value after exposure to an environment of R ₀ = 6.1Ω, 85 ° C., 85% RH for 1500 hours. Was R ₁₅₀₀ = 2888.5Ω, R ₁₅₀₀ / R ₀ = 473, and the evaluation was x.

[Example 3]
Except for replacing the transparent conductive film formed on the soda glass with a zinc oxide film (film thickness 200 nm, sheet resistance 7.6 kΩ / □ cm, light transmittance 82.5% at a wavelength of 550 nm, manufactured by Toho Kaken Co., Ltd.) In the same manner as in Example 1, a multilayer glass test piece [H-5] was produced. In the appearance of the multilayer glass test piece [H-5], defects such as bubbles, poor filling, and peeling were not observed.

As a result of evaluating the durability of the transparent conductive film of the multilayer glass test piece [H-1], the initial electrical resistance value between the tab wires was exposed to an environment of R ₀ = 1.7Ω, 85 ° C., 85% RH for 1500 hours. After that, the electric resistance value was R ₁₅₀₀ = 4.1Ω, R ₁₅₀₀ / R ₀ = 2.4, and the evaluation was good.

The following can be seen from the results of this example and the comparative example.
In a multi-layer glass produced by laminating a glass plate on which a transparent conductive film is formed with an opposing glass plate using an intermediate film composed of a modified block copolymer hydride [E] introduced with an alkoxysilyl group, Even after exposure to a high humidity environment for a long time, the increase in the resistance value of the transparent conductive film is small, indicating that the durability of the transparent conductive film is excellent (Examples 1 to 3).
It has been shown that when an intermediate film heat composed of EVA resin or PVB resin is used, the resistance value increases greatly after being exposed to a high temperature and high humidity environment for a long time, and the durability of the transparent conductive film is inferior ( Comparative Examples 1 and 2).

  The multi-layer glass of the present invention is a multi-layer glass with a transparent conductive film that suppresses the deterioration of conductivity over time even in a high-temperature and high-humidity environment, and is anti-fogging glass, building window glass, roof glass, and room heat shielding. It is useful as a wall material, automobile side glass, sunroof glass, electric automobile windshield, railcar or ship window glass, display substrate, and the like.

Claims (2)

A multi-layer glass comprising two or more glass plates and a resin intermediate film interposed between the bonding surfaces of these glass plates, and a transparent conductive film formed on at least one of the bonding surfaces of these glass plates In which the resin intermediate film has at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component and at least one structural unit derived from a chain conjugated diene compound as a main component. The weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the weight fraction of the total polymer block [B] in the entire block copolymer is comprised of the polymer block [B]. Is the main chain and side chain carbon-carbon unsaturated bonds of the block copolymer [C] in which the ratio of wA to wB (wA: wB) is 30: 70-60: 40, Aromatic carbon-charcoal It is an intermediate film containing a modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into a block copolymer hydride [D] in which 90% or more of unsaturated bonds are hydrogenated. Characteristic multilayer glass. At least a first glass plate, a transparent conductive film formed on the first glass plate, a resin intermediate film, a multi-layer glass laminated in the order of the second glass plate,
a. The end of the transparent conductive film laminated on the first glass plate is disposed 2 mm or more apart over the entire circumference with respect to the end of the first glass plate,
b. The resin intermediate film has an area larger than the area of the transparent conductive film,
c. A multi-layer glass, wherein the transparent conductive film is covered with a resin intermediate film, and the end of the resin intermediate film is located 2 mm or more away from the end of the transparent conductive film over the entire periphery.