TW201942161A - Resin composition for laminated glass interlayer, laminated glass interlayer, film material for laminated glass interlayer, laminated glass, and laminated glass manufacturing method - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition for a laminated glass interlayer, the resin composition enabling a laminated glass having excellent anti-chip properties to be produced. Provided is a resin composition for a laminated glass interlayer, the resin composition: being used to form an interlayer provided between two glass panels disposed facing each other; and including (A) a (meth)acrylic copolymer having an epoxy group, and (B) a curing agent.

Description

Resin composition for interlayer film of laminated glass, interlayer film for laminated glass, film material for interlayer film of laminated glass, laminated glass and method for producing laminated glass

The present invention relates to a resin composition for an interlayer film of laminated glass, an interlayer film for laminated glass, an interlayer film material for laminated glass, a laminated glass, and a method for producing laminated glass.

Conventionally, as glass used for vehicles such as automobiles, aircrafts, buildings, and the like, laminated glass with a small amount of scattering at the time of breakage and difficult to penetrate by flying objects has been widely used. Laminated glass generally has an interlayer film sandwiched between two glass plates. As the interlayer film for laminated glass, for example, a resin layer containing a polyvinyl acetal resin, an ionic polymer resin, an acrylic resin, or the like can be used (for example, Patent Documents 1 to 5). In addition, for transportation equipment such as vehicles and aircraft, laminated glass that is optically transparent is used.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2016-193542
[Patent Document 2] Japanese Patent Publication No. 2009-298046
[Patent Document 3] Japanese Patent Publication No. 2015-151540
[Patent Document 4] Japanese Patent Publication No. 62-028105
[Patent Document 5] Japanese Patent Laid-Open No. 2000-001345

[Problems to be Solved by the Invention]
In recent years, with respect to glass members used in automotive applications, laminated glass having excellent resistance to collisions with flying objects such as flying stones, that is, chipping resistance, is required. The shatter resistance of laminated glass can be improved by thickening the glass used, but the weight of laminated glass is increased. On the other hand, the shatter resistance of laminated glass can also be improved by using high-strength glass such as tempered glass. However, the tempered glass will spread to the entire surface of the glass due to the tiny small sheet-like scars when broken. The vision of the staff is reduced. In addition, according to the results of studies conducted by the present inventors, it is clear that the laminated glass including an intermediate film using a flexible resin such as a polyvinyl acetal resin or an ionic polymer resin has poor chipping resistance.

An object of one aspect of the present invention is to provide a resin composition for an interlayer film that can form a laminated glass having high chipping resistance.
[Means for solving problems]

An aspect of the present invention provides a resin composition for an interlayer film of a laminated glass, which is a resin composition for forming an interlayer film for a laminated glass provided between two opposing glass plates, and the resin composition includes (A) a (meth) acrylic copolymer having an epoxy group, and (B) a hardener.
[Effect of the invention]

According to one aspect of the present invention, a resin composition for an interlayer film that can form a laminated glass having high shatter resistance can be provided.

In addition, the resin composition for an interlayer film of laminated glass of several forms can form laminated glass having excellent optical transparency.

Furthermore, according to the resin composition for interlayer films of laminated glass of several forms, the interlayer film for laminated glass which is excellent in processability and adhesiveness can be provided. Laminated plexiglass using hard resins such as polycarbonate or polymethyl methacrylate can be expected to have similar effects to the case of thickened glass. However, since plexiglass is difficult to bend, it is not suitable for curved surfaces. The followability of glass is low, and the adhesiveness of laminated glass is low due to the high heat distortion temperature, and it is difficult to use it as an interlayer film for laminated glass. That is, regarding the materials used for the conventional glass material and laminated glass material, it can be said that the followability and adhesion to curved glass are inversely related to chipping resistance. On the other hand, the large-area and curved surfaces of automotive laminated glass continue to develop, which requires good interposability of the interlayer film and easy manufacturing operations.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The "(meth) acrylate" in this specification means "acrylate" or the corresponding "methacrylate". Similarly, the so-called "(meth) acrylic acid" means "acrylic acid" or the corresponding "methacrylic acid", and the "(meth) acrylfluorenyl" means the "acrylfluorenyl" or the corresponding "methyl" Acrylic acryl ". Regarding the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition. In this specification, the "resin composition for forming an intermediate film of laminated glass" may be referred to as a "resin composition for forming an intermediate film", and the "interlayer film for laminated glass" may be referred to as an "intermediate film".

FIG. 1 is a sectional view showing an embodiment of laminated glass. The laminated glass 1 shown in FIG. 1 includes two glass plates 21, a glass plate 22 facing each other, and an intermediate film 3 disposed between the glass plates 21 and the glass plates 22. The glass plate 21 and the glass plate 22 may be inorganic glass, and examples of the inorganic glass include float glass, air-cooled tempered glass, chemically strengthened glass, and double glass. The intermediate film 3 is composed of (A) an (meth) acrylic copolymer (hereinafter, sometimes referred to as (A) component) having an epoxy group, and (B) a hardener (hereinafter, sometimes referred to as (B) Component) The interlayer film of laminated glass is formed of a resin composition.

The laminated glass and the interlayer film for laminated glass are not limited to the aspect shown in FIG. 1, and can be changed within a range not departing from the gist of the present invention. The interlayer film for laminated glass may use a single layer of a resin layer formed from a resin composition for an interlayer film of a laminated glass containing the component (A) and (B), or may be used by laminating two or more layers. That is, the interlayer film for laminated glass may have one resin layer including the resin composition for intermediate film or a cured product thereof, or may include two or more of the resin layers and laminate the resins. A resin layer formed of another resin type such as a polyvinyl acetal resin and an ionic polymer resin may be further laminated. From the viewpoint of more excellent chipping resistance, the interlayer film for laminated glass is preferably a resin layer formed of the resin composition for interlayer films.

Fig. 3 is a sectional view showing another embodiment of the laminated glass. The laminated glass 100 shown in FIG. 3 includes two glass plates 210, a glass plate 220, and an interlayer film 300 disposed between the glass plates 210 and 220. The intermediate film 300 is a resin laminate including a first resin layer 310 and a second resin layer 320. The first resin layer 310 is a resin layer including the resin composition for an intermediate film or a cured product thereof, and the second resin layer 320 is a resin layer including a polyvinyl acetal resin. The laminated glass 100 includes the interlayer film 300 including the first resin layer 310 and the second resin layer 320, and thus tends to have excellent chipping resistance and penetration resistance.

The laminated glass 100 may be a member for a window of a vehicle. When the laminated glass 100 is a member for a vehicle window, one of the two glass plates 210 and 220 is an outer glass plate facing the outside of the vehicle when the laminated glass 100 is mounted on a vehicle. From the viewpoint of better cracking and penetration resistance, the first resin layer 310 of the intermediate film 300 is preferably adjacent to the outer glass plate. That is, when the laminated glass 100 is a member for a window of a vehicle, it is preferably laminated glass in which a first resin layer and a second resin layer are sequentially laminated from the outer glass plate side.

The intermediate film 300 may include two or more first resin layers, or may include two or more second resin layers. When the intermediate film 300 includes two or more first resin layers or two or more second resin layers, the first resin layer and the second resin layer may be laminated alternately.

The thickness of the first resin layer is not particularly limited, and may be 10 μm to 300 μm, 50 μm to 250 μm, or 100 μm to 200 μm. The thickness of the second resin layer is not particularly limited, and may be 300 μm to 800 μm, 350 μm to 750 μm, or 400 μm to 600 μm.

The polyvinyl acetal resin contained in the second resin layer is not particularly limited, and a polyvinyl acetal resin generally used in this technical field can be used. Examples of the polyvinyl acetal resin include polyvinyl butyral and polyvinyl formaldehyde. The degree of acetalization of the polyethylene acetal resin may also be 5 mol% to 90 mol%, 25 mol% to 80 mol%, or 50 mol% to 70 mol%.

The second resin layer may further contain a plasticizer. The plasticizer is not particularly limited, and a plasticizer generally used in this technical field can be used. From the viewpoint of more excellent penetration resistance, the plasticizer preferably contains a material selected from the group consisting of triethylene glycol di-2-ethylbutanoate, triethylene glycol di-2-ethylhexanoate, and triethylene glycol. At least one of the group consisting of ethylene glycol di-n-heptanoate, more preferably contains triethylene glycol di-2-ethylhexanoate. From the viewpoint of better penetration resistance, the content of the plasticizer may also be 10 to 70 parts by mass and 20 to 60 parts by mass relative to 100 parts by mass of the polyvinyl acetal resin in the second resin layer. Parts, 30 parts by mass to 50 parts by mass, or 35 parts by mass to 45 parts by mass.

The resin composition for an interlayer film of a laminated glass of this embodiment can also be used as an image display member and an image display member used in image display devices such as organic electroluminescence (organic EL (electroluminescence)) and liquid crystal displays. Protective material.

<Resin composition for interlayer film of laminated glass>
(A) A component should just be a unit containing a single body derived from the (meth) acrylic monomer which has an epoxy group. The content of the component (A) may be 70% by mass or more, 75% by mass or more, or 80% by mass or more based on the total mass of the resin composition for an intermediate film.

Examples of the (A) component include a singular unit derived from a (meth) acrylic monomer having an epoxy group, and a singular unit derived from a (meth) acrylic monomer having no epoxy group. And a copolymer derived from a unit of a single amount of a compound having an ethylenically unsaturated group other than the (meth) acrylic monomer, if necessary.

Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4- (meth) acrylic acid. Epoxy cyclohexyl methyl ester and the like. Among these, from the viewpoint of heat resistance and chipping resistance, glycidyl (meth) acrylate is preferably used. That is, it is preferable that the unit weight unit derived from the (meth) acrylic acid monomer which has an epoxy group contains the unit weight unit derived from the glycidyl (meth) acrylate. These compounds can be used alone or in combination of two or more.

Based on the mass of the component (A), the content of the singular unit derived from the (meth) acrylic monomer having an epoxy group in the component (A) The amount of the standard (meth) acrylic monomer having an epoxy group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass. . When the content of the monobasic unit derived from the (meth) acrylic monomer having an epoxy group is 5% by mass or more, the crack resistance of laminated glass can be made better, and if it is 50% by mass or less, the Since the reaction between epoxy groups is suppressed during the storage of the resin composition for an intermediate film, sufficient storage stability tends to be obtained.

Examples of the (meth) acrylic monomer having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2- Ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol Aliphatic (meth) acrylates such as (meth) acrylates; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, and bicyclic (meth) acrylate Aliphatic (meth) acrylates such as pentyl esters, dicyclopentenyl (meth) acrylates, and aromatic (formaldehyde) such as benzyl (meth) acrylates and phenoxyethyl (meth) acrylates (Meth) acrylic acid esters; 2-tetrahydrofurfuryl (meth) acrylate, heterocyclic (meth) acrylates such as N- (meth) acrylfluorenyloxyethylhexahydrophthalimide, etc. . Among these, in terms of cost and ease of synthesis, it is preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or (meth) acrylic acid 2 -Ethylhexyl, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, dicyclopentane (meth) acrylate Ester, benzyl (meth) acrylate, or 2-tetrahydrofurfuryl (meth) acrylate. These compounds can be used alone or in combination of two or more.

Based on the mass of the component (A), the content of the unit body of the (A) component derived from the (meth) acrylic monomer having no epoxy group (based on the total amount of the copolymerized component of the synthetic (A) component) The blending amount of the (meth) acrylic monomer having no epoxy group as a reference is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, and even more preferably 65% to 85% by mass. quality%. In the case where an aliphatic (meth) acrylate is used as the (meth) acrylic monomer having no epoxy group, based on the mass of the (A) component, the (A) component is derived from an aliphatic (a The content of the monobasic unit of the acrylic ester (the amount of the aliphatic (meth) acrylate compounded based on the total amount of the copolymerized components of the synthetic (A) component) is preferably 10% by mass to 50% by mass, more It is preferably 15% to 45% by mass, and further preferably 20% to 40% by mass. When an alicyclic (meth) acrylate is used as the (meth) acrylic monomer having no epoxy group, based on the mass of the component (A), the component derived from the alicyclic type in the component (A) The content of the unit weight of the (meth) acrylic acid ester (the amount of the alicyclic (meth) acrylic acid ester to be formulated based on the total amount of the copolymerized components of the synthetic (A) component) is preferably 30% to 80% by mass. %, More preferably 35% to 70% by mass, and even more preferably 40% to 65% by mass.

Examples of the compound having an ethylenically unsaturated group other than the (meth) acrylic monomer include styrene, (meth) acrylonitrile, N-cyclohexylmaleimide, and N-phenylmaleimide Imine, vinyl cyclohexyl ether, vinyl phenyl ether, vinyl acetate, N-vinyl pyrrolidone, vinyl pyridine, 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 interlayer film for laminated glass. . These compounds can be used alone or in combination of two or more.

Based on the mass of the component (A), the content of the unit weight of the compound having an ethylenically unsaturated group other than the (meth) acrylic monomer in the component (A) The blending amount of the compound having an ethylenically unsaturated group other than the (meth) acrylic monomer based on the total amount of the copolymerization component is preferably 0% to 40% by mass, and more preferably 5% to 35% by mass. It is more preferably 10% by mass to 30% by mass.

The glass transition temperature of the component (A) is not particularly limited, but is preferably -30 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, still more preferably 10 ° C to 50 ° C, and particularly preferably 30 ° C to 50 ° C. When the glass transition temperature of the component (A) is -30 ° C or higher, it tends to be easy to obtain laminated glass having excellent chipping resistance. When the glass transition temperature of the component (A) is 150 ° C. or lower, the toughness of the interlayer film for laminated glass tends to be high, and therefore the interlayer film for laminated glass excellent in processability tends to be easily obtained. In addition, if the glass transition temperature is 10 ° C or higher, the adhesion of the polymer to the blade during the cutting of the interlayer film for laminated glass tends to be suppressed, and if it is 50 ° C or lower, the interlayer film for laminated glass can be suppressed The tendency to crack.

The glass transition temperature of the component (A) is an intermediate point glass transition temperature measured using differential scanning calorimetry (DSC). Specifically, in order to measure the change in heat under the condition of a temperature increase rate of 10 ° C./min, the intermediate point glass transition temperature calculated by the method according to JIS K 7121: 1987. The measurement temperature may be in a range including a glass transition temperature, and may be, for example, -50 ° C to 100 ° C or -80 ° C to 80 ° C.

The glass transition temperature of the component (A) can be obtained by synthesizing a copolymerized component of the component (A), for example, the (meth) acrylic monomer having an epoxy group, the (meth) acrylic monomer having no epoxy group, and The blending ratio of the compound having an ethylenically unsaturated group other than the (meth) acrylic monomer is adjusted.

The epoxy equivalent of the component (A) is preferably 200 g / eq to 2,000 g / eq. When the epoxy equivalent of (A) component is 200 g / eq or more, since the reaction of an epoxy group can be suppressed during storage of the resin composition for intermediate films, storage stability tends to become favorable. When the epoxy equivalent of the component (A) is 2,000 g / eq or less, the laminated glass including the interlayer film formed of the interlayer film resin composition tends to have good chipping resistance. The epoxy equivalent is a value measured by a method according to JIS K 7236: 2001.

The weight-average molecular weight of the component (A) is preferably 100,000 to 3,000,000. When the weight average molecular weight of the (A) component is 100,000 or more, the toughness of the obtained interlayer film for laminated glass tends to be improved. When the weight-average molecular weight of the component (A) is 3,000,000 or less, bubbles tend to escape when the laminated glass is produced, and thus the appearance tends to be good. The weight-average molecular weight of the component (A) can be adjusted by common methods such as polymerization temperature, polymerization time, solvent used in polymerization, and addition of a chain transfer agent.

The weight average molecular weight is a polystyrene conversion value obtained by measuring by gel permeation chromatography (GPC) and converting using a calibration curve based on standard polystyrene.

The method for synthesizing the component (A) is not particularly limited, and examples thereof include the use of an appropriate thermal radical polymerization initiator for the (meth) acrylic monomer having an epoxy group and the one having no epoxy group. A method of heating and copolymerizing a (meth) acrylic monomer and a compound having an ethylenically unsaturated group other than the (meth) acrylic monomer, if necessary, and further prepared. The polymerization method is not particularly limited, and examples thereof include a block polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. If necessary, polymerization may be carried out using an appropriate chain transfer agent or the like.

The (B) curing agent used in this embodiment is a component that reacts with the epoxy group of the component (A) to form a crosslinked structure. The (B) curing agent may be any one having a functional group capable of reacting with the epoxy group of the component (A), and examples thereof include phenol compounds, acid anhydride compounds, amine compounds, imidazole compounds, imidazoline compounds, and triazine compounds. , Phosphine compounds, etc. Among these, from the viewpoint of latent hardenability and optical transparency, the hardening agent preferably contains an acid anhydride compound. From the viewpoint of shortening the curing time, the curing agent preferably contains an imidazole compound. These compounds can be used alone or in combination of two or more.

The content of the component (B) is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the component (A). When the content of the component (B) is 0.01 parts by mass or more, the interlayer film for a laminated glass formed of a resin composition can be made to have good hardenability. Therefore, it is expected to easily obtain a laminated glass with high chipping resistance and shorten the process time. If the content of the component (B) is 50 parts by mass or less, the storage stability of the resin composition tends to be good. From the same viewpoint, the content of the component (B) is more preferably 0.5 to 30 parts by mass.

Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, ethylene glycol dianhydrotrimellitic acid ester, and triglyceride trianhydride Triester, maleic anhydride, tetrahydrophthalic anhydride, methylene tetrahydrophthalic anhydride, methyl humic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecene Succinic anhydride, hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, methyltetrahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, methyl Hexahydrophthalic anhydride and the like substituted with alkyl groups. The hexahydrophthalic anhydride substituted with an alkyl group may be, for example, a hexahydrophthalic anhydride substituted with an alkyl group having 1 to 9 carbon atoms. From the viewpoint of the optical transparency of the cured product, the curing agent preferably contains a material selected from the group consisting of tetrahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalate. Formic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, and hexahydrophthalic anhydride substituted with alkyl groups At least one selected from the group consisting of at least one selected from the group consisting of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and further preferably including methylhexa Hydrophthalic anhydride.

The content of the acid anhydride compound is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the component (A), more preferably 1 to 25 parts by mass, still more preferably 5 to 20 parts by mass, and particularly preferably 10 parts by mass to 20 parts by mass. When the content of the acid anhydride compound is 0.5 parts by mass or more, the interlayer film for laminated glass formed from the resin composition for interlayer films can be made to have good hardenability. Therefore, it is expected that an interlayer with high chipping resistance and optical transparency can be obtained more easily. When the glass and the step time are shortened and the workability is improved, if it is 30 parts by mass or less, the storage stability of the resin composition for an intermediate film tends to be good. The content of the acid anhydride compound is preferably 40 parts by mass to 70 parts by mass with respect to 100 parts by mass of the unit amount of the unit unit derived from the (meth) acrylic monomer having an epoxy group in the component (A). It is 45 to 65 parts by mass, more preferably 50 to 60 parts by mass, and even more preferably 50 to 55 parts by mass.

Examples of the imidazole compound 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-methyl Imidazole, 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 adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4 , 5-Dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, chloride 1-dodecyl-2-methyl-3-benzylimidazolium and the like. Among these, from the viewpoint of storage stability of the resin composition for an intermediate film, 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-phenyl are preferably used. Imidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undi Alkyl imidazolyl- (1 ')]-ethyl-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl S-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl- 4,5-dihydroxymethylimidazole, or 2-phenyl-4-methyl-5-hydroxymethylimidazole. These compounds can be used alone or in combination of two or more.

When an imidazole compound is used, its content is not particularly limited, and it may be 1.0 part by mass or less, 0.5 part by mass or less, 0.3 part by mass or less, 0.2 part by mass or less with respect to 100 parts by mass of the component (A). Mass parts or less. When the content of the imidazole compound is within the above range, it is possible to reduce the curing temperature and shorten the curing time, and to suppress yellowing of the resin composition after curing.

The resin composition for an intermediate film may further contain a hardening accelerator as needed. Examples of the hardening accelerator include an organic phosphorus-based hardening accelerator. The imidazole compound can also function as a hardening accelerator, but is classified as a hardener in this specification. Examples of the organophosphorus-based hardening accelerator include triphenylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, ethyltriphenylphosphonium bromide, and benzyltrichloride. Phenylhydrazone, 1,4-bisdiphenylphosphinobutane, 2-ethyl-4-methylimidazolium tetraphenylborate, 1,5-diazabicyclo [4.3.0] nonene- 5-tetraphenylboronate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenyl Phenylphosphonium dicyandiamide, n-butyltriphenylphosphonium dicyandiamide, tetraphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium decanoate. These compounds can be used alone or in combination of two or more.

The content of the hardening accelerator is not particularly limited, but is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the component (A). When the content of the hardening accelerator is 0.01 parts by mass or more, the interlayer film for laminated glass formed of the interlayer film resin composition for laminated glass can have good hardenability, and therefore it is expected that it is easier to obtain an interlayer with high chipping resistance. When the glass and the step time are shortened and the workability is improved, if it is 50 parts by mass or less, the storage stability of the resin composition for an interlayer film of laminated glass tends to be good.

The resin composition for an intermediate film may further use an additive as needed. The additives used are not particularly limited, and examples thereof include a polymerization inhibitor, a silane coupling agent, a surfactant, an inorganic filler, a flame retardant, a plasticizer, and other polymers.

Examples of the polymerization inhibitor include p-methoxyphenol. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane , Γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyl Methyldiisopropenyloxysilane. Examples of the surfactant include a polydimethylsiloxane compound and a fluorine compound. These additives may be used alone, or a plurality of additives may be used in combination. When these additives are used, the content may be about 0.01 to 5 mass% relative to the total amount of the resin composition for an intermediate film.

Examples of the inorganic filler include crushed silica, fused silica, mica, clay minerals, short glass fibers or fine powders, and hollow glass, calcium carbonate, quartz powder, and metal hydrates. The content of the inorganic filler may be 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 an intermediate film. When the content of the inorganic filler is 0.01 to 100 parts by mass, the resin composition for an intermediate film tends to obtain effects such as low shrinkage, improvement in mechanical strength, and low thermal expansion coefficient. 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, phenol resins, polyvinyl acetal resins, and ionic polymer resins. When an epoxy resin or a phenol resin is used, the strength of the interlayer film for laminated glass tends to increase. When a polyvinyl acetal resin or an ionic polymer resin is used, the adhesive force of an intermediate film and a glass plate tends to become high easily.

If necessary, the resin composition for an intermediate film may be further diluted with an organic solvent. The organic solvent is not particularly limited as long as it dissolves the resin composition, and examples thereof include ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate Esters, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other organic solvents; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether Polyol alkyl ether organic solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether Polyol alkyl ether acetates such as acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate; N, N-dimethylformamide, N, N-dimethyl Amidamine-based organic solvents such as acetamide and N-methylpyrrolidone. These organic solvents may be used singly or in combination of two or more kinds.

The loss tangent tan δ of the interlayer film for laminated glass formed of the resin composition for interlayer films at a temperature of 0 ° C. and a frequency of 0.5 Hz is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.2 or less. When tan δ is 0.5 or less, since the deformation of the interlayer film for laminated glass due to an external impact can be suppressed, it tends to be easier to obtain laminated glass having excellent chipping resistance. tan δ is a value measured by a dynamic viscoelasticity test in a tensile mode. Specifically, a film material having an interlayer film for laminated glass adjusted to a thickness of 0.1 mm can be heated at 150 ° C for 2 hours, and then a dynamic viscoelasticity test device (manufactured by TA Instruments Japan Co., Ltd., RSA-G2). The measurement was 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 conditions of the temperature and time for heating the film material vary depending on the type and amount of the (A) component and (B) component contained in the resin composition. As long as the resin composition does not decompose and volatilize, it can be sufficiently The conditions for crosslinking are not particularly limited. The strain amount is preferably set to a value as large as possible in a region where the film material does not undergo plastic deformation.

＜ Interlayer film for laminated glass ＞
The interlayer film for laminated glass of this embodiment is obtained by forming the resin composition for interlayer films of the laminated glass into a film shape or a layer shape. When the interlayer film for laminated glass is formed, it can also be obtained by hardening or crosslinking the resin composition for interlayer films of laminated glass.

The interlayer film for laminated glass can be easily produced by, for example, applying a resin composition for an interlayer film of laminated glass to a support film. When the resin composition for an interlayer film of laminated glass is diluted with an organic solvent, the resin composition can be produced by applying the resin composition to a support film and removing the organic solvent by heating and drying. In this case, a film material for an interlayer film having a two-layer structure including a support film and an interlayer film for laminated glass can be obtained.

A protective film may be attached to the interlayer film for laminated glass provided on the support film as needed. In this case, a film material for an interlayer film having a three-layer structure including a support film, an interlayer film for a laminated glass, and a protective film can be obtained.

The thus-obtained film material for an interlayer film of laminated glass can be easily stored by being wound into a roll shape, for example. The roll-shaped film material can also be cut into a suitable size, and formed into a sheet shape and stored.

The supporting film is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyamide, and polyamide Amine, etc. Among these, from the viewpoint of flexibility and toughness, the supporting film is preferably polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, Polyamidamine, or polyimide. From the viewpoint of improving the releasability from the interlayer film for laminated glass, it is preferable to use a film subjected to a 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 according to the target flexibility, and is preferably 3 μm to 250 μm. When it is 3 μm or more, the film strength tends to be sufficient, and when it is 250 μm or less, sufficient flexibility tends to be obtained. From such a viewpoint, the thickness of the support film is more preferably 5 μm to 200 μm, and still more preferably 7 μm to 150 μm.

The protective film is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene. Among these, in terms of flexibility and toughness, the protective film is preferably polyethylene terephthalate, polyethylene, or polypropylene. From the viewpoint of improving the releasability from the interlayer film for laminated glass, it is preferable to use a film subjected to a 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 according to the target flexibility, and is preferably 10 μm to 250 μm. When it is 10 μm or more, the film strength tends to be sufficient, and when it is 250 μm or less, sufficient flexibility tends to be obtained. From this viewpoint, the thickness of the protective film is more preferably 15 μm to 200 μm, and further preferably 20 μm to 150 μm.

The thickness of the interlayer film for laminated glass is not particularly limited, but is preferably 10 μm to 10,000 μm. If the thickness is 10 μm or more, the thickness is sufficient, and therefore the strength of the interlayer film for laminated glass or its cured product tends to be sufficient. If it is 10,000 μm or less, the processed interlayer film for laminated glass tends to be easily processed. . From such a viewpoint, the thickness of the interlayer film for laminated glass is more preferably 50 μm to 5,000 μm, and even more preferably 100 μm to 1,000 μm. The interlayer film for laminated glass can be formed by a resin composition containing a combination of the (A) component and the (B) component. Therefore, even if the thickness of the interlayer film is increased, an excellent chipping resistance and optical transparency can be formed. Laminated glass. From such a viewpoint, the thickness of the interlayer film for laminated glass 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 interlayer film for laminated glass can also be formed by forming a film by melt molding such as extrusion molding.

The interlayer film for laminated glass can also be used in combination with a functional functional layer such as an anti-reflection layer, an antifouling layer, a pigmented layer, a hard coat layer, and a penetration-resistant layer, and a transparent protective plate of laminated glass. The anti-reflection layer may be any layer having anti-reflection properties in which the visible light reflectance is 5% or less. The anti-reflection layer may be a layer obtained by processing a transparent substrate such as a transparent plastic film by a known anti-reflection method. The antifouling layer is a layer for making it difficult to attach dirt to the surface. The pigment layer is a layer for improving color purity. The pigment layer is used to reduce light of an unwanted wavelength transmitted in the laminated glass. The hard coat layer is provided to increase surface hardness. Examples of the hard coat layer include films of acrylic resins such as acrylic urethane and epoxy acrylate, and epoxy resins. As the hard coating layer, a transparent protective plate such as a glass plate, an acrylic resin layer, or a polycarbonate resin layer, and a hard coating layer laminated on the transparent protective plate can also be used. The penetration-resistant layer is provided to prevent flying objects from penetrating the surface of the laminated glass. The penetration-resistant layer can be formed, for example, from a polyvinyl acetal resin such as polyvinyl butyral and polyvinyl formaldehyde, an ethylene-vinyl acetate copolymer resin, and an ionic polymer resin.

In the case where the interlayer film for laminated glass is combined with an anti-reflection layer, an antifouling layer, a pigmented layer, a hard coat layer, a penetration-resistant layer and other functional functional layers of a laminated glass, and a transparent protective plate The arrangement is not particularly limited, and the interlayer film for laminated glass is preferably disposed at a position adjacent to the glass on the side where the flying object such as flying stone collides.

<Manufacturing method of laminated glass>
The laminated glass of this embodiment can be produced, for example, by the following method, which includes the steps of forming a laminated body having two glass plates and an intermediate film disposed therebetween; and heating and applying the laminated body. Step of forming laminated glass. The interlayer film for laminated glass can be hardened or crosslinked during the step of forming the laminated body and any one or more of the steps of heating and pressing the laminated body. A laminated body having two glass plates and an intermediate film disposed therebetween can be formed, for example, by preparing the film material having an intermediate film and sandwiching the intermediate film with two glass plates. In addition, the intermediate film may be formed by coating the resin composition for an intermediate film on one of the glass plates, and formed by sandwiching the two glass plates.

The step of hardening or crosslinking the intermediate film is not particularly limited. From the viewpoint of shortening the working time and the viewpoint of reducing appearance defects such as bubbles, it is preferred to form two glass plates and arrange them between them. In the step of laminating the interlayer film, curing or crosslinking is performed, and from the viewpoint of reducing appearance defects such as bubbles, it is preferable to perform hardening or crosslinking in the step of heating and pressing the laminated body to form a laminated glass Link.

The method for hardening or crosslinking the intermediate film is not particularly limited as long as the resin composition in the intermediate film can be hardened or crosslinked. It is preferably 10 minutes to 80 ° C to 300 ° C. 5 hours of heating to harden or crosslink. From a viewpoint of sufficiently hardening or crosslinking and a viewpoint of reducing energy cost, the heating temperature is more preferably 100 ° C to 250 ° C, and even more preferably 120 ° C to 200 ° C. The appropriate heating time varies depending on the heating temperature, but from the same viewpoint as the heating temperature, it is more preferably 20 minutes to 4 hours, and even more preferably 30 minutes to 2 hours.

The resin composition for an interlayer film of a laminated glass and the interlayer film for a laminated glass of this embodiment have excellent flexibility and thermal fluidity before being cured or cross-linked, and therefore they have excellent followability and adhesion to curved glass Moreover, by performing post-hardening or cross-linking during or after laminating the laminated glass, it exhibits excellent mechanical strength, so the chipping resistance of the laminated glass can be improved. Furthermore, the resin composition for an interlayer film of a laminated glass and the interlayer film for a laminated glass of this embodiment have a latent hardening property that hardens or crosslinks slowly from a temperature higher than a temperature at which thermal fluidity is exhibited. Air bubbles and wrinkles tend to disappear during bonding.
[Example]

Hereinafter, the present invention will be described in more detail with examples. The present invention is not limited to these examples.

1. Production of Resin A to Resin I (Resin A)
300.0 g of butyl acrylate (BA), 550.0 g of dicyclopentyl acrylate (FA-513AS, manufactured by Hitachi Chemical Co., Ltd.), and a (meth) acrylic monomer having an epoxy group 150.0 g of glycidyl methacrylate (GMA) was mixed to obtain a single volume mixture. 5.0 g of lauryl peroxide peroxidation as a polymerization initiator and 1.0 g of n-octyl mercaptan as a chain transfer agent were dissolved in the obtained single body mixture to obtain a mixed solution containing the single body. 2000 g of ion-exchanged water and 0.3 g of polyvinyl alcohol were placed in a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, and a nitrogen introduction tube, and the mixture was stirred and added thereto. The reaction solution formed was stirred under a nitrogen atmosphere at a stirring speed of 250 revolutions per minute (rpm), and polymerization was performed at 60 ° C for 5 hours, and then polymerization was performed at 90 ° C for 2 hours, thereby Particles of a resin A containing a (meth) acrylic copolymer having an epoxy group are formed. The particles of the resin A taken out from the reaction solution were washed with water and dried.
(Resin B)
The same amount of the monomer mixture as BA 270.0 g, FA-513AS 480.0 g, and GMA 250.0 g was used in the same manner as in the resin A to obtain a (meth) acrylic copolymer containing an epoxy group. Resin B particles.
(Resin C)
The same amount of the monomer mixture as BA 240.0 g, FA-513AS 410.0 g, and GMA 350.0 g was used in the same manner as in the resin A to obtain a (meth) acrylic copolymer having an epoxy group. Resin C particles.
(Resin D)
The monomer mixture was set to a monomer mixture of BA 230.0 g, FA-513AS 620.0 g, and GMA 150.0 g, and a (meth) acrylic copolymer containing an epoxy group was obtained in the same manner as in the resin A. Resin D particles.
(Resin E)
The monomer mixture was set to a monomer mixture of BA 350.0 g, FA-513AS 500.0 g, and GMA 150.0 g, and a (meth) acrylic copolymer containing an epoxy group was obtained in the same manner as in the resin A. Resin E particles.
(Resin F)
The monomer mixture was set to a monomer mixture of BA 400.0 g, FA-513AS 450.0 g, and GMA 150.0 g, and a (meth) acrylic copolymer containing an epoxy group was obtained in the same manner as in the resin A. Resin F particles.
(Resin G)
Particles of a resin G containing an acrylic copolymer not containing an epoxy group were obtained in the same manner as in the resin A except that the monomer mixture was BA 550.0 g and FA-513AS 450.0 g.
(Resin H)
When infrared absorption spectrum measurement obtained by the corresponding hydroxy peak half-value width of 245 cm ^-1 of polyvinyl butyral (polyvinyl butyral, PVB) resin (an acetalization degree 68.0 mole%, of vinyl acetate The proportion of the components was 0.6 mol%) 100 parts by mass, and 38 parts by mass of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was mixed. The mixture was sufficiently melt-kneaded with a mixing roll to obtain a resin H.
(Resin I)
An ionic polymer resin (an ionic polymer resin formed of an ethylene-methacrylic acid copolymer and zinc ions, manufactured by DuPont-Mitsui Polychemicals Co., Ltd., Himilan 1705) was used as the resin I .

Resin A to resin I are collectively shown in Table 1 below. In Table 1 below, the blending of the unit components of the resins A to G is represented by mass% based on the total amount of the copolymerization components, and the resin H is represented by mass parts.

[Table 1]

2. Production of laminated glass (Example 1)
<Production of resin composition for interlayer film of laminated glass, interlayer film for laminated glass, and film material for interlayer film of laminated glass>
100.0 g of particles of the resin A as the component (A) and 3 or 4-methyl-hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride compound as the component (B) ) 8.0 g, and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.), an imidazole compound, 0.3 g were uniformly dissolved in 100.0 g of methyl ethyl ketone and obtained as a resin varnish Resin composition for an intermediate film. The obtained resin varnish was added dropwise to the release-treated surface of a polyethylene terephthalate film as a support film (repeated release layer), and a coating film was formed using a bar coater. The coating film was dried by heating for one minute to obtain a resin layer (interlayer film for laminated glass) having a thickness of 100 μm (0.1 mm), which was formed from the resin composition for an interlayer film. The release-treated surface of the polyethylene terephthalate film, which is a protective film (light peeling release layer), was coated on the resin layer, and it was attached by pressing it with a manual roller of 1.0 kgf to obtain A film material for an interlayer film of a laminated glass having a support film / interlayer film for a laminated glass / a protective film.

＜ Production of laminated glass ＞
Four sheets of interlayer film material were cut into a size of 110 mm in length and 110 mm in width. The light release layer was peeled off from these film materials for an interlayer film, and the resin layer (interlayer film for laminated glass) was exposed. Using two sheets of the film material for the intermediate film, the exposed surfaces of the resin layer were attached so that the four sides overlapped with each other, and the whole was pressed by a roller from above. By this operation, two sets of interlayer film materials having a resin layer with a thickness of 200 μm (a resin laminate in which two interlayer films for laminated glass with a thickness of 100 μm are laminated) are obtained. Next, for the two sets of interlayer film materials, the single-sided re-peeling release layer was peeled to expose the resin layer, and the exposed surfaces of the resin layers were adhered to each other so that the four sides overlap, and the whole was added by a roller from above Pressure. By this operation, a film material for an intermediate film having a resin layer having a thickness of 400 μm (a resin laminated body obtained by laminating four interlayer films for a laminated glass with a thickness of 100 μm) was obtained. After peeling the release layer on one side of the obtained film material for the intermediate film, the resin layer was exposed, and then the exposed resin layer was laminated with a float glass of 110 mm in length, 110 mm in width, and 2.7 mm in thickness on four sides. Attach it in the same manner and press the whole with a roller from above. Next, after peeling the heavy peeling release layer on the other side to expose the resin layer, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 1.6 mm was attached on the exposed resin layer so that the four sides overlapped. The whole is pressed by a roller from above. Thereby, a laminated body of an interlayer film (resin layer) for float glass / laminated glass / 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 at a pressure of 115 N / cm ² for 120 minutes using an autoclave set at 150 ° C. A laminated glass having a composition of float glass (2.7 mm) / intermediate film / float glass (1.6 mm) was obtained. Five pieces of laminated glass were produced by the same operation.

(Examples 2 to 14 and Comparative Example 1)
The interlayer film resin composition for laminated glass shown in the following Tables 2 to 4 was used in the same manner as in Example 1 to produce an interlayer film for laminated glass, an interlayer film material for laminated glass, and a laminated glass. In Example 8, 1-cyanoethyl-2-phenylimidazole (2PZCN, manufactured by Shikoku Chemical Industry Co., Ltd.) was used as a hardener.

(Reference Example 1)
＜ Production of PVB resin layer ＞
Resin H was compression-molded under a condition of 150 ° C. and 30 minutes using a compression molding machine to obtain a PVB resin layer having a thickness of 0.4 mm.

＜ Production of laminated glass ＞
The PVB resin layer was cut to a size of 110 mm in length and 110 mm in width, and the four sides were overlapped to be attached to a float glass of 110 mm in length, 110 mm in width, and 1.6 mm in thickness. The whole was pressed by a roller from above. . On the exposed resin layer side, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached with four sides overlapping, and the whole was pressed by a roller from above. Thereby, a laminated body of a 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 at a pressure of 115 N / cm ² for 120 minutes using an autoclave set at 150 ° C. A laminated glass having a composition of float glass (2.7 mm) / PVB resin layer / float glass (1.6 mm) was obtained. Five pieces of laminated glass were produced by the same operation.

(Reference Example 2)
＜ Production of ionic polymer resin layer ＞
For an ionic polymer resin (an ionic polymer resin formed of an ethylene-methacrylic acid copolymer and zinc ions, manufactured by DuPont-Mitsui Polychemicals Co., Ltd., Himilan 1705, "Resin I" ), Using a plastic mill with a mold (plastomill), extrusion molding was performed under the following conditions to form a resin film having a thickness of 0.4 mm as an ionic polymer resin layer.
· Screw speed: 50 revolutions per minute (rpm)
· Torque pressure: 45 N · m
· The mixing temperature in three areas: 150 ℃, 170 ℃ and 190 ℃
· Mould temperature: 190 ℃
· Mould clearance: 0.6 mm
· Speed of cooling roller and traction roller: 2.0 m / min

＜ Production of laminated glass ＞
The ionic polymer resin layer was cut into a size of 110 mm in length and 110 mm in width, and then the four sides were overlapped and attached to a float glass of 110 mm in length, 110 mm in width, and 1.6 mm in thickness. Pressurize. On the exposed resin layer side, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached with four sides overlapping, and the whole was pressed by a roller from above. Thereby, a laminated body of a float glass / ionic polymer 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 at a pressure of 115 N / cm ² for 120 minutes using an autoclave set at 150 ° C. A laminated glass having a composition of float glass (2.7 mm) / ionic polymer resin layer / float glass (1.6 mm) was obtained. Five pieces of laminated glass were produced by the same operation.

(Example 2-1)
＜ Production of laminated glass ＞
100.0 g of particles of the resin C as the component (A) and 3 or 4-methyl-hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride compound as the component (B) 18.6 g, and 0.3 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) as an imidazole compound were uniformly dissolved in 100.0 g of methyl ethyl ketone to obtain a resin varnish. The obtained resin varnish was added dropwise to the release-treated surface of a polyethylene terephthalate film as a support film (repeated release layer), and a coating film was formed using a bar coater. The coating film was dried by heating for one minute to obtain an acrylic resin layer A having a thickness of 100 μm (0.1 mm). The release-treated surface of the polyethylene terephthalate film as a protective film (light peeling release layer) is coated on the acrylic resin layer A, and it is attached by pressing it with a manual roller of 1.0 kgf. Thus, a film material for an acrylic resin layer having a configuration of a support film / acrylic resin layer A (first resin layer) / protective film was obtained.

A PVB resin layer (second resin layer) having a thickness of 0.4 mm was obtained in the same manner as in Reference Example 1.

The film material for the acrylic resin layer was cut into a size of 110 mm in length and 110 mm in width. The release layer of the film material for acrylic resin layer was lightly peeled to expose the resin layer. On the exposed resin layer, a float glass with a length of 110 mm, a width of 110 mm, and a thickness of 1.6 mm was attached so that the four sides overlapped, and the whole was pressed by a roller from above. Then, the heavy-peeling release layer on the other side was peeled off to expose the resin layer. On the exposed resin layer, a PVB resin layer cut into a size of 110 mm in length and 110 mm in width was attached with four sides overlapping, and the whole was pressed by a roller from above. Next, on the exposed PVB resin layer, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached on four sides, and the whole was pressed by a roller from above. Thereby, a laminated body of float glass (1.6 mm) / acrylic resin layer A (0.1 mm) / PVB resin layer (0.4 mm) / float glass (2.7 mm) was obtained. The obtained laminate was heated using a vacuum laminator set at 125 ° C for 25 minutes, and then heated and pressurized at a pressure of 115 N / cm ² for 120 minutes using an autoclave set at 150 ° C. Obtained laminated glass. Five pieces of laminated glass were produced by the same operation.

(Example 2-2)
A support film / acrylic acid was obtained in the same manner as in Example 2-1 except that the particles of the resin A as the component (A) were used, and the amount of HN-5500 used as the component (B) was changed to 8.0 g. Resin layer B (first resin layer) / Protective film composition Acrylic resin layer film material and float glass (1.6 mm) / acrylic resin layer B (0.1 mm) / PVB resin layer (0.4 mm) / floating Laminated glass (2.7 mm).

(Example 2-3)
It carried out similarly to Example 2-1, and obtained the film material for acrylic resin layers which has a structure of a support film / acrylic resin layer A (first resin layer) / protective film.

The obtained film material for an acrylic resin layer was cut into a size of 110 mm in length and 110 mm in width. The release layer of the film material for acrylic resin layer was lightly peeled to expose the resin layer. On the exposed fat layer, a float glass with a length of 110 mm, a width of 110 mm, and a thickness of 1.6 mm was adhered on four sides, and the whole was pressed by a roller from above. Then, the heavy-peeling release layer on the other side was peeled off to expose the resin layer. On the exposed resin layer, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached so that the four sides overlapped, and the whole was pressed by a roller from above. Thereby, a laminated body of float glass (1.6 mm) / acrylic resin layer (0.1 mm) / float glass (2.7 mm) was obtained. The obtained laminate was heated using a vacuum laminator set at 125 ° C for 25 minutes, and then heated and pressurized at a pressure of 115 N / cm ² for 120 minutes using an autoclave set at 150 ° C. Obtained laminated glass. Five pieces of laminated glass were produced by the same operation.

3. Evaluation <Evaluation of chipping resistance (flystone resistance) of laminated glass>
Evaluation of chipping resistance was performed using the apparatus shown in FIG. 2. Four sides of the 2.7 mm-thick float glass side surface of the laminated glass produced in Examples 1 to 14, Example 2-1 to Example 2-3, Comparative Example 1, and Reference Examples 1 and 2 After attaching the double-sided adhesive tape to the part 5.0 mm from the end, the laminated glass was fixed to the supporting glass (float glass) with a thickness of 10.0 mm by the adhesive tape. Next, use an air gun (600 mm length) to make one basalt crushed stone with a weight of 0.15 g ± 0.06 g (basalt crushed stone No. 7, who selected a sieve passing through a 5.6 mm sieve and a sieve that does not pass through a 4.75 mm sieve) The collision speed of the laminated glass is 200 km / h, and the collision incident angle is 0 degrees. The laminated glass has a thickness of 1.6 mm on the side of the float glass. The collision portion of the laminated glass was observed, and the presence or absence of a linear flaw (crack) having a length of 0.5 mm or more from the collision mark was confirmed. Then, an air gun was used to cause one of the same basalt crushed stones to collide at a collision speed of 200 km / h and a collision incident angle of 0 degrees without collision marks and cracks on the surface of the laminated glass. The collision portion of the laminated glass was observed, and the presence or absence of a linear flaw (crack) having a length of 0.5 mm or more from the collision mark was confirmed. After the second time, the same test as the first time was performed on the portion of the laminated glass that was free of collision marks and cracks. This operation was performed 20 times on one sheet of laminated glass, and the NG ratio was calculated by the following formula (1). Furthermore, the distance from the launch port of the air gun to the laminated glass was set to 60 mm.
NG ratio (%) = number of cracks × 100/20 Formula (1)

The same operation was performed on five pieces of laminated glass, and the average value of the NG ratio was calculated, and then the chipping resistance of the laminated glass was evaluated using the following determination criteria. Furthermore, the chipping resistance of laminated glass is A, which is the most excellent, and D, which is the worst.
A: The average value of NG ratio is less than 20.0%
B: The average value of NG ratio is 20.0% or more and less than 25.0%
C: The average value of the NG ratio is 25.0% or more and less than 30.0%
D: The average value of the NG ratio is 30.0% or more

<Evaluation of optical characteristics of laminated glass>
The spectroscopic haze meter (SH7000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the 380 nm to 380 nm of the laminated glass produced in Examples 1, 7 to 14, Comparative Example 1, and Reference Examples 1 and 2. The total light transmittance (TT), haze, and yellowness (YI value) of 780 nm were determined using the following criteria, and the optical characteristics of laminated glass were evaluated. In addition, each optical characteristic of the laminated glass is A indicating the most excellent and D indicating the worst.
(TT)
A: 90.0% or more
B: 80.0% or more and less than 90.0%
C: 70.0% or more and less than 80.0%
D: less than 70.0%
(Haze)
A: Less than 0.5
B: 0.5 or more and less than 2.0
C: 2.0 or more and less than 3.0
D: 3.0 or more (YI value)
A: Less than 0.5
B: 0.5 or more and less than 1.0
C: 1.0 or more and less than 2.0
D: 2.0 or more

<Evaluation of Penetration Resistance of Laminated Glass>
Except that the size of the resin layer and the float glass were changed to 300 mm in length and 300 mm in width, the same method as that of the laminated glass of Examples 2-1 to 2-3 and Reference Example 1 was used. The laminated glass was made into a laminated glass for penetration resistance test.

The test according to JIS R 3212: 2015 automotive safety glass test method was used to evaluate the penetration resistance of laminated glass. The laminated glass for resistance to penetration test was left to stand in a room at a temperature of 23 ° C for 4 hours. Next, the laminated glass was placed on a support frame that was horizontally supported so that the inside surface of the car (the surface on the side of the float glass having a thickness of 2.7 mm) faced upward. Towards the center of the laminated glass (within 25 mm from the center point), for a steel ball with a mass of 2.26 kg and a diameter of 82 mm, it is dropped from a height of 4 m without any force. The penetration resistance of laminated glass was evaluated as "B" when the steel ball penetrated within 5 seconds after impact, and "A" when the steel ball did not penetrate after 5 seconds. The results are shown in Table 5 below.

[Table 2]

[table 3]

[Table 4]

[table 5]

The laminated glass of Examples 1 to 14 was superior to the laminated glass of Comparative Example 1 and Reference Examples 1 and 2 in that it exhibited excellent chipping resistance. Based on the evaluation results, it was confirmed that the resin composition for an interlayer film and the interlayer film for a laminated glass of the present invention can form a laminated glass having high chipping resistance. In addition, the laminated glass of Examples 1 and 7 to 14 was superior to the laminated glass of Comparative Example 1 and Reference Examples 1 and 2 in that it exhibited excellent chipping resistance and equivalent optical characteristics. Furthermore, it was confirmed that the laminated glass of Examples 2-1 and 2-2 was superior to the laminated glass of Examples 2-3 and Reference Example 1 in penetration resistance in addition to chipping resistance.
[Industrial availability]

As described above, according to the present invention, it is possible to provide a resin composition for an interlayer film that can form a laminated glass having high chipping resistance and a laminated glass having high chipping resistance.

Laminated glass

3, 300‧‧‧ Interlayer

4‧‧‧ Fracture resistance evaluation device

5‧‧‧ support glass

6‧‧‧ double-sided adhesive tape

8‧‧‧ air gun

9‧‧‧ Stone

10‧‧‧anti-scatter cover

21, 22, 210, 220‧‧‧ glass plates

310‧‧‧The first resin layer

320‧‧‧ 2nd resin layer

FIG. 1 is a sectional view showing an embodiment of laminated glass.

FIG. 2 is a schematic diagram of an apparatus for evaluating chipping resistance of laminated glass.

Fig. 3 is a sectional view showing another embodiment of the laminated glass.

Claims (21)

A resin composition for an interlayer film of a laminated glass, which is a resin composition for forming an interlayer film for a laminated glass provided between two opposing glass plates, and The resin composition includes (A) a (meth) acrylic copolymer having an epoxy group, and (B) a hardener. The resin composition for an interlayer film for laminated glass according to item 1 of the scope of patent application, wherein (A) an (meth) acrylic copolymer having an epoxy group and (A) an (meth) acrylic acid having an epoxy group The mass of the copolymer is based on 5% to 50% by mass of a singular unit derived from a (meth) acrylic monomer having an epoxy group. The resin composition for an interlayer film of laminated glass according to item 1 or item 2 of the patent application scope, wherein the unitary unit of the unit derived from the (meth) acrylic monomer having an epoxy group includes the unit derived from ( Monomer units of glycidyl (meth) acrylate. The resin composition for an interlayer film for laminated glass according to any one of claims 1 to 3 in the scope of the patent application, wherein (B) the hardener contains an acid anhydride compound. The resin composition for an interlayer film of laminated glass according to item 4 of the scope of the patent application, wherein the content of the acid anhydride compound is 0.5 with respect to 100 parts by mass of the (A) (meth) acrylic copolymer having an epoxy group. Part by mass to 30 parts by mass. The resin composition for an interlayer film for laminated glass according to item 4 or item 5 of the scope of patent application, wherein the (B) hardener further contains an imidazole compound. The resin composition for an interlayer film of laminated glass according to item 6 of the scope of patent application, wherein the content of the imidazole compound is 1.0 with respect to 100 parts by mass of the (A) (meth) acrylic copolymer having an epoxy group. Mass parts or less. The resin composition for an interlayer film for laminated glass according to any one of claims 1 to 7 of the scope of patent application, further comprising (C) a hardening accelerator. An interlayer film for laminated glass, which comprises the resin composition for an interlayer film of a laminated glass according to any one of claims 1 to 8 or a cured product thereof. A film material for an interlayer film of laminated glass, comprising: Support film; and The interlayer film for laminated glass according to item 9 of the scope of patent application provided on the supporting film. A laminated glass includes two glass plates facing each other and an intermediate film disposed between the glass plates. The intermediate film is the intermediate film for laminated glass according to item 9 of the scope of patent application. The laminated glass according to item 11 of the scope of patent application, wherein the glass plate is an inorganic glass. A method for manufacturing laminated glass, which is a method for manufacturing laminated glass including two glass plates and an intermediate film disposed between the glass plates. The method for manufacturing laminated glass includes: A step of disposing an interlayer film for laminated glass according to item 9 of the scope of patent application between the two glass plates to form a laminated body; and A step of forming laminated glass by heating and pressing the laminated body. An interlayer film for laminated glass, which is a resin laminate including a first resin layer and a second resin layer, The first resin layer includes the resin composition for an interlayer film of a laminated glass according to any one of claims 1 to 8 of the patent application scope, or a cured product thereof, The second resin layer includes a polyvinyl acetal resin. The interlayer film for laminated glass according to item 14 of the patent application scope, wherein the second resin layer further contains a plasticizer. The interlayer film for laminated glass according to item 15 of the patent application scope, wherein the plasticizer comprises a material selected from the group consisting of triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexyl At least one of the group consisting of an acid ester and triethylene glycol di-n-heptanoate. The interlayer film for laminated glass according to any one of claims 14 to 16, in which the thickness of the first resin layer is 10 μm to 300 μm. The interlayer film for laminated glass according to any one of claims 14 to 17, wherein the thickness of the second resin layer is 300 μm to 800 μm. A laminated glass comprising two glass plates facing each other and an interlayer film disposed between the glass plates, The interlayer film is the interlayer film for laminated glass according to any one of items 14 to 18 of the scope of patent application. The laminated glass according to item 19 of the scope of patent application, wherein the laminated glass is a member for a window of a vehicle, One of the two glass plates is an outer glass plate facing the outside of the vehicle when the laminated glass is mounted on the vehicle, The first resin layer of the intermediate film is adjacent to the outer glass plate. The laminated glass according to item 19 or item 20 of the patent application scope, wherein the glass plate is an inorganic glass.