JP6828281B2 - Active energy ray-polymerizable resin composition - Google Patents

Description

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

Since the active energy ray-polymerizable resin composition has a high polymerization rate and can be generally used without a solvent, it has excellent workability and excellent properties such as extremely low energy required for polymerization. As the active energy ray-polymerizable resin composition, a radical-polymerizable active energy ray-polymerizable resin composition and a cationically polymerizable active energy ray-polymerizable resin composition are generally known, and an adhesive or a coat is known. It is used in a wide range of fields such as agents.

In recent years, the development and generalization of information and communication devices including display devices such as displays have been remarkable. In these display devices, further improvement in performance and productivity of coating agents, adhesives, sealing agents, etc. are required, and various proposals using active energy ray-polymerizable resin compositions have been made. There is. Such a display device usually includes various films depending on the application, such as an antireflection film for preventing reflection from an external light source and a protective film (protective film) for preventing scratches on the surface of the display device. Is used. For example, in a liquid crystal cell member constituting a liquid crystal display (LCD), a polarizing plate and a retardation film are laminated.

Further, the flat panel display (FPD) is not only used as a display device, but may also be used as an input device by providing a touch panel function on its surface. A protective film, an antireflection film, an ITO vapor-deposited resin film, and the like are also used for the touch panel.

Further, a backlight method in which a liquid crystal layer is illuminated from the back surface to emit light is widely used in a display device, and a backlight unit such as an edge light type or a direct type is provided on the lower surface side of the liquid crystal layer. The edge light type backlight unit is basically a linear lamp as a light source, a square plate-shaped light guide plate arranged along the end of the lamp, and arranged on the surface side of the light guide plate. It is provided with a light diffusing sheet to be formed and a prism sheet arranged on the surface side of the light diffusing sheet. Recently, as a light source, a light emitting diode (LED) having excellent color reproducibility and power saving has been used instead of a cold electrode tube (CCFL), so that the demand for heat resistance and dimensional stability is increasing. It's coming.

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

To give 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-based polarizer is produced. The polarization performance tends to deteriorate due to shrinkage due to heat and moisture. Therefore, a laminate in which a protective film is bonded to the surface of a PVA-based polarizing element is used as a polarizing plate. As the adhesive used for this bonding, an aqueous solution of a polyvinyl alcohol-based resin (PVA-based aqueous adhesive) has been widely used. However, where the water-based adhesive requires a drying step after coating, the PVA-based polarizer has low heat resistance and requires long-term drying at a low temperature, resulting in poor production efficiency. Therefore, in order to improve production efficiency, a cationic active energy ray-polymerizable adhesive using ultraviolet rays as an active energy ray is being studied instead of the water-based adhesive.

By the way, as the use of a liquid crystal display device expands, it has come to be used in various environments, and the polarizing plate constituting the liquid crystal display device is required to have high heat resistance. For example, an in-vehicle liquid crystal display device such as a car navigation system is exposed to a harsh high temperature atmosphere in summer unlike an LCD TV, and therefore requires a high degree of durability (high temperature durability). Specifically, if the adhesiveness is weak in a high temperature environment, there is a problem that the PVA-based polarizer and the protective film are peeled off due to the difference in the heat shrinkage between the PVA-based 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-acryloylmorpholin, and the Tg of the adhesive layer after curing is 60 ° C. or higher. The active energy ray-polymerizable adhesive is disclosed.

Further, 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 a dealcohol reaction of poly (tetraalkoxysilane).

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

However, the conventional polarizing plate using an adhesive containing a resin composition cannot satisfy the durability in a harsher environment such as in-vehicle use.

An object of the present invention is to provide an active energy ray-polymerizable resin composition that has excellent adhesiveness and can be used as an adhesive or a coating agent capable of forming a laminate having excellent high-temperature durability.

The active energy ray-polymerizable resin composition of the present invention comprises 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. Contains 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 described above, the inclusion of the compound (A) having an alkoxysilyl group having a polymerizable functional group enables the formation of crosslinks with the base material and the resin layer, and also inhibits the polymerization reaction. By suppressing the amount of alcohol generated, the cohesive force of the resin layer formed by curing (crosslinking) could be improved. As a result, in addition to adhesiveness (adhesiveness), the effects of excellent durability such as moisture resistance and heat resistance were obtained.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an active energy ray-polymerizable resin composition which has excellent adhesiveness and can be used as an adhesive or a coating agent capable of forming a laminate having excellent high temperature durability.

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, the "active energy ray" provides energy required for activation for causing a chemical reaction, including ultraviolet rays, rays such as visible rays, heat rays such as infrared rays, electron beams (EB), and radiation. It means an energy ray in a broad sense that can be done. In the active energy ray-polymerizable resin composition of the present invention (hereinafter, also referred to as "resin composition"), the polymerization reaction proceeds by irradiation with the above-mentioned active energy rays to form a cured product (also referred to as a resin layer). The activation 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 substituting a silane coupling agent (a1) with a polymerizable functional group-containing compound (a2) having a hydroxyl group (hereinafter, also referred to as compound (a2)). .. Since the compound (A) has an alkoxysilyl group having a polymerizable functional group, it is incorporated into the crosslinked network formed by the polymerizable functional group-containing compound (B) by irradiation with active energy, so that the cohesiveness is improved. Further, 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 the 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 groups are free of hydrolyzable groups in terms of heat resistance.

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

An example is a silane coupling agent (a1). In the present invention, the terms "epoxy", "oxylane", and "ethylene oxide" mean cyclic ethers having a three-membered ring structure unless otherwise specified. The three-membered ring ether adjacent to the cyclo ring is also used as an epoxy group. In addition, when it is described as "glycidyl", it means "oxylanmethyl".
Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane and the like.
Silane coupling agents having an epoxy group include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxy. Examples thereof include silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, and 5,6-epoxyhexyltriethoxysilane.
Silane coupling agents having a (meth) acryloyl group include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, Examples thereof 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-aminopropyltri. Examples thereof include methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.

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

An example is a compound (a2-1) having a hydroxyl group and a cationically polymerizable functional group. Oxylan-containing compounds having a hydroxyl group include, for example, allyl alcohol oxide, 3-butene-1-oloxide, 2-butene-1-oloxide, 2-methyl-2-propen-1-oloxide, 1-methyl-2-. Propen-1-oloxide, 4-pentene-1-oloxide, 3-pentene-1-oloxide, 2-penten-1-oloxide, 3-methyl-3-butene-1-oloxide, 3-methyl -2-Butene-1-oloxide, 2-methyl-2-butene-1-oloxide, 1,1-dimethyl-2-propen-1-oloxide, 1,2-dimethyl-2-propen-1- Allyl oxide, 5-hexene-1-oloxide, 6-heptene-1-oloxide, 7-octen-1-oloxide, 1-octen-3-oloxide, 2-methyl-6-hepten-2-ol Oxide, 9-decene-1-oloxide, 2,7-octadien-1-oldioxide, 7-octene-1,2-diol oxide, 1,7-octadien-3-oldioxide, 2-methyl- 3-Butene-2-oloxide, linalol oxide, 1,2-dehydrolinalol oxide, geranioldioxide, nerrol dioxide, labandurol oxide, citronellol oxide, 1,2-dihydrolinalol oxide, dehydronerolidol dioxide , Nerolidel trioxide, farnesol trioxide, bisavorol dioxide, geranilinalol tetraoxide, geranyl geraniol tetraoxide, isofitol oxide, phytol epoxide, polyglycerol polyglycidyl ether, glycerol diglycidyl ether, glycerol monoglycidyl ether, Examples thereof include aliphatic compounds such as trimethylolpropane diglycidyl ether and trimethylolpropane monoglycidyl ether.

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

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 and the like.

Vinyl ethers having a hydroxyl group include, for example, 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 thereof include glycol monovinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, and alkylene oxide-added vinyl ether having a hydroxyl group at the terminal to which alkylene oxide such as ethylene oxide and propylene oxide is repeatedly added.
The compound (a2-1) may be used alone or in combination of two or more.

Among these, the compound (a2-1) is preferably an oxylane having good cationically polymerizable property and a compound containing an oxetanyl group. Further, 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- Ethyl-3-hydroxymethyloxetane is more preferred.

An example is a compound (a2-2) having a hydroxyl group and a radically polymerizable functional group. In the present invention, when referred to as "(meth) acryloyl", "(meth) acrylic acid", "(meth) acrylate", "(meth) acryloyloxy", and "(meth) allyl", Unless otherwise stated, "acryloyl and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", "acryloyloxy and / or methacryloyloxy", and "allyl and / or", respectively. It shall represent "methacrylic".

The compound (a2-2) is, 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, mono (meth) acrylic acid ester of cyclohexanedimethanol, 12-hydroxylauryl (meth) acrylate, ethyl-α- (meth) acrylate. Monofunctional (meth) glycerol such as (hydroxymethyl) glycerol;
Fatty acid ester-based (meth) acrylic acid ester such as (meth) glycidyl lauric acid ester;
A (meth) acrylic acid ester in which a hydroxyl group is added to the molecular terminal by ring-opening addition of ε-caprolactone to compound (a2-2);
Aliphatic (meth) acrylic acid esters such as alkylene oxide-added (meth) acrylic acid esters in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to compound (a2-2);

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

(Meta) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether;
Aliphatic (meth) allyl alcohols such as alkylene oxide-added (meth) allyl ethers having a hydroxyl group at the terminal to which alkylene oxides such as ethylene oxide and propylene oxide are repeatedly added, and their (meth) allyl ethers;

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

(Meta) acrylamide 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.
The compound (a2-2) may be used alone or in combination of two or more.

Among these, the compound (a2-2) is composed of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, from the viewpoint of adhesion to the substrate. Cyclohexanedimethanol mono (meth) acrylic acid ester, ε-caprolactone 1-2 mol-added (meth) acrylate 2-hydroxyethyl, etc. α, β-ethylenically unsaturated double-bond group-containing compound having 2 to 18 carbon atoms Is preferable.

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 from 1 to 3, and R ¹ 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 an organic residue having, 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 the by-produced methanol. Demethanol reduces the reversible reaction, and compound (A) can be stably obtained. Further, the number of substitutions of the polymerizable functional group-containing organic residue contained in the compound (A) can be adjusted by adjusting the amount of demethanol. Further, in the reaction, it is also possible to adjust the number of substitutions of the polymerizable functional group-containing organic residue contained in the compound (A) by adjusting the ratio of the compound (a1) and the compound (a2). For example, when the compound (a2) is reacted with the compound (a1) at a molar ratio of 2 times, the compound (A) having 2 substitutions of the polymerizable functional group-containing organic residue can be obtained.

The reaction conditions for obtaining the compound (A) are preferably, for example, heating at 30 ° C. to 250 ° C. for 10 minutes to 10 hours. Further, the de-alcohol reaction may be carried out in a reduced pressure atmosphere. Further, if necessary, an acid, a basic substance, or a metal compound such as 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 also be used in combination with the compound (a2-1) and the compound (a2-2).
In addition, compound (A) may have other reactive functional groups.

Compound (A) has one or more alkoxysilyl groups having a polymerizable functional group. It is stably present as an alkoxysilyl group in a closed container. For example, after coating on a base material, it reacts with water in the air or in the base material, and is a cationically polymerizable functional group-containing organic residue and 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 base material and irradiating it with active energy rays is a silanol group generated by hydrolysis of the alkoxysilyl group of the compound (A). Formes chemical bonds such as covalent bonds and hydrogen bonds with the surface functional groups (for example, hydroxyl groups, carbonyl groups, etc.) of the base material, so that the adhesion is improved. Further, since the polymerizable functional group of the compound (A) reacts with the compound (B) and the alkoxysilyl group is easily incorporated into the crosslinked structure, the base material and the resin layer are very excellent because they are firmly bonded to each other. Adhesion (excellent adhesion) can be obtained. Further, as compared with the case where the compound (a1) which is a silane coupling agent is used as it is, the compound (A) generates less alcohol having no polymerizable functional group during hydrolysis, and the cured product (resin layer). The residual unreacted compound is reduced inside, and the cohesive force of the resin layer is strengthened, 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 cationically polymerizable group as the polymerizable functional group. The radically polymerizable group is preferably a (meth) acryloyl group or a vinyl group. The cationically polymerizable group is preferably a cyclic compound having two or more oxygens or a heterogroup other than oxygen, such as an epoxy group, an epoxycyclohexyl group, an oxetanyl group, a vinyl ether group. Further, the compound (B) contains the polymerizable functional group-containing compound (a2) having a hydroxyl group as described above.

The compound (B) having a cationically polymerizable group is exemplified.
The epoxy group-containing compound is also called an oxylan compound, and includes an aliphatic oxylan compound and an aromatic oxylan compound.

Aliphatic oxylan compounds include, for example, oxylan, methyloxylan, phenyloxylan, 1,2-diphenyloxylan, acetonitrile oxylan, oxylanylmethyl, oxylanylmethanol, oxylancarboxylic acid, (chloromethyl) oxylan, (bromomethyl) oxylan. , And oxylanyl acetonitrile and the like.

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

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

Examples of the epoxycyclohexyl group-containing compound include 3,4-oxylancyclohexylmethyl, 3,4-oxylancyclohexanecarboxylate, 3,4-oxylan-6-methylcyclohexylmethyl 3,4-oxylan-6-methylcyclohexanecarboxylate, and ethylene. Bis (3,4-oxylancyclohexanecarboxylate), bis (3,4-oxylancyclohexylmethyl) adipate, bis (3,4-oxylan-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxylancyclohexylmethyl) Ether), dicyclopentadiendioxide and the like.

Oxetanyl group-containing compounds include, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3-oxetanyl) methyl ether, etc. 3-Ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, and 3-ethyl-{(3-triethoxysilylpropoxy) methyl} oxetane, etc. Can be mentioned.

As the compound having two or more oxygen or a heterocycle other than oxygen, a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, a fluorine-containing cyclic compound and the like are preferable. The cyclic ester compound is preferably lactone. Further, as the cyclic formal compound, dioxolane, dioxane, trioxane and the like are more preferable. Further, the cyclic carbonate can be synthesized, for example, by a method of depolymerizing a polymer obtained by a reaction of glycol and a dialkyl carbonate (see JP-A-2-563356), or by a reaction of a corresponding alkylene oxide with carbon dioxide. .. The cyclic carbonate preferably has a structure of 5 membered ring, 6 membered ring or 7 membered ring or more.
Examples of the 5-membered ring formal compound include 1,3-dioxolane and the like.
Examples of the 6-membered ring formal compound include 1,3-dioxane and the like.
The 7-membered ring formal compound is contained in 1,3-dioxepan, but is independently classified as a cyclic carbonate because the carbon at the 2-position is a carbonyl carbon.

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

Trimethylene carbonate (1,3-dioxane-2-one), 4-methyl-1,3-dioxane-2-one, 2,2-dimethoxypropane-1,3-diyl carbonate, 5-methyl-1,3- Dioxane-2-one, 5,5-dimethyl-1,3-dioxane-2-one (neopentyl glycol carbonate), 5-methyl-5-propyl-1,3-dioxane-2-one, 5-hydroxymethyl -5-Methyl-1,3-dioxane-2-one, 4-phenyl-1,3-dioxane-2-one, 5- (hydroxymethyl) -5-ethyl-1,3-dioxane-2-one, 4-Methylene-1,3-dioxane-2-one, 5,5-dimethyl-4-vinyl-1,3-dioxane-2-one, 5-cyano-5-methyl-1,3-dioxane-2-one On, 6-membered ring carbonates such as 5- (2-oxo-1,3-dioxolan-4-ylmethoxy) -5-ethyl-1,3-dioxane-2-one;

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, 7-membered ring carbonates such as 3-dioxepan-2-one, 5,5'-(ethylenebisthiobistrimethylene) bis (1,3-dioxepan-2-one) can be mentioned.
Among these, 5-membered ring carbonates such as ethylene carbonate, propylene carbonate, and glycerin carbonate are preferable because they have good reactivity with active energy rays.

Vinyl ether group-containing compounds include, for example, 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, and the like. 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. Be done.
The compound (B) having a cationically polymerizable group can be used alone or in combination of two or more.

The compound (B) having a cationically polymerizable group is composed of 3,4-oxylancyclohexanecarboxylate, bis (3,4-oxylancyclohexylmethyl) adipate, glycidyl ether of bisphenol A, and bisphenol F from the viewpoint of excellent cationic polymerizable. Glycidyl ether is preferred.

The compound (B) having a radically polymerizable group is exemplified.
Examples of the compound (B) having a (meth) acryloyl group include the polymerizable functional group-containing compound (a2) having a hydroxyl group as described above. Among the compounds (a2), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono from the viewpoint of adhesion to the substrate. Examples thereof include (meth) acrylic acid ester and 2-hydroxyethyl (meth) acrylate having 1-2 mol of ε-caprolactone.

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, tricyclodecanedimethanol (meth) acrylate, isovonyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2 -Adamanthyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyl Didioldi (meth) acrylate, 1,3,5-adaman tiltli (meth) acrylate, 3-hydroxy-1,5-adamantyl di (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, isocyanul Acid ethylene oxide modified di and triacrylate;

(Meta) acrylate compounds that do not have a cyclic structure, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylate. (Meta) acrylic acid alkyl esters such as stearyl;
(Meta) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 3-chlor 2-propenyl, (meth) acrylic acid 2-propenyl lactyl, (meth) acrylic acid 3,7 Others such as -dimethylocta-6-ene-1-yl, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, and vinyl (meth) acrylate. (Meta) acrylic acid ester containing unsaturated groups;
Perfluoroalkyl esters of (meth) acrylates such as perfluoromethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) acrylate;
Methyl (methoxycarbonyl) (meth) acrylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, and 2- (octyloxy) (meth) acrylate. An aliphatic (meth) acrylic acid ester having one carbonyl group such as carbonyloxy) butyl;
2-oxobutanoylethyl (meth) acrylate, 3-oxobutanoylpropyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, 2,3-di (meth) acrylate An aliphatic (meth) acrylic acid ester having two carbonyl groups such as di (oxobutanoyl) hexyl and (meth) acrylic acid 2,3-di (oxobutanoyl) octyl;
Alkylate (meth) acrylate containing sulfonyl groups such as 3-sulfopropyl (meth) acrylate and sulfostearyl (meth) acrylate;
A metal salt of a (meth) acrylic acid ester containing a sulfonyl group such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, or an ammonium salt thereof;
Phosphonic acid group-containing (meth) acrylic acid esters such as (meth) acrylate acid phosphooxyethyl and (meth) acrylate acid phosphooxyethylene oxide (number of moles added with ethylene oxide: 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 esters such as 3-butoxyethyl (meth) acrylate and 4-butoxyethyl (meth) acrylate;
An alkylene oxide-containing (meth) acrylic acid derivative such as an alkylene oxide adduct of (meth) acrylic acid;
Di (meth) acrylate ethylene glycol, di (meth) acrylate triethylene glycol, di (meth) acrylate tetraethylene glycol, di (meth) acrylate 2,2-dimethylpropyldiol, di (meth) acrylate hydroxy Pivalyl hydroxypivalate, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 2,2-diethyl-1,3-propanediol , And bifunctional (meth) acrylic acid esters such as di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol;
Tri (meth) acrylate 1,2,3-propanetriol, tri (meth) acrylate trimethylolhexane, trimethylolpropane tri (meth) acrylate, and tri (meth) acrylate 1,1,1-trishydroxy Trifunctional (meth) acrylic acid ester such as methylethane;
Pentaerythritol tetra (meth) acrylate, 2,2-bis (hydroxymethyl) 1,3-propanediol tetra (meth) acrylate, and di22-bis (hydroxymethyl) 1,2-bis (hydroxymethyl) hepta (meth) acrylate 1, Polyfunctional (meth) acrylic acid ester such as 3-propanediol polyalkylene oxide;
Examples thereof include (meth) acrylonitrile, itaconic nitrile, and 2-cyanoethyl (meth) acrylate.

Further, the (meth) acrylate compound may be an oligomer other than the above-mentioned monomer. As the oligomer, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and the like are preferable.

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, an aromatic epoxy hydrogenated product, an aromatic epoxy compound, an alicyclic epoxy compound or the like. Can be 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.

Vinyl compounds having a cyclic structure include, for example, 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) Examples thereof include 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 monooxylane;
Vinyl esters such as vinyl chloride, vinylidene chloride, and allyl chloride;
(E) -Vitadiene-Vitadiene, (Z) -Octadeca-9-Vinyl Enate, and (9Z, 12Z, 15Z) -Octadeca-9,12,15-Vinyl Trienoate, Allenes, 1,2 Dienes such as -butadiene, 1,3-butadiene, and 2-methyl-1,3-butadiene;
Examples thereof include ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-tetradecene, 1-triacontene, 1-octatriacontene, 1-tetracontene and the like.

Allyl compounds are (meth) allyl esters of saturated carboxylic acids such as acetic acid (meth) allyl, propionic acid (meth) allyl, and vinyl pivalate;
Metallic salts of 2-methyl-2-propenyl sulfonic acid such as ammonium 2-methyl-2-propenyl sulfonate and sodium 2-methyl-2-propenyl sulfonate, or ammonium salts thereof; acetoacetic acid (meth) allyl, aceto An aliphatic (meth) allyl compound having an acyl group such as propionic acid (meth) allyl, propanoylacetic acid (meth) allyl, and butyrylacetic acid (meth) allyl; cis-diallyl succinate, 2-allyl dimethyldensuccinate, 2-propen. Examples include nitrile.

Among these, the compound (B) having a radically polymerizable group is preferably a (meth) acrylate compound from the viewpoint of reactivity, and the resin composition of the present invention is coated with an active energy ray-polymerizable adhesive or an active energy ray-polymerizable coat. When used as an agent, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) from the viewpoint of adhesion to the substrate. Meta) Acrylic acid ester is preferable.
Further, the compound (B) having a radically polymerizable group preferably contains a bifunctional or higher functional (meth) acrylic acid ester from the viewpoint of improving adhesive strength, heat resistance and moisture heat resistance. Specifically, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A diacrylate, hydrogenated biphenol A diacrylate, Dimethylol dicyclopentane di (meth) acrylates, isocyanurate ethylene oxide modified di and triacrylates 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 a total of 100% by weight of the compound (A) and the compound (A). B) is preferably contained in an amount of 5 to 99.5% by weight, more preferably compound (A) in an amount of 1 to 70% by weight, and compound (B) in an amount of 30 to 99% by weight. It is more preferable to contain 2 to 50% by weight and 50 to 98% by weight of compound (B). When the content of the compound (A) is more than 0.5%, the adhesiveness is improved by the chemical bond between the compound (A) and the base material and the compound (B). If it is less than 95% by weight, the viscosity becomes low and the coating suitability is excellent.

When the resin composition of the present invention contains a compound having a cationically polymerizable functional group, it preferably contains a photocationic polymerization initiator. Known compounds can be used as the photocationic polymerization initiator. Examples of commercially available products include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), Rp-2074. Examples include iodonium salts (manufactured by Rhodia Japan).

The photocationic polymerization 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.

When the resin composition of the present invention contains a compound having a radically polymerizable functional group, it preferably contains a photoradical polymerization initiator. Known compounds can be used as the photoradical polymerization initiator. Examples of commercially available products include Irgacure-184,907,651,1700,1800,819,369,261, DAROCUR-TPO (manufactured by Ciba Specialty Chemicals), DaroCure-1173 (manufactured by Merck), and Ezacure. Examples thereof include KIP150, TZT (manufactured by Nippon Kayaku), Kayacure BMS, Kayacure DMBI, (manufactured by Nippon Kayaku) and the like.

The photoradical polymerization 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 further comprises a photosensitizer, an amine-based catalyst, a phosphorus-based catalyst, a filler, an antistatic agent, an antioxidant, an antioxidant, a tackifier, and the like. It can contain an antiblocking agent, an antifoaming agent, a plasticizer, a silane coupling agent, a titanium coupling agent and the like.

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

In the production of the active energy ray-polymerizable resin composition of the present invention, as described above, the silane coupling agent (a1) and the polymerizable functional group-containing compound (a2) having a hydroxyl group are subjected to a substitution reaction to carry out the compound (A). ), And further mixed with 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 base material, and then irradiated with active energy rays to polymerize (cure) to form a resin layer (also called an adhesive layer or a coating film depending on the application). It is preferable to do so.

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

A known coating device can be used for coating. For example, minor coater, appliquer, brush, sprayer, roller, gravure coater, die coater, microgravure coater, lip coater, comma coater, Examples thereof include a carten coater, a knife coater, a river coater, and a spin coater.

The active energy ray used for curing preferably has a wavelength containing ultraviolet rays that the photocationic polymerization initiator can usually react with, 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 excited 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 of an active energy ray-curable resin composition, and can be used as an optical film for information and communication devices such as displays and touch panels. preferable.

The laminate of the present invention includes a resin layer formed from an adhesive containing an active energy ray-polymerizable resin composition, and a base material. Since it is a laminate, the base material usually includes at least a first base material and a second base material.

The active energy ray polymerization reaction of the adhesive proceeds by irradiating the active energy ray at the time of coating, laminating, or further laminating the resin composition, and irradiating the active energy ray after laminating the base material. It is preferable to proceed with the polymerization reaction. At this time, the base material needs to be made of a material that easily transmits the active energy rays in order to allow the polymerization reaction to proceed by irradiation with the active energy rays.
The base material is preferably a transparent film or a transparent glass plate. For example, if a transparent film or a transparent glass plate is used as the first base material, a base material that is difficult for active energy rays to pass through is used as the second base material, for example, wood, metal plate, plastic plate, processed paper product, etc. You may.
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 base material as the base material. The film-like substrate is
For example, cellophane, various plastic films, paper and the like can be mentioned. Of these, the use of various transparent plastic films is preferable. Further, the film-like base material may have a single layer or a multi-layer structure in which a plurality of base materials 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 of the present invention includes a resin layer formed from an active energy ray-polymerizable resin composition and a base material.

When the active energy ray-polymerizable resin composition is used as a coating agent, the active energy ray polymerization reaction involves coating the resin composition on one side or both sides of the substrate and then irradiating the active energy rays to crosslink (curing). ) Progresses. 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 particular limitation.

Hereinafter, a more specific embodiment 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 constructed by using the resin composition of the present invention as an adhesive is a plurality of transparent films such as a transparent film / adhesive layer / transparent film or a transparent film / adhesive layer / transparent film / adhesive layer / transparent film. It is a sheet-like multilayer film obtained by laminating. Further, in another form, the laminate is a sheet-like multilayer film such as a transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, and another optical member such as glass or an optical sheet. A structure bonded to is also preferable. The above-mentioned laminate can be obtained by curing the adhesive layer by polymerizing and curing the general resin composition from one side or both sides of the film with active energy rays.

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

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

The thickness of the transparent film can be appropriately determined, but in general, it is preferably 1 to 500 μm, more preferably 1 to 300 μm, from the viewpoint of workability such as strength or handleability, and thin layer property. ~ 200 μm is more preferable. Further, when used for optical applications, the thickness of the transparent film is preferably 5 to 150 μm.

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 for optical applications as a transparent film.

Optical films include, for example, hard coat film, antistatic coat film, antiglare coat film, polarizing film, retardation film, elliptical polarizing film, antireflection film, light diffusing film, brightness improving film, prism film (prism film). Examples thereof include a decorative film (also referred to as a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like.

The polarizing film is also called a polarizing plate, and is a polytriacetyl cellulose-based protective film (hereinafter referred to as "TAC film"), which is two polyacetyl cellulose-based films on both sides of a polyvinyl alcohol-based polarizer, or a polyvinyl alcohol-based polarizing film. Lamination for sheet-like optical elements with a multi-layer structure in which one or both sides of the child are laminated via an adhesive such as a polycycloolefin film, a polyacrylic film, a polycarbonate film, or a polyester film, which are polynorbornene films. The body.

The resin composition of the present invention can be used as an adhesive to form a laminate such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module.

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

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

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

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

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

(III) The end of the protective film which is the first transparent film and the polyvinyl alcohol-based polarizer, and the end of the second protective film which is laminated on the surface of the polyvinyl alcohol-based polarizer where the first protective film is not provided. After applying the active energy ray-curable adhesive to the film, pass it between the rolls and spread the adhesive between the layers. Next, there is a method of producing by irradiating with active energy rays and polymerizing and curing the active energy ray-curable adhesive, but the present invention is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, "part" is "part by weight", and "%" represents "% by weight".

Production Example of [Polyvinyl Alcohol-based Polarizer] 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 parts by weight of potassium iodide were dissolved in 480 parts by weight of water to prepare a staining solution. A PVA film (Vinylon film # 40, manufactured by Aicello Corporation) 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 shows the abbreviations of the raw materials used in the synthetic examples and the comparative examples below.

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

[Synthesis Example 11]
350 parts of KBE-802 and 650 parts of OXT101 were placed in a four-necked flask equipped with a cooling tube, a fractional distillation tube, a stirrer, a thermometer, and a nitrogen introduction tube, and the reaction was started in a nitrogen atmosphere. The temperature was raised to 130 ° C. while demethanolizing, and the mixture was kept at normal pressure for 4 hours to obtain a brown transparent compound (A). Since the number of moles of the compound (a2) is smaller than that of the alkoxy group of the silane coupling agent, the theoretical dealcoholization amount when all the compound (a2) is substituted is 62, and the actual dealcoholization amount is 60 g. there were.

[Synthesis Examples 2-10, 12, 13, 15-17]
Compounds (A) of Synthesis Examples 2 to 10 and 12 to 17, respectively, 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 shown in Table 2. The theoretical dealcoholization amount of Synthesis Examples 2, 4, 6, 10, 13, 14 and 16 is the theoretical dealcoholization amount when all the alkoxy groups of compound (a1) are substituted. Further, since the theoretical dealcoholization amount of Synthesis Examples 1, 3, 5, 7 to 9, 11, 12, 15, and 17, the amount of substance of compound (a2) is smaller than that of the alkoxy group of compound (a1). This is the theoretical amount of alcohol dealcohol when all the compounds (a2) are replaced.

<Manufacturing of compound (A)'>
[Synthesis Example 14]
Compound (A)'of Synthesis Example 14 was 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 shown in Table 2.

Table 3 shows the abbreviations of the raw materials used in the examples below.

[Example 1]
To a light-shielded glass bottle having a capacity of 300 mL, add 45 parts of 2021P, 20 parts of EX-212L, 15 parts of OXT-101, 20 parts of compound (A) obtained in Synthesis Example 1, and 2 parts of CPI-110P. The mixture was sufficiently stirred and defoamed to obtain an active energy ray-curable resin composition.

<Manufacturing example of coating sheet A>
The following coating sheet A was prepared using the active energy ray-curable resin composition.
As the transparent film, a polyacetyl cellulose-based film (manufactured by Fuji Film Co., Ltd., trade name "Fujitac: 80 μm", polytriacetyl cellulose-based film containing an ultraviolet absorber) was used. After corona-treating the surface of the transparent film at a discharge rate of 300 W / min / m ² , the film thickness of the active energy ray-curable resin composition after coating with a wire bar coater is 2 μm. It was coated so as to form a laminate having a resin layer. The laminate was dried at 80 ° C. for 2 minutes to remove the solvent, and then the four sides of the laminate were fixed to the tin plate with cellophane tape so that the transparent film was in contact with the tin plate. After replacing the inside of the UV irradiation device (high-pressure mercury lamp manufactured by Toshiba) with dry nitrogen, the coating sheet A is prepared by irradiating ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light amount of 1000 mJ / cm ^{2 at} a wavelength of 365 nm from the resin layer side. did.

With respect to the obtained coating sheet A, the adhesion, moisture heat resistance, and heat resistance were determined according to the following methods, and the results are also shown in Table 4.
"Adhesion"
A grid peeling test was performed in accordance with JIS K5600-5-6: 1999. The number of peeled cells in 100 cells was evaluated on a 4-point scale.
(Evaluation criteria)
⊚: 0 squares (extremely good)
◯: 1 to 10 squares (good)
Δ: 11 to 30 squares (usable)
×: 31 squares or more (cannot be used)

《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 a grid peeling test is performed according to JIS K5600-5-6: 1999 in the same manner as the above-mentioned adhesion force. Was carried out. The number of peeled cells in 100 cells was evaluated on a 4-point scale.
(Evaluation criteria)
⊚: 0 to 10 squares (extremely good)
◯: 11 to 30 squares (good)
Δ: 31 to 60 squares (usable)
×: 61 squares or more (cannot be used)

"Heat-resistant"
The laminate is cut into a size of 50 mm × 40 mm, exposed for 1000 hours under the condition of 100 ° C.-dry, and then a grid peeling test is carried out according to JIS K5600-5-6: 1999 in the same manner as the above-mentioned adhesion force. did. The number of peeled cells in 100 cells was evaluated on a 4-point scale.
(Evaluation criteria)
⊚: 0 to 10 squares (extremely good)
◯: 11 to 30 squares (good)
Δ: 31 to 60 squares (usable)
×: 61 squares or more (cannot be used)

<Manufacturing example of laminate B>
As the transparent film (1), a polytriacetyl cellulose-based film containing an ultraviolet absorber manufactured by Fuji Film Co., Ltd .: trade name "Fujitac: 80 μm" (thickness 80 μm) is used, and as the transparent film (2), manufactured by Fuji Film Business Supply Co., Ltd. Polytriacetyl cellulose-based film containing no ultraviolet absorber: The trade name "TAC 50 μm" (thickness 50 μm) was used. One surface of the transparent films (1) and (2) is corona-treated with a discharge amount of 300 W · min / m ² , and within 1 hour thereafter, the active energy ray-curable composition is applied to the corona-treated surface of each film. A film was formed on the film by coating with a wire bar coater so as to have a thickness of 4 μm. After drying at 80 ° C. for 2 minutes to remove the solvent, a polyvinyl alcohol-based 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 a PVA-based polarizer / resin layer / transparent film (2) was obtained. The four sides of this laminated body were fixed with cellophane tape so that the transparent film (1) was in contact with the tin plate, and fixed to the tin plate.

A laminated body B (polarizing plate) was prepared by irradiating ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light intensity 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). ..

The adhesive strength, moisture heat resistance, and heat resistance of the obtained laminate B were determined according to the following methods, and the results are similarly shown in Table 4.

《Adhesive strength》
Adhesive strength was measured according to JIS K6 854-4 Adhesive-Peeling Adhesive 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 prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyokem Co., Ltd.) is attached to one side of the sample and adhered onto a metal plate using a laminator to form a laminate for measurement of the polarizing plate and the metal plate. Obtained. The laminating body for measurement is provided with a peeling kick in advance between the transparent film and the polarizer, and the laminating body for measurement is placed at a speed of 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. The peeling force was measured by peeling at an angle of 90 °. At this time, the peeling forces of both the polyvinyl alcohol-based polarizer and the transparent film (1) and the polyvinyl alcohol-based polarizer and the transparent film (2) were measured.
This peeling force was evaluated as an adhesive force on a 4-point scale. If the evaluation is ◎, ○, △, there is no problem in practical use.
⊚: Peelable or polarizing plate broken (extremely 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) (usable)
X: Peeling force is less than 1.0 (N / 25 mm) (cannot be used)

《Moisture and heat resistance》
The laminate was cut into a size of 50 mm × 40 mm, exposed for 1000 hours under the condition of 85 ° C.-85% RH, and then the peeling force was measured according to JIS K6 854-4 in the same manner as the above adhesive force. ..
⊚: Peeling force is 2.0 (N / 25 mm) or more (extremely 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) (usable)
X: Peeling force is less than 0.5 (N / 25 mm) (cannot be used)

"Heat-resistant"
The laminate was cut into a size of 50 mm × 40 mm, exposed for 1000 hours under the condition of 100 ° C.-dry, and then the peeling force was measured according to JIS K6 854-4 in the same manner as the above adhesive force. ..
⊚: Peeling force is 2.0 (N / 25 mm) or more (extremely 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) (usable)
X: Peeling force is less than 0.5 (N / 25 mm) (cannot be used)

[Examples 2 to 13, 15 to 33, Comparative Examples 1 to 9]
Each raw material was added to a light-shielded glass bottle having a capacity of 300 mL in the same manner as in Example 1 with the compositions shown in Tables 4 and 5, and the mixture was sufficiently stirred and defoamed to obtain an active energy ray-curable resin composition.
After preparing the coating sheet A and the laminate B using the obtained active energy ray-curable resin composition, the adhesion, adhesive force, moisture heat resistance, and heat resistance were evaluated and shown in Tables 4 and 5.
However, Examples 1, 3 to 6, 8, 11, 15 to 16 are reference examples.

Examples 1 to 33 using the active energy ray-polymerizable resin composition of the present invention were excellent in adhesion, adhesiveness, moisture heat resistance, and heat resistance. The reason for this is that since compound (A) is contained, the amount of alcohol generated that leads to deterioration of physical properties is small, and part of compound (A) functions as a polyfunctional monomer and is crosslinked with compound (B). This is because a resin layer having excellent cohesive force could be formed.
On the other hand, in Comparative Example 1 of radical reactivity, the physical properties were deteriorated because a large amount of alcohol remained as an unreactant. Further, in Comparative Examples 2 to 9 of cationic reactivity, the generated alcohol acted as a chain transfer agent for cationic polymerization, and the molecular weight of the resin layer formed by cross-linking was low, so that the physical properties were significantly deteriorated.

Claims (4)

A step of substituting the silane coupling agent (a1) with the polymerizable functional group-containing compound (a2) having a hydroxyl group to synthesize the compound (A), and further mixing the polymerizable functional group-containing compound (B). Have and
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 polymerizable functional group-containing compound (B) has a radically polymerizable group.
A method for producing an active energy ray-polymerizable resin composition. The method for producing an active energy ray-polymerizable resin composition according to claim 1, wherein the polymerizable functional group of the polymerizable functional group-containing compound (a2) having a hydroxyl group is a radically polymerizable group or a cationically polymerizable group. Of the total 100% by weight of the compound (A) and the polymerizable functional group-containing compound (B), 0.5 to 95% by weight of the compound (A) and the polymerizable functional group-containing compound (B). The method for producing an active energy ray-polymerizable resin composition according to claim 1 or 2, which comprises 5 to 99.5% by weight. A step of substituting the silane coupling agent (a1) with the polymerizable functional group-containing compound (a2) having a hydroxyl group to synthesize the compound (A), and further mixing the polymerizable functional group-containing compound (B). Have and
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 polymerizable functional group-containing compound (B) has a radically polymerizable group.
Manufactures an active energy ray-polymerizable resin composition,
A method for producing a coating sheet, wherein a resin layer is formed by coating the active energy ray-polymerizable resin composition on a base material.