JP2017008306A - Active energy ray polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray polymerizable resin composition having excellent adhesiveness and capable of being used for an adhesive or a coating agent or the like capable of forming a laminate excellent in high temperature durability.SOLUTION: There is provided an active energy ray polymerizable resin composition containing (A) a compound by a substitution reaction of a silane coupling agent (a1) and a polymerizable functional group-containing compound having a hydroxyl group (a2) and (B) a polymerizable functional group-containing compound, where the silane coupling agent (a1) has an alkoxysilyl group and other functional group, the other functional group is a functional group selected from a group consisting of a vinyl group, an epoxy group, a (meth)acryloyl group, a mercapto group and an amino group.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray polymerizable resin composition that can be used for an adhesive, a coating agent, and the like.

  The active energy ray-polymerizable resin composition has a high polymerization rate and generally can be used without a solvent. Therefore, the active energy ray-polymerizable resin composition has excellent characteristics such as excellent workability and extremely low energy required for polymerization. The active energy ray polymerizable resin composition is generally known as a radical polymerizable active energy ray polymerizable resin composition or a cationic polymerizable active energy ray polymerizable resin composition. It is used in a wide range of agents.

  In recent years, the development and generalization of information communication equipment including display devices such as displays has been remarkable. In these display devices, further improvement in performance and productivity such as a coating agent, an adhesive, or a sealing agent is required, and various proposals using an active energy ray polymerizable resin composition have been made. Yes. For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting a liquid crystal display (LCD), a polarizing plate or a retardation film is laminated.

  Further, the flat panel display (FPD) is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.

  In addition, a backlight system in which a liquid crystal layer is illuminated from the backside is widely used in display devices, and an edge light type, a direct type backlight unit or the like is provided on the lower surface side of the liquid crystal layer. Such an edge light type backlight unit basically includes a linear lamp as a light source, a rectangular plate-shaped light guide plate arranged so that an end thereof is along the lamp, and a surface side of the light guide plate. And a prism sheet disposed on the surface side of the light diffusion sheet. Recently, light-emitting diodes (LEDs) with excellent color reproducibility and power saving have been used as light sources instead of cooling cathode tubes (CCFLs), and demands for heat resistance and dimensional stability have increased. It is coming.

  Such a film is attached to an adherend through an adhesive and used as a laminated body for an optical element in a display device, and an active energy ray polymerizable adhesive is used as one form.

  As a specific example of a display device, a polarizer used for an LCD is usually produced by uniaxially stretching a polyvinyl alcohol (PVA) adsorbed with iodine or a dye. This PVA polarizer is The polarization performance tends to be lowered by shrinkage due to heat or moisture. Then, the laminated body which bonded the protective film on the surface of the PVA type | system | group polarizer is used as a polarizing plate. Conventionally, an aqueous solution of polyvinyl alcohol resin (PVA aqueous adhesive) has been widely used as the adhesive used for the bonding. However, a water-based adhesive requires a drying process after coating, and PVA polarizers have low heat resistance, so that drying for a long time at a low temperature is required, resulting in poor production efficiency. Therefore, in order to improve production efficiency, cationic active energy ray-polymerizable adhesives using ultraviolet rays as active energy rays have been studied in place of aqueous adhesives.

  By the way, liquid crystal display devices are used in various environments as their uses expand, and high heat resistance is required for polarizing plates constituting liquid crystal display devices. For example, an in-vehicle liquid crystal display device such as a car navigation system is required to have a high degree of durability (high temperature durability) because it is exposed to a severe high temperature atmosphere in summer unlike an LCD TV. Specifically, when the adhesiveness is weak in a high temperature environment, there is a problem that the PVA polarizer and the protective film are peeled off due to the difference in thermal shrinkage between the PVA polarizer and the protective film.

  Therefore, Patent Document 2 contains a curable component relating to a compound having a (meth) acryloyl group containing N-hydroxyethylacrylamide and N-acryloylmorpholine, and the Tg of the adhesive layer after curing is 60 ° C. or higher. An active energy ray polymerizable adhesive is disclosed.

  Patent Document 3 discloses an active energy ray polymerizable resin composition using a compound having a hydroxyl group and an oxetanyl group and a silane-modified oligomer obtained by dealcoholization reaction of poly (tetraalkoxysilane).

Japanese Patent No. 4744496 Japanese Patent No. 2003-171459

  However, a polarizing plate using an adhesive containing a conventional resin composition has not been able to satisfy durability in a harsher environment such as in-vehicle use.

  An object of this invention is to provide the active energy ray polymeric resin composition which can be used for the adhesive agent thru | or coating agent etc. which have the outstanding adhesiveness and can form the laminated body excellent in high temperature durability.

The active energy ray polymerizable resin composition of the present invention includes a compound (A) obtained by subjecting a silane coupling agent (a1) and a polymerizable functional group-containing compound (a2) having a hydroxyl group to a substitution reaction, and a polymerizable functional group. Containing compound (B),
The silane coupling agent (a1) has an alkoxysilyl group and other functional groups,
The other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group.

  According to the present invention, by including the compound (A) having an alkoxysilyl group having a polymerizable functional group, it is possible to form a crosslink with a base material or a resin layer, and inhibit the polymerization reaction. By suppressing the amount of alcohol generated, the cohesive strength of the resin layer formed by curing (crosslinking) could be improved. As a result, in addition to adhesiveness (adhesiveness), an effect of excellent durability such as moisture heat resistance and moisture heat resistance was obtained.

  ADVANTAGE OF THE INVENTION By this invention, the active energy ray polymeric resin composition which can be used for the adhesive agent thru | or coating agent etc. which have the outstanding adhesiveness and can form the laminated body excellent in high temperature durability can be provided.

Hereinafter, embodiments of the present invention will be described.
<Active energy ray polymerizable resin composition>
The active energy ray polymerizable resin composition of the present invention (hereinafter also referred to as a resin composition) is a compound obtained by subjecting a silane coupling agent (a1) and a polymerizable functional group-containing compound (a2) having a hydroxyl group to a substitution reaction. (A) and a polymerizable functional group-containing compound (B) (hereinafter also referred to as compound (B)),
The silane coupling agent (a1) has an alkoxysilyl group and other functional groups,
The other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group.

  Here, “active energy rays” provide energy necessary for activation to cause a chemical reaction, including rays such as ultraviolet rays and visible rays, heat rays such as infrared rays, electron beams (EB), and radiation. It means energy rays in a broad sense. The active energy ray-polymerizable resin composition of the present invention (hereinafter also referred to as “resin composition”) undergoes a polymerization reaction upon irradiation with the active energy rays to form a cured product (also referred to as a resin layer). The active energy ray to be irradiated is not particularly limited, but is preferably light.

The compound (A) used in the present invention is a reaction product obtained by subjecting a silane coupling agent (a1) and a polymerizable functional group-containing compound (a2) having a hydroxyl group (hereinafter also referred to as compound (a2)) to substitution reaction. . Since the compound (A) has an alkoxysilyl group having a polymerizable functional group, the compound (A) is incorporated into a crosslinked network formed by the polymerizable functional group-containing compound (B) by irradiation with active energy, thereby improving the cohesive force. Moreover, when it is used as an adhesive or a coating agent by the reaction of an alkoxysilyl group, good adhesion to the other party can be obtained.
The silane coupling agent (a1) which is a raw material of the compound (A) has an alkoxysilyl group and other functional groups. The other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group. It is important that the other functional group does not contain a hydrolyzable group in terms of wet heat resistance.

  The number of polymerizable functional groups possessed by the compound (A) is preferably 2 to 3.

A silane coupling agent (a1) is illustrated. In the present invention, the terms “epoxy”, “oxirane”, and “ethylene oxide” represent cyclic ethers having a three-membered ring structure unless otherwise specified. A three-membered cyclic ether adjacent to the cyclo ring is also an epoxy group. In addition, the expression “glycidyl” represents “oxirane methyl”.
Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and p-styryltriethoxysilane.
Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Examples include silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, and 5,6-epoxyhexyltriethoxysilane.
Examples of the silane coupling agent having a (meth) acryloyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, Examples include 3- (meth) acryloxypropylmethyldiethoxysilane.
Examples of the silane coupling agent having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.
Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Examples include methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

  Moreover, the polymeric functional group containing compound (a2) which has a hydroxyl group which is a raw material of a compound (A) has a hydroxyl group and a cationically polymerizable functional group (a2-1), or a hydroxyl group and a radically polymerizable functional group. It is a compound (a2-2). As the cationically polymerizable functional group of the compound (a2-1), an epoxy group and an oxetanyl group which are cyclic hetero compounds, a cyclic compound containing two or more oxygen, sulfur, or phosphorus, a vinyl ether group, and the like are preferable.

  The compound (a2-1) which has a hydroxyl group and a cation polymerizable functional group is illustrated. Examples of the oxirane-containing compound having a hydroxyl group include allyl alcohol oxide, 3-buten-1-ol oxide, 2-buten-1-ol oxide, 2-methyl-2-propen-1-ol oxide, 1-methyl-2- Propen-1-ol oxide, 4-penten-1-ol oxide, 3-penten-1-ol oxide, 2-penten-1-ol oxide, 3-methyl-3-buten-1-ol oxide, 3-methyl 2-buten-1-ol oxide, 2-methyl-2-buten-1-ol oxide, 1,1-dimethyl-2-propen-1-ol oxide, 1,2-dimethyl-2-propene-1- All oxide, 5-hexen-1-ol oxide, 6-hepten-1-ol oxide, 7-octen-1-ol oxide, -Octen-3-ol oxide, 2-methyl-6-hepten-2-ol oxide, 9-decene-1-ol oxide, 2,7-octadien-1-ol dioxide, 7-octene-1, 2- Diol oxide, 1,7-octadien-3-ol dioxide, 2-methyl-3-buten-2-ol oxide, linalool oxide, 1,2-dehydrolinalool oxide, geraniol dioxide, nerol dioxide, Labandu Roll oxide, citronellol oxide, 1,2-dihydrolinalool oxide, dehydronerolidol dioxide, nerolidol trioxide, farnesol trioxide, bisabolol dioxide, geranilinalol tetraoxide, geranylgeraniol tetraoxide, isophytol Sid, phytol epoxide, polyglycerol polyglycidyl ether, glycerol diglycidyl ether, glycerol mono-glycidyl ether, trimethylolpropane diglycidyl ether, aliphatic compounds such as trimethylolpropane monoglycidyl ether, and the like.

  Examples of the oxirane-containing compound having a hydroxyl group include an oxirane-containing compound having a secondary hydroxyl group obtained by ring-opening oxirane of two or more oxirane-containing compounds with a hydroxyl group, an acid, or a basic compound. Examples of the oxirane-containing compound having a hydroxyl group obtained by ring opening of oxirane include bisphenol A type epoxy resin, bisphenol F type epoxy resin, soybean oil modified bisphenol A type epoxy resin, and the like.

Examples of the oxetanyl group-containing compound having a hydroxyl group include 3-ethyl-3-hydroxymethyloxetane.
Examples of the cyclic hetero compound containing two or more oxygen, sulfur and phosphorus having a hydroxyl group include glycerin carbonate.

Examples of the vinyl ether having a hydroxyl group include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene Examples include glycol monovinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, and alkylene oxide addition type vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide and propylene oxide is repeatedly added.
Compound (a2-1) may be used alone or in combination of two or more.

  Among these, the compound (a2-1) is preferably an oxirane having a good cationic polymerizability and an oxetanyl group-containing compound. Furthermore, from the viewpoint of good reactivity with the silane coupling agent (a1), polyglycerol polyglycidyl ether, glycerol diglycidyl ether, glycerol monoglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane monoglycidyl ether, 3- More preferred is ethyl-3-hydroxymethyloxetane.

 The compound (a2-2) which has a hydroxyl group and a radically polymerizable functional group is illustrated. In the present invention, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl”, Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or respectively”, respectively. It represents “methallyl”.

Compound (a2-2) includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- Monofunctional (meth) acrylic acid glycerol such as (hydroxymethyl);
Fatty acid ester-based (meth) acrylic acid ester such as (meth) acrylic acid glycidyl lauric acid ester;
(Meth) acrylic acid ester having a hydroxyl group attached to the molecular end by ring-opening addition of ε-caprolactone to compound (a2-2);
An alkylene oxide addition (meth) acrylate ester obtained by repeatedly adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the compound (a2-2); an aliphatic (meth) acrylate ester;

  Aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal where alkylene oxides such as hydroxyethyl vinyl ether and hydroxydecyl vinyl ether are repeatedly added;

(Meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether;
An aliphatic (meth) allyl alcohol such as an alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added; and its (meth) allyl ether;

  An α, β-ethylenically unsaturated double bond group-containing compound having a plurality of hydroxyl groups such as propenediol, butenediol, and glycerol di (meth) acrylate.

  (Meth) acrylamides such as N-hydroxyethyl (meth) acrylamide and N-hydroxypropyl (meth) acrylamide.

Examples thereof include monomers having a hydroxyl group and a vinyl group such as vinyl alcohol.
A compound (a2-2) can be used individually or in combination of 2 or more types.

  Among these, the compound (a2-2) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, from the viewpoint of adhesiveness to the substrate, Α, β-ethylenically unsaturated double bond group-containing compounds having 2 to 18 carbon atoms, such as cyclohexanedimethanol mono (meth) acrylic acid ester, ε-caprolactone 1-2 mol addition (meth) acrylic acid 2-hydroxyethyl, etc. Is preferred.

As a more specific reaction example, for example, when a silane coupling agent having a trimethoxysilyl group is used as the compound (a1), the compound (A) can be obtained by the reaction of the following general formula (1).
General formula (1)

In the general formula (1), n is an integer of 1 to 3, and R ¹ represents a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group. And R ² is a polymerizable functional group-containing organic residue.

  The reaction of the general formula (1) is preferably carried out while distilling off by-produced methanol. Demethanol reduces the reversible reaction, and the compound (A) can be obtained stably. Furthermore, the substitution number of the polymerizable functional group-containing organic residue contained in the compound (A) can be adjusted by adjusting the amount of methanol removal. Moreover, it is also possible to adjust the substitution number of the polymerizable functional group containing organic residue contained in a compound (A) by adjusting the ratio of a compound (a1) and a compound (a2) in the case of reaction. For example, when the compound (a2) is reacted with the compound (a1) at a double molar ratio, the compound (A) in which the number of substitutions of the polymerizable functional group-containing organic residue is 2 can be obtained.

  The reaction conditions for obtaining the compound (A) are preferably, for example, heating at 30 to 250 ° C. for 10 minutes to 10 hours. Further, the dealcoholization reaction may be performed in a reduced pressure atmosphere. Furthermore, if necessary, a metal compound such as an acid, a basic substance, tin, titanium, or zirconium may be used as a catalyst.

In the reaction between the compound (a1) and the compound (a2), the compound (a2) can be used in combination with the compound (a2-1) and the compound (a2-2).
Moreover, the compound (A) may further have another reactive functional group.

  The compound (A) has one or more alkoxysilyl groups having a polymerizable functional group. Although it exists stably as an alkoxysilyl group in a sealed container, for example, after coating on a base material, it reacts with moisture in the air or the base material to react with moisture in the air or cationically polymerizable functional group-containing organic residue, radically polymerizable A part of the alkoxy moiety consisting of the functional group-containing organic residue and alcohol is decomposed, and a Si—OH bond appears.

  The cured product (resin layer) formed by applying the resin composition of the present invention to a substrate and irradiating with active energy rays is a silanol group generated by hydrolysis of the alkoxysilyl group of the compound (A). However, it forms a chemical bond such as a covalent bond or a hydrogen bond with a surface functional group (for example, a hydroxyl group, a carbonyl group, etc.) of the base material, thereby improving adhesion. In addition, since the polymerizable functional group of the compound (A) reacts with the compound (B), the alkoxysilyl group is easily incorporated into the crosslinked structure, so that the base material and the resin layer are firmly bonded to each other, which is excellent. Adhesion (excellent adhesion) is obtained. Furthermore, compared with the case where the compound (a1) which is a silane coupling agent is used as it is, the compound (A) generates a small amount of alcohol having no polymerizable functional group upon hydrolysis and is a cured product (resin layer). The residual unreacted material is reduced and the cohesive strength of the resin layer becomes stronger, so that the adhesion is improved.

  The polymerizable functional group-containing compound (B) used in the present invention has a radical polymerizable group or a cationic polymerizable group as the polymerizable functional group. The radical polymerizable group is preferably a (meth) acryloyl group or a vinyl group. The cationically polymerizable group is preferably an epoxy group, an epoxycyclohexyl group, an oxetanyl group, a vinyl ether group, two or more oxygen or a cyclic compound having a hetero group other than oxygen. Moreover, a compound (B) contains the polymeric functional group containing compound (a2) which has already demonstrated the hydroxyl group.

The compound (B) which has a cationically polymerizable group is illustrated.
The epoxy group-containing product is also called an oxirane compound, and includes an aliphatic oxirane compound and an aromatic oxirane compound.

  Aliphatic oxirane compounds include, for example, oxirane, methyl oxirane, phenyl oxirane, 1,2-diphenyl oxirane, methylidene oxirane, oxiranyl methyl, oxiranyl methanol, oxirane carboxylic acid, (chloromethyl) oxirane, (bromomethyl) oxirane. And oxiranyl acetonitrile.

  Aromatic oxirane compounds include, for example, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), and 1,3-bis {(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene is preferred. When an aromatic oxirane compound is used, heat resistance and heat and humidity resistance are further improved. The aromatic oxirane compound may have a substituent on the aromatic ring.

  The oxirane equivalent of the oxirane compound is usually preferably about 30 to 3000 g / eq, more preferably 50 to 1500 g / eq. When the oxirane equivalent is 30 g / eq or more, the flexibility of the cured sheet is excellent and the adhesive strength is further improved. Moreover, when it becomes 3000 g / eq or less, compatibility with a compound (A) improves more.

  Epoxycyclohexyl group-containing compounds include, for example, 3,4-oxiranecyclohexylmethyl, 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylene Bis (3,4-oxiranecyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxiranecyclohexylmethyl) Ether), dicyclopentadiene dioxide and the like.

  Examples of the oxetanyl group-containing compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3-oxetanyl) methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) methyl} oxetane, etc. Is mentioned.

The compound having two or more oxygen or hetero rings other than oxygen is preferably a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, a fluorine-containing cyclic compound, or the like. The cyclic ester compound is preferably a lactone. The cyclic formal compound is more preferably dioxolane, dioxane, trioxane or the like. The cyclic carbonate can be synthesized by, for example, a method of depolymerizing a polymer obtained by the reaction of glycol and dialkyl carbonate (see JP-A-2-56356) or a reaction of a corresponding alkylene oxide and carbon dioxide. . The cyclic carbonate preferably has a 5-membered ring, 6-membered ring or 7-membered ring structure or more.
Examples of the 5-membered ring formal compound include 1,3-dioxolane.
Examples of the 6-membered formal compound include 1,3-dioxane.
Although the 7-membered formal compound is contained in 1,3-dioxepane, it is independently classified as a cyclic carbonate because the carbon at the 2-position is a carbonyl carbon.

  Specific examples of the cyclic carbonate include ethylene carbonate (1,3-dioxolan-2-one), propylene carbonate, butylene carbonate, 4-pentyl-1,3-dioxolan-2-one, 4-butyl-1,3-dioxolane. 2-one, 4-propyl-1,3-dioxolan-2-one, 4- (isopropoxymethyl) -1,3-dioxolan-2-one, 4-hexyl-1,3-dioxolan-2-one 4-hexyl-5-methylene-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4,5,5-tetramethyl-1,3- Dioxolan-2-one, 4-octyl-1,3-dioxolan-2-one, 4-nonyl-5-vinyl-1,3-dioxolan-2-one, 4-decyl-1,3 Dioxolan-2-one, 4,5-bismethylene-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4,4,5,5-tetraethyl-1, 3-dioxolan-2-one, hexahydro-1,3-benzodioxol-2-one, 4-isopropyl-4-methyl-5-methylene-1,3-dioxolan-2-one, vinylene carbonate, allylethylene 5-membered ring carbonates such as carbonate, allyl succinic anhydride, 4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxymethyl) -1,3-dioxolan-2-one;

  Trimethylene carbonate (1,3-dioxan-2-one), 4-methyl-1,3-dioxan-2-one, 2,2-dimethoxypropane-1,3-diyl carbonate, 5-methyl-1,3- Dioxane-2-one, 5,5-dimethyl-1,3-dioxan-2-one (neopentyl glycol carbonate), 5-methyl-5-propyl-1,3-dioxan-2-one, 5-hydroxymethyl -5-methyl-1,3-dioxan-2-one, 4-phenyl-1,3-dioxan-2-one, 5- (hydroxymethyl) -5-ethyl-1,3-dioxan-2-one, 4-methylene-1,3-dioxan-2-one, 5,5-dimethyl-4-vinyl-1,3-dioxan-2-one, 5-cyano-5-methyl-1,3-dioxane-2-one ON, 5- (2 Oxo-1,3-dioxolan-4-ylmethoxy) -5-ethyl-1,3-6-membered ring carbonates dioxan-2-one and the like;

Tetramethylene carbonate (1,3-dioxepan-2-one), 5-methyl-1,3-dioxepan-2-one, 4-methyl-1,3-dioxepan-2-one, 5,5-dimethyl-1 , 3-dioxepan-2-one, 5-phenyl-1,3-dioxepan-2-one, 4-phenyl-1,3-dioxepan-2-one, 4- [1- (phenylthio) cyclohexyl] -1, Examples thereof include 7-membered ring carbonates such as 3-dioxepane-2-one and 5,5 ′-(ethylenebisthiobistrimethylene) bis (1,3-dioxepane-2-one).
Among these, 5-membered ring carbonates such as ethylene carbonate, propylene carbonate, glycerin carbonate and the like are preferable because the reactivity of active energy rays is good.

Examples of the vinyl ether group-containing compound include methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, Examples include isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, nonyl vinyl ether, dipentaerythritol hexavinyl ether, and the like. It is done.
The compound (B) having a cationic polymerizable group may be used alone or in combination of two or more.

  The compound (B) having a cationic polymerizable group is composed of 3,4-oxiranecyclohexanecarboxylate, bis (3,4-oxiranecyclohexylmethyl) adipate, glycidyl ether of bisphenol A, bisphenol F Glycidyl ether is preferred.

The compound (B) which has a radically polymerizable group is illustrated.
Examples of the compound (B) having a (meth) acryloyl group include the polymerizable functional group-containing compound (a2) having a hydroxyl group already described. Among the compounds (a2), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (Meth) acrylic acid ester, 1-2 mol addition (epsilon) -caprolactone, 2-hydroxyethyl (meth) acrylate, etc. are mentioned.

  The compound (B) is preferably a (meth) acrylate compound having a cyclic structure, a (meth) acrylate compound having no cyclic structure, a vinyl compound having a cyclic structure, a vinyl compound having no cyclic structure, or an allyl compound. .

  Examples of the (meth) acrylate compound having a cyclic structure include hydrogenated biphenol A diacrylate, 3,3-dicyclopropyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopenta Nyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, isobornyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2 -Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3- Damantyldiol di (meth) acrylate, 1,3,5-adamantyl (meth) acrylate, 3-hydroxy-1,5-adamantyl di (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate And isocyanuric acid ethylene oxide-modified di- and triacrylates.

(Meth) acrylate compounds not having a cyclic structure, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic acid (Meth) acrylic acid alkyl esters such as stearyl;
(Meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2-propenyl lactyl, (meth) acrylic acid 3,7 Others such as -dimethyloct-6-en-1-yl, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, and vinyl (meth) acrylate (Meth) acrylic acid esters containing unsaturated groups;
(Meth) acrylic acid perfluoroalkyl esters such as (meth) acrylic acid perfluoromethyl, (meth) acrylic acid 2-perfluoroethylethyl, and (meth) acrylic acid 2-perfluorohexadecylethyl;
(Meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) hexyl, (meth) acrylic acid 2- (propoxycarbonyloxy) ethyl, and (meth) acrylic acid 2- (octyloxy) Aliphatic (meth) acrylic acid ester having one carbonyl group such as carbonyloxy) butyl;
(Meth) acrylic acid 2-oxobutanoylethyl, (meth) acrylic acid 3-oxobutanoylpropyl, (meth) acrylic acid 2,3-di (oxobutanoyl) butyl, (meth) acrylic acid 2,3- Aliphatic (meth) acrylic acid esters having two carbonyl groups such as di (oxobutanoyl) hexyl and 2,3-di (oxobutanoyl) octyl (meth) acrylate;
Sulfonyl group-containing (meth) acrylic acid alkyl esters such as (meth) acrylic acid 3-sulfopropyl and (meth) acrylic acid sulfostearyl;
Metal salts of (meth) acrylic acid esters containing a sulfonyl group such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, or ammonium salts thereof;
Phosphonic acid group-containing (meth) acrylic acid esters such as (meth) acrylic acid phosphooxyethyl and (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10);
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, Alkoxy group-containing (meth) acrylic acid ester such as 3-butoxyethyl (meth) acrylate and 4-butoxyethyl (meth) acrylate;
Alkylene oxide-containing (meth) acrylic acid derivatives such as alkylene oxide adducts of (meth) acrylic acid;
Di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid 2,2-dimethylpropyldiol, hydroxy di (meth) acrylic acid Pivalyl hydroxypivalate, 2,5-hexanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate , And bifunctional (meth) acrylic acid esters such as 2,5-dimethyl-2,5-hexanediol di (meth) acrylate;
Tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, and tri (meth) acrylic acid 1,1,1-trishydroxy Trifunctional (meth) acrylic acid esters such as methylethane;
Tetra (meth) acrylate pentaerythritol, tetra (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol, and hepta (meth) acrylate di 2,2-bis (hydroxymethyl) 1, Polyfunctional (meth) acrylic acid esters such as 3-propanediol polyalkylene oxide;
(Meth) acrylonitrile, itacon nitrile, (meth) acrylic acid 2-cyanoethyl and the like.

  The (meth) acrylate compound may be an oligomer other than the above monomer. The oligomer is preferably epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, or the like.

The epoxy (meth) acrylate is a (meth) acrylate having no epoxy group obtained by reacting an epoxy group of an epoxy compound with a monomer containing at least one of a carboxyl group and a hydroxyl group.
The epoxy compound is, for example, an aliphatic epoxy compound such as a bisphenol type epoxy compound or an allyl alcohol type epoxy compound; a phenol type epoxy compound, a hydrogenated product of an aromatic epoxy, an aromatic epoxy compound, an alicyclic epoxy compound, etc. Is mentioned.

  Urethane (meth) acrylate is a compound having a urethane bond and a (meth) acryloyl group in the molecule.

  Polyester (meth) acrylate is a compound having an ester bond and a (meth) acryloyl group in the molecule.

  Examples of the vinyl compound having a cyclic structure include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t- Butoxystyrene, 4-t-butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxy Ethoxy) styrene, 4- (1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene and the like.

Fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), and vinylidene fluoride;
Alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;
Metal salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, and sodium vinyl alkyl sulfosuccinate, or ammonium salts thereof;
Glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, and 1,3-butadiene monooxirane;
Vinyl esters such as vinyl chloride, vinylidene chloride, and allyl chloride;
(E) -but-2-enoic acid vinyl, (Z) -octadeca-9-enoic acid vinyl, and (9Z, 12Z, 15Z) -octadeca-9,12,15-vinyl trienoate, allene, 1,2 -Dienes such as butadiene, 1,3-butadiene, and 2-methyl-1,3-butadiene;
Examples include ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-tetradecene, 1-triacontene, 1-octatriatain, and 1-tetraconten.

Allyl compounds are, for example, (meth) allyl esters of saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, and vinyl pivalate;
2-methyl-2-propenylsulfonic acid ammonium, and metal salts of 2-methyl-2-propenylsulfonic acid such as sodium 2-methyl-2-propenylsulfonate, or ammonium salts thereof; (meth) allyl acetoacetate, aceto Aliphatic (meth) allyl compounds having an acyl group such as (meth) allyl propionate, propanoyl acetate (meth) allyl, and butyryl acetate (meth) allyl; cis-diallyl succinate, diallyl 2-methylidene succinate, 2-propene A nitrile etc. are mentioned.

Among these, the compound (B) having a radical polymerizable group is preferably a (meth) acrylate compound from the viewpoint of reactivity, and the resin composition of the present invention is applied to the active energy ray polymerizable adhesive or the active energy ray polymerizable coat. When used as an agent, from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono ( (Meth) acrylic acid esters are preferred.
Moreover, it is preferable that the compound (B) which has a radically polymerizable group contains (meth) acrylic acid ester more than bifunctional from a viewpoint of adhesive force, heat resistance, and wet heat resistance improvement. Specifically, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, diacrylate of bisphenol A, diacrylate of hydrogenated biphenol A, Dimethylol dicyclopentane di (meth) acrylate, isocyanuric acid ethylene oxide modified di and triacrylate are preferred.

 In the present invention, the compounding ratio of the compound (A) and the compound (B) is 0.5 to 95% by weight of the compound (A) out of 100% by weight in total of the compound (A) and the compound (A). B) is preferably contained in an amount of 5 to 99.5% by weight, more preferably 1 to 70% by weight of the compound (A), and more preferably 30 to 99% by weight of the compound (B). More preferably, it contains 2 to 50% by weight and 50 to 98% by weight of the compound (B). When the amount of the compound (A) is more than 0.5%, the adhesion is improved by the chemical bond between the compound (A), the base material and the compound (B). If it is less than 95% by weight, the viscosity will be low and the coating suitability will be excellent.

  When the resin composition of this invention contains the compound which has a cationically polymerizable functional group, it is preferable to contain a photocationic polymerization initiator. A known compound can be used as the photocationic polymerization initiator. Examples of commercially available products include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), Rp-2074. Examples thereof include iodonium salts (made by Rhodia Japan).

  It is preferable to mix | blend 0.1-10 weight% of photocationic polymerization initiators in 100 weight% of active energy ray-curable resin compositions, and 0.5-5 weight% is more preferable.

  When the resin composition of this invention contains the compound which has a radically polymerizable functional group, it is preferable to contain radical photopolymerization initiator. As the radical photopolymerization initiator, known compounds can be used. Commercially available products include, for example, Irgacure-184,907,651,1700,1800,819,369,261, DAROCUR-TPO (manufactured by Ciba Specialty Chemicals), Darocur-1173 (manufactured by Merck), Ezacure- KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI, (Nippon Kayaku Co., Ltd.) and the like can be mentioned.

  The radical photopolymerization initiator is preferably blended in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, in 100% by weight of the active energy ray-curable resin composition.

  The active energy ray-curable resin composition of the present invention may further comprise a photosensitizer, an amine catalyst, a phosphorus catalyst, a filler, an antistatic agent, an antioxidant, an antioxidant, a tackifier, if necessary. An antiblocking agent, an antifoamer, a plasticizer, a silane coupling agent, a titanium coupling agent, etc. can be contained.

  The active energy ray-curable resin composition of the present invention can be prepared by blending the raw materials described so far and stirring and mixing them.

As described above, the active energy ray-polymerizable resin composition of the present invention is produced by subjecting a silane coupling agent (a1) and a polymerizable functional group-containing compound (a2) having a hydroxyl group to substitution reaction (A). ) And further mixing the polymerizable functional group-containing compound (B),
The silane coupling agent (a1) has an alkoxysilyl group and other functional groups,
The other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group.

  The active energy ray polymerizable resin composition of the present invention is preferably used as a coating agent or an adhesive. The resin composition is applied to one side (or both sides) of the substrate, and then polymerized (cured) by irradiation with active energy rays to form a resin layer (also referred to as an adhesive layer or a coating film depending on the application). It is preferable to do.

  The thickness of the resin layer is preferably from 0.1 to 6 μm, and more preferably from 0.1 to 3 μm. When the thickness of the resin layer is 0.1 μm or more, the adhesion and adhesive force are further improved. Moreover, even if it exceeds 3 μm, there is no particular problem, but there is a disadvantage in terms of cost.

  A known coating apparatus can be used for coating. For example, a Myer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a micro gravure coater, a lip coater, a comma coater, Examples thereof include a curtain coater, a knife coater, a river coater, and a spin coater.

  The active energy ray used for curing preferably has a wavelength including ultraviolet rays that the photocationic polymerization initiator can normally react, and more preferably 150 to 550 nm. Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, an LED lamp, a xenon lamp, and a metal halide lamp. .

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . Integrated irradiation dose, expressed as the product of the irradiation intensity and the irradiation time is preferably ^{10~5000mJ / cm 2, 30~4000mJ / cm} 2 is more preferable.

  The adhesive of the present invention contains an active energy ray polymerizable resin composition as an essential component.

  The coating sheet of the present invention includes a base material and a resin layer formed from an active energy ray-curable resin composition, and can be used for optical films such as information communication devices such as displays and touch panels. preferable.

  The laminated body of this invention is equipped with the resin layer formed from the adhesive agent containing an active energy ray polymeric resin composition, and a base material. Since it is a laminate, the substrate usually comprises at least a first substrate and a second substrate.

The active energy ray polymerization reaction of the adhesive proceeds when the resin composition is applied or laminated, and further by irradiating active energy rays after laminating, but irradiating active energy rays after laminating the substrates. It is preferable to proceed the polymerization reaction. At this time, the base material needs to be made of a material that easily transmits the active energy ray in order to advance the polymerization reaction by irradiation with the active energy ray.
The substrate is preferably a transparent film or a transparent glass plate. For example, if a transparent film or a transparent glass plate is used for the first base material, a base material that does not easily transmit active energy rays is used as the second base material, for example, a wood, a metal plate, a plastic plate, or a processed paper product. You may do it.
That is, since the active energy ray irradiation to the resin layer is performed through the base material, one of the first base material and the second base material needs to transmit the active energy ray.

In the laminate of the present invention, it is preferable to use a film-like substrate as the substrate. The film substrate is
Examples include cellophane, various plastic films, and paper. Of these, the use of various transparent plastic films is preferred. Further, the film-like substrate may have a single layer or a multilayer structure in which a plurality of substrates are laminated as long as the film is transparent.

The coating agent of the present invention contains an active energy ray polymerizable resin composition as an essential component.
The sheet | seat of this invention is equipped with the resin layer formed from the active energy ray polymeric resin composition, and the base material.

  When the active energy ray polymerizable resin composition is used as a coating agent, the active energy ray polymerization reaction is carried out by crosslinking (curing) by irradiating the active energy ray after coating the resin composition on one side or both sides of the substrate. ) Goes on. The base material may be wood, a metal plate, a plastic plate, a film-like base material, a glass plate, a processed paper product, or the like, and these can be used without any particular limitation.

  Hereinafter, more specific embodiments of the laminate of the present invention will be described by taking a case where a transparent film is used as a base material as an example.

  The laminate comprising the resin composition of the present invention as an adhesive is, for example, a plurality of transparent films such as transparent film / adhesive layer / transparent film or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. It is a sheet-like multilayer film obtained by laminating. In another embodiment, the laminate may be a sheet-like multilayer film such as a transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, or another optical member such as glass or an optical sheet. A configuration in which the adhesive is adhered is also preferable. The laminate can be obtained by curing the adhesive layer by polymerizing and curing the approximate resin composition from one side or both sides of the film with active energy rays.

  A laminate comprising the resin composition of the present invention as a coating agent is typically a transparent film / coat layer (also referred to as a coating film) or a coat layer / transparent film / coat. -A sheet-like film having a structure of a sheet layer. Such a laminate can be obtained by applying a resin composition to at least one main surface of the transparent film, polymerizing and curing the resin composition, and forming a coat layer.

The transparent film is, for example, a polyvinyl alcohol film, a polytriacetyl cellulose film, a polyolefin-based film such as polypropylene, polyethylene, polycycloolefin, and an ethylene-vinyl acetate copolymer; a polyester-based film such as polyethylene terephthalate and polybutylene terephthalate; Examples of such films include poly films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, and polyoxirane films.
When a transparent film is used for the substrate, the laminate of the present invention is preferably used for optical applications.

  The thickness of the transparent film can be determined as appropriate, but in general, from the viewpoints of workability such as strength or handleability and thin layer properties, 1 to 500 μm is preferable, 1 to 300 μm is more preferable, and 5 More preferably, it is -200 micrometers. Moreover, when using for an optical use, 5-150 micrometers is preferable for the thickness of a transparent film.

  As an example of the embodiment of the laminate of the present invention, the laminate for an optical element preferably uses an optical film mainly used in optical applications as a transparent film.

  Examples of the optical film include a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, a prism film (prism sheet (prism sheet). -It), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also called a light guide plate), and the like.

  A polarizing film is also called a polarizing plate, and a polytriacetylcellulose-based protective film (hereinafter referred to as “TAC film”), which is a polyacetylcellulose-based film on both sides of a polyvinyl alcohol-based polarizer, or a polyvinyl alcohol-based polarized light. Laminate for sheet-like optical elements with a multilayer structure in which one or both sides of the element are laminated with an adhesive such as polycycloolefin film, polyacrylic film, polycarbonate film, polyester film, which are polynorbornene films Is the body.

  By using the resin composition of the present invention as an adhesive, a laminate of a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, or the like can be formed.

  The polarizing plate of the present invention includes a protective film, a resin layer formed from the active energy ray-curable resin composition, and a polarizer. In this polarizing plate, it is preferable to use an active energy ray-curable resin composition as an adhesive.

  More specifically, the polarizing plate (polarizing film) using the active energy ray-curable adhesive can be obtained as follows.

(I) An active energy ray-curable adhesive is applied to one surface of the protective film that is the first transparent film, and a first resin layer (adhesive layer) is formed.
An active energy ray-curable adhesive is applied to one surface of the second protective film, which is a transparent film, and a second resin layer (adhesive layer) is formed.

    Next, the first resin layer (adhesive layer) and the second resin layer (adhesive layer) surface are simultaneously and / or sequentially superimposed on each surface of the polyvinyl alcohol polarizer, and then the active energy rays are applied. A method of producing by irradiating and polymerizing and curing the first resin layer (adhesive layer) and the second resin layer (adhesive layer).

  (II) An active energy ray-curable adhesive is applied to one surface of the polyvinyl alcohol-based polarizer to form a first resin layer, and the surface of the formed first resin layer is a transparent film. Cover with the first protective film, and then apply an active energy ray-curable adhesive to the other surface of the polyvinyl alcohol polarizer to form a second resin layer. A method of manufacturing by covering the surface with a second protective film, irradiating active energy rays, and polymerizing and curing the first resin layer and the second resin layer.

  (III) The edge part of the 2nd protective film piled up on the surface which did not have the 1st protective film of the polyvinyl alcohol type polarizer, and the edge part which piled up the protective film and polyvinyl alcohol type polarizer which are the 1st transparent films After the active energy ray curable adhesive is dropped on, the adhesive is spread between the layers by passing between the rolls. Next, there is a method of manufacturing by irradiating active energy rays and polymerizing and curing the active energy ray-curable adhesive, but it is not particularly limited.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. “Part” is “part by weight”, and “%” represents “% by weight”.

Production Example of [Polyvinyl Alcohol Polarizer] A dyeing solution was prepared by dissolving 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 parts by weight of potassium iodide in 480 parts by weight of water. A PVA film (Vinylon film # 40, manufactured by Aicello) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to obtain a PVA polarizer having a thickness of 30 μm.

  Table 1 lists the abbreviations of the raw materials used in the synthesis examples and comparative examples.

<Production of Compound (A)>
[Synthesis Example 1]
In a four-necked flask equipped with a condenser, fractionator, stirrer, thermometer, nitrogen inlet tube, vacuum pump and manometer, 181 parts of KBE-1003, 819 parts of diglycerol triglycidyl ether, N, N-dimethyl 0.2 parts of benzylamine was charged, and the reaction was started by raising the temperature to 110 ° C. in a nitrogen atmosphere. After the temperature was stabilized at 110 ° C., decompression was started. The degree of vacuum was 4 kPa. While keeping the dealcohol as it was, it was kept for 2 hours to obtain a pale yellow transparent compound (A). When the ethoxy group of KBE-1003 was disubstituted, the theoretical deethanol amount was 113 g, and the actual deethanol amount was 108 g.

[Synthesis Example 11]
350 parts of KBE-802 and 650 parts of OXT101 were charged into a four-necked flask equipped with a condenser, fractionator, stirrer, thermometer, and nitrogen inlet tube, and the reaction was started under a nitrogen atmosphere. The temperature was raised to 130 ° C. while removing methanol, and the mixture was maintained at normal pressure for 4 hours to obtain a brown transparent compound (A). In addition, since the number of moles of the compound (a2) is smaller than the alkoxy group of the silane coupling agent, the theoretical dealcoholization amount when the compound (a2) is completely substituted is 62, and the actual dealcoholization amount is 60 g. there were.

[Synthesis Examples 2 to 10, 12, 13, 15 to 17]
The compounds (A) of Synthesis Examples 2 to 10 and 12 to 17 were obtained by producing in the same manner as in Synthesis Example 1 except that the raw materials and reaction conditions of Compound 1 were changed as described in Table 2. The theoretical dealcoholization amounts of Synthesis Examples 2, 4, 6, 10, 13, 14, and 16 are the theoretical dealcoholization amounts when the alkoxy groups of the compound (a1) are all substituted. In addition, the theoretical dealcoholization amount of Synthesis Examples 1, 3, 5, 7 to 9, 11, 12, 15, and 17 is smaller than the amount of the compound (a2) than the alkoxy group of the compound (a1). The theoretical dealcoholization amount when all of the compound (a2) is substituted.

<Production of Compound (A) '>
[Synthesis Example 14]
The compound (A) ′ of Synthesis Example 14 was obtained in the same manner as in Synthesis Example 1 except that the raw materials and reaction conditions of Compound 1 were changed as described in Table 2.

  Table 3 lists the abbreviations of the raw materials used in the examples.

[Example 1]
In a glass bottle with a capacity of 300 mL protected from light, 45 parts of 2021P, 20 parts of EX-212L, 15 parts of OXT-101, 20 parts of the compound (A) obtained in Synthesis Example 1, and 2 parts of CPI-110P were added. Stirring and defoaming were sufficiently performed to obtain an active energy ray-curable resin composition.

<Production example of coating sheet A>
Using the active energy ray-curable resin composition, the following coating sheet A was prepared.
As the transparent film, a polyacetylcellulose-based film (manufactured by Fuji Film Co., Ltd., trade name “Fujitack: 80 μm”, UV absorber-containing polytriacetylcellulose-based film) was used. After the corona treatment was performed on the transparent film surface with a discharge amount of 300 W · min / m ² , the active energy ray-curable resin composition was coated with a wire bar coater with a film thickness of 2 μm. Coating was performed to form a laminate having a resin layer. The laminate was dried at 80 ° C. for 2 minutes, and the solvent was removed. Then, the four sides of the laminate were fixed to the tinplate with a cellophane tape so that the transparent film was in contact with the tinplate. After replacing the inside of the UV irradiation device (Toshiba High Pressure Mercury Lamp) with dry nitrogen, the coating sheet A is produced by irradiating UV light with a maximum illumination of 500 mW / cm ^{2 with} a wavelength of 365 nm and an integrated light quantity of 1000 mJ / cm ² from the resin layer side. did.

About the obtained coating sheet A, the adhesive force, heat-and-moisture resistance, and heat resistance were calculated | required in accordance with the following method, and the result was similarly shown in Table 4.
"Adhesion"
According to JIS K5600-5-6: 1999, a cross-cut peel test was performed. The number of cells peeled in 100 cells was evaluated in four stages.
(Evaluation criteria)
A: 0 square (very good)
○: 1-10 mass (good)
△: 11-30 squares (usable)
×: 31 squares or more (unusable)

《Moisture and heat resistance》
The laminate is cut into a size of 50 mm × 40 mm, exposed for 1000 hours under the condition of 85 ° C.-85% RH, and then peeled off according to JIS K5600-5-6: 1999 in the same manner as the above adhesion. Carried out. The number of cells peeled in 100 cells was evaluated in four stages.
(Evaluation criteria)
A: 0 to 10 squares (very good)
○: 11-30 mass (good)
Δ: 31-60 squares (can be used)
×: 61 squares or more (unusable)

"Heat-resistant"
The laminate is cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 100 ° C.-dry and then subjected to a cross-cut peel test in accordance with JIS K5600-5-6: 1999 in the same manner as the above adhesion. did. The number of cells peeled in 100 cells was evaluated in four stages.
(Evaluation criteria)
A: 0 to 10 squares (very good)
○: 11-30 mass (good)
Δ: 31-60 squares (can be used)
×: 61 squares or more (unusable)

<Example of production of laminate B>
As the transparent film (1), an ultraviolet absorber-containing polytriacetylcellulose-based film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” (thickness 80 μm) is used, and as the transparent film (2), manufactured by Fuji Film Business Supply Co., Ltd. A polytriacetylcellulose-based film containing no UV absorber: trade name “TAC 50 μ” (thickness 50 μm) was used. The surface of one side of the transparent films (1) and (2) is subjected to corona treatment with a discharge amount of 300 W · min / m ² , and the active energy ray-curable composition is applied to the corona-treated surface of each film within 1 hour thereafter. On top, coating was performed using a wire bar coater to a thickness of 4 μm to form a film. After drying at 80 ° C. for 2 minutes to remove the solvent, a polyvinyl alcohol polarizer is sandwiched between the resin layers formed on the transparent films (1) and (2), and the transparent film (1) / resin layer / A laminate composed of PVA polarizer / resin layer / transparent film (2) was obtained. Four sides of this laminate were fixed with a cellophane tape so that the transparent film (1) was in contact with the tin plate, and was fixed to the tin plate.

A laminate B (polarizing plate) was prepared by irradiating ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light quantity of 1000 mJ / cm ² from the transparent film (2) side with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). .

  About the obtained laminated body B, adhesive force, wet heat resistance, and heat resistance were calculated | required in accordance with the following method, and the result was similarly shown in Table 4.

<Adhesive strength>
The adhesion was measured according to JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained laminate B was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) is attached to one side of the sample and adhered on a metal plate using a laminator, and a laminate for measuring the polarizing plate and the metal plate is obtained. Obtained. The measurement laminate is provided with a peeling peel between the transparent film and the polarizer in advance, and the measurement laminate is subjected to a speed of 300 mm / min at 23 ° C. and a relative humidity of 50%. Was peeled off at an angle of 90 ° and the peel force was measured. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a transparent film (1) and a polyvinyl alcohol-type polarizer and a transparent film (2) was measured.
This peeling force was evaluated as an adhesive force in four stages. If it is evaluated as ○, ○, or Δ, it is practically satisfactory.
A: Cannot be peeled off or the polarizing plate is broken (very good)
○: Peeling force is 2.0 (N / 25 mm) or more (good)
Δ: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (can be used)
X: Peeling force is less than 1.0 (N / 25 mm) (unusable)

《Moisture and heat resistance》
The laminate was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 85 ° C.-85% RH, and then the peel strength was measured according to JIS K6 854-4 in the same manner as the above adhesive strength. .
A: Peeling force is 2.0 (N / 25 mm) or more (very good)
○: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (can be used)
X: Peeling force is less than 0.5 (N / 25mm) (unusable)

"Heat-resistant"
The laminate was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 100 ° C.-dry, and then the peel strength was measured according to JIS K6 854-4 in the same manner as the above adhesive strength. .
A: Peeling force is 2.0 (N / 25 mm) or more (very good)
○: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (can be used)
X: Peeling force is less than 0.5 (N / 25mm) (unusable)

[Examples 2-13, 15-33, Comparative Examples 1-9]
In the same manner as in Example 1, each raw material was added to a light-shielded glass bottle with a capacity of 300 mL with the composition shown in Tables 4 and 5 and sufficiently stirred and degassed to obtain an active energy ray-curable resin composition.
Using the obtained active energy ray-curable resin composition, a coating sheet A and a laminate B were prepared, and the adhesion strength, adhesive strength, moist heat resistance, and heat resistance were evaluated and shown in Tables 4 and 5.

Examples 1-33 using the active energy ray polymerizable resin composition of the present invention were excellent in adhesion, adhesiveness, moist heat resistance, and heat resistance. This is because the compound (A) is contained, so that the amount of alcohol generated leading to a decrease in physical properties is small, and the compound (A) partially functions as a polyfunctional monomer and crosslinks with the compound (B). This is because a resin layer having excellent cohesive force was formed.
On the other hand, since the comparative example 1 of radical reactivity has many alcohol which remains as an unreacted substance, the physical property fell. Further, in Comparative Examples 2 to 9 having cationic reactivity, the generated alcohol worked as a chain transfer agent for cationic polymerization, and the physical properties were greatly lowered because the molecular weight of the resin layer formed by crosslinking was low.

Claims (8)

A compound (A) obtained by subjecting a silane coupling agent (a1) and a polymerizable functional group-containing compound (a2) having a hydroxyl group to a substitution reaction, and a polymerizable functional group-containing compound (B),
The silane coupling agent (a1) has an alkoxysilyl group and other functional groups,
The active energy ray-polymerizable resin composition, wherein the other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group.   The active energy ray polymerizable resin composition according to claim 1, wherein the polymerizable functional group of the compound (A) is a radical polymerizable group or a cationic polymerizable group.   Of the total 100% by weight of the compound (A) and the polymerizable functional group-containing compound (B), the compound (A) is 0.5 to 95% by weight, and the polymerizable functional group-containing compound (B) is The active energy ray polymerizable resin composition according to claim 1 or 2, comprising 5 to 99.5% by weight. A step of subjecting the silane coupling agent (a1) and the polymerizable functional group-containing compound (a2) having a hydroxyl group to substitution reaction to synthesize the compound (A), and further mixing the polymerizable functional group-containing compound (B). Have
The silane coupling agent (a1) has an alkoxysilyl group and other functional groups,
The method for producing an active energy ray polymerizable resin composition, wherein the other functional group is a functional group selected from the group consisting of a vinyl group, an epoxy group, a (meth) acryloyl group, a mercapto group, and an amino group.   The adhesive agent containing the active energy ray polymeric resin composition of any one of Claims 1-3.   The coating agent containing the active energy ray polymeric resin composition of any one of Claims 1-3.   The coating sheet provided with the resin layer formed from the active energy ray polymeric resin composition of any one of Claims 1-3, and a base material.   The laminated body provided with the 1st base material, the resin layer formed from the active energy ray polymeric resin composition of any one of Claims 1-3, and the 2nd base material.