JP2018115085A - 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 is used in forming an interlayer for laminated glass and can improve the breaking resistance of laminated glass, 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), oil gelator (D) and plasticizer (E). There are also provided a cover film-attached interlayer for laminated glass using the same, laminated glass, and a method for producing laminated glass.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photocurable resin composition for laminated glass interlayer film used for the production of laminated glass, an interlayer film for laminated glass with a cover film, laminated glass, and a laminated glass production method using the same.

  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.

JP 1987-1000046 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 manufacturing method of the intermediate film for laminated glasses with a cover film using this photocurable resin composition for laminated glass intermediate films, laminated glass, and a laminated glass.

  As a result of intensive studies to solve the above problems, the present inventors have found that a photo-curing property containing a (meth) acrylic oligomer, a (meth) acrylic monomer, a photopolymerization initiator, an oil gelling agent, and a plasticizer. It has been found that the above problems can be solved by using a resin composition. 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 a method for producing laminated glass.

  (1) Light for laminated glass interlayer film containing (meth) acrylic oligomer (A), (meth) acrylic monomer (B), photopolymerization initiator (C), oil gelling agent (D) and plasticizer (E) Curable resin composition (hereinafter sometimes simply referred to as photocurable resin composition).

  (2) The photocurable resin composition for laminated glass interlayer films according to (1), wherein the oil gelling agent (D) is at least one selected from the group consisting of hydroxy fatty acids and hydroxy fatty acid amides.

  (3) The light for laminated glass interlayer film according to (1) or (2), wherein the plasticizer (E) is at least one solid tackifier selected from the group consisting of a terpene resin and a hydrogenated terpene resin. Curable resin composition.

  (4) Laminated so as to sandwich the interlayer film for laminated glass formed from the photocurable resin composition for laminated glass interlayer film according to any one of (1) to (3) and the interlayer film for laminated glass An interlayer film for laminated glass with a cover film, comprising a substrate layer and a cover film.

  (5) Laminated glass including an intermediate film and a pair of adherends laminated so as to sandwich the intermediate film, wherein the intermediate film is any one of (1) to (3) Laminated glass which is a light-transmitting cured resin layer formed from a photocurable resin composition for laminated glass interlayer film.

(6) Glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of (1)-(3). It is a manufacturing method of a laminated glass, Comprising: The following processes (A)-(C):
<Process (A)>
The photocurable resin composition for laminated glass interlayer film according to any one of (1) to (3) is applied on the surface of one glass, and the photocurable resin composition for laminated glass interlayer film on the glass. Forming a physical layer (hereinafter sometimes simply referred to as a photo-curable resin composition layer);
<Process (B)>
The glass on which the photocurable resin composition layer for laminated glass interlayer film is formed and the other glass so that the photocurable resin composition layer for laminated glass interlayer film is located between both glasses. Bonding step; and <Step (C)>
A step of obtaining a laminated glass as a light-transmitting cured resin layer by irradiating the photocurable resin layer for laminated glass interlayer located between the two glasses with ultraviolet rays and curing it;
The manufacturing method of the laminated glass containing this.

(7) Glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of (1)-(3). It is a manufacturing method of laminated glass, Comprising: The following processes (a)-(c):
<Process (a)>
The photocurable resin composition for laminated glass interlayer film according to any one of (1) to (3) is applied on the surface of one glass, and the photocurable resin composition for laminated glass interlayer film on the glass. Forming a physical layer;
<Step (b)>
A step of irradiating the photocurable resin composition layer for laminated glass interlayer film with ultraviolet rays to form a light-transmitting cured resin layer; and <Step (c)>
Bonding the glass on which the cured resin layer is formed and the other glass so that the cured resin layer is positioned between the two glasses to obtain a laminated glass;
The manufacturing method of the laminated glass containing this.

(8) Glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of (1)-(3). A method for producing a laminated glass comprising the following steps (a ′) to (d ′):
<Step (a ′)>
The photocurable resin composition for laminated glass interlayer film according to any one of (1) to (3) is applied on the surface of one glass, and the photocurable resin composition for laminated glass interlayer film on the glass. Forming a physical layer;
<Process (b ')>
A step of forming a temporarily cured resin layer by irradiating the photocurable resin composition layer for laminated glass interlayer film with ultraviolet rays to temporarily cure;
<Process (c ')>
A step of bonding the glass on which the temporary cured resin layer is formed and the other glass so that the temporary cured resin layer is positioned between both glasses; and <Step (d ′)>
A step of obtaining a laminated glass by forming a light-transmitting cured resin layer by irradiating ultraviolet rays to the temporarily cured resin layer located between the two glasses and carrying out main curing;
The manufacturing method of the laminated glass containing this.

  By using the photocurable resin composition of the present invention and the production method using the photocurable resin composition, a pair of adherends, for example, glasses, glass-resin substrate (or film), resin It is possible to bond substrates (or films) together. By using the photocurable resin composition of the present invention, the wettability and adhesion to the surface of the adherend are improved, and the toughness of the laminate that becomes a laminated glass is improved, so that it has high splitting property. Laminated glass can be provided.

  Moreover, also in the reliability in a high humidity environment, stable transparency can be maintained without the photocurable resin layer or the intermediate film (cured resin layer film) whitening.

  According to the present invention, a photocurable resin composition for laminated glass interlayer film used for forming an interlayer film of laminated glass having excellent splitting resistance against externally applied impact, and cover film attachment using the same An interlayer film for glass, laminated glass, and a method for producing laminated glass can be provided.

The schematic cross section which shows one Embodiment of the manufacturing method of the laminated glass of this invention. The schematic cross section which shows other one Embodiment of the manufacturing method of the laminated glass of this invention. The schematic cross section which shows other one Embodiment of the manufacturing method of the laminated glass of this invention. The 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. The meaning “(meth) acryloyl” means “acryloyl” or “methacryloyl” corresponding thereto. 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 comprises (meth) acryl oligomer (A), (meth) acryl monomer (B), photopolymerization initiator (C), oil gelling agent (D) and plastic. Contains agent (E).

  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.

<(Meth) acrylic oligomer (A)>
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.

  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 via the main chain containing the (meth) acrylate compound or the like as a monomer unit, the urethane bond bonded to the main chain, and the urethane bond (meth). A modified (meth) acryl oligomer having an acryloyloxy group may be included. Such a (meth) acryl oligomer can be obtained by reacting an isocyanate with a (meth) acryl oligomer having a hydroxyl group in a side chain. 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 may have a higher molecular weight than the (meth) acryl oligomer in the photocurable resin composition by having an acrylate group bonded to the main chain via a urethane bond in the side chain. And entanglement of (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, while maintaining a high peel strength and elongation ratio to the panel, and low elasticity and high aggregation. A cured product (resin layer) having strength 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 material line.

  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-lauri (Meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and the like alkyl group having 1 to 18 carbon atoms (meth) acrylate; ethylene glycol di (meth) acrylate, Alkanediol di (meth) acrylates having 1 to 18 carbon atoms such as butanediol (meth) acrylate and nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate , Tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and other (meth) acryloyl groups in the molecule Polyfunctional (meth) acrylate; glycidyl methacrylate; alkenyl (meth) acrylate having 2 to 18 carbon atoms of alkenyl group such as 3-butenyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. (Meth) acrylate having an aromatic ring; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxypolyethylene glycol (meta ) Acrylate, methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol ( ) Alkoxypolyalkylene glycol (meth) acrylates such as acrylate and butoxydiethylene glycol (meth) acrylates; and cycloaliphatic 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) acrylic (Meth) acrylamide derivatives such as N, N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate (Meth) acrylate having an isocyanate group such as: tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol Poly (alkylene glycol mono (meth) acrylates such as mono (meth) acrylate and octapropylene glycol mono (meth) acrylate; (Meth) acrylate; (meth) acrylate having an isocyanuric ring skeleton; (meth) acrylate having a siloxane skeleton, polyisoprene (meth) acrylate having an isoprene skeleton, polybutadiene (meth) acrylate having a butadiene skeleton, and the like. 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. It is desirable that the content of the (meth) acrylic monomer is in such a range.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) (hereinafter, also 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; ester compounds of β- (acridin-9-yl) (meth) acrylic acid, 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-diphenylimidazole Dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; 2-benzyl-2-dimethylamino-1- ( Α-a, such as 4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Minoalkylphenone 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.

  (C) 0.1 mass%-5 mass% are preferable with respect to the whole quantity of a photocurable resin composition, as for content of a component, 0.2 mass%-3 mass% are more preferable, 0.3 mass% More preferably, ˜2 mass%. 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, fatty acid amides such as 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.

<Plasticizer (E)>
As the plasticizer (E), it is preferable to use a plasticizer component that is compatible with the component (A) and can also be used as a tackifier. When it is incompatible with the component (A), there is a concern that the cured product becomes cloudy and visibility decreases. Examples of the plasticizer component include a solid tackifier (1) and a liquid plasticizer component (2). Here, “solid” means that the softening point according to JISK5601-2-2 is 60 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C. Further, the liquid state means a state showing a viscosity of 0.01 to 100 Pa · s (25 ° C.) with a cone plate rheometer at 25 ° C. under atmospheric pressure.

  The solid tackifier (1) exhibiting such a softening point is not itself photocured by ultraviolet irradiation, and is an initial adhesion of a cured resin layer or a temporarily cured resin layer formed from a photocurable resin composition. This has the effect of improving the strength (so-called tackiness) and increasing the final adhesive strength of the cured resin layer obtained by further curing the temporarily cured resin layer. Specific examples of the tackifier (1) include, for example, terpene resins such as terpene resins, terpene phenol resins, hydrogenated terpene resins, natural rosins, polymerized rosins, rosin esters, rosin resins such as hydrogenated rosins, polybutadiene, Petroleum resins such as polyisoprene can be used.

  The liquid plasticizer component (2) itself is not photocured by ultraviolet irradiation, and gives flexibility to the cured resin layer or the temporarily cured resin layer after photocuring, and also cures the cured resin layer or the temporarily cured resin layer. The shrinkage rate is reduced. As such a liquid plasticizer component (2), at least one selected from the group consisting of a liquid polybutadiene plasticizer, a polyisoprene plasticizer, a phthalate ester plasticizer and an adipate ester plasticizer is used. Can be mentioned. Examples of the plasticizer include butadiene rubber, isoprene rubber, silicon rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, chlorosulfonated polyethylene rubber, fluorine rubber, hydrogenated nitrile rubber, and epichlorohydrin. Liquid materials such as rubber; Poly α-olefins such as polybutene; Hydrogenated α-olefin oligomers such as hydrogenated polybutene and polyvinyl oligomers such as atactic polypropylene; Aromatic oligomers such as biphenyl and triphenyl; Hydrogenated liquid polybutadiene and the like Hydrogenated polyene oligomers; paraffin oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffin oligomers such as naphthene oil; dimethyl phthalate, diethyl phthalate, dibutyl phthalate , Di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, di (heptyl, nonyl, undecyl) phthalate, benzyl phthalate , Phthalic acid derivatives such as butyl benzyl phthalate, dinonyl phthalate and dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate and diisooctyl isophthalate; di- (2-ethylhexyl) tetrahydro Tetrahydrophthalic acid derivatives such as phthalate, di-n-octyltetrahydrophthalate and diisodecyltetrahydrophthalate; di-n-butyladipene Adipic acid derivatives such as di- (2-ethylhexyl) adipate, diisodecyl adipate and diisononyl adipate; azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate and di-n-hexylazelate; Sebacic acid derivatives such as n-butyl sebacate and di- (2-ethylhexyl) sebacate; maleic acid derivatives such as di-n-butyl malate, dimethyl malate, diethyl maleate and di- (2-ethylhexyl) malate; Fumaric acid derivatives such as butyl fumarate and di- (2-ethylhexyl) fumarate; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate , Tri-n- Trimellitic acid derivatives such as xyl trimellitate and triisononyl trimellitate; pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate; triethyl citrate, tri-n- Citric acid derivatives such as butyl citrate, acetyl triethyl citrate and acetyl tri- (2-ethylhexyl) citrate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate and di- (2- Itaconic acid derivatives such as ethyl hexyl) itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate and diethylene glycol monooleate; methyl acetyl ricinolate, butyl acetyl ricinolate, Ricinoleic acid derivatives such as seryl monoricinoleate and diethylene glycol monoricinoleate; stearic acid derivatives such as n-butyl stearate, glycerin monostearate and diethylene glycol distearate; diethylene glycol monolaurate, diethylene glycol dipelargonate and pentaerythritol fatty acid ester Other fatty acid derivatives such as: triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate and tris (chloroethyl) Phosphate derivatives such as phosphate; diethylene glycol dibenzoate, dipropiate Glycol derivatives such as diglycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate) and dibutylmethylene bisthioglycolate; glycerol Examples include glycerin derivatives such as monoacetate, glycerol triacetate and glycerol tributyrate, and epoxy derivatives such as epoxidized soybean oil, epoxyhexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate and epoxidized oleate decyl. These compounds can be used alone or in combination of two or more.

  Among these, from the viewpoint of transparency, a terpene resin that is a solid tackifier (1) is preferable, and for example, a terpene resin, a hydrogenated terpene resin, and the like are preferable.

  The content of the plasticizer (E) is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and more preferably 1% by mass with respect to the total amount of the photocurable resin composition from the viewpoint of handleability. More preferably, it is 10 mass%.

<Other additives>
The photocurable resin composition of this embodiment may contain various additives separately from the components (A) to (E) 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 above components (A) to (E), 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. The content of the inorganic filler is preferably 0.01 parts by mass to 100 parts by mass, more preferably 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. 0.1 parts by mass to 30 parts by mass is 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, (E) component, and as needed It can manufacture by mixing and stirring the said additive used.
In addition, when any of the components is in a solid state, it is preferable that the solid component is heated and dissolved at least at one timing before mixing stirring, during mixing stirring, and after mixing 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, the volatilization temperature or lower 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.

<Interlayer film for laminated glass with cover film>
The interlayer film for laminated glass with a cover film of the present invention comprises an interlayer film for laminated glass formed from the photocurable resin composition of the present invention, and a base material layer laminated so as to sandwich the interlayer film for laminated glass And a cover film. The interlayer film for laminated glass with a cover film of the present invention includes, for example, an interlayer film for laminated glass formed from a photocurable resin composition on a substrate such as a polymer film serving as a substrate layer, and the laminated glass. The film can be produced by attaching a cover film such as a polymer film on the intermediate film. By sandwiching the interlayer film for laminated glass between the base material layer and the cover film, it becomes possible to store and transport the laminated glass interlayer film without damaging it. In addition, the interlayer film for laminated glass in the interlayer film for laminated glass with a cover film may be subjected to temporary curing such as curing the surface by ultraviolet irradiation or the like, as necessary, in order to prevent flow and run-out. There is no restriction | limiting in particular in the irradiation amount of an ultraviolet-ray, For example, about 1000 mJ / cm < ² > may be sufficient.
The base material layer and the cover film of the interlayer film for laminated glass with a cover film may be subjected to a surface treatment as necessary so that they can be peeled off when the interlayer film for laminated glass is used. As the surface treatment method, for example, a mold release treatment is performed with a silicone compound or a fluorine compound.

<Laminated glass>
The laminated glass of the present invention is a laminated glass comprising an intermediate film and a pair of adherends laminated so as to sandwich the intermediate film, and the intermediate film is photocured for the laminated glass intermediate film of the present invention. It is a light-transmitting cured resin layer formed from a conductive resin composition. Examples of the adherend include glass such as inorganic glass and organic glass, a 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 also manufacture suitably by the manufacturing method of the laminated glass of this invention. Further, using the interlayer film for laminated glass with cover film of the present invention, the interlayer film for laminated glass formed in the interlayer film for laminated glass with cover film is disposed between a pair of adherends (glass etc.) and laminated. It can also be manufactured by making a body. At that time, the laminated resin layer is formed by irradiating the interlayer film for laminated glass with ultraviolet rays before and / or after being disposed between the pair of adherends.

<Method for producing laminated glass>
The present invention provides three methods for producing a laminated glass by applying the above-described photocurable resin composition of the present invention. In the first production method, after the photocurable resin composition is applied to one glass, the other glass is laminated so that the photocurable resin composition layer is between the glasses, In this method, a laminated glass is obtained by irradiating active energy rays such as ultraviolet rays from one surface of the obtained laminate and photocuring (main curing) the photocurable resin composition layer. In the second manufacturing method, after the photocurable resin composition is applied to one glass, the photocurable resin composition layer is irradiated with active energy rays such as ultraviolet rays without passing through the temporary cured resin layer. This is a method of obtaining laminated glass by photocuring (main curing) a transparent cured resin layer and then laminating the other glass so that the cured resin layer is located between the glasses. In the third production method, after the photocurable resin composition is applied to one glass, an active energy ray such as ultraviolet rays is once irradiated to form a temporarily cured resin layer, and then the coated surface is a temporarily cured resin layer. Is laminated between the glasses so that the other glass is laminated, and then the temporarily cured resin layer is further photocured (main cured) to form a light transmissive cured resin layer.

The steps in the above three production methods of the present invention are shown in FIGS.
In the first production method of the present invention (see FIG. 1), the light-transmitting cured resin layer in which glass and glass are formed from the photocurable resin composition for laminated glass interlayer film of the present invention. Is a method for producing laminated glass laminated through the following steps (A) to (C):
<Process (A)>
The process of apply | coating the photocurable resin composition for laminated glass intermediate films of this invention to the surface of one glass 11, and forming the photocurable resin composition layer 10 for laminated glass intermediate films on this glass 11 ( FIG. 1- (a));
<Process (B)>
The glass 11 on which the photocurable resin composition layer for laminated glass interlayer film 10 is formed and the other glass 12 are arranged between the glass with the photocurable resin composition layer for laminated glass interlayer film 10 between both glasses. Step of bonding so as to be positioned (FIG. 1- (b)); and <Step (C)>
By irradiating the photocurable resin composition layer 10 for laminated glass intermediate film 10 positioned between the two glasses 11 and 12 with ultraviolet rays and carrying out main curing (FIG. 1- (c)), light transmissive curing is performed. A step of obtaining laminated glass as the resin layer 13 (FIG. 1- (d));
including.

In the second production method of the present invention (see FIG. 2), glass and glass are light-transmitting cured resin layers formed from the photocurable resin composition for laminated glass interlayer of the present invention. A method for producing laminated glass laminated through the following steps (a) to (c):
<Process (a)>
The process of apply | coating the photocurable resin composition for laminated glass intermediate films of this invention to the surface of one glass 21, and forming the photocurable resin composition layer 20 for laminated glass intermediate films on this glass 21 ( FIG. 2- (a));
<Step (b)>
A step of forming a light-transmitting cured resin layer by irradiating the photocurable resin composition layer 20 for laminated glass interlayer film with ultraviolet rays (FIG. 2- (b)); and <Step (c)>
A process of obtaining a laminated glass by laminating the glass 21 on which the cured resin layer 22 is formed and the other glass 23 so that the cured resin layer 22 is positioned between both the glasses 21 and 23 (FIG. 2). -(C));
including.

In the third production method of the present invention (see FIG. 3), the glass and the glass are formed of a light transmissive cured resin layer formed from the photocurable resin composition for laminated glass interlayer film of the present invention. A laminated glass laminated through the following steps (a ′) to (d ′):
<Step (a ′)>
The process of apply | coating the photocurable resin composition for laminated glass intermediate films of this invention to the surface of one glass 31, and forming the photocurable resin composition layer 30 for laminated glass intermediate films on this glass 31 ( FIG. 3- (a));
<Process (b ')>
A step of forming a temporarily-cured resin layer by irradiating the photocurable resin composition layer 30 for laminated glass interlayer film with ultraviolet rays and temporarily curing the layer (FIG. 3B);
<Process (c ')>
The step of bonding the glass 31 on which the temporary cured resin layer 32 is formed and the other glass 33 so that the temporary cured resin layer 32 is positioned between both the glasses 31 and 33 (FIG. 3- (c) )); And <Step (d ′)>
A light curable cured resin layer 34 is formed by irradiating the temporary cured resin layer 32 located between the glasses 31 and 33 with ultraviolet rays and curing it (FIG. 3- (d)). A step of obtaining a laminated glass (FIG. 3- (e));
including.

  In the above-described three production methods of the present invention, a liquid resin is preferably used as the photocurable resin composition used for coating on the surface of glass. In general, the viscosity of the liquid photocurable resin composition is preferably 0.1 to 100000 Pa · s under the conditions of atmospheric pressure and atmospheric temperature. When the photocurable resin composition itself is not liquid and the viscosity is too high, the photocurable resin composition is heated or liquefied by adding a solvent, and used as a coating liquid having a viscosity in the above range. Also good. When a solvent is added, after application, the solvent is dried and removed to form a photocurable resin composition layer.

In the above three production methods, the irradiation amount of ultraviolet rays is not particularly limited, but is preferably about 5.0 × 10 ² mJ / cm ^{2 to} 5.0 × 10 ³ mJ / cm ² , and is preferably 1000 mJ / more preferably cm ² ~4000mJ / cm ^2.

  In the present specification, the temporary curing of the photocurable resin composition layer means that the photocurable resin composition or the layer formed from the photocurable resin composition is prevented from dripping or flowing. It means that the layer is cured by limiting the range of the part or the degree of curing, such as only the surface part, and the main curing is to maintain the pasting state of the photocurable resin composition or the layer. , Which means that it is fully and fully cured.

  In the above three production methods, after the glass and the glass are pasted through the photocurable resin composition layer or the temporary cured resin layer, the laminate obtained by the pasting either before or after the ultraviolet irradiation The object can be subjected to heat and pressure treatment as necessary. The heat and pressure treatment conditions are such that 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, preferably 1 0.5 MPa or less, more preferably 0.6 MPa or less, for example, 0.3 MPa to 1.5 MPa, but from the viewpoint of further removing entrained bubbles, the temperature is 50 ° C. to 70 ° C., and the pressure is 0.2 MPa. -0.5 MPa is particularly preferred. The treatment time is preferably 5 minutes to 60 minutes, and more preferably 10 minutes to 30 minutes.

  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, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “ISTA”)
4HBA (4-hydroxybutyl acrylate, Osaka Organic Chemical Industry, 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, Nippon Kasei Co., Ltd., trade name “Diamid KH”)

(E) component:
P85 (hydrogenated terpene resin, manufactured by Yasuhara Chemical Co., Ltd., trade name)
Dimaron (terpene resin, manufactured by Yasuhara Chemical Co., Ltd., trade name)

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)
(Product name, manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran (THF)
Column: Column TSKGEL SuperMultipore HZ-H
(Product name, manufactured by Tosoh Corporation)
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

[Production Method I for Laminated Glass]
The photocurable resin composition is coated on a float glass of 110 mm × 110 mm × 2.7 mmt (“mmt” represents the thickness in millimeters, the same applies hereinafter), and the photocurable resin composition layer Formed. In addition, the thickness of the photocurable resin composition layer was adjusted and applied so as to be 3.8 × 10 ² μm after the main curing. Laminate a float glass with a photocurable resin composition layer on the other 110 mm x 110 mm x 2.7 mmt float glass using a vacuum laminator so that the photocurable resin composition layer is on the inside. did. Thereafter, the photocurable resin composition layer sandwiched between the glasses was irradiated with ultraviolet rays (2000 mJ / cm ² ) and was fully cured to obtain a laminated glass. Then, if necessary, heat and pressure treatment (autoclave treatment) was performed under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold.

[Laminated glass production method II]
After a photocurable resin composition is applied onto a 110 mm × 110 mm × 2.7 mmt float glass to form a photocurable resin composition layer, a light release separator (thickness) is formed on the photocurable resin composition layer. A 75 μm thick polyethylene terephthalate film (manufactured by Fujimori Kogyo Co., Ltd.) is laminated and irradiated with ultraviolet rays (1.0 × 10 ³ mJ / cm ² ) using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.). A laminate was obtained in which a cured resin layer was sandwiched between glass and a light release separator. The thickness of the photocurable resin composition layer formed by coating was adjusted so that the thickness of the cured resin layer was 3.8 × 10 ² μm. Next, the light release separator was peeled from the cured resin layer to expose the surface of the cured resin layer. Subsequently, using a vacuum laminator, in a vacuum state, a glass having a cured resin layer formed thereon is laminated on a float glass of 110 mm × 110 mm × 2.7 mmt so that the cured resin layer is on the inside. Obtained. Then, if necessary, heat and pressure treatment (autoclave treatment) was performed under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold to obtain a laminated glass.

[Laminated glass manufacturing method III]
After a photocurable resin composition is applied onto a 110 mm × 110 mm × 2.7 mmt float glass to form a photocurable resin composition layer, ultraviolet rays are applied using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.). Was irradiated (3.0 × 10 ² mJ / cm ² ) to form a temporarily cured resin layer on the glass. In addition, the thickness of the photocurable resin composition layer was adjusted and applied so as to be 3.8 × 10 ² μm after the main curing. A float glass having a temporarily cured resin layer formed thereon was laminated on the other 110 mm × 110 mm × 2.7 mmt float glass using a vacuum laminator so that the temporarily cured resin layer was inside. Thereafter, the temporarily cured resin layer sandwiched between the glasses was irradiated with ultraviolet rays for main curing to obtain a laminated glass. Then, if necessary, heat and pressure treatment (autoclave treatment) was performed under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold to obtain a laminated glass.

[Laminated glass manufacturing method IV]
The interlayer film for laminated glass obtained in Comparative Example 8 to be described later was sandwiched between two transparent float glasses having a thickness of 2.7 mm, placed in a rubber bag, and deaerated at a vacuum degree of 2660 Pa for 20 minutes. Then, it moved to oven with deaeration, and also vacuum-pressed, hold | maintaining at 90 degreeC 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.

Example 1
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 4 parts by mass, hydrogenated terpene Resin (P85, component E) 5 parts by mass, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by mass, 12-hydroxystearin 5 parts by mass of acid (HSA, D component) were weighed, and these were stirred and mixed at 80 ° C. to obtain a liquid photocurable resin composition for laminated glass interlayer at 25 ° C.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Example 2)
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-1, A component) 60 parts by mass, isostearyl acrylate (ISTA, B component) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, B component) 4 parts by mass, terpene resin ( Dimaron, E component) 5 parts by mass, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by mass, fatty acid amide (D-KH) , D component) 5 parts by mass, and these were stirred and mixed at 100 ° C. to obtain a photocurable resin composition for a laminated glass interlayer film that was liquid at 25 ° C.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Example 3)
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-2, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 4 parts by mass, hydrogenated terpene Resin (P85, component E) 5 parts by mass, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by mass, 12-hydroxystearin 5 parts by mass of acid (HSA, D component) were weighed and mixed by stirring to obtain a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C.

  Using the obtained photocurable resin composition, a laminated glass was produced by the laminated glass production method II.

Example 4
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 4 parts by mass, hydrogenated terpene Resin (P85, component E) 5 parts by mass, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (manufactured by BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by mass, 12-hydroxystearin 5 parts by mass of acid (HSA, D component) were weighed and mixed by stirring to obtain a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C.

  Using the obtained photocurable resin composition, a laminated glass was produced by a laminated glass production method III.

(Comparative Example 1)
[Production of photocurable resin composition and production of laminated glass]
(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, 1-hydroxy Weighing 0.1 part by mass of cyclohexyl phenyl ketone (I-184, component D) (BASF Japan Ltd., trade name “Irgacure-184”), 5 parts by mass of 12-hydroxystearic acid (HSA, component D). These were stirred and mixed to obtain a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Comparative Example 1)
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-1, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 4 parts by mass, hydrogenated terpene Resin (P85, E component) 5 parts by weight, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by weight, By stirring and mixing these at 80 ° C., a liquid photocurable resin composition for laminated glass interlayer film was obtained at 25 ° C.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Comparative Example 2)
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-1, A component) 60 parts by mass, isostearyl acrylate (ISTA, B component) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, B component) 4 parts by mass, terpene resin ( Weigh 5 parts by weight of dimalon, component E), 0.1 part by weight of 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (trade name “Irgacure-184” manufactured by BASF Japan Ltd.), By stirring and mixing at 100 ° C., a liquid curable resin composition for laminated glass interlayer film was obtained at 25 ° C.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Comparative Example 3)
[Production of photocurable resin composition and production of laminated glass]
(Meth) acrylic oligomer (A-2, component A) 60 parts by mass, isostearyl acrylate (ISTA, component B) 30.9 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 4 parts by mass, hydrogenated terpene Resin (P85, E component) 5 parts by weight, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by weight, By stirring and mixing these, a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C. was obtained.

  Using the obtained photocurable resin composition, a laminated glass was produced by the laminated glass production method II.

(Comparative Example 4)
[Production of photocurable resin composition and production of laminated glass]
60 parts by weight of (meth) acryl oligomer (A-1, A component), 30.9 parts by weight of isostearyl acrylate (ISTA, B component), 4 parts by weight of 4-hydroxybutyl acrylate (4HBA, B component), hydrogenated terpene Resin (P85, E component) 5 parts by weight, 1-hydroxycyclohexyl phenyl ketone (I-184, component C) (BASF Japan Ltd., trade name “Irgacure-184”) 0.1 part by weight, By stirring and mixing these, a photocurable resin composition for laminated glass interlayer film which was liquid at 25 ° C. was obtained.

  Using the obtained photocurable resin composition, a laminated glass was produced by a laminated glass production method III.

(Comparative Example 5)
[Production of photocurable resin composition and production of laminated glass]
(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, 1-hydroxy Weighing 0.1 part by mass of cyclohexyl phenyl ketone (I-184, component D) (trade name “Irgacure-184” manufactured by BASF Japan Ltd.), and stirring and mixing them, the liquids are combined at 25 ° C. A photocurable resin composition for a glass interlayer was obtained.

  A laminated glass was produced by the laminated glass production method I using the obtained photocurable resin composition.

(Comparative Example 6)
[Preparation of Photocurable Composition and Preparation of Laminated Glass]
Isostearyl acrylate (ISTA, component B) 50 parts by mass, 4-hydroxybutyl acrylate (4HBA, component B) 44.9 parts by mass, hydrogenated terpene resin (P85, component C) 5 parts by mass, 1-hydroxycyclohexyl phenyl ketone (I-184, component D) (BASF Japan Ltd., trade name “Irgacure-184”) 0.1 parts by mass, and stirring and mixing these, laminated liquid glass interlayer film at 25 ° C. A photocurable composition was obtained.

  Using the obtained photocurable composition, a laminated glass was produced by the laminated glass manufacturing method I.

(Comparative Example 7)
[Production of interlayer film for laminated glass and production of laminated glass]
Polyvinyl butyral resin (acetalization degree 68.0 mol%, vinyl acetate component ratio 0.6 mol%) having a half-value width of 245 cm ⁻¹ corresponding to a hydroxyl group obtained by measuring an infrared absorption spectrum 100 Part by mass and 38 parts by mass of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer are mixed and sufficiently melt-kneaded with a mixing roll, and then at 150 ° C. for 30 minutes with a press molding machine. Press molding was performed to obtain a resin film having a thickness of 3.8 × 10 ² μm, which was used as an interlayer film for laminated glass.

  A laminated glass was produced by the laminated glass production method IV using the obtained interlayer film for laminated glass.

(Evaluation)
About the obtained photocurable resin composition and laminated glass, the following method evaluated.
The results are shown in Table 1. In Table 1, the numerical values in the rows of the A component to the E component are values indicating the blending amount of each component in parts by mass.

<Evaluation of peel strength>
A frame-shaped spacer having a thickness of 175 μm having a space of 80 mm in length and 30 mm in width was placed on a soda glass having dimensions of 100 mm in length and width, and the spacer was pasted using a Nystack (manufactured by Nichiban Co., Ltd.). The photocurable resin composition was filled in the spacer frame without any gaps. From that, a polyester film (Toyobo Co., Ltd., trade name: Cosmo Shine A4300) larger than the spacer and having a length of 200 mm, a width of 100 mm, and a thickness of 125 μm was bonded. The photo-curable resin composition bonded with the polyester film is exposed at an illuminance of 100 mW and an exposure amount of 3.0 × 10 ³ mJ / cm ² using an exposure machine equipped with a high-power metal halide lamp. The composition was cured to obtain a test sample in a state where the soda glass plate and the polyester film were bonded together with a cured product of the photocurable resin composition. A cut having a length of 200 mm and a width of 10 mm was cut into the sample with a cutter from above the polyester film. Using a tensile tester (Orientec Co., Ltd., trade name: RTC-1210), grasp the polyester film at the incised part, and at a room temperature of 25 ° C., a peeling angle of 180 °, and a peeling speed of 60 mm / min. The polyester film was peeled off from the cured product of the photocurable resin composition in the length direction of the sample. The load at this time was measured and the peel strength (N / 25 mm) was determined.

[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 made of each 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. 4 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. 4, the specimen support frame mainly has a box-shaped support portion 40 in which a flange portion 41 for placing an outer peripheral portion of the laminated glass is formed at the upper end, and is substantially the same as the flange portion 41. It is composed of a fixed portion 42 having a shape and a steel ball 43. A plurality of through holes (not shown) are formed at corresponding positions on the flange portion 41 and the fixing portion 42 of the support portion 40, and a laminated glass is placed on the flange portion 41. After the fixing portion 42 is disposed on the laminated glass, 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. 4, the sizes of the inner peripheral portions of the flange portion 41 and the fixing portion 42 are 100 mm × 100 mm.

  The laminated glass obtained from Examples 1, 2, 3, and 4 is obtained by using a laminated glass obtained by using a photocurable resin composition that does not contain an oil gelling agent and / or a plasticizer, and a polyvinyl butyral resin. As compared with the laminated glass thus obtained, the splitting property was high in all cases.

10 Photocurable resin composition layer for laminated glass interlayer film 11 Glass 12 Glass 13 cured resin layer 20 Photocurable resin composition layer for laminated glass interlayer film 21 Glass 22 Cured resin layer 23 Glass 30 Photocured for laminated glass interlayer film Resin Composition Layer 31 Glass 32 Temporarily Cured Resin Layer 33 Glass 34 Cured Resin Layer 40 Support Portion 41 Gutter 42 Fixed Portion 43 Steel Ball

Claims (8)

  Photocurable resin for laminated glass interlayer film containing (meth) acrylic oligomer (A), (meth) acrylic monomer (B), photopolymerization initiator (C), oil gelling agent (D) and plasticizer (E) Composition.   The photocurable resin composition for laminated glass interlayer films according to claim 1, wherein the oil gelling agent (D) is at least one selected from the group consisting of hydroxy fatty acids and hydroxy fatty acid amides.   The photocurable resin composition for laminated glass interlayer film according to claim 1 or 2, wherein the plasticizer (E) is at least one solid tackifier selected from the group consisting of a terpene resin and a hydrogenated terpene resin. .   The base film laminated | stacked so that the intermediate film for laminated glasses formed from the photocurable resin composition for laminated glass intermediate films in any one of Claims 1-3, and the said intermediate film for laminated glasses may be pinched | interposed An interlayer film for laminated glass with a cover film, comprising a cover film.   It is a laminated glass containing an intermediate film and a pair of adherend laminated | stacked so that the said intermediate film may be pinched | interposed, Comprising: The said intermediate film is for laminated glass intermediate films in any one of Claims 1-3 Laminated glass which is a light-transmitting cured resin layer formed from a photocurable resin composition. The manufacturing method of the laminated glass by which glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of Claims 1-3 And the following steps (A) to (C):
<Process (A)>
The photocurable resin composition for laminated glass interlayer films according to any one of claims 1 to 3 is applied to the surface of one glass, and the photocurable resin composition layer for laminated glass interlayer films is formed on the glass. Forming a step;
<Process (B)>
The glass on which the photocurable resin composition layer for laminated glass interlayer film is formed and the other glass so that the photocurable resin composition layer for laminated glass interlayer film is located between both glasses. Bonding step; and <Step (C)>
A step of obtaining laminated glass as a light-transmitting cured resin layer by irradiating the photocurable resin layer for laminated glass interlayer located between the two glasses with ultraviolet rays and carrying out main curing;
The manufacturing method of the laminated glass containing this. The manufacturing method of the laminated glass by which glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of Claims 1-3 And the following steps (a) to (c):
<Process (a)>
The process of apply | coating the photocurable resin composition for laminated glass intermediate films of Claim 1 to the surface of one glass, and forming the photocurable resin composition layer for laminated glass intermediate films on this glass;
<Step (b)>
A step of irradiating the photocurable resin composition layer for laminated glass interlayer film with ultraviolet rays to form a light-transmitting cured resin layer; and <Step (c)>
Bonding the glass on which the cured resin layer is formed and the other glass so that the cured resin layer is positioned between the two glasses to obtain a laminated glass;
The manufacturing method of the laminated glass containing this. The manufacturing method of the laminated glass by which glass and glass were laminated | stacked through the light-transmitting cured resin layer formed from the photocurable resin composition for laminated glass intermediate films in any one of Claims 1-3 And the following steps (a ′) to (d ′):
<Step (a ′)>
The photocurable resin composition for laminated glass interlayer films according to any one of claims 1 to 3 is applied to the surface of one glass, and the photocurable resin composition layer for laminated glass interlayer films is formed on the glass. Forming a step;
<Process (b ')>
A step of forming a temporarily cured resin layer by irradiating the photocurable resin composition layer for laminated glass interlayer film with ultraviolet rays to temporarily cure;
<Process (c ')>
A step of bonding the glass on which the temporary cured resin layer is formed and the other glass so that the temporary cured resin layer is positioned between both glasses; and <Step (d ′)>
A step of obtaining a laminated glass by forming a light-transmitting cured resin layer by irradiating ultraviolet rays to the temporarily cured resin layer located between the two glasses and carrying out main curing;
The manufacturing method of the laminated glass containing this.

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