TW201817592A - Photocurable resin composition for interlayer film for laminated glass, film material for interlayer film for laminated glass, and method for manufacturing laminated glass - Google Patents

Abstract

Provided is a photocurable resin composition for an interlayer film of laminated glass which includes a (meth)acrylic polymer, a (meth)acrylic monomer, and a photoinitiator. The photocurable resin composition may further include a plasticizing agent component. Also provided is a film material for an interlayer film for laminated glass which includes an adhesive layer that contains the photocurable resin composition for an interlayer film for laminated glass and a pair of base material layers which are laminated so as to interpose the adhesive layer therebetween.

Description

Photocurable resin composition for intermediate film of laminated glass, film material for intermediate film of laminated glass, and method for producing laminated glass

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

At present, as glass used in vehicles such as automobiles, aircrafts, buildings, etc., even if it is broken by an external impact, glass fragments are rarely scattered and safe, and therefore laminated glass having an interlayer film is widely used.

An example of the interlayer film for laminated glass includes laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer. The intermediary film is interposed between at least one pair of glass plates, and is obtained by integration.

However, many of the conventional laminated glasses are required to have the same degree of crack resistance as glass of the same thickness, and are more difficult to crack when subjected to an impact from the outside, that is, laminated glass having high crack resistance. [Prior Art Literature] [Patent Literature]

Patent Literature 1: Japanese Patent Laid-Open No. 1987-100463 Patent Literature 2: Japanese Patent Laid-Open No. 2005-206445 Patent Literature 3: International Publication No. 12/091117

[Problems to be Solved by the Invention] In view of the foregoing circumstances, an object of the present invention is to provide a photocurable resin composition for an interlayer film of a laminated glass that can provide laminated glass with excellent crack resistance, and a layer using the same. Film material for interlayer film of laminated glass and method for producing laminated glass. [Means for solving problems]

The present inventors made intensive research in order to solve the above-mentioned problems, and as a result, it was found that if a (meth) acrylic polymer, a (meth) acrylic monomer (or (meth) acrylate monomer) and The photo-curable resin composition of a polymerization initiator can solve the above problems. The present invention has been completed based on the findings.

That is, one aspect of the present invention provides a (A) (meth) acrylic polymer, (B) (meth) acrylic monomer (or (meth) acrylate monomer), and (D) photopolymerization initiation. A photocurable resin composition for an intermediate film of laminated glass of an agent.

Another aspect of the present invention provides a film material for an interlayer film of a laminated glass (or an interlayer film for a laminated glass with a cover film), which includes a photocurable resin composition for an interlayer film including a laminated glass, or An adhesive layer formed of the resin composition; and a pair of base material layers laminated with the adhesive layer interposed therebetween.

According to the film material for an interlayer film of such a laminated glass (hereinafter sometimes simply referred to as a "film material"), the interlayer film for a laminated glass can be easily stored and transported without damaging the adhesive layer.

The thickness of the adhesive layer in the film material may be 10 μm to 5.0 × 10 ³ μm. Thereby, the impact resistance and visibility of the interlayer film of laminated glass are made more excellent.

According to yet another aspect of the present invention, a method for manufacturing laminated glass is provided. The laminated glass includes two glass plates facing each other, and an intermediate film sandwiched between them. The method may include the step of irradiating the adhesive layer of the film material with ultraviolet rays to harden it; and bonding two glass plates as adherends through the adhesive layer to obtain the two glass plates and the substrate. The steps of the laminated body of the adhesive layer; and the steps of heating and pressing the laminated body under the conditions of 30 ° C. to 150 ° C. and 0.3 MPa to 1.5 MPa. The interlayer film included in the obtained laminated glass is the hardened adhesive layer.

The method for manufacturing laminated glass according to the present invention may include: interposing an adhesive layer of the film material, and bonding two glass plates as adherends to obtain a laminate including the two glass plates and the adhesive layer Step of heating the laminated body under conditions of 30 ° C to 150 ° C and 0.3 MPa to 1.5 MPa; and any glass plate from the two glass plates (the adherend) On the other hand, the laminated body is irradiated with ultraviolet rays to harden it. The interlayer film included in the obtained laminated glass is the hardened adhesive layer.

The photocurable resin composition for an interlayer film of laminated glass according to one aspect of the present invention may further contain (C) a plasticizer component.

The method for manufacturing laminated glass according to one aspect of the present invention may include: (A) coating the surface of one of the glass plates with a photocurable resin composition of the above-mentioned interlayer film of the laminated glass to form photohardenability A resin layer step; (B) a step of bonding one of the glass plates to the other glass plate so that the photocurable resin layer becomes the inside; and (C) pairing the two glass plates The photocurable resin layer between the plates is irradiated with ultraviolet rays to harden it, thereby obtaining a laminated glass including an intermediate film that is the photocurable resin layer that is cured.

The method for manufacturing a laminated glass according to one aspect of the present invention may include: (a) coating the surface of one of the glass plates with a photocurable resin composition of the interlayer film of the laminated glass described above to form a photohardenability A resin layer step; (b) a step of irradiating the photocurable resin layer with ultraviolet rays to harden it; and (c) so that the cured photocurable resin layer (cured resin layer) becomes the inside One of the glass plates is bonded to the other glass plate to obtain a laminated glass including an intermediate film which is a hardened photo-curable resin layer.

The method for manufacturing laminated glass according to one aspect of the present invention may include: (a ') coating the surface of one of the glass plates with a photo-curable resin composition of the interlayer film of the laminated glass described above to form photo-hardening (B ') a step of irradiating the photocurable resin layer with ultraviolet rays to temporarily harden the photocurable resin layer; (c') placing another piece of glass so that the photocurable resin layer which is temporarily hardened becomes the inner side A step of attaching a plate to one of the glass plates; and (d ′) irradiating the temporarily hardened photocurable resin layer sandwiched between the two glass plates with ultraviolet rays to formally harden, thereby Then, a step of obtaining a laminated glass including the interlayer film which is the hardened photocurable resin layer is obtained. Regarding the laminated glass obtained in the step (d '), the glass plate and the glass plate can be laminated with a cured photocurable resin layer (light-transmissive cured resin layer) interposed therebetween.

With regard to the laminated glass obtained by the above method, the glass plate and the glass plate can be laminated with a light-transmitting hardening resin layer (cured photocurable resin layer) interposed therebetween. Herein, the "glass plate" is used as a term including not only an inorganic glass plate but also a transparent plastic plate such as a resin substrate and a resin film. By using the film material or the interlayer film on one side of the present invention, for example, inorganic glass plates, inorganic glass plates and transparent plastic plates, or transparent plastic plates can be bonded to each other.

The interlayer film of one aspect of the present invention has improved wettability to the surface of the glass plate (adhered body) and then, thereby improving the toughness of the laminated glass (laminated body). As a result, a laminated glass having high crack resistance can be provided. [Effect of the invention]

According to one aspect of the present invention, there is provided a photocurable resin composition for an interlayer film that can provide laminated glass that is hard to break when subjected to an impact from the outside, that is, laminated glass that is excellent in crack resistance. One aspect of the present invention can provide a film material for an interlayer film of a laminated glass using the photocurable resin composition, and a method for producing the laminated glass. Regarding the laminated glass of one aspect of the present invention, in terms of reliability in a high humidity environment, it is also possible to maintain stable transparency in which the interlayer film (adhesive layer) does not whiten.

Hereinafter, 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, the "(meth) acrylate" means "acrylate" or a 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 the respective components in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition. In addition, unless otherwise specified, the content of each component is expressed as a ratio based on the total amount of the photocurable resin composition (excluding solvents added for coating and the like) as a reference.

Photocurable resin composition for interlayer film of laminated glass The photocurable resin composition for interlayer film of this embodiment contains (A) (meth) acrylic polymer and (B) (meth) acrylic acid The monomer (or (meth) acrylate monomer) and (D) the photopolymerization initiator may further contain (C) a plasticizer component. This photocurable resin composition is mainly cured by a photopolymerization reaction of a (meth) acrylic monomer. That is, the hardened photocurable resin composition and a hardened adhesive layer or hardened photocurable resin layer described later including the polymer include a polymer formed by polymerization of a (B) (meth) acrylic monomer.

The photocurable resin composition for a laminated glass interlayer film of this embodiment exhibits laminated glass by improving the wettability to the surface of the adherend (glass plate) and the toughness of the laminated body (laminated glass). High rupture resistance.

Next, each component of the photocurable resin composition for intermediate films of a laminated glass is demonstrated.

(A) (meth) acrylic polymer (meth) acrylic polymer (hereinafter sometimes referred to as "(A) component") has a (meth) acrylfluorenyl group in the molecule (CH ₂ = C (X) A homopolymer in which C (= O)-, X is a hydrogen atom or a methyl) monomer ((meth) acrylate compound, etc.) is independently polymerized, or a combination of two or more of these monomers is copolymerized to The copolymer formed.

The monomer ((meth) acrylate compound etc.) constituting the (meth) acrylic polymer is usually a monofunctional monomer having one (meth) acrylfluorenyloxy group or (meth) acrylfluorenyl group. Specific examples thereof include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (formyl) (Meth) acrylate tert-butyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-methacrylate Ethylhexyl, isodecyl (meth) acrylate, dodecyl (meth) acrylate (n-lauryl (meth) acrylate), isomyristoyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbons such as stearyl acrylate and isostearyl acrylate; glycidyl (meth) acrylate; 3-butene (meth) acrylate (Meth) acrylic alkenyl esters having alkenyl groups having 2 to 18 carbons such as alkyl esters; (meth) acrylic acid having aromatic rings such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate Esters; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol Alcohol (meth) acrylic Ester, methoxypolyethylene glycol (meth) acrylate, methoxyheptadiol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (methyl Group) alkoxy polyalkylene glycol (meth) acrylates such as acrylate and butoxy diethylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate And (meth) acrylic acid esters having an alicyclic group, such as dicyclopentyl (meth) acrylate, dicyclopentenyloxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, (methyl) ) (Meth) acrylates having a hydroxyl group, such as 3-hydroxypropyl acrylate and 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N-dimethacrylate (Meth) acrylic acid esters having amine groups such as methylaminoethyl ester; (meth) acrylamidoamine, (meth) acrylamidomorpholine, N, N-dimethylaminopropyl (methyl ) Acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N- (Meth) acrylamide derivatives such as hydroxyethyl (meth) acrylamide; 2- (2-methacrylamide) (Meth) acrylates with isocyanate groups, such as oxyethyloxy) ethyl isocyanate and 2- (meth) acrylfluorenyloxyethyl isocyanate; tetraethylene glycol mono (meth) acrylate, six Ethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, and octapropylene glycol mono (meth) acrylate Isopolyalkylene glycol mono (meth) acrylate; (meth) acrylate with a siloxane skeleton. These compounds may be used singly or in combination of two or more kinds.

The (meth) acrylic polymer (or (meth) acrylate polymer) may include a modified (meth) acrylate oligomer having a (meth) ) A monomer such as an acrylate compound is a main chain of a monomer unit, a urethane bond bonded to the main chain, and (meth) propylene bonded to the main chain via the urethane bond. Fluorenyloxy. Such a (meth) acrylic polymer may be a reaction product of a (meth) acrylate oligomer (or (meth) acrylic polymer) having a hydroxyl group in a side chain and an isocyanate. Examples of the (meth) acrylate oligomer having a hydroxyl group on the side chain include (meth) acrylic acid containing 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 6-hydroxyhexyl acrylate as monomer units. polymer. The (meth) acrylic polymer has a side chain having an acrylate group bonded via a main chain and a urethane bond, thereby further increasing the molecular weight of the (meth) acrylic polymer in the photocurable resin composition. As a result, entanglement of (meth) acrylic polymer molecules with each other can be made more complicated. That is, by adding a (meth) acrylfluorenyl group to a (meth) acrylic polymer, the hardened | cured material of a photocurable resin composition can be made more tough. In the present specification, the modified (meth) acrylic polymer is classified as a type of (meth) acrylic polymer and is not a (meth) acrylic monomer (component having an ethylenically unsaturated bond) of the component (B) described below. Based compounds).

The (meth) acrylic polymer may include, as a comonomer, a compound capable of copolymerizing with the monomer such as the (meth) acrylate compound. Examples of the compound that can be copolymerized with monomers such as a (meth) acrylate compound include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, and cyclohexyl-butene. Dihydramine, phenylmaleimide, and maleic anhydride.

The content of the (meth) acrylic polymer may be 1% by mass or more, 10% by mass or more, or 20% by mass or more based on the total amount of the photocurable resin composition. The content of the (meth) acrylic polymer may be 80% by mass or less, 50% by mass or less, or 30% by mass or less based on the total amount of the photocurable resin composition. When the content of the (meth) acrylic polymer (or (meth) acrylate oligomer) is within such a range, the elongation of the cured product of the photocurable resin composition is further increased, and the viscosity is further reduced.

The weight average molecular weight of the (meth) acrylic polymer may be 10,000 to 2 million, or 100,000 to 1 million. When the weight-average molecular weight is 10,000 or more, the entanglement of molecular chains of the (meth) acrylic polymer becomes more complicated, the interlayer becomes stronger, and the impact strength of the laminated glass tends to be higher. When the weight average molecular weight of the (meth) acrylic polymer is 2 million or less, there is a tendency that the viscosity of the photocurable resin composition is not excessively high, and drawing properties are less likely to occur, thereby improving workability. Here, the weight average molecular weight refers to a standard polystyrene conversion value measured by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of the (meth) acrylic polymer may be 0 ° C or lower or -10 ° C or lower. When the Tg of the (meth) acrylic polymer is low, the impact strength of the laminated glass tends to be high. From the same viewpoint, the Tg of the (meth) acrylic polymer may be -15 ° C or lower. The lower limit of the Tg of the (meth) acrylic polymer is not particularly limited, and may be -40 ° C or higher.

(B) (meth) acrylic monomer (meth) acrylic monomer (hereinafter sometimes referred to as "(B) component") is a compound having an ethylenically unsaturated group or a (meth) acrylfluorenyl group. Specific examples thereof include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (formyl) (Meth) acrylate tert-butyl acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, isodecyl (meth) acrylate, dodecyl (meth) acrylate (n-lauryl (meth) acrylate), isomyristoyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters having 1 to 18 carbons such as stearyl acrylate; ethylene glycol di (meth) acrylate, butanediol (meth) acrylate, nonanediol di Alkane diols such as (meth) acrylic acid esters having 1 to 18 carbon dialkyl (meth) acrylates; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. have more than three (meth) acryl fluorenyl groups in the molecule Polyfunctional (meth) acrylate; glycidyl (meth) acrylate; alkenyl (meth) acrylate having 2 to 18 carbon atoms, such as 3-butenyl (meth) acrylate; (Meth) acrylates with aromatic rings such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (Meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methyl Heptaoxypropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate Alkoxy polyalkanediol (meth) acrylates such as esters; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates having alicyclic groups such as dicyclopentenyloxyethyl ester; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 4-hydroxybutyl esters have hydroxyl groups (Meth) acrylates; tetrahydrofurfuryl (meth) acrylates; (meth) acrylates with amine groups, such as N, N-dimethylaminoethyl (meth) acrylate; (meth) Acrylamide, (meth) acrylamide morpholine, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- (Meth) acrylamide derivatives such as isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2 -(2-methacrylfluorenyloxyethyloxy) ethyl isocyanate, 2- (meth) acrylfluorenyloxyethyl isocyanate, etc. (meth) acrylates with isocyanate groups; tetraethylene glycol Mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, Polyalkylene glycol mono (meth) acrylates such as octapropylene glycol mono (meth) acrylate; polyalkylene glycol di (meth) acrylates; (meth) acrylates having an isotricyanate ring skeleton; (Meth) acrylate with a siloxane skeleton, isoprene Polyisoprene skeleton (meth) acrylate, having a butadiene skeleton is polybutadiene (meth) acrylate. These may be used alone or in combination of two or more.

Alkyl (meth) acrylates having 1 to 18 carbons in alkyl groups, alkanediol di (meth) acrylates having 1 to 18 carbons in alkanes, and having more than three (meth) s in the molecule Polyfunctional (meth) acrylic acid esters having an acrylic group and an aliphatic group, glycidyl methacrylates, and alkenyl (meth) acrylates having 2 to 18 carbon atoms in alkenyl groups are sometimes collectively referred to as Aliphatic (meth) acrylate. In some cases, an alkoxy polyalkylene glycol (meth) acrylate, a polyalkylene glycol mono (meth) acrylate, a polyalkylene glycol di (meth) acrylate, and an isotricyanate ring skeleton may be used. (Meth) acrylates and (meth) acrylates having a siloxane skeleton are collectively referred to as heteroatom-based (meth) acrylates.

The content of the (meth) acrylic monomer may be 3% by mass or more, 5% by mass or more, or 10% by mass or more based on the total amount of the photocurable resin composition. The content of the (meth) acrylic monomer may be 90% by mass or less, 70% by mass or less, or 50% by mass or less based on the total amount of the photocurable resin composition.

(C) Plasticizer component The plasticizer component is a compound that is compatible with the (meth) acrylic polymer of the component (A) and does not photopolymerize itself by irradiation with ultraviolet rays. When a plasticizer component is not compatible with a (meth) acrylic polymer, there exists a possibility that hardened | cured material may become cloudy and visibility may fall. The plasticizer component may include at least one of a solid tackifier and a liquid plasticizer. Here, the "solid (solid)" means that the softening temperature measured by Japanese Industrial Standards (JIS) K5601-2-2 is 60 ° C to 150 ° C, or 80 ° C to 120 ° C. The liquid state refers to a state where the viscosity measured by a cone-plate rheometer at atmospheric pressure and 25 ° C is in a range of 0.01 Pa · s to 100 Pa · s (25 ° C).

A solid adhesion-imparting agent exhibiting such a softening temperature does not undergo photo-hardening by irradiation with ultraviolet rays, and has a photo-curable resin layer (or an adhesive layer) which enhances the hardening or temporary hardening formed by the photo-curable resin composition. ) The effect of initial bonding strength (so-called tackiness) and improving the final bonding strength of the hardened photocurable resin layer (or adhesive layer). The adhesion-imparting agent may include, for example, terpene resins such as terpene resins, terpene phenol resins, and hydrogenated terpene resins; rosin resins such as natural rosin, polymerized rosin, rosin esters, and hydrogenated rosin; and polybutadiene and polyisoprene Petroleum resins such as diene; or a combination of these.

The liquid plasticizing component is a component that does not photo-harden itself by irradiation with ultraviolet rays, imparts flexibility to the photo-curable resin layer after curing or temporary curing, and reduces curing shrinkage. Such a liquid plasticizing component may be, for example, selected from a liquid polybutadiene-based plasticizer, a polyisoprene-based plasticizer, a phthalate-based plasticizer, and an adipate-based plasticizer. At least one of the group consisting of a plasticizer.

Examples of the liquid plasticizing component (plasticizer) include butadiene rubber, isoprene rubber, silicone rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, and butyl rubber. Liquid rubber such as ethylene propylene rubber, urethane rubber, chlorosulfonated polyethylene rubber, fluorine rubber, hydrogenated nitrile rubber, and epichlorohydrin rubber; polyalphaolefin (such as polybutene), hydrogenated alpha- Polyolefin oligomers such as olefin oligomers (such as hydrogenated polybutene) and heterotactic polypropylene; aromatic oligomers such as biphenyl and terphenyl; hydrogenation of hydrogenated liquid polybutadiene Polyolefin oligomers; paraffin oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffin oligomers such as naphthenic oil; dimethyl phthalate, diethyl phthalate, orthobenzene Dibutyl dicarboxylate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, phthalate Diphenyl dicarboxylate, diisodecyl phthalate, di-tridecyl phthalate, phthalic acid -Undecyl ester, di (heptyl, nonyl, undecyl) phthalate, benzyl phthalate, butyl benzyl phthalate, dinonyl phthalate and Phthalic acid derivatives such as dicyclohexyl phthalate; isophthalic acid such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, and diisooctyl isophthalate Dicarboxylic acid derivatives; di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate and diisodecyl tetrahydrophthalate Formic acid derivatives; adipic acid derivatives such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, and diisononyl adipate; nonyl Azelaic acid derivatives such as bis (2-ethylhexyl) diacid, diisooctyl azelate and di-n-hexyl azelate; di-n-butyl sebacate and di- (2 -Ethylhexyl) esters such as sebacic acid derivatives; di-n-butyl maleate, dimethyl maleate, diethyl maleate, and di- (maleic acid) 2-ethylhexyl) esters and other maleic acid derivatives; di-n-butyl fumarate and fumarate Fumaric acid derivatives such as di- (2-ethylhexyl) ester; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, trimellitate Trimellitic acid derivatives such as isodecyl ester, triisooctyl trimellitate, tri-n-hexyl trimellitate, and triisononyl trimellitate; tetra- (2-ethylhexyl pyromellitic acid) ) Esters and pyromellitic acid derivatives such as tetra-n-octyl pyromellitic acid; triethyl citrate, tri-n-butyl citrate, ethyl ethyl triethyl citrate and ethyl trimethyl citrate (2-ethylhexyl) esters and other citric acid derivatives; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate and clothing Itaconic acid derivatives such as di- (2-ethylhexyl) conate; oleic acid derivatives such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; methyl Ricinoleic acid derivatives such as acetoic acid ricinoleate, butylacetic acid ricinoleic acid, glycerol monoricinoleic acid and diethylene glycol monoricinoleic acid ester; n-butyl stearate, glycerol mono Glycerin monostearate and diethylene glycol Stearic acid derivatives such as stearates; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters; triethyl phosphate, Tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, tri-di Phosphate derivatives such as tolyl phosphate and tris (chloroethyl) phosphate; diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, Triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexanoate), dibutyl methylene bisthioglycolate, etc. Glycol derivatives; glycerol derivatives such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate; epoxidized soybean oil, epoxy hexahydrophthalate diisodecyl, epoxy Epoxy derivatives such as triglyceride, octyl epoxide and decyl oleate. These compounds may be used singly or in combination of two or more kinds.

The content of the plasticizer component may be 5% by mass or more, 10% by mass or more, or 20% by mass or more based on the total amount of the photocurable resin composition. The content of the plasticizer component may be 90% by mass or less, 70% by mass or less, or 50% by mass or less based on the total amount of the photocurable resin composition.

(D) Photopolymerization initiator The photopolymerization initiator (hereinafter sometimes referred to as "(D) component") initiates or accelerates the hardening reaction by irradiation with active energy rays (especially caused by photoradical polymerization). Hardening reaction). Here, the active energy rays refer to ultraviolet rays, electron beams, alpha rays, beta rays, gamma rays, and the like. The photopolymerization initiator is not particularly limited, and known materials such as benzophenone-based, anthraquinone-based, benzamidine-based, sulfonium salts, diazonium salts, and onium salts can be used.

Specific examples include benzophenone, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N, N ', N'-Tetraethyl-4,4'-diaminobenzophenone, 4- (dimethylamino) -4'-methoxybenzophenone, α-hydroxyisobutylbenzene Ketones, 2-ethylanthraquinone, tert-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthracene Quinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, thiathrone, 2-chlorothiathrone, 1-hydroxycyclohexyl Phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,2- Aromatic ketone compounds such as diethoxyacetophenone; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; benzoin ether compounds such as benzoin methyl ether, benzoin ether, benzoin isobutyl ether, and benzoin phenyl ether; benzoin, Benzophenone compounds such as benzoyl dimethyl ketal; ester compounds of β- (acridin-9-yl) (meth) acrylic acid, 9-phenylacridine, 9-pyridylacridine, 1,7 -Acridine compounds such as diacridinoheptane; 2- (o-chlorophenyl) -4,5-diphenyl Diimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole Dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimers; 2-benzyl-2-dimethylamino-1 Α-Aminobenzene such as (4-morpholinylphenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-1-acetone Alkyl ketone compounds; fluorenyl phosphine oxide compounds such as bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide; and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) acetone).

Particularly, as a photopolymerization initiator that does not substantially color the photocurable resin composition, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 can be mentioned. -Ketones, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one and other α-hydroxybenzoalkyl ketone compounds; bis ( 2,4,6-trimethylbenzylidene) -phenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxide , 2,4,6-trimethylbenzylfluorenyl-diphenylphosphine oxide and other fluorenyl phosphine oxide-based compounds; oligomeric (2-hydroxy-2-methyl-1- (4- (1-methyl Vinyl) phenyl) acetone) and combinations of these.

The content of the photopolymerization initiator may be 0.1 to 5 mass%, 0.2 to 3 mass%, or 0.3 to 2 mass% with respect to the total amount of the photocurable resin composition. When the content of the photopolymerization initiator is 0.1% by mass or more, photopolymerization can be favorably initiated. When the content of the photopolymerization initiator is 5% by mass or less, the step embedding property and the self-organizing property are easily improved, and the hue of the obtained cured product is easily suppressed from being yellow.

(Other additives) The photocurable resin composition of this embodiment may contain various additives different from said (A) component-(D) component as needed. Examples of the various additives that can be contained include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, leveling agents, and inorganic fillers.

The polymerization inhibitor is added for the purpose of improving the storage stability of the photocurable resin composition. Examples thereof include p-methoxyphenol. The antioxidant is added for the purpose of improving the heat-resistant colorability of the cured product obtained by curing the photocurable resin composition by light. Examples thereof include phosphorus-based triphenyl phosphite, phenol-based, and thiol-based antioxidants. The light stabilizer is added for the purpose of improving resistance to active energy rays such as ultraviolet rays. As an example, Hindered Amine Light Stabilizer (HALS) is mentioned. The silane coupling agent is added to improve the adhesion to glass and the like. Examples thereof include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-amine Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiiso Acrylic Silane. The surfactant is added to control peelability. Examples thereof include polydimethylsiloxane-based compounds and fluorine-based compounds. The leveling agent is added to impart flatness to the photocurable resin composition. Examples thereof include silicon-based and fluorine-based compounds that reduce surface tension.

These additives can be used alone or in combination. When these additives are used, the content is generally smaller than the total content of the components (A) to (D). Generally, the content is about 0.01 to 5% by mass based on the total amount of the photocurable resin composition.

The photocurable resin composition of this embodiment may contain an inorganic filler. Examples of the inorganic filler include crushed silica, fused silica, mica, clay minerals, short glass fibers or fine powders, 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 100 parts by mass of the photocurable resin composition based on the total solid content (components other than the solvent). 0.1 to 30 parts by mass. When the content of the inorganic filler is 0.01 to 100 parts by mass, a resin composition that is particularly excellent in terms of low shrinkage, improvement in mechanical strength, and low thermal expansion rate can be obtained. A commercially available surface treatment agent such as a coupling agent and a disperser such as a three-roller, a bead mill, and a nanonomizer can be used to improve the dispersibility of the inorganic filler.

The storage elastic coefficient of the intermediate film formed by curing the adhesive layer or the photocurable resin layer can be 100,000 Pa to 100,000,000 Pa at a measurement temperature of 25 ° C and a frequency of 1000 Hz. Here, the storage elastic coefficient is measured using a master curve by a dynamic viscoelasticity measurement method.

For the intermediate film formed by curing the adhesive layer or the photocurable resin layer, the peak value (maximum value) of the loss coefficient (tanδ) measured at a measurement temperature of 25 ° C. and a frequency of 100 Hz or more may be 0.5 or more. In particular, the maximum value of the loss coefficient can be 0.5 or more in a range of a measurement temperature of 25 ° C and a frequency of 100 Hz to 100,000 Hz. If the loss coefficient measured at a measurement temperature of 25 ° C. and a frequency of 100 Hz or more is 0.5 or more, the interlayer film dissipates impact energy and the crack resistance of the laminated glass is further improved. Here, the loss coefficient is measured using a master curve by a dynamic viscoelasticity measurement method. The condition of a frequency of 100 Hz to 100,000 Hz corresponds to a strain when a steel ball or an iron ball is dropped freely from a height of tens of centimeters to hundreds of tens of centimeters in an impact resistance test described later in the Examples, and the strain when it hits a laminated glass speed.

The dynamic viscoelasticity measurement mentioned in this specification is performed using a dynamic viscoelasticity measuring machine (manufactured by TA instrument, RSA-G2). The measurement conditions and analysis methods are as follows. · Measuring mode: Stretching · Temperature: -70 ℃ ～ 100 ℃ · Frequency: 0.05, 0.5, 5, 50 (s-1) · Strain variable: 1% · Analytical method: According to the measurement results, the WLF method or Ari The Arrhenius rule is used to calculate the master curve.

Method for producing a photocurable resin composition for an intermediate film of a laminated glass The method for producing a photocurable resin composition for an interlayer film of a laminated glass according to this embodiment is not particularly limited, and the (A) The component, the (B) component, the (D) component, and the (C) component and the additive, if necessary, are produced by mixing and stirring. When any one of the components is solid, the solid component may be heated and dissolved at least one time point before mixing, during mixing, and after mixing. Thereby, each component can be disperse | distributed favorably. Thereafter, the photocurable resin composition for an interlayer film of a laminated glass can be obtained by cooling. The heating temperature is not particularly limited, and when a component having a high viscosity is stirred, it is preferably a high temperature. Among these, the volatilization temperature of the easily volatilizable component is preferably not more than. From this viewpoint, when the mixture of each component is heated, its temperature is preferably 40 ° C to 130 ° C. When the temperature is 40 ° C. or higher, even when the viscosity of the components is high, it is easy to stir sufficiently. When the temperature is 130 ° C or lower, the volatilization of the components can be suppressed, and the coloring of the resin composition can also be suppressed. The stirring time is not particularly limited, but is preferably 10 minutes to 60 minutes, and more preferably 20 minutes to 40 minutes.

Film material for interlayer films of laminated glass and method for producing the same Figure 1 is a schematic cross-sectional view showing one embodiment of a film material for interlayer films of laminated glass. The interlayer film material 2 for laminated glass shown in FIG. 1 includes an adhesive layer 5a including the photocurable resin composition of the embodiment, and a pair of substrates laminated with the adhesive layer 5a interposed therebetween.材 层 21,22. The base material layer 21 may be a light release separator (isolation film or cover film), and the base material layer 22 may be a heavy release separator (isolation film). The heavy release release layer and the light release release layer may be a polymer film such as a polyethylene terephthalate film. The light release release layer may be a cover film having the same raw material as the heavy release release layer. The film material for an interlayer film of laminated glass is applicable to various laminated glass.

In order to control the releasability between the adhesive layer 5a, the base material layer 21, and the base material layer 22, the photocurable resin composition (adhesive resin composition) for the laminated glass interlayer film may also contain polydimethylsiloxane Surfactants such as surfactants and fluorine surfactants.

The thickness of the adhesive layer may be 10 μm to 5.0 × 10 ³ μm. The light transmittance of the adhesive layer 5a to light in the visible light region (wavelength: 380 nm to 780 nm) may be 80% or more, 90% or more, or 95% or more.

The adhesive layer 5a is a layer formed by processing the laminated glass intermediate film of this embodiment into a sheet-like or film-like shape using a photocurable resin composition. A method for processing the photocurable resin composition into a sheet shape or a film shape is not particularly limited, and a known technique can be used. For example, a coating solution is prepared by diluting the photocurable resin composition of the present embodiment with a ketone solvent such as 2-butanone and cyclohexanone, and the coating solution is prepared by a flow coating method, a roll coating method, a gravure roll method, a wire rod method, This coating liquid is applied to a substrate such as a polymer film by a lip mold coating method, and the solvent is removed (dried) from the coating film, whereby the photocurable resin composition can be processed into a sheet having an arbitrary film thickness. Shaped or membranous. When preparing the coating liquid, the components may be diluted with a solvent after the components are prepared, or may be diluted with the solvent before the components are prepared.

From the viewpoint of coatability, the solid content concentration (concentration of components other than the solvent) of the coating liquid is preferably 30% by mass or more, and more preferably 40% by mass or more, based on the quality of the coating solution. From the same viewpoint, the solid content concentration of the coating liquid is preferably 70% by mass or less, and more preferably 60% by mass or less. From the viewpoint of coatability, the viscosity of the coating liquid is preferably 1 Pa · s or more at a coating temperature, and more preferably 5 Pa · s or more. From the same viewpoint, the viscosity of the coating liquid is preferably 30 Pa · s or less, more preferably 25 Pa · s or less, and even more preferably 15 Pa · s or less.

The heavy release release layer (base material layer 22) may be, for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, and polyester, or a polyethylene terephthalate film ( It is also sometimes referred to as "PET film" hereinafter). From the viewpoint of workability, the thickness of the re-peeling release layer (base material layer 22) may be 50 μm to 200 μm, 60 μm to 150 μm, or 70 μm to 130 μm. The planar shape of the re-peeling release layer (base material layer 22) may be larger than the plane shape of the adhesive layer 5a, and the outer edge of the re-peeling release layer (base material layer 22) protrudes more outward than the outer edge of the adhesive layer 5a. From the viewpoints of ease of handling, ease of peeling, and further reduction of adhesion of dust, etc., the width of the outer edge of the release layer (base material layer 22) is greater than the outer edge of the adhesive layer 5a. It can be 2 mm to 20 mm, or 4 mm to 10 mm. In the case where the planar shapes of the adhesive layer 5a and the re-peeling release layer (base material layer 22) are approximately rectangular, such as a substantially rectangular shape, the base layer 22 (repeated-release layer) has a larger thickness than the outer edge of the adhesive layer 5a. The width of the outer edge may be at least 2 mm to 20 mm on one side, 4 mm to 10 mm on at least one side, 2 mm to 20 mm on all sides, or 4 mm to 10 mm on all sides.

The light-peeling release layer (base material layer 21) may be, for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, or polyester, or a polyethylene terephthalate film. From the viewpoint of workability, the thickness of the light release release layer (base material layer 21) may be 25 μm to 150 μm, 30 μm to 100 μm, or 40 μm to 75 μm. The planar shape of the light-peeling release layer (base material layer 21) may be larger than the planar shape of the adhesive layer 5a, and the outer edge of the light-peeling release layer (base material layer 21) protrudes more outward than the outer edge of the adhesive layer 5a. From the viewpoints of ease of handling, ease of peeling, and further reduction of adhesion of dust, etc., the width of the outer edge of the release layer (base material layer 21) is slightly larger than the outer edge of the adhesive layer 5a by the width of the protrusion. It can be 2 mm to 20 mm, or 4 mm to 10 mm. When the planar shape of the adhesive layer 5a and the light release release layer (base material layer 21) is a substantially rectangular shape such as a substantially rectangular shape, the release layer (base material layer 21) is lightly peeled off compared to the outer edge of the adhesive layer 5a. The width of the outer edge may be at least 2 mm to 20 mm on one side, 4 mm to 10 mm on at least one side, 2 mm to 20 mm on all sides, or 4 mm to 10 mm on all sides.

The peeling strength between the light peeling release layer (base material layer 21) and the adhesive layer 5a is preferably lower than the peeling strength between the heavy peeling release layer (base material layer 22) and the adhesive layer 5a. Thereby, it is more difficult for the heavy release release layer (base material layer 22) to peel off from the adhesive layer 5a than the light release release layer (base material layer 21). The peeling strength between the heavy release barrier layer and the adhesive layer, and the light peeling barrier layer and the adhesive layer can be adjusted by, for example, performing a surface treatment of the heavy release barrier layer and the light release barrier layer. Examples of the surface treatment method include a mold release treatment using a silicone compound or a fluorine compound.

Laminated glass Fig. 2 is a side sectional view schematically showing an embodiment of laminated glass. The laminated glass 1 shown in FIG. 2 includes a glass plate 11 (for example, float glass), an interlayer film 5 (for example, hardened adhesive layer), and a glass plate 12 (for example, float glass), which are laminated in this order. In other words, the laminated glass 1 includes two glass plates 11, a glass plate 12, and an intermediate film 5 sandwiched between them.

The glass plate 11 and the glass plate 12 may be inorganic glass plates, and examples thereof include float glass, air-cooled tempered glass, chemically strengthened glass, and double glass. The laminated glass may also have a functional layer such as an anti-reflection layer, an antifouling layer, a pigment layer, a hard coat layer, and / or a transparent protective plate (such as a transparent plastic plate). One or two of the two glass plates 11 and 12 may be a transparent protective plate (such as a transparent plastic plate). An interlayer film formed of a photocurable resin composition for an interlayer film of laminated glass can also be used for bonding these. The thickness of the glass plate 11 and the glass plate 12 is not particularly limited, and may be, for example, 0.01 mm to 20 mm. Laminated glass may also include more than three glass plates. At this time, the intermediate film of the embodiment may be provided between any two adjacent glass plates.

(Anti-reflection layer) The anti-reflection layer is a layer that prevents reflection of light, and may be an anti-reflection layer having a visible light reflectance of 5% or less. The anti-reflection layer may be a transparent substrate such as a transparent plastic film treated by a known anti-reflection method.

(Antifouling Layer) The antifouling layer is a layer provided to prevent dirt from adhering to the surface. As the antifouling layer, a known layer composed of a fluorine-based resin, a silicone-based resin, or the like can be used in order to reduce the surface tension.

(Pigment Layer) The pigment layer is a layer provided to improve color purity. The pigment layer is used to reduce light of an unnecessary wavelength transmitted in the laminated glass. The dye layer may include a base film such as a polyethylene film and a polyester film, and a layer of a resin containing a dye that absorbs light of an unnecessary wavelength, which is laminated on the base.

(Hard Coating) The hard coating is a layer provided to improve the surface strength. The hard coat layer may include, for example, a base film such as a polyethylene film, and a layer of an acrylic resin such as acrylic urethane and epoxy acrylate and / or an epoxy resin laminated on the base film. Similarly, in order to improve the surface hardness, a hard coating layer formed on a transparent protective plate such as glass, acrylic resin, polycarbonate, or the like may be used.

These layers can be laminated using a roll laminator, a vacuum laminator, or a single-sheet laminator while sandwiching the adhesive layer 5a.

Method for producing laminated glass The laminated glass according to the embodiment can be produced, for example, by the following method. First, the light peeling release layer (base material layer 21) is peeled from the interlayer film material 2 for laminated glass, and the surface of the adhesive layer 5a is exposed. Then, the surface of the adhesive layer 5a is stuck to the glass plate 11 which is a 1st to-be-adhered body, and it presses with a roller etc. Then, the heavy release separation layer (base material layer 22) was peeled from the adhesive layer 5a, and the surface (surface on the opposite side from the glass plate 11) of the adhesive layer 5a was exposed. The exposed surface of the adhesive layer 5 a is attached to a glass plate 12 as a second adherend. The obtained laminated body is heated and pressurized by, for example, an autoclave process. The glass plate 12 as the second adherend may be, for example, an inorganic glass plate or a transparent protective plate (transparent plastic plate). As described above, the adherends (glass plates) can be bonded to each other through the adhesive layer 5a or the intermediate film 5 formed by curing the adhesive layer 5a. Regarding heating and pressure, for example, the temperature is 30 ° C to 150 ° C, and the pressure is 0.3 MPa to 1.5 MPa. From the viewpoint of further removing the entangled air bubbles, the temperature may be 50 ° C to 70 ° C, and the pressure may be 0.3 MPa to 0.5 MPa. The heating and pressing time may be 5 minutes to 60 minutes, or 10 minutes to 30 minutes.

The manufacturing method may further include the steps of irradiating the adhesive layer 5a with ultraviolet rays from either side of two adherends (for example, an inorganic glass plate or a transparent protective plate) before or after heating and pressing the laminated body. . Thereby, the adhesive layer 5a is sufficiently hardened, and the adhesion reliability (reduction of generation of bubbles and suppression of peeling) and adhesion force under high temperature and high humidity conditions can be further improved.

The amount of ultraviolet radiation is not particularly limited, and may be about 500 mJ / cm ² to 5000 mJ / cm ² . From the viewpoint of improving the reliability of adhesion under high-temperature and high-humidity conditions, the step of irradiating ultraviolet rays may be performed after heating and pressing the laminated body.

Regarding the structure (laminated glass) obtained as described above, when an inorganic glass plate (soda-lime glass) or an acrylic resin substrate is used as an adherend, the interlayer film and the glass The peel strength between the plates may be 5 N / 10 mm or more, 8 N / 10 mm or more, or 10 N / 10 mm or more, and may be 30 N / 10 mm or less. Here, the peel strength can be measured by a 180-degree peel test using a tensile tester (manufactured by Orientec Co., Ltd. under the trade name "Tensilon RTC-1210"). The peeling speed was 300 mm / min for 3 seconds, and the measurement temperature was 25 ° C.).

Instead of the method using the film material for an interlayer film of laminated glass, the photocurable resin composition for a glass interlayer film may be applied instead, and laminated glass may be produced by the following three methods.

The first manufacturing method is to apply a photocurable resin composition to one of the glass plates, and then laminate the other glass plate thereon so that the coating film is positioned between the glass plate and the glass plate. A method for obtaining a laminated glass by irradiating an active energy ray such as ultraviolet rays on the side and photocuring a coating film. The second manufacturing method is to apply a light-curable resin composition to one of the glass plates, and then to irradiate active energy rays such as ultraviolet rays to light-harden the coating film without temporary curing to form a light-transmissive cured resin. And a method of obtaining a laminated glass by laminating another glass plate thereon such that a curable resin layer is positioned between the glass plate and the glass plate. The third manufacturing method is to apply a photocurable resin composition to one of the glass plates, and then irradiate the coating film with active energy rays such as ultraviolet rays to form a temporarily hardened resin layer. The temporarily hardened resin layer is located between the glass plate and the glass. The method of laminating | stacking another glass plate here, and the method of making a temporary hardening resin layer light-harden further, and forming a translucent hardening resin layer.

3 (a) to 3 (c) are step diagrams showing an embodiment of the first manufacturing method. The method shown in FIGS. 3 (a) to 3 (c) includes: (A) applying a photocurable resin composition (liquid photocurable resin composition) for a laminated glass interlayer film to one of the glass plates; Step of forming a photocurable resin layer 5a (may also be an adhesive layer) on the surface of 11 (refer to FIG. 3 (a)); (B) pasting one of the glass plates 11 so that the photocurable resin layer 5a becomes the inside A step of bonding to another glass plate 12 (see FIG. 3 (b)); and (C) irradiating the photocurable resin layer 5 a sandwiched between the two glass plates 11 and 12 with ultraviolet rays to harden ( 3 (c)), thereby obtaining the interlayer film 5 which is a photocurable resin layer (transparent hardening resin layer) which is shown in FIG. 2 and is laminated with two glass plates 11 and 12 Steps of laminating glass 1.

4 (a) and 4 (b) are step diagrams showing an embodiment of a second manufacturing method. The method shown in FIG. 4 (a) and FIG. 4 (b) includes the following steps: (a) Applying a photocurable resin composition (liquid photocurable resin composition) of an interlayer film of laminated glass to A step of forming a photocurable resin layer 5a (or an adhesive layer) on the surface of one of the glass plates 11 (see FIG. 4 (a)); (b) a step of irradiating the photocurable resin layer with ultraviolet rays to harden it ( 4 (b)); and (c) one of the glass plates 11 is adhered to the other glass plate 12 so that the photocurable resin layer 5a becomes the inner side, so that the light hardened by the barrier shown in FIG. 2 is obtained. A step of laminating a laminated glass 1 having two glass plates 11 and a glass plate 12 with an intermediate film 5 as a curable resin layer (light-transmitting curable resin layer).

5 (a) to 5 (d) are step diagrams showing an embodiment of a third manufacturing method. The method shown in FIGS. 5 (a) to 5 (d) includes the following steps: (a ') Applying a photocurable resin composition (liquid photocurable resin composition) for a laminated glass interlayer film to A step of forming a photocurable resin layer 5a (or an adhesive layer) on the surface of one of the glass plates 11 (refer to FIG. 5 (a)); (b ') irradiate the photocurable resin layer 5a with ultraviolet rays to temporarily harden it (Refer to FIG. 5 (b)); (c ′) a step of attaching another glass plate 12 to one of the glass plates 11 such that the temporarily cured photocurable resin layer 5 a becomes the inner side (see FIG. 3 ( c)); and (d ') The temporarily hardened photocurable resin layer 5a sandwiched between the two glass plates 11 and 12 is irradiated with ultraviolet rays to formally harden it (refer to FIG. 3 (d)). In this way, a step of obtaining a laminated glass 1 having two glass plates 11 and a glass plate 12 laminated therebetween via the intermediate film 5 which is a hardened photocurable resin layer (transparent hardening resin layer) shown in FIG. 2 is obtained. Here, "temporarily hardened" means that the photo-curable resin composition is cured to such an extent that it is not completely cured. The temporarily hardened photocurable resin layer is in a state of being further hardened by irradiation with ultraviolet rays. "Formal hardening" means that the temporarily hardened photocurable resin composition is further hardened until the polymerization reaction of the (meth) acrylic monomer is substantially completed. [Example]

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

(A) Ingredient: Synthesis of (meth) acrylic polymer (meth) acrylic polymer (A-1) Acrylic acid was added to a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and a nitrogen introduction tube. 96.0 g of isostearyl ester (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "ISTA"), 24.0 g of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "HEA"), and 150.0 g of methyl ethyl ketone was used as an initial monomer, and the reaction solution in the reaction container was heated from 25 ° C to 80 ° C in 15 minutes while replacing with nitrogen at an air volume of 100 ml / min. Thereafter, 24.0 g of isostearyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers were dissolved dropwise over 120 minutes while maintaining the temperature at 80 ° C. in tert-butyl peroxide-2. -A solution obtained in 5.0 g of ethylhexanoate. After completion of the dropwise addition, a reaction was further performed for 2 hours. Then, a (meth) acrylic polymer (A-1) (a weight average molecular weight of 30,000) as a copolymer of isostearyl acrylate and 2-hydroxyethyl acrylate was obtained by distilling off methyl ethyl ketone. .

Synthesis of (meth) acrylic polymer (A-2) In a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and a nitrogen introduction tube, 2-ethylhexyl acrylate (Wako Pure Chemical Industries, Ltd.) Co., Ltd., trade name "EHA") 96.0 g, 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "HEA") 24.0 g, and methyl ethyl ketone 150.0 g as initial monomers While replacing the nitrogen with an air volume of 100 ml / min, the reaction solution in the reaction container was heated from 25 ° C to 80 ° C in 15 minutes. Thereafter, 24.0 g of 2-ethylhexyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers were added dropwise over 120 minutes while maintaining the temperature at 80 ° C. in a third butyl peroxide- The solution obtained in 5.0 g of 2-ethylhexanoate. After completion of the dropwise addition, a reaction was further performed for 2 hours. Then, a (meth) acrylic polymer (A-2) (a weight average molecular weight of 28,000) as a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate was obtained by distilling off methyl ethyl ketone. ).

(B) Ingredients: (meth) acrylic monomer · ISTA (isostearyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "ISTA") · 4HBA (4-hydroxybutyl acrylate, Osaka Organic Chemistry) Industrial Co., Ltd., trade name "4-HBA") · EHA (2-ethylhexyl acrylate, Wako Pure Chemical Industries, Ltd., trade name "EHA") · FA-512AS (dicyclopentene acrylate Ethyloxyethyl, manufactured by Hitachi Chemical Co., Ltd., trade name "FA-512AS") · FA-129AS (nonanediol diacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name "FA-129AS")

(C) Ingredients: Plasticizer ingredients · P85 (hydrogenated terpene resin, manufactured by Yasuhara Chemical Co., Ltd.) · Daimaron (terpene resin, manufactured by Anyuan Chemical Co., Ltd.)

(D) Ingredient: Photopolymerization initiator I-184 (1-hydroxycyclohexylphenyl ketone, manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184")

Measurement of weight average molecular weight The weight average molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The GPC apparatus and measurement conditions are as follows. The weight average molecular weight is a value determined by conversion using a standard curve of standard polystyrene. For the preparation of the standard curve, a 5-sample set (PStQuick MP-H, PStQuick B [manufactured by Tosoh Corporation, trade name]) was used as the standard polystyrene. Device: High-speed GPC device HLC-8320GPC (detector: differential refractometer) (manufactured by Tosoh Corporation, trade name) Solvent: Tetrahydrofuran (THF) Tube column: column column TSK gel Super Multipore HZ -H (manufactured by Tosoh Corporation, trade name) Column size: 15 cm column length, 4.6 mm inside diameter Measurement temperature: 40 ° C Flow rate: 0.35 mL / min Sample concentration: 10 mg / THF 5 mL injection volume: 20 μL

1. Production and Evaluation of Laminated Glass Using Film Material (Example 1-1) [Production of Film Material for Interlayer Film of Laminated Glass (Interlayer Film for Laminated Glass with Cover Film)] Layer, using polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) with a thickness of 75 μm, and light-peeling release layer, using polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) ), And a film material for an interlayer film of a laminated glass was prepared by the following procedures (I) and (II).

(I): 60 mass parts of the (meth) acrylic polymer (A-1) synthesized above, and (B) component isostearyl acrylate (ISTA) 30.9 mass as the (meth) acrylic monomer Parts, 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), 1-hydroxycyclohexylphenyl ketone (I-184, manufactured by BASF Japan Co., Ltd., trade name as a photopolymerization initiator, component (C) Irgacure-184 ") 0.1 parts by mass, and these were mixed while stirring to obtain a photocurable resin composition for an intermediate film of a laminated glass that was liquid at 25 ° C.

(II): The intermediate film of the laminated glass obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive layer might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an intermediate film of laminated glass, and the surface of the adhesive layer for forming an intermediate film was exposed. Float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer and pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, in a vacuum state, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Example 1-2) [Production of film material for interlayer film of laminated glass (interlayer film for laminated glass with cover film)] As a re-peeling release layer, polyethylene terephthalate having a thickness of 75 μm was used. Ester (made by Fujimori Industry Co., Ltd.), as a light peeling release layer, a polyethylene terephthalate (made by Fujimori Industry Co., Ltd.) having a thickness of 75 μm is used, and the following (I), (II) The film material for an interlayer film of laminated glass was produced sequentially.

(I): 60 parts by mass of (meth) acrylic polymer (A-2), 30.9 parts by mass of isostearyl acrylate (ISTA), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), and 1-hydroxyl 0.1 part by mass of cyclohexylphenyl ketone (I-184, manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184"), and these were mixed while stirring to obtain a liquid layer at 25 ° C. Photocurable resin composition for glass interlayer film.

(II): The laminated glass intermediate film obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive layer might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an intermediate film of laminated glass, and the surface of the adhesive layer for forming an intermediate film was exposed. The exposed surface of the adhesive layer was attached to a float glass having a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm, and was pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, the exposed surface of the adhesive layer was attached to a float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm in a vacuum state to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Example 1-3) [Production of film material for interlayer film of laminated glass (interlayer film for laminated glass with cover film)] As a re-peeling release layer, polyethylene terephthalate having a thickness of 75 μm was used. Ester (made by Fujimori Industry Co., Ltd.), as a light peeling release layer, a polyethylene terephthalate (made by Fujimori Industry Co., Ltd.) having a thickness of 75 μm is used, and the following (I), (II) The film material for an interlayer film of laminated glass was produced sequentially.

(I): 60 parts by mass of (meth) acrylic polymer (A-1), 30.9 parts by mass of isostearyl acrylate (ISTA), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), and 1- 0.1 part by mass of hydroxycyclohexylphenyl ketone (I-184, manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184"), and these were mixed while stirring to obtain a liquid at 25 ° C. A photocurable resin composition for a laminated glass intermediate film.

(II): The laminated glass intermediate film obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive layer might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an intermediate film of laminated glass, and the surface of the adhesive layer for forming an intermediate film was exposed. Float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer and pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, in a vacuum state, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment held at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes. Furthermore, one side of the self-laminated body was irradiated with ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) to obtain a hardened adhesive layer. Laminated glass for interlayer film.

(Comparative Example 1-1) [Production of film material for interlayer film of laminated glass] As a heavy release barrier layer, polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used. The release layer was peeled, and a polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used to produce a film material for an interlayer film of laminated glass in the following order (I) and (II): .

(I): 50.0 parts by mass of isostearyl acrylate (ISTA), 49.9 parts by mass of 4-hydroxybutyl acrylate (4HBA), and 1-hydroxycyclohexylphenyl ketone (I-184, BASF Japan Co., Ltd.) (Production, trade name "Irgacure-184") 0.1 parts by mass, and these were mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C.

(II): The laminated glass intermediate film obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive layer might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an intermediate film of laminated glass, and the surface of the adhesive layer for forming an intermediate film was exposed. Float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer and pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, in a vacuum state, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Comparative Example 1-2) [Production of film material for interlayer film of laminated glass] As a heavy release barrier layer, polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used. The release layer was peeled, and a polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used to produce a film material for an interlayer film of laminated glass in the following order (I) and (II): .

(I): 99.9 parts by mass of (meth) acrylic polymer (A-1) and 1-hydroxycyclohexylphenyl ketone (I-184, manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184") 0.1 mass part, and these were mixed while stirring, and the photocurable resin composition for laminated glass intermediate films which was liquid at 25 degreeC was obtained.

(II): The laminated glass intermediate film obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive agent might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an interlayer film of laminated glass to expose the surface of the adhesive layer. Float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer and pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, in a vacuum state, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Comparative Example 1-3) [Production of film material for interlayer film of laminated glass] As a heavy peeling release layer, polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used. The release layer was peeled, and a polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used to produce a film material for an interlayer film of laminated glass in the following order (I) and (II): .

(I): 50.0 parts by mass of isostearyl acrylate (ISTA), 49.9 parts by mass of dicyclopentenyloxyethyl acrylate (FA-512AS), and 1-hydroxycyclohexylphenyl ketone (I-184) 0.1 parts by mass of "Irgacure-184" manufactured by BASF Japan Co., Ltd. These are mixed while stirring to obtain a photocurable resin for a laminated glass intermediate film that is liquid at 25 ° C.组合 物。 Composition.

(II): The intermediate film of the laminated glass obtained in (I) is coated with a photocurable resin composition on a re-peeling release layer to form a coating film (adhesive layer). The light release release layer is laminated on the adhesive layer to obtain a film material for an interlayer film of laminated glass having an adhesive layer sandwiched between the heavy release release layer and the light release release layer. An ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a laminated body (laminated glass) having a hardened adhesive layer. Film material for intermediate film). The photocurable resin composition was adjusted so that the thickness of the adhesive layer might be 3.8 × 10 ² μm.

[Production of laminated glass] Next, the lightly peelable release layer was peeled from the film material for an intermediate film of laminated glass, and the surface of the adhesive layer for forming an intermediate film was exposed. Float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer and pressed with a roller. Then, the heavy peeling release layer was peeled from the adhesive layer, and the surface on the opposite side of the adhesive layer was exposed. Using a vacuum laminator, in a vacuum state, the float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was attached to the surface of the exposed adhesive layer to obtain two pieces of float glass and sandwiched between them. Laminated body that holds the adhesive layer. This laminated body was heated and pressurized under the conditions of an autoclave treatment at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Comparative Example 1-4) [Production of film material for interlayer film of laminated glass] As a heavy release barrier layer, polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used. The release layer was peeled, and a polyethylene terephthalate (manufactured by Fujimori Industry Co., Ltd.) having a thickness of 75 μm was used to produce a film material for an interlayer film of laminated glass in the following order (I) and (II): .

(I): 50.0 parts by mass of isostearyl acrylate (ISTA), 46.1 parts by mass of 4-hydroxybutyl acrylate (4HBA), 3 parts by mass of nonanediol diacrylate (FA-129AS), and 1-hydroxy ring 0.1 mass part of hexyl phenyl ketone (I-184) was stirred and mixed, and the photocurable resin composition for laminated glass intermediate films which was liquid at 25 degreeC was obtained.

(II): After applying the photocurable resin composition for the laminated glass intermediate film obtained in (I) to a heavy release barrier layer to form a coating film, a light release barrier layer is laminated on the coating film , Using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) to irradiate ultraviolet rays (1.0 × 10 ³ mJ / cm ² ), thereby obtaining a heavy peeling release layer and a light peeling release layer. The interlayer is laminated. The coating was adjusted so that the thickness of the intermediate film became 3.8 × 10 ² μm.

[Production of laminated glass] Next, the light-peeling release layer was peeled from the interlayer film for laminated glass with a cover film to expose the surface of the interlayer film. Next, the surface of the interlayer film was attached to a float glass having a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm, and was pressed with a roller. Then, the heavy peeling release layer was peeled from the intermediate film, and the surface of the intermediate film was exposed. Then, using a vacuum laminator, the surface of the interlayer film was attached to a float glass having a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm in a vacuum state. Thereafter, heat and pressure treatment (autoclave treatment) was performed under conditions of maintaining the temperature at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

(Comparative Example 1-5) (1) Production of interlayer film for laminated glass A polyvinyl butyral resin (condensation at half maximum of a peak width corresponding to a hydroxyl group obtained when the infrared absorption spectrum was measured was 245 cm ^-1 The degree of aldolization is 68.0 mole%, the ratio of the vinyl acetal component is 0.6 mole%) 100 parts by mass, and 38 parts by mass with triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer The ingredients are mixed and fully melt-kneaded using a mixing roll. The kneaded product was press-molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film having a thickness of 3.8 × 10 ² μm, which was used as an interlayer film for laminated glass.

The obtained interlayer film for laminated glass was sandwiched between two transparent glass plates having a thickness of 2.7 mm, put it into a rubber bag, and degassed the rubber bag for 20 minutes under a vacuum of 2660 Pa. . The degassed rubber bag was transferred to an oven, and further held at 90 ° C. for 30 minutes and vacuum-pressed. In the autoclave, the laminated glass pre-bonded in this manner was pressure-bonded under conditions of 135 ° C. and a pressure of 118 N / cm ² for 20 minutes to obtain a laminated glass.

The obtained interlayer film for laminated glass and laminated glass were evaluated by the following methods. The results are shown in Table 1.

[Impact resistance test] Support the periphery of the laminated glass with a length of 110 mm and a width of 110 mm square, and point to a position within 25 mm from its center point, so that the steel has a mass of about 1040 g and a diameter of 63.5 mm The ball dropped from the height of 5 cm to 5 cm in order from 5 cm to 100 cm, and the height of the glass when it broke was recorded. Six sheets of laminated glass were tested, and the average height was calculated. The larger the average height value, the higher the rupture resistance. The support frame which supports a test piece (laminated glass) in an impact resistance test is shown in FIG.

FIG. 6 is an exploded perspective view schematically showing an example of a measurement device used in an impact resistance test for evaluating the crack resistance of laminated glass. The measuring device shown in FIG. 6 mainly includes a box-shaped support portion 140 having a flange portion 141 for placing an outer peripheral portion of a laminated glass on an upper end, a fixing portion 142 having a shape substantially the same as the flange portion 141, and a steel ball. 143 composition. A plurality of through holes are formed in the flange portion 141 and the fixing portion 142 of the support portion 140 at positions corresponding to each other. After the laminated glass is placed on the flange portion 141 and the fixing portion 142 is disposed on the laminated glass, the fixing member such as a screw is screwed to the through hole, so that the laminated glass is placed on the outer periphery of the laminated glass. Parts are kept fixed. The sizes of the inner peripheral portions of the flange portion 141 and the fixing portion 142 are 100 mm × 100 mm.

[Table 1]

Laminated glass having an interlayer film made of a photocurable resin composition for a laminated glass interlayer film as compared to laminated glass having an interlayer film using a polyvinyl butyral resin of Comparative Examples 1-5. Shows high impact resistance (crack resistance). About the intermediate film which does not contain the (meth) acrylic polymer ((A) component) of Comparative Example 1-1, Comparative Example 1-3, and Comparative Example 1-4, and does not contain (A) of Comparative Example 1-2 The laminated glass of the intermediate film based on the acrylic monomer (component (B)) has low impact resistance (crack resistance).

2. Production and Evaluation of Laminated Glass by Application of Photocurable Resin Composition [Manufacturing Method of Laminated Glass I] Two floats of 110 mm in length, 110 mm in width, and 2.7 mm in thickness were prepared. glass. A photocurable resin composition is applied on one of the float glass to form a coating film (photocurable resin layer). The thickness of the coating film was adjusted so that it became 3.8 × 10 ² μm after the hardening of the photocurable resin composition was completed, and the photocurable resin composition was applied. Using a vacuum laminator, the float glass coated with the photocurable resin layer was laminated on another float glass so that the photocurable resin layer became the inside. Thereafter, the photocurable resin layer sandwiched between the two pieces of float glass was irradiated with ultraviolet rays to formally harden it, thereby obtaining a laminated glass having an intermediate film that is a cured photocurable resin layer. Thereafter, if necessary, the laminated glass is heated and pressurized by an autoclave treatment under conditions of maintaining a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes.

[Manufacturing method of laminated glass II] A photocurable resin composition is applied to float glass (110 mm in length, 110 mm in width, and 2.7 mm in thickness) to form a coating film (photocurable resin layer). The photocurable resin composition was applied so as to adjust the thickness of the coating film to 3.8 × 10 ² μm. The light release barrier layer was laminated on the photocurable resin layer and irradiated with ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.). A laminated body having a coating film (cured photocurable resin layer) sandwiched between the float glass and the light release barrier layer was obtained. Next, the light peeling release layer was peeled from the coating film, and the surface of the coating film was exposed. Using a vacuum laminator, a float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was laminated on the surface of the exposed coating film under vacuum to obtain a laminated glass. Thereafter, if necessary, the laminated glass is heated and pressurized by an autoclave treatment under conditions of maintaining a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes.

[Manufacturing Method III of Laminated Glass] Two pieces of float glass with a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm were prepared. A photocurable resin composition is applied on one of the float glass to form a coating film (photocurable resin layer). The thickness of the coating film was adjusted so that it became 3.8 × 10 ² μm after being cured. Use an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) to irradiate ultraviolet rays (3.0 × 10 ² mJ / cm ² ), thereby temporarily curing the photocurable resin layer on the float glass . Using a vacuum laminator, the float glass coated with the photocurable resin layer was laminated on another float glass so that the photocurable resin layer became the inside. Thereafter, the photocurable resin layer sandwiched between the two pieces of float glass was irradiated with ultraviolet rays to formally harden to obtain a laminated glass. Thereafter, if necessary, the laminated glass is heated and pressurized by an autoclave treatment under conditions of maintaining a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes.

[Manufacturing Method IV of Laminated Glass] An interlayer film for laminated glass is sandwiched between two transparent pieces of float glass having a thickness of 2.7 mm and placed in a rubber bag. Degas the inside of the rubber bag for 20 minutes under a vacuum of 2660 Pa. The degassed rubber bag was transferred to an oven, and further held at 90 ° C. for 30 minutes and vacuum-pressed. In the autoclave, the laminated glass pre-bonded in the above-mentioned manner was crimped for 20 minutes under the conditions of 135 ° C. and a pressure of 118 N / cm ² .

(Example 2-1) 60 parts by mass of a (meth) acrylic polymer (A-1), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 4-hydroxybutyl acrylate (4HBA, B Ingredients) 4 parts by mass, 5 parts by mass of hydrogenated terpene resin (components P85 and C), and 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd. under the trade name "Irgacure- 184 ") 0.1 parts by mass, and these were mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Example 2-2) Weighed 60 parts by mass of (meth) acrylic polymer (A-1), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 4-hydroxybutyl acrylate (4HBA, B Ingredients) 4 parts by mass, terpene resin (Daimaron, component C) 5 parts by mass, and 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd. under the trade name "Irgacure-184 ") 0.1 parts by mass, and these are mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film which is liquid at 25 ° C. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Example 2-3) 60 parts by mass of (meth) acrylic polymer (A-2), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 4-hydroxybutyl acrylate (4HBA, B) Ingredients) 4 parts by mass, 5 parts by mass of hydrogenated terpene resin (components P85 and C), and 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd. under the trade name "Irgacure- 184 ") 0.1 parts by mass, and these were mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C. Using the obtained composition, a laminated glass was produced by the manufacturing method II of laminated glass.

(Example 2-4) 60 parts by mass of a (meth) acrylic polymer (A-1), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 4-hydroxybutyl acrylate (4HBA, B Ingredients) 4 parts by mass, 5 parts by mass of hydrogenated terpene resin (components P85 and C), and 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd. under the trade name "Irgacure- 184 ") 0.1 parts by mass, and these were mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C. Using the obtained composition, laminated glass was produced by the method III for producing laminated glass.

(Example 2-5) 60 parts by mass of a (meth) acrylic polymer (A-1), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 4-hydroxybutyl acrylate (4HBA, B Ingredients) 9 parts by mass and 1 part by mass of 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184"), and mixing these while stirring Thus, a photocurable resin composition for a laminated glass interlayer film that is liquid at 25 ° C is obtained. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Comparative Example 2-1) 50 parts by mass of isostearyl acrylate (ISTA, B component), 44.9 parts by mass of 4-hydroxybutyl acrylate (4HBA, B component), and hydrogenated terpene resin (P85, C component) were weighed 5 parts by mass and 0.1 part by mass of 1-hydroxycyclohexylphenyl ketone (components I-184, D) (manufactured by BASF Japan Co., Ltd. under the trade name "Irgacure-184"), and mixing these while stirring, borrow Thus, a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C was obtained. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Comparative Example 2-2) 90 parts by mass of a (meth) acrylic polymer (A-1), 9.9 parts by mass of a hydrogenated terpene resin (components P85 and C), and 1-hydroxycyclohexylphenyl ketone (I-184 , D component) (manufactured by BASF Japan Co., Ltd., trade name "Irgacure-184") 0.1 parts by mass, and mixing these while stirring to obtain a laminated glass interlayer film which is liquid at 25 ° C Photocurable resin composition. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Comparative Example 2-3) 50 parts by mass of isostearyl acrylate (ISTA, B component), 41.9 parts by mass of dicyclopentenyloxyethyl acrylate (FA-512AS, component B), and nonanediol di 3 parts by mass of acrylate (FA-129AS, component B), 5 parts by mass of hydrogenated terpene resin (components P85 and C), and 1-hydroxycyclohexylphenyl ketone (components I-184, D) (BASF Japan Limited) 0.1 mass part of "Irgacure-184" (manufactured by the company), and these were mixed while stirring to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C. Using the obtained composition, a laminated glass was produced by the manufacturing method I of laminated glass.

(Comparative Example 2-4) A polyvinyl butyral resin having a half-value width of a peak corresponding to a hydroxyl group obtained when the infrared absorption spectrum was measured was 245 cm ^-1 (the degree of acetalization was 68.0 mole%, the vinyl group was 100 parts by mass of the acetal component) was mixed with 38 parts by mass of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, and the mixture was sufficiently melt-mixed with a mixing roller. Refining. The kneaded product was press-molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film having a thickness of 3.8 × 10 ² μm, which was used as an interlayer film for laminated glass. Using this interlayer film, laminated glass was produced by the method IV for producing laminated glass.

The obtained photocurable resin composition and laminated glass were evaluated by the following methods. The results are shown in Table 2.

<Evaluation of Peel Strength> Using a Nistack (manufactured by Nichiban Co., Ltd.), a frame-shaped spacer having a thickness of 175 μm and an opening having a length of 80 mm and a width of 30 mm was attached to Soda-lime glass with dimensions of 100 mm. The photocurable resin composition is filled into the frame of the spacer without a gap. From there, a polyester film 200 mm long, 100 mm wide, and 125 μm thick (made by Toyobo Co., Ltd., trade name: Cosmosine A4300) larger than the spacer is laminated. Using an exposure machine equipped with a high-power metal halide lamp, the photocurable resin composition to which the polyester film was bonded was exposed at an illuminance of 100 mW and an exposure amount of 3.0 × 10 ³ mJ / cm ² to make the photocurable resin composition. The sample was cured to obtain a test sample in which a soda-lime glass plate and a polyester film were bonded together with a cured product of a photocurable resin composition. For this test sample, a long cut of 200 mm in length and 10 mm in width was cut from the polyester film using a cutter. Using a tensile tester (manufactured by Orientec Co., Ltd., trade name: RTC-1210), grasp the polyester film where the cutout was cut, and peel it at an angle of 180 ° at room temperature of 25 ° C 2. The peeling speed is 60 mm / minute, and the polyester film is peeled from the cured product of the photocurable resin composition along the length of the sample. The load at this time was measured to determine the peel strength (N / 25 mmm).

<Impact resistance test> The impact resistance of the laminated glass was evaluated by the same method as the impact resistance test in "1. Production and Evaluation of Laminated Glass Using a Film Material". [Table 2]

Laminated glass having an interlayer film made of a photocurable resin composition for a laminated glass interlayer film, as compared to laminated glass having an interlayer film using a polyvinyl butyral resin of Comparative Examples 2-4. Shows high impact resistance (crack resistance). About the photocurable resin composition which does not contain the (meth) acrylic polymer ((A) component) from Comparative Example 2-1 and Comparative Example 2-3, or does not contain (meth) The laminated glass of the intermediate film formed from the photocurable resin composition of the acrylic monomer (component (B)) has low impact resistance (crack resistance).

1‧‧‧ laminated glass

2‧‧‧ Film material for interlayer of laminated glass

5‧‧‧ Interlayer

5a‧‧‧Adhesive layer (photocurable resin layer)

11, 12‧‧‧ glass plate

21‧‧‧Substrate layer (light peeling release layer, release film, cover film)

22‧‧‧ substrate layer (repeated release layer, release film)

140‧‧‧ support

141‧‧‧ flange

142‧‧‧Fixed section

143‧‧‧steel ball

FIG. 1 is a schematic cross-sectional view showing an embodiment of a film material for an interlayer film of laminated glass. FIG. 2 is a schematic sectional view showing an embodiment of the laminated glass. 3 (a) to 3 (c) are step diagrams showing an embodiment of a method for producing a laminated glass. 4 (a) and 4 (b) are process diagrams showing an embodiment of a method for manufacturing a laminated glass. 5 (a) to 5 (d) are step diagrams showing an embodiment of a method for producing a laminated glass. FIG. 6 is an exploded perspective view schematically showing an example of a measurement device used in an impact resistance test of a laminated glass.

Claims (8)

A photocurable resin composition for an interlayer film of a laminated glass, comprising: a (meth) acrylic polymer, a (meth) acrylic monomer, and a photopolymerization initiator. A film material for an interlayer film of a laminated glass, comprising: an adhesive layer comprising the photocurable resin composition for an interlayer film of the laminated glass according to item 1 of the scope of patent application; A pair of substrate layers laminated as an adhesive layer. A method for manufacturing laminated glass, the laminated glass comprising two glass plates facing each other and an interlayer film sandwiched between them, the manufacturing method of the laminated glass comprises: The step of irradiating the adhesive layer of the film material for an interlayer film of laminated glass according to the second item of the patent scope to harden it with ultraviolet rays; bonding the two glass plates through the adhesive layer to obtain the two pieces A step of a glass plate and the laminated body of the adhesive layer; and heating and pressing the laminated body under the conditions of 30 ° C. to 150 ° C. and 0.3 MPa to 1.5 MPa to obtain the hardened adhesive layer. The step of laminating the glass of the interlayer film. A method is a method for manufacturing laminated glass, the laminated glass includes two glass plates facing each other and an intermediate film sandwiched between them, and the manufacturing method of the laminated glass includes: The step of bonding the two glass plates to the adhesive layer of the film material for an interlayer film of laminated glass according to item 2 of the scope of the patent application, a step of obtaining a laminated body including the two glass plates and the adhesive layer; A step of heating and pressing the laminated body under conditions of 30 ° C. to 150 ° C. and 0.3 MPa to 1.5 MPa; and from the side of at least any one of the two glass plates, the laminated layer The body is irradiated with ultraviolet rays to harden it, thereby obtaining the laminated glass including the hardened adhesive layer, that is, the interlayer film. The photocurable resin composition for an interlayer film of laminated glass according to item 1 of the scope of patent application, further comprising a plasticizer component. A method for manufacturing laminated glass, the laminated glass comprising two glass plates facing each other and an interlayer film sandwiched between them, the manufacturing method of the laminated glass comprises: A step of coating the surface of one of the glass plates with a photo-curable resin composition on the interlayer film of the laminated glass according to the first or the fifth aspect of the patent, to form a photo-curable resin layer; A step of bonding the one glass plate to the other glass plate so that the resin layer becomes the inside; and irradiating the photocurable resin layer sandwiched between the two glass plates with ultraviolet rays to harden, Thereby, the step of obtaining the laminated glass including the intermediate film, which is the cured photo-curable resin layer, is obtained. A method for manufacturing laminated glass, the laminated glass comprising two glass plates facing each other and an interlayer film sandwiched between them, the manufacturing method of the laminated glass comprises: The step of applying the photocurable resin composition to the surface of one of the glass plates to form the photocurable resin layer of the interlayer film of the laminated glass according to item 1 or 5 of the patent scope; A step of irradiating the resin layer with ultraviolet rays to harden it; bonding one of the glass plates to the other glass plate so that the cured photo-curable resin layer becomes an inner side to obtain the cured photo-curable resin layer That is, the step of laminating the glass of the interlayer film. A method for manufacturing laminated glass, the laminated glass comprising two glass plates facing each other and an interlayer film sandwiched between them, the manufacturing method of the laminated glass comprises: The step of applying the photocurable resin composition to the surface of one of the glass plates to form the photocurable resin layer of the interlayer film of the laminated glass according to item 1 or 5 of the patent scope; A step of irradiating the resin layer with ultraviolet rays to temporarily harden the same; a step of bonding another glass plate to one of the glass plates such that the temporarily hardened photocurable resin layer becomes an inner side; A step of obtaining the laminated glass having the hardened photo-curable resin layer, that is, the interlayer film, by temporarily curing the photo-curable resin layer which is temporarily cured between two sheets of glass by ultraviolet rays .