JP2022128738A - Laminated glass for vehicle, door for vehicle, and method for manufacturing laminated glass for vehicle - Google Patents

Abstract

To provide a laminated glass for a vehicle which has excellent penetration resistance against an impact from a certain direction, and has reduced penetration resistance against an impact from a side opposite to the direction.SOLUTION: A laminated glass for a vehicle includes a pair of glass plates, and a first intermediate layer and a second intermediate layer arranged between the pair of glass plates, wherein the first intermediate layer contains a cured product of a resin composition containing (A) a (meth)acrylic copolymer having an epoxy group, and (B) a curing agent, and the second intermediate layer contains a polyvinyl butyral resin.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present disclosure relates to a laminated vehicle glass, a vehicle door, and a method of manufacturing a laminated vehicle glass.

Tempered glass is generally used for the door glass of vehicles such as automobiles, but in recent years, PVB laminated glass, in which polyvinyl butyral (PVB) is sandwiched between glass and glass, has been used for the purpose of improving sound insulation of door glass and crime prevention. is adopted.

For example, Patent Literature 1 discloses a laminated glass for a vehicle having a pair of glass plates and an intermediate adhesive film between the pair of glass plates, wherein the intermediate adhesive film is disposed inside the vehicle to provide a signal between the outside of the vehicle and the light. and a continuous transmission region including an optical aperture for transmission and reception of the signal of the information acquisition device that transmits and receives the above, and a light shielding region provided around the entire circumference of the optical aperture except for a part thereof. and a light-shielding region of the laminated glass for a vehicle corresponding to the light-shielding region of the intermediate adhesive film has a visible light transmittance of 3% or less. In Patent Document 1, a polyvinyl butyral resin is exemplified as a thermoplastic resin used for the intermediate adhesive film.

On the other hand, from the viewpoint of improving various properties, other materials are also being studied as an intermediate film to be arranged between a pair of glass plates.

For example, Patent Document 2 discloses an interlayer film for laminated glass comprising two glass plates facing each other and an interlayer disposed between them, wherein the interlayer film is provided between the two glass plates facing each other. An interlayer film for laminated glass, wherein the resin composition contains (A) a (meth)acrylic copolymer having an epoxy group and (B) a curing agent. Disclosed is a laminated glass comprising a resin composition for glass. Patent Literature 2 describes that this configuration can provide a laminated glass having high chipping resistance.

JP 2019-026248 A JP 2020-040869 A

PVB laminated glass in which polyvinyl butyral resin is sandwiched between glasses, as disclosed in Patent Document 1 and the like, is useful from the viewpoint of improving the sound insulation of door glass and crime prevention. However, in vehicles using PVB laminated glass, from the viewpoint of crime prevention, while it has a high penetration resistance against impacts from the outside of the vehicle, it is relatively easy to penetrate against impacts from the inside of the vehicle. There is a demand for laminated glass for vehicles with properties. In view of these facts, a laminated glass for vehicles has been developed which has excellent penetration resistance against impact from a certain direction, but has reduced penetration resistance against impact from the opposite direction. It has been demanded.

Accordingly, an object of the present disclosure is to provide a vehicular structure having excellent penetration resistance against impact from a certain direction, while having reduced penetration resistance against impact from the opposite direction. To provide laminated glass.

The present inventors have made intensive studies to solve the above problems, and found that between a pair of glass plates, a first intermediate layer containing a cured product of a predetermined resin composition and a second intermediate layer containing a polyvinyl butyral resin The inventors have found that the above-described problems of the present disclosure can be solved by forming the present disclosure.

Therefore, an example of a mode of this embodiment is as follows.

(1) A laminated glass for a vehicle comprising a pair of glass plates, and a first intermediate layer and a second intermediate layer disposed between the pair of glass plates,
The first intermediate layer contains a cured product of a resin composition containing (A) a (meth)acrylic copolymer having an epoxy group and (B) a curing agent,
A laminated glass for vehicles, wherein the second intermediate layer includes a polyvinyl butyral resin.
(2) The laminated glass for vehicles according to (1), wherein the first intermediate layer and the second intermediate layer are arranged such that the first intermediate layer is located on the inner side of the vehicle than the second intermediate layer. .
(3) The laminated glass for vehicles according to (1) or (2), wherein the first intermediate layer and the second intermediate layer are in direct contact.
(4) (A) the (meth)acrylic copolymer having an epoxy group is derived from a (meth)acrylic monomer having an epoxy group, based on the mass of (A) the (meth)acrylic copolymer having an epoxy group The laminated glass for vehicles according to any one of (1) to (3), which contains 5 to 50% by mass of the monomer unit.
(5) The laminated glass for vehicles according to (4), wherein the monomer units derived from (meth)acrylic monomers having an epoxy group contain monomer units derived from glycidyl (meth)acrylate.
(6) The laminated glass for vehicles according to any one of (1) to (5), wherein (B) the curing agent contains an acid anhydride compound.
(7) The vehicle use according to (6), wherein the content of the acid anhydride compound is 0.5 to 30 parts by mass with respect to 100 parts by mass of (A) the (meth)acrylic copolymer having an epoxy group. laminated glass.
(8) The laminated glass for vehicles according to (6) or (7), wherein (B) the curing agent further contains an imidazole compound.
(9) The laminated glass for vehicles according to (8), wherein the content of the imidazole compound is 1.0 parts by mass or less with respect to 100 parts by mass of (A) the (meth)acrylic copolymer having an epoxy group.
(10) The laminated glass for vehicles according to any one of (1) to (9), wherein the resin composition further contains (C) a curing accelerator.
(11) The laminated glass for vehicles according to any one of (1) to (10), wherein the glass plate is inorganic glass.
(12) A vehicle door comprising the laminated glass for vehicles according to any one of (1) to (11).
(13) A method for manufacturing the laminated glass for vehicles according to any one of (1) to (11),
A laminate is formed by disposing a resin layer containing the resin composition described in any one of (1) to (11) or a cured product thereof and a resin layer containing a polyvinyl butyral resin between a pair of glass plates. forming;
heating and pressing the laminate to form a laminated glass;
A method, including

The present disclosure provides a laminated glass for a vehicle that has excellent penetration resistance against impact from one direction, while having reduced penetration resistance against impact from the opposite direction. can do.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing for demonstrating the structural example of the laminated glass for vehicles which concerns on this embodiment.

As used herein, “(meth)acrylate” means “acrylate” or its corresponding “methacrylate”. Similarly, "(meth)acrylic" means "acrylic" or its corresponding "methacrylic", and "(meth)acryloyl" means "acryloyl" or its corresponding "methacryloyl". The content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.

The present embodiment will be described below.

This embodiment is a laminated glass for a vehicle including a pair of glass plates, and a first intermediate layer and a second intermediate layer disposed between the pair of glass plates, wherein the first intermediate layer comprises ( A laminated glass for vehicles comprising a cured product of a resin composition comprising A) a (meth)acrylic copolymer having an epoxy group and (B) a curing agent, and wherein the second intermediate layer comprises a polyvinyl butyral resin. .

FIG. 1 is a schematic cross-sectional view for explaining a configuration example of a laminated glass for a vehicle according to this embodiment. The laminated glass for a vehicle according to the present embodiment is not limited to the aspect of FIG. 1, and modifications can be made without departing from the gist of the present disclosure. The laminated glass 100 shown in FIG. 1 comprises two opposing glass plates 101a, 101b and a first intermediate layer 102 and a second intermediate layer 103 disposed between the glass plates 101a, 101b. The first intermediate layer 102 is arranged on the inner side of the vehicle than the second intermediate layer 103 . That is, in FIG. 1, the upper side of the laminated glass 100 corresponds to the inner side of the vehicle, and the lower side of the laminated glass 100 corresponds to the outer side of the vehicle. In FIG. 1, the first intermediate layer 102 is arranged closer to the vehicle inner side than the second intermediate layer 103 to describe the present embodiment, but the present disclosure is not limited to this. do not have.

According to the present embodiment, a laminated glass for a vehicle having excellent penetration resistance against impact from a certain direction and reduced penetration resistance against impact from the opposite direction is provided. can provide. For example, the present embodiment provides a laminated glass for a vehicle that has excellent penetration resistance against impacts from the outside of the vehicle and reduced penetration resistance against impacts from the inside of the vehicle. be able to. Specifically, since the laminated glass for a vehicle according to the present embodiment has the second intermediate layer containing the polyvinyl butyral resin on the outside of the vehicle, it exhibits excellent penetration resistance against impacts from the outside of the vehicle. On the other hand, in the laminated glass for a vehicle according to the present embodiment, since the first intermediate layer is provided closer to the vehicle inner side than the second intermediate layer, the penetration resistance is reduced against the impact from the vehicle inner side. Specifically, it has a lower penetration resistance than the penetration resistance against an impact from the outside of the vehicle. Therefore, the laminated glass for a vehicle according to the present embodiment has excellent penetration resistance against impacts from the outside of the vehicle, so it has excellent crime prevention properties, and relatively penetration resistance against impacts from the inside of the vehicle. It has the property that it is easy to The laminated glass for vehicles according to the present embodiment has excellent penetration resistance against impact from a certain direction, but exhibits reduced penetration resistance against impact from the opposite direction. The reason for this is presumed as follows. In the laminated glass for vehicles according to the present embodiment, when an impact is given by an object such as a hammer from the second intermediate layer side (for example, the outside of the vehicle), the object penetrates the glass, and then the second intermediate layer containing polyvinyl butyral resin is struck. It reaches the second middle layer. Polyvinyl butyral resin has excellent toughness and high tenacity, so it can efficiently absorb impacts. On the other hand, when an impact is given by an object such as a hammer from the side of the first intermediate layer (for example, inside the vehicle), after penetrating the glass, the object first hits the first intermediate layer containing the cured product of the predetermined resin composition. reach the layers. When this first intermediate layer is present, before the toughness of the first intermediate layer and the second intermediate layer containing the polyvinyl butyral resin is developed, the broken glass fragments are exposed to the first layer having high hardness. The intermediate layer and the second intermediate layer are slit at the same time. Therefore, the penetration resistance against the impact from the first intermediate layer side becomes low. Therefore, the laminated glass for vehicles according to the present embodiment has excellent penetration resistance against impact from the second intermediate layer side, while reducing impact from the first intermediate layer side. It is presumed that there is an excellent effect of having a high penetration resistance. Note that the estimation does not limit the present embodiment.

Hereinafter, constituent requirements of the laminated glass for vehicles according to the present embodiment will be described.

<Glass plate>
The glass plate may be inorganic glass or organic glass.

Examples of inorganic glass include, but are not particularly limited to, ordinary soda lime glass (also referred to as soda lime silicate glass), aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass. Among these, soda-lime glass is preferred. Examples of inorganic glass include float glass, air-cooled tempered glass, chemically tempered glass, and multi-layer glass.

The organic glass (resin) is not particularly limited, but may be polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, polycondensate of halogenated bisphenol A and ethylene glycol. , acrylic urethane resin, or halogenated aryl group-containing acrylic resin. Among these, polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethyl methacrylate acrylic resins are preferred, and polycarbonate resins are more preferred. Furthermore, among polycarbonate resins, bisphenol A-based polycarbonate resins are preferred. The organic glass material may be used singly or in combination of two or more.

<First intermediate layer>
The first intermediate layer comprises (A) a (meth)acrylic copolymer having an epoxy group (hereinafter also abbreviated as component (A)) and (B) a curing agent (hereinafter also abbreviated as component (B)). including a cured product of the first intermediate layer resin composition containing

The first intermediate layer is a resin layer formed from a resin composition containing components (A) and (B), and may be composed of a single layer or multiple layers. The second intermediate layer may also be a single layer or may be composed of multiple layers.

The resin composition that can be used to form the first intermediate layer, that is, the resin composition for the first intermediate layer will be described below.

As described above, the first intermediate layer resin composition contains at least (A) a (meth)acrylic copolymer having an epoxy group and (B) a curing agent.

The component (A) contains a monomer unit derived from a (meth)acrylic monomer having an epoxy group. The content of component (A) is, for example, 70% by mass or more, 75% by mass or more, or 80% by mass or more based on the total mass of the first intermediate layer resin composition.

As the component (A), for example, a monomer unit derived from a (meth)acrylic monomer having an epoxy group, a monomer unit derived from a (meth)acrylic monomer having no epoxy group, and optionally ( and a copolymer containing a monomer unit derived from a compound having an ethylenically unsaturated group other than a meth)acrylic monomer.

The (meth)acrylic monomer having an epoxy group is not particularly limited, but examples include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, or 3,4-epoxycyclohexylmethyl (meth)acrylate. ) acrylates and the like. Among these, glycidyl (meth)acrylate is preferably used from the viewpoint of heat resistance and chipping resistance. That is, the monomer units derived from (meth)acrylic monomers having an epoxy group preferably include monomer units derived from glycidyl (meth)acrylate. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of monomer units derived from a (meth)acrylic monomer having an epoxy group in the component (A) ((meth)acrylic monomer having an epoxy group, based on the total amount of copolymerization components for synthesizing component (A) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, based on the mass of component (A). . If the content of the monomer units derived from the (meth)acrylic monomer having an epoxy group is 5% by mass or more, the easy penetration from the first intermediate layer side can be improved. Further, if the content of the monomer units derived from the (meth)acrylic monomer having an epoxy group is 50% by mass or less, the reaction between the epoxy groups during storage of the first intermediate layer resin composition is suppressed. Therefore, there is a tendency that sufficient storage stability can be obtained.

(Meth)acrylic monomers having no epoxy group are not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate or methoxypolypropylene glycol (meth)acrylate; aliphatic (meth)acrylates; cyclohexyl (meth)acrylate, isobornyl Alicyclic (meth)acrylates such as (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate or dicyclopentenyl (meth)acrylate; benzyl (meth)acrylate or phenoxyethyl (meth)acrylate, etc. and heterocyclic (meth)acrylates such as 2-tetrahydrofurfuryl (meth)acrylate or N-(meth)acryloyloxyethylhexahydrophthalimide. Among these, from the viewpoint of cost and ease of synthesis, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Preference is given to using acrylates, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate or 2-tetrahydrofurfuryl (meth)acrylate. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of monomer units derived from (meth)acrylic monomers having no epoxy groups in component (A) (based on the total amount of copolymerization components for synthesizing component (A), having no epoxy groups ( Amount of meth)acrylic monomer) is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and 65 to 85% by mass, based on the mass of component (A). is more preferred. When using an aliphatic (meth) acrylate as the (meth) acrylic monomer having no epoxy group, the content of monomer units derived from the aliphatic (meth) acrylate in the component (A) (component (A) Based on the total amount of the copolymerization component for synthesizing the aliphatic (meth) acrylate) is preferably 10 to 50% by weight, based on the weight of the component (A), 15 to 45% by weight and more preferably 20 to 40% by mass. When using an alicyclic (meth)acrylate as the (meth)acrylic monomer having no epoxy group, the content of monomer units derived from the alicyclic (meth)acrylate in the component (A) ((A The amount of the alicyclic (meth)acrylate based on the total amount of the copolymerization component for synthesizing the component) is preferably 30 to 80% by mass, based on the mass of the component (A), and 35 to 70% by mass. More preferably, 40 to 65% by mass is even more preferable.

The compound having an ethylenically unsaturated group other than the (meth)acrylic monomer is not particularly limited, but examples include styrene, (meth)acrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, vinylcyclohexyl ether, vinyl phenyl ether, vinyl acetate, N-vinylpyrrolidone, vinylpyridine, vinyl chloride, vinylidene chloride and the like. Among these, (meth)acrylonitrile, N-cyclohexylmaleimide, or N-phenylmaleimide is preferably used from the viewpoint of easily improving the toughness of the first intermediate layer. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of monomer units derived from a compound having an ethylenically unsaturated group other than (meth)acrylic monomer in component (A) (based on the total amount of copolymerization components for synthesizing component (A), (meth) The amount of the compound having an ethylenically unsaturated group other than the acrylic monomer) is preferably 0 to 40% by mass, more preferably 5 to 35% by mass, based on the mass of the component (A). , more preferably 10 to 30% by mass.

Although the glass transition temperature of component (A) is not particularly limited, it is preferably -30°C to 150°C, more preferably 0°C to 100°C, even more preferably 10 to 50°C. 30°C to 50°C is particularly preferred. When the glass transition temperature of the component (A) is −30° C. or higher, there is a tendency to easily obtain a laminated glass having excellent chipping resistance while having easy penetration against impact from the first intermediate layer side. . When the glass transition temperature of the component (A) is 150° C. or less, the toughness of the first intermediate layer tends to be high, so that the first intermediate layer with excellent workability tends to be easily obtained. Further, when the glass transition temperature is -30°C or higher, there is a tendency that the adhesion of the polymer to the blade during cutting of the first intermediate layer can be suppressed. Further, when the glass transition temperature is 50° C. or less, cracking of the first intermediate layer tends to be suppressed.

The glass transition temperature of component (A) is the midpoint glass transition temperature measured using differential scanning calorimetry (DSC). Specifically, it is the midpoint glass transition temperature calculated by a method based on JIS K 7121:1987 by measuring changes in the amount of heat under the condition of a heating rate of 10° C./min. The measurement temperature may be in the range including the glass transition temperature, for example -50 to 100°C or -80 to 80°C.

The glass transition temperature of the component (A) is determined by the copolymerization components for synthesizing the component (A), such as the (meth)acrylic monomer having an epoxy group, the (meth)acrylic monomer having no epoxy group and the (meth) It can be adjusted by the mixing ratio of the compound having an ethylenically unsaturated group other than the acrylic monomer.

The epoxy equivalent of component (A) is preferably 200 to 2,000 g/eq. When the epoxy equivalent of the component (A) is 200 g/eq or more, the reaction between the epoxy groups can be suppressed during storage of the first resin composition for intermediate layer, so storage stability tends to be good. There is If the epoxy equivalent of component (A) is 2,000 g/eq or less, the laminated glass provided with the first intermediate layer has excellent chipping resistance while having easy penetration against impact from the first intermediate layer side. tend to have Epoxy equivalent is a value measured by a method conforming to JIS K 7236:2001.

The weight average molecular weight of component (A) is preferably from 100,000 to 3,000,000. When the weight average molecular weight of component (A) is 100,000 or more, the resulting first intermediate layer tends to have improved toughness. When the weight-average molecular weight of the component (A) is 3,000,000 or less, the appearance tends to be good because air bubbles are easily removed during production of the laminated glass. The weight average molecular weight of component (A) can be adjusted by conventional methods such as polymerization temperature, polymerization time, solvent used for polymerization, addition of chain transfer agent, and the like.

The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

The method for synthesizing component (A) is not particularly limited, but for example, the above (meth)acrylic monomer having an epoxy group, the above (meth)acrylic monomer having no epoxy group, and optionally the above A method of copolymerizing a compound having an ethylenically unsaturated group other than the (meth)acrylic monomer in (1) using an appropriate thermal radical polymerization initiator while heating. The polymerization method is not particularly limited, but examples thereof include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Polymerization can also be carried out using a suitable chain transfer agent or the like, if necessary.

The (B) curing agent is a component that forms a crosslinked structure by reacting with the epoxy groups of the (A) component. (B) As the curing agent, any one having a functional group capable of reacting with the epoxy group of component (A) may be used. A phosphine compound etc. are mentioned. Among these, the curing agent preferably contains an acid anhydride compound from the viewpoint of latent curability and optical transparency. From the viewpoint of shortening the curing time, the curing agent preferably contains an imidazole compound. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of component (B) is preferably 0.01 to 50 parts by mass per 100 parts by mass of component (A). If the content of the component (B) is 0.01 parts by mass or more, the curability of the first intermediate layer formed from the resin composition can be improved. It is expected that it will be easy to obtain a laminated glass having high resistance to chipping while having easy penetrability against impact, shortening of the process time, and improvement of workability. If the content of component (B) is 50 parts by mass or less, there is a tendency that the storage stability of the resin composition can be improved. From the same point of view, the content of component (B) is more preferably 0.5 to 30 parts by mass.

Acid anhydride compounds include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanehydrotrimellitate, maleic anhydride, Tetrahydrophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, Methylhimic anhydride, Methylbutenyltetrahydrophthalic anhydride, Dodecenylsuccinic anhydride, Hexahydrophthalic anhydride, Succinic anhydride, Methylcyclohexenedicarboxylic anhydride, Methyltetrahydroanhydride Examples thereof include phthalic acid, methylendomethylenetetrahydrophthalic anhydride, and hexahydrophthalic anhydride substituted with an alkyl group such as methylhexahydrophthalic anhydride. The alkyl-substituted hexahydrophthalic anhydride may be, for example, a C1-C9 alkyl-substituted hexahydrophthalic anhydride. From the viewpoint of optical transparency of the cured product, the curing agent includes tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylendomethylene. It preferably contains at least one selected from the group consisting of tetrahydrophthalic anhydride and hexahydrophthalic anhydride substituted with an alkyl group, and at least one selected from the group consisting of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. It more preferably contains seeds, and even more preferably contains methylhexahydrophthalic anhydride.

The content of the acid anhydride compound is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). is more preferable, and 10 to 20 parts by mass is particularly preferable. When the content of the acid anhydride compound is 0.5 parts by mass or more, the curability of the first intermediate layer formed from the resin composition for the first intermediate layer can be improved. It is expected that it will be easier to obtain laminated glass that has excellent chipping resistance and high optical transparency while maintaining easy penetration against impact from the intermediate layer side, shortening the process time, and improving workability. can. When the content of the acid anhydride compound is 30 parts by mass or less, there is a tendency that the storage stability of the first intermediate layer resin composition can be improved. The content of the acid anhydride compound is preferably 40 to 70 parts by mass with respect to 100 parts by mass of the monomer units derived from the (meth)acrylic monomer having an epoxy group in the component (A). It is more preferably 45 to 65 parts by mass, even more preferably 50 to 60 parts by mass, and more preferably 50 to 55 parts by mass.

Examples of imidazole compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2 '-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H -pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and the like. Among these, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-[2 '-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- Preference is given to using s-triazineisocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the imidazole compound is not particularly limited. parts or less, or 0.03 parts by mass or less. When the content of the imidazole compound is within the above range, the curing temperature can be lowered and the curing time can be shortened, and yellowing of the resin composition after curing tends to be suppressed. be.

The first intermediate layer resin composition may optionally further contain a curing accelerator. Examples of curing accelerators include, for example, organophosphorus curing accelerators. Although imidazole compounds can also function as curing accelerators, they are classified as curing agents in this specification. Examples of organophosphorus curing accelerators include triphenylphosphine, tripparatolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, 1,4-bisdiphenylphosphinobane, 2 -ethyl-4-methylimidazolium tetraphenylborate, 1,5-diazabicyclo[4.3.0]nonene-5-tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri Phenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, n-butyltriphenylphosphonium dicyanamide, tetraphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, or tetrabutylphosphonium decanoic acid salt. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Although the content of the curing accelerator is not particularly limited, it is preferably 0.01 to 50 parts by weight per 100 parts by weight of component (A). When the content of the curing accelerator is 0.01 parts by mass or more, the curability of the first intermediate layer formed from the first intermediate layer resin composition can be improved. It can be expected that it will be easier to obtain a laminated glass that has high chipping resistance while having easy penetration against impact from the intermediate layer side, that the process time will be shortened, and workability will be improved. When the content of the curing accelerator is 50 parts by mass or less, there is a tendency that the storage stability of the first intermediate layer resin composition can be improved. The content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of component (A).

The first intermediate layer resin composition may further contain additives, if necessary. Examples of additives include, but are not limited to, polymerization inhibitors, silane coupling agents, surfactants, inorganic fillers, flame retardants, plasticizers, and other polymers. An additive may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the additive is, for example, 0.01 to 5% by mass with respect to the total amount of the resin composition for the first intermediate layer.

Examples of polymerization inhibitors include para-methoxyphenol. Examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or γ-glycidoxypropylmethyldiisopropenoxysilane. Examples of surfactants include polydimethylsiloxane compounds and fluorine compounds.

Examples of inorganic fillers include crushed silica, fused silica, mica, clay minerals, short glass fibers or fine powders and hollow glass, calcium carbonate, quartz powder, or metal hydrates. The content of the inorganic filler is, for example, 0.01 to 100 parts by mass, 0.05 to 50 parts by mass, or 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition for the first intermediate layer. is. When the content of the inorganic filler is 0.01 to 100 parts by mass, the resin composition for the first intermediate layer tends to exhibit effects such as low shrinkage, improved mechanical strength, and low coefficient of thermal expansion. . The inorganic filler may be treated with a commercially available surface treatment agent such as a coupling agent.

Examples of other polymers include epoxy resins, phenolic resins, polyvinylacetal resins, or ionomer resins. The use of epoxy resin or phenol resin tends to increase the strength of the first intermediate layer. The use of polyvinyl acetal resin or ionomer resin tends to increase the adhesion between the first intermediate layer and the glass plate.

The first intermediate layer resin composition may further contain an organic solvent, if necessary. The organic solvent is not particularly limited as long as it can dissolve the resin composition. Examples include ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, methyl lactate, and lactic acid. Ester organic solvents such as ethyl or γ-butyrolactone; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether or diethylene glycol Polyhydric alcohol alkyl ether organic solvents such as dimethyl ether; polyhydric alcohol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate or diethylene glycol monomethyl ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide Alternatively, amide-based organic solvents such as N-methylpyrrolidone can be used. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

The resin layer of the first intermediate layer resin composition (that is, the first intermediate layer resin layer) is obtained by forming the first intermediate layer resin composition into a film or layer. The first intermediate layer resin layer may be obtained by curing (including cross-linking) the first intermediate layer resin composition. That is, the first intermediate layer resin layer is a resin layer containing the first intermediate layer resin composition or a cured product thereof.

The first intermediate layer resin layer can be produced, for example, by applying the first intermediate layer resin composition to a support film. When the first resin composition for intermediate layer is diluted with an organic solvent, the resin composition is applied to a support film, and the organic solvent is removed by heating and drying to obtain the first resin composition used for manufacturing laminated glass. One intermediate layer resin layer can be manufactured. In this case, the first intermediate layer film material having a two-layer structure composed of the support film and the first intermediate layer resin layer can be obtained.

If necessary, a protective film can be attached to the first intermediate layer resin layer provided on the support film. In this case, the first intermediate layer film material having a three-layer structure composed of the support film, the first intermediate layer resin layer, and the protective film can be obtained.

The first intermediate resin layer preferably has a loss tangent tan δ at a temperature of 0° C. and a frequency of 0.5 Hz of 0.5 or less, more preferably 0.3 or less, and 0.2 or less. It is even more preferable to have When the tan δ is 0.5 or less, deformation of the first intermediate layer due to an external impact is suppressed, so chipping resistance is improved while maintaining easy penetration against impact from the first intermediate layer side. This tends to make it easier to obtain excellent laminated glass. tan δ is a numerical value measured by a dynamic viscoelasticity test in tensile mode. Specifically, a film material with a resin layer adjusted to a thickness of 0.1 mm was heated at 150 ° C. for 2 hours, and then subjected to a dynamic viscoelasticity tester (RSA-G2, manufactured by TA Instruments Japan Co., Ltd.). , the measurement can be performed under the conditions of a sample width of 5 mm, a sample length of 5 mm, a strain amount of 0.05%, a temperature of 0° C., and a frequency of 0.5 Hz.

The temperature and time conditions for heating the film material vary depending on the types and amounts of the components (A) and (B) contained in the resin composition, but the resin composition can be sufficiently crosslinked without decomposing or volatilizing. There are no particular restrictions as long as the conditions are met. It is preferable to set the strain amount to a value as large as possible in a region where the film material does not undergo plastic deformation.

The first intermediate layer film material thus obtained can be wound into a roll, for example, and stored in the form of a roll. It is also possible to cut the roll-shaped film material into a suitable size and store it in the form of a sheet.

The support film is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyamide, polyimide, and the like. Among these, the support film is preferably polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polyamide, or polyimide from the viewpoint of flexibility and toughness. From the viewpoint of improving releasability from the first resin layer for intermediate layer, it is preferable to use a film that has been subjected to release treatment with a silicone-based compound, a fluorine-based compound, or the like, as the support film.

The thickness of the support film can be appropriately changed depending on the desired flexibility, but it is preferably 3 to 250 μm. If the thickness of the support film is 3 μm or more, the film strength tends to be sufficient. If the thickness of the support film is 250 μm or less, there is a tendency that sufficient flexibility can be obtained. From this point of view, the thickness of the support film is more preferably 5 to 200 μm, even more preferably 7 to 150 μm.

The protective film is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene and the like. Among these, from the viewpoint of flexibility and toughness, the protective film is preferably polyethylene terephthalate, polyethylene, or polypropylene. From the viewpoint of improving releasability from the first resin layer for intermediate layer, it is preferable to use a film that has been subjected to release treatment with a silicone-based compound, a fluorine-based compound, or the like, as the protective film.

The thickness of the protective film can be appropriately set depending on the desired flexibility, but is preferably 10 to 250 μm. If the thickness of the protective film is 10 μm or more, the film strength tends to be sufficient. If the thickness of the protective film is 250 μm or less, sufficient flexibility tends to be obtained. From this point of view, the thickness of the protective film is more preferably 15 to 200 μm, even more preferably 20 to 150 μm.

Although the thickness of the first intermediate layer resin layer is not particularly limited, it is preferably 10 to 10,000 μm. When the thickness of the first intermediate layer resin layer is 10 μm or more, the thickness is sufficient, and the strength of the first intermediate layer resin layer tends to be sufficient. When the thickness of the first intermediate layer resin layer is 10,000 μm or less, the first intermediate layer resin layer tends to be easily processed. From this point of view, the thickness of the first intermediate resin layer is more preferably 50 μm to 5,000 μm, and even more preferably 100 to 1,000 μm. Since the first resin layer for intermediate layer is formed of a resin composition containing a combination of components (A) and (B), even if the thickness of the first resin layer for intermediate layer is increased, A laminated glass having excellent chipping resistance and optical transparency can be formed. From this point of view, the thickness of the first intermediate layer resin layer may be 150 μm or more, 200 μm or more, 250 μm or more, 300 μm or more, 350 μm or more, or 400 μm or more.

The first intermediate layer resin layer can also be formed by forming a film by melt molding such as extrusion molding.

The first resin layer for intermediate layer may be used for lamination in combination with a functional layer such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer of laminated glass. The antireflection layer may be a layer having antireflection properties such that the visible light reflectance is 5% or less. The antireflection layer may be a layer obtained by treating a transparent substrate such as a transparent plastic film with a known antireflection method. The antifouling layer is intended to make the surface difficult to be fouled. The dye layer is a layer for enhancing color purity. The dye layer is used to reduce the transmission of unwanted wavelengths of light through the laminated glass. The hard coat layer is provided to increase surface hardness. The hard coat layer may be, for example, a film of an acrylic resin such as urethane acrylate or epoxy acrylate, or an epoxy resin.

However, the first intermediate resin layer is preferably arranged at a position adjacent to the second intermediate layer, that is, the first intermediate resin layer can be arranged in contact with the second intermediate layer. preferable.

<Second intermediate layer>
The second intermediate layer contains polyvinyl butyral resin. Polyvinyl butyral resin has excellent penetration resistance. Polyvinyl butyral resin also has excellent heat-sealing properties.

The second intermediate layer may contain additives as needed. Examples of additives include infrared absorbers, ultraviolet absorbers, antioxidants, light stabilizers, colorants, and the like.

The thickness of the second intermediate layer is, for example, 0.1-3.0 mm, preferably 0.2-2.5 mm. If the thickness of the second intermediate layer is 0.1 mm or more, it is possible to effectively improve the penetration resistance of the laminated glass against impacts from the outside of the vehicle. If the thickness of the second intermediate layer is 3.0 mm or less, it is possible to effectively improve the easy penetration of the laminated glass against impact from the first intermediate layer side.

To produce the second intermediate layer resin layer, for example, a resin composition containing a polyvinyl butyral resin is extruded in a heated and melted state using an extruder. After that, the extruded resin film is stretched appropriately according to the size and shape of the glass plate, thereby forming the second intermediate layer resin layer. The form of the second intermediate resin layer is preferably a film.

Hereinafter, a method for manufacturing a laminated glass for vehicles according to this embodiment will be described.

<Method for manufacturing laminated glass for vehicles>
Although the laminated glass for vehicles according to the present embodiment is not particularly limited, for example, the first intermediate resin layer and the second intermediate resin layer are arranged between a pair of glass plates. and forming a laminated body by heating and pressing the laminated body to form a laminated glass.

The first intermediate layer resin layer can be cured during at least one or more of the step of forming the laminate and the step of heating and pressing the laminate. A laminate having two glass plates and a first intermediate layer and a second intermediate layer disposed therebetween is, for example, the above-described film material for the first intermediate layer and the above-described film material for the second intermediate layer. can be formed by sandwiching the film material between two glass plates. Alternatively, the first resin layer for intermediate layer may be formed by applying the first resin composition for intermediate layer onto one of the glass plates.

The step of curing the first intermediate layer resin layer is not particularly limited. Curing or cross-linking is preferably performed in the step of forming a laminate having the first intermediate layer resin layer and the second intermediate layer resin layer. In addition, the step of curing the first intermediate layer resin layer is not particularly limited, but from the viewpoint of reducing appearance defects such as air bubbles, the laminate is heated and pressed to form a laminated glass. Crosslinking is preferred.

The method of curing the first intermediate layer is not particularly limited as long as the resin composition for the first intermediate layer can be cured, but a method of heating in the temperature range of 80 to 300° C. for 10 minutes to 5 hours. Preferably. The heating temperature is more preferably 100 to 250° C., even more preferably 120 to 200° C., from the viewpoints of sufficiently advancing curing (including cross-linking) and reducing energy costs. Appropriate heating time varies depending on the heating temperature, but from the same viewpoint as the heating temperature, 20 minutes to 4 hours is more preferable, and 30 minutes to 2 hours is more preferable.

The resin composition for the first intermediate layer or the resin layer for the first intermediate layer has excellent flexibility and/or thermal fluidity before curing or cross-linking, so that it has excellent conformability to curved glass and bonding properties. tend to be superior to In addition, the first intermediate layer resin composition or the first intermediate layer resin layer expresses excellent mechanical strength by post-curing or crosslinking during or after lamination of the laminated glass. The chipping resistance of glass can be improved. The resin composition for the first intermediate layer or the resin layer for the first intermediate layer has a latent curability in which curing or cross-linking progresses slowly from a temperature higher than the temperature at which thermal fluidity is exhibited. Air bubbles and wrinkles tend to disappear at times. Since the second resin layer for the intermediate layer has thermoplasticity, it can be formed satisfactorily by heating and pressurizing steps, and has excellent conformability to curved glass and bonding properties.

The present embodiment will be described below using examples.

[Example 1]
<Preparation of Resin A>
300.0 g of butyl acrylate (BA), 550.0 g of dicyclopentanyl acrylate (FA-513AS, manufactured by Hitachi Chemical Co., Ltd.), and 150 g of glycidyl methacrylate (GMA) as a (meth)acrylic monomer having an epoxy group. 0 g was mixed to obtain a monomer mixture. 5.0 g of lauroyl peroxide as a polymerization initiator and 1.0 g of n-octylmercaptan as a chain transfer agent were dissolved in the resulting monomer mixture to obtain a mixture containing the monomers. 2000 g of ion-exchanged water and 0.3 g of polyvinyl alcohol were placed in a reactor equipped with a cooling tube, a thermometer, a stirrer, and a nitrogen inlet tube, and the mixture was added thereto while stirring. The formed reaction solution is stirred at 250 revolutions per minute (rpm) under a nitrogen atmosphere, and the polymerization reaction is allowed to proceed at 60° C. for 5 hours and then at 90° C. for 2 hours to convert epoxy groups. Particles of Resin A were formed comprising a (meth)acrylic copolymer having a Particles of resin A taken out from the reaction solution were washed with water and dried.

<Production of First Intermediate Layer Resin Composition and First Intermediate Layer Film Material>
100.0 g of the resin A particles as component (A), 8.0 g of 3 or 4-methyl-hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.), which is an acid anhydride compound as component (B), And 0.3 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) which is an imidazole compound is uniformly dissolved in 100.0 g of methyl ethyl ketone, and the resin composition for the first intermediate layer is used as a resin varnish. Obtained. The resulting resin varnish is dropped onto the release-treated surface of a polyethylene terephthalate film as a support film (heavy release separator), a coating film is formed using a bar coater, and the coating film is heated at 80° C. for 30 minutes. It was dried by heating to obtain a resin layer (first intermediate layer resin layer) having a thickness of 100 μm (0.1 mm) formed from the first intermediate layer resin composition. The resin layer is covered with a release-treated surface of a polyethylene terephthalate film as a protective film (light release separator), which is pressed with a hand roller of 1.0 kgf to attach the support film/first intermediate layer. A first film material for intermediate layer having a structure of resin layer for layer/protective film was obtained.

<Production of laminated glass>
A required number of first intermediate layer film materials cut into a size of 300 mm long and 300 mm wide were prepared. After peeling off the light release separator and the heavy release separator of the first intermediate layer film material to expose both sides of the first intermediate layer resin layer, the exposed first intermediate layer resin layer is coated with PVB. A composite resin layer was formed by laminating resin sheets (length: 300 mm, width: 300 mm, thickness: 0.76 mm) so that four sides overlap. Next, the composite resin layer was laminated on the float glass so that the four sides of the PVB resin sheet overlapped with the four sides of the float glass (length: 300 mm, width: 300 mm, thickness: 2.0 mm). Then, a float glass (vertical: 300 mm, horizontal: 300 mm, thickness: 2.0 mm) was placed on the composite resin layer so that the four sides of the first intermediate resin layer of the composite resin layer and the four sides of the float glass overlapped. Laminated in layers. Thus, a laminate of float glass/first intermediate layer/second intermediate layer (PVB resin layer)/float glass was obtained. The obtained laminate was heated using a vacuum laminator set at 125°C for 25 minutes, and then heated and pressurized using an autoclave set at 150°C under conditions of a pressure of 115 N/cm ² for 120 minutes. , a laminated glass having a structure of float glass (2.0 mm)/first intermediate layer (0.1 mm)/PVB resin layer (0.76 mm)/float glass (2.0 mm) was obtained. A required number of laminated glasses were produced by the same operation.

[Comparative Example 1]
<Preparation of PVB resin layer>
A commercially available PVB resin layer with a thickness of about 0.4 mm was used.

<Production of PVB laminated glass>
A PVB resin sheet (length: 300 mm, width: 300 mm, thickness: 0.76 mm) is laminated on float glass (length: 300 mm, width: 300 mm, thickness: 2.0 mm) so that four sides overlap, and further PVB Another sheet of float glass (length: 300 mm, width: 300 mm, thickness: 2.0 mm) was laminated so as to be in contact with the resin sheet. Thus, a laminate of float glass/PVB resin layer/float glass was obtained. The obtained laminate was heated using a vacuum laminator set at 125°C for 25 minutes, and then heated and pressurized using an autoclave set at 150°C at a pressure of 115 N/cm ² for 120 minutes. , a laminated glass having a structure of float glass (2.0 mm)/PVB resin layer (0.76 mm)/float glass (2.0 mm) was obtained. A required number of laminated glasses were produced by the same operation.

[Evaluation 1]
The laminated glass (300 mm long×300 mm wide) obtained in Example 1 and Comparative Example 1 was adjusted to have a surface temperature of 23°C. Next, in accordance with 5.5 penetration resistance test of JIS R 3212:2015, a steel ball with a mass of 2.26 kg is placed on the central part of the laminated glass from a height of 4 m or 6 m on the surface side (first intermediate layer side) ). Similarly, a steel ball was dropped from the back side (second intermediate layer side) onto the central portion of the separately obtained laminated glass.

As a result, in the laminated glass of Example 1, which corresponds to the laminated glass according to the present embodiment, when a steel ball was dropped from the surface side (first intermediate layer side), it penetrated at a height of 4 m (n = 1) When a steel ball was dropped from the back side (second intermediate layer side), it did not penetrate even at a height of 6 m (n=7). Further, in the laminated glass of Comparative Example 1, which corresponds to the conventional PVB laminated glass, even when a steel ball was dropped from a height of 6 m from both the front side and the back side, it did not penetrate (n=7).

[Evaluation 2]
The central portion of the laminated glass obtained in Example 1 and Comparative Example 1 was manually struck with a commercially available round hammer from the surface side (first intermediate layer side) to confirm the presence or absence of penetration. Similarly, the central portion of the separately obtained laminated glass was manually struck with a commercially available round hammer from the back side (second intermediate layer side) to confirm the presence or absence of penetration.

As a result, the laminated glass of Example 1, which corresponds to the laminated glass according to the present embodiment, penetrated when struck from the front side, but did not penetrate when struck from the back side. Further, the laminated glass of Comparative Example 1, which corresponds to the conventional PVB laminated glass, did not penetrate even when hit from both the front side and the back side.

Based on the above results, the laminated glass for vehicles according to the present embodiment has excellent penetration resistance against impact from the second intermediate layer side, while against impact from the first intermediate layer side. was confirmed to have reduced penetration resistance.

The upper and/or lower limits of the numerical ranges described herein can be combined arbitrarily to define a preferred range. For example, a preferred range can be defined by arbitrarily combining the upper and lower limits of the numerical range, a preferred range can be defined by arbitrarily combining the upper limits of the numerical range, and the lower limit of the numerical range Any combination of values can be used to define a preferred range.

The claims following this written disclosure are hereby expressly incorporated into this written disclosure, with each claim standing on its own as a separate embodiment. The present disclosure includes all replacements of independent claims by their dependent claims. Furthermore, additional embodiments deriving from the independent and subsequent dependent claims are also expressly incorporated into this written specification.

One skilled in the art can use the above description to utilize the present disclosure to its fullest extent. The claims and embodiments disclosed herein are to be construed as merely illustrative and exemplary, and not limiting the scope of the disclosure in any way. With the aid of this disclosure, changes can be made in the details of the above embodiments without departing from the underlying principles of this disclosure. In other words, various modifications and improvements of the embodiments specifically disclosed in the above specification are within the scope of this disclosure.

REFERENCE SIGNS LIST 100 laminated glass 101a glass plate 101b glass plate 102 first intermediate layer 103 second intermediate layer

Claims (13)

A laminated glass for a vehicle comprising a pair of glass sheets, and a first intermediate layer and a second intermediate layer disposed between the pair of glass sheets,
The first intermediate layer contains a cured product of a resin composition containing (A) a (meth)acrylic copolymer having an epoxy group and (B) a curing agent,
A laminated glass for vehicles, wherein the second intermediate layer includes a polyvinyl butyral resin. 2. The laminated glass for vehicles according to claim 1, wherein the first intermediate layer and the second intermediate layer are arranged such that the first intermediate layer is closer to the inner side of the vehicle than the second intermediate layer. The laminated glass for vehicles according to claim 1 or 2, wherein the first intermediate layer and the second intermediate layer are in direct contact with each other. (A) a (meth)acrylic copolymer having an epoxy group, based on the mass of (A) a (meth)acrylic copolymer having an epoxy group, a monomer derived from a (meth)acrylic monomer having an epoxy group The laminated glass for vehicles according to any one of claims 1 to 3, comprising 5 to 50% by mass of body units. 5. The laminated glass for vehicles according to claim 4, wherein the monomer unit derived from the (meth)acrylic monomer having an epoxy group contains the monomer unit derived from glycidyl (meth)acrylate. The laminated glass for vehicles according to any one of claims 1 to 5, wherein (B) the curing agent contains an acid anhydride compound. 7. The laminated glass for vehicles according to claim 6, wherein the content of the acid anhydride compound is 0.5 to 30 parts by mass with respect to 100 parts by mass of (A) the (meth)acrylic copolymer having an epoxy group. The laminated glass for vehicles according to claim 6 or 7, wherein (B) the curing agent further contains an imidazole compound. 9. The laminated glass for vehicles according to claim 8, wherein the content of the imidazole compound is 1.0 parts by mass or less with respect to 100 parts by mass of (A) the (meth)acrylic copolymer having an epoxy group. The laminated glass for vehicles according to any one of claims 1 to 9, wherein the resin composition further contains (C) a curing accelerator. The laminated glass for vehicles according to any one of claims 1 to 10, wherein the glass plate is inorganic glass. A vehicle door comprising the vehicle laminated glass according to any one of claims 1 to 11. A method for producing the laminated glass for vehicles according to any one of claims 1 to 11,
A laminate is formed by disposing a resin layer containing the resin composition or a cured product thereof according to any one of claims 1 to 11 and a resin layer containing a polyvinyl butyral resin between a pair of glass plates. process and
heating and pressing the laminate to form a laminated glass;
A method, including

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