JP2018115084A - Photocurable resin composition for interlayer for laminated glass, cover film-attached interlayer for laminated glass, laminated glass, and method for producing laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition for an interlayer for laminated glass that has improved breaking resistance, a cover film-attached interlayer for laminated glass using the same, laminated glass, and a method for producing laminated glass.SOLUTION: A photocurable resin composition for an interlayer for laminated glass contains a (meth) acryl oligomer (A), a (meth) acryl monomer (B), a photopolymerization initiator (C), and oil gelator (D). There are also provided: laminated glass using the same; a cover film-attached interlayer for laminated glass that is an adhesive layer and has an interlayer for laminated glass, and a substrate layer and a cover film laminated so as to hold the interlayer for laminated glass therebetween, where the interlayer for laminated glass is formed from the photocurable resin composition for an interlayer for laminated glass; and a method for producing laminated glass using the cover film-attached interlayer for laminated glass.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a photocurable resin composition for laminated glass interlayer film used for forming an interlayer film of laminated glass. Moreover, this invention relates to the intermediate film for laminated glasses with a cover film, and laminated glass which are produced using this photocurable resin composition for laminated glass intermediate films. Moreover, this invention relates to the manufacturing method of the laminated glass using said intermediate film for laminated glasses with a cover film.

  Currently, laminated glass is widely used as glass for vehicles such as automobiles, aircraft, buildings, etc., even if it is damaged by an external impact, it is safe because the glass fragments do not scatter. Yes.

  As an example of the interlayer film for laminated glass, an interlayer film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer is interposed between and integrated with at least a pair of glass plates. And the like. (See Patent Documents 1 to 3)

JP-A-62-100463 JP-A-2005-206445 International Publication No. 2012-0911117 Pamphlet

  However, many of the conventional laminated glasses have the same degree of splitting properties as compared to glasses of equivalent thickness, and there has been a demand for laminated glasses with high splitting properties that do not break.

  In view of the above-mentioned present situation, the present invention aims to provide a photocurable resin composition for a laminated glass interlayer film that is used for forming a laminated glass interlayer film that has excellent splitting resistance against an externally applied impact. And Moreover, an object of this invention is to provide the intermediate film for laminated glasses with a cover film and laminated glass which use this photocurable resin composition for laminated glass intermediate films. Moreover, an object of this invention is to provide the manufacturing method of the laminated glass using said intermediate film for laminated glasses with a cover film.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a resin composition containing a (meth) acryl oligomer, a (meth) acryl monomer, a photopolymerization initiator, and an oil gelling agent. I found that it could be solved. The present invention has been completed based on such findings.

That is, the present invention provides the following photocurable resin composition for laminated glass interlayer film, interlayer film for laminated glass with cover film, laminated glass, and laminated glass manufacturing method.
(1) Photocurable resin composition for laminated glass interlayer film containing (meth) acrylic oligomer (A), (meth) acrylic monomer (B), photopolymerization initiator (C) and oil gelling agent (D) ( Hereinafter, it may be simply referred to as a “photocurable resin composition”.

  (2) The photocurable resin composition for laminated glass interlayer film according to claim 1, wherein the oil gelling agent (D) is selected from the group consisting of hydroxy fatty acid and hydroxy fatty acid amide.

  (3) An interlayer film for laminated glass with a cover film, comprising an interlayer film for laminated glass, and a base material layer and a cover film laminated so as to sandwich the interlayer film for laminated glass. An intermediate film for laminated glass with a cover film, wherein the intermediate film is an adhesive layer formed from the photocurable resin composition for laminated glass intermediate film described in (1) or (2) above.

  According to such an interlayer film for laminated glass with a cover film (hereinafter sometimes simply referred to as “interlayer film”), it is easy to store and transport the interlayer film for laminated glass without damaging the adhesive layer. Can do.

(4) The interlayer film for laminated glass with a cover film according to (2) or (3), wherein the adhesive layer has a thickness of 10 μm to 5.0 × 10 ³ μm.
By setting the thickness of the adhesive layer in the above range, the interlayer film for laminated glass becomes more excellent in impact resistance and visibility.

  (5) The cover film according to (3) or (4), wherein the pressure-sensitive adhesive layer is formed by irradiating an ultraviolet ray onto a layer formed from the photocurable resin composition for glass interlayer film. Intermediate film for glass.

  (6) A laminated glass comprising an intermediate film and a pair of adherends laminated so as to sandwich the intermediate film, wherein the intermediate film is the laminated glass intermediate according to (1) or (2) Laminated glass which is a cured resin layer formed from the photocurable resin composition for a film.

  (7) A step of bonding a pair of adherends together to obtain a laminate through the adhesive layer provided in the interlayer film for laminated glass with a cover film according to any one of (3) to (5) above; The laminate is heated and pressurized at 30 ° C. to 150 ° C. and 0.3 MPa to 1.5 MPa, and the laminate is irradiated with ultraviolet rays from at least one side of the adherend. A process for producing a laminated glass.

  (8) A step of obtaining a laminate by bonding a pair of adherends to each other through the adhesive layer included in the interlayer film for laminated glass with a cover film described in (5) above, And a step of heat and pressure treatment under the conditions of ° C to 150 ° C and 0.3 MPa to 1.5 MPa.

  By using the photocurable resin composition and the intermediate film of the present invention, adherends, for example, glasses, glass-resin substrate (or film), and resin substrates (or films) are bonded together. Is possible.

  By using the photocurable resin composition and the intermediate film of the present invention, the wettability and adhesion to the surface of the adherend are improved, and the toughness of the laminate is improved. Glass can be provided.

  In addition, by using the photocurable resin composition and the interlayer film of the present invention, it is possible to provide a laminated glass that maintains stable transparency without whitening of the adhesive layer even in reliability under a high humidity environment. it can.

  According to the present invention, there are provided an interlayer film for laminated glass excellent in splitting resistance against an externally applied impact, an interlayer film for laminated glass with a cover film using the same, a laminated glass, and a method for producing the same. Can do.

It is a cross-sectional schematic diagram explaining one Embodiment of the intermediate film for laminated glasses with a cover film of this invention. It is a cross-sectional schematic diagram explaining one Embodiment of the laminated glass of this invention. It is a disassembled perspective view explaining the specimen support frame used for an impact resistance test.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  In the present specification, “(meth) acryl” means “acryl” or “methacryl” corresponding thereto, and “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. To do. Similarly, “(meth) acryloyl” means “acryloyl” or a corresponding “methacryloyl”. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .

<Photocurable resin composition for laminated glass interlayer film>
The photocurable resin composition for laminated glass interlayer film of the present embodiment contains (meth) acryl oligomer (A), (meth) acryl monomer (B), photopolymerization initiator (C) and oil gelling agent (D). To do.

  The photocurable resin composition of the present embodiment exhibits high splitting properties by improving wettability to the adherend surface and improving toughness of the laminate.

  Next, each component of the photocurable resin composition will be described.

  In this specification, (meth) acrylic oligomer (A) (hereinafter sometimes referred to as “component (A)”) is a monomer that has one (meth) acryloyl group in the molecule alone. Or the thing copolymerized in combination of 2 or more types is shown.

<(Meth) acrylic oligomer (A)>
The monomer having one (meth) acryloyl group in the molecule constituting the (meth) acryl oligomer is usually a monofunctional monomer having one (meth) acryloyl group or one (meth) acryloyloxy group in the molecule, Specific examples thereof include, for example, (meth) acrylic acid; (meth) acrylic amide; (meth) acryloylmorpholine; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (Meth) acrylate, de Alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms such as syl (meth) acrylate (n-lauryl (meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate and isostearyl acrylate; glycidyl Methacrylate; (Meth) acrylate having 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, methoxyheptapropylene glycol (me ) Acrylates, ethoxytetraethylene glycol (meth) acrylates, butoxyethylene glycol (meth) acrylates and butoxydiethylene glycol (meth) acrylates and other alkoxypolyalkylene glycol (meth) acrylates; cyclohexyl (meth) acrylates, isobornyl (meth) acrylates and di (Meth) acrylates having an alicyclic group such as cyclopentanyl (meth) acrylate; hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate (Meth) acrylate having tetrahydrofurfuryl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylamide derivatives such as propyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; (Meth) acrylate having an isocyanate group such as 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate; 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 and octapropylene glycol Polyalkylene glycol mono (meth) acrylates such as glycol monomethyl (meth) acrylate; having a siloxane skeleton (meth) acrylate. These compounds can be used alone or in combination of two or more.

In addition, the (meth) acryl oligomer may contain a polyfunctional monomer having two or more (meth) acryloyl groups in the molecule as a copolymerization monomer unit as long as the effects of the present invention are not impaired. By copolymerizing such a polyfunctional monomer, the cured product of the photocurable resin composition can be further toughened.
Further, the (meth) acryl oligomer is a monomer having one (meth) acryloyl group and at least one other group having a polymerizable unsaturated bond in the molecule, for example, as long as the effects of the present invention are not impaired. An alkenyl (meth) acrylate having an alkenyl group having 2 to 18 carbon atoms such as 3-butenyl (meth) acrylate may be included as a copolymerization monomer unit.

In addition, the (meth) acryl oligomer may contain a compound copolymerizable with the monomer having the acryloyl group as a copolymerization monomer unit as long as the effects of the present invention are not impaired. Examples of such copolymerizable compounds include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride.
The (meth) acryl oligomer used in the present embodiment is a monofunctional monomer unit having one (meth) acryloyl group in the molecule, and 30% by mass to 100% by mass based on the total amount of the (meth) acryl oligomer. It is preferable to contain, and it is more preferable to contain 50 mass%-100 mass%.
The (meth) acryl oligomer is bonded to the main chain through the main chain containing a monofunctional monomer such as the above (meth) acrylate compound as a monomer unit, the urethane bond bonded to the main chain, and the urethane bond. A modified (meth) acryl oligomer having a (meth) acryloyloxy group may be included. Such a (meth) acryl oligomer can be obtained by subjecting a (meth) acryl oligomer having a hydroxyl group in the side chain to an isocyanate reaction. Examples of the (meth) acryl oligomer having a hydroxyl group in the side chain include (meth) acryl oligomers containing 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate and the like as monomer units. The (meth) acryl oligomer has a higher molecular weight than the (meth) acryl oligomer in the photo-curable resin composition by having a (meth) acryl group bonded to the main chain via a urethane bond in the side chain. The entanglement between (meth) acryl oligomer molecules can be made more complicated. In this specification, this modified (meth) acryl oligomer is not a compound having an ethylenically unsaturated bond group, which will be described later as component (C), but is classified as one type of (meth) acryl oligomer.

  When the modified (meth) acryl oligomer is used, the content is preferably 0.001% by mass to 2.0% by mass based on the total amount of the (meth) acryl oligomer in the photocurable resin composition. 005 mass%-1.0 mass% are more preferable, and the range of 0.01 mass%-0.5 mass% is still more preferable. When the content of the modified (meth) acrylic oligomer is within the above range, the photocurable resin composition tends to have a low viscosity and has low elasticity while maintaining high peel strength and elongation with respect to a panel such as glass. A cured product (adhesive layer or interlayer film for laminated glass) having a high cohesive force can be formed.

  The weight average molecular weight of the (meth) acryl oligomer is preferably 5000 to 150,000, more preferably 7500 to 100,000, and still more preferably 10,000 to 50,000 from the viewpoint of applicability. In the present specification, the weight average molecular weight is a value measured using gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

  The content of the (meth) acryl oligomer is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more based on the total amount of the photocurable resin composition. Is more preferable. The content of the (meth) acryl oligomer is preferably 80% by mass or less, more preferably 50% by mass or less, and 30% by mass or less based on the total amount of the photocurable resin composition. Is more preferable. When the content of the (meth) acrylic oligomer is in such a range, the elongation of the cured product of the photocurable resin composition is further improved and the viscosity is further reduced.

<(Meth) acrylic monomer (B)>
The (meth) acrylic monomer (B) (hereinafter sometimes referred to as “component (B)”) is a compound having one or more ethylenically unsaturated groups, preferably (meth) acryloyl groups in the molecule, Specific examples include (meth) acrylic acid; (meth) acrylic amide; (meth) acryloylmorpholine; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) Acrylate, dodecyl (meth) acrylate (n-laur (Meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl acrylate, etc. alkyl (meth) acrylate having 1 to 18 carbon atoms; ethylene glycol di (meth) acrylate, butanediol Alkanediol di (meth) acrylate having 1 to 18 carbon atoms such as (meth) acrylate and nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetra Many having three or more (meth) acryloyl groups in the molecule such as methylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. (Meth) acrylate; glycidyl methacrylate; alkenyl (meth) acrylate having 2 to 18 carbon atoms of alkenyl group such as 3-butenyl (meth) acrylate; aromatic ring such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate (Meth) acrylate having methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (meth) Alkoxypolyalkylene glycol (meth) acrylates such as acrylate and butoxydiethylene glycol (meth) acrylate; alicyclic groups such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate (meth) Acrylate; (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N- Dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, , N-diethyl (meth) acrylamide, (meth) acrylamide derivatives such as N-hydroxyethyl (meth) acrylamide; isocyanates such as 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate (Meth) acrylate having a group: tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meta) ) Acrylates, polyalkylene glycol mono (meth) acrylates such as octapropylene glycol mono (meth) acrylate; ) Acrylate; isocyanuric having a ring skeleton (meth) acrylate; having a siloxane skeleton (meth) acrylates, polyisoprene (meth) acrylate having an isoprene backbone, such as polybutadiene (meth) acrylates having a butadiene skeleton. These may be used alone or in combination of two or more. In addition, polyfunctionality having 3 or more alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group, alkanediol di (meth) acrylate having 1 to 18 carbon atoms in the alkane, and (meth) acryloyl groups in the molecule ( The meth) acrylate, glycidyl methacrylate, and alkenyl (meth) acrylate having 2 to 18 carbon atoms in the alkenyl group may be collectively referred to as aliphatic (meth) acrylate. In addition, alkoxy polyalkylene glycol (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol di (meth) acrylate, (meth) acrylate having an isocyanuric ring skeleton, and (meth) acrylate having a siloxane skeleton are heteroatoms. Sometimes referred to as system (meth) acrylate. These (meth) acrylic monomers can be used alone or in combination of two or more.

  The content of the (meth) acrylic monomer (component (B)) is preferably 10% by mass or more, more preferably 15% by mass or more, based on the total amount of the photocurable resin composition. More preferably, it is at least mass%. The content of the (meth) acrylic monomer is preferably 70% by mass or less, more preferably 60% by mass or less, and 50% by mass or less based on the total amount of the photocurable resin composition. Is more preferable. When the content of the (meth) acrylic monomer is in such a range, it is desirable in terms of transparency.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) (hereinafter sometimes referred to as “component (C)”) promotes the curing reaction by irradiation with active energy rays. Here, active energy rays refer to ultraviolet rays, electron beams, α rays, β rays, γ rays and the like. There is no restriction | limiting in particular as a photoinitiator, It is possible to use well-known photoinitiators, such as a benzophenone series, anthraquinone series, a benzoyl series, a sulfonium salt, a diazonium salt, an onium salt.

  Specifically, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4,4′- Dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1, 2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyl D Aromatic ketone compounds such as N-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,2-diethoxyacetophenone; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin ether compounds such as methyl ether, benzoin ethyl ether, benzoin isobutyl ether and benzoin phenyl ether; benzyl compounds such as benzyl and benzyldimethyl ketal; β- (acridin-9-yl) (meth) acrylic acid ester compounds, 9- Acridine compounds such as phenylacridine, 9-pyridylacridine, 1,7-diacridinoheptane; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 -Di (m-met Ciphenyl) 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-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl 2,4,5-triarylimidazole dimers such as imidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; 2-benzyl-2-dimethylamino-1- Α- such as (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Aminoalkylphenone compounds; acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methyl) Vinyl) phenyl) propanone) and the like.

In particular, polymerization initiators that do not color the photocurable resin composition include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- ( Α-hydroxyalkylphenone compounds such as 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Acylphosphine oxide compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) Ropanon) and a combination thereof are preferred.
These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (C) is preferably 0.1% by mass to 5% by mass, more preferably 0.2% by mass to 3% by mass with respect to the total amount of the photocurable resin composition, and 0.3% by mass to 2% by mass is more preferable. Photopolymerization can be favorably started when the content of the component (C) is 0.1% by mass or more. When the content of the component (C) is 5% by mass or less, the step embedding property and the self-organizing property are easily excellent, and the hue of the cured product is easily suppressed from being yellowish.

<Oil gelling agent (D)>
Examples of the oil gelling agent (D) (hereinafter also referred to as “component (D)”) include hydroxystearic acid, particularly hydroxy fatty acids such as 12-hydroxystearic acid, and hydroxys such as 12-hydroxystearic acid amide. Fatty acid amide such as fatty acid amide, hydrogenated castor oil mainly composed of hydroxy fatty acid, n-lauroyl-L-glutamic acid-α, β-dibutyramide, di-p-methylbenzylidene sorbitol glucitol, 1,3: 2, 4-bis-O-benzylidene-D-glucitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato) hydroxyaluminum, Examples thereof include compounds represented by 1) to (12). These may be used alone or in combination of two or more.

In general formula (1), m is an integer of 3 to 10, n is an integer of 2 to 6, R ₁ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X is sulfur or oxygen.
In the general formula (2), R ₂ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, Y ₁ is a bond or a benzene ring.
In the general formula (3), R ₃ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ₂ is a bond or a benzene ring.
In the general formula _(4), R 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (6), R ₅ and R ₆ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (7), R ₇ is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In general formula (8), R < ₈ > is a C1-C20 saturated hydrocarbon group.
In General Formula (10), R ₉ and R ₁₀ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (13), R ₁₁ is a saturated hydrocarbon group having 1 to 10 carbon atoms. R ₁₂ and R ₁₃ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or a saturated hydrocarbon group having 1 to 20 carbon atoms having at least one hydroxyl group in the molecular skeleton.

  Due to the presence of the oil gelling agent (D), it is possible to adjust the viscosity of the photocurable resin composition, and it is possible to suppress the bleeding and to be easily applied to a substrate having a curved surface. Among the oil gelling agents exemplified above, hydroxy fatty acid and hydroxy fatty acid amide are preferably used from the viewpoints of transparency, workability, and compatibility.

  The content of the oil gelling agent (D) is preferably 0.1% by mass to 20% by mass with respect to the total amount of the photocurable resin composition. When it is 0.1% by mass or more, it can be sufficiently gelled, and when it is 20% by mass or less, the content of the compound (B) having a photopolymerizable functional group is relatively large, It can be photocured. In this respect, the content is more preferably 0.2% by mass to 15% by mass, and further preferably 0.3% by mass to 10% by mass.

<Other additives>
The photocurable resin composition of this embodiment may contain various additives separately from the components (A) to (D) as necessary. Examples of various additives that can be included include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, leveling agents, inorganic fillers, and the like.

The polymerization inhibitor is added for the purpose of enhancing the storage stability of the photocurable resin composition, and examples thereof include paramethoxyphenol.
Antioxidants are added for the purpose of enhancing the heat-resistant colorability of a cured product obtained by curing a photocurable resin composition with light, and are phosphorus-based such as triphenyl phosphite; phenol-based; thiol-based antioxidant. Agents and the like.
The light stabilizer is added for the purpose of increasing resistance to active energy rays such as ultraviolet rays, and examples thereof include HALS (Hindered Amine Light Stabilizer).
The silane coupling agent is added to improve adhesion to glass or the like, and methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Examples include propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane.
The surfactant is added to control the peelability, and examples thereof include polydimethylsiloxane compounds and fluorine compounds.
A leveling agent is added in order to provide the flatness of a photocurable resin composition, and the compound etc. which reduce the surface tension of a silicon type and a fluorine type are mentioned.

  These additives may be used alone, or a plurality of additives may be used in combination. In addition, content in the case of using these additives is usually small compared with the total content of the components (A) to (D), and generally 0.01 mass relative to the total amount of the photocurable resin composition. % To about 5% by mass.

  The photocurable resin composition of the present embodiment may contain an inorganic filler, such as crushed silica, fused silica, mica, clay mineral, short glass fiber or fine powder, and hollow glass, calcium carbonate, quartz. Examples thereof include powders and metal hydrates. When using an inorganic filler, the content thereof is preferably 0.01 parts by mass to 100 parts by mass, and 0.05 parts by mass to 50 parts by mass with respect to 100 parts by mass of the photocurable resin composition based on the total solid content. Mass parts are more preferable, and 0.1 to 30 parts by mass are even more preferable. When the content of the inorganic filler is from 0.01 parts by mass to 100 parts by mass, sufficient low shrinkage, improvement in mechanical strength, low thermal expansion coefficient, and the like can be obtained. The filler may be treated with a commercially available surface treatment agent such as a coupling agent, a three-roller, a bead mill, or a nanomizer to improve the dispersibility of the inorganic filler.

<The manufacturing method of the photocurable resin composition for laminated glass intermediate films>
There is no restriction | limiting in particular in the manufacturing method of the photocurable resin composition of this embodiment, The said (A) component and (B) component, (C) component, (D) component, and the said additive used as needed Can be mixed and stirred.
In addition, when any of the components is in a solid state, it is preferable that the solid component is heated and dissolved at at least one timing before mixing and stirring, and after mixing and stirring. Thereby, each component disperse | distributes favorably, and the photocurable resin composition for laminated glass intermediate films is obtained by cooling after that.
Although there is no restriction | limiting in particular in this heating temperature, When stirring a component with high viscosity, high temperature is suitable. Moreover, since there are components that easily volatilize depending on the components, a temperature lower than the volatility is preferable. When heating from this point of view, it is preferable to heat to 40 ° C to 130 ° C. When the heating temperature is 40 ° C. or higher, sufficient stirring can be achieved even when the viscosity of the component is high. When it is 130 ° C. or lower, the volatilization of components can be suppressed, and coloring of the resin composition can also be suppressed.
Although there is no restriction | limiting in particular in stirring time, Preferably it is 10 minutes-60 minutes, More preferably, they are 20 minutes-40 minutes.

<Method for producing interlayer film for laminated glass>
The interlayer film for laminated glass using the photocurable resin composition for laminated glass (photocurable resin composition) of the present invention is produced by processing the photocurable resin composition into a sheet or film. In this embodiment, a well-known technique can be used as a method of processing the photocurable resin composition into a sheet or film. For example, the photocurable resin composition for laminated glass interlayer film according to the present embodiment is diluted with a ketone solvent such as 2-butanone and cyclohexanone to prepare a coating liquid, and then the coating liquid is polymer film. It is applied to a substrate such as a flow coat method, a roll coat method, a gravure roll method, a wire bar method, a lip die coat method, etc., and then dried into a sheet or film having an arbitrary film thickness by drying the solvent. Can be processed. In preparing the coating liquid, each component may be blended and then diluted with a solvent, or may be diluted in advance with a solvent before blending each component.

  From the viewpoint of coating properties, the solid content concentration of the coating solution is preferably 30% by mass or more, and more preferably 40% by mass or more. 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 above viewpoint, the viscosity of the coating liquid is preferably 1 Pa · s or more, 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 further preferably 15 Pa · s or less. In addition, when the photocurable resin composition itself is in a form that can be applied in a liquid state or the like under the application conditions, it may be used as it is without being diluted with a solvent. In addition, after processing the photocurable resin composition into a sheet or film, if necessary, the surface can be temporarily cured by curing the surface by ultraviolet irradiation or the like to prevent deformation or dripping of the sheet or film. Also good.

<Interlayer film for laminated glass with cover film>
The interlayer film for laminated glass with a cover film of the present invention was laminated so as to sandwich the interlayer film for laminated glass, which is an adhesive layer formed from the photocurable resin composition of the present invention, and the interlayer film for laminated glass. A base material layer and a cover film are included. The interlayer film for laminated glass with a cover film of the present invention is, for example, a photocurable resin composition on a substrate such as a polymer film to be a substrate layer, in the same manner as in the method for producing the interlayer film for laminated glass. It can manufacture by providing the adhesion layer formed from and attaching a cover film, such as a polymer film, on the adhesion layer. By sandwiching the adhesive layer between the base material layer and the cover film, it becomes possible to store and transport the laminated glass without damaging the interlayer film. Similarly to the method for producing the interlayer film for laminated glass described above, the adhesive layer of the interlayer film for laminated glass with a cover film is also subjected to surface irradiation by ultraviolet irradiation or the like, in order to prevent dripping or protrusion of the adhesive layer. You may make it harden | cure, such as hardening. The dose of ultraviolet rays, particularly although not limited, is preferably ^{5.0 × 10 2 mJ / cm 2} ~5.0 × 10 3 mJ / cm 2 or so. The thickness of the adhesive layer is not particularly limited, but is preferably 10 μm to 5.0 10 ³ μm.

  In FIG. 1, the cross-sectional schematic diagram explaining one Embodiment of the intermediate film for laminated glasses with a cover film of this invention is shown. In the present embodiment, the pressure-sensitive adhesive layer 11 (interlayer film for laminated glass) is sandwiched between a heavy release separator 12 that is a base material layer and a light release separator 10 that is a cover film. Each of the heavy release separator 12 and the light release separator 10 is a polymer film such as a polyethylene terephthalate film, and the light release separator 10 has a structure or material that is more easily peeled from the adhesive layer 11 than the heavy release separator 12. preferable. At this time, in order to control the peelability between the pressure-sensitive adhesive layer 11 and the base material such as the polyethylene terephthalate film and the cover film, the photocurable resin composition includes a polydimethylsiloxane surfactant, a fluorine-based interface. A surfactant such as an activator can be contained.

  These additives may be used alone or in combination with a plurality of additives. The content of these other additives is usually small compared to the total content of the above components (A), (B), (C) and (D), and generally the light for laminated glass interlayer film. It is preferable to set it as about 0.01 mass%-5 mass% with respect to the total mass of curable resin composition.

  The light transmittance of the adhesive layer 11 with respect to light in the visible light region (wavelength: 380 nm to 780 nm) is preferably 80% or more, more preferably 90% or more, and 95% or more. Further preferred.

As the heavy release separator 12, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, and polyester is preferable, and among them, a polyethylene terephthalate film (hereinafter sometimes referred to as “PET film”) is more preferable. The thickness of the heavy release separator 12, from the viewpoint of workability, preferably from 50μm~2.0 × 10 ² μm, more preferably 60Myuemu～150myuemu, in 70μm~1.3 × 10 ² μm More preferably it is. The planar shape of the heavy release separator 12 is larger than the planar shape of the pressure-sensitive adhesive layer 11, and the outer edge of the heavy release separator 12 preferably projects outward from the outer edge of the pressure-sensitive adhesive layer 11. The width at which the outer edge of the heavy release separator 12 protrudes from the outer edge of the pressure-sensitive adhesive layer 11 is preferably 2 mm to 20 mm from the viewpoint of ease of handling, ease of peeling, and reduction of adhesion of dust and the like, and preferably 4 mm to 10 mm. It is more preferable that When the planar shape of the pressure-sensitive adhesive layer 11 and the heavy release separator 12 is a substantially rectangular shape such as a substantially rectangular shape, the width of the outer edge of the heavy release separator 12 protruding from the outer edge of the pressure-sensitive adhesive layer 11 is 2 mm at least on one side. Is preferably 20 mm, more preferably 4 mm to 10 mm on at least one side, further preferably 2 mm to 20 mm on all sides, and particularly preferably 4 mm to 10 mm on all sides. .

As the light release separator 10, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester is preferable, and a polyethylene terephthalate film is more preferable. The thickness of the light release separator 10, from the viewpoint of workability, preferably from 25μm~1.5 × 10 ² μm, more preferably 30μm~1.0 × 10 ² μm, in 40μm~75μm More preferably it is. The planar shape of the light release separator 10 is larger than the planar shape of the pressure-sensitive adhesive layer 11, and the outer edge of the light release separator 10 preferably projects outward from the outer edge of the pressure-sensitive adhesive layer 11. The width at which the outer edge of the light release separator 10 projects beyond the outer edge of the pressure-sensitive adhesive layer 11 is preferably 2 mm to 20 mm from the viewpoint of ease of handling, ease of peeling, and reduction of adhesion of dust and the like. It is more preferable that When the planar shape of the pressure-sensitive adhesive layer 11 and the light release separator 10 is a substantially rectangular shape such as a substantially rectangular shape, the width at which the outer edge of the light release separator 10 protrudes from the outer edge of the pressure-sensitive adhesive layer 11 is 2 mm at least on one side. Is preferably 20 mm, more preferably 4 mm to 10 mm on at least one side, further preferably 2 mm to 20 mm on all sides, and particularly preferably 4 mm to 10 mm on all sides. .

  The peel strength between the light release separator 10 and the adhesive layer 11 is preferably lower than the peel strength between the heavy release separator 12 and the adhesive layer 11. As a result, the heavy release separator 12 is less likely to peel from the adhesive layer 11 than the light release separator 10. The peel strength between the heavy release separator 12 and the pressure-sensitive adhesive layer 11 and between the light release separator 10 and the pressure-sensitive adhesive layer 11 can be adjusted, for example, by subjecting the heavy release separator 12 and the light release separator 10 to surface treatment. Examples of the surface treatment method include a mold release treatment with a silicone compound or a fluorine compound.

<Laminated glass and manufacturing method thereof>
The laminated glass of the present invention includes an intermediate film and a pair of adherends laminated so as to sandwich the intermediate film, and the intermediate film is formed from the photocurable resin composition for a laminated glass intermediate film of the present invention. It is a formed cured resin layer. Examples of the adherend include inorganic glass, organic glass, transparent resin plate, and other functional layers having various functions. There is no restriction | limiting in particular in the manufacturing method of the laminated glass of this invention, For example, it can manufacture suitably with the manufacturing method of this invention using the intermediate film for laminated glasses with a cover film of this invention.

The following (1) and (2) are mentioned as a manufacturing method of the present invention using an interlayer film for laminated glass with a cover film.
(1) A step of bonding a pair of adherends together to obtain a laminated body through an adhesive layer provided in the interlayer film for laminated glass with a cover film of the present invention, and the laminated body at 30 ° C to 150 ° C and 0 ° C. A method for producing laminated glass, comprising: a step of performing heat and pressure treatment under conditions of 3 MPa to 1.5 MPa; and a step of irradiating the laminate with ultraviolet rays from at least one side of the adherend.
(2) A pressure-sensitive adhesive layer provided in the interlayer film for laminated glass with a cover film of the present invention, wherein a pair of layers formed from a photocurable resin composition is irradiated with ultraviolet rays, and a pair of Production of laminated glass including a step of bonding adherends together to obtain a laminate, and a step of subjecting the laminate to heat and pressure treatment under conditions of 30 ° C. to 150 ° C. and 0.3 MPa to 1.5 MPa. Method.

  As another manufacturing method, for example, an adhesive layer formed from a photocurable resin composition by, for example, directly applying the photocurable resin composition of the present invention on a first adherend such as glass. May be produced by laminating a second adherend on the exposed surface of the adhesive layer, subjecting the laminate to heat and pressure treatment, and forming the adhesive layer as a cured resin layer by ultraviolet irradiation. The ultraviolet irradiation can be performed at the time of formation of the pressure-sensitive adhesive layer at least at one point before or after the heat and pressure treatment of the laminate.

  The photocurable resin composition of the present invention, the interlayer film for laminated glass and the interlayer film for laminated glass with cover glass formed using the same can be applied to various types of laminated glass. Examples of the laminated glass include float glass, air-cooled tempered glass, chemically tempered glass, and multilayer glass. The intermediate film of the present embodiment can also be used to combine and bond a functional layer having functionality such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer of laminated glass, a transparent protective plate, and the like. .

(Antireflection layer)
The antireflection layer may be an antireflection layer having a visible light reflectance of 5% or less. As the antireflection layer, a layer obtained by treating a transparent substrate such as a transparent plastic film with a known antireflection method can be used.
(Anti-fouling layer)
The antifouling layer is intended to make it difficult to get dirt on the surface. In order to lower the antifouling layer and the surface tension, a known layer composed of a fluorine-based resin or a silicone-based resin can be used.
(Dye layer)
The dye layer is used to increase color purity. The dye layer is used to reduce unnecessary wavelength light transmitted through the laminated glass. The dye layer can be obtained by dissolving a dye that absorbs light having an unnecessary wavelength in a resin and forming or laminating it on a base film such as a polyethylene film or a polyester film.
(Hard coat layer)
The hard coat layer is used to increase the surface hardness. As said hard-coat layer, what formed or laminated | stacked acrylic resin, such as urethane acrylate and an epoxy acrylate; base materials films, such as a polyethylene film, can be used, for example. Similarly, in order to increase the surface hardness, a hard coat layer formed or laminated on a transparent protective plate such as glass, acrylic resin, or polycarbonate can be used.

  When setting it as such a laminated body, the adhesion layer 11 can be laminated | stacked using a roll lamination, a vacuum bonding machine, or a single wafer bonding machine.

Hereinafter, an embodiment of a method for producing a laminated glass according to the present invention will be described in detail.
FIG. 2 is a side sectional view schematically showing an embodiment of the laminated glass of the present invention. The laminated glass shown in FIG. 2 is a laminated glass in which a float glass 20, an intermediate film 21 (cured resin layer), and a float glass 22 are laminated in this order. In addition, the laminated glass of this invention is not limited to embodiment shown in FIG.
The laminated glass which concerns on this embodiment can be manufactured with the following method using the intermediate film for laminated glasses with a cover film of this invention, for example. For example, the intermediate film for laminated glass with a cover film of the embodiment shown in FIG. 1 is used as follows in assembling laminated glass and the like. First, the light release separator 10 is peeled from the pressure-sensitive adhesive layer 11 of the interlayer film for laminated glass with cover film (intermediate film for laminated glass, hereinafter the same) to expose the surface of the pressure-sensitive adhesive layer 11. Then, the surface of the adhesion layer 11 is affixed on the float glass 20 which is a 1st adherend, and it presses with a roller. Subsequently, the heavy release separator 12 is peeled from the adhesive layer 11 to expose the surface of the adhesive layer 11. Subsequently, the surface of the pressure-sensitive adhesive layer 11 is attached to the float glass 22 as the second adherend, and the obtained laminate is subjected to a heat and pressure treatment (autoclave treatment). The first and second adherends are not limited to float glass, and other kinds of adherends that are usually used for laminated glass, such as various types of glass and a transparent protective plate such as a transparent resin plate, can be used. Thus, float glass which is the 1st and 2nd adherends can be pasted together via adhesion layer 11. In addition, as for the heating and pressurizing treatment conditions at this time, the temperature is preferably 30 ° C. to 150 ° C., more preferably 40 ° C. to 80 ° C., and the pressure is preferably 0.1 MPa or more, more preferably 0.3 MPa or more. Yes, preferably 1.5 MPa or less, more preferably 0.6 MPa or less, for example 0.3 MPa to 1.5 MPa, but from the viewpoint of more removal of entrained bubbles, the temperature is 50 ° C. to 70 ° C., It is particularly preferable that the pressure is 0.2 MPa to 0.5 MPa. The treatment time is preferably 5 minutes to 60 minutes, and more preferably 10 minutes to 30 minutes. By irradiating the adhesive layer 11 with ultraviolet rays at any point in the manufacturing process to form a cured resin layer, a pair of adherends were bonded together with the cured resin layer of the photocurable resin composition disposed therebetween. Laminated glass can be obtained.

  In addition, before or after the autoclave treatment, the above production method applies ultraviolet rays from either side of both adherends (for example, glass, transparent protective plate, etc.) to the adhesive layer 11 (interlayer film for laminated glass). It is preferable to include the process of irradiating. Thereby, the adhesive reliability (reduction of bubble generation and suppression of peeling) and adhesive strength under high temperature and high humidity conditions can be further improved. From the viewpoint of further improving the adhesion reliability under high temperature and high humidity conditions, it is preferable to irradiate ultraviolet rays from the side of an adherend (for example, touch panel) having no step.

The dose of ultraviolet rays, particularly although not limited, is preferably ^{5.0 × 10 2 mJ / cm 2} ~5.0 × 10 3 mJ / cm 2 or so. In addition, it is preferable to perform the process of irradiating an ultraviolet-ray after an autoclave process from a viewpoint of improving the adhesive reliability in high temperature, high humidity conditions. In the structure thus obtained, when a glass substrate (soda lime glass) or an acrylic resin substrate is adopted as an adherend, peeling between the interlayer film for laminated glass in the obtained laminated glass and these substrates is performed. The strength is preferably 5 N / 10 mm or more, more preferably 8 N / 10 mm or more, and still more preferably 10 N / 10 mm or more. Further, it is preferably 30 N / 10 mm or less. The peel strength is measured as 180 degree peel (3 seconds at a peel rate of 300 mm / min, measurement temperature 25 ° C.) using a tensile tester (made by Orientec Co., Ltd., trade name “Tensilon RTC-1210”). be able to.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not restrict | limited to these Examples.

(A) component:
(A) Synthesis of (meth) acryl oligomer (A-1)
96.0 g of isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “ISTA”) and 2-hydroxy as an initial monomer in a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introducing tube 24.0 g of ethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “HEA”) and 150.0 g of methyl ethyl ketone were added, and the mixture was heated from 25 ° C. to 80 ° C. for 15 minutes while purging 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 in 5.0 g of t-butylperoxy-2-ethylhexanoate while maintaining the temperature at 80 ° C. The solution was added dropwise over 120 minutes. After completion of dropping, the reaction was further continued for 2 hours. Subsequently, methyl ethyl ketone was distilled off to obtain a copolymer resin of isostearyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 30,000).

(A) Synthesis of (meth) acryl oligomer (A-2)
96.0 g of 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd., trade name “EHA”) as an initial monomer in a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introduction tube Add 24.0 g of hydroxyethyl acrylate (trade name “HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 150.0 g of methyl ethyl ketone, and heat from 25 ° C. to 80 ° C. for 15 minutes while purging with nitrogen at an air volume of 100 ml / min. did. Thereafter, while maintaining the temperature at 80 ° C., 24.0 g of 2-ethylhexyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers were converted to 5.0 g of t-butylperoxy-2-ethylhexanoate. The dissolved solution was added dropwise over 120 minutes. After completion of dropping, the reaction was further continued for 2 hours. Subsequently, methyl ethyl ketone was distilled off to obtain a copolymer resin of 2-ethyhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 28,000).

(B) component:
ISTA (isostearyl acrylate, Osaka Organic Chemical Industries, trade name “ISTA”), 4HBA (4-hydroxybutyl acrylate, Osaka Organic Chemical Industries, trade name “4-HBA”)

Component (C):
I-184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Japan Ltd., trade name “Irgacure-184”)

(D) component:
HSA (12-hydroxystearic acid, manufactured by Wako Pure Chemical Industries, Ltd.)
D-KH (fatty acid amide, manufactured by Nippon Kasei Co., Ltd., trade name “Diamid KH”

The weight average molecular weight is measured using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and converted using a standard polystyrene calibration curve using the following apparatus and measurement conditions. It is the determined value. In preparing the calibration curve, 5 sample sets (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corporation]) were used as standard polystyrene.
Device: High-speed GPC device HLC-8320GPC (detector: differential refractometer) (trade name, manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran (THF)
Column: Column TSKGEL SuperMultipore HZ-H (manufactured by Tosoh Corporation, trade name)
Column size: Column length is 15 cm, column inner diameter is 4.6 mm
Measurement temperature: 40 ° C
Flow rate: 0.35 mL / min Sample concentration: 10 mg / THF 5 mL
Injection volume: 20 μL

Example 1
[Production of interlayer film for laminated glass with cover film]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass with a cover film was prepared according to the procedure.

  (I) (Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts, 4-hydroxybutyl acrylate (4HBA, component B) 9 parts by mass, 0.1 part by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”), 5 parts by mass of 12-hydroxystearic acid (HSA, E component), Were weighed and mixed with stirring to obtain a photocurable resin composition for a laminated glass interlayer film which was liquid at 25 ° C.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (cover film) in which an interlayer film for laminated glass is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film for laminated glass) was obtained. In addition, it adjusted so that the thickness of the intermediate film for laminated glasses in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film for laminated glass. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt (representing a thickness in “mmt” millimeters, hereinafter the same), and pressed with a roller. Subsequently, the heavy release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film for laminated glass. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass.

(Example 2)
[Production of interlayer film for laminated glass with cover film]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass was prepared by the procedure.

  (I) 60 parts by mass of (meth) acryl oligomer (A-2, A component), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA, B component), 0.1 part by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”), 5 parts by mass of fatty acid amide (D-KH, component E) These were weighed and stirred and mixed at 90 ° C. to obtain a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (cover film) in which an interlayer film for laminated glass is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film for laminated glass) was obtained. In addition, it adjusted so that the thickness of the intermediate film for laminated glasses in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film for laminated glass. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt and pressed with a roller. Subsequently, the heavy release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass.

(Example 3)
[Production of interlayer film for laminated glass]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass was prepared by the procedure.

  (I) (Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts, 4-hydroxybutyl acrylate (4HBA, component B) 9 parts by mass, 0.1 part by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”), 5 parts by mass of 12-hydroxystearic acid (HSA, E component), Were weighed and stirred and mixed at 80 ° C. to obtain a photocurable resin composition for a laminated glass interlayer film which was liquid at 25 ° C.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (laminated glass with cover film) in which an intermediate film is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film) was obtained. In addition, it adjusted so that the thickness of the intermediate film for laminated glasses in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film for laminated glass. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt and pressed with a roller. Subsequently, the heavy release separator was peeled from the interlayer film for laminated glass to expose the surface of the interlayer film for laminated glass. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes. UV light (1.0 × 10 ³ mJ / cm ² ) was used to obtain a laminated glass.

(Comparative Example 1)
[Production of interlayer film for laminated glass with cover film]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass was prepared by the procedure.

  (I) (Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts, 4-hydroxybutyl acrylate (4HBA, component B) 9 parts by mass, By weighing 0.1 parts by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (trade name “Irgacure-184”, manufactured by BASF Japan Ltd.), and stirring and mixing them at 25 ° C. A liquid photocurable resin composition for laminated glass interlayer film was obtained.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (cover film) in which an interlayer film for laminated glass is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film for laminated glass) was obtained. In addition, it adjusted so that the thickness of the intermediate film for intermediate laminated glass in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt and pressed with a roller. Subsequently, the heavy release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass.

(Comparative Example 2)
[Production of interlayer film for laminated glass with cover film]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass with a cover film was prepared according to the procedure.

  (I) 60 parts by mass of (meth) acryl oligomer (A-2, A component), 30.9 parts by mass of isostearyl acrylate (ISTA, B component), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA, B component), 25 parts by weighing 0.1 parts by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”) and stirring and mixing them at 90 ° C. A photocurable resin composition for a laminated glass interlayer film that was liquid at 0 ° C. was obtained.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (cover film) in which an interlayer film for laminated glass is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film for laminated glass) was obtained. In addition, it adjusted so that the thickness of the intermediate film for laminated glasses in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt and pressed with a roller. Subsequently, the heavy release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass.

(Comparative Example 3)
[Production of interlayer film for laminated glass with cover film]
Using the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the heavy release separator and the 75 μm thick polyethylene terephthalate (made by Fujimori Kogyo Co., Ltd.) as the light release separator, the following (I) and (II) An interlayer film for laminated glass with a cover film was prepared according to the procedure.

  (I) (Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts, 4-hydroxybutyl acrylate (4HBA, component B) 9 parts by mass, By weighing 0.1 parts by mass of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”), and stirring and mixing them at 80 ° C., A photocurable resin composition for a laminated glass interlayer film which was liquid at 25 ° C. was obtained.

(II) After coating the photocurable resin composition obtained in (I) on a heavy release separator to form a coating film, a light release separator is laminated on the coating film, and an ultraviolet irradiation device (eye A laminated body (cover film) in which an interlayer film for laminated glass is sandwiched between a heavy release separator and a light release separator by irradiating ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using a graphics company) Intermediate film for laminated glass) was obtained. In addition, it adjusted so that the thickness of the intermediate film for laminated glasses in a laminated body might be set to 3.8 * 10 < ² > micrometer.

[Production of laminated glass]
Next, the light release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt and pressed with a roller. Subsequently, the heavy release separator was peeled from the laminated glass interlayer film to expose the surface of the laminated glass interlayer film. Subsequently, the surface of the interlayer film for laminated glass was attached to a float glass of 110 mm × 110 mm × 2.7 mmt in a vacuum state using a vacuum laminator to obtain a laminate. Thereafter, the obtained laminate was subjected to heat and pressure treatment (autoclave treatment) under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes. UV light (1.0 × 10 ³ mJ / cm ² ) was used to obtain a laminated glass.

(Comparative Example 4)
(1) Manufacture of interlayer film for laminated glass Polyvinyl butyral resin (acetalization degree: 68.0 mol%, vinyl acetate) whose half-value width of the peak corresponding to the hydroxyl group obtained when measuring the infrared absorption spectrum is 245 cm ^-1 After mixing 100 parts by mass of component 0.6 mol%) and 38 parts by mass of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, the mixture is sufficiently melt-kneaded with a mixing roll. And press molding 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.

(2) Manufacture of laminated glass Next, the obtained interlayer film for laminated glass was sandwiched between two transparent float glasses having a thickness of 2.7 mm, and this was put in a rubber bag, and a vacuum degree of 2660 Pa was applied for 20 minutes. After deaeration, it was transferred to an oven while being deaerated, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.

The interlayer films for laminated glass and laminated glass obtained in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Table 1. The unit of the blending amount of the components (A) to (D) shown in Table 1 is part by mass.
[Shock resistance test]
A steel ball having a mass of about 1040 g and a diameter of 63.5 mm is dropped at a position within 25 mm from the center point of the produced 110 mm × 110 mm square laminated glass (peripheral support) in the order of 5 cm to 100 cm in 5 cm increments, and the glass is Record the height when cracked. Six laminated glasses having each laminated glass interlayer film were tested, the average height was calculated, and the larger the value, the higher the splitting glass. A specimen support frame for the impact resistance test is shown in FIG.

FIG. 3 is an exploded perspective view schematically showing an example of a measuring device used when measuring the splitting property of the laminated glass of the present invention.
As shown in FIG. 3, the specimen support frame mainly includes a box-shaped support portion 31 having a flange portion 32 on which an outer peripheral portion of the laminated glass is placed on the upper end, and substantially the same as the flange portion 32. It is composed of a fixed portion 33 having a shape and a steel ball 34. A plurality of through holes (not shown) are formed at corresponding positions on the flange portion 32 and the fixing portion 33 of the support portion 31, and a laminated glass is placed on the flange portion 32. After the fixing portion 33 is disposed above, a fixing member such as a screw is screwed into the through hole so that the laminated glass can be held and fixed at the outer peripheral portion thereof. That is, in the specimen support frame shown in FIG. 3, the sizes of the inner peripheral portions of the flange portion 32 and the fixing portion 33 are 100 mm × 100 mm.

実施例１、２及び３の合わせガラス中間膜用光硬化性樹脂組成物を用いて作製した合わせガラスは、オイルゲル化剤を含まない光硬化性樹脂組成物を用いた比較例１、２及び３の合わせガラス、並びに、ポリビニルブチラーブ樹脂及び可塑剤を含有する樹脂組成物からなる中間膜を用いた比較例４の合わせガラスと比較して、いずれも更に防割性が高くなった。

The laminated glass produced using the photocurable resin composition for laminated glass interlayer film of Examples 1, 2, and 3 is Comparative Examples 1, 2, and 3 using the photocurable resin composition not containing an oil gelling agent. As compared with the laminated glass of Comparative Example 4 using an interlayer film made of a laminated glass and a resin composition containing a polyvinyl butyralb resin and a plasticizer, the splitting property was further improved.

10 ... Light release separator 11 ... Adhesive layer (interlayer film for laminated glass)
12 ... Heavy release separator 20 ... Float glass 21 ... Intermediate film (cured resin layer)
22 ... float glass 31 ... support part 32 ... collar part 33 ... fixing part 34 ... steel ball

Claims (8)

  A photocurable resin composition for a laminated glass interlayer film comprising (meth) acrylic oligomer (A), (meth) acrylic monomer (B), photopolymerization initiator (C) and oil gelling agent (D).   The photocurable resin composition for laminated glass interlayer films according to claim 1, wherein the oil gelling agent (D) is selected from the group consisting of hydroxy fatty acids and hydroxy fatty acid amides.   An intermediate film for laminated glass, and an intermediate film for laminated glass with a cover film, including a base material layer and a cover film laminated so as to sandwich the intermediate film for laminated glass, wherein the intermediate film for laminated glass is An interlayer film for laminated glass with a cover film, which is an adhesive layer formed from the photocurable resin composition for laminated glass interlayer film according to claim 1 or 2. The interlayer film for laminated glass with a cover film according to claim ³ , wherein the adhesive layer has a thickness of 10 μm to 5.0 × 10 ³ μm.   The interlayer film for laminated glass with a cover film according to claim 3 or 4, wherein the adhesive layer is formed by irradiating an ultraviolet ray onto a layer formed from the photocurable resin composition for a glass interlayer film.   A laminated glass comprising an intermediate film and a pair of adherends laminated so as to sandwich the intermediate film, wherein the intermediate film is photocurable for a laminated glass intermediate film according to claim 1 or 2. Laminated glass which is a cured resin layer formed from a resin composition.   A step of bonding a pair of adherends together to obtain a laminate through the adhesive layer included in the interlayer film for laminated glass with a cover film according to any one of claims 3 to 5; A step of heat-pressing under conditions of ℃ to 150 ℃ and 0.3 MPa to 1.5 MPa, and a step of irradiating the laminate with ultraviolet rays from at least one side of the adherend, A method for producing laminated glass.   A step of bonding a pair of adherends together to obtain a laminated body through the adhesive layer included in the interlayer film for laminated glass with a cover film according to claim 5, and the laminated body at 30 ° C to 150 ° C and And a step of heat-pressing under conditions of 0.3 MPa to 1.5 MPa.

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