JP6992244B2 - Laminates for active energy ray-polymerizable compositions, sheets and optics - Google Patents

Description

The present invention relates to an active energy ray-polymerizable composition.

The active energy ray polymerization composition has various properties such as its fast polymerization rate, good workability due to being generally solvent-free, and energy saving of an extremely low energy requirement, and in recent years, due to environmental pollution problems, environmental pollution has occurred. Since it has the advantage of being able to reduce energy, its application fields are expanding in fields such as building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, and displays.

The active energy ray-polymerized composition contains an active energy ray-polymerizable resin and the like, an α, β-ethylenically unsaturated double bond group-containing monomer and the like, and the monomer also functions as a solvent. There is an advantage that the solvent does not volatilize when forming the film. The active energy ray-polymerizable resin is an oligomer having an α, β-ethylenic unsaturated double bond group at the molecular end of a low molecular weight polyester resin, a polyurethane resin, a polyepoxy resin, a polyacrylic resin, or the like. It is produced by bonding a monomer having an α, β-ethylenic unsaturated double bond group or the like.

In recent years, the sophistication and generalization of information and communication equipment including displays has been remarkable, and at the same time, the coating agents, adhesives, sealing agents, etc. used in information and communication equipment have further improved performance and productivity. Is required. Display devices such as liquid crystal displays (FPDs) used in information and communication equipment usually have an antireflection film to prevent reflection from an external light source and protection to prevent scratches on the surface of the display device. Various films such as films (protective films) are used depending on the intended use. For example, a polarizing plate and a retardation film are laminated on a liquid crystal cell member constituting a liquid crystal display (LCD).

Further, the LCD is not only used as a display device, but may also be used as an input device by providing a touch panel function on the surface thereof. Protective films, antireflection films, ITO vapor deposition resin films, and the like are also used for touch panels.

In addition, a backlight system that illuminates the liquid crystal layer from the back surface to emit light has become widespread in the LCD, and a backlight unit such as an edge light type or a direct type is equipped 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, light emitting diodes (LEDs) with excellent color reproducibility and power saving have been used as light sources from the cathode ray tubes (COFL), so that a high level of heat resistance and dimensional stability are required. ..

The films described so far are usually 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 composition is used as an adhesive. Often.

To give an example of an adhesive, a polarizing element used in a field related to liquid crystal display is usually produced by adsorbing iodine or a dye on polyvinyl alcohol (PVA) and stretching it uniaxially. This polyvinyl alcohol-based polarized light is produced. The child shrinks due to heat and moisture, causing a decrease in polarization performance. Therefore, a polarizing plate having a protective film attached to the surface of the PVA-based polarizing element is used. As an adhesive for attaching a protective film to a polarizing element, a water-based adhesive (PVA-based adhesive) made of a polyvinyl alcohol-based resin has been widely used (see Patent Documents 1 and 2). However, although the water-based adhesive requires a drying step after coating, the PVA-based polarizing element has low heat resistance, so that it needs to be dried at a low temperature for a long time, resulting in poor production efficiency. Therefore, instead of the water-based adhesive, Patent Document 3 discloses a cationically polymerizable ultraviolet curable adhesive.

However, since the cationically polymerizable UV-curable adhesive has a dark reaction after UV irradiation, when a long coated sheet is rolled up into a roll, there is a problem that the yield is lowered because it tends to have a curl during storage. there were. Further, the cationically polymerizable ultraviolet curable adhesive has a problem that quality control is difficult because it is easily affected by the humidity at the time of curing, the adhesive and the moisture in the film, and the cured state is liable to vary. Therefore, in order to realize a uniform curing state, it is necessary to strictly control the water content of the adhesive and the PVA-based polarizing element, not to mention the environmental humidity. On the other hand, the radically polymerizable ultraviolet curable adhesive is excellent in that such problems are relatively few, but generally has a large curing shrinkage and it is difficult to secure sufficient adhesiveness.

By the way, the use of LCDs is expanding, but for example, in an in-vehicle LCD such as a car navigation system, a polarizing plate is required to have high heat resistance and durability. In this case, if the adhesiveness is weak in a high temperature environment, there is a problem that the PVA-based polarizing element and the protective film are peeled off due to the difference in the heat shrinkage between the PVA-based polarizing element and the protective film. The polarizing plate using the above has insufficient durability in such a harsh environment.

Therefore, Patent Document 4 describes the adhesive as an active energy ray-curable adhesive containing a curable component of a compound having a (meth) acryloyl group containing N-hydroxyethylacrylamide and N-acryloylmorpholine. An adhesive having a glass transition temperature) Tg) of the agent layer of 60 ° C. or higher is disclosed.

Japanese Unexamined Patent Publication No. 09-258023 Japanese Unexamined Patent Publication No. 2005-208456 Japanese Unexamined Patent Publication No. 2008-23874 Japanese Unexamined Patent Publication No. 2008-287207

The durability required for the polarizing plate is becoming stricter year by year, and the adhesive of Patent Document 4 is insufficient in durability where durability under high temperature and high temperature and high humidity is required. In addition, since the adhesive has a large curing shrinkage, wrinkles and irregularities may occur on the polarizing plate, which causes a problem of insufficient dimensional stability.

An object of the present invention is to provide an active energy ray-polymerizable composition which has durability (heat resistance, moisture heat resistance) under high temperature and high humidity after curing and can be used for an adhesive application having good dimensional stability. And.

The active energy ray-polymerizable composition of the present invention contains an α, β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and water, and An active energy ray-polymerizable composition comprising the following (1) and (2).
(1) 0.01 water is added to 100 parts by weight of the active energy ray-reactive compound containing the α, β-ethylenically unsaturated double bond group-containing compound (A) and the active energy ray polymerization initiator (B). Contains up to 10 parts by weight.
(2) The active energy ray-polymerizable composition contains 0.05 to 20% by weight of the active energy ray polymerization initiator (B).

According to the above invention, when the active energy ray-curable polymerizable composition contains a predetermined amount of water, chain transfer during radical polymerization is suppressed, the growth reaction is improved, and the molecular weight of the cured product is increased, so that the cured product is cured. Aggregation power and degree of cross-linking increase. Furthermore, water tends to form hydrogen bonds with the substrate and the active energy ray-reactive composition. Due to these actions, when the polymerizable composition is used as an adhesive, for example, the effect of improving heat resistance, moisture heat resistance, and dimensional stability is obtained.

According to the present invention, the present invention provides an active energy ray-polymerizable composition which has durability (heat resistance, moisture heat resistance) under high temperature and high humidity after curing and can be used for adhesive applications having good dimensional stability. Can be provided.

The active energy ray-polymerizable composition of the present invention contains an α, β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and water, and An active energy ray-polymerizable composition comprising the following (1) and (2).
(1) Water is added to 100 parts by weight of the active energy ray-reactive composition containing the α, β-ethylenically unsaturated double bond group-containing compound (A) and the active energy ray polymerization initiator (B). Contains 01 to 10 parts by weight.
(2) The active energy ray-polymerizable composition contains 0.05 to 20% by weight of the active energy ray polymerization initiator (B).
The active energy ray-polymerizable composition is preferably used as an adhesive or a paint, and an adhesive is more preferable. When used as an adhesive, it is preferable to apply it to a base material and use it as a sheet (laminated body) that is bonded to another base material and cured.

The cationically polymerizable component in the present application refers to a compound containing substantially only a cationically polymerizable group such as epoxy, and contains both an α, β-ethylenically unsaturated double bond and a cationically polymerizable group. Compounds are defined as belonging to α, β-ethylenically unsaturated double-bonding group-containing compounds.

Here, the "active energy ray" means an energy ray in a broad sense capable of providing the energy required for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. .. In the active energy ray-polymerizable composition of the present invention (hereinafter referred to as "polymerizable composition"), the polymerization reaction proceeds by irradiation with the above-mentioned active energy rays to form a cured product. Although not particularly limited, in one embodiment of the present invention, the active energy ray is preferably light energy including ultraviolet rays.

Hereinafter, the constituent components of the polymerizable composition will be specifically described.
(A) Ingredient:
The α, β-ethylenically unsaturated double bond group-containing compound (A) can be used without particular limitation as long as it is a compound containing one or more α, β-unsaturated double bond groups. The α, β-ethylenically unsaturated double bond group-containing compound (A) is an α, β-ethylenically unsaturated double bond group-containing compound (AA) having a hydrogen-binding functional group in its structure, and one or more. One or more selected from the group consisting of an α, β-ethylenic unsaturated double bond-containing compound (A-2) having a cyclic structure and an oligomer (A-3) having a weight average molecular weight of 300 to 30,000. It preferably contains a compound.

An α, β-ethylenically unsaturated double bond group-containing compound (AA) having a hydrogen-bonding functional group (hereinafter referred to as compound (AA)) will be described. When the polymerizable composition contains the compound (AA), the compatibility with water is further improved. Further, since it has a hydrogen-bonding functional group, a hydrogen bond with water works, and the cohesive force and the degree of cross-linking of the active energy ray-curable polymerizable composition can be further improved. If so, heat resistance, moisture heat resistance, and dimensional stability are further improved. Further, when the compound (AA) is used, it has an effect of forming a hydrogen bond with the surface functional group of the base material and improving the adhesiveness.

The compound (AA) may be any compound having a hydrogen-bonding functional group. Examples of the hydrogen-bonding functional group include a hydroxyl group , a carboxyl group, and an amino group . The hydrogen-bonding functional group has a strong hydrogen-bonding action with water and can improve the cohesive force and the degree of cross-linking of the cured product of the polymerizable composition. Moisture resistance and dimensional stability are further improved. The hydrogen-bonding functional group is preferably a hydroxyl group .

As described above, the compound (AA) preferably contains a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (A-1) (hereinafter referred to as compound (A-1)). Since the hydroxyl group forms a strong hydrogen bond with water, the cohesive force and the degree of cross-linking of the polymerizable composition are particularly improved, and therefore, when used in a laminate, heat resistance, moisture heat resistance, and dimensional stability are particularly improved. ..

The compound (A-1) is, for example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-Hydroxyoctyl (meth) acrylic acid, cyclohexanedimethanol mono (meth) acrylic acid ester, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid, ethyl-α- (meth) acrylic acid Fatty acid esters such as (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, or (meth) acrylic acid glycidyl lauric acid ester, (meth) acrylic acid glycidyl oleic acid ester, and (meth) acrylic acid glycidyl stearate ester. (Meta) acrylic acid ester;
Further, a (meth) acrylic acid ester having a hydroxyl group at the terminal synthesized by subjecting (A-1) to a ring-opening addition reaction of ε-caprolactone lactone;
A hydroxyl group-containing aliphatic (meth) acrylic acid ester such as an alkylene oxide-added (meth) acrylic acid ester in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to (A-1);

Hydroxyl ethyl 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, or terminals with repeated addition of alkylene oxides such as ethylene oxide and propylene oxide. A hydroxyl group-containing aliphatic vinyl ether such as an alkylene oxide-added vinyl ether having a hydroxyl group in

(Meta) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether, hydroxy Repeated octyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide. A hydroxyl group-containing aliphatic (meth) allyl alcohol such as an alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the added terminal, and its (meth) allyl ether;

An α, β-ethylenically unsaturated double bond-containing compound having multiple hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glucerol di (meth) acrylate;
N-Hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as "N-hydroxyethyl (meth) acrylamide"], N-hydroxypropyl (meth) acrylamide, N-hydroxy Hydroxylamide-containing (meth) acrylamides such as butyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, and N-hydroxyoctyl (meth) acrylamide;

(Meta) Acrylic Acid 1,2-Cyclohexanedimethanol, (Meta) Acrylic Acid 1,3-Cyclohexanedimethanol, (Meta) Acrylic Acid 1,4-Cyclohexanedimethanol, (Meta) Acrylic Acid 2-Hydroxy-3- Phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, (meth) acrylic acid 2-Hydroxy-3-phenoxydecyl, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethylphthalate (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) (meth) acrylate. A (meth) acrylic acid ester having a cyclic structure other than a hydroxyl group such as ethyl and a heterocycle;

2-Hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone [2-hydroxy-4- {2-acryloyloxy} ethoxybenzophenone and 2-hydroxy-4- {2-methacryloyloxy} ethoxybenzophenone together "2-Hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone"], 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2'-dihydroxy-4- Hydroxyl-containing benzophenone-based (meth) acrylic acid such as {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4'-(2-hydroxyethoxy) benzophenone ester;

2- (2'-Hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H -Benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5 -Chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy-3) Hydroxy group-containing benzotriazole-based (meth) acrylic acid ester such as'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole;

2,4-Diphenyl-6- [2-Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy- 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]] -S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-) Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy- 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxy. Ethoxy}]-S-triazine, and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine, etc. Hydroxy group-containing triazine (meth) acrylic acid ester;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol.
(A-1) can be used alone or in combination of two or more.
The compound (A-1) has 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexane because of its excellent adhesion to the substrate. Α, β-ethylenically unsaturated double-bonding group-containing compounds having 2 to 18 carbon atoms such as dimethanol mono (meth) acrylic acid ester and ε-caprolactone 1-2 mol addition (meth) acrylate 2-hydroxyethyl Especially preferable.

Among the compounds (AA), a compound having a carboxyl group is referred to as a compound (AA-2). The compound (AA-2 is not limited as long as it has a carboxyl group in its structure.
The compound (AA-2) is, for example, (meth) acrylic acid [acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”], (meth) acrylic acid 2-carboxyethyl, and (meth) acrylic acid 2. -Carboxypropyl, (meth) acrylic acid 3-carboxypropyl, (meth) acrylic acid 4-carboxybutyl, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconic acid, sorbic acid , Acrylic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tigric acid, angelic acid, senesioic acid, crotonic acid, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, Aconytic acid, penicic acid, geranoic acid, citronellic acid, 4-acrylamide butanoic acid, 6-acrylamide hexane acid, 2- (meth) acryloyloxyethyl succinate ;, mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc. Polylactone-based (meth) acrylic acid ester having a carboxyl group at the end synthesized by ring-opening addition reaction of a lactone ring, alkylene oxide addition system with a carboxyl group at the end to which alkylene oxides such as ethylene oxide and propylene oxide are repeatedly added. A carboxyl group-containing aliphatic α, β-unsaturated double-bonding group-containing carboxylic acid such as an acid, an ester of (meth) acrylic acid, and an acid anhydride thereof;

2- (Meta) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropylphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyloxyhexyl Phtalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, katsura acid , 7-Amino-3-vinyl-3-cephem-4-carboxylic acid and other carboxyl group-containing alicyclic and aromatic rings α, β-unsaturated double-bonding group-containing carboxylic acid, and acid anhydrides thereof. Kind and the like.

Among the compounds (AA), the compound (AA-3) having an amino group may be any compound having an amino group in its structure. The amino group is preferably an acyclic amino group or a cyclic amino group. The compound having an acyclic amino group is, for example, monomethylaminoethyl (meth) acrylate [monomethylaminoethyl acrylate and monomethylaminoethyl methacrylate are collectively referred to as monomethylaminoethyl (meth) acrylate]. Monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic (Meta) acrylic acid-monoalkylamino esters such as dimethylaminopropyl acid, diethylaminopropyl (meth) acrylic acid, and their di-alkylamino esters;

Monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethyl Examples thereof include mono or di-alkylaminoalkyl (meth) acrylamides such as aminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide.

Compounds having a cyclic amino group include, for example, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2'-hydroxy-5'-acryloyloxy). "2- (2'-Hydroxy-5'-(meth) acryloyl" is a combination of ethylphenyl) -2H-benzotriazole and 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole. Oxyethylphenyl) -2H-benzotriazole "], 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-" 5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2) '-Hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyl (Meth) acrylic acid ester having an amino group with a polycyclic structure such as oxyethylphenyl) -5-chloro-2 H-benzotriazole;

2,4-Diphenyl-6- [2-Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-Bis (2-methylphenyl) -6- [2-Hydroxy- 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-) Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy- 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxy}] Ethoxy}]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine, etc. (Meta) acrylic acid ester having a membered ring amino group;

(Meta) acrylic having an alicyclic amino group such as pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, 4- (pyrimidine-2-yl) piperazin-1-yl (meth) acrylate Acid ester;

1-vinylpyrrole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 4,5-Dihydro-2-vinyl-1H-imidazole, 1-vinyl imidazole, 2-vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole, 3 -Vinyl group-containing compound having a 5-membered ring amino group such as methyl-5-phenyl-1-vinylpyrazole;

2-vinyl piperazine, 4-vinyl piperazine, 1-benzyl-2-vinyl piperazine, 1-benzyl-3-vinyl piperazine, 1,4-dimethyl-3-vinyl piperazine, 2-vinylpyridine, 3-vinylpyridine, 4 -Vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2- Vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-triazine-2,4-diamine, 3-vinyl-1, Vinyl group-containing compounds having a 6-membered ring amino group such as 2,4,5-tetrazine;

1-vinyl indole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl -1H-benzimidazole, 1-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinylisoxalin, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1 -Vinyl group-containing compound having a polycyclic amino group such as vinylcarbazole;

1-Methyl-4,5-divinyl-1H-imidazole, 1,1'-divinyl-2,2'-bi (1H-imidazole), 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5 -A compound having a cyclic amino group and two or more vinyl groups such as divinylpyridine and 2,6-divinylpyridine;

1- (meth) Allyl-1H-imidazole [1- (meth) allyl-1H-imidazole is collectively referred to as "1- (meth) allyl-1H-imidazole"], 1- (meth). Allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazole-3-ium, 1- (meth) allyl-3-ethyl-1H-imidazole-3-ium, 4- (Meta) Allyl-3,5-dimethyl-1H-pyrazole, 5-bromo-1-1- (meth) allyl-1H-pyrazole, 1- (meth) allyl piperazine, 5- (1-methylpropyl) -5 -(Meta) allyl pyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 1- (meth) allyl-5,5-diethylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3 , 6-Dihydro-3- (meth) allylpyridine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5 -A (meth) allyl group-containing compound having a cyclic amino group such as triazine-2-amine;

2- (Meta) allyl-1H-indole, 3- (meth) allyl-1H-indole, 1- (meth) allyl-1H-benzoimidazole, 2- (meth) allyl indazole, 1- (meth) allyl-3 -Methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, N- (meth) allylquinoline-4-amine, di (meth) allylquinoline, 3-phenyl-4- (meth) Examples thereof include (meth) allyl group-containing compounds having a polycyclic amino group such as allylisoquinolin, 1,2-di (meth) allyl-1,2-dihydroisoquinolin, 9- (meth) allyl-9H-carbazole and the like. ..

The α, β-ethylenically unsaturated double bond-containing compound (A-2) having one or more cyclic structures (hereinafter referred to as compound (A-2)) does not contain compound (AA). The compound (A-2) is an α, β-ethylenically unsaturated double-bonding group-containing compound (A-2-1) having a ring structure containing no hetero atom in the molecule (hereinafter, compound (A-2-). 1)) and α, β-ethylenically unsaturated double-bonding group-containing compound (A-2-2) having a ring structure containing a hetero atom in the molecule (hereinafter referred to as compound (A-2-2)). ), The compound (A-2-1) is preferable because it causes less yellowing over time at high temperature. By containing the compound (A-2), durability such as heat resistance or moisture heat resistance is further improved.

The compound (A-2-1) may be any compound having a ring structure other than the heterocycle in its structure. For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth). ) 1-Methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate , (Meta) benzyl acrylate, (meth) iso-bornyl acrylate, (meth) phenyl acrylate, (meth) 2-phenoxyethyl acrylate, (meth) 2-oxo-1,2-phenylethyl acrylate, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1 (meth) acrylate -Anthryl, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (meth) acrylic Dicyclopentanyl acid, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyl (meth) acrylate Adamanthyl-2-yl, 2-isopropyl (meth) acrylate Adamanthyl-2-yl, 1- (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, 1- (meth) acrylic acid 1- (adamantan-) 1-yl) -1-ethyl, (meth) acrylate 1- (adamantan-1-yl) -1-methylpropyl, (meth) acrylate 1- (adamantan-1-yl) -1-ethylpropyl, ( Meta) Acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nona-2-yl, (meth) Acrylic acid-5-oxo-4-oxa-tricyclo [5. 2.1.0 ^3,8 ] Deca-2-yl, dihydro-α-terpinyl (meth) acrylic acid, -6-oxo-7-oxa-bicyclo [3.2.1] octa- (meth) acrylic acid 2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] octa-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl Phtalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate, 2- (meth) acryloyloxyethyl Hexahydrophthalate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid cyclohexylglycidyl ether, (meth) acrylic acid phenylglycidyl ether, etc. (Meta) Acryloyl cyclic ester;

N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (meth) ) Acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- (phenyl) (Meta) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (meth) ) (Meta) acrylamide containing cyclic structure such as acrylamide;

(Meta) Acrylic acid cyclic ester containing a sulfonyl group such as (meth) sulfophenoxyethyl acrylate, (meth) sulfocyclohexyl acrylate, (meth) sulfobenzyl acrylate;

(Meta) Acryloyloxyethyl dimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- (meth) Metallic salts of (meth) acrylic acid cyclic esters containing sulfonyl groups such as acryloyloxyethyl phosphate, and ammonium salts thereof;

Di (meth) acrylic acid tricyclodecanedihydroxymethyl, di (meth) acrylic acid tricyclodecanedihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantandiol, di (meth) acrylic acid 1,3 -Adamantanediol, di (meth) acrylate 1,4-adamantandiol, di (meth) acrylate tricyclodecanyl dimethylol, di (meth) acrylate dicyclopentanyl, di (meth) acrylate dicyclopentenyl , Dicyclopentenyloxyethyl di (meth) acrylate ,, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxypropyl) di (meth) acrylate Tetraethylene oxide adduct of benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid 2,2-bis (hydroxyphenyl) methane, di (Meta) Acrylic Acid-4,4'-Sulfonyl Diphenol Tetraethylene Oxide Addendum, Di (Meta) Acrylic Acid-Water Addition 2,2-Bis (Hydroxyphenyl) Propane Tetraethylene Oxide Additive, Di (Meta) ) Acrylic acid-water added 2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct, di (meth) acrylic acid-water added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propene Acid-Water-added 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (meth) acrylic acid -2,2-Bis (hydroxyphenyl) methane tetraethylene oxide adduct-bifunctional (meth) acrylic acid cyclic ester such as dicaprolactonate;

5-vinylbicyclo [2.2.1] hepta-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxylannorbornane, 2- (2-propenyl) bicyclo [2.2] .1] Heptane, 5-vinylbicyclo [2.2.1] hepta-2-ene, 2-ethenylidene adamantan, 1-allyl adamantan, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid , 4-Isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexylvinyl ether, cyclohexylmaleimide, vinylcyclohexenemonooxylan and other alkenyl group-containing cyclic compounds;

Vinyl benzoyl acrylate, vinyl benzoyl acetate, vinyl benzoyl propionate, vinyl benzoyl butyrate, vinyl benzoyl valerate, vinyl benzoyl hexanoate, vinyl benzoyldodecanoate, vinyl 1-naphthoyl acetate, vinyl vinyl naphthoyl propionate, 1-naphthoyl butyric acid Vinyl, 1-naphthoylvalephosphate vinyl, 1-naphthoylhexanoate vinyl, 2-naphthoyl vinyl acetate, 2-naphthoylpropionate vinyl, 2-naphthoylbutyrate vinyl, 2-naphthoylvalephosphate vinyl, 2-naphthoyl Vinyl hexaneate, vinyl nicotinoyyl acetate, vinyl nicotinoyyl propionate, vinyl nicotinoyyl butyrate, vinyl nicotinoyle valerate, vinyl nicotinoyyl hexaneate, vinyl nicotinoyle decanoate, vinyl nicotinoid decanoate, vinyl isonicotinoyl acetate, isonicotinoyl propion. Vinyl Acid, Isonicotinoyyl Butyrate Vinyl, Isonicotinoyle Valephosphate Vinyl, Isonicotinoyle Hexanoate Vinyl, Isonicotinoyle Decanoate Vinyl, Isonicotinoyl Dodecanoate Vinyl, 2-Floyl Acetate Vinyl, 2-Floyl Propionate Vinyl, 2 -Floyl Butyrate Vinyl, 2-Floyl Valephosphate Vinyl, 2-Floyl Hexanoate Vinyl, 2-Floyl Decanoate Vinyl, 2-Floyldodecanoate Vinyl, 3-Floyl Acetate Vinyl, 3-Floyl Propionate Vinyl, 3 -Floyl Butyrate Vinyl, 3-Floyl Vallephosphate Vinyl, 3-Floyl Hexanoate Vinyl, 3-Floyl Decanoate Vinyl, 3-Floyldodecanoate Vinyl, Anthranilolyl Acetate Vinyl Acetate, Anthraniloyl Propionate Vinyl, Anthraniloyl Butyrate Vinyl, Vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyloxy) styrene, 4- (2-t-butoxy) Aromatic vinyl compounds having an acyl group such as carbonylethyloxy) styrene and 4- (2-t-butoxycarbonylpropyloxy) styrene;

Benzoyl allylic acid (meth) allyl, benzoyl acetate (meth) allyl, benzoyl propionic acid (meth) allyl, benzoyl butyrate (meth) allyl, benzoyl valeric acid (meth) allyl, benzoyl hexanoic acid (meth) allyl, benzoyl dodecanoic acid (meth) ) Allyl, 1-naphthylacetic acid (meth) allyl, 1-naphthylpropionic acid (meth) allyl, 1-naphthylbutyric acid (meth) allyl, 1-naphthylvaleric acid (meth) allyl, 1-naphthylhexanoic acid ( Meta) allyl, 2-naphthylacetic acid (meth) allyl, 2-naphthylpropionic acid (meth) allyl, 2-naphthoylbutyrate (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoylhexanoic acid A carbonyl group-containing ethylenically unsaturated cyclic monomer such as an aromatic (meth) allyl compound having an acyl group such as (meth) allyl;

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-ethoxyethoxy) styrene, 4- (1-) Aromatic vinyl monomers such as ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

Hexil 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, 4 -Octadecyl vinyl benzoate, eikosyl 4-vinyl benzoate, docosyl 4-vinyl benzoate, hexyl 4-isopropenyl benzoate, octyl 4-isopropenyl benzoate, nonyl 4-isopropenyl benzoate, 4-isopropenyl benzoic acid Decyl, 4-isopropenyl benzoate dodecyl, 4-isopropenyl benzoate tetradecyl, 4-isopropenyl benzoate hexadecyl, 4-isopropenyl benzoate octadecyl, 4-isopropenyl benzoate eikosyl, 4-isopropenyl benzoate docosyl, etc. Vinyl benzoic acid ester-based or isopropenyl benzoic acid ester-based monomer having a long-chain alkyl group;

Tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether, n -Pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxytetra (propylene oxide) vinyl phenyl ether, n -Butyltetra (propylene oxide) vinylphenyl ether, n-pentoxytetra (propylene oxide) vinylphenyl ether, poly (ethyleneoxide) vinylphenyl ether, methylpoly (ethyleneoxide) vinylphenyl ether, ethylpoly (ethyleneoxide) vinylphenyl ether, Poly (propylene oxide) vinyl phenyl ether, methyl poly (propene oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ) Ethenyl benzyl ether, poly (propylene oxide) vinyl benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) Long-chain polyalkylenes such as vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether, methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether, etc. Vinyl phenyl ether-based monomer having an oxide moiety;

Isopropenylphenylmethylbutyl ether, isopropenylphenylmethylpentyl ether, isopropenylphenylmethylhexyl ether, isopropenylphenylmethylheptyl ether, isopropenylphenylmethyloctyl ether, isopropenylphenylmethylnonyl ether, isopropenylphenylmethyldecyl ether, isopropenyl Phenylmethylundecyl ether, isopropenylphenylmethyldodecyl ether, isopropenylphenylmethyltridecyl ether, isopropenylphenylmethyltetradecyl ether, isopropenylphenylmethylpentadecyl ether, isopropenylphenylmethylhexadecyl ether, isopropenylphenylmethylhepta It has a long-chain alkyl group such as decyl ether, isopropenylphenylmethyl octadecyl ether, isopropenylphenylmethyl nonadecyl ether, isopropenylphenylmethyleicosyl ether, isopropenylphenylmethylheneicosyl ether, and isopropenylphenylmethyldocosyl ether. Isopropenylphenyl-based monomer;

Poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl ether, Ethylpoly (propeneoxide) isopropenylphenyl ether, poly (ethylene oxide) isopropenylbenzyl ether, methylpoly (ethyleneoxide) isopropenylbenzyl ether, ethylpoly (ethyleneoxide) isopropenylbenzyl ether, poly (propylene oxide) isopropenylbenzyl ether, Methylpoly (propylene oxide) isopropenyl Isopropenyl-based monomer having a polyalkylene oxide moiety such as benzyl ether;

Mono-long-chain alkyl ester-based cyclic monomers of dicarboxylic acids such as vinylphenyl phenylnonyl succinate, vinyl phenylmethyl decyl hexahydrophthalate, vinyl phenylethyl dodecyl terephthalate;

Monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenylphenyl succinate (ethylene oxide), vinyl phenylmethyl poly hexahydrophthalate (ethylene oxide), vinyl phenylethyl terephthalate (ethylene oxide);
Polyalkylene oxides such as 4-vinylbenzoate methyl poly (ethylene oxide), 4-vinyl benzoate ethyl poly (ethylene oxide), 4-isopropenyl benzoate methyl poly (propylene oxide), 4-isopropenyl benzoate ethyl poly (propylene oxide) Vinyl benzoic acid ester-based or isopropenyl benzoic acid ester-based monomer having a moiety;

An alkenyl group-containing cyclic sulfonic acid such as styrene sulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene zen sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate. Styrene sulfonic acid such as ammonium, tetraethylammonium styrene sulfonate, propyl ammonium styrene sulfonate, dipropyl ammonium styrene sulfonate, tripropyl ammonium styrene sulfonate, butyl ammonium styrene sulfonate, pentyl ammonium styrene sulfonate or hexyl ammonium styrene sulfonate Ammonium salt;
Metallic salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metallic salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, and ammonium salts thereof;
2-Methyl-2-propenyloxybenzenesulfonic acid such as 2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonated sodium, 2-methyl-2-propenyloxybenzenesulfonated potassium, etc. Examples include metal salts of acids and ammonium salts.

Further, if o-di (meth) allyl bisphenol A, hydrogenated bisphenol A having an aromatic ring structure, or the like also has an α, β-unsaturated double bond group, it can be converted into a compound (A-2-1). included.
The compound (A-2-1) can be used alone or in combination of two or more.

Since the compound (A-2-1) has good durability such as heat resistance and water resistance, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, Dicyclopentanyl acrylate, dicyclopentanyl diacrylic acid, dicyclopentenyl acrylate, dicyclopentenyl dicyclopentenyl, 2-ethyladamantyl-2-yl acrylate and the like are particularly preferable.

The compound (A-2-2) may have a heterocyclic structure in its structure. The compound (A-2-2) is, for example ,

Iimide (meth) acrylate, 2- (4-oxazoline-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone-modified tris -It has a heterocyclic structure containing oxygen atoms in addition to nitrogen atoms such as (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, and tri (meth) acrylic acid isocyanuric acid ethylene oxide modification. Meta) Acrylic acid ester;

4-Acryloyl morpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2-yl) Heterocyclic acrylamide such as methoxymethyl) (meth) acrylamide;

Maleimide derivatives having both nitrogen and oxygen atoms such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

2-vinyloxazole, 2-phenyl-4-vinyloxazole, 2-phenyl-5-vinyloxazole, 5-ethoxy-2-vinyloxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5-diphenyl A vinyl group having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as oxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and 2-vinylbenzoxazole. Containing compound;

Glycidyl (meth) acrylate, (meth) acrylate (3,4-epoxycyclohexyl) methyl, (meth) acrylate (3-methyl-3-oxetanyl) methyl, (meth) tetrahydrofurfuryl acrylate, (meth) Acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4 -Il, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrachloride-3-yl, (meth) acrylic acid-2,2-dimethyl- 5-Oxotetra-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetra-3-yl, (meth) acrylic acid-2-oxotetra-3-yl, (meth) acrylic acid -4,4-dimethyl-2-oxotetra-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetra-3-yl, (meth) acrylic acid-2-oxotetra-3-yl Il, (meth) acrylic acid-5-oxotetrachloride-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahexyl-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl- Heterocyclic-containing (meth) acrylic acid ester having an oxygen atom such as 5-oxotetratetra-2-ylmethyl;

Glycidyl group-containing vinyl ester such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxylan;

2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzothiazole, etc. Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to the nitrogen atom of the above.
The compound (A-2-2) can be used alone or in combination of two or more.

The compound (A-2-2) contains glycidyl acrylate, glycidyl methacrylate, and methyl methacrylate (3,4-epoxycyclohexyl) in terms of compatibility with water and durability such as heat resistance and water resistance. , Tetrahydrofurfuryl acrylate, 4-acryloylmorpholin, 1-vinylimidazole, N-vinyl-ε-caprolactam, 1-vinylpyridine-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, tri ( Meth) Acrylic acid ethoxylated isocyanuric acid and the like are preferable.

The α, β-ethylenically unsaturated double bond group-containing compound (A) preferably contains an oligomer (A-3) having a weight average molecular weight of 300 to 30,000 (hereinafter referred to as oligomer (A-3)). ..
The oligomer (A-3) is a compound other than the compound (AA), (A-1), (A-2), and the compound (A-4) described later. The oligomer (A-3) is at least selected from the group consisting of polyester-based oligomers (A-3-1), polyurethane-based oligomers (A-3-2), and polyepoxy-based oligomers (A-3-3). One or more types are preferable.
By containing the oligomer (A-3), the cohesive force of the cured product of the polymerizable composition can be further improved. Therefore, when used as a laminated body, heat resistance, moisture heat resistance, and dimensional stability are further improved. Further, the oligomer (A-3) has an effect of improving the adhesiveness with the base material.

The polyester-based oligomer (A-3-1) is obtained by polycondensing a polybasic acid and a polyhydric alcohol on the main chain skeleton, and the terminal of the ester or the hydroxyl group in the polyester chain and (meth) acrylic acid, maleic acid, etc. A compound obtained by esterification with an α, β-ethylenically unsaturated double-bonding group-containing compound having one or more carboxyl groups in the molecule, or a carboxyl group at the end of a polyester or in a polyester chain and (meth) acrylic. It is a compound obtained by esterification with the above compound (A-1) such as 2-hydroxyethyl acid and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester-based oligomer (A-3-1).

Examples of the polybasic acid include an aliphatic polybasic acid, an alicyclic polybasic acid, and an aromatic polybasic acid.
The aliphatic polybasic acids include, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, etc. Examples thereof include aliphatic dicarboxylic acids such as glutaric acid, itaconic acid, succinic anhydride and maleic anhydride, and acid anhydrides thereof.
Derivatives of succinic anhydride (methyl succinic acid, 2,2-dimethyl succinic acid, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic acid, dodecenyl succinic anhydride, phenyl succinic anhydride Etc.), Derivatives of maleic anhydride (glutaric anhydride, 3-allyl maleic anhydride, 2,4-dimethyl maleic anhydride, 2,4-diethyl maleic anhydride, butyl maleic anhydride, hexyl maleic anhydride, etc.), Derivatives of maleic anhydride (2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride Anhydrous derivatives such as acid, 2,3-dichloro maleic anhydride, phenyl maleic anhydride, 2,3-diphenyl maleic anhydride, etc.) can also be mentioned.

As the alicyclic dicarboxylic acid, the alicyclic polybasic acid is, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid, cyclopropane-1β, 2α-dicarboxylic acid. , Cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -cyclopentane-1β, 2α-dicarboxylic acid , Trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1,3-dicarboxylic acid, (1S, 2S) -1,2-Cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, Kuban-1,4-dicarboxylic acid Saturated alicyclic dicarboxylic acids such as acids, 2,3-norbornandicarboxylic acids, hexahydroterephthalic acids, hexahydroisophthalic acids, hexahydrophthalic acids, tetrahydrophthalic acids;
1-Cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1, 2-Dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,3-dicarboxylic acid, 2,5-hexadien-1α, 4α-dicarboxylic acid Examples thereof include unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring, an alicyclic dicarboxylic acid thereof, and an anhydride thereof.

Derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3-methyl- 1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) Examples thereof include phthalic anhydride derivatives.

As the aromatic dicarboxylic acid, the aromatic polybasic acid is, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, 2,5-dimethylterephthalic acid, 2,2'-biphenyldicarboxylic acid, 4, 4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindandicarboxylic acid, 1,2-azurenjicarboxylic acid, 1 , 3-azurenjicarboxylic acid, 4,5-azurenjicarboxylic acid, (-)-1,3-acenaftendicarboxylic acid, 1,4-anthracendicarboxylic acid, 1,5-anthracendicarboxylic acid, 1,8-anthracendicarboxylic acid Aromatic dicarboxylic acids such as acids, 2,3-anthracenedicarboxylic acids, 1,2-phenantrange carboxylic acids, 4,5-phenantrange carboxylic acids, and 3,9-perylene dicarboxylic acids, phthalic anhydride, and 4-methylphthalic anhydride. Examples thereof include aromatic dicarboxylic acid anhydrides such as acids.

In addition, chlorendic anhydride, hetic anhydride, biphenyldicarboxylic acid anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrochloride phthalic acid, methyl-3,6-endomethylene-1,2,3 , 6-Tetrahydrohydroanhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

The polyhydric alcohol is preferably a relatively low molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500, or a relatively high molecular weight polyol having a number average molecular weight (Mn) of 500 to 30,000.

Glycols having a relatively low molecular weight include, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentane. Diol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (additional moles: 10 or less), poly Oxypropylene glycol (additional number of moles 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neo An aliphatic or alicyclic type such as pentylglycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, and dimerdiol. Glycol;

1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-methylenediphenol, 4, 4'-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropyridenephenol, addition type bisphenol with alkylene oxide added to bisphenol Aromatic diols and the like can be mentioned.

Examples of the raw material bisphenol of the addition type bisphenol include bisphenol A and bisphenol F. Examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.
Examples of the relatively high molecular weight polyol include high molecular weight polyester polyol, high molecular weight polyamide polyol, high molecular weight polycarbonate polyol and high molecular weight polyurethane polyol.
Examples of the high molecular weight polycarbonate polyol include the reaction product of the relatively low molecular weight diol with a carbonic acid ester or phosgene.

In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diols, poly (β-methyl-γ-valerolactone) diols, and polyvalerolactone diols can also be used as the above high molecular weight polyols. include.

The polyurethane-based oligomer (A-3-2) is (1) a compound obtained by reacting a compound having one or more isocyanate groups with the compound (A-1), or (2) one or more isocyanate groups. A compound obtained by reacting a urethane prepolymer having a terminal isocyanate group synthesized by reacting a compound having the above compound (A-1) with a polyhydric alcohol, or (3) one or more isocyanate groups. A terminal isocyanate group urethane prepolymer obtained by reacting a compound having a compound with a polyhydric alcohol, a terminal isocyanate group urethane prepolymer obtained by reacting a compound having one or more amino groups, and the above-mentioned compound ( A compound obtained by reacting with A-1) is preferable. Further, the polyurethane-based oligomer (A-3-2) also contains a compound containing a urea-binding group obtained by reacting an isocyanate group with an amino group.

As the compound having one or more isocyanate groups, monofunctional isocyanate (having one isocyanate group) and polyfunctional isocyanate (having two or more isocyanate groups) are preferable. As the polyfunctional isocyanate, aromatic isocyanate, aliphatic isocyanate, aromatic aliphatic isocyanate, alicyclic isocyanate and the like are preferable.
The monofunctional isocyanate may be, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, etc. 2-Chloroethyl isocyanate, 2,4-dichlorophenylisocyanate, 3-chloro-4-methylphenylisocyanate, trichloroacetylisocyanate, chlorosulfonylisocyanate, (R)-(+)-α-methylbenzylisocyanate, (S)-( -)-Α-Methylbenzyl isocyanate, (R)-(-)-1-(1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethylisocyanate, (S)-(-)-1 -Phenylethyl isocyanate, p-toluenesulfonyl isocyanate and the like can be mentioned.

Among the polyfunctional isocyanates, aromatic isocyanates include, for example, 1,3-phenylenedi isocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and the like. 2,6-Tolylene diisocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4, 4', 4 "-triphenylmethane triisocyanate and the like can be mentioned.

The aliphatic isocyanate is, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, dodecamethylene. Examples thereof include diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
The aromatic aliphatic isocyanate is, for example, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1, Examples thereof include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

Examples of the alicyclic isocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexanediisocyanate. Examples thereof include methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like.

Further, as the polyfunctional isocyanate, for example, a 2-methylpentane-2,4-diol adduct, a trimer having an isocyanurate ring, or the like can also be used in combination. Further, polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and modified products of these polyisocyanates can be used.
As the polyisocyanate modified product, a modified product having one or more functional groups such as a carbodiimide group, a uretdione group, a uretoimine group, a buretto group reacted with water, and an isocyanurate group can be used. Further, the reaction product of the polyol and diisocyanate can be used as a compound having at least two isocyanate groups.

The amines include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2,2,4. -Trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) Diamines, (di-2-hydroxyethylpropylene) diamines, (2-hydroxypropylethylene) diamines, (di-2-hydroxypropylethylene) diamines, aliphatic polyamines such as piperazine;
Alicyclic polyamines such as isophorone diamine, dicyclohexylmethane-4,4'-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis- ( Examples thereof include aromatic diamines such as sec-butyl) diphenylmethane.

The polyepoxy-based oligomer (A-3-3) contains two or more α, β-unsaturated double bond groups having an ester produced by the reaction of a glycidyl group and a carboxyl group (including an acid anhydride group). Refers to a compound. Examples of the polyepoxy-based oligomer (A-3-3) include a bisphenol type, an epoxidized oil type, a phenol novolac type, and an alicyclic type. The bisphenol-type polyepoxy-based oligomer is an α, β-unsaturated binary having one or more carboxyl groups in the molecule such as bisphenol-type diglycidyl ether and (meth) acrylic acid obtained by reacting bisphenols with epichlorohydrin. It is a compound reacted with a compound containing a heavy bond group.

Epoxide oil The polyepoxide-based oligomer is an α, β-unsaturated double-bonding group having one or more carboxyl groups in the molecule of epoxidized oil such as soybean oil and (meth) acrylic acid and maleic acid. It is a compound obtained by reacting with the contained compound. The novolak-type polyepoxy oligomer is a compound obtained by reacting a novolak-type epoxy resin with an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in a molecule such as (meth) acrylic acid. be. The alicyclic polyepoxy oligomer is obtained by reacting an alicyclic epoxy resin with an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in a molecule such as (meth) acrylic acid. It is a compound.

The weight average molecular weight (Mw) of the oligomer (A-3) having at least one α, β-unsaturated double bond group in the molecule (hereinafter referred to as oligomer (A-3)) is 300 to 30, 000 is preferable, and 400 to 20,000 is more preferable. When the MW is 300 to 30,000, compatibility of the cured product, good durability (heat resistance, moisture heat resistance), and aggregation density can be easily obtained.

The α, β-ethylenically unsaturated double bond group-containing compound (A) contained in the active energy ray-polymerizable composition of the present invention includes the above-mentioned compound (A-1), compound (A-2), and oligomer. In addition to (A-3), other α, β-ethylenically unsaturated double bond group-containing compound (A-4) (hereinafter referred to as compound (A-4)) can be further contained.

The compound (A-4) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, (Meta) acrylate sec-butyl, (meth) acrylate iso-butyl, (meth) acrylate tert-butyl, (meth) acrylate n-amyl, (meth) acrylate iso-amyl, (meth) acrylate n-hexyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic iso-nonyl, (meth) ) (Meta) acrylic acid alkyl esters such as (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid lauryl, (meth) acrylic acid stearyl;

(Meta) Acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl-3- Butenyl, 2-chlor 2-propenyl (meth) acrylate, 3-chlor 2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2-propenyllac (meth) acrylate Chill, (meth) acrylic acid 3,7-dimethylocta-6-en-1-yl, (meth) acrylic acid (E) -3,7-dimethylocta-2,6-dien-1-yl, (meth) ) (Meta) acrylic acid ester containing further unsaturated groups such as rosinyl acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;
Perfluoromethyl (meth) acrylic acid, perfluoroethyl (meth) acrylic acid, perfluoropropyl (meth) acrylic acid, perfluorobutyl (meth) acrylic acid, perfluorooctyl (meth) acrylic acid, (meth) acrylic acid Trifluoromethylmethyl, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate -2-Perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( (Meta) Acrylic acid Perfluoroalkyl esters such as 2-perfluorodecylethyl acrylic propenate and 2-perfluorohexadecylethyl (meth) acrylic acid;

(Meta) Acrylic acid (methoxycarbonyl) methyl, (meth) Acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic acid (meth) Methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl, ( Meta) Acrylic acid (ethoxycarbonyl) hexyl, (meth) Acrylic acid (ethoxycarbonyl) octyl, (meth) acrylate 2- (ethoxycarbonyloxy) ethyl, (meth) acrylate 2- (ethoxycarbonyloxy) propyl, ( 2- (ethoxycarbonyloxy) butyl (meth) acrylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxy) (meth) acrylate Carbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) butyl, (meth) acrylate 2- (octyloxycarbonyloxy) ethyl, (meth) ) Acrylic acid 2- (octyloxycarbonyloxy) An aliphatic (meth) acrylic acid ester having one carbonyl group such as butyl;

2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (meth) ) 2-oxobutanoyloctyl acrylate, (meth) 2-oxobutanoyldecyl acrylate, 2-oxobutanoyldodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth) acrylic Acid 3-oxobutanoylpropyl, (meth) acrylic acid 3-oxobutanoylbutyl, (meth) acrylic acid 3-oxobutanoylhexyl, (meth) acrylic acid 3-oxobutanoyloctyl, (meth) acrylic acid 3 -Oxobutanoyldecyl, 3-oxobutanoyldodecyl (meth) acrylate, 4-cyanooxobutanoylethyl (meth) acrylate, 4-cyanooxobutanoylpropyl (meth) acrylate, 4 (meth) acrylic acid -Cyanooxobutanoylbutyl, (meth) acrylate 4-cyanooxobutanoylhexyl, (meth) acrylate 4-cyanooxobutanoyloctyl, (meth) acrylate 2,3-di (oxobutanoyl) propyl, 2,3-Di (oxobutanoyl) butyl (meth) acrylic acid, 2,3-di (oxobutanoyl) hexyl (meth) acrylic acid, 2,3-di (oxobutanoyl) octyl (meth) acrylic acid An aliphatic (meth) acrylic acid ester having two carbonyl groups such as;

3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxyshisilane, 3 -(Meta) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (Meta) Acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (Meta) Acryloyl group-containing (meth) acrylic acid ester such as acryloyloxypropyltripropoxysilane;

Sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) acrylate 4-Sulfobutyl, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulflauryl (meth) acrylate, (meth) acrylic (Meta) acrylic acid alkyl ester containing a sulfonyl group such as sulfostearyl acid;

Metal salts and ammonium of sulfonyl group-containing (meth) acrylic acid esters such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate;

Acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxybutyl (meth) acrylate, -3-chloro-2-acid phosphooxyethyl (meth) acrylate, (meth) Acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid acid phospho Phosphonate group-containing (meth) acrylic acid ester such as oxyethylene oxide (number of moles added with ethylene oxide: 4 to 10), acid phosphooxypropylene oxide (number of moles added with propylene oxide: 4 to 10), (meth) acrylic acid acid;

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 (meth) acrylic acid 3-butoxyethyl, (meth) acrylic acid 4-butoxyethyl;

An alkylene oxide-containing (meth) acrylic acid derivative such as an alkylene oxide adduct of (meth) acrylic acid;

Di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (meth) acrylic acid ) Dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentenoxide, di (meth) acrylic acid 2,2-dimethylpropyl, di (meth) acrylic acid hydroxypivalyl hydroxypivalate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di (meth) acrylic acid 1,6-hexanediol, Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol di, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol di, di (meth) acrylic acid 1 , 2-Decandiol, Di (meth) acrylic acid 1,10-decanediol, Di (meth) acrylic acid 1,2-decanediol, Di (meth) acrylic acid 1,12-dodecanediol, Di (meth) acrylic Acids 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) ) Acrylic acid 1,2-hexadecanediol, di (meth) acrylic acid 2-methyl-2,4-pentanediol, di (meth) acrylic acid 3-methyl-1,5-pentanediol, di (meth) acrylic acid 2-Methyl-2-propyl-1,3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3- Propanediol, di (meth) acrylic acid 2,2,4-trimethyl-1,3-pentanediol, di (meth) acrylic acid dimethylol octane, di (meth) acrylic acid 2-ethyl-1,3-hexanediol , Di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-methyl- 1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylic acid, 2,4-diethyl-1,5-pentanediol di (meth) acrylic acid, di (meth) ) 2-Methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylic acid, 2,2-diethyl-1 di (meth) acrylic acid , 3-Propanediol, di (meth) acrylic acid 2,2,4-trimethyl-1,3-pentanediol, di (meth) acrylic acid dimethylol octane, di (meth) acrylic acid 2-ethyl-1,3 -Hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-butyl-2-ethyl-1,3-propanediol, di (meth) acrylic acid Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol and di (meth) acrylic acid 1,1,1-trishydroxymethylethane;

Tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol, tri (meth) acrylic acid 2-methylpentane-2,4-diol tricapro Lactate, tri (meth) acrylic acid 2,2-dimethylpropane-1,3-diol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, tri (meth) acrylic acid 2, 2-Bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, tri ( Trifunctional (meth) acrylic acid ester such as pentaerythritol acrylate;

Pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-tetra (meth) acrylate Bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1,2, 3-Propanetriol, di2-methylpentane tetra (meth) acrylate-2,4-diol, di2-methylpentane tetra (meth) acrylate-2,4-diol tetracaprolactonate, tetra (meth) Di2,2-dimethylpropane-1,3-diol acrylate, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethylol octane, tetra (meth) Di 2,2-bis (hydroxymethyl) 1,3-propanediol acrylate, dihexa (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol, tri 2 hexa (meth) acrylate , 2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylate tri 2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylate tri 2,2-bis Polyfunctional (meth) acrylic acid esters such as (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylic acid di2,2-bis (hydroxymethyl) 1,3-propanediol polyalkylene oxide;
Vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatic acid, vinyl pivalate, vinyl palmitate, vinyl stearate;

Vinyl Acetate Acetate, Vinyl Acet Propionate, Vinyl Acetisobutyrate, Vinyl Acet Butyrate, Vinyl Acetvalephosphate, Vinyl Acethexanoate, Vinyl Acet 2-Ethylhexanate, Vinyl Acet n-Vinyl Octanoate, Vinyl Acetdecanoate, Vinyl Acetododecanoate , Vinyl Acetoctadecanoate, Vinyl Acetopivalate, Vinyl Acetcaprate, Vinyl Acetcrotonate, Vinyl Acetsorbate, Vinyl Acetanoyl Acetate, Vinyl Butyryl Acetate, Vinyl Isobutyryl Acetate, Vinyl Palmitoyl Acetate, Vinyl Stearoyl Acetate, Vinyl Pyrvoyl Acetate, Propa Vinyl Noyl Vallephosphate, Vinyl Butyryl Valephosphate, Vinyl Isobutyryl Valephosphate, Vinyl Palmitoyl Vallephosphate, Vinyl Stearoyl Valephosphate, Vinyl Pyrvoyl Vallephosphate, 2-Acetacetoxyethyl Vinyl Ether, 2-Acetoacetoxybutyl Vinyl Ether, 2-Acetoacetoxy An aliphatic vinyl compound having an acyl group such as hexyl vinyl ether and 2-acetoacetoxyoctyl vinyl ether;
Ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n-octyl Alibo vinyl ethers such as vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

Fluorine-containing etenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), and vinylidene fluoride;
(Meta) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane, Alkoxysilyl group-containing α, β-unsaturated double-bonding group-containing compounds such as vinyltris (2-methoxyethoxy)silane;

Alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, vinyl sulfuric acid;
Metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metallic salts of 2-methyl-2-propenyl sulfonic acid such as ammonium 2-methyl-2-propenyl sulfonate, sodium 2-methyl-2-propenyl sulfonate, potassium 2-methyl-2-propenyl sulfonate, and ammonium thereof. salt;

(Meta) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) ) Acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecil (meth) ) Acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleinamide, fumalamide, Mesaconamide, Citraconamide, Itaconamide, 2-Methylpropa-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N', N'-dimethyl) Amino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethaneamide, N-vinylacetamide and other aliphatic (meth) acrylamide;

N-Methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxyoctyl ( Meta) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N -Ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-isopropoxyethyl (Meta) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxyoctyl (meth) acrylamide, N-butoxymethyl ( Methoxy) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide, N-butoxyoctyl (meth) acrylamide, N -Isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N -Isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N- (oxetan-2-ylmethoxymethyl) (meth) N-alkoxy groups such as acrylamide, N- (oxetan-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) meta) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide. Contains (meth) acrylamide;

N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- (2-) (Meta) acrylamide having carbonyl groups such as oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

(Meta) acrylamide containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
Α, β-containing nitrile groups such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinenitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconenitrile, 2-propennitrile, and 2-cyanoethyl (meth) acrylate. Unsaturated double bond group-containing compound;

Saturated carboxylic acids such as acetic acid (meth) allyl, propionic acid (meth) allyl, butyric acid (meth) allyl, capric acid (meth) allyl, lauric acid (meth) allyl, octylate allyl, coconut oil fatty acid, vinyl pivalate, etc. (Meta) allyl ester;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, and 1,3-butadiene monooxylan;

Acetacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovalerate (meth) allyl, acetohexanoic acid (meth) allyl, aceto2-ethylhexane Acid (meth) allyl, acet n-octanoic acid (meth) allyl, acetdecanoic acid (meth) allyl, acetododecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetcapric acid (acetocapric acid ( Meta) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoylacetic acid (meth) allyl, butyryl acetate (meth) allyl, isobutylylacetic acid (meth) allyl, palmitoylacetic acid (meth) allyl, stearoylacetic acid. An aliphatic (meth) allyl compound having an acyl group such as (meth) allyl or (meth) allyl aldehyde;

Vinyl esters such as vinyl chloride, vinylidene chloride, allyl chloride;
Dienes such as allenes, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
cis-diallyl saturate, 2-allyl methylden succinate, (E) -buta-2-vinyl enoate, (Z) -octadeca-9-vinyl enoate, (9Z, 12Z, 15Z) -octadeca-9,12, Α, β-unsaturated double bond group-containing compound containing a polyfunctional unsaturated bond such as 15-vinyl trienate;

Ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1 -Dodecene, 1-Tetracosen, 1-Hexacosen, 1-Octene, 1-Triacontene, 1-Dodecene, 1-Tetratoacontene, 1-Hexatriacontene, 1-Octenetoriacontene, 1-Tetracontene, etc. Examples thereof include alkenes such as the mixture, polybutene-1, polypentene-1, poly4-methylpentene-1, and the like. Compound (A-4) can be used alone or in combination of two or more.

Among these, the compound (A-4) is preferably a compound having a (meth) acryloyl group from the viewpoint of reactivity. When the polymerizable composition is used as an adhesive, a bifunctional or higher functional (meth) acrylic acid ester is preferable from the viewpoint of the activation energy ray polymerization rate.

The α, β-ethylenically unsaturated double bond group-containing compound (A) contains active energy containing the α, β-ethylenically unsaturated double bond group-containing compound (A) and the active energy ray polymerization initiator (B). With respect to 100% by weight of the linearly reactive composition, 1 to 70% by weight of compound (AA), 1 to 70% by weight of compound (A-2), 1 to 50% by weight of oligomer (A-3), and compound (A). -4) is preferably 50% by weight or less. When the above constituents are used in the above ratio, the cohesive force and the degree of cross-linking of the active energy ray-curable polymerizable composition can be further improved. .. In addition, the affinity with the surface functional group of the base material is improved, and the adhesiveness is further improved.

The active energy ray polymerization initiator (B) may be any compound that generates radicals by irradiation with active energy rays, and can be arbitrarily selected from known compounds and used. In the present invention, the active energy ray polymerization initiator (B) is contained in an amount of 0.05 to 20% by weight in the total amount of the active energy ray-polymerizable composition. When used in the above range, curability and desired cured product performance can be obtained.

The active energy ray polymerization initiator (B) is, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-. Diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- Examples thereof include 1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

Commercially available products of the active energy ray polymerization initiator (B) include, for example, Irgacure 184,907,651,1700,1800,819,369, and 261 (manufactured by BASF), DAROCUR-TPO (manufactured by BASF, 2, 2,). 4,6-trimethylbenzoyl-diphenyl-phosphine oxide), DaroCure-1173 (manufactured by Merck), EzaCure KIP150, and TZT (manufactured by Nippon Kayaku Hegner), KayaCure BMS, and KayaCure DMBI (manufactured by Nippon Kayaku Co., Ltd.). Be done.
It is also possible to use a photopolymerization initiator having at least one (meth) acryloyl group in the molecule.

In addition, sulfonium salts such as UVACURE 1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by Sun Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 (manufactured by Wako Pure Chemical Industries), Rp-2074 (manufactured by Wako Pure Chemical Industries, Ltd.) Photoacid generators exemplified for iodonium salts such as (manufactured by Rhodia Japan) can also be used. When a photoacid generator is used, the curing speed is increased, and it becomes easy to form a cured product having excellent durability against heat and humidity.
The active energy ray polymerization initiator (B) may be used alone or in combination of two or more.

Further, the cross-linking rate can be improved by using the active energy ray sensitizer together with the active energy ray polymerization initiator (B). Examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compound buildings. Among these, compounds such as anthracene-based, benzophenone-based, thioxanthone-based, perylene, phenothiazine, and rose bengal are preferable.

The active energy ray-polymerizable composition of the present invention comprises an α, β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and water (simply "water"). There is) and. The water content is 0.01 to 100 parts by weight of the active energy ray-reactive composition containing the α, β-ethylenically unsaturated double bond group-containing compound (A) and the active energy ray polymerization initiator (B). Contains 10 parts by weight. By containing a predetermined amount of water, curability, adhesion to a base material, heat resistance, dimensional stability and the like are improved. These effects are due to the fact that the water causes the chain transfer in radical polymerization to be suppressed and the growth reaction is improved, so that the cohesive force of the cured product is increased. Further, the water forms hydrogen bonds with the base material and the active energy ray-reactive composition, and improves the cohesive force and the adhesion to the base material. The water content is preferably 0.5 to 7 parts by weight, more preferably 1 to 5 parts by weight.

The polymerizable composition of the present invention preferably does not contain an organic solvent, but may contain a small amount of an organic solvent in order to dissolve the active energy ray polymerization initiator (B). The content of the organic solvent is preferably 5% by weight or less in the polymerizable composition.

The active energy ray-polymerizable composition of the present invention may further contain a cationically polymerizable compound in addition to the α, β-ethylenically unsaturated double bond group-containing compound (A).

As the cationically polymerizable compound, for example, an oxylan compound is preferable. Oxylan compounds include, for example, oxylan, methyloxylan, phenyloxylan, 1,2-diphenyloxylan, methylideneoxylan, oxylanylmethyl, oxylanylmethanol, oxylancarboxylic acid, (chloromethyl) oxylan, (bromomethyl) oxylan, oxy. An aliphatic cyclic ether group such as lanyl acetonitrile;
3,4-Oxylancyclohexylmethyl 3,4-oxylancyclohexanecarboxylate, 3,4-oxylan-6-methylcyclohexanemethyl 3,4-oxylan-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxylancyclohexanecarboxylate) Rate), bis (3,4-oxyranecyclohexylmethyl) adipate, bis (3,4-oxylan-6-methylcyclohexylmethyl) adipate, diethyleneglycolbis (3,4-oxyranecyclohexylmethyl ether), ethyleneglycolbis (3, 4-Oxylane Cyclohexyl Methyl Ether), 2,3,14,15-Dioxirane-7,11,18,21-Tetraoxatrispyro- [5.2.2.5.2.2] Henikosan (also 3, 4-Oxylancyclohexanespiro-2', 6'-dioxanespiro-3'', 5''-dioxanespiro-3''', 4'''-a compound that can also be named oxylancyclohexane), 4- (3,4) -Fats such as oxylancyclohexyl) -2,6-dioxa-8,9-oxylancepyro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxylancyclopentyl ether, and dicyclopentadiendioxide. Examples thereof include a three-membered cyclic cyclic ether group bonded to a cyclic ring. The oxylan compound may be used alone or in combination of two or more.

The oxylan compound is more preferably an oxylan compound having an aromatic ring in order to improve heat resistance and moist heat resistance.

Substituents of the aromatic ring include, for example, phenyl, phenylene, tolyl, trileno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalidene, isophthalidene, terephthalidene, phenethylidene, phenethylidine, styryl, styrylidene, as-psoidcumyl, v-psoidcumyl, s. -Psoid cumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamylden, cinnamyldin, juryl, julylen, timil, carbacryl, kuminyl, kuminyllidene, neofil, xenyl, benzhydryl, benzhydryllidene, trityl and the like.

In addition, cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadiene;

[4n + 2] annulene (but not containing benzene) having 3 or more carbon atoms constituting the ring can be mentioned.

Aromatic polycyclic compounds such as biphenyl and triphenylmethane;

Pentalene, Inden, Indan, Ninhydrin, Naphthalene, Tetraline, Decalin, Sapotalene, Cadalen, Eudaren, Naftor, Menadiol, Gosipole, Naftquinone, Lausson, Yuglon, Menadione, Plumbagin, Futhiocol, Echinochrome A, Alkannin, Sikonin Carbon-condensed bicyclic system such as naphthoyl, naphthalic acid, naphthalate, acetomenafton, naphthoic acid, naphthionate, naphthionyl, dansyl, croseic acid, flabian acid, chromotropic acid, neocuperon, azulene, camazulene, guaiazulene, heptalene, octalene, purprogalin:

as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaften, phenanthren, phenanthryl, phenanthrylium, phenanthrlidene, phenanthrylene, Phenantrol, Morhole, Phenantron, Phenantraquinone, Pimantolen, Reten, Anthracene, Anthracene, Anthrilium, Anthracene, Anthracene, Anthrol, Anthranol, Anthralobin, Anthralin, Ditranol, Anthroyl, Anthron, Biantron, Anthraquinone, Anthraquinonel , Anthracene, alizarin, quinizarin, anthralfin, chrysadine, anthragalol, purpurin, flavopurpurin, anthraquinone, quinalizarin, tectoquinone, chrysophanol, chrysophanolic acid, emodin, rain, kelmesic acid, carmic acid, Carbon-condensed tricyclic system of dianthrimid, anthrimid, chrysamic acid, corhitin, etc.;

Triphenylene, Trindane, Fluoranthene, Acephenanthrene, Acephenanthrene, Aceanthrene, Aceanthrene, Triphenylene, Pyrene, Chrysene, Tetracycline, Tetracycline, Naftacene, Rubrene, Tetracycline, Chlortetracycline, Oxytetracycline, Playaden, Benzoanthrone, etc. Carbon-condensed tetracycline system;

Carbon-condensed pentacyclic system such as picene, perylene, pentaphene, pentacene, tetraphenylene, colantrilen, colantolen;

Corannulene, Fluminen, Anthanthrene, Zethrene, Hexacene, Hexaphen, Hexacene, Rubisen, Coronene, Trinaphthylene, Heptacene, Heptacene, Pyrantren, Octaphen, Octacene, Terylene, Naftasenonaphthacene, Nonaphen, Nonacen, Violantren, Biolantron, Isobiolan Examples thereof include carbon-fused ring systems having 6 or more rings, such as trene, isobiolantron, ovalenne, decaphene, decasene, decacyclene, pentasenopentacene, quaterylene, and hexasenohexacene.

As the cationically polymerizable composition other than the oxylan compound, an oxetanyl group-containing compound which is a 4-membered ring ether, a cyclic ether compound having 5 or more membered rings, or a cyclic heterocompound having two or more oxygens or a heterogroup other than oxygen is preferable. ..

Examples of the oxetanyl group-containing compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and 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. Can be mentioned. The oxetanyl group-containing compound may be used alone or in combination of two or more.

As the cyclic hetero compound, 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 a lactone. The cyclic formal compound is more preferably a compound selected from dioxolane, dioxane and trioxane.

The cyclic carbonate can be synthesized, for example, by a method of depolymerizing a polymer obtained by a reaction of glycol with a dialkyl carbonate (see JP-A-2-5636), or by a reaction of a corresponding alkylene oxide with carbon dioxide. Cyclic carbonate has a structure of 5-membered ring, 6-membered ring or 7-membered ring or more, 1,3-dioxolane in the 5-membered ring, 1,3-dioxane in the 6-membered ring, and 1,3 in the 7-membered ring. -Although it is contained in dioxepan, it is independently classified as a cyclic carbonate because the carbon at the 2-position is a carbonyl carbon.
Cyclic carbonates are, for example, ethylene carbonate (also referred to as 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-dioxolane-2-one , 4-Hexyl-5-methylene-1,3-dioxolane-2-one, 4,5-dimethyl-1,3-dioxolane-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- On, 4,5-bismethylene-1,3-dioxolane-2-one, 4,4-dimethyl-1,3-dioxolane-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 Anhydrous, 4-vinyl-1,3-dioxolane-2-one, 4-phenethyl-5-vinyl-1,3-dioxolane-2-one, 4-methylene-1,3-dioxolane-2-one, 4 -(3-Butenyl) -1,3-dioxolane-2-one, 4- (5-hydroxy-6,6-dimethyltetrahydro-2H-pyran-2-yl) -1,3-dioxolane-2-one, 4-[(E) -Iodomethylene] -5-cyclopropyl-1,3-dioxolane-2-one, 4-cyclohexyl-5-vinyl-1,3-dioxolane-2-one, 4- (allyloxy)- 4,5,5-trimethyl-1,3-dioxolane-2-one, 4-[(1E) -1,3-butadienyl] -1,3-dioxolane-2-one, 4-ethyl-4-methyl- 5-Methylene-1,3-dioxolane-2-one, 4- (2-methyl-2-propenylidene) -5,5-dimethyl-1,3-dioxolane-2-one, 4- [4- (methoxycarbonyl) Oxy) Butyl] -1,3-dioxolane-2-one, 4-vinyl-5,5-diethyl-1,3-dioxolane-2-one, 4-phenyl-5-bi Nyl-1,3-dioxolane-2-one, 4,5,5-trimethyl-4- (1-propynyl) -1,3-dioxolane-2-one, 4-vinyl-5,5-bis (2-) Cyclohexylethyl) -1,3-dioxolane-2-one, 4,5,5-trimethyl-4- (3-methyl-3-butene-1-ynyl) -1,3-dioxolane-2-one, 4- (Vinyloxymethyl) -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(E) -3-butene-1-iriden] -1,3-dioxolane-2-one, 4- [(E) -3-Buten-1-iriden] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(Z) -1-phenyl-3-butene-1-iriden]- 1,3-Dioxolane-2-one, methyl methacrylate (2-oxo-1,3-dioxolane-4-yl), 4-methyl-5-[(E) -3-butene-1-iriden] -1 , 3-Dioxolane-2-one, 4-methyl-5-[(Z) -3-butene-1-iriden] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(Z) ) -2-Butin-1-iriden] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(E) -ethylidene] -1,3-dioxolane-2-one, 4,4 -Dimethyl-5-[(Z) -3-butene-1-iriden] -1,3-dioxolane-2-one, 4- (1-hexynyl) -4-methyl-1,3-dioxolane-2-one , 4- (1-Propenyloxymethyl) -1,3-dioxolane-2-one, 4-[(1E) -1-methyl-3-butenylidene] -1,3-dioxolane-2-one, 4-[ (1Z) -1-phenyl-3-butenylidene] -1,3-dioxolane-2-one, 4,4-dipentyl-5-[(1E) -1,3-butadienyl] -1,3-dioxolane-2 -On, 4-phenyl-5-methylene-1,3-dioxolane-2-one, 4-methyl-5-methylene-1,3-dioxolane-2-one, 4-methyl-4-vinyl-5-methylene -1,3-Dioxolane-2-one, 4-propargyl-5-methylene-1,3-dioxolane-2-one, 4-[(E) -bromomethylene] -1,3-dioxolane-2-one, [(E) -2-oxo-5,5-dimethyl-1,3-dioxolane-4-iriden] ethyl acetate, 4-[(E) -2- (tert-butoxycarbonyloxy) ethylidene]- 1,3-Dioxolan-2-one, 4-ethyl-5-methylene-1,3-dioxolan-2-one, 4- (hydroxymethyl) -1,3-dioxolan-2-one, 4-[(E) ) -2- (tert-butoxycarbonyloxy) ethylidene] -5-methyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, 4- (1-naphthyl) ) -5-Vinyl-1,3-dioxolan-2-one, 4,4-bis (2-cyclohexylethyl) -5-[(1E) -1,3-butadienyl] -1,3-dioxolan-2- On, (4S) -4-phenyl-4-methyl-5- (1,3-butadienyl) -1,3-dioxolan-2-one, 4- (2-propin-1-iriden) -5,5- Dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 5-butyl-5-methyl-4-methylene-1,3-dioxolan- 2-one, glycerin carbonate, 4- (butoxymethyl) -1,3-dioxolan-2-one, 4- (allyloxymethyl) -1,3-dioxolan-2-one, 4- (hydroxymethyl) -1 , 3-Dioxolan-2-one, 4- (methoxymethyl) -1,3-dioxolan-2-one, 4- (4-ethenylbenzyloxymethyl) -1,3-dioxolan-2-one, 4- Ethyl-4-methyl-5- (3-phenylpropyridene) -1,3-dioxolan-2-one, 4-ethyl-4-methyl-5-benzylidene-1,3-dioxolan-2-one, 4-( Hexylthiomethyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(E) -2-phenylethylidene] -1,3-dioxolan-2-one, 4- (p-tolyl) )-1,3-Dioxolan-2-one, 4-methyl-5-phenyl-1,3-dioxolan-2-one, 4-benzyl-1,3-dioxolan-2-one, 4- (benzyloxymethyl) )-1,3-Dioxolan-2-one, 4-phenyl-1,3-dioxolan-2-one, 4-phenyl-4-methyl-5-methylene-1,3-dioxolan-2-one, 4- Phenyl-1,3-dioxolan-2-one, 4-methyl-4-phenyl-1,3-dioxolan-2-one, 4-phenoxy-1,3-dioxolan-2-one, 4-butoxy-4, 5-dimethyl-5-phenyl-1,3-dioki Solan-2-one, (4S) -4β- (phenylethynyl) -4-phenethyl-5-[(Z) -benzylidene] -1,3-dioxolane-2-one, 4- [4- (phenoxycarbonyloxy) ) Butyl] -1,3-dioxolane-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1,3-dioxolane-2-one, 4-oxylanyl-1,3-dioxolane-2-one , 4- [4- (2-oxo-1,3-dioxolane-4-ylmethylcarbamoyloxy) butyl] -1,3-dioxolane-2-one, 4- (2-oxo-1,3-dioxolane-) 4-Ilmethylcarbamoyloxymethyl) -1,3-dioxolane-2-one, 4,4'-bi [1,3-dioxolane-2-one], 4,4'-tetramethylenebis (1,3-) Dioxolane-2-one), 4,4'-(ethylenebisthiobistetramethylene) bis (1,3-dioxolane-2-on), 4,4'-[1,6-hexanediylbis (oxymethylene)) ] Bis (1,3-dioxolane-2-on), 4,4'-[hexamethylenebis (thioethylene)] bis (1,3-dioxolane-2-on), 4,4'-[isobutylidenebis (4,1-phenylene) bisoxybismethylene] bis (1,3-dioxolane-2-one), 4,4'-[isopropyridenebis [(4,1-phenylene) oxymethylene]] bis (1, 3-Dioxolane-2-one), 4,4-dimethyl-5-[(Z) -benzylidene] -1,3-dioxolane-2-one, 4- [2- (benzyloxy) ethyl] -1,3 -Dioxolane-2-one, 4- [2- (trityloxy) ethyl] -1,3-dioxolane-2-one, 4,5-diphenyl-1,3-dioxolane-2-one, 4,4-dimethyl -5- [1- (1-naphthyl) ethenyl] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[1- (2-naphthyl) ethenyl] -1,3-dioxolane-2 -On, 4,4-dimethyl-5- [1- (4-methylphenyl) ethenyl] -1,3-dioxolane-2-one, 4,4-dimethyl-5- [1- (4-methoxyphenyl) Ethenyl] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[1- (4-hydroxyphenyl) ethenyl] -1,3-dioxolane-2-one, 4,4-dimethyl-5 -(1-Methylene-2-phenyl-2-prope Nyl) -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(E) -1-methylene-3-phenyl-2-propenyl] -1,3-dioxolane-2-one, 4 , 4-dimethyl-5- (1-phenylethenyl) -1,3-dioxolane-2-one, 4-methyl-5- (1-phenylethenyl) -1,3-dioxolane-2-one, 4 , 4-dimethyl-5-[(E) -3-phenyl-1-propenyl] -1,3-dioxolane-2-one, 4- (1-phenylethenyl) -1,3-dioxolane-2-one , 4,4-dimethyl-5- (1-phenyl-1-propenyl) -1,3-dioxolane-2-one, 4,4-dimethyl-5- (1,2-diphenylethenyl) -1,3 -Dioxolane-2-one, 4,4-dimethyl-5- (2-methyl-1-phenyl-1-propenyl) -1,3-dioxolane-2-one, 4,4,5-trimethyl-5-( 1-phenylethenyl) -1,3-dioxolane-2-one, 4- (benzyloxymethyl) -1,3-dioxolane-2-one, 4,4-diphenyl-1,3-dioxolane-2-one , 4,4'-[(1,3-phenylene) bis (oxymethylene)] bis (1,3-dioxolane-2-one, 4,4-dimethyl-5-[(Z) -1-naphthylmethylene]] -1,3-Dioxolane-2-one, 4,4-dimethyl-5-[(Z) -4-methoxybenzylidene] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[((Z) -4-methoxybenzylidene] -1,3-dioxolane-2-one Z) -4-hydroxybenzylidene] -1,3-dioxolane-2-one, 4- (phenylethynyl) -4-methyl-1,3-dioxolane-2-one, 4- (phenylethynyl) -4,5 -Didimethyl-1,3-dioxolane-2-one, 4- [1- (4-methoxyphenoxy) vinyl] -5,5-diethyl-1,3-dioxolane-2-one, 4- [1- (4) - -[2- (2-oxo-1,3-dioxolane-4-yl) ethoxy] -2H-1-benzopyran-2-one, 7- [2- (2-oxo-4-methyl-1,3-) Dioxolane-4-yl) ethoxy] -2H-1-benzopyran-2-one, 5- (benzyloxy) -1,3-dioxolane-2-one , 4- (Isobutoxymethyl) -1,3-dioxolane-2-one, 4- (4-nonylbenzyloxymethyl) -1,3-dioxolane-2-one, 4- (4-chlorophenylthiomethyl)- 1,3-Dioxolane-2-one, 4- [3- (chloromethyl) phenyl]-




1,3-Dioxolane-2-one, 4- [4- (chloromethyl) phenyl] -1,3-dioxolane-2-one, 4,4-dipropyl-5- [1- (4-methoxyphenoxy) ethenyl ] -1,3-Dioxolane-2-one, 4,4-dipentyl-5-[1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolane-2-one, 4,4-diisopropyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolane-2-one, 4,4-diphenethyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolane-2- On, 4,4-bis (2-cyclohexylethyl) -5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolane-2-one, 4- [1- (phenylthio) cyclohexyl] -1 , 3-Dioxolane-2-one, 4- (3-methoxy-4-ethoxyphenyl) -5 (hydroxymethyl) -1,3-dioxolane-2-one, 4- (phenoxycarbonyloxymethyl) -1, 3-Dioxolane-2-one, 4-benzylidene-5,5-dimethyl-1,3-dioxolane-2-one, 4-[(2-naphthyl) methylene] -5,5-dimethyl-1,3-dioxolane -2-one, 4- (4-chlorobenzylidene) -5,5-dimethyl-1,3-dioxolane-2-one, 5-methyl-5-phenyl-4- (3-phenylpropyridene) -1,3 -Dioxolane-2-one, 5,5-dimethyl-4- (3-phenylpropyridene) -1,3-dioxolane-2-one, 4- [4- (chlorocarbonyloxy) butyl] -1,3-dioxolane -2-one, 4-chloro-1,3-dioxolane-2-one, 4-chloro-4,5-dimethyl-1,3-dioxolane-2-one, 4- (chlorocarbonyloxymethyl) -1, 3-Dioxolane-2-one, 4- (p-chlorophenoxymethyl) -1,3-dioxolane-2-one, 4- (chloromethyl) -1,3-dioxolane-2-one, 4,5-dichloro -1,3-Dioxolane-2-one, (4S, 5R) -4,5-diphenyl-1,3-dioxolane-2-one, 4α, 5α-dimethyl-1,3-dioxolane-2-one, ( 4R, 5R) -4,5-dimethyl-1,3-dioxolane-2-one, (4S, 5S) -4,5-dimethyl-1,3-dioxolane-2-one, (4S) -4β-methyl -1, 3-Dioxolane-2-one, (R) -4-methyl-1,3-dioxolane-2-one, (S) -5-ethyl-1,3-dioxolane-2-one, 4-[(triphenyl) Cyril) Methyl] -5,5-dimethyl-1,3-dioxolane-2-one, 4- [9- (3-thienyl) nonyl] -1,3-dioxolane-2-one, 4- (methylaminomethyl) )-1,3-Dioxolane-2-one, 4- (4-chlorophenylthio) -1,3-dioxolane-2-one, 4- (phenylthio) -1,3-dioxolane-2-one, 4- ( 4-methoxyphenylthio) -1,3-dioxolane-2-one, 4- (4-bromophenylthio) -1,3-dioxolane-2-one 4- (phenylthiomethyl) -1,3-dioxolane- 2-on, 4,4'-[sulfonylbis (p-phenyleneoxymethylene)] bis (1,3-dioxolane-2-one), 4- (4-methylphenylthio) -1,3-dioxolane-2 -On, 4,4,5,5-tetramethyl-2- (phenylsulfonyloxyimino) -1,3-dioxolane, 2- (4-nitrophenoxy) -4-methyl-2-phospha (V) -1 , 3-Dioxolane-2-one, 4- (glycidyloxymethyl) -1,3-dioxolane-2-one, glycidylcarbamide acid (2-oxo-1,3-dioxolan-4-yl) methyl, 4-( Norborna-5-en-2-yl) -1,3-dioxolane-2-one, 4- [2- (2-naphthyl) ethyl] -5-methoxy-1,3-dioxolane-2-one, 4- [2- (1-naphthyl) ethyl] -5-methoxy-1,3-dioxolane-2-one, 4,4-dimethyl-5- (3-thienylmethylene) -1,3-dioxolane-2-one, 4- [2- [dimethyl (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolane-2-one, 4- [2-[(methyl) bis (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolane -2-one, 4- [2- (trimethylsilyl) ethyl] -1,3-dioxolane-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1,3-dioxolane-2-one, 4 -[4- (2-oxo-1,3-dioxolane-4-ylmethylcarbamoyloxy) butyl] -1,3-dioxolane-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1, 3-Geo 5-membered ring carbonates such as xoran-2-one, 4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxymethyl) -1,3-dioxolane-2-one;

Trimethylene carbonate (also called 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 (also called 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-ethenyl-1,3-dioxane-2-one, 5-cyano-5-methyl-1,3- Dioxane-2-one, 4,4-dimethyl-1,3-dioxane-2-one, 5-butyl-1,3-dioxane-2-one, 5,5-dioxane-1,3-dioxane-2-one On, 5-ethyl-5-phenyl-1,3-dioxane-2-one, 2-oxo-5-ethyl-1,3-dioxane-5-ylmethyl methacrylate, 5-methyl-5-phenyl-1, 3-Dioxane-2-one, 4-styryl-5,5-dimethyl-1,3-dioxane-2-one, 4-stylyl-1,3-dioxane-2-one, 4- (1-heptenyl)- 1,3-Dioxane-2-one, 4-ethenyl-6-phenyl-1,3-dioxane-2-one, 4-isopropenyl-6-phenyl-1,3-dioxane-2-one, 4-allyl -6-Phenyl-1,3-dioxane-2-one, 4-ethenyl-6-tert-butyl-1,3-dioxane-2-one, 4-styryl-5,5-dimethyl-6-isopropyl-1 , 3-Dioxane-2-one, 5- [2- (2-amino-9H-purine-9-yl) ethyl] -1,3-dioxane-2-one, 4- (1-phenylethenyl)- 1,3-Dioxane-2-one, 5,5-diphenyl-1,3-dioxane-2-one, 5-methyl-4- (1-phenylethenyl) -1,3-dioxane-2-one, 4,4-dimethyl-6- (1-phenylethenyl) -1,3-dioxane-2-one, 5-methylene-1,3-dioxane-2-one, 4-[(E) -styryl]- 1,3-Dioxane-2-one, 5-octyl-1,3-dioxane-2-one, 5-dodecyl-1,3-di Oxane-2-one, 2-oxo-5-methyl-1,3-dioxane-5-carboxylate benzyl, 4,6-dimethyl-1,3-dioxane-2-one, 4-methoxybenzoate 2-oxo -5-Methyl-1,3-dioxane-5-ylmethyl, 2-oxo-5-methyl-1,3-dioxane-5-ylmethyl, 4-nitrobenzoate 2-oxo-5-methyl-1, 3-Dioxane-5-ylmethyl, 4,4,6-trimethyl-1,3-dioxane-2-one, 5-ethyl-5- (methoxycarbonyloxymethyl) -1,3-dioxane-2-one, 5 -Ethyl-5- (ethoxycarbonyloxymethyl) -1,3-dioxane-2-one, 5- (4-butoxyphenyl) -1,3-dioxane-2-one, 5- [4- (pentyloxy) Phenyl] -1,3-dioxane-2-one, 5- (4-propoxyphenyl) -1,3-dioxane-2-one, 5- [4- (hexyloxy) phenyl] -1,3-dioxane- 2-one, 5-allyl-1,3-dioxane-2-one, 5- (benzyloxycarbonyl) -1,3-dioxane-2-one, 5-methyl-4- (benzoyloxymethyl) -1, 3-Dioxane-2-one, 5-methyl-4- (4-nitrobenzoyloxymethyl) -1,3-dioxane-2-one, 5-methyl-4- (4-methoxybenzoyloxymethyl) -1, 3-Dioxane-2-one, 5- (4-methylene-5-hexene-1-iriden) -1,3-dioxane-2-one, 5-ethyl-5- (4-vinylbenzyloxymethyl) -1 , 3-Dioxane-2-one, 5-ethyl-5- (4-vinylbenzyloxymethyl) -1,3-dioxane-2-one, 5- (benzyloxy) -1,3-dioxane-2-one , 5-Hydroxy-1,3-dioxane-2-one, 4-methylene-5,5-dimethyl-1,3-dioxane-2-one, 5-ethyl-5- (2-hydroxyethyl) -1, 3-Dioxane-2-one, 4- [1- (phenylthio) cyclohexane] -1,3-dioxane-2-one, 4- [4- (octyloxy) phenylazo] -6-hexyl-1,3-dioxane -2-one, 4- (4-methoxyphenylazo) -6-hexyl-1,3-dioxane-2-one, 4- [4- (octyloxy) phenylazo] -6-decyl-1,3-dioxane -2-on, 2- Allyl oxo-5-methyl-1,3-dioxane-5-carboxylate, 4- [1- (phenylthio) cyclohexyl] -5,5-dimethyl-1,3-dioxane-2-one, 4-allyl-6 -Methyl-1,3-dioxane-2-one, 5-ethyl-5- (benzyloxymethyl) -1,3-dioxane-2-one, 5- [2- (benzyloxy) ethoxy] -1,3 -Dioxane-2-one, 5- (allyloxy) -1,3-dioxane-2-one, 5- [3- (2-hydroxyethylthio) propoxy] -1,3-dioxane-2-one, 5- (Benzyloxycarbonylamino) -1,3-dioxane-2-one, 5- [6- [4- (4-pentylcyclohexyl) phenoxy] hexyloxy] -1,3-dioxane-2-one, 4-( Iodomethyl) -6- [2- (4-methoxybenzyloxy) ethyl] -1,3-dioxane-2-one, (5S) -4-vinyl-5β- (2,2-dimethoxyethyl) -1 , 3-Dioxane-2-one, 5-allyl-5-propargyl-1,3-dioxane-2-one, 4-vinyl-5- (1-methyl-5-imidazolylmethyl) -1,3-dioxane- 2-on, 5-benzylidene-1,3-dioxane-2-one, 5- (glycidyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5- (allyloxymethyl) -5 Ethyl-1,3-dioxane-2-one, 5,5-bis (azidomethyl) -1,3-dioxane-2-one, 5-methyl-5-[[2- (vinylsulfonyl) ethyl] thiomethyl]- 1,3-Dioxane-2-one, 5- (allyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5,5'-(oxybismethylene) bis (5-ethyl-1,5, 3-dioxane-2-one), 5,5'-(4,7-dioxanedecane-1,10-diyl) bis (1,3-dioxane-2-one), 5,5'-(ethylenebisthiobis) Tetramethylene) bis (1,3-dioxane-2-one), 5-methyl-5- (2-oxo-1,3-dioxolan-4-ylmethyl) -1,3-dioxane-2-one, 5- Ethyl-5- (2-oxo-1,3-dioxolan-4-ylmethyl) -1,3-dioxane-2-one, 5-[(2-oxo-1,3-dioxolan-4-yl) methyl] -5-propyl-1,3-dioxane-2-one, 5- (2-oxo-1,3- 6-membered ring carbonate such as 3-dioxolane-4-ylmethoxy) -5-ethyl-1,3-dioxane-2-one;

Tetramethylene carbonate (also called 1,3-dioxepan-2-one), 5-methyl-1,3-dioxepan-2-one, 4-methyl-1,3-dioxepan-2-one, 5,5-dimethyl -1,3-Geoxepane-2-one, 5-Phenyl-1,3-Gyoxepane-2-one, 4-Phenyl-1,3-Gyoxepane-2-one, 4- [1- (Phenylthio) cyclohexyl]- Examples thereof include 7-membered ring carbonates such as 1,3-dioxepan-2-one and 5,5'-(ethylenebisthiobistrimethylene) bis (1,3-dioxepan-2-one).
Among these, 5-membered ring carbonates such as ethylene carbonate, propylene carbonate and glycerin carbonate are preferable in terms of reactivity.

In the polymerizable composition of the present invention, various additives can be appropriately blended as long as the problems of the present invention can be solved. For example, organic or inorganic fillers from the viewpoints of reducing polymerization curing shrinkage rate, reducing thermal expansion rate, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, and improving coloring. Can be blended. As such a filler, materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments are preferable. The shape of the filler is not particularly limited and may be, for example, particulate or fibrous. When the above polymer material is blended, a silane coupling agent, a flexibility-imparting agent, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropy-imparting agent, a dispersion stabilizer, and a flow. It is also possible to dissolve, semi-dissolve or microdisperse in the polymerizable composition as a polymer blend or polymer alloy rather than as a stand-alone filler such as a sex-imparting agent and a defoaming agent.

The polymerizable composition of the present invention can be prepared by uniformly mixing each component described above by a known method. The polymerizable composition can be applied to various uses in any form of liquid, paste or film. The polymerizable composition of the present invention is preferably used as a coating agent or an adhesive.

It is preferable that the viscosity of the polymerizable composition of the present invention is appropriately adjusted according to the mode of use thereof. The polymerizable composition of the present invention preferably does not contain an organic solvent, but a solvent may be used to adjust the viscosity. Examples of the solvent include hydrocarbon compounds such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene and xylene. By using an organic solvent, the viscosity of the polymerizable composition can be easily adjusted.

The sheet of the present invention comprises a base material and a resin layer formed of a polymerizable composition.
The resin layer is formed by applying a polymerizable composition onto a substrate and then irradiating it with active energy rays to promote the polymerization reaction of α, β-ethylenically unsaturated bond groups.

When the resin layer is used for optical purposes, its thickness is preferably about 0.1 to 6 μm, more preferably 0.1 μm to 3 μm. By setting the thickness to about 0.1 to 6 μm, sufficient adhesion and adhesive strength are further improved. In this case, the viscosity of the polymerizable composition is preferably about 1 to 1,500 mPa · s, more preferably about 10 to 1,300 mPa · s, and even more preferably about 20 to 1,000 mPa · s. When the viscosity is set to 1 to 1,500 mPa · s, the resin layer is easily formed and the optical characteristics are improved. The optical application is an application such as a hard coat film and a laminate for an optical element such as a polarizing film.

When the resin layer is used for forming a touch panel, its thickness is preferably about 6 to 300 μm, more preferably about 20 μm to 250 μm. By setting the thickness to about 6 to 300 μm, it is possible to efficiently fill the gaps of the touch panel, and it is easy to obtain stress relaxation properties and creep characteristics. In this case, the viscosity of the polymerizable composition is preferably about 1,500 to 100,000 mPa · s, preferably 3,000 to 50,000 mPa · s, in order to secure the specified coating thickness and the uniformity of the film thickness. The degree is more preferable.

The polymerizable composition of the present invention is preferably used for coating agents and adhesives. The sheet of the present invention may be provided with a resin layer on one side or both sides of the base material. The resin layer is cured by irradiation with active energy rays after coating.

The method of applying the polymerizable composition is, for example, a Meyer 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, a curtain coater, a knife coater, a reverse coater, and a spin. A known coating method such as a coater can be used.

The active energy ray preferably has light energy including a wavelength range of 150 to 550 nm, and more preferably ultraviolet light. Examples of light energy light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, and metal halide lamps. Further, in the present invention, a laser beam, an electron beam, or the like can also be used as an active energy ray.

The irradiation intensity of the active energy ray is preferably about 10 to 2000 mW / cm ² . When used at the above irradiation intensity, it can be cured in a short time, and the base material is not easily deteriorated by the irradiation heat. The integrated irradiation amount expressed as the product of the irradiation intensity and the irradiation time is preferably 30 to 5,000 mJ / cm ² . When the integrated irradiation amount is within the above range, curing can be performed in a short time, and the productivity of the sheet is improved. The conventional active energy ray-polymerizable composition requires an integrated irradiation dose of 1,000 mJ / cm ² or more, whereas the polymerizable composition of the present invention has a low integrated irradiation dose of less than 500 mJ / cm ² . Even if there is, curing progresses.

The sheet of the present invention can be used as a laminate which is a resin layer formed by forming a plurality of substrates from a polymerizable composition. The resin layer is a layer cured by irradiation with active energy rays, and its glass transition temperature (hereinafter referred to as Tg) is preferably about -80 ° C to 150 ° C, more preferably -40 to 120 ° C, and 0 to 120. ° C is more preferred. When the Tg is about -80 ° C to 150 ° C, the punching workability of the laminated body is further improved. The form of the laminated body is preferably plate-shaped or sheet-shaped.

The polymerizable composition of the present invention can be used as an active energy ray polymerizable coating agent (hereinafter referred to as a coating agent). In the coating agent, the polymerizable composition covers one or both sides of the base material to form a coating layer. In such an embodiment, 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.

Further, the polymerizable composition of the present invention can be used as an active energy ray-polymerizable adhesive (hereinafter referred to as an adhesive).
When the adhesive is applied to the sheet of the present invention, it is necessary to use a material that easily transmits the active energy rays as the base material in order to proceed the polymerization reaction by irradiation with the active energy rays.
It is preferable to use a transparent film or a transparent glass plate as the base material. However, if a transparent film or a transparent glass plate is used for one of the multiple base materials, the other base material is a base material that is difficult for active energy rays to pass through, for example, wood, metal plate, or plastic plate. , A base material made of a material such as a processed paper product can also be used.
Further, the transparent film may have a single layer or a multilayer structure in which a plurality of base materials are laminated.

An example of the case where a transparent film is used as a base material for the laminate of the present invention will be described.

When the resin layer contained in the laminate of the present invention is a coat layer, the laminate preferably has, for example, a transparent film / coat layer or a coat layer / transparent film / coat layer. Such a laminate is obtained by applying a polymerizable composition to at least one surface of a transparent film and polymerizing and curing the polymerizable composition to form a coat layer.

When the resin layer contained in the laminate of the present invention is an adhesive layer, the laminate is preferably, for example, a transparent film / adhesive layer / transparent film, or a transparent film / adhesive layer / transparent film / adhesive layer / transparent film. Further, as the laminate, a transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film is also preferable. It is preferable to irradiate the resin layer with active energy rays after laminating.

When a transparent film is used as the base material, the laminate can be suitably used for optical applications. From the viewpoint of obtaining good optical properties, the transparent film used in the above-mentioned laminate is made of, for example, a thermoplastic resin having excellent optical properties such as transparency, mechanical strength, thermal stability, moisture barrier property, and isotropic property. It is preferably a transparent film to be composed. Such a transparent film is also referred to as a plastic film or a plastic sheet, for example, a polyolefin film such as a polyvinyl alcohol film, a polytriacetyl cellulose film, polypropylene, polyethylene, a polycycloolefin, and an ethylene-vinyl acetate copolymer, polyethylene. Polyester film such as terephthalate and polybutylene terephthalate, polycarbonate film, polynorbornen film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film , And polyoxylan-based films.

In the laminated body of the present invention, when a plurality of transparent films are laminated to form a multilayer film, the transparent films used may have the same composition or different. For example, a polyacrylic film may be laminated on a polycycloolefin film via an adhesive layer.

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

In the laminate for an optical element of the present invention, it is preferable to use an optical film mainly used for optical applications as a transparent film for a base material. Here, the optical film is a transparent film itself subjected to a special treatment, and is a film having at least one or more optical functions such as light transmission light diffusion, light collection, refraction, and scattering. The optical film may be a laminated body. The laminate for optical elements of the present invention can form a laminate for optical elements by forming a resin layer made of a polymerizable composition on at least one surface of an optical film.

The laminate for an optical element is, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptical polarizing film, an antireflection film, a light diffusion film, a brightness improving film, and a prism film (prism sheet). Also referred to as), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like. Further, the polymerizable composition of the present invention may be used as an adhesive to attach the laminate for an optical element to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, or an organic EL module. Further, the polymerizable composition of the present invention may be used as an adhesive to attach the laminate for an optical element to another optical film.

A polarizing film will be specifically described as an example of a laminate for an optical element.
The polarizing film, also called a polarizing plate, is an optical film having a multilayer structure in which a polarizing element is sandwiched between two film-like substrates. When a transparent film is provided on both sides of the polarizing element in the polarizing film, a transparent film made of the same polymer material may be used on the front and back sides thereof, or a transparent film made of a different polymer material or the like may be used. The polarizing film has, for example, a structure in which both sides of a polyvinyl alcohol-based polarizing element are sandwiched between two poly-triacetyl cellulose-based protective films (hereinafter referred to as “TAC films”) which are polyacetyl cellulose-based films. As another example, in the polarizing film, one side or both sides of the polyvinyl alcohol-based polarizing element is sandwiched between films such as polycycloolefi-based film, polyacrylic-based film, polycarbonate-based film, and polyester-based film, which are polynorbornene-based films. It has a structure.

Although not particularly limited, for example, the above-mentioned polarizing plate (polarizing film) can be manufactured as follows.
(I) The polymerizable composition of the present invention is coated on one main surface of the first transparent film (first protective film) as an adhesive to form a first polymerizable adhesive layer. Further, the polymerizable composition of the present invention is coated on one main surface of the second transparent film (second protective film) as an adhesive to form a second polymerizable adhesive layer. Next, the first polymerizable adhesive layer and the second polymerizable adhesive layer are superposed on both main surfaces of the polyvinyl alcohol-based polarizing element at the same time / or in order. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second adhesive layers.

(II) The polymerizable composition of the present invention is coated on one main surface of a polyvinyl alcohol-based polarizing element as an adhesive to form a first polymerizable adhesive layer, and the first polymerizable adhesive layer is formed. The surface is covered with a first transparent film (first protective film). Next, the polymerizable composition of the present invention is coated on the other main surface of the polyvinyl alcohol-based polarizing element as an adhesive to form a second polymerizable adhesive layer, and the surface of the second polymerizable adhesive layer is formed. Is covered with a second protective film. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second polymerizable adhesive layers.

(III) A second protective film is laminated on one main surface of the first transparent film (first protective film) and an end portion on which a polyvinyl alcohol-based polarizing element is laminated, and on the other surface of the polyvinyl alcohol-based polarizing element. The polymerizable composition of the present invention is applied to each of the end portions as an adhesive, and the laminate is passed between the rolls to spread the adhesive between the layers. Next, the laminated body is irradiated with active energy rays to polymerize and cure the active energy ray-polymerizable adhesive.

As described above, as an embodiment of the laminated body for optical elements, a polarizing film has been described as an example. However, the laminate is characterized in that the polymerizable composition of the present invention is used as a coating agent or an adhesive for various substrates. Therefore, it should be easily understood that a laminate that can be suitably used for optical applications can be constructed not only in a polarizing film but also in other embodiments using various other substrates.

Hereinafter, the present invention will be described with reference to specific examples. However, the present invention is not limited to the following examples. Further, in the following, "part" is "part by weight", and "%" is "% by weight".

"Weight average molecular weight" is a numerical value measured using gel permeation chromatography "HLC-8220GPC" manufactured by Tosoh Corporation, and separation columns: "TSK-GEL SUPER H5000" and "TSK-GEL" manufactured by Tosoh Corporation. Polystyrene measured at a flow rate of 0.6 ml / min by connecting four SUPER H4000, TSK-GEL SUPER H3000, and TSK-GEL SUPER H2000 in series and using tetrahydrofuran at a temperature of 40 ° C as the mobile phase. Converted weight Average molecular weight.

<Preparation of active energy ray-polymerizable composition>
[Formulation Examples 1-18, 20-31, 33-38 ]
In a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less, the mixture was charged at the ratio (part by weight) shown in Table 1, sufficiently stirred with a disper, and after sufficient defoaming, a compounding example was performed. The active energy ray-polymerizable compositions shown in the above were obtained respectively. The water content of the active energy ray-reactive composition was measured by the Karl Fischer titration method according to JIS K0113-2005, and was adjusted by appropriately adding purified water so as to have the values shown in Table 1. The blanks in Table 1 represent 0 parts by weight.

For the active energy ray-polymerizable composition of the formulation example shown in Table 1, the solution view and viscosity were determined according to the following method, and the results are shown in Table 2.

The abbreviations in the table are as follows.
4HBA: 4-Hydroxybutyl acrylate 2HEA: 2-Hydroxyethyl acrylate 2HPA: 2-Hydroxypropyl acrylate CHDMMA: 1,4-Cyclohexanedimethanol acrylate IBXA: Isobornyl acrylate DCPA: Dicyclopentanyl acrylate M- 315: Triacrylic acid isocyanuric acid ethylene oxide modified product (manufactured by Toagosei Co., Ltd.)
ACMO: 4-acryloyl morpholine GMA: Glucidyl acrylate Ebecryl 810: Polyester oligomer (polyester acrylate) manufactured by Dycel Cytec Co., Ltd.
UV3000B: Polyurethane-based oligomer (urethane acrylate) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
Ebecryl600: Polyepoxy oligomer (epoxy acrylate) manufactured by Dycel Cytec Co., Ltd.
nBA: Butyl acrylate NPGDA: Neopentyl glycol diacrylate DEAA: Diethylacrylamide TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BA)
Made by SF, DAROCUR TPO)
CPI110P: Triarylsulfonium salt type photoacid generator (manufactured by San-Apro)
2021P: 3,4-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (Daicel's Celoxide 2021P)
OXT-101: 3-Ethyl-3-hydroxymethyloxetane (Aron Oxetane OXT-101 manufactured by Toagosei Co., Ltd. )

"exterior"
The appearance of the obtained polymerizable composition was observed and visually evaluated.

"viscosity"
Using the obtained polymerizable composition in an atmosphere of 23 ° C. with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.), about 1.2 ml was used as a measurement sample, and the rotation speed was 0.5 to 100 rpm, 1 It was measured under the condition of rotation for 1 minute and used as the solution viscosity (mPa · s).

<Manufacturing example of laminated body (A)>
[Reference Examples 1 to 5] [Examples 6 to 13, 15 to 26, 28 to 40 ] [Comparative Examples 1 to 7]
The films shown in Table 3 were used as the transparent films (1) and (2), and a laminated body was prepared by the following method.
The surfaces of the transparent films (1) and (2) are corona-treated at a discharge rate of 300 W · min / m ² , and within 1 hour after the surface treatment, the active energy ray-polymerizable adhesive shown in Table 1 is applied to the wire bar coater. A polyvinyl alcohol-based polarizing element is sandwiched between the active energy ray-polymerizable adhesive layer and the active energy ray-polymerizable adhesive layer, and a transparent film (1) is formed. A laminate composed of / adhesive layer / PVA-based polarizing element / adhesive 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.
In addition, Examples 1 to 5 in Table 3 mean Reference Examples 1 to 5.

A laminated body (polarizing plate) was prepared by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm ² and an integrated light amount of 100 mJ / cm ² from the transparent film (2) side with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba Corporation).

The peel strength, gel fraction, punching processability, shrinkage rate, heat resistance and moisture heat resistance of the obtained laminated body (polarizing plate) itself were determined according to the following methods, and the results are shown in Table 3.

《Peeling 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 polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was attached onto a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) using a laminator to obtain a laminate for measurement between the polarizing plate and the metal plate. The polarizing plate of the laminated body for measurement is provided with a peeling kick in advance between the protective film and the polarizing element, and the laminated body for measurement is 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. The peeling force was obtained by peeling at the speed of. At this time, the peeling force of both the polyvinyl alcohol-based polarizing element and the protective film (1) and the polyvinyl alcohol-based polarizing element and the protective film (2) was measured. This peeling force was evaluated as an adhesive force on a four-point scale. If the evaluation is "△" or higher, there is no particular problem during actual use.
(Evaluation criteria)
⊚: Peeling is impossible or polarizing plate is broken ◯: Peeling force is 2.0 (N / 25 mm) or more and less than 5.0 (N / 25 mm).
Δ: The peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm).
X: The peeling force is less than 1.0 (N / 25 mm).

《Gel fraction》
A polynorbornne-based film manufactured by Nippon Zeon Corporation that has not been subjected to corona treatment (trade name "Zeonoa ZF-14: 100 μm") is coated with an active energy ray-polymerizable adhesive to a thickness of 20 to 25 μm using a wire bar coater. To form an active energy ray-polymerizable adhesive layer. Further, Zeonoa ZF-14 without corona treatment was layered on the active energy ray-polymerizable adhesive layer to obtain a three-layered laminate. After that, the active energy ray-polymerizable adhesive layer was polymerized and cured by irradiating the active energy ray with a maximum illuminance of 300 mW / cm ² and an integrated light amount of 100 mJ / cm ² with an active energy ray irradiator (high-pressure mercury lamp manufactured by Toshiba Corporation). The Zeonoa ZF-14 of the laminated body made of the above was peeled off to obtain an adhesive layer.
After measuring the weight of the adhesive layer (weight 1), the adhesive layers were sandwiched between the metal meshes so that the adhesive layers did not overlap with each other, and the mixture was refluxed in methyl ethyl ketone (MEK) for 3 hours. Further, it was dried at 80 ° C. for 30 minutes, and the weight of the adhesive layer was measured (weight 2). The gel fraction was calculated from the following formula and evaluated on a three-point scale. If the evaluation is "△" or higher, there is no particular problem during actual use.
Gel fraction (%) = {1- (weight 1-weight 2) / weight 1)} x 100
(Evaluation criteria)
◯: Gel fraction is 90% or more Δ: Gel fraction is 80% or more and less than 90% ×: Gel fraction is less than 80%

《Punching workability》
The prepared polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peeling distance around the punched polarizing plate was measured with a ruler and evaluated in the following four stages. If the evaluation is "△" or higher, there is no particular problem during actual use.
(Evaluation criteria)
⊚: 0 mm
○: 1 mm or less Δ: 1 to 3 mm
×: 3 mm or more

"Shrinkage factor"
The small pieces of the polarizing plate were left in a constant temperature and humidity chamber of 80 ° C.-dry and 60 ° C.-90RH%, and the amount of shrinkage in the stretching direction after 60 hours was measured, and the ratio of the amount of shrinkage to the original length (100 mm) was measured. Was calculated as the shrinkage rate, and was evaluated in the following three stages.
In addition, "dry" is a test condition in the case where only the temperature is controlled and the humidity is not controlled in the oven with the humidity adjustment function. If the evaluation is "△" or higher, there is no particular problem during actual use.
(Evaluation criteria)
◯: Shrinkage rate is 0.2% or less Δ: Shrinkage rate is greater than 0.2% and 0.4% or less ×: Shrinkage rate exceeds 0.4%.

"Heat-resistant"
The obtained polarizing plate was cut into a size of 50 mm × 40 mm and exposed under the conditions of 80 ° C.-dry and 100 ° C.-dry for 1000 hours, respectively. After exposure, the presence or absence of peeling of the edge of the polarizing plate was visually evaluated in the following four stages. If the evaluation is "△" or higher, there is no particular problem during actual use.
( Evaluation criteria)
⊚: No peeling even under the condition of 100 ° C.-dry.
◯: No peeling under 80 ° C.-dry conditions.
Δ: Peeling of less than 1 mm under 80 ° C.-dry conditions.
X: Peeling of 1 mm or more under 80 ° C.-dry conditions.

《Moisture and heat resistance》
The obtained polarizing plate was cut into a size of 50 mm × 40 mm and exposed under the conditions of 60 ° C.-90% RH and 85 ° C.-85% RH for 1000 hours. After exposure, the presence or absence of peeling of the edge of the polarizing plate was visually evaluated in the following four stages. If the evaluation is "△" or higher, there is no particular problem during actual use.
( Evaluation criteria)
⊚: No peeling even under the condition of 85 ° C-85% RH.
◯: No peeling at all under the condition of 60 ° C.-90% RH.
Δ: Peeling of less than 1 mm under the condition of 60 ° C.-90% RH.
X: There is peeling of 1 mm or more under the condition of 60 ° C.-90% RH.

In the present invention, as a representative example of the optical film, the exemplary compounds are specifically shown in Table 3 below, but are not limited thereto.
As a notation of the example film,
TAC80: Polytriacetyl cellulose-based film manufactured by Fuji Film Co., Ltd. (containing UV absorber, thickness 80 μm),
TAC50: Polytriacetyl cellulose-based film manufactured by Fuji Film Business Supply Co., Ltd. (no UV absorber, film thickness 50 μm),
ZF-14: Polynorbornene film manufactured by Zeon Corporation (without UV absorber, thickness 100 μm),
HBD-002: Polyacrylic film manufactured by Mitsubishi Rayon (without UV absorber, thickness 50 μm) ,
Is shown.

When the polymerizable composition of the present invention is used as an adhesive, there is no particular problem in Examples 7 to 10, 15 to 26 , 28 , 29 , 32 to 40 , as shown in Table 3. Further, in Examples 6, 11 to 13, 30 and 31, the peel strength, punching workability, shrinkage rate, heat resistance and the like are not at the highest level, but are sufficiently within the practical range. On the other hand, in Comparative Examples 1 to 7, the adhesive strength is low, the punching processability and the shrinkage rate are particularly difficult, and the adhesion, heat resistance, moisture heat resistance and the like are inferior.

Claims (5)

The α, β-ethylenic unsaturated double bond group-containing compound (A), the active energy ray polymerization initiator (B), and water are contained, and the following (1), (1-1), ( A cationically polymerizable compound other than the cationically polymerizable compound contained in the active energy ray-reactive composition, comprising 1-1-1), (1-2), (1-3), (2) and (3). Active energy ray-polymerizable adhesive that does not contain.
(1) With respect to 100 parts by weight of an active energy ray-reactive composition composed of an α, β-ethylenically unsaturated double-bonding group-containing compound (A), an active energy ray polymerization initiator (B) and a cationically polymerizable compound. , Contains 0.01 to 10 parts by weight of water.
(1-1) The α, β-ethylenic unsaturated double bond-containing compound (A) has an α, β-ethylenic unsaturated group having a hydrogen-binding functional group selected from a hydroxyl group, a carboxyl group and an amino group. Includes a double bond group containing compound (AA).
(1-1-1) The α, β-ethylenically unsaturated double bond group-containing compound (AA) having the hydrogen-binding functional group is a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound. (A-1) is included.
(1-2) The α, β-ethylenically unsaturated double bond group-containing compound (A) has an α, β-ethylenically unsaturated double bond group-containing compound (A-2) having one or more cyclic structures. ) (However, α, β-ethylenically unsaturated double bond group-containing compound (AA) is excluded).
(1-3) A group in which the α, β-ethylenic unsaturated double bond group-containing compound (A) comprises a polyester-based oligomer, a polyurethane-based oligomer, and a polyepoxy-based oligomer having a weight average molecular weight of 300 to 30,000. Contains at least one oligomer (A-3) selected from.
(2) The active energy ray-polymerizable adhesive contains 0.05 to 20% by weight of the active energy ray polymerization initiator (B).
(3) In 100% by weight of the active energy ray-reactive composition composed of the α, β-ethylenically unsaturated double bond group-containing compound (A), the active energy ray polymerization initiator (B) and the cationically polymerizable compound. It may contain 0-10% by weight of the cationically polymerizable compound. The compound in 100% by weight of the active energy ray-reactive composition comprising the α, β-ethylenically unsaturated double bond group-containing compound (A), the active energy ray polymerization initiator (B) and the cationically polymerizable compound. The active energy ray-polymerizable adhesion according to claim 1, wherein (AA) is contained in an amount of 1 to 70% by weight, the compound (A-2) is contained in an amount of 1 to 70% by weight, and the oligomer (A-3) is contained in an amount of 1 to 50% by weight. Agent. A sheet comprising a base material and a resin layer formed of the active energy ray-polymerizable adhesive according to claim 1 or 2. A transparent film whose base material is selected from the group consisting of a polyacetyl cellulose-based film, a polynorbornen-based film, a polypropylene-based film, a polyacrylic-based film, a polycarbonate-based film, a polyester-based film, a polyvinyl alcohol-based film, and a polyimide-based film. The sheet according to claim 3. From the group consisting of the sheet according to claim 4 and other polyacetylcellulose-based films, polynorbornene-based films, polypropylene-based films, polyacrylic-based films, polycarbonate-based films, polyester-based films, polyvinyl alcohol-based films, and polyimide-based films. A laminate for an optical element, which is formed by laminating a selected transparent film.