KR102456269B1 - Active-energy-ray-polymerizable resin composition and laminate - Google Patents

Abstract

The present invention provides a novel active energy ray-polymerizable resin composition having excellent adhesion, and a laminate using the same, which is superior in punching processability and durability to heat or humidity, in particular, a laminate for optical elements compared to the prior art. An active energy ray polymerizable resin composition comprising an α,β-ethylenically unsaturated double bond-containing compound (M) and boric acid and/or a boric acid derivative, and a cationically polymerizable compound (K) and a boric acid and/or a boric acid derivative and cationic polymerization An active energy ray polymerizable resin composition containing an initiator (KE), and also an α,β-ethylenically unsaturated double bond group-containing compound (M) and a cationically polymerizable compound (K) containing boric acid and/or a boric acid derivative It relates to an active energy ray-polymerizable resin composition.

Description

An active energy ray-polymerizable resin composition and a laminated body {ACTIVE-ENERGY-RAY-POLYMERIZABLE RESIN COMPOSITION AND LAMINATE}

The present invention relates to a novel active energy ray polymerizable resin composition suitable for an adhesive or a coating agent, and a laminate using the composition.

The active energy ray-polymerizable resin composition has characteristics such as a high polymerization rate and can be generally used without a solvent, excellent workability, and very low energy required at the time of polymerization. An active energy ray-polymerizable resin composition contains the resin component which can superpose|polymerize by an active energy ray, and the monomer component which has (alpha), (beta)-ethylenically unsaturated double bond group typically.

As the resin component, an oligomer having a low molecular weight and an α,β-ethylenically unsaturated double bond group at the molecular terminal, such as a polyester resin, a polyurethane resin, a polyepoxy resin, and a polyacrylic resin, is used. By irradiation with an active energy ray, the monomer component is polymerized together with the resin component, but can function as a solvent until polymerization is completed. Therefore, the said active energy ray polymeric resin does not require a solvent separately, and has the advantage that volatilization of a solvent does not arise at the time of coating-film formation by it by it.

Moreover, in recent years, the development and generalization of information and communication devices including display devices such as displays are remarkable. In such a display device, performance improvement, such as a coating agent, an adhesive agent, or a sealing agent, and the improvement of productivity are calculated|required, and various proposals using an active energy ray-polymerizable material are made. In such a display device, various films are usually used depending on the purpose, such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing damage to the surface of the display device, for example, In the member for liquid crystal cells which comprises a liquid crystal display (LCD), a polarizing plate and retardation film are laminated|stacked.

In addition, a flat panel display (FPD) is not only used as a display apparatus, but the function of a touch panel is provided in the surface, and it is also used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, etc. are used also for a touchscreen.

Moreover, the backlight system which illuminates the liquid crystal layer from the back surface and emits light is widespread in a display apparatus, and backlight units, such as an edge light type and a direct type, are equipped on the lower surface side of a liquid crystal layer. Such an edge light type backlight unit is basically a linear lamp as a light source, a rectangular plate-shaped light guide plate disposed so as to have an end along the lamp, a light diffusing sheet disposed on the surface side of the light guide plate, and a light diffusing sheet disposed on the surface side A prism sheet is provided. In recent years, since a light emitting diode (LED) excellent in color reproducibility and power saving has been used instead of a cooling cathode tube (CCFL) as a light source, the demand for more heat resistance and dimensional stability is increasing.

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

Give specific examples. Polarizers used in liquid crystal display-related fields, etc. are usually manufactured by uniaxially stretching polyvinyl alcohol (PVA) adsorbed with iodine or dye. cause a decline Then, what bonded the protective film on the surface of a PVA system polarizer is used as a polarizing plate. As an adhesive agent for sticking a protective film to a polarizer, the aqueous solution of polyvinyl alcohol-type resin (PVA-type adhesive agent) is conventionally used widely (refer patent documents 1 and 2). However, although the water-based adhesive requires a drying process after coating, since the heat resistance of a PVA-type polarizer is low, drying at low temperature for a long time is required, and production efficiency is bad. From the above reasons, instead of the water-based adhesive, it is proposed to use a cationic active energy ray-polymerizable adhesive using an ultraviolet ray as an active energy ray (refer to Patent Document 3).

However, since a cationic active energy ray-polymerizable adhesive agent has a dark reaction after ultraviolet irradiation, when a long hardened|cured material is wound into roll shape, there exists a problem that the winding property is easy to produce at the time of storage. Moreover, a cationic active energy ray-polymerizable adhesive agent has the problem that it is easy to be influenced by the humidity at the time of polymerization and hardening, and the water|moisture content in an adhesive agent and a film, and a cured state is easy to be disturbed. Then, in order to express a uniform cured state, not to mention environmental humidity, it is necessary to manage the moisture content of an adhesive agent and a PVA system polarizer with difficulty. Although it is excellent from a viewpoint that there are comparatively few such problems in a radical type active energy ray-polymerizable adhesive agent, cure shrinkage is large in general, and it was difficult to ensure sufficient adhesiveness.

By the way, as the use expands, a liquid crystal display device comes to be used in various environments, and high heat resistance is calculated|required by the polarizing plate which comprises a liquid crystal display device. For example, high heat resistance durability is calculated|required by vehicle-mounted liquid crystal display devices, such as a car navigation.

In a high-temperature environment, when adhesiveness is weak, the problem that a PVA-type polarizer and a protective film peel by the difference of the thermal contraction rate of a PVA-type polarizer and a protective film may generate|occur|produce.

Patent Document 4 contains a curable component according to a compound having a (meth)acryloyl group containing N-hydroxyethyl acrylamide and N-acryloylmorpholine, and the Tg of the adhesive layer after curing is 60°C or higher Active energy ray polymerizable adhesives are disclosed. The durability performance calculated|required of a polarizing plate is becoming difficult, and the durability in the harsher environment under high humidity and high temperature is calculated|required. However, in the said polarizing plate, durability under the said harsh environment could not be satisfied.

In addition, in recent years, thinning of the polarizer or protective film is progressing, and when a polarizing plate is formed with an active energy ray-polymerizable adhesive containing a curable component according to a compound having a (meth)acryloyl group, the curing shrinkage of the adhesive is large. Wrinkles and irregularities may occur in the polarizing plate.

Moreover, although the active energy ray polymeric resin composition using the ultraviolet-ray which consists of a (meth)acrylamide compound (A) which does not have a hydroxyl group, and boric acid (B) in patent document 5 is disclosed, About strength deterioration by cure shrinkage No examination was made and the adhesive strength and the like were insufficient.

Japanese Patent Laid-Open No. Hei 09-258023 Japanese Patent Laid-Open No. 2005-208456 Japanese Patent Laid-Open No. 2008-233874 Japanese Patent Publication No. 4744496 Japanese Patent Laid-Open No. 2013-194083

The present invention relates to a novel active energy ray-polymerizable resin composition suitable for an adhesive or coating agent and having excellent adhesion, and a laminate using the same, which is superior in punching processability and durability to heat and humidity, especially for optical elements It aims to provide a laminated body.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination so that the said subject may be solved, this inventor discovered that the said objective could be achieved with the active energy ray polymerizable resin composition shown below, and came to complete this invention.

That is, the present invention is an active energy ray resin composition comprising a polymerizable compound and boric acid and/or a boric acid derivative, wherein the polymerizable compound is an α,β-ethylenically unsaturated double bond-containing compound (M) and a cationically polymerizable compound ( It is an active energy ray polymerizable resin composition which is at least 1 sort(s) chosen from the group which consists of K).

A first aspect of the present invention is an active energy ray resin composition comprising a polymerizable compound, boric acid and/or a boric acid derivative, wherein the polymerizable compound is an α,β-ethylenically unsaturated double bond-containing compound (M). It is an energy-beam polymerizable resin composition.

It is preferable that the active energy ray-polymerizable resin composition in the 1st aspect of this invention contains the at least 1 initiator chosen from the group which consists of active energy ray polymerization initiators (KE) and (RE).

Further, a second aspect of the present invention is an active energy ray resin composition comprising a polymerizable compound, boric acid and/or a boric acid derivative, wherein the polymerizable compound is a cationically polymerizable compound (K), and a cationic polymerization initiator (KE) It is an active energy ray polymeric resin composition further containing.

Further, a third aspect of the present invention is an active energy ray resin composition comprising a polymerizable compound, boric acid and/or a boric acid derivative, wherein the polymerizable compound is an α,β-ethylenically unsaturated double bond-containing compound (M) and It is a cationically polymerizable compound (K).

It is preferable that the active energy ray polymeric resin composition in the 3rd aspect of this invention contains the at least 1 initiator chosen from the group which consists of active energy ray polymerization initiators (KE) and (RE).

In the active energy ray polymerizable resin composition of the present invention, the α,β-ethylenically unsaturated double bond group-containing compound (M) preferably contains a hydroxyl group-containing α,β-ethylenically unsaturated double bond group-containing compound (X). do.

Moreover, it is preferable that the alpha, beta -ethylenically unsaturated double bond group containing compound (M) contains the amino group containing (alpha), beta -ethylenically unsaturated double bond group containing compound (Y).

Further, the α,β-ethylenically unsaturated double bond group-containing compound (M) is an 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. It is preferable to include

The α,β-ethylenically unsaturated double bond-containing compound (M) preferably includes an oligomer (D) having a weight average molecular weight of 300 to 30,000.

The active energy ray polymerizable resin composition of this invention WHEREIN: It is preferable that the cationically polymerizable compound (K) contains an oxirane compound (k1).

It is preferable that the said oxirane compound (k1) contains the oxirane compound (k1-1) which has an aromatic ring.

As for the active energy ray-polymerizable resin composition in this invention, it is preferable that a boric-acid derivative has 3 or more hydroxyl groups in 1 molecule.

Moreover, it is preferable that the active-energy-ray-polymerizable resin composition in this invention contains 0.1 weight part - 20 weight part of said boric acid and/or a boric-acid derivative in 100 weight part of said compositions.

This invention relates to the adhesive agent or coating agent containing said active energy ray polymerizable resin composition.

This invention relates to the laminated body formed by laminating|stacking the layer which consists of said active-energy-ray-polymerizable resin composition on one side or both surfaces of a base material (F).

The base material (F) is a polyacetyl cellulose-based film, a polynorbornene-based film, a polypropylene-based film, a polyacrylic-based film, a polycarbonate-based film, a polyester-based film, a polyvinyl alcohol-based film, and a polyimide-based film. It is preferable that it is at least 1 sort(s) chosen from the group which consists of.

This invention relates to the laminated body for optical elements formed using said laminated body.

The active energy ray-polymerizable resin composition of this invention can provide the laminated body excellent in punching processability and durability with respect to heat|fever and humidity compared with the past, especially the laminated body for optical elements.

The present invention is an active energy ray resin composition comprising a polymerizable compound and boric acid and/or a boric acid derivative, wherein the polymerizable compound is an α,β-ethylenically unsaturated double bond-containing compound (M) and a cationically polymerizable compound (K) ), which is at least one selected from the group consisting of an active energy ray polymerizable resin composition.

It is preferable that the active-energy-ray-polymerizable resin composition in this invention is contained in an active-energy-ray-polymerizable adhesive agent or an active-energy-ray-polymerizable coating agent.

In addition, in the present invention, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylate", "(meth)acryloyloxy", and "(meth)aryl" In this case, unless otherwise specified, "acryloyl and/or methacryloyl", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", "acryloyloxy and/or methacryloyloxy" and "aryl and/or metharyl".

EMBODIMENT OF THE INVENTION Hereinafter, embodiment (1st - 3rd aspect) of this invention is described.

(Explanation of the first aspect)

First, an active energy ray polymerizable resin composition in which boric acid and/or a boric acid derivative is used in combination with an α,β-ethylenically unsaturated double bond-containing compound (M) (hereinafter also referred to as “radical active energy ray polymerizable resin composition”) Note that "resin composition" is also referred to as "adhesive" or "coating agent").

The radical type active energy ray polymerizable resin composition in this invention contains the compound (M) containing an alpha, beta -ethylenically unsaturated double bond group, and boric acid and/or a boric acid derivative.

As the α,β-ethylenically unsaturated double bond group-containing compound (M) used as the main component of the radical-based active energy ray-polymerizable resin composition, all compounds containing an α,β-ethylenically unsaturated double bond in the molecule are included. The α,β-ethylenically unsaturated double bond-containing compound (M), from the viewpoint of reactivity with active energy rays, in the total weight of α,β-ethylenically unsaturated double bonds contained in the active energy ray-polymerizable resin composition, It is preferable that the (meth) acryloyl group is designed to occupy 50 to 100% by weight.

Specifically as the compound (M), a compound (X) containing a hydroxyl group-containing α,β-ethylenically unsaturated double bond group, a compound containing an amino group containing an α,β-ethylenically unsaturated double bond group (Y), and a cyclo having two or more ring structures At least one compound selected from the group consisting of an α,β-ethylenically unsaturated double bond-containing compound (C) having an alkane skeleton and/or a cycloalkene skeleton, and an oligomer (D) having a weight average molecular weight of 300 to 30,000. desirable.

First, 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/or a boric acid derivative, and forms a crosslinked coating film after curing with an active energy ray. In addition, the compound (X) has an effect of improving adhesion by forming a bond with the surface functional group of the substrate (F) through boric acid and/or a boric acid derivative.

The compound (X) is not particularly limited as long as it has a hydroxyl group in its structure. For example, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxypropyl, (meth)acrylic acid 3-hydroxy Propyl, (meth) acrylate 4-hydroxybutyl, (meth) acrylate 6-hydroxyhexyl, (meth) acrylate 8-hydroxy octyl, (meth) acrylate 12-hydroxy lauryl, (meth) acrylate ethyl-α -(hydroxymethyl), monofunctional (meth)acrylic acid glycerol, or fatty acid ester-based (meth)acrylic acid ester such as (meth)acrylic acid glycidyl lauric acid ester, or the hydroxyl group-containing α,β-ethylenically unsaturated (meth)acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone to the compound containing a double bond group; aliphatic (meth)acrylic acid esters containing a hydroxyl group, such as alkylene oxide addition (meth)acrylic acid esters obtained by repeatedly adding alkylene oxides such as ene oxide;

Cyclohexanedimethanol mono(meth)acrylic acid ester, 2-hydroxy-3-phenoxymethyl mono(meth)acrylic acid ester, (meth)acrylic acid monohydroxyethyl phthalate, (meth)acrylic acid 2-(4-benzoyl-3 -hydroxyphenoxy) (meth)acrylic acid esters having a cyclic structure with a hydroxyl group such as ethyl;

aliphatic vinyl ethers containing a hydroxyl group, such as alkylene oxide addition-based vinyl ethers having a hydroxyl group at the terminal of repeated addition of alkylene oxide such as hydroxyethyl vinyl ether and hydroxydecyl vinyl ether;

(Meta) aryl alcohol, isopropenyl alcohol, dimethyl (meth) aryl alcohol, hydroxyethyl (meth) aryl ether, or alkylene oxide having a hydroxyl group at the end of repeated addition of an alkylene oxide such as ethylene oxide or propylene oxide aliphatic (meth)aryl alcohols or (meth)aryl ethers containing hydroxyl groups such as addition-based (meth)aryl ethers;

α,β-ethylenically unsaturated double bond-containing compounds having a plurality of hydroxyl groups, such as propenediol, butenediol, and di(meth)glycerol;

Hydroxyl group-containing (meth)acrylamides, such as N-hydroxyethyl (meth)acrylamide and N-hydroxypropyl (meth)acrylamide;

Although monomers having a hydroxyl group and a vinyl group, such as vinyl alcohol, etc. are mentioned, It is not specifically limited to these. These may use only 1 type, or may use multiple types together.

As the compound (X), from the viewpoint of adhesion to the substrate, (meth) acrylate 2-hydroxyethyl, (meth) acrylate 2-hydroxypropyl, (meth) acrylate 4-hydroxybutyl, cyclohexanedimethanol mono ( Particularly preferred are ?,?-ethylenically unsaturated double bond-containing compounds having 2 to 18 carbon atoms, such as meth) acrylic acid ester and 1-2 mol addition of ?-caprolactone (meth)acrylic acid 2-hydroxyethyl.

Next, 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-containing compound (Y) (hereinafter referred to as compound (Y)) contains at least one amino group and at least one α,β-ethylenically unsaturated group in the molecule. It is a compound containing a double bond group. The amino group of the compound (Y) interacts with boric acid and/or a boric acid derivative described later to provide stable and uniform liquid properties as a non-aqueous active energy ray polymerization composition. At the same time, when used as an active energy ray-polymerizable adhesive or coating agent of the present invention due to its interaction, it has a great effect on the improvement of adhesiveness, and forms a good coating agent layer such as heat resistance and water resistance, or an adhesive layer it becomes possible to do

Examples of the compound (Y) include 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 bond group-containing compound (y2).

As the acyclic amino group-containing α,β-ethylenically unsaturated double bond-containing compound (y1), for example, (meth)acrylic acid-monoethyl (meth)acrylic acid monomethylaminoethyl, (meth)acrylate dimethylaminoethyl, etc. or dialkylaminoesters;

Mono or dialkylaminoalkyl (meth)acrylamide, such as monomethyl amino ethyl (meth)acrylamide and diethylaminopropyl (meth)acrylamide, etc. are mentioned.

Examples of the cyclic amino group-containing α,β-ethylenically unsaturated double bond-containing compound (y2) include a cyclic amino group-containing compound and (meth)acryloyl group-containing compound (y2-I), a cyclic amino group-containing compound and a vinyl group-containing compound (y2). -II), a cyclic amino group containing compound and (meth)allyl group containing compound (y2-III) are mentioned.

As the cyclic amino group-containing and (meth)acryloyl group-containing compound (y2-I), for example, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzo (meth)acrylic acid having an amino group in a polycyclic structure such as triazole and 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole esters;

2,4-diphenyl-6-[2-hydroxy-4-{2-(meth)acryloyloxyethoxy}]-S-triazine, 2,4-bis(2,4-diethylphenyl (meth)acrylic acid esters having a 6-membered ring amino group such as )-6-[2-hydroxy-4-{2-(meth)acryloyloxyethoxy})]-S-triazine;

Pentamethyl piperidinyl (meth) acrylate [Acrylate and meth acrylate are collectively described as (meth) acrylate. (meth)acrylic acid esters having an alicyclic amino group such as tetramethylpiperidinyl (meth)acrylate and 4-(pyrimidin-2-yl)piperazin-1-yl(meth)acrylate) , and the like.

As the cyclic amino group-containing and vinyl group-containing compound (y2-II), more specifically, for example, 2-vinylpyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1 -vinyl group-containing compounds having a 5-membered ring amino group, such as vinylimidazole and 3-methyl-5-phenyl-1-vinylpyrazole;

2-vinyl piperazine, 4-vinyl piperazine, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl pyrimidine, 2-vinyl-4,6-diamino-1,3,5-triazine, etc. Vinyl group-containing compounds having a 6-membered ring amino group;

1-vinylindole, 1-vinyl-1H-benzoimidazole, 2-vinyl quinoline, 2-vinyl isoquinoline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinyl cinnoline, 1-vinyl vinyl group-containing compounds having a polycyclic amino group such as carbazole;

Compounds having a cyclic amino group, such as 1-methyl-4,5-divinyl-1H-imidazole and 2,6-divinyl pyridine, and two or more vinyl groups;

As the cyclic amino group-containing and (meth)allyl group-containing compound (y2-III), more specifically, for example, 1-(meth)aryl-1H-imidazole, 5-bromo-1-1-(meth ) having a cyclic amino group such as aryl-1H-pyrazole, 1-(meth)aryl piperazine, N-(meth)aryl-4,6-dichloro-1,3-5-triazin-2-amine ) allyl group-containing compounds;

2-(meth)aryl-1H-indole, 1-(meth)aryl-1H-benzoimidazole, 2-(meth)aryl indazole, 1,2-di(meth)aryl-1,2-dihydroiso (meth)allyl group containing compounds which have polycyclic amino groups, such as quinoline and 9-(meth)aryl-9H-carbazole, etc. are mentioned.

Compound (Y) used in the present invention is an acyclic amino group-containing α,β-ethylenically unsaturated double from the viewpoint of adhesiveness with various substrates (F) when used as an active energy ray-polymerizable adhesive or coating agent. A compound (y2) containing a cyclic amino group containing α,β-ethylenically unsaturated double bond group is more preferable than the compound containing a bonding group (y1). Especially, when it uses together with compounds (M) other than a compound (Y) and it is set as an active energy ray polymerizable composition, cyclic amino-group containing and vinyl group containing compound (y2-II) are preferable.

The coating film structure of the active energy ray polymerizable resin composition after active energy ray polymerization of the compound (y2-II) is microscopic due to the difference in the relative reaction rate and main chain structure with the acryloyl group-containing compound used as the compound (M). It is easy to form a phase-separated structure, and in particular, it becomes easy to form a sea-island structure. For this reason, since it becomes a coating film structure that has both elasticity and stress relaxation properties, when used as an active energy ray-polymerizable adhesive, it not only expresses high adhesiveness and high adhesiveness due to high cohesive force, but also reaches extremely high temperature from cryogenic temperature. Since it becomes possible to maintain practicality, for example, floating or peeling by external environmental change and moisture being suppressed, it is the most preferable.

In addition, if the α,β-ethylenically unsaturated double bond group of the compound (Y) is a (meth)allyl group (y2-III), the reaction rate that tends to form a microphase-separated structure is slow, so that the high molecular weight of the coating film becomes insufficient there is Therefore, when it uses as an active-energy-ray-polymerizable adhesive agent, a fall of durability and cohesive failure of a contact bonding layer may occur easily. A preferable order as the α,β-ethylenically unsaturated double bond group of the compound (Y) that tends to form a microphase-separated structure of the coating film is a vinyl group (y2-II) > (meth) an allyl group (y2-III) > (meta) It is an acryloyl group (y2-I).

Moreover, as a ring structure containing one or more nitrogen atoms in the molecule|numerator of compound (Y), a 5-membered ring or more is preferable. In the case of a 3 or 4 membered ring, a ring-opening reaction may be caused by heat or an active energy ray.

As the amino group-containing α,β-ethylenically unsaturated double bond-containing compound (Y), 2-vinylpyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-vinylimidazole 2 -Vinyl piperazine, 4-vinyl piperazine, 2-vinylpyridine, 4-vinylpyridine, 1-vinylindole, 1-vinyl-1H-benzoimidazole, 2-vinyl quinoline, 2-vinyl isoquinoline, 2-vinyl Quinoxaline, 2-vinyl quinazoline, 2-vinyl cinnoline, and 1-vinyl carbazole are most preferable industrially and in terms of price.

Further, a compound (C) containing an α,β-ethylenically unsaturated double bond group having a cycloalkane skeleton and/or a cycloalkene skeleton having two or more ring structures (hereinafter referred to as compound (C)) will be described. The compound (C) is preferably 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), the cycloalkane skeleton and/or the cycloalkene skeleton having two or more ring structures are separated from each other by an alkyl group, an ether group, an ester group, or the like, the compound (c1), and norbornane and compounds having a cyclo-ring bridge structure such as compound (c2) having a norbornene skeleton and compound (c3) having an adamantane structure. Since it is excellent in such heat resistance, the compound (c2) which has norbornane or a norbornene skeleton, or the compound (c3) which has an adamantane structure is more preferable than the compound (c1).

As the α,β-ethylenically unsaturated double bond-containing compound (c1) having a cycloalkane skeleton and/or a cycloalkene skeleton having two or more ring structures and having a ring structure separated from the ring structure, hydrogenated biphenol A is diacrylate, 3,3-dicyclopropyl acrylate, and the like.

As the α,β-ethylenically unsaturated double bond group-containing compound (c2) having norbornene and/or norbornane skeleton, at least one norbornene skeleton and/or norbornane skeleton and an ethylenically unsaturated double bond are It is sufficient to have at least one, for example, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethyloldicyclopentane di(meth)acrylic Late, tricyclodecanedimethanol (meth)acrylate, isobornyl (meth)acrylate, etc. are mentioned.

Among the compounds (c2), the compound (c2') having three or more cyclic skeletons is particularly preferable because it suppresses cure shrinkage by increasing the volume and improves the adhesive force. pentenyl (meth) acrylate, dicyclo pentenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethyloldicyclopentane di (meth) acrylate, and the like.

The α,β-ethylenically unsaturated double bond-containing compound (c3) having an adamantane structure is a radically polymerizable compound having three or more cyclic skeletons similar to those of the compound (c2′), and improves heat resistance and adhesiveness can see. Specific examples of the compound (c3) include 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. Acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyl diol di (meth) acrylic Late, 1,3,5-adamantyl tri(meth)acrylate, 3-hydroxy-1,5-adamantyl di(meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, etc. are mentioned. Among them, from the viewpoint of excellent adhesion, one α,β-ethylenically unsaturated double bond is 3-hydroxy-1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, and 2-ethyl-2 -Adamantyl acrylate is preferred.

Furthermore, the oligomer (D) (hereinafter referred to as oligomer (D)) having a weight average molecular weight of 300 to 30,000 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 particular limitation.

As the polyester oligomer (d1), α having at least one carboxyl group in the molecule such as (meth)acrylic acid, maleic acid, and the hydroxyl group in the terminal or polyester chain obtained by polycondensation of a polybasic acid and a polyhydric alcohol in the main chain backbone , a compound obtainable by esterification with a compound containing a β-ethylenically unsaturated double bond group may be used. As another example, it can be obtained by esterification of a carboxyl group at the end of a polyester or in a polyester chain with the above-mentioned compound (X) such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. A compound may be sufficient. 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).

As said polybasic acid, an aliphatic type, an alicyclic type, and an aromatic type are mentioned, Each can be used especially without a restriction|limiting. As the aliphatic polybasic acid, more specifically, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, sveric acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimeric acid , citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids or anhydrides thereof can be used.

In addition, derivatives of succinic anhydride, such as methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, phenyl succinic anhydride, glutaric anhydride, such as glutaric anhydride, 3- aryl glutaric anhydride, 2,4-dimethyl glutaric anhydride,

Derivatives of maleic anhydride, for example, anhydride derivatives such as 2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, dodecyl maleic anhydride, and phenyl maleic anhydride can also be used.

As the alicyclic polybasic acid, more specifically, for example, an alicyclic dicarboxylic acid or an anhydride thereof can be used. Examples of these include dimer acid, cyclopropane-1α,2α-dicarboxylic acid, cyclobutane-1α,2β-dicarboxylic acid, (1R)-cyclopentane-1β,2α-dicarboxylic acid, 1,2-Cyclohexane dicarboxylic acid, 1,1-cycloheptane dicarboxylic acid, cuban 1,4-dicarboxylic acid, 2,3-norbornane dicarboxylic acid, hexahydro terephthalic acid, hexahydro saturated alicyclic dicarboxylic acids such as isophthalic acid, hexahydrophthalic acid, and tetrahydrophthalic acid, and

1-Cyclobutene-1,2-dicarboxylic acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2,5-hexadiene-1α and unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring, such as ,4α-dicarboxylic acid.

In addition, derivatives of hexahydrophthalic anhydride as alicyclic dicarboxylic acid anhydrides, such as 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, and derivatives of tetrahydrophthalic anhydride, such as Hydrogenated phthalic anhydride derivatives such as , 1,2,3,6-tetrahydrophthalic anhydride and 3-methyl-1,2,3,6-tetrahydrophthalic anhydride can also be used.

More specifically, as an aromatic polybasic acid, an aromatic dicarboxylic acid, its anhydride, etc. can be used, for example. Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, 2,5-dimethyl terephthalic acid, 4,4-biphenyldicarboxylic acid, and 1,4-naphthalenedica. carboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindane dicarboxylic acid, 1,2-azulenedicarboxylic acid, 1,3-azulene Dicarboxylic acid, 4,5-azulenedicarboxylic acid, (-)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,2-phenanthrenedicarboxylic acid, and 3,9-perylene dicarboxylic acid, and examples of the aromatic dicarboxylic acid anhydride include phthalic anhydride and 4-methyl phthalic anhydride.

In addition, as polybasic acids, chlorendic anhydride, hetic 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 acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexenedicarboxylic acid anhydride, 1 Acid anhydrides such as ,8-naphthalenedicarboxylic acid anhydride and octahydro 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used.

In addition, as the polyhydric alcohol, a relatively low molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500, and a relatively high molecular weight polyol having a number average molecular weight (Mn) of about 500 to 30,000, respectively, In particular, it can be used without restrictions.

As the relatively low molecular weight polyols, more specifically, for example, 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, poly Oxyethylene glycol (10 or less added moles), polyoxypropylene glycol (10 or less added moles), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, 1,9-nonanediol, neopentyl glycol, octanediol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexane dimethanol, tricyclodecanedimethanol, cyclopentadienedi aliphatic or alicyclic diols such as methanol and dimer-diol;

1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'- Methylene diphenol, 4,4'-(2-norbornylidene) diphenol, 4,4'-dihydroxy biphenol, o-, m- and p-dihydroxybenzene, 4,4'-iso Aromatic diols, such as propylidene phenol and the addition type bisphenol which added alkylene oxide to bisphenol, etc. are mentioned.

Examples of the raw material bisphenol of the 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. A high molecular weight polycarbonate polyol can be obtained by the reaction of said comparatively low molecular weight diol, carbonate ester, or phosgene.

Said comparatively high molecular weight polyols can be obtained also as a commercial item. For example, as a commercial item of the said high molecular weight polyester polyol, the Byron series manufactured by Toyo Spinning Co., Ltd., Kuraray Polyol P series manufactured by Kurare Corporation, and the Kyouwapol series manufactured by Kyowa Fermentation Chemicals Co., Ltd. are mentioned.

As a commercially available product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Chemical Industry Co., Ltd. or the like can be used.

Examples of commercially available products of the high molecular weight polycarbonate polyol include Oxima N112 manufactured by Fastov, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray Polyol PMHC series manufactured by Kuraray Corporation, Kuraray Polyol C series, and the like. can

As a commercial item of the said high molecular weight polyurethane polyol, For example, the Byron UR series manufactured by Toyo Spinning Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3), Takelac E551T (hydroxyl value = 30, acid value <3), and Takelac Y2789 (hydroxyl value = 10, acid value <2), etc. are mentioned.

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. have.

The polyurethane-based oligomer (d2) may be a compound obtained by reacting a compound having at least one isocyanate group with the compound (X). Further, as another example, a compound obtained by reacting the compound (X) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having at least one isocyanate group with the polyhydric alcohol described above may be used. As another example, a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having at least one isocyanate group and a polyhydric alcohol, and a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having at least one or more amino groups, and a urethane prepolymer, A compound obtained by reacting the compound (X) may be used. Polyurethane-based oligomers (d2) also include those containing a urea bonding group obtained by reacting an isocyanate group with an amino group.

Examples of the compound having at least one isocyanate group include monofunctional polyisocyanate and polyfunctional isocyanate. Specific examples of the compound include aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate.

As the monofunctional polyisocyanate, more specifically, 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 (R)-(+)-α-methylbenzyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenyl ethyl isocyanate, p-toluenesulfonyl isocyanate, and the like.

Among the 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-torylene diisocyanate, 2,6-torylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5- triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, etc. are mentioned.

Examples of the aromatic aliphatic polyisocyanate include ω,ω'-diisocyanate-1,3-dimethylbenzene and 1,4-tetramethyl xylylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (another name: IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclo Hexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanate methyl) cyclohexane and the like.

In addition, as a part of the polyurethane oligomer (d2), a 2-methylpentane-2,4-diol adduct of the polyisocyanate, a trimer having an isocyanurate ring, and the like can also be used in combination. In addition, polyphenyl methane polyisocyanate (alias: PAPI), naphthalene isocyanate, and a modified product of such polyisocyanate can be used. In addition, as a polyisocyanate-modified product, any group of a carbodiimide group, a uretdion group, a uretimine group, a water-reacted biuret group, an isocyanurate group, or two or more of these groups Modifications 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.

In addition, as a compound having an amino group, more specifically, for example, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene tetramine, diethylene triamine, triamino propane, 2,2,4-trimethyl hexamethylene diamine, 2,2,4-trimethyl hexamethylene diamine, 2-hydroxyethyl ethylene diamine, hexamethylene diamine 2-hydroxy ethylene diamine, N-(2-hydroxyethyl) propylene Diamine, (2-hydroxyethyl propylene) diamine, (di 2-hydroxyethyl ethylene) diamine, (di 2-hydroxyethyl propylene) diamine, (2-hydroxypropyl ethylene) diamine, (di 2-hydroxy propyl ethylene) aliphatic polyamines such as diamine and piperazine;

alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4,4'-diamine;

phenylene diamine, xylylene diamine, 2,4-torylene diamine, 2,6-torylene diamine, diethyl toluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4, Aromatic diamines, such as 4'-bis- (sec-butyl) diphenylmethane, etc. can be used.

The polyepoxy oligomer (d3) can be obtained by reacting a compound having a glycidyl group with an α,β-ethylenically unsaturated double bond-containing compound having one or more carboxyl groups in the molecule, such as (meth)acrylic acid and maleic acid. is a compound in Representative examples include bisphenol type, epoxidation type, phenol novolak type, and alicyclic type. As the bisphenol-type polyepoxy oligomer, bisphenol-type diglycidyl ether obtained by reacting bisphenol with epichlorohydrin, (meth)acrylic acid, etc. having one or more carboxyl groups in the molecule, α,β-ethylenically unsaturated It can be obtained by reacting a compound containing a double bond group.

As an epoxidized type polyepoxy oligomer, an epoxidized oil such as soybean oil is reacted with an α,β-ethylenically unsaturated double bond-containing compound having one or more carboxyl groups in the molecule, such as (meth)acrylic acid and maleic acid. You can use what you can get. As a phenol novolac-type polyepoxy oligomer, a phenol novolac-type epoxy resin can be obtained by reaction with an α,β-ethylenically unsaturated double bond-containing compound having at least one carboxyl group in its molecule, such as (meth)acrylic acid. can use what is available. As the alicyclic polyepoxy oligomer, one synthesized by reaction of an alicyclic epoxy resin with an α,β-ethylenically unsaturated double bond-containing compound having at least one carboxyl group in a molecule such as (meth)acrylic acid can be used. .

The weight average molecular weight (hereinafter referred to as Mw) of the oligomer (D) having at least one α,β-ethylenically unsaturated double bond group in the molecule is determined by compatibility with other components in the resin composition and good durability (heat resistance, It is preferable that it is the range of 300-30000 from a viewpoint of heat-and-moisture resistance) and aggregation density. Moreover, the range of 400-20,000 Mw is more preferable. When Mw of an oligomer (D) exceeds 30,000, since fluidity|liquidity will fall or compatibility with compounds (M) other than an oligomer (D) will also fall, coatability of an active energy ray-polymerizable resin composition falls. Moreover, when it is set as an active-energy-ray-polymerizable adhesive agent and a coating agent, the adhesiveness and durability of a polymerization coating film may fall, or a coating film may whiten. When the Mw of the oligomer (D) is less than 300, after coating and laminating the active energy ray polymerizable adhesive and the coating agent on the various substrates (F), cohesive failure of the adhesive layer and the coating agent layer tends to occur in some cases.

With respect to the α,β-ethylenically unsaturated double bond group-containing compound (M) contained in the active energy ray-polymerizable resin composition of the present invention, the compound (Y), the compound (X), the compound (C), and the oligomer (D) ), as other components, an α,β-ethylenically unsaturated double bond-containing compound (m) (hereinafter referred to as compound (m)) can be used as needed.

Examples of the compound (m) include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) n-hexyl acrylate, lauryl (meth) acrylate, and (meth) stearyl (meth) acrylate. Acrylic acid alkyl esters;

(meth) acrylic acid cyclohexyl, (meth) acrylic acid 1-methyl-1-cyclopentyl, (meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid (ethoxylated o-phenyl phenol), ( Having one cycloalkane skeleton or cycloalkene skeleton, such as meth) 1-naphthyl acrylate, 2-anthryl (meth) acrylate, and 2-(meth) acryloyloxy ethyl hexahydro phthalate, or an aromatic ring Eggplant (meth) acrylic acid esters;

(meth) acrylic acid (meth) aryl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 3-chloro 2-propenyl, (meth) acrylic acid 2-propenyl lactyl, (meth) acrylic acid 3,7-dimethylocta -6-en 1-yl, (meth) rhodinyl acrylate, (meth) acrylic acid cinnamyl, 2-(2-vinyloxyethoxy) ethyl acrylate, and (meth) containing new unsaturated groups such as (meth) vinyl acrylate ) acrylic acid esters;

(meth)acrylic acid perfluoroalkyl esters, such as (meth)acrylic acid perfluoromethyl, (meth)acrylic acid 2-perfluoroethyl ethyl, and (meth)acrylic acid 2-perfluorohexadecylethyl;

(meth) glycidyl acrylate, 4-(glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid-4-propyl-2 -Oxotetrahydropyren-4-yl, and (meth)acrylic acid-3,4-epoxy cyclohexylmethyl containing heterocyclic ring-containing (meth)acrylic acid esters having an oxygen atom;

(meth)acrylic acid (methoxycarbonyl) methyl, (meth)acrylic acid 2-(ethoxycarbonyloxy)hexyl, (meth)acrylic acid 2-(propoxycarbonyloxy)ethyl, and (meth)acrylic acid 2-( aliphatic (meth)acrylic acid esters having one carbonyl group such as octyloxycarbonyloxy) butyl;

(meth) acrylate 2-oxobutanoylethyl, (meth) acrylate 3-oxobutanoylpropyl, (meth) acrylate 2,3-di(oxobutanoyl) butyl, (meth) acrylic acid 2,3-di(oxobuta) aliphatic (meth)acrylic acid esters having two carbonyl groups such as noyl)hexyl and (meth)acrylic acid 2,3-di(oxobutanoyl)octyl;

Alkoxy silyl groups such as 3-(meth)acryloyloxypropyl methyl dimethoxy silane, 3-(meth)acryloyloxypropyl ethyl dimethoxy silane, and 3-(meth)acryloyloxypropyl tripropoxy silane containing (meth)acrylic acid esters;

(meth)acrylic acid alkyl esters containing a sulfonyl group, such as (meth)acrylic acid 3-sulfopropyl and (meth)acrylic acid sulfostearyl;

metal salts or ammonium salts of (meth)acrylic acid esters containing a sulfonyl group such as (meth)acryloyloxydimethylethylammonium ethyl sulfate;

phosphonic acid group-containing (meth)acrylic acid esters such as (meth)acrylic acid acid phosphooxyethyl and (meth)acrylic acid acid phosphooxyethylene oxide (the number of added moles of ethylene oxide: 4 to 10);

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

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

Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2,2-dimethylpropyl diol di(meth)acrylic acid, hydroxy di(meth)acrylate fivaryl hydroxy Pivalate, di(meth)acrylic acid 2,5-hexanediol, di(meth)acrylic acid 1,2-octanediol, di(meth)acrylic acid 2,2-diethyl-1,3-propanediol, and di(meth)acrylic acid ) bifunctional (meth)acrylic acid esters such as acrylic acid 2,5-dimethyl-2,5-hexanediol;

Tri(meth)acrylic acid 1,2,3-propane triol, tri(meth)acrylic acid trimethylol hexane, tri(meth)acrylic acid trimethylol octane, and tri(meth)acrylic acid 1,1,1-tris hydroxy trifunctional (meth)acrylic acid esters such as methyl ethane;

Tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, and hepta (meth) acrylic acid di 2,2-bis (hydroxymethyl) 1,3 -polyfunctional (meth)acrylic acid esters such as propanediol polyalkylene oxide;

vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate;

aliphatic vinyl compounds having an acyl group such as vinyl acetoacetate, vinyl acetopropionate, 2-acetoacetoxy hexyl vinyl ether, and 2-acetoacetoxy octyl vinyl ether;

Ethyl 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-ethyl hexyl vinyl ether and aliphatic vinyl ethers such as stearyl vinyl ether;

fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro(propyl vinyl ether), and vinylidene fluoride;

(meth)arylchlorosilane and (meth)aryltrimethoxysilane, etc. alkoxysilyl group-containing α,β-ethylenically unsaturated double bond-containing compounds;

alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

metal salts or ammonium salts such as ammonium vinylsulfonate, sodium vinylsulfonate, potassium vinylsulfonate, and sodium vinylalkylsulfosuccinate;

metal salts or ammonium salts of 2-methyl-2-propenyl sulfonic acid such as ammonium 2-methyl-2-propenyl sulfonate and sodium 2-methyl-2-propenyl sulfonate;

(meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, croton amide, maleinamide, fumaamide, mesaconamide, citracon aliphatic (meth)acrylamides such as amide, itaconamide, and 2-methylpropane-2-enoylamine;

N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxy hexyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-isopropoxy hexyl (meth)acrylamide, N-butoxy octyl (meth)acrylamide, N,N-di(methoxymethyl)meth)acrylamide, and N,N-di(ethoxymethyl)(meth)acrylamide, etc. (meth)acrylamides containing N-alkoxy groups;

N-(2-oxobutanoylethyl) (meth) acrylamide, N-(2-oxobutanoyl octyl) (meth) acrylamide, and (meth) acrylamide having a carbonyl group such as diacetone (meth) acrylamide Drew;

sulfonic acid-containing (meth)acrylamides such as (meth)acrylamide sulfonic acid, tert-butyl-(meth)acrylamide sulfonic acid, and (meth)acrylamide-2-methyl-1-propanesulfonic acid;

(meth)acrylonitrile, itaconnitrile, 2-propenenitrile, and (meth)acrylic acid 2-cyanoethyl group-containing α,β-ethylenically unsaturated double bond-containing compounds;

(meth)aryl esters of saturated carboxylic acids such as (meth)aryl acetate, (meth)aryl propionic acid, and vinyl pivalate;

glycidyl group-containing vinyl esters such as glycidyl cinnamate, aryl glycidyl ether, and 1,3-butadiene monooxirane;

aliphatic (meth)aryl compounds having an acyl group such as acetoacetic acid (meth)aryl, acetopropionic acid (meth)aryl, propanoylacetic acid (meth)aryl, and butyryl acetate (meth)aryl;

vinyl esters such as vinyl chloride, vinylidene chloride, and aryl chloride;

dienes such as allene, 1,2-butadiene, 1,3-butadiene, and 2-methyl-1,3-butadiene;

cis-diallyl succinate, 2-methylidene cohaxanediaryl, (E)-buta-2-vinyl enoate, (Z)-octadeca-9-vinyl enoate, and (9Z, 12Z, 15Z)-octadeca- α,β-ethylenically unsaturated double bond-containing compounds containing polyfunctional unsaturated bonds such as 9,12,15-vinyl trienoate;

ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-tetradecene, 1-triacontene, 1-octatriacontene, and 1-tetracontene, and mixtures thereof;

Alkenes, such as polybutene-1, polypentene-1, and poly4-methylpentene-1, etc. are mentioned. In particular, it is not limited to these. These may use only 1 type, or may use multiple types together.

As said compound (m), the compound which has a (meth)acryloyl group from a reactive viewpoint is preferable. Moreover, when using as an active energy ray polymerizable adhesive agent and a coating agent, it is preferable from a viewpoint of an active energy ray polymerization rate to contain bifunctional or more than (meth)acrylic acid ester.

Further, as the α,β-ethylenically unsaturated double bond-containing compound (m), (meth)glycidyl acrylate, 4-(glycidyloxy)butyl (meth)acrylate, (meth)acrylic acid (3-methyl-3) When using heterocyclic-containing (meth)acrylic acid esters having 3-membered or 4-membered ring oxygen atoms such as -oxetanyl)methyl and (meth)acrylic acid-3,4-epoxy cyclohexylmethyl, if necessary It is preferable to use together a well-known photo-acid generator (henceforth cationic polymerization initiator (KE)). Thereby, crosslinking progresses, and the adhesive layer excellent in durability with respect to heat|fever or humidity, or a coating agent layer can be formed. Examples of such a cationic polymerization initiator (KE) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytech) and CPI-110P (manufactured by San Afro), or IRGACURE250 (Ciba Specialty Chemicals). product), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and iodonium chloride such as Rp-2074 (manufactured by Rhodia Japan), and the like.

As a preferable ratio of the component constituting the α,β-ethylenically unsaturated double bond group-containing compound (M), the total amount of the α,β-ethylenically unsaturated double bond group-containing compound (M) in the active energy ray-polymerizable resin composition is 100 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), 0 to 50% by weight of oligomer (D), and It is preferable that the other α,β-ethylenically unsaturated double bond group-containing compound (m) is 0 to 50% by weight. Especially, it is preferable that the total of compound (Y) and compound (X) is 10 weight% or more and 100 weight% or less. When the total of the compound (Y) and the compound (X) is less than 10% by weight, the solubility of boric acid and/or boric acid derivatives is poor, and it does not become a homogeneous system, or when liquid sedimentation occurs, crystals are precipitated over time There may be problems such as

The boric acid and boric acid derivative contained in the active-energy-ray-polymerizable resin composition of this invention are demonstrated. Boric acid and boric acid derivatives interact with the hydroxyl group-containing α,β-ethylenically unsaturated double bond group-containing compound (X), and/or amino group-containing α,β-ethylenically unsaturated double bond group-containing compound (Y) By forming a salt, it is possible to form a stable and uniform fluid of the active energy ray-polymerizable adhesive and coating agent without containing water or an organic solvent. After curing the adhesive and the coating agent with an active energy ray, a coating film is formed in which boric acid and a boric acid derivative are bonded to a hydroxyl group derived from compound (X) and/or an amino group derived from compound (Y). In addition, boric acid and a boric acid derivative have an effect of improving adhesion by bonding with a functional group on the surface of the base (F) described later. Boric acid and a boric acid derivative can be used individually or in mixture, respectively.

As the boric acid derivative of the present invention, any compound having one or more BOH bonds in one molecule, or a number of boron-containing compounds capable of forming one or more BOH bonds by hydrolysis in the presence of water can be suitably used without limitation. . Specific but non-limiting examples of boric acid derivatives include boric acid oxide (eg, B ₂ O ₃ );

What can be obtained by reaction of boric acid with alcohol or phenol, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, triisopropyl borate, boric acid tri-t-amyl, triphenyl borate, trimethoxyboroxine, tri-2-cyclohexyl borate, triethylalcohol amine borate, triisopropyl amine borate, mannitol borate, glycerol borate, and triisopropanolamine borate, etc. of boric acid esters.

Moreover, the derivative of boronic acid is also contained in the boric acid derivative of this invention. alkyl or alkenyl boronic acids, for example, methyl boronic acid, ethyl boronic acid, butyl boronic acid, and cyclohexyl boronic acid;

and arylboronic acids such as phenyl boronic acid, naphthalene boronic acid, and anthracene boronic acid, or substituted arylboronic acids having an optional substituent on these aryl groups.

In addition, other amino-containing borates and tertiary amine salts of boric acid are useful. Examples of such boron-containing compounds include 2-(β-dimethylamino isopropoxy)-4,5-dimethyl-1,3,2-dioxaborolane, 2-(β-diethylaminoethoxy)-4, 4,6-trimethyl-1,3,2-dioxaborinane, 2-(β-dimethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane, 2-( β-diisopropylamino ethoxy)-1,3,2-dioxavonarin, 2-(β-diisopropylamino ethoxy)-4-methyl-1,3,2-dioxaborinane, 2 -(γ-dimethylamino propoxy)-1,3,6, 9-tetrapoxa 2-boracycloundecane, and 2-(β-dimethylaminoethoxy)-4,4-(4-hydroxybutyl) -1,3,2-dioxaborinane, but is not limited thereto.

Further, the boric acid derivative includes a metal salt of boric acid (that is, metal borate) on the condition that it can be easily dissociated in an aqueous medium to form boric acid. Suitable examples of metal borate include, for example, calcium borate, potassium borate (eg potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate and potassium octaborate), sodium borate (eg per sodium borate, sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, sodium hexaborate, and sodium octaborate). Similarly, ammonium borate is also useful.

Further, examples of the boric acid derivative include organic oligomers and polymer compounds containing a boron-containing moiety. For example, obtained by reacting a polymeric boric acid ester (e.g., an active hydrogen-containing polymer (e.g., a hydroxyl functional group-containing acrylic polymer or polysiloxane polymer)) with boric acid and/or a boric acid ester to form a polymer having a boric acid ester group. It is preferable to be able to

The polymer used as the raw material of the polymer boric acid ester includes one of various active hydrogen-containing polymers, for example, at least selected from the group consisting of acrylic polymers, polyester polymers, polyurethane polymers, and polyether polymers. One paper is preferred.

As the boric acid or boric acid derivative used in the present invention, boric acid, boric acid ester, or a tertiary amine salt of boric acid is preferable from the viewpoint of solubility, and from the viewpoint of adhesion, boric acid is particularly preferable.

Moreover, in this invention, it is preferable that a boric-acid derivative has 3 or more hydroxyl groups in 1 molecule. Examples of the boric acid derivative having three or more hydroxyl groups in one molecule include 1,4-benzenediboronic acid (the number of hydroxyl groups: 4), tetrahydroxydiborane (the number of hydroxyl groups: 4), and triethyl alcoholamine salt of boric acid (the number of hydroxyl groups: 3). can be heard

The amount of boric acid and/or boric acid derivative used in the present invention is preferably 0.1 parts by weight or more and 20 parts by weight or less when the total amount of the α,β-ethylenically unsaturated double bond group-containing compound (M) is 100 parts by weight. .

If it is less than 0.1 part by weight, the desired adhesive force expression may not be achieved, and if it is 20 parts by weight or more, problems such as precipitation over time or the viscosity as a liquid increases too much and gelation may occur.

More preferably, it is 0.3 weight part or more and 12 weight part or less. Especially preferably, it is 0.3 weight part or more and 7 weight part or less.

Moreover, when it considers in 100 weight part of active energy ray polymerization compositions, it is preferable that it is 0.1 weight part - 20 weight part of boric acid and/or a boric acid derivative, Especially preferably, they are 0.3 weight part - 12 weight part. More preferably, it is 0.3 weight part - 7 weight part.

The active energy ray polymerizable resin composition may further contain an active energy ray polymerization initiator (E). Examples of the active energy ray polymerization initiator (E) include a radical polymerization initiator (RE) and an above-described cationic polymerization initiator (KE).

Specifically as the radical polymerization initiator (RE), 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xantofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzo Phenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphor quinone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-on, and the like. Examples of commercially available products include Ilgacure 184, 907, 651,1700, 1800, 819, 369, 261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF); Darocure 1173 (manufactured by Merck Corporation), Ezacure KIP150, TZT (manufactured by Seibel Hegna, Japan), Kayacure BMS, and Kayacure DMBI (manufactured by Japanese Gunpowder Corporation), and the like. Moreover, the radical polymerization initiator which has at least 1 piece(s) of (meth)acryloyl group in a molecule|numerator can be used as a radical polymerization initiator (RE) of this invention.

Next, as a cationic polymerization initiator (KE) (also referred to as an acid generator), as described above, sulfonium salt-based cations such as UVACURE1590 (manufactured by Daicel Cytech) and CPI-110P (manufactured by San Afro), etc. iodonium salt-type cationic initiators, such as an initiator, IRGACURE250 (made by BASF), WPI-113 (made by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (made by Rhodia Japan).

Moreover, in order to improve the performance of the said cationic polymerization initiator (KE), you may use together an active energy ray sensitizer. 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-based, benzophenone-based, thioxanthone-based, perylene, phenothiazine, rose bengal, and the like are preferably used.

Although such an active energy ray polymerization initiator (E) can be used individually or as a mixture of 2 or more types, in the 1st aspect of this invention, it is preferable to contain a radical polymerization initiator (RE).

The mixing ratio of the active energy ray polymerization initiator (E) is 0.01 parts by weight of the active energy ray polymerization initiator (E) with respect to 100 parts by weight of the α,β-ethylenically unsaturated double bond group-containing compound (M) from the viewpoint of reactivity. It is preferable to contain ~20 parts by weight.

(Explanation of the second aspect)

Then, the active energy ray polymerizable resin composition (hereinafter also referred to as "cationic active energy ray polymerizable resin composition") in which boric acid and/or a boric acid derivative, which is a second aspect of the present invention, is used in combination with the cationically polymerizable composition (K). ) is explained.

The cationic active energy ray-polymerizable resin composition contains a cationically polymerizable compound (K) and boric acid and/or a boric acid derivative.

First, the cationically polymerizable compound (K) in a cationic active energy ray-polymerizable resin composition is demonstrated.

A cationically polymerizable compound (K) contains all the compounds which superpose|polymerize by a cation. As a cationically polymerizable compound (K), a cyclic hetero compound is preferable from a reactive viewpoint by an active energy ray, and the oxirane compound (k1) which is 3-membered ring ether is especially preferable. In addition, among the compound (M), a vinyl ether compound may also be used for cationic polymerization.

Examples of the oxirane compound (k1) include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, and oxiranecarboxylic acid. , (chloromethyl) oxirane, (brommethyl) oxirane, and compounds having an aliphatic cyclic ether group such as oxiranyl acetonitrile;

3,4-oxirane cyclohexylmethyl 3,4-oxirane cyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis(3,4-oxiranecyclohexanecarboxylate), bis(3,4-oxirane cyclohexylmethyl) adipate, bis(3,4-oxirane-6-methylcyclohexylmethyl) adipate; and compounds having a three-membered cyclic ether group bonded to an alicyclic ring such as diethylene glycol bis(3,4-oxirane cyclohexylmethyl ether) and dicyclopentadiene dioxide. In addition, a compound in which a group in a form in which one or more hydrogen atoms have been removed from these three-membered cyclic ether group-containing compounds is bonded to another chemical structure may be an oxirane compound (k1).

The oxirane compounds illustrated here may be used individually, respectively, and a some oxirane compound may be mixed and used for them.

The oxirane equivalent of an oxirane compound (k1) is 30-3000 g/eq normally, and 50-1500 g/eq is preferable. When the oxirane equivalent is 30 g/eq or more, the flexibility of the optical film after curing is excellent and the adhesive strength is high. On the other hand, in the case of 3000 g/eq or less, compatibility with other components is excellent.

It is more preferable that the oxirane compound (k1) is an oxirane compound (k1-1) which has an aromatic ring from heat resistance and heat-and-moisture resistance improvement.

The oxirane compound (k1-1) having an aromatic ring may include a substituent derived from an aromatic ring. Examples of such substituents include benzene, toluene, xylene, styrene, hemimelitene, pseudocumene, mesitylene, cumene, plening, isodurene, durene, cymene, and melitene, which may be bound to other chemical structures. and groups in which one or more hydrogen atoms in the benzene derivative have been removed. Examples of the substituent include phenyl, phenylene, tolyl, toryleno, benzyl, benzylidene, benzylidene, xylyl, xylylene, butarylidene, isobutarylidene, terephthalidene, phenethylidene, phenethylidine, styryl, styrylidene, as-psoidcumyl, v-psoidcumyl, s-psoidcumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamylidene, and cinnamylidine, juril, jurylene, densyl, carvacryl, cuminyl, cuminylidene, neophyll, xenyl, benzhydryl, benzhydrylidene, and trityl.

Other examples include cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadiene;

[4n+2] annulene having 3 or more carbon atoms constituting a ring other than benzene is exemplified.

Further, for example, aromatic polycyclic compounds such as biphenyl and triphenylmethane;

*Pentarene, Indene, Indan, Ninhydrin, Naphthalene, Tetraline, Decalin, Sapotalene, Cardarene, Oidaren, Naphthol, Menadiol, Gossyful, Naphthoquinone, Lawson, Eugloon, Menadione, plumbagin, phthiochol, echinochrome A, alkanine, cykonine, acetonaphthone, naphthoic acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphthone, naphthionic acid, naphthionate, naphthionyl, Carbon condensed bicyclic compounds such as dansyl, crocenic acid, flavian acid, chromatotropic acid, neo-cuperone, azulene, camazulene, guaiazulene, heptalene, octalene, and furfurogalin:

as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenarene, pelinaphthene, phenanthrene, Phenanthryl, phenanthrylium, phenantrylidene, phenanthrylene, phenantrol, morphol, phenanthrone, phenanthraquinone, pimanthrene, rethene, anthracene, anthryl, anthrylium, antrylidene, anthrylene , anthrol, anthranol, anthrobin, anthrine, dithranol, anthroyl, anthrone, bianthrone, anthraquinone, anthraquinonyl, anthraquinonylene, alizarin, quinizarine, anthralphine, chrysazin, Anthragalol, Purpurin, Pravopurpurin, Anthrapurpurin, Quinalizarine, Techtoquinone, Chrysophanol, Chrysophanol, Emodine, Raine, Carmesic acid, Carminic acid, Dianthrimide, Anthrimide Condensed carbon tricyclic compounds such as chrysanamic acid and colchicine;

Thorinden, Thorindan, Fluorantene, Acphenanthrylene, Acphenanthrene, Acethrylene, Acanthrene, Triphenylene, Pyrene, Chrysene, Tetraphene, Tetracene, Naphthacene, Rubrene, Tetracycline Condensed carbon tetracyclic compounds such as chlorotetracycline, oxytetracycline, pleiadenum, and benzoanthrone;

Condensed carbon pentacyclic compounds such as picene, perylene, pentapene, pentacene, tetraphenylene, cholantorylene, and cholantrene;

Collanurene, Pullminene, Antanthrene, Jetren, Hexahelicene, Hexaphene, Hexacene, Rubycene, Coronene, Trinaphthylene, Heptaphene, Heptacene, Pyrantrene, Octaphene, Octacene, Terylene, Naphtha Cenonaphthacene, Nonaphen, Nonacene, Biolanthrene, Biolanthrone, Isviolanthrene, Isobiolanthrone, Obalen, Decafen, Decacene, Decacyclene, Pentacenopentacene, Quaterylene, Hexa Among cyclic compounds such as fused-ring compounds having 6 or more rings, such as cenohexacene, aromatic rings in which one or more hydrogen atoms are removed can be bonded to other chemical structures.

As the oxirane compound (k1-1) having an aromatic ring, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, and 1,3-phenylenebis(methylene)bis(7-oxa) excellent in heat resistance and adhesive strength Particular preference is given to bicyclo[4.1.0]heptane-3-carboxylate), and 1,3-bis{(7-oxabicyclo[4.1.0]heptan-3-yl methoxy)methyl}benzene.

Examples of the cyclic hetero compound (k2) other than the oxirane compound include a compound having an oxetanyl group which is a 4-membered ring ether, a 5-membered ring or more cyclic ether compound, and a compound having two or more oxygen or hetero groups other than oxygen.

Examples of the oxetanyl group-containing compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, and di(1-ethyl-3- oxetanyl) methylether, 3-ethyl-3-(phenoxymethyl) oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane, phenolnovolacoxetane, and 3-ethyl-{ (3-triethoxy silyl propoxy) methyl} oxetane etc. are mentioned. An oxetanyl group containing compound may be used independently and may use 2 or more types together.

As another cyclic hetero compound (k2), a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, a fluorine-containing cyclic compound, etc. are mentioned. It is preferable that a cyclic ester compound is lactones. The cyclic formal compound is more preferably a compound selected from dioxolanes, dioxanes and trioxanes.

As the cyclic carbonate, a method of depolymerizing a polymer obtained by reaction of glycol with a dialkyl carbonate (refer to Japanese Patent Laid-Open No. 2-56356), or a corresponding reaction between an alkylene oxide and carbon dioxide can be synthesized by Cyclic carbonates have a structure of 5 or more, 6 or 7-membered rings, 1,3-dioxolanes in 5-membered rings, 1,3-dioxanes in 6-membered rings, 1,3-dioxepanes in 7-membered rings is included, but because the carbon in the second position is a carbonyl carbon, it is independently classified as cyclic carbonates. Specific examples thereof include ethylene carbonate (also referred to as 1,3-dioxolan-2-one), propylene carbonate, butylene carbonate, 4-pentyl-1,3-dioxolan-2-one, and 4-butyl -1,3-dioxolan-2-one, 4-propyl-1,3-dioxolan-2-one, 4- (isopropoxy methyl) -1,3-dioxolan-2-one, 4-hexyl -1,3-dioxolan-2-one, 4-hexyl-5-methylene-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4, 4,5,5-tetramethyl-1,3-dioxolan-2-one, 4-octyl-1,3-dioxolan-2-one, 4-nonyl-5-vinyl-1,3-dioxolane- 2-one, 4-decyl-1,3-dioxolan-2-one, 4,5-bismethylene-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolane- 2-one, 4,4,5,5-tetraethyl-1,3-dioxolan-2-one, hexahydro-1,3-benzodioxoldioxol-2-one, 4-isopropyl-4-methyl -5-Methylene-1,3-dioxolan-2-one, vinylene carbonate, allylethylene carbonate, aryl succinic anhydride, 4-(2-oxo-1,3-dioxolan-4-ylmethyl carbamoyloxy methyl ) 5-membered ring carbonates such as -1,3-dioxolan-2-one;

For example, trimethylene carbonate (also called 1,3-dioxane 2-one), 4-methyl-1,3-dioxane 2-one, 2,2-dimethoxypropane-1,3-diyl carbonate, 5-methyl-1,3-dioxane 2-one, 5,5-dimethyl-1,3-dioxane 2-one (also called neopentylglycol carbonate), 5-methyl-5-propyl-1,3- Dioxane 2-one, 5-hydroxymethyl-5-methyl-1,3-dioxane 2-one, 4-phenyl-1,3-dioxane 2-one, 5-(hydroxymethyl)-5- Ethyl-1,3-dioxane 2-one, 4-methylene-1,3-dioxane 2-one, 5,5-dimethyl-4-vinyl-1,3-dioxan 2-one, 5-cyano -5-methyl-1,3-dioxane 2-one, 5-(2-oxo-1,3-dioxolan-4-yl methoxy)-5-ethyl-1,3-dioxane 2-one, etc. 6-membered ring carbonates;

For example, tetramethylene carbonate (also called 1,3-dioxepan 2-one), 5-methyl-1,3-dioxepan 2-one, 4-methyl-1,3-dioxepan 2-one, 5 ,5-Dimethyl-1,3-dioxepan 2-one, 5-phenyl-1,3-dioxepan 2-one, 4-phenyl-1,3-dioxepan 2-one, 4-[1-(phenyl 7-membered ring carbonates such as thio) cyclohexyl]-1,3-dioxepan 2-one and 5,5'-(ethylenebisthiobistrimethylene)bis(1,3-dioxepan2-one); However, 5-membered ring carbonates, such as ethylene carbonate, propylene carbonate, and glycerol carbonate, are used preferably from a reactive viewpoint.

Further, among the α,β-ethylenically unsaturated double bond-containing compounds (M), as vinyl ethers that also undergo cationic polymerization, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, aryl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, Vinyl ethers, such as isohexyl vinyl ether, 2-ethyl butyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, nonyl vinyl ether, dipentaerythritol hexavinyl ether, are mentioned. .

The boric acid and boric acid derivative contained in the cationic active energy ray-polymerizable resin composition are demonstrated. In addition, especially in interaction with a cationically polymerizable compound (K), the preferable system is mentioned here. Boric acid and boric acid derivatives interact with the cationically polymerizable compound (K) to make it possible to stably form a uniform solution of the active energy ray polymerizable resin composition without water or organic solvents, the composition After curing with an active energy ray, the cationically polymerizable compound (K) forms a coating film bonded to a hydroxyl group formed by polymerization. In addition, there is an effect of improving adhesion by forming a bond with a surface functional group of the substrate (F) to be described later. By bringing such an effect, boric acid as well as boric acid derivatives described below can be used alone or in combination with boric acid.

The boric acid derivative of the present invention can be suitably used without limitation as long as it has one or more BOH bonds, or a plurality of boron-containing compounds capable of forming one or more BOH bonds by hydrolysis in the presence of water. Specific but non-limiting examples of boric acid derivatives include boric acids such as boric acid oxide (eg, B ₂ O ₃ ), orthoboric acid, metaboric acid, perboric acid, hypoboric acid, boronic acid, and borinic acid;

For example, those obtainable by reaction of boric acid with alcohol or phenol, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, tri borate Isopropyl, tri-t-amyl borate, triphenyl borate, trimethoxy boroxine, tri-2-cyclohexyl cyclohexyl borate, triethanolamine borate, triisopropyl amine borate, mannitol borate, glycerol borate, and triisopropanol borate and boric acid esters such as amines.

Moreover, the derivative of boronic acid is also contained in the boric acid derivative of this invention. For example, alkyl or alkenyl boronic acids such as methyl boronic acid, ethyl boronic acid, butyl boronic acid, and cyclohexyl boronic acid;

For example, aryl boronic acids, such as phenyl boronic acid, naphthalene boronic acid, and anthracene boronic acid, or a substituted aryl boronic acid having an arbitrary substituent on these aryl groups are mentioned.

In addition, other amino-containing borates and tertiary amine salts of boric acid are usefully obtained. Examples of such boron-containing compounds include 2-(β-dimethylamino isopropoxy)-4,5-dimethyl-1,3,2-dioxaborolane, 2-(β-diethylaminoethoxy)-4, 4,6-trimethyl-1,3,2-dioxaborinane, 2-(β-dimethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane, 2-( β-diisopropylamino ethoxy)-1,3,2-dioxavonarin, 2-(β-diisopropylamino ethoxy)-4-methyl-1,3,2-dioxaborinane and 2 -(β-dimethylaminoethoxy)-4,4-(4-hydroxybutyl)-1,3,2-dioxaborinane.

The boric acid derivative also includes a metal salt of boric acid (that is, metal borate) under the condition that it can be easily dissociated in an aqueous medium to form boric acid. Suitable examples of metal borate include, for example, calcium borate, potassium borate (eg potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate and potassium octaborate), sodium borate (eg per sodium borate, sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, sodium hexaborate and sodium octaborate). Similarly, ammonium borate is also useful.

Further, examples of the boric acid derivative include organic oligomers and polymer compounds containing a boron-containing moiety. A suitable example is formed by reacting a polymeric boric acid ester (e.g., an active hydrogen-containing polymer (e.g., a hydroxyl functional group-containing acrylic polymer or polysiloxane polymer)) with boric acid and/or a boric acid ester to form a polymer having a boric acid ester group. can be heard

Suitable polymers for this purpose include any of a variety of active hydrogen-containing polymers, which are, for example, selected from at least one of polyacrylic polymers, polyester polymers, polyurethane polymers, and polyether polymers. .

Moreover, in this invention, it is preferable that a boric-acid derivative has 3 or more hydroxyl groups in 1 molecule. Examples of the boric acid derivative having three or more hydroxyl groups in one molecule include 1,4-benzenediboronic acid (the number of hydroxyl groups: 4), tetrahydroxydiborane (the number of hydroxyl groups: 4), and triethyl alcoholamine salt of boric acid (the number of hydroxyl groups: 3). can be heard

The proportion of boric acid and/or boric acid derivative is 0.1 parts by weight to 20 parts by weight, preferably 0.3 parts by weight to 12 parts by weight, more preferably 0.3 parts by weight to 7 parts by weight in 100 parts by weight of the active energy ray polymerization composition. is wealth

If the content of boric acid and/or boric acid derivative is 0.1 parts by weight or more, it is possible to express a desired adhesive force, and when it is 0.3 parts by weight or more, it becomes more remarkable.

In addition, if it is 20 parts by weight or less, problems such as precipitation over time or gelation due to excessively high viscosity as a liquid do not occur, and if it is 7 parts by weight or less, it is more preferable.

By using a cationically polymerizable compound (K), it becomes possible to improve the appearance defect of the laminated body resulting from a large cure shrinkage.

In addition, when boric acid and/or a boric acid derivative are used in combination, a bond is formed with a hydroxyl group produced by polymerization of the cationically polymerizable compound (K) with a functional group on the surface of the substrate to improve adhesion.

It is preferable that a cationic polymerization initiator (KE) is further contained in a cationic active energy ray-polymerizable resin composition.

As the cationic polymerization initiator (KE), as described above, a sulfonium salt-based cationic initiator such as UVACURE1590 (manufactured by Daicel Cytech), CPI-110P (manufactured by San Apro Corporation), IRGACURE250 (manufactured by BASF), WPI -113 (manufactured by Wako Pure Chemical Industries, Ltd.) and Rp-2074 (manufactured by Rhodia Japan) and other iodonium chloride-based cationic initiators.

It is preferable to contain 0.01-20 weight part of said compounding ratios of a cationic polymerization initiator (KE) with respect to 100 weight part of active energy ray polymeric compositions.

(Explanation of the third aspect)

Finally, active energy ray polymerizability in which boric acid and/or a boric acid derivative, which is a third aspect of the present invention, is used in combination with an α,β-ethylenically unsaturated double bond group-containing compound (M) and a cationically polymerizable composition (K) A resin composition (henceforth hybrid type active energy ray-polymerizable resin composition) is demonstrated.

The hybrid type active energy ray polymerizable resin composition contains an α,β-ethylenically unsaturated double bond group-containing compound (M), a cationically polymerizable compound (K), and boric acid and/or a boric acid derivative.

Further, as boric acid and/or boric acid derivatives, α,β-ethylenically unsaturated double bond group-containing compounds (M) and cationically polymerizable compounds (K), specifically, the exemplary compounds described in the first and second embodiments can be used. can

As the α,β-ethylenically unsaturated double bond group-containing compound (M) of the hybrid type active energy ray-polymerizable resin composition, all compounds containing an α,β-ethylenically unsaturated double bond in a molecule are included. The α,β-ethylenically unsaturated double bond-containing compound (M) has 50 to 100 (meth)acryloyl groups in the total weight of the α,β-ethylenically unsaturated double bond from the viewpoint of reactivity with an active energy ray. It is preferably designed to account for % by weight.

Specific examples of the compound (M) include a hydroxyl group-containing α,β-ethylenically unsaturated double bond-containing compound (X), an α,β-ethylenically unsaturated double bond-containing compound having two or more cycloalkane skeletons and/or cycloalkene skeletons It is preferable that at least one compound selected from the group consisting of (C) is included.

A preferable ratio of the α,β-ethylenically unsaturated double bond group-containing compound (M), the cationically polymerizable compound (K), and boric acid and/or boric acid derivative is α,β-ethylene in 100 parts by weight of the active energy ray polymerization composition. 9 to 99 parts by weight of the polyunsaturated double bond group-containing compound (M), 0.5 to 90 parts by weight of the cationically polymerizable compound (K), and 0.1 parts by weight to 20 parts by weight of boric acid and/or boric acid derivative.

More preferably, α,β-ethylenically unsaturated double bond group-containing compound (M) 30 to 80 parts by weight, cationically polymerizable compound (K) 20 to 70 parts by weight, boric acid and/or boric acid derivative 0.3 to 12 parts by weight (especially Preferably 0.3 to 7 parts by weight).

When the amount of the α,β-ethylenically unsaturated double bond group-containing compound (M) is less than 9 parts by weight, the cationically polymerizable compound (K) is relatively large, and curing failure tends to occur due to moisture or humidity in the substrate. When the α,β-ethylenically unsaturated double bond group-containing compound (M) is more than 99 parts by weight, cure shrinkage becomes large, and when thin film substrates are bonded, wrinkles are likely to form and cause poor appearance. If the amount of boric acid and/or boric acid derivative is less than 0.1 parts by weight, the desired adhesive force expression cannot be achieved, and if it is 20 parts by weight or more, problems such as precipitation over time or gelation due to excessive viscosity as a liquid may occur.

A hybrid type active energy ray-polymerizable resin composition is an α,β-ethylenically unsaturated double bond group-containing compound (M) by using an α,β-ethylenically unsaturated double bond group-containing compound (M) and a cationically polymerizable compound (K) together. ) can suppress the poor appearance of the laminate due to the large curing shrinkage and the curing failure due to moisture, which is a characteristic of the cationically polymerizable compound.

In addition, when boric acid and/or a boric acid derivative are used in combination, the hydroxyl group formed by polymerization of the compound (X) and/or the cationically polymerizable compound (K) forms a bond with the hydroxyl group of the substrate, and the adhesion is improved.

The hybrid type active energy ray-polymerizable resin composition can further contain an active energy ray polymerization initiator (E). By using an active energy ray polymerization initiator (E), a polymerization reaction can be accelerated|stimulated. Moreover, as an active energy ray polymerization initiator (E) in a hybrid type active energy ray polymeric resin composition, a radical polymerization initiator (RE) and a cationic polymerization initiator (KE) are mentioned.

The radical polymerization initiator (RE) and the cationic polymerization initiator (KE) are specifically as described in the first and second aspects.

A radical polymerization initiator (RE) and a cationic polymerization initiator (KE) can be used individually or in mixture, and it is preferable to use it in mixture.

It is preferable to contain 0.01-20 weight part of said initiators (total amount of a radical polymerization initiator (RE) and a cationic polymerization initiator (KE)) with respect to 100 weight part of active energy ray polymeric compositions.

Hereinafter, the matters common to "the 1st - 3rd aspect" are described about "a solvent, a sensitizer, an additive, a viscosity, a film thickness, a coating method, a base material, a laminated body, and a lamination|stacking method."

(solvent)

In this invention, it is preferable not to contain water or an organic solvent substantially from a viewpoint of the facilities and energy required for a drying process. However, when the active energy ray polymerization initiator (E) is sparingly soluble in the α,β-ethylenically unsaturated double bond group-containing compound (M) and has a high viscosity, in order to dissolve the active energy ray polymerization initiator (E), A small amount of water or an organic solvent may be included. It is preferable that content of the said water or organic solvent in an active energy ray-polymerizable resin composition is 5 weight% or less. 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, and xylene; Other organic solvents, such as hydrocarbon solvents, and water may further be added, and the viscosity of an active energy ray-polymerizable resin composition may be adjusted, and an active energy ray-polymerizable resin composition may be heated and a viscosity may be reduced.

(sensitizer)

In addition, when using a cationic polymerization initiator (KE) as an active energy ray polymerization initiator (E), in order to improve the performance of a cationic polymerization initiator (KE), you may use an active energy ray sensitizer together. Representative examples of active energy ray sensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. Lylene, phenothiazine, rose bengal and the like are preferably used.

(additive)

It is possible to mix|blend additives other than the said component suitably with the active energy ray polymeric resin composition of this invention as long as it is a range which does not impair the effect of this invention. For example, from the viewpoint of reducing polymerization curing shrinkage, reducing thermal expansion, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, and improving coloration, organic or inorganic fillers can be blended. . As such fillers, polymers, ceramics, metals, metal oxides, metal salts, salt pigments, and the like can be used. It does not specifically limit about a shape, For example, it is particulate form, a fibrous form, etc. In addition, when blending a polymer, it is not a filler such as a flexibility imparting agent, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent and an antifoaming agent, but a polymer blend or It is also possible to melt|dissolve, semi-dissolve or micro-disperse in an active-energy-ray-polymerizable adhesive agent as a polymer alloy.

(viscosity)

Although the active energy ray polymeric resin composition of this invention can be used even if it is liquid, paste form, and any form of a film form, it is preferable from a viewpoint of easiness of use that it is liquid.

It is preferable to adjust the viscosity of the active-energy-ray-polymerizable resin composition in this invention according to the thickness which implements the said composition, and a use use. For example, when the thickness of the layer is 0.1 to 6 µm, the viscosity is 1 to 1500 mPa·s, preferably 10 to 1300 mPa·s, more preferably 20 to 1000 mPa·s. When a viscosity is higher than 1500 mPa*s and it coats to the base material F, thin film coating of 0.1-6 micrometers cannot be performed, but optical properties, such as transmittance|permeability, will deteriorate. On the other hand, when the viscosity is lower than 1 mPa·s, it becomes difficult to control the thickness of the active energy ray-polymerizable resin composition layer.

Moreover, when the film thickness of an active energy ray-polymerizable resin composition layer shall be 6-300 micrometers according to a use use, a viscosity is 1500-100,000 mPa*s, Preferably it is 3,000-50,000 mPa*s. Actually, the viscosity of the resin composition is largely determined by the viscosity of the α,β-ethylenically unsaturated double bond group-containing compound (M) and/or the cationically polymerizable compound (K). Therefore, management of the viscosity of a resin composition becomes easy by managing the viscosity of compound (M) and/or compound (K) in the range of 1-100,000 mPa*s. Adjustment of the viscosity which concerns on the said embodiment, and coating of a resin composition can be performed easily by adding a solvent to the said resin composition as needed.

(behind the scenes)

When using an active energy ray polymeric resin composition for the use of laminated bodies for optical elements, such as a hard coat film or a polarizing film (it is also mentioned a polarizing plate) mentioned later, a thin film coats an active energy ray polymerizable resin composition. It is preferable that it is thin film coating of 0.1-6 micrometers, and, as for the thickness of the resin layer formed by coating, it is more preferable that they are 0.1 micrometer - 3 micrometers. By setting it as 0.1 micrometer or more, when a resin composition is used as a coating agent or an adhesive agent, it is easy to acquire sufficient adhesiveness or adhesive force. On the other hand, when the thickness of the resin layer exceeds 6 µm, no change is seen in properties such as adhesiveness or adhesive force in many cases.

In addition, when using an active energy ray-polymerizable resin composition for the use of laminated bodies for optical elements, such as a decorative film (meaning the filling sheet for touch panels), the thickness of the said resin layer formed by coating is 6 It is preferable that it is -300 micrometers thick film coating, and it is more preferable that it is 20 micrometers - 250 micrometers. If it is less than 6 micrometers, sufficient stress relaxation property may not be acquired, and when it exceeds 300 micrometers, coatability, such as resin coating, falls in many cases.

(coating method)

As a method of coating the energy ray polymerizable resin composition of the present invention to a substrate or the like, a Meyer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a micro gravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, Although various coating methods, such as a reverse coater and a spin coater, are mentioned, Thin film coating, thick film coating, etc. can be used according to the use, There is no restriction|limiting in particular.

(active energy ray)

The active energy ray-polymerizable resin composition of the present invention is applied on a substrate by a known and conventional method, and the formed coating layer is irradiated with active energy rays to obtain an α,β-ethylenically unsaturated double bond group-containing compound (M). In the case of radical polymerization, in the case of cationic polymerizability (K), polymerization hardening is carried out by cationic polymerization. As a light source for irradiating active energy rays, mainly 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 excited mercury lamp, LED lamp, xenon lamp A lamp or a metal halide lamp or the like can be preferably used. In addition, a laser beam, an electron beam, etc. can be used as an active energy beam for exposure.

It is preferable that the irradiation intensity of an ultraviolet-ray is 10-3000 mW/cm<2>. If the light irradiation intensity is less than 10 mW/cm2, curing requires a long time, and when it exceeds 3000 mW/cm2, the heat radiated from the lamp may cause deterioration of the substrate in various substrates (F), so it is not preferable. not. It is preferable that the integrated irradiance expressed as a product of irradiation intensity and irradiation time is 50-20,000 mJ/cm<2>. When the accumulated irradiance is less than 50 mJ/cm 2 , polymerization and curing requires a long time, and when it is larger than 20,000 mJ/cm 2 , the irradiation time becomes very long and productivity is inferior, which is not preferable. A typical active energy ray-polymerizable resin composition generally requires an integrated irradiance of 1000 mJ/cm 2 or more. However, in the resin composition according to the present invention, polymerization proceeds favorably even at a low integrated irradiance of less than 1000 mJ/cm 2 .

(Write (F))

Next, the base material F is demonstrated.

There is no restriction|limiting in particular as a base material (F) to which the active-energy-ray-polymerizable resin composition of this invention can apply, such as a film-form base material, a glass plate, and a processed paper. On the other hand, when the active energy ray-polymerizable resin composition of the present invention is used as an adhesive by bonding two or more substrates (F), it is not necessary to use a substrate through which active energy rays are easily transmitted for polymerization by irradiation with active energy rays. have. In particular, it is preferable to use a transparent film or a transparent glass plate. For the other side of the bonded substrate, use a substrate that is difficult to transmit active energy rays, such as wood, metal plate, plastic plate, paper processed product, etc., and use a transparent film or transparent glass plate for the other side, It can also be irradiated from the transparent glass plate side, and polymerization hardening can also be performed.

It is preferable that the active energy ray polymeric resin composition of this invention uses a film-form base material among the base materials (F). Examples of the film-like substrate include film-like substrates such as cellophane, various plastic films, and paper, and the use of various transparent plastic films is preferred. Moreover, as a film-form base material, if it is transparent, the thing of a single layer may be sufficient, and the thing of the multilayer state formed by laminating|stacking a some base material can also be used.

(Description of the laminate)

Here, using an active energy ray-polymerizable resin composition, it laminates|stacks on one side or both surfaces of the base material F, The laminated body characterized by the above-mentioned is demonstrated generally.

The polymerization reaction by active energy ray of the active energy ray-polymerizable resin composition of the present invention is, among the above-mentioned substrates (F), a transparent film which is a film-like substrate, and an active energy ray in which the transparent film is located on at least one surface. It is preferable to be used for formation of a laminated body provided with a polymerizable resin composition layer.

In this invention, the laminated body of a transparent film can be obtained as follows.

Coating the resin composition of the present invention on one side of the transparent film as a film-like substrate, laminating another transparent film on the surface of the resin composition layer, and further coating the resin composition on one side or both sides of the laminate, another transparent film A laminate can be obtained by laminating|stacking on glass, or a transparent molded object.

The active energy ray polymerization reaction of the resin composition of the present invention used as an adhesive proceeds by irradiating active energy ray during coating, lamination, and after lamination of the resin composition, but polymerization reaction by irradiating active energy ray after lamination It is preferable to proceed with

In this invention, a transparent film can be used for optical films, such as information communication devices, such as a display and a touch panel.

(Explanation of the laminate for optical elements)

Here, a general description will be given of the laminate for optical elements.

The basic lamination configuration of the optical laminate is a sheet-like active energy ray polymerizable adhesive in which a plurality of layers are laminated, such as a transparent film/adhesive layer/transparent film, or a transparent film/adhesive layer/transparent film/adhesive layer/transparent film. it's a chain In addition, it is used as a laminate for an optical element in which a multilayer optical film such as a transparent film/adhesive layer/transparent film/adhesive layer/transparent film/adhesive layer/transparent film, glass, or an optical molded body is fixed to an optical member. As said contact bonding layer, the resin composition of 1st - 3rd aspect of this invention can be used.

As various transparent films used as an optical film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable. The various transparent films are also referred to as various plastic films and plastic sheets, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polypropylene, polyethylene, polycycloolefins, and polyolefin-based films such as ethylene-vinyl acetate copolymers. Polyester films, such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, poly and vinyl-based films, polyamide-based films, polyimide-based films, and polyoxylan-based films.

When the transparent film of this invention is used as a multilayer film, each film may have the same composition or a difference may be sufficient as it. For example, a polycycloolefin-based film may be used on one side, and now a polyacrylic-based film may be used on one side of the other side.

The thickness of the transparent film can be appropriately determined, but is generally about 1 to 500 µm from the viewpoints of workability such as strength and handleability, and thin layer properties. Especially, 1-300 micrometers is preferable, and 5-200 micrometers is more preferable. A transparent film is especially suitable in the case of 5-150 micrometers.

Moreover, when providing a transparent film on both sides of the polarizer of the polarizing plate film which is an optical film, the transparent film which consists of the same polymer material may be used for the front and back, and the transparent film (H) which consists of a different polymer material etc. may be used.

Next, an optical film is demonstrated.

As for the laminated body for optical elements in this invention, the optical film mainly used for an optical use is used suitably among said various transparent films. As the optical film, a special treatment is applied to the above-mentioned transparent film, and one having an optical function (functions such as light transmission, light diffusion, condensing, refraction, scattering, and HAZE) is called an optical film. In order to impart such an optical function, these functional materials are kneaded into a film or laminated by sputtering, and an adhesive or coating agent containing a functional material is used, or a film containing a functional material is laminated by bonding with an adhesive. , it is common to give an optical function. In addition, the optical film is used individually or laminated|stacking several types of optical films in multilayer with a coating agent or an adhesive agent. Examples of such an optical film include a hard coat film, an antistatic coating film, an anti-glare coating film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light-diffusion film, a brightness enhancing film, a prism film (also referred to as a prism sheet). ), and a light guide film (also referred to as a light guide plate).

A polarizing film is also called a polarizing plate, and a polytriacetyl cellulose protective film (hereinafter referred to as "TAC film") which is two polyacetyl cellulose films on both sides of a polyvinyl alcohol polarizer, or a polyvinyl alcohol polarizer It is a sheet-like optical film having a multilayer structure in which one or both sides of a polynorbornene-based film, such as a polycycloolefin-based film, a polyacrylic film, a polycarbonate-based film, and a polyester-based film, are laminated through an adhesive. As the said adhesive agent, the active-energy-ray-polymerizable resin composition of this invention can be used suitably.

The optical film laminated using the active energy ray-polymerizable resin composition of the present invention is applied to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module, and a transparent film such as various plastic films described above. It is preferable that the active energy ray-polymerizable resin composition of the present invention is further laminated and adhered, and used as a laminate for optical elements.

The polarizing plate (polarizing film) using the active energy ray-polymerizable resin composition as an adhesive agent can be obtained more specifically as follows.

A polarizing plate (polarizing film) using an active energy ray-polymerizable adhesive can be obtained, for example, by any of the following methods (I) to (III).

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

Next, on each surface of the polyvinyl alcohol-based polarizer, the first active energy ray polymerizable adhesive layer surface and the second active energy ray polymerizable adhesive layer surface are simultaneously/or sequentially polymerized, and then irradiated with active energy rays, A method for producing by polymerization curing the active energy ray polymerizable adhesive layer of 1 and the second active energy ray polymerizable adhesive layer;

(II) coating an active energy ray polymerizable adhesive on one side of the polyvinyl alcohol polarizer to form a first active energy ray polymerizable adhesive layer, and the surface of the formed first active energy ray polymerizable adhesive layer Covered with a first protective film, which is a transparent film, then, on the other side of the polyvinyl alcohol-based polarizer, an active energy ray polymerizable adhesive is applied to form a second active energy ray polymerizable adhesive layer, and the formed second The surface of the 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 active energy ray polymerizable adhesive layer are polymerized and cured to produce method, and

(III) Active energy ray polymerization at the end of the first transparent film, the protective film and the polyvinyl alcohol-based polarizer, and the second protective film, the polyvinyl alcohol-based polarizer, overlapping the side without the first protective film After pouring the adhesive, pass it between the rolls to spread the adhesive between each layer. Next, although there exists the method of manufacturing by irradiating an active energy ray and polymerization-hardening an active energy ray-polymerizable adhesive agent, etc., it does not specifically limit.

Example

Specific Examples of the present invention will be described below in conjunction with Comparative Examples, but the present invention is not limited to the following Examples. In addition, in the following Example and a comparative example, "part" and "%" represent "weight part" and "weight%", respectively.

In addition, "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" are values measured using gel permeation chromatography "HLC-8220 GPC" manufactured by Dongsoh Corporation, and separation column: " TSK-GELSUPERH5000", "TSK-GELSUPERH4000", "TSK-GELSUPERH3000", and "TSK-GELSUPERH2000" were connected in series, using tetrahydrofuran with a temperature of 40°C as a mobile phase, and a flow rate of 0.6ml/min. The polystyrene conversion weight average molecular weight and the number average molecular weight measured by

In addition, in this specification, about each at the time of using the active energy ray-polymerizable resin composition of this invention as 1. adhesive agent and 2. coating agent, it divides into 1st aspect, 2nd aspect, 3rd aspect of this invention. Examples will be described.

1. Glue

(1st aspect)

[Examples 1 to 19, and Comparative Examples 1 to 8, Examples 20 to 35, and Comparative Examples 9 to 24, and Examples 36 to 45]

Compound (X), compound (Y), compound (C), oligomer (D), compound (m), boric acid or a derivative of boric acid, The active energy ray polymerization initiator (E), the sensitizer, and the acid generator were respectively charged in the compositions and ratios (parts by weight) shown in Tables 1 and 2 according to Examples and Comparative Examples. Next, each active energy ray-polymerizable resin composition was obtained by fully stirring the mixture injected|thrown-in by the disper, and fully defoaming after that. About this active-energy-ray-polymerizable resin composition, the following method created and evaluated the laminated body, respectively. The evaluation result was also shown in Tables 1-5.

In addition, the abbreviation of Tables 1-5 is as follows.

4HBA: 4-hydroxybutyl acrylic acid

HEA: 2-hydroxyethyl acrylate

CHDMMA: cyclohexanedimethanol monomethacrylate

DMAEA: Dimethylaminoethyl acrylate

DMAPAA: Dimethylaminopropyl acrylate

PMPMA: pentamethyl piperidinyl methacrylate

VIM: 1-vinylimidazole

VRP: 4-vinylpyridine

DCPA: dicyclofentanyl acrylate

IBXA: Isobornyl acrylate

DCPDMDA: Tricyclodecanedimethanol diacrylate

Oligomer 1: Self-Gwang UV3000B: Polyurethane acrylate manufactured by Japan Synthetic Chemical Industry 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 salt manufactured by Daicel Allnex Mw=1500

Oligomer 5: EBECRYL810: Polyester acrylate Mw=1000 by Daicel Allnex Jehum

tBA: t-butyl acrylate

nBA: n-butyl acrylate

THFA: tetrahydrofurfuryl acrylate

PEA: ethyl phenoxy acrylate salt

BzA: benzyl acrylate

EPPA: ethoxylated o-phenyl phenol acrylate (A-LEN-10: Shin-Nakamura Chemical Co., Ltd.)

VEEA: 2-(2-vinyloxyethoxy) ethyl acrylate

BDDA: 1,4-butanediol diacrylate

DPHA: Dipentaerythritol Hexaacrylate

PET3A: Pentaerythritol Triacrylate

INATA: Isocyanuric acid EO-modified triacrylate (Dong-A Synthetic Chemicals:

Aronix M-315)

NPDA: Neopentyl glycol diacrylate

GMA: glycidyl methacrylate

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei, alias: 4-(glycidyloxy) butyl acrylate)

DMAA: N,N-dimethylacrylamide

TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

DAROCUR1173: Darocure 1173 (Merck)

DETX-S: A thioxanthone-based sensitizer manufactured by Nihon Kayaku Co., Ltd.

CPI-110P: A triarylsulfonium salt type photoacid generator manufactured by San Afro.

<Synthesis example 1 of oligomer (oligomer 2)>

In a 5-neck separable flask equipped with a stirrer, reflux cooling tube, gas introduction tube, thermometer, and dropping funnel, 81.6 parts of polytetramethylene glycol (Hodogaya Chemical Co., Ltd.: PTG850, hydroxyl value 127.1 mgKOH/g), isophorone 41.4 parts of diisocyanate were injected|thrown-in, and it heated up at 60 degreeC, introduce|transducing 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 parts of hydroquinone monomethyl ether were thrown into the dropping funnel, and it was dripped at the separable flask over 1 hour. After completion|finish of dripping, after continuing stirring at 80 degreeC for 3 hours, when it confirmed that there was no absorption peak of an isocyanate group in an infrared absorption spectrum, reaction was complete|finished and the oligomer 2 was obtained. The weight average molecular weight of the product was 4000.

In addition, the measuring method of the hydroxyl value of this invention is as follows. Precisely weigh approximately 1 g of the sample in a static Erlenmeyer flask, add 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture to dissolve, and further dissolve an acetylating agent (25 g of acetic anhydride with pyridine, , solution with a volume of 100 ml) was added exactly 5 ml, and the mixture was stirred for about 1 hour. To this, a phenolphthalein reagent solution is added as an indicator, and it is continued for 30 seconds. Then, it titrated with 0.1 N alcoholic potassium hydroxide solution until the solution showed pink color, and the hydroxyl value was calculated|required by the following formula. The hydroxyl value was made into the numerical value of the dry state of resin (unit: mgKOH/g).

Hydroxyl value (mgKOH/g)=[{(b-a)×F×28.25}/S]/(non-volatile matter concentration/100)+D

However, S: Sample collection amount (g)

a: Consumption of 0.1 N alcoholic potassium hydroxide solution (ml)

b: Consumption (ml) of 0.1 N alcoholic potassium hydroxide solution in the blank experiment

F: titer of 0.1 N alcoholic potassium hydroxide solution

D: Acid value (mgKOH/g)

<Synthesis example 2 of oligomer (oligomer 3)>

A compound obtained by adding 2 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate in a 5-neck separable flask equipped with a stirrer, reflux cooling tube, gas introduction tube, thermometer, and dropping funnel (Daisel Chemicals: Decorative plate 113.4 parts of cell FA2D, the hydroxyl value of 163.0 mgKOH/g), 36.6 parts of isophorone diisocyanate, and 0.15 part of hydroquinone monomethyl ether were thrown in, and it heated up to 60 degreeC while introducing dry air. 0.04 parts of dibutyltin dilaurate was added here, temperature was raised, and it was made to react at 80 degreeC for 3 hours. The reaction was terminated when it was confirmed that there was no absorption peak of the isocyanate group in the infrared absorption spectrum. The weight average molecular weight of the product was 1300. In addition, the measurement of a hydroxyl value is the same as that of the synthesis example 1 of an oligomer.

Using the active energy ray polymerizable adhesive mix|blended in the ratio of Tables 1-5, the laminated body was created by the following method, respectively.

<Production example of laminate A>

As the transparent film (1), a UV absorber-containing polytriacetyl cellulose film manufactured by Fujifilm Corporation: A UV absorber manufactured by Fujifilm Business Supply as a transparent film (2) using the trade name “FUJITAC: 80 μm” (thickness 80 μm). A polytriacetyl cellulose-based film not containing: a trade name “TAC50μ” (thickness of 50 μm) was used. The surface of one side of the transparent films (1) and (2) was corona-treated with a discharge amount of 300 W µm in/m 2 , and then, within 1 hour, active energy ray polymerization shown in Tables 1, 2, and 5 The adhesive was applied to the corona-treated face of each film using a wire bar coater to form a film thickness of 4 µm to form an active energy ray-polymerizable adhesive layer. A polyvinyl alcohol-based polarizer is sandwiched between the active energy ray-polymerizable adhesive layer formed on the transparent films (1) and (2), and the transparent film (1)/adhesive layer/PVA-based polarizer/adhesive layer/transparent film (2) ) was obtained. All sides of this laminated body were fixed with cellophane tape, and it fixed to the leak board so that the transparent film 1 might contact|connect the leak board.

The transparent film 2 side was irradiated with ultraviolet rays with a maximum illuminance of 300 mW/cm 2 and a cumulative light amount of 300 mJ/cm 2 with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation) to prepare a laminate A (polarizing plate).

<Production example of laminate B>

On a polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 50 µm, the active energy ray-polymerizable adhesives in Tables 1 to 5 were applied with a bar coater to a thickness of 8 µm. After sticking a PET film with a thickness of 50 µm to this with a nip roll to face it, ultraviolet rays with a maximum illuminance of 300 mW/cm2 and an accumulated light amount of 300 mJ/cm2 were emitted from one side with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation). It was investigated and the laminated body B was obtained.

About the obtained laminated body A, peeling strength, punching processability, heat resistance, and heat-and-moisture resistance were calculated|required according to the following method. In addition, in the obtained laminated body B, the transmittance|permeability and coloring after a moist-and-heat resistance test were confirmed according to the following method. The results were similarly shown to Tables 1-5.

<Production example of laminate C>

In Tables 3 and 4, as the transparent film (1) and the transparent film (2), the following,

ZF: A polynorbornene-based film (100 μm thick) that does not contain a ZF-14 ultraviolet absorber manufactured by Zeon of Japan;

HBD: HBD-002 UV absorber-free polyacrylic film (thickness 50 µm) manufactured by Mitsubishi Rayon, and

TAC: FUJIFILM BUSINESS SUPPLY CO., LTD. TAC50μ UV absorber-free polytriacetyl cellulose film (50 μm thick)

3 types were used. The surface of each side is corona-treated with a discharge amount of 300 W μmin/m2, and within 1 hour thereafter, the active energy ray-polymerizable adhesive shown in Tables 3 and 4 is applied to the corona-treated face of each film, It coated so that it might become a film thickness of 4 micrometers using a wire bar coater, and the active energy ray polymerizable adhesive layer was formed. A polyvinyl alcohol-based polarizer was sandwiched between the active energy ray polymerizable adhesive layer formed on each of the above films, and a laminate consisting of a transparent film (1)/adhesive layer/PVA-based polarizer/adhesive layer/transparent film (2) was obtained. . All sides of this laminated body were fixed with cellophane tape, and it fixed to the leak board so that the transparent film 1 might contact|connect the leak board.

The transparent film 2 side was irradiated with ultraviolet rays with a maximum illuminance of 300 mW/cm 2 and an accumulated light amount of 300 mJ/cm 2 with an active energy ray irradiation apparatus (a high-pressure mercury lamp manufactured by Toshiba Corporation), to prepare a laminate C (polarizing plate).

<Peel strength>

Adhesive force was measured based on JIS K6 854-4 adhesive agent - peel adhesive strength test method - part 4: the floating roller method.

That is, the obtained laminated body A or laminated body C was cut using the cutter to the size of 25 mm x 150 mm, and it was set as the sample for a measurement. A double-sided adhesive tape (DF8712S, manufactured by Toyo Chemical Industries, Ltd.) was affixed on one side of the sample and adhered on a metal plate using a laminator to obtain a measurement laminate of the polarizing plate and the metal plate. In the laminate for measurement, a trigger for peeling is previously provided between the transparent film and the polarizer. It was pulled and peeled, and it was set as the peeling force. At this time, the peeling force of both of 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 in 4 grades as adhesive force. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: Impossible to peel, or destruction of polarizing plate

○: Peeling force 2.0 (N/25 mm) or more

△: Peeling force of 1.0 (N/25 mm) or more and 2.0 (N/25 mm) or less

×: Peeling force less than 1.0 (N/25 mm)

<Punching processability>

The polarizing plate which produced the obtained laminated body A or laminated body C using the 100 mm x 100 mm blade of the Dumbbell company punched out from the transparent film (1) side.

The peripheral peeling distance of the punched-out polarizing plate was measured with a ruler, and the following four steps evaluated. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: 0mm

○: Less than 1 mm

△: 1 mm or more and less than 3 mm

X: 3mm or more

<Heat resistance>

The laminated body A or the laminated body C joined with each adhesive was cut to a size of 50 mm x 40 mm, and exposed under the conditions of 80°C-dry and 100°C-dry for 1000 hours, respectively. The presence or absence of peeling of the edge part of a polarizing plate after exposure was evaluated visually in the following four steps. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: No peeling even under 100℃-dry conditions

○: Completely no peeling under 80℃-dry conditions

△: Less than 1 mm peeling under 80°C-dry conditions

×: There is peeling of 1 mm or more under 80°C-dry conditions

<Moisture and heat resistance>

The laminate A or the laminate C bonded with each adhesive was cut to a size of 50 mm×40 mm, and exposed for 1000 hours under the conditions of a temperature of 60°C-humidity 90% and a temperature of 85°C-humidity 85%. did. The presence or absence of peeling of the edge part of the laminated body A after exposure was evaluated visually in the following four steps. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: No peeling even under the condition of 85℃-85%RH

○: Completely no peeling under the conditions of 60℃-90%RH

△: There is peeling of less than 1 mm under the conditions of 60°C-90%RH

x: There is peeling of 1 mm or more under the conditions of 60°C-90%RH

<Yellow Index (ΔYI)>

The laminate B bonded with each adhesive was cut to a size of 50 mm × 40 mm, exposed for 1000 hours under the conditions of temperature 85° C.-humidity 85%, and an integrating sphere type spectral transmittance meter (DOT-, manufactured by Murakami Color Material Technology Research Institute) 3 C) to measure ΔYI. Here, ΔYI was expressed as 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. ΔYI was evaluated in the following four steps. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: Less than 0.5

○: 0.5 or more and less than 1.0

△: 1.0 or more and less than 1.5

x: The result of 1.5 or more is shown to Tables 1-5.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

As shown in Table 1, when the active energy ray-polymerizable adhesive of the present invention containing boric acid or a boric acid derivative is applied to a polytriacetyl cellulose-based film, peel strength, punching processability, heat resistance, and heat-and-moisture resistance , all were practical level. In particular, Examples 3-19 have favorable peeling strength and tolerance. Moreover, in Examples 1 and 2, although the level of tolerance is low, it can be used.

In contrast, as shown in Table 2, in Comparative Examples 1 to 8 containing no boric acid or boric acid derivative, either peel strength, punching workability, heat resistance, and heat-and-moisture resistance did not reach the practical range.

In addition, as shown in Table 3, even when the active energy ray polymerizable adhesive of the present invention containing boric acid or a boric acid derivative is used for a polyacrylic film or a polynorbornene film, as in Examples 20 to 31, In all of peeling strength, punching processability, heat resistance, and heat-and-moisture resistance, the evaluation result was favorable. Although the level of heat resistance and heat-and-moisture resistance are not so high also in Examples 32-35 which do not contain a compound (Y), a compound (C), and an oligomer (D), it is possible to use at a practical level.

On the other hand, as shown in Table 4, in Comparative Examples 9 to 24 not containing boric acid or a boric acid derivative, the peel strength was low, on the other hand, the evaluation results of several tolerances of heat resistance and heat-and-moisture resistance were low, and did not reach the practical range. .

Furthermore, as shown in Table 5, the active energy ray-polymerizable adhesives of the present invention containing various boric acid derivatives are also useful, particularly in Examples 42 to 45 containing 1,4-benzenediboronic acid and tetrahydroxydiborane. In this case, it is excellent in peeling strength etc. more than equal to the case where only boric acid is included.

(Second aspect)

[Examples 101 to 125, Comparative Examples 101 and 102]

A cationically polymerizable compound (K), boric acid or boric acid derivative, and a cationically polymerizable initiator (KE) were added to a 300 ml mayonnaise bottle in which the oxygen concentration was substituted at 10% or less and shaded according to each Example and Comparative Example, respectively. It injected|threw-in with the composition and ratio (weight part) shown in Table 6 and Table 7. Next, each active energy ray-polymerizable resin composition was obtained by fully stirring the mixture injected|thrown-in by the disper, and defoaming sufficiently after that. About this active-energy-ray-polymerizable resin composition, the following method created and evaluated the laminated body, respectively.

In addition, the abbreviation in Tables 6 and 7 is as follows.

JER828: 2,2'-(dimethyl methylene) bis [(p-phenylene) oxymethylene] bis oxirane (manufactured by Mitsubishi Chemical Corporation)

P-01:1,3-phenylenebis(methylene)bis(7-oxabicyclo[4.1.0]heptane-3-carboxylate)

CEP-10:1,3-bis{(7-oxabicyclo[4.1.0]heptan-3-yl methoxy)methyl}benzene

ZX1658:2-[{4-(oxiran-2-ylmethoxy)cyclohexyl}methoxy]oxirane (manufactured by Toto Chemical Co., Ltd.)

2021P: 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021 P manufactured by Daicel)

OXT-101: 3-ethyl-3-hydroxymethyloxetane (Aronoxetane OXT-101 manufactured by Dong-A Synthetic Co., Ltd.)

OXT-221: di(1-ethyl-3-oxetanyl)methyl ether (Aronoxetane OXT-221 manufactured by Dong-A Synthetic Company)

B1: boric acid (the number of hydroxyl groups 3) (also called orthoboric acid)

B2: 1,4-benzenediboronic acid (4 hydroxyl groups)

B3: tetrahydroxy diborane (the number of hydroxyl groups 4)

B4: boric acid triethanolamine salt (3 hydroxyl groups)

B5: methyl boronic acid (number of hydroxyl groups 2)

B6: phenyl boronic acid (number of hydroxyl groups 2)

B7: triethyl borate (number of hydroxyl groups 0)

WPI-113: sulfonium salt-based cationic polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)

CPI-110P: Triarylsulfonium salt type photoacid generator (manufactured by San Afro)

<Production example of laminate D>

As the transparent film (1), a UV absorber-containing polytriacetyl cellulose film manufactured by Fujifilm Corporation: A UV absorber manufactured by Fujifilm Business Supply as a transparent film (2) using the trade name “FUJITAC: 80 μm” (thickness 80 μm). A polytriacetyl cellulose-based film not containing: a trade name “TAC50μ” (thickness of 50 μm) was used. The surface of one side of the transparent films (1) and (2) was corona-treated with a discharge amount of 300 W mu m in/m2, and then, within 1 hour after that, the active energy ray polymerizable resin composition shown in Tables 6 and 7 was prepared. It coated so that it might become a film thickness of 4 micrometers using a wire bar coater, and the active energy ray polymerizable adhesive layer was formed. A polyvinyl alcohol-based polarizer is sandwiched between the active energy ray-polymerizable adhesive layer formed on the transparent films (1) and (2), and the transparent film (1)/adhesive layer/PVA-based polarizer/adhesive layer/transparent film (2) ) was obtained. All sides of this laminated body were fixed with cellophane tape, and it fixed to the leak board so that the transparent film 1 might contact|connect the leak board.

The transparent film 2 side was irradiated with ultraviolet rays with a maximum illuminance of 300 mW/cm 2 and a cumulative light amount of 300 mJ/cm 2 with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation) to prepare a laminate D (polarizing plate). For the obtained laminate D, peel strength, gel fraction, punching workability, shrinkage, heat resistance, and heat-and-moisture resistance were determined according to the following methods (Tables 6 and 7).

《Peel Strength》

Adhesive force was measured based on JIS K6 854-4 adhesive agent - peel adhesive strength test method - part 4: the floating roller method.

That is, the obtained polarizing plate was cut into the size of 25 mm x 150 mm using a cutter, and it was set as the sample for a measurement. A double-sided adhesive tape (DF8712S, manufactured by Toyo Chemical Industries, Ltd.) was affixed on one side of the sample and adhered on a metal plate using a laminator to obtain a measurement laminate of the polarizing plate and the metal plate. In the laminate for measurement, the trigger for peeling is previously provided between the protective film and the polarizer, and the laminate for measurement is pulled and peeled at a rate of 300 mm/min under the conditions of 23° C. and 50% of relative humidity, and peeling force did it with At this time, the peeling force of both of 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 in 4 steps as adhesive force. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

◎: Impossible to peel, or destruction of polarizing plate

○: Peeling force is 2.0 (N/25 mm) or more - less than 5.0 (N/25 mm).

(triangle|delta): Peeling force 1.0 (N/25 mm) or more - 2.0 (N/25 mm) less.

x: Peeling force is less than 1.0 (N/25 mm).

《Gel fraction》

The active energy ray-polymerizable resin composition of the present invention was applied to one side of a polynorbornene-based film (trade name: “Zeonoa ZF-14”: 100 µm thick) manufactured by Zeon Corporation in Japan, which was not subjected to corona treatment, using a wire bar coater. was coated so as to have a film thickness of 20 to 25 µm using Further, after stacking Zeonoa ZF-14 not subjected to corona treatment on the adhesive layer to obtain a three-layer laminate, the maximum illuminance 300 mW/cm 2 was accumulated with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba Corporation). The adhesive layer was polymerized and cured by irradiating an active energy ray with a light quantity of 300 mJ/cm 2 . Zeonoa ZF-14 on both sides of the adhesive layer constituting the laminate consisting of three layers of Zeonoa ZF-14/adhesive layer/zeonoa ZF-14 was peeled off to obtain an adhesive layer.

After measuring the weight of the adhesive layer (weight 1), the adhesive layer was sandwiched between the metal mesh and the metal mesh so that the adhesive layers did not overlap, and the mixture was refluxed in methyl ethyl ketone (MEK) for 3 hours. Moreover, it dried at 80 degreeC for 30 minutes, and the weight of the adhesive bond layer was measured (weight 2). The gel fraction was calculated|required from the following formula, and three-step evaluation was carried out. In the case of evaluation of (circle) and (triangle|delta), there is no problem in particular at the time of actual use.

Gel fraction (%)={1-(weight 1-weight 2)/weight 1)}×100

(Evaluation standard)

○: The gel fraction is 90% or more

△: The gel fraction is 80% or more and less than 90%

x: gel fraction less than 80%

《Punching workability》

The polarizing plate produced using the 100 mm x 100 mm blade of a dumbbell company was punched out from the protective film (1) side.

The peripheral peeling distance of the punched-out polarizing plate was measured with a ruler, and the following four steps evaluated. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

*◎: 0mm

○: 1mm or less

△: 1-3mm

X: 3mm or more

《Shrinkage rate》

The polarizing plate small piece is left in a constant temperature and humidity chamber of 60 ° C.-dry and 60 ° C.-90 RH%, the amount of shrinkage in the stretching direction after 60 hours is measured, and the ratio of the amount of shrinkage to the length of the circle (100 mm) is calculated as the shrinkage rate below was evaluated in step 3.

In addition, "dry" is an oven with a humidity control function, and it controls for every temperature, and is a test condition at the time of not controlling the humidity. In the case of evaluation of (circle) and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

○: Shrinkage of 0.2% or less

△: Shrinkage is greater than 0.2% and less than or equal to 0.4%

×: Shrinkage exceeds 0.4%

《Heat resistance》

The polarizing plate obtained in each Example and the comparative example was cut to the size of 50 mm x 40 mm, and it exposed under 80 degreeC-dry and 100 degreeC-dry conditions for 1000 hours, respectively. The presence or absence of peeling of the edge part of a polarizing plate after exposure was evaluated by visual observation in the following four steps. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

(double-circle): There is no peeling even under the condition of 100 degreeC-dry.

○: Completely no peeling under 80℃-dry conditions.

(triangle|delta): There is peeling of less than 1 mm under 80 degreeC-dry conditions.

x: There is peeling of 1 mm or more under 80 degreeC-dry conditions.

<< moisture and heat resistance >>

The polarizing plate obtained in each Example and the comparative example was cut to the size of 50 mm x 40 mm, and it exposed under the conditions of 60 degreeC-90%RH and the conditions of 85 degreeC-85%RH for 1000 hours. The presence or absence of peeling of the edge part of a polarizing plate after exposure was evaluated visually in the following four steps. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

(double-circle): There is no peeling even under the conditions of 85 degreeC-85%RH.

○: Completely no peeling under the conditions of 60°C-90%RH.

(triangle|delta): There is peeling of less than 1 mm under the conditions of 60 degreeC-90%RH.

x: There is peeling of 1 mm or more under the conditions of 60 degreeC-90%RH.

[Table 6]

[Table 7]

In Comparative Examples 101 and 102 in which neither boric acid or a boric acid derivative nor a cationic polymerization initiator was added, various physical properties required by the present application could not be obtained at all. When an oxirane compound (k1) is used as a cationically polymerizable compound (K), compared with the case where it is not used (Examples 124 and 125), various physical properties are favorable. In addition, when K1-1 having an aromatic ring is used as the oxirane compound (for example, Example 103), the shrinkage rate under humidification is suitable as compared with Examples 122 and 123 in which K1-1 is not used.

Furthermore, boric acid and/or boric acid derivatives are more suitable when the hydroxyl group is 3 or more (for example, Examples 103, 108, 110, 111) than when the hydroxyl group is less than 3 (for example, Examples 113 to 115). Moreover, it turned out that 0.3 weight part - 20 weight part are suitable with respect to 100 weight part of active energy ray resin compositions as for the addition amount of a boric acid and/or a boric acid derivative (refer Examples 101-110).

(Third aspect)

[Examples 201 to 220, Comparative Example 201]

Compound (X), compound (C), compound (m), oligomer, cationically polymerizable compound (B), boric acid or boric acid derivative, active The energy-beam polymerization initiator (E) and the sensitizer were respectively injected|thrown-in by the composition and ratio (weight part) shown in Table 8 according to each Example and a comparative example. Next, each active energy ray-polymerizable resin composition was obtained by fully stirring the mixture injected|thrown-in by the disper, and fully defoaming after that. About this active-energy-ray-polymerizable resin composition, the following method created and evaluated the laminated body, respectively. The evaluation results are also shown in Table 8.

In addition, the abbreviation in a table|surface is as follows.

4HBA: 4-hydroxybutyl acrylic acid

HEA: 2-hydroxyethyl acrylate

CHDMMA: cyclohexanedimethanol monomethacrylate

DCPA: dicyclofentanyl acrylate

IBXA: Isobornyl acrylate

FA-511AS: Dicyclopentenyl acrylate (Pancryl 511 AS manufactured by Hitachi Chemical Co., Ltd.)

nBA: n-butyl acrylate

NPDA: Neopentyl glycol diacrylate

PET3A: Pentaerythritol Triacrylate

INATA: Isocyanuric acid EO-modified triacrylate (Dong-A Synthetic Chemicals: Aronix M-315)

Oligomer 6: Polyurethane acrylate obtained in Synthesis Example 3 Mw=4000

Compound 1:

[Tue 1]

1,4-phenylenebis(methylene)bis(7-oxabicyclo[4.1.0]heptane-3-carboxylate)

JER806: Bisphenol F diglycidyl ether (manufactured by Mitsubishi Chemical)

CEL2021P: 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021 P manufactured by Daicel)

OXT-121: Xylylenebisoxetane (Aronoxetane OXT-121 manufactured by Dong-A Synthetic Co., Ltd.)

EC: Ethylene carbonate

CPI-110P: A triarylsulfonium salt type photoacid generator manufactured by San Afro.

IRG250: 4-isobutylphenyl (4-methylphenyl) iodonium hexafluorohosmophyto (Ilga Cure 250 manufactured by BASF)

TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (leucitin TPO manufactured by BASF)

DETX-S: A thioxanthone-based sensitizer manufactured by Nihon Kayaku Co., Ltd.

<Synthesis example 3 of oligomer (oligomer 6)>

In a five-neck separable flask equipped with a stirrer, reflux cooling tube, gas introduction tube, thermometer, and dropping funnel, 81.6 parts of polytetramethylene glycol (Hodogaya Chemical Company: PTG850, hydroxyl value 127.1 mgKOH/g) was added, isophorone di 41.4 parts of isocyanates were injected|thrown-in, and it heated up to 60 degreeC, introduce|transducing 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 parts of hydroquinone monomethyl ether were thrown into the dropping funnel, and it was dripped at the separable flask over 1 hour. After completion|finish of dripping, after continuing stirring at 80 degreeC for 3 hours, when it confirmed that there was no absorption peak of an isocyanate group in an infrared absorption spectrum, reaction was complete|finished and the oligomer 6 was obtained. The weight average molecular weight of the product was 4000.

In addition, the measuring method of the hydroxyl value of this invention is as having described in the 1st aspect.

Using the active energy ray-polymerizable resin composition mix|blended by the ratio shown in Table 8, the laminated body was created by the following method, respectively.

<Production example of laminate E>

As the transparent film (1), a UV absorber-containing polytriacetyl cellulose film manufactured by Fujifilm Corporation: A UV absorber manufactured by Fujifilm Business Supply as a transparent film (2) using the trade name “FUJITAC: 80 μm” (thickness 80 μm). A polytriacetyl cellulose-based film not containing: a trade name “TAC50μ” (thickness of 50 μm) was used. The surface of one side of the transparent films (1) and (2) was corona-treated with a discharge amount of 300 W µm in/m 2 , and the active energy ray-polymerizable resin composition shown in Table 8 was coated with a wire bar coater within 1 hour thereafter. was coated so that it might become a film thickness of 4 micrometers using , and the active energy ray polymerizable resin layer was formed. A polyvinyl alcohol-based polarizer is sandwiched between the active energy ray-polymerizable resin layer formed on the transparent films (1) and (2), and the transparent film (1)/resin layer/PVA-based polarizer/resin layer/transparency A laminate comprising the film (2) was obtained. All sides of this laminated body were fixed with cellophane tape, and it fixed to the leak board so that the transparent film 1 might contact|connect the leak board.

The transparent film 2 side was irradiated with the ultraviolet-ray of 300 mW/cm<2> of maximum illumination intensity, 300 mJ/cm<2|

<Production example of laminate F>

On a polyethylene terephthalate (hereinafter, abbreviated as PET) film having a thickness of 50 µm, the active energy ray polymerizable resin composition of Table 8 was applied with a bar coater to a thickness of 8 µm. After attaching a PET film with a thickness of 50 µm to this with a nip roll to face it, an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation) was irradiated with ultraviolet rays with a maximum illuminance of 300 mW/cm2 and an accumulated light amount of 300 mJ/cm2 from one side. A laminate F was obtained.

<Production example of laminate G>

As the transparent film (1) and the transparent film (2), respectively,

ZF: A polynorbornene-based film (100 μm thick) that does not contain a ZF-14 ultraviolet absorber manufactured by Zeon of Japan;

HBD: HBD-002 UV absorber-free polyacrylic film (thickness 50 µm) manufactured by Mitsubishi Rayon, and

TAC: FUJIFILM BUSINESS SUPPLY CO., LTD. TAC50μ UV absorber-free polytriacetyl cellulose film (50 μm thick)

3 types were used. Each surface of one side is corona-treated with a discharge amount of 300 W micrometer/m2, and the active energy ray-polymerizable resin composition shown in Table 8 is applied to the corona-treated surface of each film within 1 hour after that, a wire bar. It coated so that it might become a film thickness of 4 micrometers using the coater, and the active energy ray polymerizable resin layer was formed. A polyvinyl alcohol-based polarizer is sandwiched between the active energy ray-polymerizable resin layer formed on each of the above films, and a laminate comprising a transparent film (1)/resin layer/PVA-based polarizer/resin layer/transparent film (2) got a sieve All sides of this laminated body were fixed with cellophane tape, and it fixed to the leak board so that the transparent film 1 might contact|connect the leak board.

The transparent film 2 side was irradiated with ultraviolet rays with a maximum illuminance of 300 mW/cm 2 and a cumulative light amount of 300 mJ/cm 2 with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation) to prepare a laminate G (polarizing plate).

About the obtained laminated body E, peeling strength, punching processability, heat resistance, and heat-and-moisture resistance, and the laminated body external appearance were evaluated with respect to the laminated body F, and the laminated body external appearance was evaluated according to the following method. Moreover, in the laminated body G, the transmittance|permeability and coloring after a moist-and-heat resistance test were confirmed according to the following method. The results are also shown in Table 8.

<Peel strength>

Adhesive force was measured based on JIS K6 854-4 adhesive agent (polymerizable resin composition) - peel adhesive strength test method - part 4: the floating roller method.

That is, the obtained laminated body E was cut to the size of 25 mm x 150 mm using a cutter, and it was set as the sample for a measurement. A double-sided adhesive tape (DF8712S, manufactured by Toyo Chemical Industries, Ltd.) was affixed on one side of the sample and adhered on a metal plate using a laminator to obtain a measurement laminate of the polarizing plate and the metal plate. In the laminate for measurement, a trigger for peeling was previously made between the transparent film and the polarizer, and the laminate for measurement was cut at an angle of 90° at a speed of 300 mm/min under the conditions of 23° C. and 50% relative humidity. It was pulled and peeled, and it was set as the peeling force. At this time, the peeling force of both of 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 in 4 steps as adhesive force. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

◎: Impossible to peel, or destruction of polarizing plate

○: Peeling force 2.0 (N/25 mm) or more

△: Peeling force of 1.0 (N/25 mm) or more and 2.0 (N/25 mm) or less

×: Peeling force less than 1.0 (N/25 mm)

<Punching processability>

The polarizing plate produced using the 100 mm x 100 mm blade made by Dumbbell Corporation was punched out from the transparent film (1) side.

The peripheral peeling distance of the punched-out polarizing plate was measured with a ruler, and the following four steps evaluated. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

◎: 0mm

○: Less than 1 mm

△: 1 mm or more and less than 3 mm

X: 3mm or more

<Heat resistance>

The laminate E bonded with each adhesive was cut to a size of 50 mm x 40 mm, and exposed under the conditions of 80°C-dry and 100°C-dry for 1000 hours, respectively. The presence or absence of peeling of the edge part of a polarizing plate after exposure was evaluated by visual observation in the following four steps. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

◎: No peeling even under 100℃-dry conditions

○: Completely no peeling under 80℃-dry conditions

△: Less than 1 mm peeling under 80°C-dry conditions

×: There is peeling of 1 mm or more under 80°C-dry conditions

<Moisture and heat resistance>

The laminate E bonded with each adhesive was cut into a size of 50 mm x 40 mm and exposed for 1000 hours under conditions of a temperature of 60°C and a humidity of 90% and a temperature of 85°C and a humidity of 85%. The presence or absence of peeling of the edge part of the laminated body A after exposure was evaluated by visual observation in the following four steps. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

◎: No peeling even under the condition of 85℃-85%RH

○: Completely no peeling under the conditions of 60℃-90%RH

△: There is peeling of less than 1 mm under the conditions of 60°C-90%RH

x: There is peeling of 1 mm or more under the conditions of 60°C-90%RH

<Laminated body appearance>

The appearance of each laminate was visually evaluated in the following three steps. In the case of evaluation of (circle) and (triangle|delta), there is no problem in particular at the time of actual use.

○: No wrinkles or irregularities in the laminate

△: There are some wrinkles or irregularities in the laminate

×: Wrinkles or irregularities are present on the entire surface of the laminate

<Yellow Index (ΔYI)>

The laminate G bonded with each adhesive was cut to a size of 50 mm x 40 mm, exposed for 1000 hours under the conditions of temperature 85° C.-humidity 85%, and an integrating sphere type spectral transmittance meter (DOT-3 manufactured by Murakami Color Materials Technology Research Institute) C) measured ΔYI. Here, ΔYI was expressed as 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. ΔYI was evaluated in the following four steps. If it is evaluation of (double-circle), (circle), (triangle|delta), it is a level without a problem practically.

◎: 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

[Table 8]

As shown in Table 8, when the active energy ray-polymerizable resin composition of this invention is used, in Examples 203-210, 212, 213, 215-218, 220, it has favorable peeling strength, tolerance, and laminated body external appearance. . Moreover, in Examples 201, 202, 211, 214, and 219, although there are test items with a low level of tolerance, it is possible to use. On the other hand, in Comparative Example 201 which does not contain boric acid or a boric acid derivative, peeling strength is low, and punching process resistance does not reach a practical use range.

2. Coating agent

(1st aspect)

[Examples 501 to 536, Comparative Examples 501 to 525]

Like Example 1, in the compositions and ratios (parts by weight) shown in Tables 9-1, 9-2, 10-1, and 10-2, the active energy rays of Examples 501 to 536 and Comparative Examples 501 to 525 A polymerizable resin composition was obtained. The obtained resin composition was used as an active energy ray polymerizable coating agent, and the following laminated body was created. In addition, in Tables 9-1, 9-2, and Tables 10-1, 10-2, the abbreviation is as Tables 1-5.

<Production example of laminate H>

As the optical film, a polyacrylic film containing no ultraviolet absorber manufactured by Mitsubishi Rayon Corporation: trade name "HBD-002: 50 µm” (thickness of 50 µm) was used. The surface of the optical film was corona-treated with a discharge amount of 300 W mu m in/m2, and the resin compositions shown in Tables 9-1, 9-2, and Tables 10-1 and 10-2 were activated within 1 hour after the surface treatment. As an energy ray polymerizable coating agent, using a wire bar coater, coating was carried out so that the film thickness was 4 µm to form a coating agent layer.

All sides of this laminated body were fixed to the leak board with cellophane tape so that an optical film might contact|connect the leak board.

After replacing the inside of the UV irradiation device (high-pressure mercury, etc. manufactured by Toshiba Corporation) with dry nitrogen, ultraviolet rays with a wavelength of 365 nm and a maximum illuminance of 300 mW/cm 2 and a cumulative light amount of 300 mJ/cm 2 are irradiated from the coating layer side, A laminate was produced.

About the obtained laminated body, adhesive force and heat resistance were calculated|required according to the following method, and the result was shown to Table 9-1, 9-2, and Table 10-1, 10-2 similarly.

《Adhesiveness》

According to JISK5400, the board|substrate scale peeling test was implemented. Four stages were evaluated for the number of the peeled masses out of 100 masses, and adhesive force was made into adhesive judgment. In the case of evaluation of (double-circle), (circle), and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

◎: 0 trout

○: 1-10 trout

△: 11-30 trout

X: More than 31 trouts

《Heat resistance》

The laminate obtained by each Example and the comparative example was cut out to the magnitude|size of 50 mm - 40 mm, and it exposed under 80 degreeC-dry conditions for 1000 hours. The presence or absence of peeling of the edge part of the laminated body after exposure was evaluated by visual observation in the following three steps. In the case of evaluation of (circle) and (triangle|delta), there is no problem in particular at the time of actual use.

(Evaluation standard)

○: Completely no peeling

△: With peeling of less than 1 mm

×: With peeling of 1 mm or more

[Table 9]

[Table 10]

[Table 11]

[Table 12]

(Second aspect)

[Examples 601 to 630, Comparative Examples 601 to 602]

Like Example 101, the active energy ray-polymerizable resin composition of Examples 601-630 and Comparative Examples 601-602 was obtained with the composition and ratio (weight part) shown in Table 11-1, 11-2. About the obtained resin composition, the laminated body H was created like 1st aspect of the said 1. coating agent. In addition, the abbreviation in Tables 11-1 and 11-2 is as Table 6 and 7.

About the obtained laminated body, adhesive force and heat resistance were evaluated like the 1st aspect of the said 2.coating agent. The results are shown in Tables 11-1 and 11-2.

[Table 13]

[Table 14]

(Third aspect)

[Examples 701 to 725, Comparative Example 701]

Like Example 201, the active energy ray polymerizable resin composition of Examples 701-725 and the comparative example 701 was obtained with the composition and ratio (weight part) shown in Table 12-1, 12-2. About the obtained resin composition, the laminated body H was created like the 1st aspect of the said 2.coating agent. In addition, the abbreviation in Table 12-1, 12-2 is as Table 8.

About the obtained laminated body, adhesive force and heat resistance were evaluated like the 1st aspect of the said 2.coating agent. The results are shown in Tables 12-1 and 12-2.

[Table 15]

[Table 16]

In the present invention, exemplary compounds as representative examples of the optical film are specifically shown in Tables 9 to 12 above, but are not limited thereto. In addition, as a notation of the example film, TAC: TAC50μ UV absorber-free polytriacetyl cellulose film (50 μm thick) manufactured by Fujifilm Business Supply, ZF: ZF-14 UV absorber-free poly made by Zeon Japan Norbornene-based film (thickness 100 µm), HBD: Mitsubishi Rayon Corporation HBD-002 UV absorber-free polyacrylic film (50 µm thick), R140: Kaneka’s R-140 UV absorber-free poly Carbonate film (thickness 43 μm), Envet: Polyester film containing UV absorber Envet S manufactured by Unitica (50 μm thick), TUX: Polyethylene containing TUX-HZ UV absorber manufactured by Higashi Cello Corporation A system film (thickness of 50 µm) is shown.

When the resin composition of this invention is used as a coating agent, in Examples 503-536, 602-605, 607-612, 616-623, 626-630, 702-718, 720-725, there is no problem in particular. Moreover, in Examples 501, 502, 601, 606, 613-615, 624, 625, 701, and 719, although the level of adhesiveness or heat resistance is low, it can be used. On the other hand, in Comparative Examples 501 to 525, 601, 602, and 701, it turns out that especially adhesiveness or heat resistance is inferior.

Claims (21)

A polymerizable compound, boric acid and/or a boric acid derivative, and a cationic polymerization initiator (KE), wherein the polymerizable compound is a cationically polymerizable compound (K) containing a cyclic hetero compound, wherein the boric acid derivative is in one molecule A compound having one or more BOH bonds, a boron-containing compound that hydrolyzes in the presence of water to form one or more BOH bonds, calcium borate, potassium borate, sodium borate, or ammonium borate, an active energy ray polymerizable resin composition.
delete delete delete delete delete delete delete delete delete delete delete According to claim 1,
The active energy ray polymerizable resin composition in which a cationically polymerizable compound (K) contains an oxirane compound (k1).
14. The method of claim 13,
The active energy ray polymerizable resin composition in which an oxirane compound (k1) contains the oxirane compound (k1-1) which has an aromatic ring.
According to claim 1,
The active energy ray polymerizable resin composition in which a boric acid derivative has 3 or more hydroxyl groups in 1 molecule.
According to claim 1,
The active energy ray-polymerizable resin composition which contains 0.1 weight part - 20 weight part of said boric acid and/or a boric-acid derivative in 100 weight part of active energy ray-polymerizable resin compositions.
The adhesive containing the active energy ray polymerizable resin composition of Claim 1.
A coating agent comprising the active energy ray polymerizable resin composition according to claim 1 .
A laminate formed by laminating the layer comprising the active energy ray polymerizable resin composition according to claim 1 on one or both surfaces of the base material (F).
20. The method of claim 19,
The base material (F) is made of a polyacetyl cellulose-based film, a polynorbornene-based film, a polypropylene-based film, a polyacrylic-based film, a polycarbonate-based film, a polyester-based film, a polyvinyl alcohol-based film, and a polyimide-based film. The laminate which is at least 1 sort(s) selected from the group.
A laminate for an optical element formed by using the laminate according to claim 19.