JP5688519B1 - Active energy ray-polymerizable adhesive and laminate - Google Patents

Abstract

The present invention relates to a novel active energy ray-polymerizable adhesive having excellent adhesiveness, and a laminate using the same, excellent in punching workability and durability against heat and humidity, It aims at providing the laminated body for optical elements especially. [MEANS FOR SOLVING PROBLEMS] As a result of intensive studies to solve the above problems, the present inventors have found that an activity comprising an α, β-ethylenically unsaturated double bond group-containing compound (M) and boric acid as essential components. The present inventors have found that the above-mentioned target can be achieved with an energy beam polymerizable adhesive, and have completed the present invention. . [Selection figure] None

Description

  The present invention relates to a novel active energy ray-polymerizable adhesive and a laminate.

In addition to various characteristics such as fast polymerization rate, good workability due to the absence of solvent, energy saving of extremely low energy requirements, active energy ray polymerization technology has recently reduced environmental pollution due to environmental pollution problems. Therefore, the field of use is expanding in the fields of building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, displays, and the like.

These contain a resin that can be polymerized with active energy rays and a monomer having an α, β-ethylenically unsaturated double bond group, and the coating film is formed because the monomer also functions as a solvent. There is an advantage that the solvent does not volatilize sometimes. And as this resin having active energy ray polymerizability, α, β-ethylenically unsaturated double bond group at the molecular terminal of low molecular weight polyester resin, polyurethane resin, polyepoxy resin, polyacrylic resin, etc. And oligomers having an α, β-ethylenically unsaturated double bond group are used.

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

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

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

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

A specific example is given. Polarizers used in the fields related to liquid crystal displays are usually produced by uniaxially stretching polyvinyl alcohol (PVA) with iodine or dye adsorbed, but this polyvinyl alcohol polarizer is contracted by heat or moisture. However, the polarization performance is deteriorated. Then, what stuck the protective film on the surface of the PVA type | system | group polarizer is used as a polarizing plate. As an adhesive for sticking a protective film to a polarizer, an aqueous solution (PVA adhesive) of a polyvinyl alcohol resin has been widely used (see Patent Documents 1 and 2). However, the water-based adhesive requires a drying process after coating, and the PVA polarizer has low heat resistance, so that drying at a low temperature for a long time is required, resulting in poor production efficiency. For the reasons described above, it has been proposed to use a cationic polymerizable ultraviolet curable adhesive instead of the water-based adhesive (see Patent Document 3).

However, since the cationic polymerizable ultraviolet curable adhesive has a dark reaction after being irradiated with ultraviolet rays, there is a problem that when a long cured product is formed into a take-up roll shape, curling tends to occur during storage. In addition, the cationic polymerizable UV curable adhesive is susceptible to the effects of humidity during curing, moisture in the adhesive and the film, and the cured state tends to vary. Therefore, in order to develop a uniform cured state, it is necessary to strictly control the moisture content of the adhesive and the PVA polarizer, not to mention the environmental humidity. Radical polymerizable ultraviolet curable adhesives are excellent in that these problems are relatively small, but generally they have a large cure shrinkage and it is difficult to ensure sufficient adhesion.

By the way, liquid crystal display devices are used in various environments as their uses expand, and high heat resistance is required for polarizing plates constituting liquid crystal display devices. For example, in-vehicle liquid crystal display devices such as car navigation systems are required to have high heat resistance and durability.
If the adhesiveness is weak in a high temperature environment, there may be a problem that the PVA polarizer and the protective film are peeled off due to the difference in thermal shrinkage between the PVA polarizer and the protective film.

Patent Document 4 includes an active energy ray-curable adhesive containing a curable component relating to a compound having a (meth) acryloyl group containing N-hydroxyethylacrylamide and N-acryloylmorpholine. An adhesive having a Tg of 60 ° C. or higher is disclosed. The durability performance required for polarizing plates has become strict, and durability under more severe environments is required under high humidity and high temperature. However, the polarizing plate has not been able to satisfy the durability under the harsh environment.

Japanese Patent Laid-Open No. 09-258023 JP-A-2005-208456 JP 2008-233874 A Japanese Patent No. 4744496

    The present invention relates to a novel active energy ray-polymerizable adhesive having excellent adhesiveness, and a laminate, particularly an optical element, which is superior in punching workability and durability against heat and humidity as compared with conventional active energy ray polymerizable adhesives. It aims at providing the laminated body for use.

 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned target can be achieved by the active energy ray polymerizable adhesive shown below, and have completed the present invention.

That is, the present invention relates to an active energy ray-polymerizable adhesive having an α, β-ethylenically unsaturated double bond group-containing compound (M) and boric acid as essential components.
However, the α, β-ethylenically unsaturated double bond group-containing compound (M) is an α, β-ethylenically unsaturated double compound having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures. A linking group-containing compound (C) and a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (X) are included.

Furthermore, this invention relates to the said active energy ray polymeric adhesive which further contains an active energy ray polymerization initiator (E).

Furthermore, this invention relates to the laminated body characterized by laminating | stacking the layer which consists of said active energy ray polymeric adhesive on the single side | surface or both surfaces of a base material (F).

Further, in the present invention, the base material (F) is a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film or a polyimide film. It is related with the said laminated body characterized by the above-mentioned.

Furthermore, this invention relates to the laminated body for optical elements which uses the said laminated body.

INDUSTRIAL APPLICABILITY According to the present invention, a novel active energy ray-polymerizable adhesive having excellent adhesiveness, and a laminate using the same, superior in punching workability and durability against heat and humidity as compared with the prior art, particularly optical elements A laminated body can be provided.

The active energy ray polymerizable adhesive of the present invention contains an α, β-ethylenically unsaturated double bond group-containing compound (M) and boric acid as essential components.
The α, β-ethylenically unsaturated double bond group-containing compound (M) as the main component of the active energy ray polymerizable adhesive of the present invention contains an α, β-ethylenically unsaturated double bond in the molecule. All compounds to be included are included. The α, β-ethylenically unsaturated double bond-containing compound (M) is preferably an α, β-ethylenically unsaturated divalent compound contained in the active energy ray polymerizable adhesive from the viewpoint of reactivity with active energy rays. It is preferable that the (meth) acryloyl group accounts for 50% to 100% by weight of the total weight of the heavy bonds.

 As the compound (M), specifically, a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (X), an amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (Y) Containing α, β-ethylenically unsaturated double bond group-containing compound (C) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures, and an oligomer having a weight average molecular weight of 300 to 30,000 It is preferable that one or more compounds selected from the group consisting of (D) are included. In particular, in the present application, the compound (M) includes a compound containing a α, β-ethylenically unsaturated double bond group (C) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures. It is essential.

 The hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (X) (hereinafter referred to as compound (X)) will be described. Compound (X) forms a bond with boric acid and forms a crosslinked coating after curing with active energy rays. Moreover, there exists an effect which forms a bond through the surface functional group of a base material (F) and boric acid, and improves adhesiveness.

 Compound (X) is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic acid 4-hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylate 10-hydroxydecyl, (meth) acryl Acid 12-hydroxylauryl, ethyl (meth) acrylate-α Fatty acid esters such as (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate (Meth) acrylic acid ester, or (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, Hydroxyl group-containing α-, β-ethylenically unsaturated double bond group-containing compounds such as alkylene oxide-added (meth) acrylic acid esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. fat (Meth) acrylic acid esters;

 For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

 For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (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 Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;
For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As compound (X), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol An α, β-ethylenically unsaturated double bond group-containing compound having 2 to 18 carbon atoms such as mono (meth) acrylic acid ester, 1 to 2 mol of ε-caprolactone and 2-hydroxyethyl addition (meth) acrylate is particularly preferable. .

The amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (Y) will be described.
In the present invention, the amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (Y) (hereinafter referred to as compound (Y)) has at least one amino group and at least one α in the molecule. , A compound containing a β-ethylenically unsaturated double bond group. The amino group of the compound (Y) interacts with boric acid described later to provide a stable and uniform liquid property as a non-aqueous active energy ray polymerization composition, and the interaction results in the active energy ray polymerizable adhesive of the present invention. When used as an agent, it is possible to form a coating agent layer or an adhesive layer having a great effect on improving adhesion and having good heat resistance and water resistance.

As such a compound (Y), an acyclic amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (y1) and a cyclic amino group-containing α, β-ethylenically unsaturated double And a linking group-containing compound (y2).
Examples of the acyclic amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (y1) include, for example, monomethylaminoethyl (meth) acrylate [monomethylaminoethyl acrylate and monomethylaminoethyl methacrylate] Collectively, monomethylaminoethyl (meth) acrylate is described. The same shall apply hereinafter). Monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid-mono or di-alkylamino esters such as dimethylaminopropyl acid, diethylaminopropyl (meth) acrylate, and the like;

 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.

 As the cyclic amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (y2), a cyclic amino group-containing and (meth) acryloyl group-containing compound (y2-I), a cyclic amino group-containing compound and Ethenyl group-containing compound (y2-II), cyclic amino group-containing and (meth) allyl group-containing compound (y2-III) [Allyl group and methallyl group are collectively referred to as (meth) allyl group. The same shall apply hereinafter). Is mentioned.

 Examples of the cyclic amino group-containing and (meth) acryloyl group-containing compound (y2-I) include 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2′-Hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole and 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole are combined together in “2- (2 '-Hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole ". The same applies below. ], 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) acryloyloxyethylphenyl) -5-chloro-2H -(Meth) acrylic acid esters having an amino group with a polycyclic structure such as benzotriazole;

 For example, 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 and the like (Meth) acrylic acid esters having a membered amino group;

 For example, having an alicyclic amino group such as pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate (meta ) Acrylic acid esters.

More specifically, examples of the cyclic amino group-containing and ethenyl group-containing compound (y2-II) include 1-vinylpyrrole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, and 1-vinyl. 2-imidazoline, 2-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 4,5-dihydro-2-vinyl-1H-imidazole, 1-vinylimidazole, 2-vinyl-1H- Ethenyl group-containing compounds having a 5-membered ring amino group such as imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole ;

 For example, 2-vinylpiperazine, 4-vinylpiperazine, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 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- Ethenyl group-containing compounds having a six-membered amino group such as 1,2,4,5-tetrazine;

 For example, 1-vinylindole, 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-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline Ethenyl group-containing compounds having a polycyclic amino group such as 1-vinylcarbazole;

 For example, 1-methyl-4,5-divinyl-1H-imidazole, 1,1′-divinyl-2,2′-bi (1H-imidazole), 2,3-divinylpyridine, 2,4-divinylpyridine, 2 And compounds having a cyclic amino group and two or more ethenyl groups, such as 2,5-divinylpyridine and 2,6-divinylpyridine.

 More specifically, examples of the cyclic amino group-containing (meth) allyl group-containing compound (y2-III) include 1- (meth) allyl-1H-imidazole [1-allyl-1H-imidazole and 1-methallyl. It is described as “1- (meth) allyl-1H-imidazole” together with −1H-imidazole. The same applies below. ], 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- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5-bromo-1--1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 5- ( 1-methylpropyl) -5- (meth) allylpyrimidine, 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 Having a cyclic amino group such as dichloro -1,3-5- triazin-2-amine (meth) allyl group-containing compounds;

 For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 1- (meth) allyl-1H-benzimidazole, 2- (meth) allylindazole, 1- (meth) allyl -3-methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 3-phenyl-4- ( (Meth) allylisoquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline, (meth) allyl group-containing compounds having a polycyclic amino group such as 9- (meth) allyl-9H-carbazole, etc. Is mentioned.

The compound (Y) used in the present invention is an acyclic amino group-containing α, β-ethylene from the viewpoint of adhesiveness to various substrates (F) when used as an active energy ray polymerizable adhesive. The cyclic amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (y2) is preferred to the polymerizable unsaturated double bond group-containing compound (y1). Among them, when the active energy ray polymerizable composition is used in combination with the compound (M) other than the compound (Y), a cyclic amino group-containing and ethenyl group-containing compound (y2-II) is preferable. Compound (y2-II) has a coating structure after active energy ray polymerization of the active energy ray-polymerizable adhesive due to the difference in relative reaction rate and main chain structure with the acryloyl group-containing compound used as compound (M). It is easy to form a microphase separation structure, and in particular, it is easy to form a sea-island structure. For this reason, since it becomes a coating film structure having both elasticity and stress relaxation properties, when used as an active energy ray polymerizable adhesive, not only exhibits high adhesion and high adhesion due to high cohesive force, It is most preferable because it is possible to maintain practicality, for example, it is possible to maintain the practicability such as suppression of floating or peeling due to changes in the external environment from extremely low temperatures to extremely high temperatures. In addition, when the α, β-ethylenically unsaturated double bond group of the compound (Y) is a (meth) allyl group (y2-III), the reaction rate is slow although a microphase separation structure is easily formed. Since high molecular weight of the film may be insufficient, when used as an active energy ray-polymerizable adhesive, durability may decrease and cohesive failure of the coat layer or adhesive layer may occur. Need attention. As the α, β-ethylenically unsaturated double bond group of the compound (Y) that easily forms a microphase separation structure of the coating film, the preferred order is ethenyl group (y2-II)> (meth) allyl group (y2 -III)> (meth) acryloyl group (y2-I).

Furthermore, the ring structure containing one or more nitrogen atoms in the molecule of the compound (Y) is preferably a 5-membered ring or more. A 3- or 4-membered ring is not preferable because it is likely to cause a ring-opening reaction by heat or active energy rays.
Examples of the amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (Y) include 2-vinylpyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-vinylimidazole, 2 -Vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 4-vinylpyridine, 1-vinylindole, 1-vinylisoindole, 1-vinyl- 1H-benzimidazole, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-1H-benzimidazole, 1-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinyl Isoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnori And 1-vinylcarbazole are most preferred from the industrial and price points.

 The α, β-ethylenically unsaturated double bond group-containing compound (C) (hereinafter referred to as compound (C)) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures will be described. The compound (C) is a compound having two or more cycloalkane skeletons and / or cycloalkene skeletons and one or more α, β-ethylenically unsaturated double bonds. As the compound (C), a cycloalkene skeleton having two or more ring structures and / or a compound (c1) in which the ring structure is separated from the ring structure by an alkyl group, an ether group, an ester group, and the like, and Examples of the compound include a norbornane or norbornene skeleton (c2), and a compound having a cyclocyclic bridge structure such as the compound (c3) having an adamantane structure. However, the compound has a norbornane, norbornene, or adamantane skeleton because of excellent heat resistance. Compound (c2) or compound (c3) is preferred to compound (c1).

As an α, β-ethylenically unsaturated double bond group-containing compound (c1) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures, the ring structure and the ring structure being separated from each other Examples include hydrogenated biphenol A diacrylate and 3,3-dicyclopropyl acrylate.
The α, β-ethylenically unsaturated double bond group-containing compound (c2) having norbornene and / or norbornane skeleton may have at least one norbornene and / or norbornane skeleton and ethylenically unsaturated double bond. For example, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol (meth) Examples include acrylate and isobornyl (meth) acrylate.

 Among the above compounds (c2), the compound (c2 ′) having 3 or more cyclic skeletons is particularly preferable because it suppresses curing shrinkage by increasing the bulk and improves the adhesive force. ') Includes dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and the like.

 The α, β-ethylenically unsaturated double bond group-containing compound (c3) having an adamantane skeleton is a radically polymerizable compound having three or more cyclic skeletons similar to the above compound (c2 ′). Adhesion is improved. Specific examples of the compound (c3) include 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 2-propyl. -2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol di (meth) acrylate, 1,3,5-adamantyl (meth) acrylate, 3- Hydroxy-1,5-adamantyl di (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate and the like can be mentioned, but α, β-ethylenically unsaturated double bonds are excellent in terms of adhesion. 1 3-hydroxy-1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2 -Adamantyl acrylate is preferred.

 The oligomer (D) having a weight average molecular weight of 300 to 30,000 (hereinafter referred to as oligomer (D)) will be described. First, the oligomer (D) does not contain the compounds (X), (Y), (C) and the compound (m) described later. The oligomer (D) is preferably at least one oligomer selected from the group consisting of a polyester-based oligomer (d1), a polyurethane-based oligomer (d2), and a polyepoxy-based oligomer (d3), and can be used without any particular limitation. .

 As the polyester-based oligomer (d1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton, or a hydroxyl group in the polyester chain and a molecule such as (meth) acrylic acid or maleic acid A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups, or a carboxyl group in the terminal or polyester chain of polyester and (meth) acrylic acid 2- It is a compound obtained by esterification with the aforementioned compound (X) such as hydroxyethyl 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 oligomer (d1).

 Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used. .

 More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, 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, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Saturated cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid 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-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

 Also, derivatives of hexahydrophthalic anhydride ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (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.) The hydrogenated phthalic anhydride derivative can also be used as an alicyclic dicarboxylic acid anhydride.

 More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedica Aromatic dicarboxylic acids such as boronic acid, 1,2-phenanthenedicarboxylic acid, 4,5-phenanthenedicarboxylic acid, 3,9-perylenedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

 Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

 Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000. Each can be used without any particular limitation.

 More specific examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol Octanediol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadiene engine methanol, aliphatic or cycloaliphatic diols and dimer diol;

 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′-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol Aromatic diols and the like.

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.
More specific examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonate or phosgene.

As a commercial item of the said high molecular weight polyester polyol, the Byron series by Toyobo Co., Ltd., the Kuraray polyol P series by Kuraray, and the Kyowapol series by Kyowa Hakko Chemical Co., Ltd. are mentioned, for example.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.
Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series, and Kuraray polyol C series manufactured by Kuraray.

Examples of commercially available high molecular weight polyurethane polyols include Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3) manufactured by Mitsui Chemicals Polyurethane, Takelac E551T (hydroxyl value = 30, Acid value <3), Takelac Y2789 (hydroxyl value = 10, acid value <2) and the like.
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, and polyvalerolactone diol can also be used as the high molecular weight polyol. Included in polyols.

 The polyurethane oligomer (d2) is a compound obtained by reacting a compound having at least one isocyanate group with the compound (X), or a compound having at least one isocyanate group and the polyhydric alcohol described above. A terminal isocyanate group obtained by reacting a compound having at least one isocyanate group with a polyhydric alcohol, or a compound obtained by reacting the urethane prepolymer of the terminal isocyanate group obtained by reacting with the compound (X). This is a compound obtained by reacting the compound (X) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a urethane prepolymer of the above and a compound having at least one amino group. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also contained in a polyurethane-type oligomer (d2).

 Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, 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, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

 Among polyfunctional isocyanates, as aromatic polyisocyanate, more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4, Examples thereof include 4′-diphenyl ether diisocyanate and 4,4 ′, 4 ″ -triphenylmethane triisocyanate.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Moreover, 2-methylpentane-2,4-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, etc. can be used together. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

More specifically, as amines having an amino group, 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) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di- - hydroxypropyl ethylene) diamine, aliphatic such as piperazine polyamine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( Aromatic diamines such as sec-butyl) diphenylmethane can be used.

 The polyepoxy oligomer (d3) is composed of a compound having a glycidyl group and an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as (meth) acrylic acid and maleic acid. These are compounds obtained by reaction, and typical examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

 Epoxidized oil Polyepoxy oligomer includes epoxidized oil such as soybean oil and α, β-unsaturated double bond having one or more carboxyl groups in the molecule such as (meth) acrylic acid and maleic acid. Those obtained by reaction with a group-containing compound can be used. The novolak type polyepoxy oligomer is obtained by a reaction between a novolak type epoxy resin and an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as (meth) acrylic acid. Things can be used. As an alicyclic polyepoxy oligomer, a reaction between an alicyclic epoxy resin and an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as (meth) acrylic acid. The synthesized one can be used.

 The weight average molecular weight (hereinafter referred to as Mw) of the oligomer (D) having at least one α, β-unsaturated double bond group in the molecule is compatible with the polymer coating and good durability (heat resistance). Properties, wet heat resistance) and agglomeration density, it is necessary to be in the range of 300 to 30,000. Furthermore, Mw is more preferably in the range of 400 to 20,000. If the Mw of the oligomer (D) exceeds 30,000, the fluidity is lowered and the compatibility with the compound (M) other than the oligomer (D) is also lowered. Or when the active energy ray polymerizable adhesive is used, the durability of the polymerized coating film may decrease, the coating film may whiten, and the Mw of the oligomer (D) may be If it is less than 300, after the active energy ray polymerizable adhesive is applied and laminated on various substrates (F) or the like, cohesive failure of the active energy ray polymerizable adhesive layer may easily occur.

 Regarding the α, β-ethylenically unsaturated double bond group-containing compound (M) contained in the active energy ray-polymerizable adhesive of the present invention, the aforementioned compound (Y), compound (X), compound (C), and In addition to the oligomer (D), other α, β-ethylenically unsaturated double bond group-containing compound (m) (hereinafter referred to as compound (m)) is not limited to use as required.

 Examples of other α, β-ethylenically unsaturated double bond group-containing compound (m) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, (meth) 2-propyl acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate , (Meth) acrylic acid iso-amyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid iso-octyl, (meth) acrylic Acid n-nonyl, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, octa (meth) acrylate (Meth) acrylic acid alkyl esters such as decyl, lauryl (meth) acrylate, stearyl (meth) acrylate;

 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 , Benzyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-oxo- (meth) acrylate 1,2-diphenylethyl, (meth) acrylic acid (ethoxylated o-phenylphenol), ( T) 1-naphthyl acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, (meth) acrylic acid 9-anthryl, (meth) acrylic acid 9-anthrylmethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) One cycloalkane skeleton or cycloalkene skeleton such as acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, etc. Have an aromatic ring (Meth) acrylic acid esters having;

For example, (meth) 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, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, It further contains unsaturated groups such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, vinyl (meth) acrylate, and the like. Meth) acrylic acid esters;
For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, (meth) acrylic acid glycidyl, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic Acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4- Yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2-dimethyl-5 -Oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydro Lan-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, etc. Heterocycle-containing (meth) acrylic acid esters having an oxygen atom;

 For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

 For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

 For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

 For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

 For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

 For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

 For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di (Meth) acrylic acid dipropylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polypropylene glycol, di (meth) acrylic acid 1,2-butanediol, di (meth) acrylic acid 1,2 -Pentanediol, di (meth) acrylic acid 2,2-dimethylpropyldiol, di (meth) acrylic acid hydroxypivalyl hydroxypivalate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di ( Meta) acrylic acid 1 4-butanediol, di (meth) acrylic acid 1,5-heptanediol, di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7-heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) 1,2-octanediol acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1,2-decanediol di (meth) acrylic acid, 1,10-decanediol di (meth) acrylic acid, di (Meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 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, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1, di (meth) acrylate, 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, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Xanthdiol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2 di (meth) acrylate -Ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 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, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-di (meth) acrylic acid Methyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di Bifunctional (meth) acrylic acid esters such as (meth) acrylic acid 1,1,1-trishydroxymethylethane;

 For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-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, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;
For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;
For example, 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 -Aliphatic vinyl ethers such as octyl 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;

For example, fluorine-containing ethenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;
For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;
For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, (meth) 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-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

 For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) 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-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) 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- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

 For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

For example, vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;
For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, 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-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

As the other α, β-ethylenically unsaturated double bond group-containing compound (m), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and more active as an active energy ray polymerizable adhesive. From the viewpoint of the energy ray polymerization rate, it is preferable to contain bifunctional or higher (meth) acrylic acid esters.
Further, as other α, β-ethylenically unsaturated double bond group-containing compound (m), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3- A heterocycle-containing (meth) acrylic acid ester having a 3-membered or 4-membered ring oxygen atom, such as methyl-3-oxetanyl) methyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and the like. If necessary, known photoacid generators such as sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 (Japanese) Iodonium salts such as Ryo-2074 (manufactured by Rhodia Japan) By using together those exemplified, it is preferable because crosslinking proceeds and an adhesive layer having excellent durability against heat and humidity is formed.

 As a preferred ratio of the components constituting the α, β-ethylenically unsaturated double bond group-containing compound (M), active energy ray-polymerizable adhesion of the α, β-ethylenically unsaturated double bond group-containing compound (M) When the total amount in the agent is 100% by weight, 0 to 70% by weight of compound (X), 0 to 95% by weight of compound (Y), 0 to 70% by weight of compound (C), oligomer (D) Is preferably 0 to 50% by weight, and the other α, β-ethylenically unsaturated double bond group-containing compound (m) is preferably 0 to 50% by weight. Among these, it is preferable that the sum total of a compound (Y) and a compound (X) is 10 to 100 weight%. When the total of the compound (Y) and the compound (X) is less than 10% by weight, the solubility of boric acid is inferior, and it does not become a homogeneous system, or crystals are deposited when time passes as a liquid. Such problems may occur.

 The boric acid contained in the active energy ray polymerizable adhesive of the present invention will be described. Boric acid interacts with a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (X) and / or an amino group-containing α, β-ethylenically unsaturated double bond group-containing compound (Y ) And a salt to form a stable and uniform active energy ray-polymerizable adhesive liquid without containing water or an organic solvent, and after curing the adhesive with active energy rays, the compound ( A coating film bonded with a hydroxyl group derived from X) and / or an amino group derived from compound (Y) is formed. Moreover, there exists an effect which forms a bond with the surface functional group of the below-mentioned base material (F), and improves adhesiveness.

 The amount of boric acid used in the present invention is 0.1% by weight or more, 20 when the total amount of the α, β-ethylenically unsaturated double bond group-containing compound (M) is 100% by weight. It is preferable that it is below wt%. If the amount is less than 0.1% by weight, the desired adhesive strength cannot be obtained, and if it is 20% by weight or more, problems such as precipitation over time or gelation due to excessive increase in viscosity as a liquid. May occur. In particular, it is preferably 0.3% by weight or more and 12% by weight or less.

   The active energy ray-polymerizable adhesive of the present invention can further contain an active energy ray polymerization initiator (E). The active energy ray polymerization initiator (E) can be arbitrarily selected from known ones, and specific examples thereof include, 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, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one etc. It is. Examples of commercially available products include Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF), Darocur- 1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like.

 An active energy ray polymerization initiator having at least one (meth) acryloyl group in the molecule can also be used. These active energy ray polymerization initiators (E) can be used alone or as a mixture of two or more.

 The blending ratio of the active energy ray polymerization initiator (E) is reactive energy ray polymerization with respect to 100 parts by weight of the α, β-ethylenically unsaturated double bond group-containing compound (M) in terms of reactivity. It is preferable to contain 0.01-20 weight part of initiators (E).

 The active energy ray-polymerizable adhesive of the present invention preferably contains substantially no water or organic solvent in terms of drying equipment and drying energy. However, when the active energy ray polymerization initiator (E) becomes hardly soluble or highly viscous in the α, β-ethylenically unsaturated double bond group-containing compound (M), the active energy ray polymerization is started. A small amount of water or an organic solvent may be included to dissolve the agent (E). The content of water or organic solvent in the active energy ray polymerizable adhesive is within 5% by weight. The organic solvent that can be used is not particularly limited, but specifically, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbons An organic solvent such as a system solvent and water can be further added to adjust the viscosity of the active energy ray polymerizable adhesive, or the active energy ray polymerizable adhesive can be heated to lower the viscosity. .

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (E), an active energy ray sensitizer may be used in combination. Examples of active energy ray sensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. Anthracene, benzophenone, thioxanthone, perylene, phenothiazine, rose bengal and the like are preferably used.

 In the active energy ray polymerizable adhesive of the present invention, additives other than the above-described components can be appropriately blended as long as the effects of the present invention are not impaired. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, when blending the above polymers, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, dissipators. It is also possible to dissolve, semi-dissolve or micro-disperse in the active energy ray-polymerizable adhesive as a polymer blend or a polymer alloy, not as a filler, such as a foaming agent.

The active energy ray-polymerizable adhesive of the present invention can be used in any form of liquid, paste, and film, but is preferably liquid from the viewpoint of ease of use.
In the active energy ray polymerizable adhesive according to the present invention, it is important that the viscosity of the active energy ray polymerizable adhesive layer is 1 to 1500 mPa · s when the film thickness of the active energy ray polymerizable adhesive layer is 0.1 to 6 μm depending on the intended use. Preferably 10 to 1300 mPa · s, more preferably 20 to 1000 mPa · s. When the viscosity is higher than 1500 mPa · s, when the base material (F) is coated, a thin film coating of 0.1 to 6 μm cannot be performed, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the active energy ray polymerizable adhesive layer.

 In addition, when the film thickness of the active energy ray polymerizable adhesive layer is 6 to 300 μm depending on the intended use, it is important that the viscosity is 1500 to 100,000 mPa · s, preferably 3,000 to 50. More preferably, it is 1,000 mPa · s.

Next, the application process of the active energy ray polymerizable adhesive will be described.
Laminate by applying an active energy ray-polymerizable adhesive on one side or both sides of the base material in an appropriate manner according to a conventional method, and laminating another base material on the surface of the active energy ray-polymerizable adhesive. The body can be formed. When the required film thickness of the active energy ray polymerizable adhesive layer is 0.1 to 6 μm depending on the intended use, the thickness of the active energy ray polymerizable adhesive layer is 0.1 to 6 μm thin film coating. It is preferable that it is 0.1 μm to 3 μm. When the thickness is less than 0.1 μm, sufficient adhesion and adhesive strength may not be obtained. When the thickness exceeds 3 μm, characteristics such as adhesion and adhesion are often not improved further.

On the other hand, when the required film thickness of the active energy ray polymerizable adhesive layer is 6 to 300 μm depending on the intended use, the thickness of the active energy ray polymerizable adhesive layer is 6 to 300 μm thick coating. It is preferably 20 μm to 250 μm. When the thickness is less than 6 μm, sufficient stress relaxation properties may not be obtained. When the thickness exceeds 300 μm, coating properties such as streaking often decrease.
The method for applying the active energy ray polymerizable adhesive of the present invention to a substrate or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater. Various coating methods such as a comma coater, a curtain coater, a knife coater, a reverse coater, and a spin coater can be used, but they can be used depending on applications such as thin film coating and thick film coating, and are not particularly limited.

 The active energy ray-polymerizable adhesive of the present invention is applied onto a substrate by a known and usual method, and the formed coating layer is irradiated with active energy rays to activate a compound having an α, β-unsaturated bond group Polymerized and cured by energy ray polymerization. The active energy ray irradiation light source mainly consists of light in the wavelength range of 150 to 550 nm. Low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, chemical lamp, black light lamp, microwave excitation mercury lamp, LED A lamp, a xenon lamp or a metal halide lamp is suitable. In addition, laser beams, electron beams, and the like can also be used as active energy rays for exposure.

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . If the light irradiation intensity is less than 10 mW / cm ² , a long time is required for curing, and if it exceeds 500 mW / cm ² , the substrate may be deteriorated in various substrates (F) due to the heat radiated from the lamp. This is not preferable because of its properties. The integrated dose expressed as the product of irradiation intensity and irradiation time is preferably 50 to 5,000 mJ / cm ² . When the integrated irradiation amount is less than 50 mJ / cm ² , it takes a long time for polymerization and curing, and when it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity is inferior.

Next, the base material (F) will be described.
When the active energy ray-polymerizable adhesive of the present invention is used, the substrate (F) can be used without particular limitation, such as a film-like substrate, a glass plate, and a processed paper product. On the other hand, when using as an adhesive to bond two or more base materials (F), it is necessary to use a base material that easily transmits active energy rays in order to polymerize by irradiation with active energy rays. In particular, it is preferable to use a transparent film or a transparent glass plate. Even when using a base material that does not easily transmit active energy rays on one side, such as wood, metal plates, plastic plates, and paper products, the other side uses a transparent film or transparent glass plate. It can be used if it is irradiated from the plate side and polymerized and cured.

 The active energy ray-polymerizable adhesive of the present invention preferably uses a film-like substrate among the substrates (F), and the film-like substrate is a film-like substrate such as cellophane, various plastic films, or paper. Examples of the material include transparent plastic films. Moreover, as a film-form base material, as long as it is transparent, a single-layer thing may be used, and the thing in the multilayer state formed by laminating | stacking a several base material can also be used.

 Here, the laminated body characterized by laminating | stacking on the single side | surface or both surfaces of a base material (F) using an active energy ray polymeric adhesive is demonstrated generally.

When using the polymerization reaction by the active energy ray of the active energy ray polymerizable adhesive of the present invention, that is, among the above-mentioned base material (F), at least one of the transparent film which is a film-like base material and the transparent film It is preferably used for the formation of a laminate comprising an active energy ray-polymerizable adhesive layer located on the surface.
The laminate of the transparent film of the present invention can be obtained as follows.

 The adhesive of the present invention is applied to one side of a transparent film that is a film-like substrate, and another transparent film is laminated on the surface of the adhesive layer, or an adhesive is applied to one or both sides of this laminate. Furthermore, a laminated body can be obtained by laminating on another transparent film, glass, or transparent molded body.

 The active energy ray polymerization reaction of the adhesive proceeds at the time of coating or laminating the adhesive, and further by irradiating the active energy ray after laminating. It is preferable to proceed.

The transparent film of the present invention will be described.
The transparent film of this invention can be used for optical films, such as information communication apparatuses, such as a display and a touch panel.

Here, a general description of the optical element laminate will be given.
The basic laminate structure of the optical laminate is a transparent film / adhesive layer / transparent film or a sheet-like double-sided active energy ray polymerizable adhesive laminate such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film. Is the body. Furthermore, as a laminated body for an optical element in which a multilayer optical film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, glass, or optical molded article is fixed to an optical member. used.

 As the transparent film used as the optical film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is used. Various transparent films are also referred to as various plastic films and plastic sheets. For example, polyvinyl alcohol films, polytriacetyl cellulose films, polypropylene, polyethylene, polycycloolefin, polyolefin-based films such as ethylene-vinyl acetate copolymer, polyethylene Polyester film such as terephthalate and polybutylene terephthalate, polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film And polyoxirane films.

The transparent film of the present invention may have the same composition or different when used in multiple layers. For example, a polycycloolefin film may be used on one side, and a polyacrylic film may be used on the other side.
Although the thickness of a transparent film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The transparent film is particularly suitable when the thickness is 5 to 150 μm.

   In addition, when providing a transparent film on the both sides of the polarizer of the polarizing film which is an optical film, you may use the transparent film which consists of the same polymer material by the front and back, and uses the transparent film (H) which consists of a different polymer material etc. May be.

Next, the optical film will be described.
As the laminate for an optical element in the present invention, among the above-mentioned various transparent films, an optical film mainly used for optical applications is preferably used. As the optical film, the transparent film is subjected to a special treatment, and an optical film having optical functions (various functions such as light transmission, light diffusion, light collection, refraction, scattering, and HAZE) is an optical film. It is called. These optical films are used alone or as a laminate for optical elements by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive. For example, hard coat film, antistatic coat film, antiglare coat film, polarizing film, retardation film, elliptically polarizing film, antireflection film, light diffusion film, brightness enhancement film, prism film (also called prism sheet), light guide Examples thereof include a film (also referred to as a light guide plate).

 A polarizing film is also called a polarizing plate, and a polytriacetylcellulose-based protective film (hereinafter referred to as “TAC film”), which is a polyacetylcellulose-based film on both sides of a polyvinyl alcohol-based polarizer, or a polyvinyl alcohol-based polarized light. It is a multilayered sheet-like laminate for optical elements in which one or both sides of the element are laminated with an adhesive such as polycycloolefin film, polyacrylic film, polycarbonate film, polyester film, which is a polynorbornene film. Yes, the active energy ray polymerizable adhesive of the present invention can be suitably used as the adhesive.

 The optical film laminate using the active energy ray-polymerizable adhesive of the present invention is attached to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, or an organic EL module, or a transparent film such as the above-described various plastic films. Thus, it is preferably used as a laminate for optical elements.

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

(I) An active energy ray-polymerizable adhesive is applied to one surface of the protective film, which is the first transparent film, to form a first polymerizable adhesive layer (2 ′),
Applying an active energy ray-polymerizable adhesive on one surface of the second protective film, which is a transparent film, to form a second active energy ray-polymerizable adhesive layer,

   Next, the first active energy ray-polymerizable adhesive layer and the second active energy ray-polymerizable adhesive layer surface are simultaneously and / or sequentially superimposed on each surface of the polyvinyl alcohol-based polarizer, and then irradiated with active energy rays. And a method of producing the first active energy ray polymerizable adhesive layer and the second active energy ray polymerizable adhesive layer by polymerizing and curing the first active energy ray polymerizable adhesive layer and the second active energy ray polymerizable adhesive layer.

 (II) An active energy ray-polymerizable adhesive is applied to one surface of a polyvinyl alcohol polarizer to form a first active energy ray-polymerizable adhesive layer. The surface of the adhesive layer is covered with a first protective film, which is a transparent film, and then an active energy ray-polymerizable adhesive is applied to the other surface of the polyvinyl alcohol polarizer, so that the second active energy ray-polymerizable property is obtained. An adhesive layer is formed, the surface of the formed second active energy ray polymerizable adhesive layer is covered with a second protective film, irradiated with active energy rays, and the first active energy ray polymerizable adhesive layer and the second A method for producing an active energy ray-polymerizable adhesive layer by polymerizing and curing.

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

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
The “weight average molecular weight” is a value measured using gel permeation chromatography “HLC-8220GPC” manufactured by Tosoh Corporation. Separation columns: “TSK-GEL SUPER H5000” and “TSK” manufactured by Tosoh Corporation. -GEL SUPER H4000 "," TSK-GEL SUPER H3000 ", and" TSK-GEL SUPER H2000 "are connected in series and measured at a flow rate of 0.6 ml / min using tetrahydrofuran at a temperature of 40 ° C as the mobile phase. The weight average molecular weight in terms of polystyrene.

[Examples 5, 8, 10-15, 18, 20-24, 26-31, Reference Examples 1-4, 6, 7, 9, 16, 17, 19, 25, 32-35, Comparative Examples 1- 24]
A light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less was charged at the ratios (parts by weight) shown in Tables 1 to 4 and sufficiently stirred with a disper to sufficiently degas. Thereafter, an active energy ray-polymerizable adhesive was obtained. Each of these active energy ray polymerizable adhesives was prepared and evaluated by the following methods. The evaluation results are also shown in Tables 1 to 4.

Abbreviations in the table are as follows.
4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate CHDMMA: cyclohexanedimethanol monomethacrylate DMAEA: dimethylaminoethyl acrylate DMAPAA: dimethylaminopropyl acrylate PMPMA: pentamethylpiperidinyl methacrylate VIM: 1-vinylimidazole VRP : 4-vinylpyridine DCPA: dicyclopentanyl acrylate IBXA: isobornyl acrylate DCPDMDA: tricyclodecane dimethanol diacrylate oligomer 1: purple light UV3000B: polyurethane acrylate manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd. Mw = 18000
Oligomer 2: Polyurethane acrylate obtained in Synthesis Example 1 Mw = 4000
Oligomer 3: Polyurethane acrylate obtained in Synthesis Example 2 Mw = 1300
Oligomer 4: EBECRYL3708: Modified Epoxy Acrylate Mw = 1500 manufactured by Daicel Ornex
Oligomer 5: EBECRYL810: manufactured by Daicel Ornex Co., Ltd. Polyester acrylate Mw = 1000
tBA: t-butyl acrylate nBA: n-butyl acrylate THFA: tetrahydrofurfuryl acrylate PEA: phenoxyethyl acrylate BzA: benzyl acrylate EPPA: ethoxylated o-phenylphenol acrylate (A-LEN-10: manufactured by Shin-Nakamura Chemical Co., Ltd.)
VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate BDDA: 1,4-butanediol diacrylate DPHA: Dipentaerythritol hexaacrylate PET3A: Pentaerythritol triacrylate IATA: Isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.) : Aronix M
-315)
NPDA: neopentyl glycol diacrylate GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd., also known as: 4- (glycidyloxy) butyl acrylate)
DMAA: N, N-dimethylacrylamide TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide DETX-S: Thioxanthone sensitizer manufactured by Nippon Kayaku Co., Ltd. CPI-110P: Triarylsulfonium salt type manufactured by San Apro Photo acid generator

<Oligomer Synthesis Example 1 (Oligomer 2)>
Polytetramethylene glycol (Hodogaya Chemical Co., Ltd .: PTG850, hydroxyl value 127.1 mgKOH / g) was added to a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel. 81.6 parts and 41.4 parts of isophorone diisocyanate were charged, and the temperature was raised to 60 ° C. while introducing dry air. 0.05 part of dibutyltin dilaurate was added here, and it was made to react for 1 hour. Separately, 27.0 parts of 4-hydroxybutyl acrylate and 0.15 part of hydroquinone monomethyl ether were charged into a dropping funnel and dropped into a separable flask over 1 hour. After completion of the dropping, stirring was continued at 80 ° C. for 3 hours, and then it was confirmed by infrared absorption spectrum that there was no absorption peak of isocyanato group. The weight average molecular weight of the product was 4000.

In addition, the measurement of the hydroxyl value of this invention is as follows. About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution, and further added with an acetylating agent (25 g of acetic anhydride). 5 ml of a solution dissolved in pyridine to a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red, and the hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Oligomer Synthesis Example 2 (Oligomer 3)>
Compound obtained by adding 2 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate to a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel FA2D, hydroxyl value 163.0 mg KOH / g) was 113.4 parts, isophorone diisocyanate was 36.6 parts, hydroquinone monomethyl ether was 0.15 part, and the temperature was raised to 60 ° C. while introducing dry air. To this, 0.04 part of dibutyltin dilaurate was added, and the temperature was raised and reacted at 80 ° C. for 3 hours. The reaction was terminated after confirming that there was no absorption peak of the isocyanato group in the infrared absorption spectrum. The weight average molecular weight of the product was 1300. The measurement of the hydroxyl value is the same as in Synthesis Example 1 of the oligomer.

 Using the active energy ray polymerizable adhesives blended at the ratios shown in Tables 1 to 4, laminates were prepared by the following methods, respectively.

<Example of production of laminate A>
As the transparent film (1), an ultraviolet absorber-containing polytriacetylcellulose-based film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” is used. As the transparent film (2), an ultraviolet absorber manufactured by Fuji Film Business Supply Co., Ltd. is used. Polytriacetylcellulose-based film that does not contain: The product name “TAC 50 μ” (thickness 50 μm) is used, and each surface is subjected to corona treatment with a discharge amount of 300 W · min / m ² , and within 1 hour after the surface treatment, The active energy ray-polymerizable adhesive shown in Table 1 and Table 2 is coated using a wire bar coater so as to have a film thickness of 4 μm, and an active energy ray-polymerizable adhesive layer is formed. A polyvinyl alcohol polarizer is sandwiched between the transparent film (1) / adhesive layer / PVA polarizer / adhesive layer. / The laminated body which consists of a transparent film (2) was obtained. Four sides of this laminate were fixed with cellophane tape so that the transparent film (1) was in contact with the tin plate, and was fixed to the tin plate.

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

<Example of production of laminate B>
On the polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 50 μm, the active energy ray polymerizable adhesives shown in Tables 1 and 2 were applied to a thickness of 8 μm by a bar coater. A 50 μm-thick PET film was bonded to this by a nip roll, and then irradiated with ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ² from one side with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation). A laminate B was obtained.
About the obtained laminated body A, peel strength, punching workability, heat resistance, and moist heat resistance were determined according to the following methods. Moreover, in the obtained laminated body B, the transmittance | permeability and coloring after a heat-and-moisture resistance test were confirmed in accordance with the following method. The results are similarly shown in Tables 1 and 2.

<Example of production of laminate C>
As the transparent film (1) and transparent film (2), ZF: ZF-14 manufactured by Nippon Zeon Co., Ltd. Polynorbornene-based film (100 μm) containing no UV absorber, HBD: HBD-002 UV absorber manufactured by Mitsubishi Rayon Co., Ltd. Polyacrylic film (50 μm) that does not contain TAC: TAC50μ manufactured by Fuji Film Business Supply Co., Ltd. Polytriacetylcellulose-based film (thickness 50 μm) that does not contain an ultraviolet absorber is used, and 300 W · min / m ^{2 on} the surface thereof. The corona treatment is performed with the discharge amount, and within 1 hour after the surface treatment, the active energy ray-polymerizable adhesives shown in Tables 3 and 4 are applied with a wire bar coater so as to have a film thickness of 4 μm. A linear polymerizable adhesive layer is formed, and between the active energy ray polymerizable adhesive layer Sandwiching the polyvinyl alcohol-based polarizer, to obtain a transparent film (1) / adhesive layer / PVA-based polarizer / adhesive layer / made of transparent film (2) laminate. Four sides of this laminate were fixed with cellophane tape so that the transparent film (1) was in contact with the tin plate, and was fixed to the tin plate.

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

<Example of production of laminate B>
On the polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 50 μm, the active energy ray polymerizable adhesives shown in Tables 3 and 4 were applied to a thickness of 8 μm using a bar coater. A 50 μm-thick PET film was bonded to this by a nip roll, and then irradiated with ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ² from one side with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation). A laminate B was obtained.
About the obtained laminated body C, peel strength, punching workability, heat resistance, and moist heat resistance were determined according to the following methods. Moreover, in the obtained laminated body B, the transmittance | permeability and coloring after a heat-and-moisture resistance test were confirmed in accordance with the following method. The results are similarly shown in Tables 3 and 4.

<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained laminate A or laminate C was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was affixed on a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) using a laminator to obtain a laminate for measurement of the polarizing plate and the metal plate. The polarizing plate of the laminate for measurement is provided with a peeling flicker between the transparent film and the polarizer in advance, and this laminate for measurement is 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. The film was peeled off at an angle of 90 ° at a speed of 2 to obtain a peeling force. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a transparent film (1) and a polyvinyl alcohol-type polarizer and a transparent film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
A: Unpeelable or polarizing plate breakage O: Peeling force is 2.0 (N / 25 mm) or more Δ: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) ×: Peeling force Is less than 1.0 (N / 25mm) (no practicality)

<Punching workability>
The obtained laminate A or laminate C was punched out from the transparent film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler and evaluated according to the following four levels.
A: 0 mm
○: Less than 1 mm △: 1 mm or more and less than 3 mm ×: 3 mm or more (no practicality)

<Heat resistance>
The laminate A or laminate C pasted with each adhesive was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the conditions of 80 ° C.-dry and 100 ° C.-dry. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages.
A: No peeling even at 100 ° C. dry condition ○: No peeling at 80 ° C.-dry condition Δ: Less than 1 mm peeling at 80 ° C.-dry condition X: 1 mm under 80 ° C.-dry condition Exfoliation above (no practicality)

<Heat and heat resistance>
Laminate A or Laminate C pasted with each adhesive is cut into a size of 50 mm × 40 mm, and the temperature is 60 ° C. and the humidity is 90%, and the temperature is 85 ° C. and the humidity is 85%. Exposure for 1000 hours. The presence or absence of peeling at the end of the laminate A after exposure was visually evaluated in the following three stages. ◎: No peeling at all even under the condition of 85 ° C-85% RH ○: 60 ° C-90% RH No peeling at all. Δ: Peeling of less than 1 mm under conditions of 60 ° C.-90% RH. X: Peeling of 1 mm or more under conditions of 60 ° C.-90% RH (no practicality).
<Yellow Index (ΔYI)>
The laminated body B bonded with each adhesive is cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of a temperature of 85 ° C. and a humidity of 85%, and an integrating sphere type spectral transmittance measuring device (Murakami color) ΔYI was measured by DOT-3C, manufactured by Materials Research Laboratory. Here, ΔYI is represented by the difference between the YI value of the laminate film after the heat resistance test and the YI value of the PET film before the test.
◎: Less than 0.5 ○: 0.5 or more and less than 1.0 △: 1.0 or more and less than 1.5 ×: 1.5 or more (no practicality)
The above results are shown in Tables 1-4.

表３および４中の透明フィルム（１）および（２）について
ＺＦ：日本ゼオン社製ＺＦ−１４ 紫外線吸収剤を含有しないポリノルボルネン系フィルム（１００μｍ）
ＨＢＤ：三菱レイヨン社製ＨＢＤ−００２ 紫外線吸収剤を含有しないポリアクリル系フィルム（５０μｍ）
ＴＡＣ：富士フィルムビジネスサプライ社製ＴＡＣ５０μ 紫外線吸収剤を含有しないポリトリアセチル
セルロース系フィルム（厚み５０μｍ）

About transparent films (1) and (2) in Tables 3 and 4 ZF: ZF-14 manufactured by Nippon Zeon Co., Ltd. Polynorbornene-based film containing no UV absorber (100 μm)
HBD: Mitsubishi Rayon Co., Ltd. HBD-002 Polyacrylic film containing no UV absorber (50 μm)
TAC: TAC50μ manufactured by Fuji Film Business Supply Co., Ltd. Polytriacetyl cellulose-based film containing no UV absorber (thickness 50μm)

本発明の活性エネルギー線重合性接着剤としてポリトリアセチルセルロース系フィルムに用いた場合は、表１に示すように、実施例５、８、１０〜１５、１８では、良好な剥離強度や耐性を有する。れに対して、ホウ酸を含まない比較例１〜８では、剥離強度が低いか、いずれかの耐性や加工性で実用範囲に至らない。また、ポリアクリル系フィルムやポリノルボルネン系フィルムに用いた場合でも、表３の実施例２０〜２４、２６〜３１に示すように良好な剥離強度や耐性を有する。一方、ホウ酸を含まない比較例９〜２４では、剥離強度が低いか、いずれかの耐性で実用範囲に至らない。

When used in a polytriacetylcellulose-based film as the active energy ray polymerizable adhesive of the present invention, as shown in Table 1, in Examples 5, 8, 10-15, and 18, good peel strength and resistance are obtained. Have. On the other hand, in Comparative Examples 1 to 8 not containing boric acid, the peel strength is low, or any resistance or workability does not reach the practical range. Moreover, even when it uses for a polyacrylic-type film and a polynorbornene-type film, as shown in Examples 20-24 of Table 3, and 26-31, it has favorable peeling strength and tolerance. On the other hand, in Comparative Examples 9 to 24 containing no boric acid, the peel strength is low, or any resistance does not reach the practical range.

Claims (5)

An active energy ray-polymerizable adhesive comprising an α, β-ethylenically unsaturated double bond group-containing compound (M) and boric acid as essential components.
However, the α, β-ethylenically unsaturated double bond group-containing compound (M) is an α, β-ethylenically unsaturated double compound having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures. A linking group-containing compound (C) and a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (X) are included. Further active energy ray polymerizable adhesive of claim 1, wherein comprising an active energy ray polymerization initiator (E). A laminate comprising the active energy ray-polymerizable adhesive according to claim 1 or 2 laminated on one side or both sides of the substrate (F). The substrate (F) is a polyacetylcellulose film, polynorbornene film, polypropylene film, polyacryl film, polycarbonate film, polyester film, polyvinyl alcohol film or polyimide film. The laminate according to claim 3 . The laminated body for optical elements which uses the laminated body of Claim 3 or 4 .