JP2020063181A - Resin composition for interlayer of glass laminate, interlayer fro glass laminate, film material for interlayer of glass laminate, glass laminate, and manufacturing method of glass laminate - Google Patents

Abstract

To provide an interlayer for glass laminate capable of providing a glass laminate having high chipping resistance, and having good processability and adhesion property.SOLUTION: There is related a resin composition used for forming an interlayer for glass laminate arranged between facing two glass sheets. The resin composition contains (A) a (meth)acrylic copolymer having a crosslinking group, and (B) a curing agent reacting with the crosslinking group. A glass transition temperature of the (A) a (meth)acrylic copolymer having the crosslinking group is 10°C to 50°C.SELECTED DRAWING: Figure 1

Description

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

  2. Description of the Related Art Conventionally, laminated glass, which is less scattered when broken, has been widely used as glass for vehicles such as automobiles, aircraft, buildings and the like. Laminated glass generally has an interlayer sandwiched between two glass plates. As the interlayer film for laminated glass, for example, a resin layer containing a polyvinyl acetal resin, an ionomer resin, an acrylic resin, or the like is used (for example, Patent Documents 1 to 5).

Publication of JP-A-2016-193542 Publication of JP-A-2009-298046 JP-A-2015-151540 Publication of Japanese Patent Publication No. 62-028105 JP, 2000-001345, A

  BACKGROUND ART A glass member such as a windshield used for automobiles is required to have excellent resistance to collision of flying particles such as flying stones during traveling, that is, excellent chipping resistance. Conventional laminated glass for automobiles has room for improvement in chipping resistance. In addition, the laminated glass for automobiles has become more curved and has a larger area, and an interlayer film used for laminated glass for automobiles is required to have good processability and laminating property.

  An object of one aspect of the present invention is to provide an interlayer film for laminated glass, which can provide a laminated glass having high chipping resistance, and also has good processability and bondability.

  An aspect of the present invention is to provide an interlayer film resin composition for laminated glass, which is used for forming an interlayer film for laminated glass, which is provided between two glass plates facing each other, and an interlayer film for laminated glass containing the same. provide. The resin composition contains (A) a (meth) acrylic copolymer having a crosslinking group, and (B) a curing agent that reacts with the crosslinking group, and (A) a (meth) acrylic copolymer having a crosslinking group. Has a glass transition temperature of 10 ° C to 50 ° C.

  The interlayer film for laminated glass containing the resin composition for interlayer film of laminated glass according to the present invention can provide a laminated glass having high chipping resistance, and has good processability and laminating property.

  Another aspect of the present invention provides a film material for an interlayer film of laminated glass, which comprises a support film and the interlayer film for laminated glass provided on the support film. Since the intermediate film in the film material for intermediate films has good workability that can be cut, laminated glass can be easily manufactured. In addition, the interlayer film is soft and can exhibit good laminating properties when it is laminated to a glass plate, and by being cured after being laminated to the glass plate, it gives a laminated glass having high chipping resistance. be able to.

  Yet another aspect of the present invention provides a laminated glass including two glass plates facing each other and the interlayer film for laminated glass arranged therebetween. At least a part of the (meth) acrylic copolymer having a crosslinkable group (A) in the interlayer film for laminated glass is crosslinked by a reaction between the crosslinkable group and a curing agent (B). This laminated glass has excellent chipping resistance. The laminated glass can be easily manufactured without leaving bubbles even when it includes a curved portion.

  Yet another aspect of the present invention provides a method for producing a laminated glass including two glass plates facing each other and an intermediate film arranged between them. This manufacturing method includes a step of forming the laminated body by disposing the intermediate film between two glass plates facing each other, and a step of heating and pressing the laminated body to form a laminated glass. According to this method, it is possible to easily manufacture a laminated glass having excellent chipping resistance even when the laminated glass includes a curved portion.

  According to one aspect of the present invention, there is provided an interlayer film for laminated glass, which can provide a laminated glass having high chipping resistance and has good processability and bondability.

It is sectional drawing which shows one Embodiment of laminated glass. It is sectional drawing which shows one Embodiment of the film material for interlayer films of laminated glass.

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

  In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, "(meth) acryl" means "acryl" or its corresponding "methacryl", 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 there is a plurality of substances corresponding to each component in the composition, unless otherwise specified.

  FIG. 1 is a cross-sectional view showing an embodiment of laminated glass. The laminated glass 1 shown in FIG. 1 includes two glass plates 11 and 12 facing each other, and an intermediate film 5 arranged between the glass plates 11 and 12.

  The glass plates 11 and 12 may be inorganic glass such as float glass, air-cooled tempered glass, chemically tempered glass, or double glazing. The thickness of the glass plates 11 and 12 may be 100 to 5000 μm. The glass plates 11 and 12 may have the same thickness or different thicknesses.

  The intermediate film 5 is a resin layer containing a resin composition for an intermediate film of laminated glass. The resin composition for an interlayer film of laminated glass (hereinafter, may be simply referred to as “resin composition”) has a (A) cross-linking group-containing (meth) acrylic copolymer (hereinafter, referred to as “component (A)”). A) and a curing agent (B) that reacts with the crosslinking group (hereinafter sometimes referred to as “component (B)”). At least a part of the (meth) acrylic copolymer contained in the intermediate film 5 is crosslinked by the reaction between the crosslinking group and the curing agent (B).

  The component (A) contains at least a monomer unit derived from a monomer having a crosslinking group. The monomer having a crosslinking group may be a monofunctional monomer. The monomer having a crosslinking group may be a (meth) acrylate compound having a crosslinking group. The component (A) may be crosslinked by a reaction between crosslinkable groups or a reaction between a crosslinkable group and a curing agent described below. By cross-linking the component (A), a laminated glass having higher chipping resistance can be provided.

  The crosslinking group is a reactive group other than a (meth) acryloyl group, and may be at least one selected from an epoxy group, a carboxyl group, a hydroxy group, an amide group, an alkenyl group, an alkynyl group, and an isocyanate group, It may be an epoxy group. Examples of the (meth) acrylate compound having an epoxy group include glycidyl (meth) acrylate. Examples of the (meth) acrylate compound having a carboxyl group include (meth) acrylic acid. Examples of the (meth) acrylate compound having a hydroxy group include hydroxyethyl (meth) acrylate. Examples of the (meth) acrylate compound having an amide group include (meth) acrylic acid amide. Examples of the (meth) acrylate compound having an alkenyl group include esters of (meth) acrylic acid and alkenyl alcohol having 2 to 18 carbon atoms. Examples of the (meth) acrylate compound having an alkynyl group include esters of alkynyl alcohol having 2 to 18 carbon atoms and (meth) acrylic acid. 2-methacryloyloxy ethyl isocyanate is mentioned as an example of the (meth) acrylate compound which has an isocyanate group. These compounds may be used alone or in combination of two or more.

  The content of the monomer unit derived from the monomer having a crosslinking group may be 0.1% by mass or more, 5% by mass or more, or 10% by mass or more based on the mass of the component (A). , 50 mass% or less, 45 mass% or less, or 40 mass% or less. When the content of the monomer unit derived from the monomer having a crosslinking group is within these ranges, the crosslinked structure tends to be uniformly formed in the entire interlayer film.

  The component (A) may further contain a monomer unit derived from a linear or branched alkyl (meth) acrylate. A linear or branched alkyl (meth) acrylate is an ester of a linear or branched alkyl alcohol and (meth) acrylic acid. The linear or branched alkyl (meth) acrylate here is a monomer having no crosslinking group. The linear or branched alkyl (meth) acrylate may be a monofunctional monomer having one (meth) acryloyl group and one linear or branched alkyl group. The linear or branched alkyl group in the linear or branched alkyl (meth) acrylate may have 1 to 18 carbon atoms. Specific examples of the linear or branched alkyl (meth) acrylate having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl. (Meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (Meth) acrylate (n-lauryl (meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate are mentioned. These compounds may be used alone or in combination of two or more.

  The content of the monomer unit derived from the linear or branched alkyl (meth) acrylate may be 5% by mass or more, 10% by mass or more, or 15% by mass or more based on the mass of the component (A). , 60 mass% or less, 55 mass% or less, or 45 mass% or less.

  The component (A) may further contain a monomer unit derived from an alicyclic (meth) acrylate. The alicyclic (meth) acrylate is an ester of alicyclic alcohol and (meth) acrylic acid. The alicyclic (meth) acrylate here is a monomer having no crosslinking group. The alicyclic (meth) acrylate may be a monofunctional monomer having one (meth) acryloyl group and one alicyclic group. Examples of cycloaliphatic (meth) acrylates include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate. These compounds may be used alone or in combination of two or more.

  The content of the monomer unit derived from alicyclic (meth) acrylate may be 5% by mass or more or 30% by mass or more, and 80% by mass or less or 70% by mass based on the mass of the component (A). It may be less than or equal to mass%. When the content of the monomer unit derived from alicyclic (meth) acrylate is within these ranges, the component (A) tends to have a high glass transition temperature, and the interlayer film has good flowability and sticking property. Tend to be compatible.

  The component (A) is derived from a monomer unit derived from a (meth) acrylate compound having a crosslinking group, a monomer unit derived from a linear or branched alkyl (meth) acrylate, and an alicyclic (meth) acrylate. It may be a copolymer containing the monomer unit.

  The component (A) may further contain a monomer unit derived from a compound having an ethylenically unsaturated group other than the (meth) acrylate compound. Examples of the compound having an ethylenically unsaturated group other than the (meth) acrylate compound include styrene, (meth) acrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, vinylcyclohexyl ether, vinylphenyl ether, vinyl acetate, N- Mention may be made of vinylpyrrolidone, vinylpyridine, vinyl chloride, and vinylidene chloride. Among these, (meth) acrylonitrile, N-cyclohexylmaleimide, or N-phenylmaleimide may be used from the viewpoint of easily improving the toughness of the interlayer film for laminated glass. These compounds may be used alone or in combination of two or more.

  The content of the monomer unit derived from the compound having an ethylenically unsaturated group other than the (meth) acrylate compound is 0% by mass or more, 5% by mass or more, or 10% by mass based on the mass of the component (A). It may be more than 40% by mass, 35% by mass or less, 30% by mass or less, 25% by mass or less or 20% by mass or less.

  The glass transition temperature of the component (A) is 10 ° C to 50 ° C. The glass transition temperature here is a value measured by differential scanning calorimetry (DSC) as described later. When the glass transition temperature of the component (A) is 10 ° C. or higher, the resin layer can be prevented from sticking to the blade during cutting of the intermediate film, so that an intermediate film having excellent processability can be obtained. When the glass transition temperature of the component (A) is 50 ° C. or lower, cracking of the intermediate film can be suppressed, so that an intermediate film having excellent laminating properties can be obtained. From the same viewpoint, the glass transition temperature of the component (A) may be 15 ° C. or higher and 45 ° C. or lower.

  The weight average molecular weight of the component (A) may be 50,000 or more, 100,000 or more, 150,000 or more, 200,000 or more, or 240,000 or more, 650,000 or less, 500,000 or less, It may be 450,000 or less, 400,000 or less, 350,000 or less, or 300,000 or less. The weight average molecular weight here is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). When the weight average molecular weight of the component (A) is 50,000 or more, there is a tendency that an interlayer film having a particularly high laminating property can be obtained. When the weight average molecular weight of the component (A) is 650,000 or less, the interlayer film tends to have appropriate flowability and high laminating property.

  The component (A) can be synthesized by a usual polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization.

  The content of the component (A) is 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more or 90% by mass based on the mass of the intermediate film 5 or the resin composition for forming the same. % Or more. In the present specification, when the resin composition contains an organic solvent, the content of each component in the resin composition means a ratio based on the total mass of components other than the organic solvent in the resin composition.

  The component (B) is a component that reacts with the crosslinking group of the component (A) to form a crosslinked structure. The component (B) may be any one having a functional group capable of reacting with the crosslinking group of the component (A), and examples thereof include acid anhydride compounds. The acid anhydride compound may be a compound capable of reacting with a crosslinking group such as an epoxy group, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and ethylene glycol bis. Anhydro trimellitate, glycerol tris anhydro trimellitate, maleic anhydride, tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methylhymic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydro Examples include phthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic acid anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. These compounds may be used alone or in combination of two or more.

  From the viewpoint of easy mixing and dispersibility in the resin composition, the component (B) may be a liquid acid anhydride compound. The liquid acid anhydride compound is an acid anhydride compound having fluidity at normal temperature and pressure (25 ° C., 1 atm). Liquid acid anhydride compounds are prepared from methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylcyclohexenedicarboxylic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. It may be at least one acid anhydride compound selected from the group consisting of: From the viewpoint of transparency of the intermediate film, the liquid acid anhydride compound may include methylhexahydrophthalic anhydride.

  The content of the component (B) may be 25 to 150 mol% with respect to the amount of the crosslinking group in the component (A). When the content of the component (B) is within this range, the mechanical properties of the interlayer film tend to be high. From the same viewpoint, the content of the component (B) may be 30 mol% or more, 35 mol% or more, or 40 mol% or more with respect to the amount of the crosslinking group in the component (A), and may be 125 mol. % Or less, 100 mol% or less, 75 mol% or less, or 60 mol% or less. In the intermediate film 5 constituting the laminated glass, at least a part of the component (B) is a residue formed by the reaction with the crosslinking group in the (A) (meth) acrylic copolymer. Usually, this residue crosslinks the (A) (meth) acrylic copolymer.

  The intermediate film 5 or the resin composition for forming the intermediate film 5 may further contain (C) a curing accelerator, if necessary. Examples of curing accelerators include imidazole compounds and organic phosphorus compounds. Here, the imidazole compound may be able to exhibit the function of a curing agent in some cases.

  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-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 '-Me Ruimidazolyl- (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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, and 1-dodecyl-2-methyl-3-benzylimidazolium chloride. These compounds may be used alone or in combination of two or more.

  Examples of the organic phosphorus compound include triphenylphosphine, triparatolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, 1,4-bisdiphenylphosphinobutane, tetraphenylphosphonium tetra -P-tolylborate, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, n-butyltriphenylphosphonium dicyanamide, tetraphenylphosphonium bromide, n-butyltriphenyl Phosphonium bromide, tetrabutylphosphonium bromide , And tetrabutylphosphonium decanoate. These compounds may be used alone or in combination of two or more. You may use together an imidazole compound and an organic phosphorus compound.

  The content of the curing accelerator may be 0.001 to 10 mol%, or 0.01 to 5 mol% with respect to the amount of the crosslinking group in the component (A). When the content of the curing accelerator is within these ranges, the crosslinking reaction tends to proceed efficiently by heating while ensuring high storage stability of the resin composition.

  The intermediate film 5 and the resin composition for forming the intermediate film 5 may further contain other various additives, if necessary. Examples of additives include, for example, antioxidants, polymerization inhibitors, silane coupling agents, surfactants, inorganic fillers, and other polymers.

  Examples of antioxidants include phenolic compounds and phosphite compounds. Examples of the phenol compound include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 4,4 ′, 4 ″-(1-methylpropan-3-ylidene) tris (6-tert-butyl-m-cresol), 6,6′-di-tert-butylidene-di -M-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaeryltriol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], 3,9-bis {2- [3-tert-butyl-4-hydroxy-5-methylphenyl] propionyloxy] -1,1-dimethylethyl}- 2,4,8,10-Tetraoxaspiro [5.5] undecane, and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6- Trimethylbenzene may be mentioned. Examples of the phosphite compound include 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and 3,9-bis (2,6). -Di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2-2'-methylenebis (4,6-di-tert- Butylphenyl) -2-ethylhexylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra-C12-15-alkyl (propane-2,2-diylbis ( 4,1-phenylene)) bis (phosphite), 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite Triisodecyl phosphite, and include triphenyl phosphite. These compounds may be used alone or in combination of two or more. You may use together a phenol compound and a phosphite compound.

  When the antioxidant is used, the content of the antioxidant is 0.01 to 50% by mass, 0.1 to 30% by mass with respect to the mass of the intermediate film 5 or the resin composition for forming this, or It may be 0.2 to 15% by mass. When the content of the antioxidant is within these ranges, there is a tendency that an interlayer film having a sufficient antioxidant function and excellent light resistance can be obtained.

  Examples of the polymerization inhibitor include paramethoxyphenol. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxy. Examples include propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane. Examples of surfactants include polydimethylsiloxane compounds and fluorine compounds. These additives may be used alone or in combination of a plurality of additives. The respective contents of the polymerization inhibitor, the silane coupling agent and the surfactant may be about 0.01 to 5% by mass with respect to the mass of the intermediate film 5 or the resin composition for forming the same. Good.

  Examples of inorganic fillers include crushed silica, fused silica, mica, clay minerals, short glass fibers or fine powder and hollow glass, calcium carbonate, quartz powder, and metal hydrates. The content of the inorganic filler is 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 forming the intermediate film 5 or this. It may be a department. When the content of the inorganic filler is 0.01 to 100 parts by mass, effects such as low shrinkability, improvement in mechanical strength, and low coefficient of thermal expansion can be obtained for the interlayer film. 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, polyvinyl acetal resins, and ionomer 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 ionomer resin is used, the adhesive force between the interlayer film and the glass plate tends to increase. The content of the other polymer may be 0% by mass or more or 10% by mass or more, and 70% by mass or less, 50% by mass or less, with respect to the mass of the intermediate film 5 or the resin composition for forming the same. Alternatively, it may be 30% by mass or less.

  The resin composition for forming the intermediate film 5 may contain an organic solvent, if necessary. The resin composition containing an organic solvent can be used, for example, as a coating liquid for forming an intermediate film. The organic solvent is not particularly limited as long as it can dissolve or disperse the resin composition. Examples of the organic solvent include ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based organic solvents such as ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and 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, diethylene glycol dimethyl ether, and other polyhydric alcohol alkyl ether organic solvents; ethylene glycol monomethyl ether acetate , Propylene glycol Ether acetate, polyhydric alcohol alkyl ether acetates such as diethylene glycol monomethyl ether acetate; N, N- dimethylformamide, N, N- dimethylacetamide, an amide-based organic solvents such as N- methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

  FIG. 2 is a cross-sectional view showing an embodiment of a film material for interlayer film of laminated glass. The film material 2 shown in FIG. 2 has a support film 21, an intermediate film 5a provided on the support film 21, and a separator 22 provided on the intermediate film 5a. The intermediate film 5a is a resin layer formed from the resin composition according to the above embodiment. The intermediate film 5a is used, for example, to form the intermediate film 5 of the laminated glass 1 of FIG. The support film 21 may be a heavy release separator and the separator 22 may be a light release separator.

  The thickness of the intermediate film 5a is not particularly limited, but may be 10 to 10,000 μm. When the thickness is 10 μm or more, the interlayer film tends to have sufficient strength. When the thickness is 10,000 μm or less, the processing of the interlayer film tends to be easy. From the same viewpoint, the thickness of the intermediate film 5a may be 50 μm to 5,000 μm, or 100 to 1,000 μm. Even if the thickness of the intermediate film 5a is increased, a laminated glass having excellent chipping resistance and optical transparency can be formed. From this viewpoint, the thickness of the intermediate film 5a 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 thickness of the interlayer film in the laminated glass can also be within the same range. The glass transition temperature of the intermediate film 5a or the intermediate film 5 before curing may be 5 ° C or higher, 10 ° C or higher, 15 ° C or higher or 20 ° C or higher, and 45 ° C or lower or 40 ° C or lower from the viewpoint of processability. May be

  For the film material 2, for example, a coating liquid, which is a resin composition containing an organic solvent, is applied onto the support film 21, and the solvent is removed from the obtained coating film to form the intermediate film 5a. It can be obtained by a method including and. Examples of the method of applying the coating liquid on the support film 21 include a flow coating method, a roll coating method, a gravure roll method, a wire bar method, and a lip die coating method. The intermediate film 5a may be sandwiched between the support film 21 and the separator 22 by stacking the separator 22 on the intermediate film 5a. The intermediate film 5a may be formed by melt-molding the resin composition.

  From the viewpoint of coatability, the concentration of solids (components other than the organic solvent) in the coating liquid may be 30% by mass or more or 40% by mass or more, based on the mass of the coating liquid, 70% by mass. % Or 60% by mass or less. The viscosity of the coating liquid may be 1 Pa · s or higher or 5 Pa · s or higher at a coating temperature of 25 ° C., and may be 30 Pa · s or lower, 25 Pa · s or lower or 15 Pa · s or lower.

  Examples of the support film 21 include resin films of polyethylene terephthalate, polypropylene, polyethylene, polyester and the like. The thickness of the support film 21 may be 50 to 200 μm, 60 to 150 μm, or 70 to 130 μm from the viewpoint of workability.

  Examples of the separator 22 include resin films of polyethylene terephthalate, polypropylene, polyethylene, polyester and the like. From the viewpoint of workability, the thickness of the separator 22 may be 25 to 150 μm, 30 to 100 μm, or 40 to 75 μm.

  The laminated glass 1 includes, for example, a step of forming a laminated body having two glass plates 11 and 12 facing each other and an intermediate film 5 arranged therebetween, and heating and pressurizing the laminated body to form the laminated glass 1 It can be manufactured by a method including a step of forming. The (meth) acrylic copolymer may be crosslinked during one or more steps of forming an interlayer film, forming a laminate, and heating and pressing the laminate.

  In the step of heating and pressurizing the laminate, the heating temperature may be 25 to 150 ° C and the pressure may be 0.1 to 2 MPa.

  After the step of heating and pressing the laminated body, the obtained laminated glass may be further heated at 80 to 200 ° C. The (meth) acrylic copolymer may be crosslinked by this heating.

  The laminated glass and the interlayer film for laminated glass are not limited to the embodiment shown in FIG. 1 and can be changed within the scope not departing from the gist of the present invention. The interlayer film for laminated glass may have one resin layer containing the resin composition, may have two or more resin layers, and may have these resin layers laminated. A resin layer formed of other resin species such as polyvinyl acetal resin and ionomer resin may be further laminated. When the intermediate film 5 has two or more resin layers, the (meth) acrylic copolymers contained in each resin layer may be the same or different. The total number of resin layers may be 5 or less.

  The laminated glass may further have various functional layers other than the glass plate and the intermediate film, or a transparent protective plate. The functional layer may be, for example, a layer having a function selected from an antireflection layer, an antifouling layer, a dye layer, a hard coat layer, and a penetration resistant layer. An interlayer film may be used to combine and bond the functional layer and the transparent protective plate.

  The antireflection layer is a layer having an antireflection property 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 a layer for making it difficult for dirt to attach to the surface. The dye layer is a layer for increasing color purity. The dye layer is a layer that reduces unnecessary wavelength light transmitted through the laminated glass. The hard coat layer is a layer provided to increase the surface hardness. The hard coat layer may be, for example, an acrylic resin film such as urethane acrylate or epoxy acrylate, or an epoxy resin film. The hard coat layer may be a transparent protective plate such as a glass plate, an acrylic resin layer or a polycarbonate resin layer, and a hard coat layer laminated on the transparent protective plate. The penetration resistant layer is a layer provided to prevent flying objects from penetrating the surface of the laminated glass. The penetration-resistant layer can be formed of, for example, a polyvinyl acetal resin such as polyvinyl butyral or polyvinyl formal, an ethylene / vinyl acetate copolymer resin, or an ionomer resin.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

1. Synthesis of (meth) acrylic copolymer (meth) acrylic copolymer A
30 g of butyl acrylate (BA), 55 g of dicyclopentanyl acrylate (FA-513AS, manufactured by Hitachi Chemical Co., Ltd.), and 15 g of glycidyl methacrylate (GMA) were mixed to obtain a monomer mixture. 0.5 g of dilauroyl peroxide as a polymerization initiator and 0.1 g of n-octyl mercaptan as a chain transfer agent were dissolved in the obtained monomer mixture to obtain a mixed liquid containing a monomer. In a 500 mL reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping funnel and a nitrogen introducing tube, 0.2 g of polyvinyl alcohol and 200 g of ion-exchanged water were added as a suspending agent, and a single amount was added thereto with stirring. The above mixture containing the body was added. While stirring the formed reaction solution at a rotational speed of 250 rpm, the polymerization reaction was allowed to proceed at 60 ° C. for 5 hours and then at 90 ° C. for 2 hours under a nitrogen atmosphere to have an epoxy group as a crosslinking group. Resin particles containing the (meth) acrylic copolymer A were formed. The polymerization rate measured by the mass method was 99%. The resin particles taken out from the reaction solution were washed with water, dehydrated and dried to obtain a particulate (meth) acrylic copolymer A.

The weight average molecular weight (Mw) of the (meth) acrylic copolymer A was 264,000. The weight average molecular weight was converted from a calibration curve using standard polystyrene by gel permeation chromatography under the following conditions.
Device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TSKgel Super Multipore HZ-M (3 connected) (manufactured by Tosoh Corporation)
Column size: 4.6 mm ID x 15 cm
Eluent: THF (tetrahydrofuran)
Sample concentration: 1 mg / mL
Flow rate: 1.0 mL / min Measuring temperature: 25 ° C

The glass transition temperature (Tg) of the (meth) acrylic copolymer A was 24 ° C. The glass transition temperature was the temperature at the midpoint calculated by extrapolating the glass transition portion in the obtained DSC curve by measuring the change in the amount of heat using DSC measurement under the following conditions. The midpoint is obtained by extrapolating the intersection point A between the straight line obtained by extrapolating the high temperature side of the glass transition part in the DSC curve and the straight line obtained by extrapolating the glass transition part, and the low temperature side of the glass transition part. It means the midpoint of the line segment connecting the intersection B of the obtained straight line and the straight line obtained by extrapolating the glass transition portion.
Device: DSC250 (manufactured by TA Instruments Japan Co., Ltd.)
Temperature range: -50 ℃ to 100 ℃
Temperature rising rate: 10 ° C / min

(Meth) acrylic copolymers B to J
Regarding the (meth) acrylic copolymers B to F and H to J, the same procedure as that of the (meth) acrylic copolymer A was performed except that the monomer mixture was changed to the monomer mixture shown in Table 1 below. A particulate (meth) acrylic copolymer was obtained. Regarding the (meth) acrylic copolymer G, a particulate (meth) acrylic copolymer was prepared in the same manner as the (meth) acrylic copolymer A except that the amount of the chain transfer agent n-octyl mercaptan added was 0.05 g. Got united. The weight average molecular weight (Mw) and the glass transition temperature (Tg) of the obtained (meth) acrylic copolymers B to J were measured in the same manner as the (meth) acrylic copolymer A. In Table 1, the unit of the blending amount of the monomer component was g.

2. Preparation of Film Material Having Intermediate Films A to J By mixing each component in the mixing ratio (parts by mass) shown in Tables 2 and 3 below and 100 parts by mass of methyl ethyl ketone (MEK), a (meth) acrylic copolymer was obtained. A coating liquid of a resin composition containing the above was obtained. The obtained coating liquid was applied to the release-treated surface of a polyethylene terephthalate film (heavy release separator) using a bar coater. The obtained coating film was dried by heating at 60 ° C. for 15 minutes and then at 80 ° C. for 10 minutes to form intermediate films A to J having a thickness of 100 μm. A polyethylene terephthalate film (light release separator) was covered on the intermediate film, which was attached with a 1.0 kgf hand roller to obtain film materials A to J having intermediate films A to J, respectively. Details of components other than the (meth) acrylic copolymer shown in Tables 2 and 3 are as follows. In Example 1, the amount of the epoxy group contained per 100 g of (meth) acrylic copolymer A was 106 mmol, the molar amount of 8 g of HN-5500 was 48 mmol, and the content of HN-5500 was (meth). ) It was 45 mol% based on the amount of epoxy groups in the acrylic copolymer. In Example 2, the content of HN-5500 was 47 mol% with respect to the amount of epoxy groups in the (meth) acrylic copolymer, and in Example 3, the content of HN-5500 was ( It was 46 mol% with respect to the amount of epoxy groups in the (meth) acrylic copolymer.
HN-5500: 3 or 4-methyl-hexahydrophthalic anhydride (anhydride compound, manufactured by Hitachi Chemical Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Chemicals Co., Ltd.)

3. Production of laminated glass (Example 1)
The film material having the intermediate film A was cut into a size of 110 mm in length and 110 mm in width. The light release separator was peeled from the film material, and the exposed interlayer film A was pressed by a roller onto a float glass having a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm. Subsequently, the heavy release separator was peeled from the intermediate film A, and a float glass having a length of 110 mm, a width of 110 mm, and a thickness of 1.6 mm was placed on the exposed intermediate film A. Next, the laminated body having the two float glasses and the intermediate film A was heated and pressed by holding at a temperature of 125 ° C. for 30 minutes under vacuum using a vacuum laminator to obtain a laminated glass. The obtained laminated glass was further heated by keeping it in a constant temperature bath at 150 ° C. for 2 hours.

(Examples 2 to 7 and Comparative Examples 1 to 3)
A laminated glass was obtained in the same manner as in Example 1 except that a film material having the intermediate films B to J was used instead of the film material having the intermediate film A.

4. Evaluation 4-1. Workability The film material was cut with a cutter, the appearance of the cut end face was visually observed, and the workability of the interlayer film was judged according to the following criteria. As for workability, A is excellent and B and C are inferior.
A: When burrs and cracks are not generated on the film B: When burrs or cracks are generated on the film C: When sticking of the film to the cutter occurs

4-2. Lamination property The appearance of the laminated glass was visually observed and the number of bubbles was recorded. Based on the number of bubbles, the sticking property was judged according to the following judgment criteria.
A: No bubbles B: Number of bubbles is 1 or more

4-3. Chipping resistance A double-sided pressure-sensitive adhesive tape was attached to four sides of the 2.7-mm-thick float glass side surface of the laminated glass within a range of 5.0 mm from the end. The laminated glass was fixed to a float glass having a thickness of 10.0 mm with this adhesive tape. Next, one basalt crushed stone having a weight of 0.1 g was made to collide with the surface of the laminated glass having a thickness of 1.6 mm on the side of the float glass by an air gun. The collision speed was 200 km / h and the collision incident angle was about 0 degree. The collision portion of the laminated glass was observed, and it was confirmed from the collision trace whether or not a linear crack having a length of 0.5 mm or more was generated. Then, one basalt crushed stone having a weight of 0.1 g was made to collide with an air gun against a portion of the same laminated glass having no collision mark or crack on the same surface. The collision speed was 200 km / h and the collision incident angle was about 0 degree. The collision portion of the laminated glass was observed, and it was confirmed from the collision trace whether or not a linear crack having a length of 0.5 mm or more was generated. From the second time onward, the same test as the first time was performed on a portion of the same laminated glass on the same surface where there were no collision marks or cracks. This operation was performed 20 times on one piece of laminated glass, and the NG ratio was calculated by the following formula (1).
NG rate (%) = number of cracks generated x 100/20 formula (1)

The same operation was carried out for five laminated glasses, and the average value of the NG ratios thereof was calculated. Based on the average value of NG rates, the chipping resistance of the laminated glass was judged according to the following criteria. A small average value of the NG ratio means that the laminated glass has excellent chipping resistance.
A: Less than 20.0% B: 20.0% or more, less than 25.0% C: 25.0% or more, less than 30.0% D: 30.0% or more

  As shown in Tables 2 and 3, formed from a resin composition containing a (meth) acrylic copolymer having a cross-linking group having a glass transition temperature of 10 to 50 ° C. and a curing agent that reacts with the cross-linking group. It was confirmed that the obtained interlayer film can give a laminated glass having good processability and laminating property and excellent chipping resistance.

  1 ... Laminated glass, 2 ... Film material, 5, 5a ... Intermediate film, 11, 12 ... Glass plate, 21 ... Support film, 22 ... Separator.

Claims (12)

A resin composition used for forming an interlayer film for laminated glass, which is provided between two glass plates facing each other,
The resin composition contains (A) a (meth) acrylic copolymer having a crosslinking group, and (B) a curing agent that reacts with the crosslinking group,
(A) A resin composition for a laminated glass interlayer film, wherein the (meth) acrylic copolymer having a crosslinking group has a glass transition temperature of 10 ° C to 50 ° C.   The resin composition for an interlayer film of a laminated glass according to claim 1, wherein the weight average molecular weight of the (A) (meth) acrylic copolymer having a crosslinking group is 50,000 to 650,000.   The resin composition for interlayer film of laminated glass according to claim 1 or 2, wherein the (A) cross-linking group-containing (meth) acrylic copolymer contains a monomer unit derived from an epoxy group-containing (meth) acrylate. object.   The resin composition for a laminated glass interlayer film according to claim 3, wherein the monomer unit derived from the (meth) acrylate having an epoxy group includes a monomer unit derived from glycidyl (meth) acrylate. (A) a (meth) acrylic copolymer having a crosslinking group,
A monomer unit derived from a linear or branched alkyl (meth) acrylate that is an ester of a linear or branched alkyl alcohol and (meth) acrylic acid, and an ester of an alicyclic alcohol and (meth) acrylic acid. The resin composition for an interlayer film of a laminated glass according to any one of claims 1 to 4, further comprising a monomer unit derived from an alicyclic (meth) acrylate.   The resin composition for an interlayer film of laminated glass according to any one of claims 1 to 5, wherein the curing agent (B) contains an acid anhydride compound.   The content of the curing agent (B) is 25 mol% to 150 mol% with respect to the amount of the crosslinking group in the (A) crosslinking group-containing (meth) acrylic copolymer. A resin composition for an interlayer film of a laminated glass according to any one of items.   The resin composition for interlayer film of laminated glass according to any one of claims 1 to 7, further comprising (C) a curing accelerator.   An interlayer film for laminated glass, comprising the resin composition for interlayer film of laminated glass according to any one of claims 1 to 8. A support film,
An interlayer film for laminated glass according to claim 9, which is provided on the support film,
A film material for an interlayer film of laminated glass, which comprises: Two glass plates facing each other,
An interlayer film for laminated glass according to claim 9 disposed between them,
Laminated glass in which at least a part of the (meth) acrylic copolymer having a crosslinking group (A) in the interlayer film for laminated glass is crosslinked by a reaction between the crosslinking group and a curing agent (B). A method for producing a laminated glass, comprising two glass plates facing each other, and an intermediate film arranged between the two glass plates,
A step of disposing the interlayer film for laminated glass according to claim 9 between two facing glass plates to form a laminated body;
Heating and pressing the laminated body to form a laminated glass;
A method for manufacturing a laminated glass, comprising:

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