TW201512284A - Active energy ray-polymerizable resin composition, adhesive agent, coating agent, laminate and laminate for optical device - Google Patents

Abstract

This invention provides a novel active energy ray-polymerizable resin composition with an excellent adhesive property and a laminate using the same, more specifically, a laminate for optical devices. The laminate has an excellent punching processability and durability to heat or moisture compared to prior art. This invention relates to an active energy ray-polymerizable resin composition including a compound (M) containing a [alpha],[beta]-ethylenically unsaturated double bond and a boric acid and/or boric acid derivatives.

Description

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 same.

The active energy ray-polymerizable resin composition has a high polymerization rate and can be used in a solvent-free state. Therefore, it has excellent workability and extremely low energy required for polymerization. Typically, the active energy ray-polymerizable resin composition contains a resin component polymerizable by an active energy ray and a monomer component having an α,β-ethylenically unsaturated double bond group.

The resin component is a low molecular weight such as a polyester resin, a polyurethane resin, a polyepoxy resin, or a polyacrylic resin, and has an α,β-ethylenically unsaturated double bond at the molecular terminal. Oligomer. The monomer component is polymerized together with the resin component by irradiation with an active energy ray, but functions as a solvent until the end of polymerization. Therefore, the active energy ray-polymerizable resin has an advantage that no solvent is additionally required, so that the volatilization of the solvent does not occur at the time of formation of the coating film.

In addition, in recent years, an information communication machine including a display device such as a display The development and generalization are amazing. In these display devices, it is required to further improve the performance of a coating agent, an adhesive, a sealant, and the like, and to improve productivity, and various proposals for using an active energy ray-polymerizable material have been proposed. In such a display device, a plurality of films such as an anti-reflection film for preventing reflection from an external light source or a protective film for preventing damage of the surface of the display device are generally used depending on the application, for example, to constitute a liquid crystal. In a liquid crystal cell member for a liquid crystal display (LCD), a polarizing plate or a retardation film is laminated.

In addition, a flat panel display (FPD) is not only used as a display device, but also a function of a touch panel on the surface of the flat panel display to be used as an input device. A protective film, an anti-reflection film, or an indium tin oxide (ITO) vapor-deposited resin film is also used for the touch panel.

Further, in the display device, a backlight (light) that emits light from the back surface to emit light is widely used, and a backlight unit such as an edge light type or a direct type is provided on the lower surface side of the liquid crystal layer. The edge light type backlight unit basically includes a linear lamp as a light source, a square plate-shaped light guide plate disposed on the lamp along an end portion, and a light diffusion sheet disposed on a surface side of the light guide plate, and A cymbal disposed on the surface side of the light diffusing sheet. Recently, instead of a cold cathode fluorescent lamp (CCFL), a light emitting diode (LED) having excellent color reproducibility or power saving is used as a light source, and therefore heat resistance or dimensional stability is further required. improve.

The film is attached to the adherend via an adhesive, and is used as a display device for an optical element, and the active energy ray polymerizable adhesive is used as a shape. State to use.

List specific examples. The polarizing element used in the field of liquid crystal display or the like is usually produced by uniaxially stretching a urethane or a dye adsorbed on polyvinyl alcohol (PVA), and the polyvinyl alcohol-based polarizing element is shrunk by heat or moisture. , resulting in a decrease in polarizing performance. Therefore, a polarizing plate is used as a protective film bonded to the surface of the PVA-based polarizing element. In the past, an aqueous solution (PVA-based adhesive) of a polyvinyl alcohol-based resin has been widely used as an adhesive for attaching a protective film to a polarizing element (see Patent Document 1 and Patent Document 2). However, the water-based adhesive requires a drying step after application. However, since the PVA-based polarizing element has low heat resistance, it requires a long-time drying at a low temperature, and the production efficiency is poor. For the reason described above, it is proposed to use a cationic active energy ray-polymerizable adhesive using ultraviolet rays as an active energy ray instead of the water-based adhesive (see Patent Document 3).

However, since the cationic active energy ray-polymerizable adhesive has a dark reaction after ultraviolet irradiation, when the long cured product is wound into a roll, there is a problem that curling tends to occur during storage. Further, the cationic active energy ray-polymerizable adhesive is likely to be affected by the humidity at the time of polymerization hardening, the influence of moisture in the adhesive and the film, and the hardened state is likely to be uneven. Therefore, in order to exhibit a uniform hardened state, the environmental humidity is self-evident, and the moisture content of the adhesive or the PVA-based polarizing element must be strictly managed. The radical-based active energy ray-polymerizable adhesive is excellent in that the above-described problems are relatively small, but generally the curing shrinkage is large, and it is difficult to ensure sufficient adhesion.

However, liquid crystal display devices have been used in various environments as their use has expanded. For the polarizing plate constituting the liquid crystal display device, high heat resistance is required. For example, in a vehicle-mounted liquid crystal display device such as car navigation, high heat resistance durability is required.

When the adhesiveness is weak in a high-temperature environment, there is a problem that the PVA-based polarizing element and the protective film are peeled off due to the difference in heat shrinkage ratio between the PVA-based polarizing element and the protective film.

Patent Document 4 discloses an active energy ray-polymerizable adhesive containing hardening associated with a compound having a (meth)acryl fluorenyl group containing N-hydroxyethyl acrylamide and N-propenyl morpholine. The Tg of the adhesive layer after hardening is 60 ° C or more. The durability required for the polarizing plate can be made strict, and durability under a more severe environment is required under high humidity and high temperature. However, in the polarizing plate, the durability in the severe environment cannot be satisfied.

Further, in recent years, in the case where a polarizing plate is formed by using an active energy ray-polymerizable adhesive containing a curable component related to a compound having a (meth)acryl fluorenyl group, the polarizing element is promoted by a thin film. Since the curing shrinkage of the adhesive is large, wrinkles or irregularities are generated on the polarizing plate.

Further, Patent Document 5 discloses an active energy ray-polymerizable resin composition using ultraviolet rays, which comprises a (meth) acrylamide compound (A) having no hydroxyl group, and a boric acid (B), but The strength deterioration caused has not been studied, and the bonding strength and the like are insufficient.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 09-258023

Patent Document 2: Japanese Patent Laid-Open Publication No. 2005-208456

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-233874

Patent Document 4: Japanese Patent No. 4744496

Patent Document 5: Japanese Patent Laid-Open Publication No. 2013-194083

An object of the present invention is to provide a novel active energy ray-polymerizable resin composition having excellent adhesion to an adhesive or a coating agent, and a laminate using the same, particularly a laminate for an optical element, The laminate has excellent press workability and durability against heat or humidity as compared with the prior art.

In order to solve the problem, the inventors of the present invention have repeatedly conducted active research, and have found that the above-described active energy ray-polymerizable resin composition can be used to achieve the above object, and the present invention has been completed.

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

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

The active energy ray-polymerizable resin composition of the first aspect of the present invention preferably comprises a group selected from the group consisting of an active energy ray polymerization initiator (KE) and an active energy ray polymerization initiator (RE). At least one starter.

Further, the second aspect of the present invention is an active energy ray-polymerizable resin composition which is an active energy ray resin composition containing a polymerizable compound and a boric acid and/or a boric acid derivative, and the polymerizable compound is a cation. The polymerizable compound (K) further contains a cationic polymerization initiator (KE).

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

The active energy ray-polymerizable resin composition of the third aspect of the present invention preferably comprises a group selected from the group consisting of active energy ray polymerization initiator (KE) and active energy ray polymerization initiator (RE). At least one starter.

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

Further, the compound (M) containing an α,β-ethylenically unsaturated double bond group preferably contains the compound (Y) containing an α,β-ethylenically unsaturated double bond group containing an amine group. .

Further, the compound (M) containing an α,β-ethylenically unsaturated double bond group preferably contains a compound (C) containing an α,β-ethylenically unsaturated double bond group, and the compound (C) includes 2 More than one ring structure of a cycloalkane skeleton and/or a cyclic olefin skeleton.

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

In the active energy ray-polymerizable resin composition of the present invention, the cationically polymerizable compound (K) preferably contains an oxirane compound (k1).

The oxirane compound (k1) preferably contains an oxirane compound (k1-1) having an aromatic ring.

In the active energy ray-polymerizable resin composition of the present invention, the boric acid derivative preferably has three or more hydroxyl groups in one molecule.

Further, the active energy ray-polymerizable resin composition of the present invention preferably contains 0.1 to 20 parts by weight of the boric acid and/or boric acid derivative in 100 parts by weight of the composition.

The present invention relates to an adhesive or coating agent comprising the active energy ray-polymerizable resin composition.

The present invention relates to a laminate in which a laminate comprising the active energy ray-polymerizable resin composition is laminated on one or both sides of a substrate (F).

The substrate (F) is preferably selected from the group consisting of a polyethylene-based cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, and a poly At least one of a group consisting of a vinyl alcohol film and a polyimide film.

The present invention relates to a laminate for an optical element which is obtained by using the laminate.

The active energy ray-polymerizable resin composition of the present invention can provide a laminate having excellent press workability and durability against heat or humidity, in particular, a laminate for an optical element, compared to the prior art.

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

The active energy ray-polymerizable resin composition of the present invention is preferably contained in an active energy ray-polymerizable adhesive or an active energy ray-polymerizable coating agent.

Further, in the present invention, the expressions are "(meth)acrylonitrile", "(meth)acrylic acid", "(meth)acrylate", "(meth)acryloxy group", and "( In the case of methyl)allyl, unless otherwise specified, "acryloyl ketone and/or methacryl oxime", "acrylic acid and/or methacrylic acid", "acrylate" and/or "Acrylate", "acryloxy" and/or methacryloxy", and "allyl and/or methallyl".

Hereinafter, embodiments (first aspect to third aspect) of the present invention will be described.

(Description of the first aspect)

First, an active energy ray-polymerizable resin composition in which a boric acid and/or a boronic acid derivative is used together with a compound (M) containing an α,β-ethylenically unsaturated double bond group (hereinafter, sometimes referred to as a "radical system" "Active energy ray-polymerizable resin composition"; "Resin composition" may be referred to as "adhesive" or "coating agent".

The radical active energy ray-polymerizable resin composition of the present invention comprises a compound (M) containing an α,β-ethylenically unsaturated double bond group, and a boric acid and/or a boronic acid derivative.

The α,β-ethylenically unsaturated double bond-containing compound (M) which is a main component of the radical active energy ray-polymerizable resin composition contains all compounds having an α,β-ethylenically unsaturated double bond in the molecule. . From the viewpoint of utilizing the reactivity of the active energy ray, the compound (M) containing an α,β-ethylenically unsaturated double bond is preferably designed to be α,β contained in the active energy ray-polymerizable resin composition. The (meth) acrylonitrile group accounts for 50% by weight to 100% by weight based on the total weight of the ethylenically unsaturated double bond.

Specifically, the compound (M) is preferably one or more compounds selected from the group consisting of the following compounds: a compound containing a hydroxyl group containing an α,β-ethylenically unsaturated double bond group (X) a compound (Y) containing an α,β-ethylenically unsaturated double bond group containing an amine group, an α,β-ethylenically unsaturated group including a cycloalkane skeleton having two or more ring structures and/or a cyclic olefin skeleton The double bond group compound (C) and the oligomer (D) having a weight average molecular weight of 300 to 30,000.

First, a compound (X) (hereinafter referred to as a compound (X)) containing a hydroxyl group-containing α,β-ethylenically unsaturated double bond group will be described. The compound (X) is bonded to a boric acid and/or a boric acid derivative, and is hardened by an active energy ray to form a crosslinked coating film. Further, the compound (X) has an effect of forming a bond with a surface functional group of the substrate (F) via a boric acid and/or a boric acid derivative, thereby improving the adhesion.

The compound (X) is not particularly limited as long as it has a hydroxyl group in its structure, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate , (meth)acrylic acid ethyl-α-(hydroxymethyl)ester, monofunctional (meth)acrylic acid glyceride, or fatty acid ester (meth)acrylic acid such as glycidyl laurate (meth)acrylate An ester; or a (meth) acrylate having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone, or a compound having a hydroxyl group-containing α,β-ethylenically unsaturated double bond group, or An alkylene oxide addition obtained by repeatedly adding an alkylene oxide-containing compound having an α,β-ethylenically unsaturated double bond group to an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide (A) Hydroxy-containing aliphatic (meth) acrylates such as acrylates; cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-benzene mono(meth)acrylate Oxyloxymethyl, hydroxyethyl (meth) acrylate, 2-(4-benzylidene-3-hydroxyphenoxy)ethyl (meth)acrylate, etc. having a hydroxyl group and a cyclic structure (meth) acrylates; hydroxyethyl vinyl ether, hydroxy decyl vinyl ether, etc. a hydroxyl group-containing aliphatic vinyl ether such as an alkylene oxide-added vinyl ether having a hydroxyl group at the terminal; (meth)allyl alcohol, isopropenol, dimethyl(methyl)allyl alcohol, hydroxyethyl group (meth)allyl ether or a hydroxyl group-containing aliphatic group such as an alkylene oxide addition-type (meth)allyl ether having a hydroxyl group at the terminal end, or an alkylene oxide such as ethylene oxide or propylene oxide (meth)allyl alcohols or (meth)allyl ethers; propylene glycol, butene diol, glyceryl di(meth) acrylate, etc., containing α,β-ethylenic unsaturation a compound having a double bond group; a (meth) acrylamide containing hydroxyl group such as N-hydroxyethyl (meth) acrylamide or N-hydroxypropyl (meth) acrylamide; and a hydroxyl group such as vinyl alcohol And a monomer of a vinyl group, etc., but it is not specifically limited to these compounds. These compounds may be used alone or in combination of two or more.

From the viewpoint of adhesion to a substrate, the compound (X) is particularly preferably: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid 4- Hydroxybutyl ester, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate added with 1 mol to 2 mol of ε-caprolactone, and α with a carbon number of 2-18 a compound having a β-ethylenically unsaturated double bond group.

Next, the compound (Y) containing an α,β-ethylenically unsaturated double bond group containing an amine group will be described.

In the present invention, the amine-containing compound (Y) containing an α,β-ethylenically unsaturated double bond group (hereinafter referred to as the compound (Y)) contains at least one amine group and at least one α in the molecule. A compound having a β-ethylenically unsaturated double bond group. Amine group of compound (Y) The boric acid and/or boric acid derivative described later interacts to obtain stable and uniform liquid characteristics as a non-aqueous active energy ray polymerization composition. In addition, when it is used as the active energy ray-polymerizable adhesive or the coating agent of the present invention by the interaction, it has a large effect on the improvement of the adhesion, and can form heat resistance or water resistance. A good coating agent layer or an adhesive layer.

Examples of such a compound (Y) include an acyclic group-containing α,β-ethylenically unsaturated double bond group-containing compound (y1), and a cyclic amine group-containing α,β-ethyl group. Unsaturated double bond group compound (y2).

The acyclic compound (y1) containing an amino group-containing α,β-ethylenically unsaturated double bond group may, for example, be monomethylaminoethyl (meth)acrylate or dimethyl (meth)acrylate. (meth)acrylic acid-mono or di-alkylamino esters such as aminoethyl ester; monomethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) propylene oxime Mono or di-alkylaminoalkyl (meth) acrylamide such as amine.

The cyclic amino group-containing α,β-ethylenically unsaturated double bond group-containing compound (y2) may, for example, be a cyclic amino group-containing (meth)acrylonyl group-containing compound (y2-I). A cyclic amino group-containing compound (y2-II) having a vinyl group and a cyclic (amino)allyl-containing compound (y2-III) having an amine group.

Examples of the cyclic (meth)acryloyl group-containing compound (y2-I) having a cyclic group include 2-(2'-hydroxy-5'-(meth)acryloxyethylphenyl). -2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxyethylphenyl)-2H-benzotriazole Structure (meth) acrylate having an amine group; 2,4-diphenyl-6-[2-hydroxy-4-{2-(meth) propylene oxyethoxy}]-symmetry Triazine, 2,4-bis(2,4-diethylphenyl)-6-[2-hydroxy-4-{2-(methyl)acryloxyethoxyethoxy})]-symmetric triazine (meth) acrylate having a six-membered cyclic amino group; pentamethylpiperidine (meth) acrylate [ acrylate and methacrylate are collectively referred to as (meth) acrylate; the same applies hereinafter (meth)acrylates having an alicyclic amine group such as tetramethylpiperidyl (meth)acrylate or 4-(pyrimidin-2-yl)piperazin-1-yl (meth)acrylate Wait.

More specifically, the cyclic amino group-containing compound having a vinyl group (y2-II) may, for example, be 2-vinylpyrrole, 1-vinyl-2-imidazoline or 2-vinyl-2-imidazole. a vinyl-containing compound having a five-membered cyclic amine group such as phenyl, 1-vinylimidazole, 3-methyl-5-phenyl-1-vinylpyrazole; 2-vinylpiperazine, 4-vinyl Piperazine, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyrimidine, 2-vinyl-4,6-diamino-1,3,5-triazine, etc. having a six-membered cyclic amine group Vinyl-containing compounds; 1-vinylindole, 1-vinyl-1H-benzimidazole, 2-vinylquinoline, 2-vinylisoquinoline, 2-vinylquinoxaline, 2- a vinyl group-containing compound having a polycyclic amine group such as a vinylquinazoline, a 2-vinylporphyrin or a 1-vinylcarbazole; 1-methyl-4,5-divinyl-1H-imidazole; A compound having a cyclic amine group and two or more vinyl groups such as 2,6-divinylpyridine.

More specifically, the cyclic (amino)allyl-containing compound (y2-III) having an amine group may, for example, be 1-(methyl)allyl-1H-imidazole or 5-bromo-1. 1-(methyl)allyl-1H-pyrazole, 1-(methyl)allylpiperazine, N-(methyl)allyl-4,6-dichloro-1,3-5 a (meth)allyl-containing compound having a cyclic amino group such as triazine-2-amine Class; 2-(methyl)allyl-1H-indole, 1-(methyl)allyl-1H-benzimidazole, 2-(methyl)allyl carbazole, 1,2-di (Methyl)allyl-containing compounds having a polycyclic amine group such as (meth)allyl-1,2-dihydroisoquinoline or 9-(methyl)allyl-9H-carbazole Wait.

From the viewpoint of adhesion to various substrates (F) used as an active energy ray-polymerizable adhesive or a coating agent, a non-cyclic amino group-containing α,β-ethylenically unsaturated In the compound (y1) of the double bond group, the compound (Y) used in the present invention is more preferably a cyclic amino group-containing compound (y2) containing an α,β-ethylenically unsaturated double bond group. In the case where the active energy ray-polymerizable composition is used in combination with the compound (M) other than the compound (Y), a cyclic amino group-containing compound (y2-II) containing an amino group is preferred.

The coating film structure of the active energy ray-polymerizable resin composition after active energy ray polymerization due to the difference in the relative reaction rate or the main chain structure of the compound (y2-II) with the propylene group-containing compound used as the compound (M) It is easy to form a microphase separation structure, and it is particularly easy to form an island structure. Therefore, since it is a coating film structure which combines elasticity and stress relaxation property, when it is used as an active energy ray-polymerizable adhesive agent, it exhibits not only high adhesiveness and high adhesiveness by high cohesion, but also. It is preferable because the external environment changes from extremely low temperature to extremely high temperature, or the floating or peeling caused by the wetting is suppressed, and the practicality can be maintained.

Further, when the α,β-ethylenically unsaturated double bond group of the compound (Y) is a (meth)allyl group (y2-III), a micro phase separation structure is easily formed but the reaction rate is slow, so that a coating film exists. The case where the high molecular weight is insufficient. Therefore, for use as a living In the case of the performance-quantity polymerizable adhesive, there is a case where the durability is lowered or the aggregation of the adhesive layer is broken. The preferred sequence of the α,β-ethylenically unsaturated double bond group of the compound (Y) which easily forms the microphase-separated structure of the coating film is: vinyl (y2-II)>(methyl)allyl (y2- III) > (Meth) acrylonitrile (y2-I).

Further, the ring structure containing one or more nitrogen atoms in the molecule of the compound (Y) is preferably a 5-membered ring or more. In the case of a 3-membered ring or a 4-membered ring, there is a case where an open-loop reaction is caused by heat or an active energy ray.

As the amino group-containing compound (Y) containing an α,β-ethylenically unsaturated double bond group, 2-vinylpyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1 -vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 4-vinylpyridine, 1-vinylindole, 1-vinyl-1H-benzimidazole, 2 -vinylquinoline, 2-vinylisoquinoline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylporphyrin, 1-vinylcarbazole, both industrially and in price For the best.

Further, a compound (C) (hereinafter referred to as a compound (C)) containing an α,β-ethylenically unsaturated double bond group having a cycloalkane skeleton and/or a cyclic olefin skeleton having two or more ring structures will be described. The compound (C) is preferably a compound having two or more cycloalkane skeletons and/or cyclic olefin skeletons and one or more α,β-ethylenically unsaturated double bonds. The compound (C) may, for example, be a compound in which two or more ring structures having a cycloalkane skeleton and/or a cyclic olefin 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 (c1). And a compound having a bridged structure of a cyclic ring like a compound (c2) having a norbornane or norbornene skeleton and a compound (c3) having an adamantane structure. Among these compounds, in terms of excellent heat resistance In other words, the compound (c2) having a norbornane or norbornene skeleton or the compound (c3) having an adamantane skeleton is superior to the compound (c1).

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

The compound (c2) having an α,β-ethylenically unsaturated double bond group having a norbornene and/or a norbornane skeleton has one or more norbornene skeletons and/or a norbornane skeleton, and one The above ethylenically unsaturated double bond may be used, and examples thereof include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dimethylol dicyclopentane di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, isobornyl (meth)acrylate, and the like.

Among the compounds (c2), in particular, the compound (c2') having three or more cyclic skeletons inhibits hardening shrinkage by increasing the volume, and the adhesion is also improved, so that the specific compound (c2') is: Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate Wait.

The compound (c3) having an α,β-ethylenically unsaturated double bond group having an adamantane skeleton is a radically polymerizable compound having three or more cyclic skeletons similar to the compound (c2′), and has heat resistance and Improved adhesion. Specific examples of the compound (c3) include 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl (meth)acrylate. Alkyl-adamantyl ester, 2-propyl-2-adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate Ester, 1,3-adamantyl glycol di(meth)acrylate, 1,3,5-adamantyl tris(meth)acrylate, 3-hydroxy-1,5-di(meth)acrylate Adamantyl ester, 3,5-dihydroxy-1-adamantyl (meth)acrylate, and the like. Among them, in terms of excellent adhesion, 3-hydroxy-1-adamantyl acrylate and 1-methyl-2-gold acrylate are preferred in which the α,β-ethylenically unsaturated double bond is one. Alkyl ester, 2-ethyl-2-adamantyl acrylate.

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

The polyester-based oligomer (d1) may be a terminal of a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol in a main chain skeleton or a hydroxyl group in a polyester chain, and (meth)acrylic acid, maleic acid A compound obtained by esterification of a compound containing an α,β-ethylenically unsaturated double bond group having one or more carboxyl groups in the molecule. Another example may be an ester of the compound (X) such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate by a carboxyl group or a carboxyl group in a polyester chain. Compound obtained by chemical conversion. In addition to this, a polyester oligomer or the like 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).

The polybasic acid may, for example, be an aliphatic, alicyclic or aromatic system, and may be used without particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, and octane. Diacid, maleic acid, chloro maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, cis-butane As the enedic acid anhydride or the like, these aliphatic dicarboxylic acids or anhydrides thereof can be used.

Further, derivatives of succinic anhydride can also be used, for example, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, phenyl succinic anhydride; derivatives of glutaric anhydride, for example It is also possible to use: glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethylglutaric anhydride; derivatives of maleic anhydride, for example, 2-methyl maleic anhydride An anhydride derivative such as 2,3-dimethyl maleic anhydride, butyl maleic anhydride, dodecyl maleic anhydride or phenyl maleic anhydride.

More specifically, as the alicyclic polybasic acid, for example, an alicyclic dicarboxylic acid or an anhydride thereof can be used. Examples of the alicyclic polybasic acid include dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, (1R)-cyclopentane-1β, 2α. -dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, six a saturated alicyclic dicarboxylic acid such as hydrogen terephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid or 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, 4α-dicarboxylic acid, etc. have one in the ring Or 2 unsaturated double bond unsaturated alicyclic dicarboxylic acids.

Further, an alicyclic dicarboxylic acid anhydride may also be used: a derivative of hexahydrophthalic anhydride such as 3-methyl-hexahydrophthalic anhydride or 4-methyl-hexahydrophthalic anhydride. And derivatives of tetrahydrophthalic anhydride, such as 1,2,3,6-tetrahydrophthalic acid A hydrogenated phthalic anhydride derivative such as an acid anhydride or 3-methyl-1,2,3,6-tetrahydrophthalic anhydride.

More specifically, as the aromatic polybasic acid, for example, an aromatic dicarboxylic acid or an anhydride thereof can be used. Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, and 4,4-biphenyl group. Dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindane dicarboxylic acid, 1,2-decanedicarboxylic acid , 1,3-nonanedicarboxylic acid, 4,5-nonanedicarboxylic acid, (-)-1,3-ethanenaphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,2-phenanthrene Examples of the carboxylic acid and the 3,9-nonanedicarboxylic acid and the aromatic dicarboxylic acid anhydride include phthalic anhydride and 4-methylphthalic anhydride.

Further, a polybasic acid may also be used: chlorendic anhydride, HET anhydride, biphenyldicarboxylic anhydride, himic anhydride, endomethylene-1, 2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethyl-1,2,3,6-tetrahydrophthalic anhydride, 1,2-cyclohexane Carboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, octahydro-1,3-dioxo-4,5- An acid anhydride such as isobenzofuran dicarboxylic anhydride.

Further, the polyhydric alcohol may be a relatively low molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500 or a relatively high molecular weight polyol having a number average molecular weight (Mn) of about 500 to 30,000, respectively. Use without special restrictions.

More specifically, examples of the relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, and 3-methyl. Base-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane , 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition molar number is 10 or less), polyoxypropylene glycol (addition molar number is 10 or less), propylene glycol, 1 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butyl Ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol, etc. Aliphatic or alicyclic diols; 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethyl) Oxy)benzene, 4,4'-methylene diphenol, 4,4'-(2-norbornene) diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxy An aromatic diol such as benzene, p-dihydroxybenzene or 4,4'-isopropylidene phenol, or an addition bisphenol such as an alkylene oxide added to bisphenol.

Examples of the raw material bisphenol to be added to the bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

More specifically, examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamine polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by the reaction of the relatively low molecular weight diol with a carbonate or phosgene.

The relatively high molecular weight polyols are also available as commercially available products. For example, commercially available products of the high molecular weight polyester polyols include a Vylon series manufactured by Toyobo Co., Ltd., and a cola manufactured by Kuraray Co., Ltd. Kyowa Paul series made by Li P-P series and Concord Fermentation Chemical Company.

As a commercial item of the high molecular weight polyamine polyol, TPAE617 manufactured by Fuji Chemical Industry Co., Ltd., or the like can be used.

Commercial products of the high molecular weight polycarbonate polyol include, for example, Oxymer N112 manufactured by Perstorp Co., Ltd., PCDL series manufactured by Asahi Kasei Chemical Co., Ltd., and Kuraray manufactured by Kuraray Co., Ltd. Polyol PMHC series, Claret polyol C series, etc.

The commercially available product of the high molecular weight polyurethane polyol may, for example, be a Vylon UR series manufactured by Toyobo Co., Ltd., and a Takelac E158 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. (hydroxyl value = 20, acid value <3), Takelac E551T (hydroxyl value = 30, acid value <3), and Takelac Y2789 (hydroxyl value = 10, acid value < 2) and the like.

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

The polyurethane-based oligomer (d2) may be a compound obtained by reacting a compound having at least one or more isocyanate groups with the compound (X). In addition, another example may also be a reaction of a compound having at least one isocyanate group with the polyol to obtain a terminal isocyanate group urethane prepolymer, and then the urethane prepolymer. A compound obtained by reacting the compound (X). Further, another example may be an amine group which is obtained by reacting a compound having at least one isocyanate group and a polyol to obtain a terminal isocyanate group. An acid ester prepolymer, which further reacts the urethane prepolymer with a compound having at least one amine group to obtain a terminal isocyanate group urethane prepolymer, and then the amine A compound obtained by reacting a urethane prepolymer with the compound (X). Further, a urea-bonding group containing a reaction between an isocyanate group and an amine group is also contained in the polyurethane-based oligomer (d2).

The compound having at least one isocyanate group may, for example, be a monofunctional polyisocyanate or a polyfunctional isocyanate. Specific examples of the compound include aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate.

More specifically, the monofunctional polyisocyanate may, for example, be methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate or isocyanate. Octadecyl acid ester, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, isocyanide Acid (R)-(+)-α-methylbenzyl ester, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate Ester, p-toluenesulfonyl isocyanate, and the like.

Among the polyfunctional isocyanates, more specifically, the aromatic polyisocyanate may, for example, be 1,3-benzene diisocyanate, 4,4'-diphenyl diisocyanate or 1,4-phenylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1, 3,5-triisocyanate benzene, diansamine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like.

The aliphatic polyisocyanate may, for example, be trimethylene diisocyanate or tetra Methyl diisocyanate, hexamethylene diisocyanate (alias: HDI (hexamethylene diisocyanate)), pentamethylene diisocyanate, 1,2-propyl diisocyanate, 2,3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

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

The alicyclic polyisocyanate may be exemplified by 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: IPDI (isophorone diisocyanate), 1,3-cyclopentane) Alkyl diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, and the like.

Further, as the polyurethane-based oligomer, a 2-methylpentane-2,4-diol adduct of the polyisocyanate, a trimer having an isocyanurate ring, or the like may be used in combination. Part of (d2). Further, polyphenylmethane polyisocyanate (alias: PAPI (polyphenylmethane polyisocyanate), naphthalene diisocyanate, and polyisocyanate modified products thereof, etc. may be used. Further, the polyisocyanate modified product may have a carbodiimide group or a urea group. Any one of a keto group, a ureaimine group, a biuret group or an isocyanurate group which reacts with water, or a modified form of two or more of these groups. A reactant of a polyol and a diisocyanate It can also be used as a compound having at least two isocyanate groups.

In addition, more specifically, a compound having an amine group can be used, for example: Ethyldiamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, tris-ethyltetramine, diethylidenetriamine,triaminepropane , 2,2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylidene diamine, hexamethylenediamine 2 -hydroxyethylethylidene diamine, N-(2-hydroxyethyl) propyl diamine, (2-hydroxyethyl propyl) diamine, (di-2-hydroxyethyl stretch ethyl) diamine, (di-2-hydroxyethyl-propyl)diamine, (2-hydroxypropylexeneethyl)diamine, (di-2-hydroxypropylethyl)diamine, piperazine and other aliphatic polyamines; An alicyclic polyamine such as a ketone diamine or a dicyclohexylmethane-4,4'-diamine; a phenyldiamine, a xylylenediamine, a 2,4-methylphenylene diamine, 2 , 6-methylphenylene diamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis-(second butyl An aromatic diamine such as diphenylmethane.

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

As the epoxidized oil type polyepoxy oligomer, α,β-ethylene having one or more carboxyl groups in a molecule such as (meth)acrylic acid or maleic acid can be used, such as an oil such as epoxidized soybean oil. Obtained by the reaction of a compound having a polyunsaturated double bond group. A phenol novolak type polyepoxy oligomer can be used by a phenol novolak type epoxy resin A compound obtained by a reaction of a compound containing an α,β-ethylenically unsaturated double bond group having one or more carboxyl groups in a molecule such as (meth)acrylic acid. As the alicyclic polyepoxy oligomer, a compound containing an α,β-ethylenically unsaturated double bond group having one or more carboxyl groups in a molecule such as an alicyclic epoxy resin and (meth)acrylic acid can be used. Reaction and synthesis.

There are at least one or more α,β-ethylenic unsaturation in the molecule in terms of compatibility with other components in the resin composition, good durability (heat resistance, moist heat resistance), and cohesive density. The weight average molecular weight (hereinafter referred to as Mw) of the double bond group-containing oligomer (D) is preferably in the range of 300 to 30,000. Further, the Mw is preferably in the range of 400 to 20,000. When the Mw of the oligomer (D) exceeds 30,000, the fluidity is lowered, or the compatibility with the compound (M) other than the oligomer (D) is also lowered, so that the active energy ray-polymerizable resin composition is coated. Sexual decline. Further, when the active energy ray-polymerizable adhesive and the coating agent are prepared, the adhesiveness or durability of the polymer coating film may be lowered, or the coating film may be whitened. When the Mw of the oligomer (D) is less than 300, the active energy ray-polymerizable adhesive and the coating agent are applied to various substrates (F) and the like, and the adhesive is likely to be generated. The case where the layer and the coating agent layer are agglomerated and broken.

The compound (M) containing an α,β-ethylenically unsaturated double bond group contained in the active energy ray-polymerizable resin composition of the present invention, except for the compound (Y), the compound (X), and the compound (C) In addition to the oligomer (D), a compound (m) (hereinafter referred to as a compound (m)) containing an α,β-ethylenically unsaturated double bond group may be used as the other component as needed.

The compound (m) is, for example, methyl (meth) acrylate, (A) Ethyl acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and alkyl (meth) acrylate such as stearyl (meth) acrylate; cyclohexyl (meth) acrylate , 1-methyl-1-cyclopentyl (meth)acrylate, 2-oxo-1,2-diphenylethyl (meth)acrylate, (meth)acrylic acid (ethoxylated o-phenyl) Phenol), 1-naphthyl (meth)acrylate, 2-decyl (meth)acrylate, and 2-(meth)acryloxyethyl hexahydrophthalate have one naphthene a skeleton or a cyclic olefin skeleton, or a (meth) acrylate having an aromatic ring; (meth)acrylic acid (meth) acrylic acid ester, (meth)acrylic acid 1-butenyl ester, (meth)acrylic acid 3 -Chloro-2-propenyl ester, 2-propenyl geraldyl (meth)acrylate, 3,7-dimethyloct-6-en-1-yl (meth)acrylate, (meth)acrylic acid Rosin ester, cinnamyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, and (meth)acrylic acid ester, etc., further containing an unsaturated group (meth) acrylate ; (meth)acrylic acid perfluoromethyl ester, (meth)acrylic acid 2-perfluoroethyl ethyl ester And (meth)acrylic acid perfluoroalkyl esters such as 2-(perfluorohexadecyl)ethyl (meth)acrylate; glycidyl (meth)acrylate; 4-(glycidyloxy) (meth)acrylate Butyl ester, (3-methyl-3-oxetanyl)methyl (meth)acrylate, 4-propyl-2-oxotetrahydropyran-4-yl (meth)acrylate (meth)acrylates containing a heterocyclic ring having an oxygen atom, such as an ester, and a 3,4-epoxycyclohexylmethyl (meth)acrylate; (methoxy)methyl (meth)acrylate , 2-(ethoxycarbonyloxy)hexyl (meth)acrylate, 2-(propoxycarbonyloxy)ethyl (meth)acrylate, and 2-(octyloxycarbonyl)(meth)acrylate An aliphatic (meth) acrylate having one carbonyl group such as oxy)butyl ester; 2-oxobutyl decyl ethyl (meth)acrylate, 3-oxobutyl propyl (meth) acrylate, 2,3-bis(oxobutyl) butyl (meth)acrylate, (meth)acrylic acid 2 , an aliphatic (meth) acrylate having two carbonyl groups, such as 3-di(oxobutanyl)hexyl ester and 2,3-bis(oxobutanyl)octyl (meth)acrylate; 3-( Methyl) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl ethyl dimethoxy decane, and 3-(methyl) propylene methoxy propyl (A) oxyalkylene group-containing (meth) acrylates such as tripropoxy decane; 3-sulfopropyl (meth) acrylate; and sulfonyl group-containing sulfolyl (meth) acrylate a metal salt or an ammonium salt of a sulfonyl group-containing (meth) acrylate such as an alkyl (meth) acrylate; a (meth) propylene methoxy dimethyl ethyl ammonium sulfonate; a phosphonic acid group-containing (meth) group such as acrylic acid type phosphorus oxyethyl ester and (meth)acrylic acid phosphorus oxyethylene oxide (ethylene oxide addition molar number: 4 to 10) Acrylates; 2-methoxyethyl (meth)acrylate, 2-ethoxyl (meth)acrylate Ethyl ester, 2-propoxyethyl (meth)acrylate, 3-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 3-butyl (meth)acrylate An alkoxy group-containing (meth) acrylate such as oxyethyl ester or 4-butoxyethyl (meth)acrylate; an alkylene oxide adduct of (meth)acrylic acid; (meth)acrylic acid derivatives; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, di(meth)acrylic acid 2,2 - dimethyl propyl diol, di (methyl) Hydroxy trimethyl ethinyl hydroxy trimethyl acetate acrylate, 2,5-hexanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, di(meth)acrylic acid 2-functional (meth) acrylate such as 2,2-diethyl-1,3-propanediol and 2,5-dimethyl-2,5-hexanediol di(meth)acrylate; 1,1,3,3-propanetriol, trimethylolhexane tris(meth)acrylate, trimethylol octane tris(meth)acrylate, and tris(meth)acrylic acid 1,1, a trifunctional (meth) acrylate such as 1-trihydroxymethylethane; pentaerythritol tetra(meth)acrylate; 2,2-bis(hydroxymethyl)1,3-propanediol tetra(meth)acrylate; a polyfunctional (meth) acrylate such as bis(2,2-bis(hydroxymethyl)1,3-1,3-propanediol polyalkylene oxide; vinyl formate, vinyl acetate, vinyl propionate, Vinyl esters of carboxylic acids such as vinyl butyrate and vinyl stearate; ethylene vinyl acetate, vinyl acetate, 2-ethyl ethoxy hexyl vinyl ether, and 2-ethyl acetonitrile An aliphatic vinyl compound having a mercapto group such as a nonyloxyoctyl vinyl ether; ethyl ethyl Ether, 2-propyl vinyl ether, n-butyl vinyl ether, second butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl, 2-ethylhexylethylene An aliphatic vinyl ether such as an ether or a stearyl vinyl ether; a fluorine-containing vinyl compound such as perfluoroethylene, perfluoropropylene, perfluoro(propyl vinyl ether) or vinylidene fluoride; a compound containing an α,β-ethylenically unsaturated double bond group containing an alkoxyalkylene group such as allyl chlorodecane or (meth)allyltrimethoxydecane; Alkenyl-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulphate; ammonium vinyl sulfonate, sodium vinyl sulfonate, vinyl a metal salt or an ammonium salt such as potassium sulfonate or sodium vinyl sulfosuccinate; ammonium 2-methyl-2-propenyl sulfonate, sodium 2-methyl-2-propenyl sulfonate, etc. a metal salt or an ammonium salt of 2-methyl-2-propenyl sulfonic acid; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide , N-butyl (meth) acrylamide, butenylamine, maleimide, fumaride, mesaconamine, citraconazole, itaconamide, and 2- An aliphatic (meth) acrylamide such as methyl propane-2-enylamine; N-methoxymethyl (meth) acrylamide, N-methoxyethyl (methyl) Acrylamide, N-methoxyhexyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N- Butoxy-octyl (meth) acrylamide, N,N-bis(methoxymethyl)(meth)acrylamide, and N,N-bis(ethoxymethyl)(methyl) N-alkoxy-containing (meth) acrylamides such as ketamine; N-(2-oxobutyl decylethyl)(methyl) decylamine, N-(2-oxobutylphosphonyl) (meth) acrylamide, and (meth) acrylamide having a carbonyl group such as diacetone (meth) acrylamide; (meth) propylene sulfonamide, tert-butyl-(methyl) a sulfonic acid-containing (meth) acrylamide such as (meth) acrylamide-methyl-1-propanesulfonic acid; (meth)acrylonitrile, itacononitrile, a compound containing a nitrile group containing an α,β-ethylenically unsaturated double bond group, such as 2-acrylonitrile and 2-cyanoethyl (meth)acrylate; (meth)allyl esters of saturated carboxylic acids such as (meth)allyl acetate, (meth)allyl propionate, and trimethylvinyl acetate; glycidyl cinnamate, allyl shrinkage Glycidyl ether, and glycidyl group-containing vinyl esters such as 1,3-butadiene monooxirane; (meth)acetic acid (meth)allyl ester, acetaminopropionate (meth)allyl ester, C Aliphatic (meth)allyl compounds having a mercapto group such as (meth) allysyl mercaptoacetate and (meth)allyl butyl decyl acetate; vinyl chloride, vinylidene chloride, and allylic acid Vinyl esters such as chlorine; allenes such as allene, 1,2-butadiene, 1,3-butadiene, and 2-methyl-1,3-butadiene; cis- Diallyl succinate, diallyl 2-methylidene succinate, vinyl (E)-but-2-enoate, (Z)-octadec-9-enoate, and a compound containing an α,β-ethylenically unsaturated double bond group containing an unsaturated bond, such as 9Z, 12Z, 15Z)-octadec-9,12,15-trienoic acid vinyl ester; ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-tetradecene, 1-triacontene, 1-octadecene Iacontene), 1-tetracontene, and the like, and mixtures thereof; olefins such as polybutene-1, polypentene-1, and poly-4-methylpentene-1. It is not particularly limited to these compounds. These compounds may be used alone or in combination of two or more.

From the viewpoint of reactivity, the compound (m) is preferably a compound having a (meth) acrylonitrile group. Further, as an active energy ray polymerizable adhesive In the case of the coating agent, from the viewpoint of the active energy ray polymerization rate, it is preferred to contain a bifunctional or higher (meth) acrylate.

In addition, use of glycidyl (meth)acrylate, 4-(glycidoxy)butyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate And a (meth) acrylate having a three-membered ring or a 4-membered ring having an oxygen atom, such as a (meth)acrylic acid -3,4-epoxycyclohexylmethyl ester, as a ?,? In the case of the compound (m) having an ethylenically unsaturated double bond group, it is preferred to use a known photoacid generator (hereinafter sometimes referred to as a cationic polymerization initiator (KE)) as needed. Thereby, crosslinking is carried out, and an adhesive layer or a coating agent layer excellent in durability against heat or humidity can be formed. Such a cationic polymerization initiator (KE) can be exemplified by, for example, UVACURE 1590 (manufactured by Daicel Cytec Co., Ltd.) and CPI-110P (manufactured by San-Apro Co., Ltd.). Nippon Salt, or IRGACURE 250 (manufactured by Ciba Specialty Chemicals), WPI-113 (made by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (Rhodia Japan) Manufacture), etc.

A preferred ratio of the component constituting the compound (M) containing an α,β-ethylenically unsaturated double bond group is preferably α,β-ethylenic unsaturation in the active energy ray-polymerizable resin composition. When the total amount of the compound (M) having a double bond group is 100% by weight, the compound (X) is 0% by weight to 70% by weight, the compound (Y) is 0% by weight to 95% by weight, and the compound (C) is 0%. The weight % to 70% by weight, the oligomer (D) is 0% by weight to 50% by weight, and the other compound (m) containing the α,β-ethylenically unsaturated double bond group is 0% by weight to 50% by weight. . Among them, preferred is compound (Y) The total amount of the compound (X) is 10% by weight or more and 100% by weight or less. When the total of the compound (Y) and the compound (X) is less than 10% by weight, the solubility of the boric acid and/or the boric acid derivative may be poor, and it may not become a uniform system, or in the case where the liquid is allowed to stand, over time. A problem such as crystallization and precipitation.

The boric acid and the boric acid derivative contained in the active energy ray-polymerizable resin composition of the present invention will be described. Boric acid and boric acid derivatives have an interaction with a hydroxyl group-containing compound (X) containing an α,β-ethylenically unsaturated double bond group, and/or an α,β-ethylenically unsaturated double bond containing an amine group The compound (Y) of the group forms a salt, and a stable and uniform active energy ray-polymerizable binder and a solution of a coating agent can be formed even without water or an organic solvent. The adhesive and the coating agent are hardened by an active energy ray to form a coating film in which boric acid and a boric acid derivative are bonded to a hydroxyl group derived from the compound (X) and/or an amine group derived from the compound (Y). . Further, boric acid and a boric acid derivative have an effect of bonding to a surface functional group of a substrate (F) to be described later to improve adhesion. The boric acid and the boric acid derivative may be used singly or in combination.

The boric acid derivative of the present invention can be suitably used without limitation as long as it is a compound having one or more BOH bonds in one molecule or a plurality of boron-containing compounds which can be hydrolyzed in the presence of water to form one or more BOH bonds. use. Specific but non-limiting examples of the boronic acid derivative include a boric acid oxide (for example, B ₂ O ₃ ); and are obtained by a reaction of boric acid with an alcohol or phenol, for example, trimethyl borate or triethyl borate. , tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, triisopropyl borate, tri-p-pentyl borate, triphenyl borate, trimethoxyboroxine, Boric acid esters such as tris-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropylamine borate, mannitol borate, glyceryl borate, and triisopropanolamine borate.

Further, the boronic acid derivative of the present invention also contains a derivative of boric acid. For example, alkylboronic acid, ethylboronic acid, butylboronic acid, and alkylboronic acid or alkenylboronic acid such as cyclohexylboronic acid; phenylboronic acid, naphthaleneboronic acid, and arylboronic acid such as bariumboronic acid, or the boronic acid A substituted aryl boronic acid having an arbitrary substituent on the aryl group.

Further, other amine group-containing borate salts and tertiary acid amine salts of boric acid are also useful. Examples of such a boron-containing compound include 2-(β-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborolan, 2-(β- Diethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborolane, 2-(β-dimethylaminoethoxy)-4 ,4,6-trimethyl-1,3,2-dioxaborolane, 2-(β-diisopropylaminoethoxy)-1,3,2-dioxaborane Hexane, 2-(β-diisopropylaminoethoxy)-4-methyl-1,3,2-dioxaborolane, 2-(γ-dimethylaminopropoxyl -1,3,6,9-tetraoxa-2-borane undecane, and 2-(β-dimethylaminoethoxy)-4,4-(4-hydroxybutyl) -1,3,2-dioxaborolane, but is not limited to these compounds.

Further, among the boric acid derivatives, a metal salt of boric acid (that is, a metal borate) may be mentioned under the condition that it can be easily dissociated in an aqueous medium to form boric acid. Suitable examples of the metal borate include, for example, calcium borate, potassium borate (e.g., potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate), and sodium borate (e.g., sodium perborate, 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 an organic oligomer containing a boron-containing site and a polymer compound. For example, it is preferred to react with a boric acid ester and/or a boric acid ester by a polymer borate such as an active hydrogen-containing polymer (for example, a hydroxyl functional group-containing acrylic polymer or a polyoxyalkylene polymer). A compound obtained by forming a polymer having a borate ester group.

Examples of the polymer which is a raw material of the polymer borate include any of a plurality of active hydrogen-containing polymers. For example, it is preferably selected from the group consisting of an acrylic polymer, a polyester polymer, and a polyurethane polymer. And at least one of the groups consisting of polyether polymers.

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

Further, in the present invention, the boric acid derivative preferably has three or more hydroxyl groups in one molecule. Examples of the boronic acid derivative having three or more hydroxyl groups in one molecule include 1,4-benzenediboronic acid (having a hydroxyl number of 4), tetrahydroxydiborane (having a hydroxyl number of 4), and a triethanolamine borate (the number of hydroxyl groups is 3). )Wait.

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

If it is less than 0.1 part by weight, the desired adhesive force cannot be exhibited, and if it is 20 parts by weight or more, it may be precipitated as time passes, or may be used as a solution. A situation in which the degree is excessively increased and gelation occurs.

It is particularly preferably 0.3 parts by weight or more and 12 parts by weight or less. It is particularly preferably 0.3 parts by weight or more and 7 parts by weight or less.

Further, in consideration of 100 parts by weight of the active energy ray-polymerizable composition, the boric acid and/or boric acid derivative is preferably from 0.1 part by weight to 20 parts by weight, particularly preferably from 0.3 part by weight to 12 parts by weight. It is particularly preferably from 0.3 part by weight to 7 parts by weight.

The active energy ray-polymerizable resin composition may further comprise an active energy ray polymerization initiator (E). The active energy ray polymerization initiator (E) may, for example, be a radical polymerization initiator (RE) and the above cationic polymerization initiator (KE).

Specifically, the radical polymerization initiator (RE) may, for example, be 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, anthrone, Benzaldehyde, hydrazine, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxaindole Ketone, camphorquinone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one. Commercially available products include, for example, Irgacure 184, 907, 651, 1700, 1800, 819, 369, 261, DAROCURE-TPO (manufactured by BASF Corporation, 2, 4, 6- Trimethyl benzhydryl-diphenyl-phosphine oxide), DAROCURE 1173 (Merck), Esacure KIP150, TZT (Nihon Siber Hegner) Made by the company), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, it is possible to use self having at least one (meth)acryl fluorenyl group in the molecule. A radical polymerization initiator (RE) of the present invention is used as the radical polymerization initiator.

Then, as described above, the cationic polymerization initiator (KE) (sometimes referred to as an acid generator) may be exemplified by: UVACURE 1590 (manufactured by Daicel Co., Ltd.), CPI-110P (manufactured by Sanya Pro) ) 鋶 salt-based cationic initiator, 佳 固 固 (IRGACURE) 250 (manufactured by BASF Corporation), WPI-113 (made by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (manufactured by Rhohiya Corporation, Japan) Cationic starter.

Further, in order to improve the performance of the cationic polymerization initiator (KE), an active energy ray sensitizer may be used in combination. Examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, and chlorine-containing compounds, or nitriles or other nitrogen-containing compounds. Preferably, an anthraquinone, a benzophenone type, a thioxanthone type, a perylene, a phenothiazine, and a rose Bengal are used.

These active energy ray polymerization initiators (E) may be used singly or as a mixture of two or more kinds. In the first aspect of the invention, it is preferred to contain a radical polymerization initiator (RE).

In terms of reactivity, the ratio of the active energy ray polymerization initiator (E) is preferably 100 parts by weight relative to the compound (M) containing an α,β-ethylenically unsaturated double bond group, and The active energy ray polymerization initiator (E) is contained in an amount of from 0.01 part by weight to 20 parts by weight.

(Description of the second aspect)

Then, in the second aspect of the present invention, that is, boric acid and/or boric acid derivatives are The active energy ray-polymerizable resin composition (hereinafter sometimes referred to as "cationic active energy ray-polymerizable resin composition") used in combination with the cationically polymerizable composition (K) will be described.

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

First, the cationically polymerizable compound (K) in the cationic active energy ray-polymerizable resin composition will be described.

The cationically polymerizable compound (K) contains all compounds polymerized by a cation. From the viewpoint of utilizing the reactivity of the active energy ray, the cationically polymerizable compound (K) is preferably a cyclic hetero compound, and particularly preferably an oxirane compound (k1) which is a 3-membered cyclic ether. Further, the vinyl ether compound in the compound (M) is also subjected to cationic polymerization, and thus can be used.

Examples of the oxirane compound (k1) include ethylene oxide, methyl oxirane, phenyl oxirane, 1,2-diphenylethylene oxide, and methine oxirane. , oxiranylmethyl, oxiranyl methanol, ethylene oxide carboxylic acid, (chloromethyl)oxirane, (bromomethyl)oxirane, and oxiranyl acetonitrile And other compounds having an aliphatic cyclic ether group; 3,4-oxirane cyclohexanecarboxylic acid 3,4-oxirane cyclohexylmethyl ester, 3,4-ethylene oxide-6- Methylcyclohexanecarboxylic acid 3,4-oxirane-6-methylcyclohexylmethyl ester, bis(3,4-oxiranecyclohexanecarboxylic acid) ethyl ester, adipic acid bis ( 3,4-oxirane cyclohexylmethyl)ester, bis(3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4- A compound having a three-membered cyclic ether group bonded to an alicyclic ring such as oxirane cyclohexyl methyl ether or a dicyclopentadiene dioxide. In addition, these The compound in which one or more of the hydrogen atoms in the compound having a three-membered cyclic ether group is bonded to another chemical structure can be an oxirane compound (k1).

The oxirane compounds exemplified herein may be used singly or in combination of a plurality of oxirane compounds.

The oxirane compound (k1) has an oxirane equivalent of usually 30 g/eq to 3000 g/eq, preferably 50 g/eq to 1500 g/eq. When the ethylene oxide equivalent is 30 g/eq or more, the cured optical film is excellent in flexibility and has high adhesive strength. On the other hand, when it is 3000 g/eq or less, compatibility with other components is excellent.

In order to improve heat resistance or moist heat resistance, the oxirane compound (k1) is particularly preferably an oxirane compound (k1-1) having an aromatic ring.

The oxirane compound (k1-1) having an aromatic ring may contain a substituent derived from an aromatic ring. The substituents may be exemplified by benzene, toluene, xylene, styrene, 1,2,3-trimethylbenzene (methimellitene), pseudocumene (meth), 1,3,5-trimethyl (mesitylene), Alkene, 1,2,3,4-tetramethylbenzene, isodurene, durene, cymene, and melitene may be bonded to other chemical structures. A hydrogen atom in the benzene derivative is removed in the form of one or more. Examples of the substituent include phenyl, phenyl, tolyl, methylphenyl, benzyl, benzylidene, benzylidene, xylyl, xylylene, phthalylidene. , m-xylylene, p-xylylene, phenethylidene, phenethylidyne, styryl, styrylidene, as-false As-pseudocumyl, v-pseudo-, s-pseudo, mesityl, cumenyl, α-cumyl, hydrogen cinnamate, cinnamyl, cinnamylidene , cinnamylidyne, duryl, durylene, thymyl, carvacryl, cuminyl, cuminylidene, Neophyl, neon (xenyl), benzhydryl, benzhydrylidene, trityl, and the like.

Other examples include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, and cycloheptadiene. And a cycloolefin such as cyclooctadiene; and [4n+2] annulene having a carbon number of 3 or more in a ring other than benzene.

Further, for example, an aromatic ring in which a group in which one or more hydrogen atoms in the following cyclic compound are removed may be bonded to another chemical structure: an aromatic group such as a biphenyl group or a triphenylmethane Cyclic compounds; pentalene, indene, indan, ninhydrin, naphthalene, tetralin, decalin, sapotalene , cadalene, eudalene, naphthol, menadiol, gossypol, naphthoquinone, lawsone, walnut (juglone), menadione, plumbagin, phthiocol, echinochrome A, alkannin, shikonin, Acetonaphthone, naphthoic acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphthone, naphthylamine Naphthionic acid, naphthionate, naphthionyl, dansyl, 2-naphthol-8-sulfonic acid, flavianic acid, chromotropic acid, neocupferron, azulene, chamazulene, melon Carbon condensed bicyclic compounds such as guaiazulene, heptalene, octalene, purpurogallin; asymmetry-as-indacene, symmetry- Anthraquinone, asymmetric-hydrothionrene, symmetry-hydrothionene, biphenyl, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene ), perinaphthene, phenanthrene, phenanthryl, phenanthrylium, phenanthrylidene, phenanthrylene, phenanthrol, 3,4-phenanthrene Morphos, phenanthrone, phenanthraquinone, pimanthrene, retene, anthraquinone, sulfhydryl, anthrylium, anthrylidene, extensor Anthrylene, anthrol, anthranol, anthrarobin, anthralin, ninhydrin Ithranol), anthroyl, anthrone, bianthrone, anthraquinonyl, anthraquinonylene, alicarin, anthraquinone (quinizarin), anthrarufin, chrysazin, anthragallol, purpurin, flavopurpurin, anthrapurpurin, quinain (quinalizarin), tectoquinone, chrysophanol, chrysophanic acid, emodin, rhein, kermesic acid, rouge Carbon condensed tricyclic compounds such as carminic acid, dianthrimide, anthrimide, chrysamminic acid, colchicine, etc. Trindene), trindane, 1,2-fluoranthene, acephenanthrylene, acephenanthrene, aceanthrylene, aceanthrene, hydrazone Triphenylene, pyrene, (chrysene), tetraphene, tetracene, naphthacene, rubrene, tetracycline, chlorotetracycline, oxytetracycline, pleiadene, benzo Carbon condensed tetracyclic compounds such as benzanthrone; picene, pentaphene, pentacene, tetraphenylene, cholanthrylene, 1,2 - Carbon condensed pentacyclic compounds such as dihydrobenzene [j] cholanthrene; corannulene, benzo[c]picene (fulminene), anthanthrene ), dibenzo[de,mn]tetracene (zethrene), hexahelicene, hexaphene, hexacene, jade red (rubicene), coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, three Benzo[de,kl,rst]pentan (tribenzo[de,kl,rst]pentaphene)(terrylene), thick tetrabenzoxanthene (naphthacenonaphthacene), nonaphene, nonacene, Viollanthrene, violanthrone, isoviolanthrene, isoviolanthrone, ovaleene, decaphene, decaceene, decacyclomethene Decacyclene), carbon condensed ring-based compounds having a ring number of 6 or more, such as pentacenopentacene, quaterrylene, and hexacenohexacene.

The oxirane compound (k1-1) having an aromatic ring is particularly preferably a glycidyl ether of bisphenol A excellent in heat resistance and adhesion, a glycidyl ether of bisphenol F, and a 1,3-phenylene double ( Methylene) bis(7-oxabicyclo[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 an oxetanyl group-containing compound of a 4-membered cyclic ether, a cyclic ether compound of 5 or more rings, and two or more oxygen atoms or A compound of a hetero group other than oxygen.

The oxetane-containing compound may, for example, be 3-ethyl-3-hydroxymethyloxetane or 1,4-bis[(3-ethyl-3-oxetanyl)methoxy group. Methyl]benzene, bis(1-ethyl-3-oxetanyl)methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, and 3-ethyl-{(3-triethoxydecylpropoxy)methyl}oxyl Heterocyclic butane and the like. Oxygen The heterocyclic butyl compound may be used singly or in combination of two or more.

Examples of the other cyclic hetero compound (k2) include a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing cyclic compound. The cyclic ester compound is preferably a lactone. The cyclic formal compound is more preferably a compound selected from the group consisting of dioxolane, dioxane and trioxane.

The cyclic carbonate can be subjected to a method of depolymerizing a polymer obtained by a reaction of a diol with a dialkyl carbonate (refer to Japanese Laid-Open Patent Publication No. Hei 2-56356), or a corresponding alkylene oxide and carbon dioxide. The reaction to synthesize. The cyclic carbonate has a 5-membered ring, a 6-membered ring or a 7-membered ring or more, a 5-membered ring is contained in the 1,3-dioxolane, and a 6-membered ring is contained in the 1,3-dioxane. The 7-membered ring is contained in the 1,3-dioxepane. However, since the carbon at the 2-position is a carbonyl carbon, it is independently classified into a cyclic carbonate. Specific examples thereof include, for example, ethyl carbonate (also known as 1,3-dioxol-2-one), propyl carbonate, butyl carbonate, 4-pentyl-1,3- Dioxolane-2-one, 4-butyl-1,3-dioxol-2-one, 4-propyl-1,3-dioxol-2-one , 4-(isopropoxymethyl)-1,3-dioxol-2-one, 4-hexyl-1,3-dioxol-2-one, 4-hexyl- 5-methylene-1,3-dioxol-2-one, 4,5-dimethyl-1,3-dioxol-2-one, 4,4,5, 5-tetramethyl-1,3-dioxol-2-one, 4-octyl-1,3-dioxol-2-one, 4-mercapto-5-vinyl -1,3-dioxol-2-one, 4-mercapto-1,3-dioxol-2-one, 4,5-bismethylene-1,3-di Oxolane-2-one, 4,4-dimethyl-1,3-dioxolane-2-one, 4,4,5,5-tetraethyl-1,3-di Oxolane-2-one, hexahydro-1,3-benzodioxole-2-one, 4-isopropyl-4-methyl-5-methylene- 1,3- Dioxolane-2-one, ethylene carbonate, allyl ethyl acrylate, allyl succinic anhydride, 4-(2-oxo-1,3-dioxolane-4 5-membered cyclic carbonates such as methylaminomethylmercaptooxymethyl)-1,3-dioxolane-2-one; for example, trimethylene carbonate (also known as 1,3-diethyl carbonate) Oxan-2-one), 4-methyl-1,3-dioxan-2-one, 2,2-dimethoxypropane-1,3-diester, 5-methyl-1 , 3-dioxan-2-one, 5,5-dimethyl-1,3-dioxan-2-one (also known as neopentyl glycol carbonate), 5-methyl-5-propane -1,3-dioxan-2-one, 5-hydroxymethyl-5-methyl-1,3-dioxan-2-one, 4-phenyl-1,3-dioxane- 2-keto, 5-(hydroxymethyl)-5-ethyl-1,3-dioxan-2-one, 4-methylene-1,3-dioxan-2-one, 5,5 - dimethyl-4-vinyl-1,3-dioxan-2-one, 5-cyano-5-methyl-1,3-dioxan-2-one, 5-(2-oxo 6-membered cyclic carbonates such as 1,3-dioxalan-4-ylmethoxy)-5-ethyl-1,3-dioxan-2-one; for example, tetramethylene carbonate Base ester (also known as 1,3-dioxan-2-one), 5-methyl-1,3-dioxepane-2-one, 4-methyl-1,3 -dioxoheptan-2-one, 5,5- Dimethyl-1,3-dioxepane-2-one, 5-phenyl-1,3-dioxepane-2-one, 4-phenyl-1,3-dioxo Heterocyclic heptane-2-one, 4-[1-(phenylthio)cyclohexyl]-1,3-dioxepane-2-one, 5,5'-(extended ethyldithio 7-membered cyclic carbonates such as bistrimethylene) bis(1,3-dioxan-2-one), and in terms of reactivity, it is preferred to use ethyl carbonate and carbonic acid 5-membered cyclic carbonates such as esters and glycerol carbonates.

Further, in the compound (M) containing an α,β-ethylenically unsaturated double bond group, a vinyl ether which can be subjected to cationic polymerization may, for example, be methyl vinyl ether, ethyl vinyl ether or 2-chlorovinyl ether. N-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl Enyl ether, n-pentyl vinyl ether, isoamyl vinyl ether, third amyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, positive Vinyl ethers such as heptyl vinyl ether, n-octyl vinyl ether, mercapto vinyl ether, dipentaerythritol hexavinyl ether.

The boric acid and the boric acid derivative contained in the cationic active energy ray-polymerizable resin composition will be described. Further, a preferred system for the interaction with the cationically polymerizable compound (K) will be specifically described herein. The boric acid and the boric acid derivative interact with the cationically polymerizable compound (K) to form a stable and uniform solution of the active energy ray-polymerizable resin composition without using an aqueous or organic solvent, and harden the composition by an active energy ray. Thereafter, a coating film formed by bonding a hydroxyl group formed by polymerization of the cationically polymerizable compound (K) is formed. Moreover, it has an effect of forming a bond with the surface functional group of the base material (F) mentioned later, and adhesiveness is favorable. Boric acid can of course be used as such an effect, and the boric acid derivative described below can also 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 per se or a plurality of boron-containing compounds which can be hydrolyzed in the presence of water to form one or more BOH bonds. Specific boronic acid derivative but non-limiting examples include: boric oxide (e.g. B ₂ O _3), orthoboric acid, metaboric acid, perborates, boric times, boric acid (boronic acid), borinic (borinic acid a boric acid; for example, a compound obtained by the reaction of boric acid with an alcohol or phenol, for example: trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, boric acid Isopropyl ester, tri-p-pentyl borate, triphenyl borate, trimethoxyboroxane terpolymer, tris-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropylamine borate, boric acid Borate esters such as mannitol, boryl glyceride, and triisopropanolamine borate.

Further, the boronic acid derivative of the present invention also contains a derivative of boric acid. For example, an alkyl group or an alkenylboronic acid such as methylboronic acid, ethylboronic acid, butylboronic acid or cyclohexylboronic acid; an arylboronic acid such as phenylboronic acid, naphthaleneboronic acid or decanoic acid or an aryl group of the boronic acid may be mentioned. A substituted aryl boronic acid of any substituent.

Further, other amine group-containing borate and tertiary acid amine salt of boric acid can be used. Examples of such a boron-containing compound include 2-(β-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborolan, 2-(β- Diethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborolane, 2-(β-dimethylaminoethoxy)-4 ,4,6-trimethyl-1,3,2-dioxaborolane, 2-(β-diisopropylaminoethoxy)-1,3,2-dioxaborane Hexane, 2-(β-diisopropylaminoethoxy)-4-methyl-1,3,2-dioxaborolane and 2-(β-dimethylaminoethoxy) 4-) 4-(4-hydroxybutyl)-1,3,2-dioxaborolane, but is not limited to these compounds.

Further, among the boric acid derivatives, a metal salt of boric acid (that is, a metal borate) may be mentioned under the condition that it can be easily dissociated in an aqueous medium to form boric acid. Suitable examples of the metal borate include, for example, calcium borate, potassium borate (e.g., potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate), and sodium borate (e.g., sodium perborate, sodium metaborate). , sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, six Sodium borate and sodium octaborate). Similarly, ammonium borate can also be used.

Further, examples of the boric acid derivative include an organic oligomer containing a boron-containing moiety and a polymer compound. Suitable examples include the reaction of a boric acid ester (for example, an active hydrogen-containing polymer (for example, a hydroxyl functional group-containing acrylic polymer or a polyoxyalkylene polymer)) with boric acid and/or a boric acid ester. A compound formed by forming a polymer having a borate ester group.

Among the polymers suitable for the purpose, any of a variety of active hydrogen-containing polymers may be mentioned, among which, for example, self-polyacrylic acid polymers, polyester polymers, polyurethane polymers, polyether polymers Choose at least one of them.

Further, in the present invention, the boric acid derivative preferably has three or more hydroxyl groups in one molecule. Examples of the boronic acid derivative having three or more hydroxyl groups in one molecule include 1,4-benzenediboronic acid (having a hydroxyl number of 4), tetrahydroxydiborane (having a hydroxyl number of 4), and a triethanolamine borate (the number of hydroxyl groups is 3). )Wait.

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

When the boric acid and/or the boric acid derivative is 0.1 part by weight or more, the desired adhesive strength can be exhibited, and if it is 0.3 part by weight or more, it becomes more remarkable. In addition, when it is 20 parts by weight or less, it is difficult to cause precipitation over time, or to cause gelation of the viscosity of the solution excessively, and it is especially preferable that it is 7 parts by weight or less.

By using the cationically polymerizable compound (K), it is possible to improve the appearance defect of the laminate due to the large hardening shrinkage.

Further, by using a boric acid and/or a boric acid derivative in combination, a hydroxyl group formed by polymerization of the cationically polymerizable compound (K) forms a bond with a surface functional group of the substrate to improve adhesion.

The cationic active energy ray-polymerizable resin composition preferably further contains a cationic polymerization initiator (KE).

As described above, the cationic polymerization initiator (KE) may be a cesium salt cation initiator such as UVACURE 1590 (manufactured by Daicel Co., Ltd.) or CPI-110P (manufactured by Sanya Pro). A sulfonium-based cationic initiator such as Irgacure 250 (manufactured by BASF Corporation), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (manufactured by Rhoji Co., Ltd.).

The compounding ratio of the cationic polymerization initiator (KE) is preferably from 0.01 part by weight to 20 parts by weight per 100 parts by weight of the active energy ray-polymerizable composition.

(Description of the third aspect)

Finally, the third aspect of the present invention, that is, the activity of combining a boric acid and/or a boronic acid derivative with a compound (M) containing an α,β-ethylenically unsaturated double bond group and a cationically polymerizable composition (K) The energy ray polymerizable resin composition (hereinafter sometimes referred to as a mixed active energy ray polymerizable resin composition) will be described.

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

In addition, boric acid and/or boric acid derivatives, α,β-ethylenically unsaturated double bond groups Specifically, the compound (M) and the cationically polymerizable compound (K) can be used as the exemplified compounds described in the first aspect and the second aspect.

The compound (M) containing an α,β-ethylenically unsaturated double bond group of the mixed active energy ray-polymerizable resin composition contains all compounds having an α,β-ethylenically unsaturated double bond in the molecule. From the viewpoint of utilizing the reactivity of the active energy ray, the compound (M) containing an α,β-ethylenically unsaturated double bond is preferably designed to have a total weight of the α,β-ethylenically unsaturated double bond. The (meth)acrylonitrile group accounts for 50% by weight to 100% by weight.

Specifically, the compound (M) preferably contains a compound (X) selected from the group consisting of a hydroxyl group-containing α,β-ethylenically unsaturated double bond group, and having two or more naphthene skeletons and/or cyclic olefins. One or more compounds in the group consisting of the compound (C) having an α,β-ethylenically unsaturated double bond group of the skeleton.

A preferred ratio of the compound (M) containing an α,β-ethylenically unsaturated double bond group, a cationically polymerizable compound (K), and a boric acid and/or a boric acid derivative is 100 parts by weight of the active energy ray-polymerizable composition. The compound (M) containing an α,β-ethylenically unsaturated double bond group is 9 parts by weight to 99 parts by weight, and the cationically polymerizable compound (K) is 0.5 parts by weight to 90 parts by weight, derived from boric acid and/or boric acid. The amount is from 0.1 part by weight to 20 parts by weight.

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

If the compound (M) containing an α,β-ethylenically unsaturated double bond group is less than 9 parts by weight, On the other hand, the cationically polymerizable compound (K) is increased, and it is easy to cause hardening failure due to moisture or humidity in the substrate. When the compound (M) containing an α,β-ethylenically unsaturated double bond group is more than 99 parts by weight, the curing shrinkage is increased, and when the film substrate is bonded, wrinkles are generated and appearance defects are likely to occur. When the boric acid and/or the boric acid derivative is less than 0.1 part by weight, the desired adhesive strength cannot be exhibited, and if it is 20 parts by weight or more, precipitation occurs over time, or the viscosity of the solution is excessively increased. The situation of problems such as gelation.

The mixed active energy ray-polymerizable resin composition can suppress α,β-ethylenicity by using a compound (M) containing an α,β-ethylenically unsaturated double bond group and a cationically polymerizable compound (K). The compound (M) having an unsaturated double bond group has a poor curing shrinkage and a poor appearance of the laminate, or a characteristic of the cationically polymerizable compound, that is, a hardening failure due to moisture.

Further, a hydroxy group formed by polymerization of the compound (X) and/or the cationically polymerizable compound (K) in combination with boric acid and/or a boronic acid derivative forms a bond with a hydroxyl group of the substrate, and the adhesiveness is improved.

The active energy ray-polymerizable initiator (E) may be further contained in the mixed active energy ray-polymerizable resin composition. The polymerization reaction can be promoted by using the active energy ray polymerization initiator (E). Further, examples of the active energy ray polymerization initiator (E) in the mixed active energy ray-polymerizable resin composition include a radical polymerization initiator (RE) and a cationic polymerization initiator (KE).

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

The radical polymerization initiator (RE) and the cationic polymerization initiator (KE) may be used singly or in combination, and are preferably used in combination.

The initiator (the total amount of the radical polymerization initiator (RE) and the cationic polymerization initiator (KE)) is preferably contained in an amount of 0.01 part by weight based on 100 parts by weight of the active energy ray polymerizable composition. 20 parts by weight.

Hereinafter, the items "solvent, sensitizer, additive, viscosity, film thickness, coating method, substrate, laminate, and lamination method" which are common to the "first aspect to the third aspect" will be disclosed.

(solvent)

In the present invention, from the viewpoint of equipment or energy required for the drying step, it is preferred that the material is substantially free of water or an organic solvent. However, in the case where the active energy ray polymerization initiator (E) is insoluble to the compound (M) containing an α,β-ethylenically unsaturated double bond group, and in the case of high viscosity, in order to carry out the active energy ray The polymerization initiator (E) is dissolved, and may also contain a small amount of water or an organic solvent. The content of the water or the organic solvent in the active energy ray-polymerizable resin composition is preferably 5% by weight or less. The organic solvent which can be used is not particularly limited, and specifically, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, acetic acid may be further added. The active energy ray-polymerizable resin composition may be adjusted by adjusting the viscosity of the active energy ray-polymerizable resin composition, such as butyl ester, cyclohexane, toluene, and xylene, and other organic solvents such as a hydrocarbon solvent, and water. Heating causes the viscosity to decrease.

(sensitizer)

Further, when a cationic polymerization initiator (KE) is used as the active energy ray polymerization initiator (E), in order to improve the performance of the cationic polymerization initiator (KE), an active energy ray sensitizer may be used in combination. The active energy ray sensitizer is preferably an amine, a urea, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile or another nitrogen-containing compound, and is preferably an anthracene-based sensitizer. Or benzophenone, thioxanthone or anthraquinone, phenothiazine, bengal rose red, and the like.

(additive)

In the active energy ray-polymerizable resin composition of the present invention, an additive may be appropriately formulated in addition to the above-mentioned components as long as it does not impair the effects of the present invention. For example, in terms of reduction in polymerization hardening shrinkage, reduction in thermal expansion rate, improvement in dimensional stability, improvement in elastic modulus, viscosity adjustment, improvement in thermal conductivity, improvement in strength, improvement in toughness, and improvement in coloring, organic or inorganic materials may be blended. Filler. Such fillers can be used: polymers, ceramics, metals, metal oxides, metal salts, and dye pigments. The shape is not particularly limited, and examples thereof include a particulate shape and a fibrous shape. Further, in the case of blending a polymer, it may not be used as a softness imparting agent, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropic imparting agent, a dispersion stabilizer, or a fluidity imparting property. The agent and a filler such as an antifoaming agent are dissolved, semi-dissolved or micro-dispersed in the active energy ray polymerizable adhesive as a polymer blend or a polymer alloy.

(viscosity)

The active energy ray-polymerizable resin composition of the present invention can be used in any form of a liquid, a paste or a film, but is preferably liquid in view of ease of use.

The viscosity of the active energy ray-polymerizable resin composition of the present invention is preferably adjusted depending on the thickness of the composition to be applied or the intended use. For example, when the thickness of the layer is set to 0.1 μm to 6 μm, the viscosity is 1 mPa. s~1500mPa. s, preferably 10 mPa. s~1300mPa. s, especially good for 20mPa. s~1000mPa. s. If the viscosity is higher than 1500mPa. When s is applied to the substrate (F), film application of 0.1 μm to 6 μm cannot be performed, and optical characteristics such as transmittance are deteriorated. On the other hand, if the viscosity is less than 1mPa. s, the film thickness control of the active energy ray polymerizable resin composition layer becomes difficult.

In addition, when the film thickness of the active energy ray polymerizable resin composition layer is 6 μm to 300 μm depending on the intended use, the viscosity is 1500 mPa. s~100,000mPa. s, preferably 3,000 mPa. s~50,000mPa. s. Actually, the viscosity of the resin composition is basically determined by the viscosity of the compound (M) and/or the cationically polymerizable compound (K) containing an α,β-ethylenically unsaturated double bond group. Therefore, by at 1mPa. s~100,000mPa. When the viscosity of the compound (M) and/or the compound (K) is managed within the range of s, the management of the viscosity of the resin composition is facilitated. The adjustment of the viscosity of the embodiment and the application of the resin composition can be easily carried out by adding a solvent to the resin composition.

(film thickness)

When the active energy ray-polymerizable resin composition is used for a laminate of an optical element such as a hard coat film or a polarizing film (also referred to as a polarizing plate) to be described later, the active energy ray-polymerizable resin composition is subjected to film coating. cloth. The thickness of the resin layer formed by coating is preferably from 0.1 μm to 6 μm, more preferably from 0.1 μm to 3 Mm. When it is set to 0.1 μm or more, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain sufficient adhesion or adhesion. On the other hand, when the thickness of the resin layer exceeds 6 μm, there are many cases where no change is observed in characteristics such as adhesion or adhesion.

In the case where the active energy ray-polymerizable resin composition is used for a laminate of an optical element such as a decorative film (refer to a filler sheet for a touch panel), the resin layer formed by coating is used. The thickness is preferably a thick film coating of 6 μm to 300 μm, more preferably 20 μm to 250 μm. When it is less than 6 μm, sufficient stress relaxation property may not be obtained, and when it exceeds 300 μm, coating properties such as streaking may be reduced.

(coating method)

The method of applying the energy ray-polymerizable resin composition of the present invention to a substrate or the like can be exemplified by a Meyer bar, an applicator, a brush, a spray, and a roller. ), gravure coater, die coater, microgravure coater, lip coater, comma coater , a curtain coater, a knife coater, a reverse coater, a spin coater, etc., can be coated according to the film. It is not particularly limited as long as it is used for applications such as cloth or thick film coating.

(active energy line)

The active energy ray-polymerizable resin composition of the present invention is applied onto a substrate by a conventionally known method, and the formed coating layer is irradiated with an active energy ray. In the case of the compound (M) containing an α,β-ethylenically unsaturated double bond group, the polymerization hardening is carried out by cationic polymerization in the case of cationic polymerization (K) by radical polymerization. The irradiation source of the active energy ray is a light source mainly composed of light in a wavelength region of 150 nm to 550 nm, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, or an LED can be preferably used. Lamps, xenon lamps or metal halide lamps. In addition to this, laser light, electron beam, or the like can also be used as an active energy ray for exposure.

The irradiation intensity of ultraviolet rays is preferably from 10 mW/cm ² to 3,000 mW/cm ² . When the light irradiation intensity is less than 10 mW/cm ² , curing takes a long time, and if it exceeds 3000 mW/cm ² , there is a possibility that deterioration of the substrate in various substrates (F) occurs due to heat radiated from the lamp. Therefore, it is not good. The cumulative irradiation amount expressed as the product of the irradiation intensity and the irradiation time is preferably 50 mJ/cm ² to 20,000 mJ/cm ² . When the cumulative irradiation amount is less than 50 mJ/cm ² , the polymerization hardening takes a long time, and if it exceeds 20,000 mJ/cm ² , the irradiation time becomes extremely long and the productivity is poor, which is not preferable. A representative active energy ray-polymerizable resin composition usually requires a cumulative irradiation amount of 1000 mJ/cm ² or more. However, even in the case of a low total irradiation amount of less than 1000 mJ/cm ² , the resin composition of the present invention is favorably polymerized.

(substrate (F))

Next, the substrate (F) will be described.

The base material (F) to which the active energy ray-polymerizable resin composition of the present invention is applied is, for example, a film-form substrate, a glass plate, a paper-processed product, or the like, and is not particularly limited. On the other hand, the active energy ray-polymerizable resin composition of the present invention is used as a substrate for making two or more sheets (F) In the case of a bonded adhesive, it is necessary to use a substrate that easily transmits the active energy ray in order to polymerize the active energy ray. It is particularly preferable to use a transparent film or a transparent glass plate. A substrate that is difficult to pass through the active energy ray, such as wood, a metal plate, a plastic plate, a paper processed product, or the like, may be used for one of the substrates to be bonded, and a transparent film or a transparent glass plate may be used for the other substrate. The polymerization is hardened by irradiation from the side of the transparent film or the transparent glass plate.

The active energy ray-polymerizable resin composition of the present invention is preferably a film-form substrate in the substrate (F). Examples of the film-form substrate include film-like substrates such as cellophane, various plastic films, and paper, and it is preferable to use various transparent plastic films. Further, the film-form substrate may be a single-layer substrate as long as it is transparent, or a substrate in a multilayer state in which a plurality of layers are laminated.

(Description of laminated body)

Here, a laminate in which one layer or both surfaces of the base material (F) are laminated using an active energy ray-polymerizable resin composition is generally described.

The polymerization reaction using the active energy ray of the active energy ray-polymerizable resin composition of the present invention is preferably used for forming a transparent film including the film-form substrate in the substrate (F), and at least at the transparent film. A laminate of active energy ray polymerizable resin composition layers on one side.

In the present invention, the laminate of the transparent film can be obtained in the following manner.

The resin composition of the present invention can be applied to one surface of the transparent film as a film-form substrate, and another transparent film can be laminated on the surface of the resin composition layer, and then coated on one or both sides of the laminate. Resin composition, and further, layering on another A transparent film, glass, or a transparent molded body to obtain a laminate.

The active energy ray polymerization reaction of the resin composition of the present invention used as an adhesive is carried out at the time of coating the resin composition, or at the time of lamination, and further, after spraying the active energy ray, but preferably after lamination The polymerization is carried out by irradiating the active energy ray.

In the present invention, the transparent film can be used for an optical film such as a display communication device such as a display or a touch panel.

(Description of laminated body for optical element)

Here, the laminated body for optical elements is generally described.

The basic laminated structure of the optical laminate is a layered active energy such as a transparent film/adhesive layer/transparent film, or a transparent film/adhesive layer/transparent film/adhesive layer/transparent film. A laminate of a linear polymerizable adhesive. Further, as an optical body 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 optical molded body is fixed to an optical member The component is used as a laminate. As the adhesive layer, the resin composition of the first aspect to the third aspect of the present invention can be used.

The various transparent films used as the optical film are preferably thermoplastic resins excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy. The various transparent films are also referred to as various plastic films or plastic sheets, and examples thereof include polyvinyl alcohol film, polytrimethylene cellulose film, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer. Polyolefin film, polyester film such as polyethylene terephthalate or polybutylene terephthalate, polycarbonate film, polynorbornene Membrane, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamine film, polyimide film, and polyethylene oxide Alkane film or the like.

In the case where the transparent film of the present invention is used as a multilayer film, each film may have the same composition or may be different. For example, a polycycloolefin film may be used on one side and a polyacrylic film may be used on the other side.

The thickness of the transparent film can be appropriately determined. However, the thickness is usually about 1 μm to 500 μm from the viewpoints of workability such as strength and workability, and thin layer properties. It is particularly preferably 1 μm to 300 μm, more preferably 5 μm to 200 μm. The transparent film is particularly suitable for the case of 5 μm to 150 μm.

Further, in the case where a transparent film is provided on both sides of a polarizing element of a polarizing film film as an optical film, a transparent film containing the same polymer material may be used on the front and back surfaces thereof, and a different polymer material may be used. Transparent film (H).

Next, the optical film will be described.

The laminated body for an optical element of the present invention suitably uses an optical film mainly used for optical applications among the various transparent films. The optical film is a film obtained by performing special treatment on the transparent film, and a film having an optical function (light transmission, light diffusion, condensing, refraction, scattering, haze, and the like) is called an optical film. In order to impart these optical functions, generally, not only the functional materials are kneaded in the film, but also laminated by sputtering, and an adhesive or a coating agent containing a functional material or an adhesive is used for lamination. A film containing a functional material is laminated to impart an optical function. In addition, the optical film can be used alone, or a plurality of optical films can be laminated by using a coating agent or an adhesive. Layer to use. Examples of such an optical film include a hard coat film, an antistatic coating film, an antiglare coating film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, and a ruthenium film. (also known as bracts), and light-guiding films (also known as light guides).

The polarizing film is also called a polarizing plate, and is a polytrimethylene cellulose-based protective film which is a polyethylene-based cellulose film in two layers of a polyvinyl alcohol-based polarizing element via an adhesive (hereinafter referred to as a polarizing plate). "TAC film", or a polycycloolefin film, a polyacryl film, a polycarbonate film, a polyester film, or the like which is a polynorbornene film in one or both of the polyvinyl alcohol-based polarizing elements. A multi-layered sheet-like optical film. As the binder, the active energy ray-polymerizable resin composition of the present invention can be suitably used.

The optical film laminated using the active energy ray-polymerizable resin composition of the present invention is preferably a liquid crystal display device, a plasma display panel (PDP) module, a touch panel module, or an organic electroluminescence (electroluminescence). In the transparent film such as the glass plate of the EL module or the above-mentioned various plastic films, the active energy ray-polymerizable resin composition of the present invention is laminated and attached to form a laminate for an optical element.

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

There is (I) a method of manufacturing by: as the first transparent One side of the protective film of the film is coated with an active energy ray-polymerizable adhesive to form a first polymerizable adhesive layer (2'), and an active energy ray is applied to one side of the second protective film as a transparent film. The second active energy ray-polymerizable adhesive layer is formed by a polymerizable adhesive, and then the first active energy ray-polymerizable adhesive layer and the second active layer are simultaneously and/or sequentially superposed on each surface of the polyvinyl alcohol-based polarizing element. After the energy ray polymerizable bonding layer, the active energy ray is irradiated to polymerize and cure the first active energy ray polymerizable adhesive layer and the second active energy ray polymerizable adhesive layer; (II) is manufactured by the following operation; Method: Applying an active energy ray-polymerizable adhesive to one side of a polyvinyl alcohol-based polarizing element to form a first active energy ray-polymerizable adhesive layer, and forming a first active energy ray-polymerizable adhesive layer The surface is covered with a first protective film as a transparent film, and then the active energy ray-polymerizable adhesive is applied to the other surface of the polyvinyl alcohol-based polarizing element to form a second active energy ray-polymerizable adhesive layer. Second active energy The surface of the line-polymerizable adhesive layer is covered with a second protective film, and the active energy ray is irradiated to polymerize and cure the first active energy ray-polymerizable adhesive layer and the second active energy ray-polymerizable adhesive layer; and (III) A method of producing a protective film having a first transparent film and a polyvinyl alcohol-based polarizing element, and a surface of the polyvinyl alcohol-based polarizing element that is not coated with the first protective film. The end of the second protective film flows through the active energy ray polymerizable adhesive, and then passes between the rolls to spread the adhesive between the layers. Then, irradiating the active energy ray, the active energy ray polymerizable adhesive Polymerization hardening is carried out; however, it is not particularly limited.

Example

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "parts" and "%" indicate "parts by weight" and "% by weight", respectively.

In addition, the "weight average molecular weight (Mw)" and the "quantitative average molecular weight (Mn)" are values measured using a gel permeation chromatography "HLC-8220GPC" manufactured by Tosoh Corporation, and the separation column is: "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000" and "TSK-GEL SUPER H2000" manufactured by Tosoh Corporation are connected in series, and the temperature is 40 for the mobile phase. The polystyrene-equivalent weight average molecular weight and the number average molecular weight of tetrahydrofuran at ° C measured at a flow rate of 0.6 ml/min.

In addition, in the present specification, the active energy ray-polymerizable resin composition of the present invention is used as the first and second aspects of the invention in the case of using the adhesive and the coating agent. The third embodiment will be described with reference to the embodiments.

Adhesive

(1st aspect)

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

In a 300 ml mayonnaise jar whose oxygen concentration was replaced by 10% or less and which was shielded from light, Table 1 corresponding to each of Examples and Comparative Examples, respectively. And the composition and ratio (parts by weight) shown in Table 2, input compound (X), compound (Y), compound (C), oligomer (D), compound (m), boric acid or boric acid derivative, active energy A line polymerization initiator (E), a sensitizer, and an acid generator. Then, the charged mixture was sufficiently stirred by a disperser, and then defoamed sufficiently, whereby each active energy ray-polymerizable resin composition was obtained. The active energy ray-polymerizable resin composition was each formed into a laminate by the following method and evaluated. The evaluation results are also shown in Tables 1 to 5.

Further, the abbreviations in Tables 1 to 5 are as follows.

4HBA: 4-hydroxybutyl acrylate

HEA: 2-hydroxyethyl acrylate

CHDMMA: cyclohexanedimethanol monomethacrylate

DMAEA: dimethylaminoethyl acrylate

DMAPAA: Dimethylaminopropyl acrylate

PMPMA: pentamethylpiperidine methacrylate

VIM: 1-vinylimidazole

VRP: 4-vinylpyridine

DCPA: Dicyclopentyl acrylate

IBXA: Isobornyl acrylate

DCPDMDA: tricyclodecane dimethanol diacrylate

Oligomer 1: Violet UV3000B: manufactured by Japan Synthetic Chemical Industry Co., Ltd., polyacrylic acid urethane, Mw=18000

Oligomer 2: Polyacrylic acid urethane obtained in Synthesis Example 1, Mw=4000

Oligomer 3: Polyacrylic acid urethane obtained in Synthesis Example 2, Mw=1300

Oligomer 4: Ebeckly (EBECRYL) 3708: Made by Daicel Allnex, modified epoxy acrylate, Mw=1500

Oligomer 5: Ebeckly (EBECRYL) 810: manufactured by Olympus, Daicel, polyester acrylate, Mw=1000

tBA: tert-butyl acrylate

nBA: n-butyl acrylate

THFA: tetrahydrofurfuryl acrylate

PEA: phenoxyethyl acrylate

BzA: benzyl acrylate

EPPA: ethoxylated o-phenylphenol acrylate (A-LEN-10: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate

BDDA: 1,4-butanediol diacrylate

DPHA: dipentaerythritol hexaacrylate

PET3A: pentaerythritol triacrylate

INATA: EO-modified triacrylate of iso-cyanuric acid (manufactured by East Asia Synthetic Chemical Co., Ltd.: Aronix M-315)

NPDA: neopentyl glycol diacrylate

GMA: glycidyl methacrylate

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd., alias: 4-(glycidoxy) butyl acrylate)

DMAA: N,N-dimethyl methacrylate

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

DAROCURE 1173: DAROCURE 1173 (Merck)

DETX-S: manufactured by Nippon Kayaku Co., Ltd., thioxanthone sensitizer

CPI-110P: manufactured by Sanya Pro, a triaryl sulfonium type photoacid generator

<Synthesis Example 1 of Oligomer (Oligomer 2)>

In a 5-section separable flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, and a dropping funnel, polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.: PTG850, hydroxy) was charged. The value was 81.6 mgKOH/g), 81.6 parts, and 41.4 parts of isophorone diisocyanate, and the temperature was raised to 60 ° C while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 27.0 parts of 4-hydroxybutyl acrylate and 0.15 parts of hydroquinone monomethyl ether were placed in a dropping funnel, and the mixture was dropped into a separate flask over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 80 ° C for 3 hours, and the reaction was terminated at the time when the absorption peak of the isocyanate group was not observed in the infrared absorption spectrum, and the oligomer 2 was obtained. The product had a weight average molecular weight of 4,000.

Further, the method for measuring the hydroxyl value of the present invention is as follows. Approximately 1 g of the sample was accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture was added thereto to be dissolved, and then 5 ml of acetamidine was accurately added. Agent (25 g of acetic anhydride was dissolved in pyridine to set the volume to 100 ml) Solution), stir for about 1 hour. A phenolphthalein reagent was added thereto as an indicator for 30 seconds. Then, the solution was titrated with a 0.1 N alcoholic potassium hydroxide solution until the solution showed a reddish color, and the hydroxyl value was determined by the following formula. The hydroxyl value is a value (unit: mgKOH/g) of the dry state of the resin.

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

Among them, S: sample collection amount (g)

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

b: consumption of 0.1N alcoholic potassium hydroxide solution in blank test (ml)

F: titer of 0.1N alcoholic potassium hydroxide solution

D: acid value (mgKOH/g)

<Synthesis Example 2 of Oligomer (Oligomer 3)>

Into a 5-point separable flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, and a dropping funnel, a compound obtained by adding 2 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate was added. Chemical production: Placcel FA2D, 113.4 parts of hydroxyl value 163.0 mgKOH/g), 36.6 parts of isophorone diisocyanate, 0.15 parts of hydroquinone monomethyl ether, and heated to 60 while introducing dry air. °C. 0.04 part of dibutyltin dilaurate was added thereto, the temperature was raised, and the reaction was carried out at 80 ° C for 3 hours. The reaction was terminated at the time when the absorption peak of the isocyanate group was not observed in the infrared absorption spectrum. Weight average molecular weight of the product For 1300. Further, the measurement of the hydroxyl value was the same as in the synthesis example 1 of the oligomer.

The active energy ray polymerizable adhesive prepared by mixing the ratios of Tables 1 to 5 was used to form a laminate by the following method.

<Production Example of Laminate A>

A polytrimethylene cellulose film containing a UV absorber manufactured by Fujifilm Co., Ltd.: "Fujitac: 80 μm" (thickness: 80 μm) was used as a transparent film (1), and commercial use of Fujifilm was used. A polytrimethylene cellulose film containing no ultraviolet absorber manufactured by Fujifilm Business Supply Co., Ltd.: trade name "TAC50μ" (thickness: 50 μm) as a transparent film (2). For the one side of the transparent film (1) and the transparent film (2), at 300 W. The discharge amount of min/m ² was subjected to corona treatment, and then, within 1 hour, on a corona-treated surface of each film, a wire bar coater was used to coat Table 1 and Table 2 with a film thickness of 4 μm. The active energy ray polymerizable adhesive shown in Table 5 forms an active energy ray polymerizable adhesive layer. The polyvinyl alcohol-based polarizing element is sandwiched between the active energy ray-polymerizable adhesive layers formed on the transparent film (1) and the transparent film (2) to obtain a transparent film (1)/adhesive layer/PVA. It is a laminate of a polarizing element/adhesive layer/transparent film (2). The periphery of the laminated body was fixed with a cellophane tape so that the transparent film (1) was in contact with the tin plate, and was fixed to the tinplate.

The active energy ray irradiation apparatus (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) was irradiated with ultraviolet rays having a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² from the side of the transparent film (2) to form a laminate A (polarizing plate). ).

<Production Example of Laminate B>

The active energy ray-polymerizable adhesives of Tables 1 to 5 were applied to a thickness of 8 μm on a polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 50 μm by a bar coater. After the PET film thereon having a thickness of 50μm laminated to the use of nip rolls, with an active energy ray irradiation apparatus (manufactured by Toshiba Corporation, a high-pressure mercury lamp), the maximum illuminance of the irradiation from one side 300mW / cm ^2, and the integrated amount of light 300mJ Ultraviolet light of /cm ² to obtain laminate B.

With respect to the obtained layered product A, peel strength, press workability, heat resistance, and moist heat resistance were obtained by the following methods. Further, in the obtained layered product B, the transmittance and coloration after the moisture heat resistance test were confirmed by the following methods. The results are shown in Tables 1 to 5 in the same manner.

<Production Example of Laminate C>

The following three types of films were used as the transparent film (1) and the transparent film (2) in Tables 3 and 4: ZF: ZF-14 manufactured by Japan Zeon Co., Ltd., and a polymer containing no ultraviolet absorber. Norbornene-based film (thickness: 100 μm), HBD: HBD-002 manufactured by Mitsubishi Rayon Co., Ltd., polyacrylic-based film (thickness: 50 μm) containing no UV absorber, and TAC: Fujifilm commercial supply The company produced TAC 50μ, a polytrimethylene cellulose film (having a thickness of 50 μm) containing no UV absorber. For each of the unilateral surfaces, at 300W. The discharge amount of min/m ² was subjected to corona treatment, and then, within 1 hour, on the corona-treated surface of each film, a wire bar coater was used to coat Tables 3 and 4 in such a manner that the film thickness was 4 μm. The active energy ray polymerizable adhesive is formed to form an active energy ray polymerizable adhesive layer. A polyvinyl alcohol-based polarizing element is interposed between the active energy ray-polymerizable adhesive layers formed on the respective films to obtain a transparent film (1)/adhesive layer/PVA-based polarizing element/adhesive layer/transparent A laminate of the film (2). The transparent film (1) was placed in contact with the tinplate, and the periphery of the laminate was fixed with a cellophane tape and fixed to the tinplate.

An active energy ray irradiation apparatus (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) was used to irradiate ultraviolet rays having a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² from the side of the transparent film (2) to form a laminated body C (polarizing plate). ).

<peel strength>

Adhesive strength is determined according to JIS K6 854-4 Adhesive-Peel Bond Strength Test Method - Part 4: Floating Roll Method.

In other words, the obtained laminated body A or laminated body C was cut into a size of 25 mm × 150 mm using a cutter, and used as a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to one side of the sample, and bonded to a metal plate by a bonding machine to obtain a laminate for measuring a polarizing plate and a metal plate. In the laminated body for measurement, a peeling opening was provided in advance between the transparent film and the polarizing element, and the laminated body for measurement was subjected to a temperature of 300 mm/min and a temperature of 30° under conditions of 23° C. and a relative humidity of 50%. The angle is peeled off as a peeling force. At this time, the peeling force of both the polyvinyl alcohol-based polarizing element and the transparent film (1), and the polyvinyl alcohol-based polarizing element and the transparent film (2) was measured. The peeling force was evaluated as adhesion strength in four grades. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: Cannot be peeled off, or the polarizing plate is broken

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

△: peeling force is 1.0 (N/25 mm) or more and less than 2.0 (N/25 mm)

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

<Stamping workability>

The obtained laminated body A or laminated body C was punched from the transparent film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell Co., Ltd.

The peeling distance of the periphery of the stamped polarizing plate was measured with a ruler, and it evaluated by the following four grades. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: 0mm

○: less than 1mm

△: 1 mm or more and less than 3 mm

×: 3mm or more

<heat resistance>

The laminate A or the laminate C bonded by the respective adhesives was cut into a size of 50 mm × 40 mm, and exposed to 1000 ° C - dry, and 100 ° C - dry, respectively, for 1000 hours. After the exposure, the presence or absence of peeling of the end portion of the polarizing plate was evaluated by visual observation in the following four levels. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: no peeling at 100 ° C - dry conditions

○: no peeling at 80 ° C - dry condition

△: peeling less than 1 mm at 80 ° C - dry conditions

×: 1 mm or more peeling at 80 ° C - dry conditions

<moisture and heat resistance>

The laminate A or the laminate C bonded by the respective adhesives is cut into a size of 50 mm × 40 mm, and exposed to 1000 under the conditions of a temperature of 60 ° C - a humidity of 90% and a temperature of 85 ° C - a humidity of 85%. hour. After the exposure, the presence or absence of peeling of the end portion of the laminated body A was evaluated by visual observation in the following four levels. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: No peeling at 85 ° C - 85% RH

○: no peeling at 60 ° C - 90% RH

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

×: 1 mm or more peeling under the condition of 60 ° C - 90% RH

<yellow index (△YI)>

The laminated body B bonded by each adhesive is cut into a size of 50 mm × 40 mm, exposed to a temperature of 85 ° C - humidity of 85% for 1000 hours, and an integrating sphere type spectroscopic transmittance measuring device (Village color material technology) DOT-3C manufactured by the Research Institute Co., Ltd.) was used to measure ΔYI. Here, ΔYI is represented by the difference between the YI value of the laminate film after the heat resistance test and the YI value of the PET film before the test. ΔYI was evaluated in the following four levels. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: 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

The above results are shown in Tables 1 to 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 polytrimethylene cellulose film, peel strength, press formability, and heat resistance are exhibited. And the heat and humidity resistance are all practical levels. In particular, in Examples 3 to 19, it had good peel strength or resistance. Further, in Example 1 and Example 2, although the level of resistance is low, it can be used.

On the other hand, as shown in Table 2, in Comparative Examples 1 to 8 in which no boric acid or boric acid derivative was contained, any of peel strength, press formability, heat resistance, and moist heat resistance did not reach the practical range. .

Further, as shown in Table 3, in the case where the active energy ray-polymerizable adhesive of the present invention containing a boric acid or a boric acid derivative is used for a polyacrylic film or a polynorbornene film, as in Example 20 In the same manner as in Example 31, all the evaluation results of the peel strength, the press workability, the heat resistance, and the moist heat resistance were good. In Examples 32 to 35 which did not contain the compound (Y), the compound (C), and the oligomer (D), the heat resistance and the heat and humidity resistance were not so high, but they could be used at a practical level.

On the other hand, as shown in Table 4, in Comparative Examples 9 to 24 in which no boric acid or boric acid derivative was contained, the peel strength was low, and the evaluation results of any of heat resistance and moist heat resistance were low. Achieve practical range.

Further, as shown in Table 5, the active energy ray-polymerizable adhesive of the present invention containing various boronic acid derivatives is also useful, particularly in Example 42 containing 1,4-benzenediboronic acid and tetrahydroxydiborane. In the case of Example 45, the peel strength and the like are excellent as compared with the case where only boric acid is contained.

(the second aspect)

[Example 101 to Example 125, Comparative Example 101, Comparative Example 102]

The cation was introduced into the 300 ml of the melamine bottle in which the oxygen concentration was replaced by 10% or less and was shielded by light, and the compositions and ratios (parts by weight) shown in Tables 6 and 7 corresponding to the respective Examples and Comparative Examples, respectively. A polymerizable compound (K), a boric acid or a boric acid derivative, and a cationically polymerizable initiator (KE). Then, the charged mixture was sufficiently stirred by a disperser, and then defoamed sufficiently, whereby each active energy ray-polymerizable resin composition was obtained. The active energy ray-polymerizable resin composition was each formed into a laminate by the following method and evaluated.

Further, the abbreviations in Tables 6 and 7 are as follows.

JER828: 2,2'-(dimethylmethylene) bis[(p-phenylene)oxymethylene]diethylene oxide (manufactured by Mitsubishi Chemical Corporation)

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

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

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

2021P: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, Celloxide 2021P)

OXT-101: 3-ethyl-3-hydroxymethyl oxetane (manufactured by Toagosei Co., Ltd., Aron Oxetane OXT-101)

OXT-221: bis(1-ethyl-3-oxetanyl) methyl ether (manufactured by Toagosei Co., Ltd.) Made, Aron Oxetane OXT-221)

B1: boric acid (hydroxyl number 3) (also known as orthoboric acid)

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

B3: tetrahydroxydiborane (hydroxyl number 4)

B4: triethanolamine borate (hydroxyl number 3)

B5: methylboronic acid (hydroxyl number 2)

B6: Phenylboronic acid (hydroxyl number 2)

B7: Triethyl borate (hydroxyl number is 0)

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

CPI-110P: Photo-acid generator of triarylsulfonium type (manufactured by Sanya Pro)

<Production Example of Laminate D>

A polytrimethylene cellulose film containing a UV absorber manufactured by Fujifilm Co., Ltd.: "Fujitac: 80 μm" (thickness: 80 μm) was used as a transparent film (1), and commercial use of Fujifilm was used. Polytrimethylene cellulose film containing no ultraviolet absorber manufactured by the company: trade name "TAC50μ" (thickness: 50 μm) as a transparent film (2). For the one side of the transparent film (1) and the transparent film (2), at 300 W. The discharge amount of min/m ² was subjected to a corona treatment, and then the active energy ray-polymerizable resin composition shown in Table 6 and Table 7 was applied in a thickness of 4 μm using a wire bar coater within 1 hour. Forming an active energy ray polymerizable adhesive layer. The polyvinyl alcohol-based polarizing element is sandwiched between the active energy ray-polymerizable adhesive layers formed on the transparent film (1) and the transparent film (2) to obtain a transparent film (1)/adhesive layer/PVA. It is a laminate of a polarizing element/adhesive layer/transparent film (2). The transparent film (1) was placed in contact with the tinplate, and the periphery of the laminate was fixed with a cellophane tape and fixed to the tinplate.

The active energy ray irradiation device (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) was irradiated with ultraviolet rays having a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² from the side of the transparent film (2) to form a laminate D (polarizing plate). ). With respect to the obtained layered product D, the peeling strength, the gel fraction, the press workability, the shrinkage ratio, the heat resistance, and the moist heat resistance were determined by the following methods (Tables 6 and 7).

Peel Strength

The adhesion was measured in accordance with JIS K6 854-4 Adhesive-Peel Bond Strength Test Method - Part 4: Floating Roll Method.

That is, the obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter, and it was used as a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyo Chemical Co., Ltd.) was attached to one side of the sample, and bonded to a metal plate by a bonding machine to obtain a laminate for measuring a polarizing plate and a metal plate. In the laminated body for measurement, a peeling opening was provided in advance between the protective film and the polarizing element, and the laminated body for measurement was peeled off at a rate of 300 mm/min at 23 ° C and a relative humidity of 50%. Peel force. At this time, the peeling force of both the polyvinyl alcohol-based polarizing element and the transparent film (1), and the polyvinyl alcohol-based polarizing element and the transparent film (2) was measured. The peeling force was evaluated as adhesion strength in four grades. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

(evaluation benchmark)

◎: Cannot be peeled off, or the polarizing plate is broken

○: The peeling force was 2.0 (N/25 mm) or more and less than 5.0 (N/25 mm).

△: The peeling force was 1.0 (N/25 mm) or more and less than 2.0 (N/25 mm).

×: The peeling force is less than 1.0 (N/25 mm).

Gel fraction

One side of a polynorbornene film (trade name "Zeonor ZF-14": 100 μm thick) manufactured by ZEON Co., Ltd., which was not subjected to corona treatment, was coated with a wire bar. The active energy ray-polymerizable resin composition of the present invention is applied so as to have a film thickness of 20 μm to 25 μm to form an adhesive layer. Furthermore, Zeonor ZF-14 which was not subjected to corona treatment was superposed on the adhesive layer, and a laminate including three layers was obtained, and then irradiated with an active energy ray irradiation apparatus (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp). An active energy ray having a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² causes polymerization of the adhesive layer. Separation of Zeonor ZF-14 on both sides of the adhesive layer constituting the three-layer laminate of Zeonor ZF-14/bonding layer/Zeonor ZF-14 , to obtain a layer of adhesive.

After measuring the weight of the adhesive layer (weight 1), it is sandwiched between the metal mesh and the metal mesh, and is carried out in methyl ethyl ketone (MEK) in such a manner that the adhesive layers do not overlap each other. 3 hours reflux. Further, it was dried at 80 ° C for 30 minutes, and the weight (weight 2) of the adhesive layer was measured. The gel fraction was determined by the following formula, and evaluation was performed in three grades. In the case of evaluation of ○ and Δ, there is no particular problem in actual use.

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

(evaluation benchmark)

○: The gel fraction is 90% or more

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

×: The gel fraction is less than 80%

"Stamping Processability"

The produced polarizing plate was punched from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell Corporation.

The peeling distance of the periphery of the stamped polarizing plate was measured with a ruler, and it evaluated by the following four grades. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

(evaluation benchmark)

◎: 0mm

○: 1 mm or less

△: 1mm~3mm

×: 3mm or more

"Shrinkage"

The polarizing plate piece was placed in a 60 ° C-dried and 60 ° C - 90 RH % constant temperature and humidity machine, and the amount of shortening in the extending direction after 60 hours was measured, and the ratio of the shortening amount to the original length (100 mm) was determined as Shrinkage rate, in the following three levels Evaluation.

In addition, the term "drying" refers to a test condition in which only the temperature is controlled in the oven with the humidity adjustment function, and the humidity control is not performed. In the case of evaluation of ○ and Δ, there is no particular problem in actual use.

(evaluation benchmark)

○: The shrinkage rate is 0.2% or less

△: Shrinkage ratio is more than 0.2% and is 0.4% or less

×: The shrinkage ratio exceeds 0.4%.

Heat resistance

The polarizing plates obtained in the respective Examples and Comparative Examples were cut into a size of 50 mm × 40 mm, and exposed to 1000 ° C - dry, and 100 ° C - dry conditions, respectively, for 1000 hours. After the exposure, the presence or absence of peeling of the end portion of the polarizing plate was evaluated by visual observation in the following four levels. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

(evaluation benchmark)

◎: No peeling at 100 ° C - dry conditions.

○: No peeling at 80 ° C - dry conditions.

△: Peeling of less than 1 mm at 80 ° C - dry conditions.

×: Peeling of 1 mm or more at 80 ° C - dry conditions.

Heat and Moisture Resistance

The polarizing plates obtained in the respective examples and comparative examples were cut to a size of 50 mm × 40 mm, and were subjected to the conditions of 60 ° C - 90% RH and 85 ° C - 85% RH. Dew for 1000 hours. After the exposure, the presence or absence of peeling of the end portion of the polarizing plate was evaluated by visual observation in the following four levels. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

(evaluation benchmark)

◎: No peeling at all under the conditions of 85 ° C to 85% RH.

○: No peeling at 60 ° C - 90% RH.

△: Peeling of less than 1 mm under the conditions of 60 ° C - 90% RH.

×: There was a peeling of 1 mm or more under the conditions of 60 ° C - 90% RH.

In Comparative Example 101 and Comparative Example 102 in which no boric acid or boric acid derivative and a cationic polymerization initiator were added, the physical properties required by the present application were not obtained at all. When the oxirane compound (k1) was used as the cationically polymerizable compound (K), the physical properties were better than those in the case of not using (Example 124, Example 125). Further, in the case where the oxirane compound is K1-1 having an aromatic ring (for example, Example 103), the shrinkage ratio under humidification is compared with Example 122 and Example 123 in which K1-1 is not used. appropriate.

Further, as the boric acid and/or the boric acid derivative, when the hydroxyl group is 3 or more (for example, Example 103, Example 108, Example 110, and Example 111), it is preferable that the hydroxyl group is less than 3 (for example, Examples 113 to Examples) 115).

Further, it is understood that the amount of boric acid and/or boric acid derivative added is preferably from 0.3 part by weight to 20 parts by weight per 100 parts by weight of the active energy ray resin composition (see Examples 101 to 110).

(3rd aspect)

[Example 201 to Example 220, Comparative Example 201]

The compound (X) was added to the composition and ratio (parts by weight) shown in Table 8 corresponding to each of the examples and the comparative examples in a 300 ml merlot bottle in which the oxygen concentration was replaced by 10% or less and was shielded from light. And a compound (C), a compound (m), an oligomer, a cationically polymerizable compound (B), a boric acid or a boric acid derivative, an active energy ray polymerization initiator (E), and a sensitizer. Then, the charged mixture was sufficiently stirred by a disperser, and then defoamed sufficiently, whereby each active energy ray-polymerizable resin composition was obtained. For the active energy ray polymerizable resin composition, respectively The laminate was produced by the following method and evaluated. The evaluation results are also shown in Table 8.

In addition, the abbreviations in the table are as follows.

4HBA: 4-hydroxybutyl acrylate

HEA: 2-hydroxyethyl acrylate

CHDMMA: cyclohexanedimethanol monomethacrylate

DCPA: Dicyclopentyl acrylate

IBXA: Isobornyl acrylate

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

nBA: n-butyl acrylate

NPDA: neopentyl glycol diacrylate

PET3A: pentaerythritol triacrylate

INATA: EO-modified triacrylate of iso-cyanuric acid (manufactured by East Asia Synthetic Chemical Co., Ltd.: Aronix M-315)

Oligomer 6: Polyacrylic acid urethane obtained in Synthesis Example 3, Mw=4000

Compound 1: [Chemical 1]

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

JER806: bisphenol F diglycidyl ether (manufactured by Mitsubishi Chemical Corporation)

CEL2021P: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, Celloxide 2021P)

OXT-121: xylylene dioxetane (manufactured by Toagosei Co., Ltd., Aron Oxetane OXT-121)

EC: ethyl carbonate

CPI-110P: manufactured by Sanya Pro, a triaryl sulfonium type photoacid generator

IRG250: 4-isobutylphenyl (4-methylphenyl) fluorene. Hexafluorophosphate (manufactured by BASF, Irgacure 250)

TPO: 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide (manufactured by BASF, Lucirin TPO)

DETX-S: manufactured by Nippon Kayaku Co., Ltd., thioxanthone sensitizer

<Synthesis Example 3 of Oligomer (Oligomer 6)>

In a 5-port separable flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, and a dropping funnel, polytetramethylene glycol was introduced. The company manufactured: PTG850, having a hydroxyl value of 127.1 mgKOH/g, 81.6 parts, and 41.4 parts of isophorone diisocyanate, and the temperature was raised to 60 ° C while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 27.0 parts of 4-hydroxybutyl acrylate and 0.15 parts of hydroquinone monomethyl ether were placed in a dropping funnel, and the mixture was dropped into a separate flask over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 80 ° C for 3 hours, and the reaction was terminated at the time when the absorption peak of the isocyanate group was not observed in the infrared absorption spectrum, and the oligomer 6 was obtained. The product had a weight average molecular weight of 4,000.

Further, the method for measuring the hydroxyl value of the present invention is as described in the first aspect.

The active energy ray-polymerizable resin composition prepared by the ratio shown in Table 8 was used to form a laminate by the following method.

<Production Example of Laminate E>

A polytrimethylene cellulose film containing a UV absorber manufactured by Fujifilm Co., Ltd.: "Fujitac: 80 μm" (thickness: 80 μm) was used as a transparent film (1), and commercial use of Fujifilm was used. Polytrimethylene cellulose film containing no ultraviolet absorber manufactured by the company: trade name "TAC50μ" (thickness: 50 μm) as a transparent film (2). For the one side of the transparent film (1) and the transparent film (2), at 300 W. The discharge amount of min/m ² was subjected to a corona treatment, and then the active energy ray-polymerizable resin composition shown in Table 8 was applied to a film thickness of 4 μm to form an activity within 1 hour using a wire bar coater. Energy ray polymerizable resin layer. A polyvinyl alcohol-based polarizing element is interposed between the active energy ray-polymerizable resin layers formed on the transparent film (1) and the transparent film (2) to obtain a transparent film (1)/resin layer/PVA-based polarizing film. A laminate of the element/resin layer/transparent film (2). The transparent film (1) was placed in contact with the tinplate, and the periphery of the laminate was fixed with a cellophane tape and fixed to the tinplate.

The active energy ray irradiation device (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) was irradiated with ultraviolet rays having a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² from the side of the transparent film (2) to form a layered body E (polarizing plate). ).

<Production Example of Laminate F>

The active energy ray-polymerizable resin composition of Table 8 was applied to a thickness of 8 μm on a polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 50 μm by a bar coater. After a PET film having a thickness of 50 μm was attached thereto by a nip roll, the maximum illuminance was 300 mW/cm ² from one side and the cumulative light amount was 300 mJ by an active energy ray irradiation device (manufactured by Toshiba Co., Ltd., high pressure mercury lamp). / cm ² of ultraviolet rays, to obtain a laminate F.

<Production Example of Laminated Body G>

The following three types of films were used as the transparent film (1) and the transparent film (2): ZF: ZF-14 manufactured by Japan Zeon Co., Ltd., and polynorbornene film containing no ultraviolet absorber (thickness is 100 μm), HBD: HBD-002 manufactured by Mitsubishi Rayon Co., Ltd., polyacrylic film (50 μm thick) containing no UV absorber, and TAC 50% of TAC manufactured by Fujifilm Commercial Supply Co., Ltd. Triethylenesulfonate cellulose film (thickness: 50 μm). The surface of one side of it is respectively 300W. The discharge amount of min/m ² was subjected to corona treatment, and then the activity shown in Table 8 was applied to the corona-treated surface of each film using a wire bar coater at a film thickness of 4 μm within 1 hour. The energy ray polymerizable resin composition forms an active energy ray polymerizable resin layer. A polyvinyl alcohol-based polarizing element is interposed between the active energy ray-polymerizable resin layers formed on the respective films to obtain a transparent film (1)/resin layer/PVA-based polarizing element/resin layer/transparent film (2) The layered body. The transparent film (1) was placed in contact with the tinplate, and the periphery of the laminate was fixed with a cellophane tape and fixed to the tinplate.

With an active energy ray irradiation apparatus (produced by Toshiba Corporation, a high-pressure mercury lamp) from the transparent film (2) side of the maximum illuminance of 300mW / cm ^2, and the accumulated light quantity of ultraviolet 300mJ / cm ² to prepare a layered product G (polarizing plate ).

The obtained laminate E was evaluated for peel strength, press formability, heat resistance, heat and humidity resistance, and laminate appearance by the following method, and the laminate F was evaluated for the laminate body appearance. Further, in the layered product G, the transmittance and coloration after the moisture heat resistance test were confirmed by the following method. The results are shown in Table 8 in the same manner.

<peel strength>

The adhesion was measured in accordance with JIS K6 854-4 Adhesive (Polymerizable Resin Composition) - Peel Bonding Strength Test Method - Part 4: Floating Roll Method.

That is, the obtained laminated body E was cut into a size of 25 mm × 150 mm using a cutter, and used as a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyo Chemical Co., Ltd.) was attached to one side of the sample, and bonded to a metal plate by a bonding machine to obtain a laminate for measuring a polarizing plate and a metal plate. In the laminated body for measurement, a peeling opening is provided in advance between the transparent film and the polarizing element, and the measurement layer is laminated. The body was peeled off at a speed of 300 mm/min and at an angle of 90° under conditions of 23° C. and a relative humidity of 50%, as a peeling force. At this time, the peeling force of both the polyvinyl alcohol-based polarizing element and the transparent film (1), and the polyvinyl alcohol-based polarizing element and the transparent film (2) was measured. The peeling force was evaluated as adhesion strength in four grades. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

◎: Cannot be peeled off, or the polarizing plate is broken

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

△: peeling force is 1.0 (N/25 mm) or more and less than 2.0 (N/25 mm)

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

<Stamping workability>

The produced polarizing plate was punched from the side of the transparent film (1) using a 100 mm × 100 mm blade manufactured by Dumbbell Corporation.

The peeling distance of the periphery of the stamped polarizing plate was measured with a ruler, and it evaluated by the following four grades. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

◎: 0mm

○: less than 1mm

△: 1 mm or more and less than 3 mm

×: 3mm or more

<heat resistance>

The laminated body E bonded by each adhesive is cut into a size of 50 mm × 40 mm, and exposed to 1000 ° C under a condition of 80 ° C - drying and 100 ° C - drying, respectively. Time. After the exposure, the presence or absence of peeling of the end portion of the polarizing plate was evaluated by visual observation in the following four levels. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

◎: no peeling at 100 ° C - dry conditions

○: no peeling at 80 ° C - dry condition

△: peeling less than 1 mm at 80 ° C - dry conditions

×: 1 mm or more peeling at 80 ° C - dry conditions

<moisture and heat resistance>

The layered body E bonded by each of the adhesives was cut into a size of 50 mm × 40 mm, and exposed to a condition of a temperature of 60 ° C to a humidity of 90% and a temperature of 85 ° C to a humidity of 85% for 1,000 hours. After the exposure, the presence or absence of peeling of the end portion of the laminated body A was evaluated by visual observation in the following four levels. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

◎: No peeling at 85 ° C - 85% RH

○: no peeling at 60 ° C - 90% RH

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

×: 1 mm or more peeling under the condition of 60 ° C - 90% RH

<Layer appearance>

The appearance of each laminate was evaluated by visual inspection in the following three levels. In the case of evaluation of ○ and Δ, there is no particular problem in actual use.

○: There are no wrinkles or bumps on the laminate.

△: There are some wrinkles or bumps on the laminate.

×: on the laminated body, wrinkles or bumps on the entire surface

<yellow index (△YI)>

The laminated body G bonded by each adhesive is cut into a size of 50 mm × 40 mm, exposed to a temperature of 85 ° C - humidity of 85% for 1000 hours, and an integrating sphere type spectroscopic transmittance measuring instrument (Village color material technology) DOT-3C manufactured by the Research Institute Co., Ltd.) was used to measure ΔYI. Here, ΔYI is represented by the difference between the YI value of the laminate film after the heat resistance test and the YI value of the PET film before the test. ΔYI was evaluated in the following four levels. If it is the evaluation of ◎, ○, and △, it is a level which is practically problem-free.

◎: 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

As shown in Table 8, in the case of using the active energy ray-polymerizable resin composition of the present invention, Examples 203 to 210, Example 212, Example 213, Example 215 to Example 218, and Example 220 Among them, it has good peel strength or resistance, and the appearance of the laminate. Further, in Example 201, Example 202, Example 211, Example 214, and Example 219, although a test item having a low level of resistance was also available, it can be used. On the other hand, in Comparative Example 201 containing no boric acid or boric acid derivative, the peeling strength was low, and the press working resistance was not in the practical range.

2. Coating agent

(1st aspect)

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

In the same manner as in the first embodiment and the like, in the compositions and ratios (parts by weight) shown in Table 9-1, Table 9-2, Table 10-1, and Table 10-2, Examples 501 to 536 were obtained. And the active energy ray-polymerizable resin composition of Comparative Example 501 to Comparative Example 525. The obtained resin composition was used as an active energy ray-polymerizable coating agent, and the following laminated body was produced. In addition, the abbreviations in Table 9-1, Table 9-2, and Table 10-1 and Table 10-2 are the same as Tables 1 to 5.

<Production Example of Laminate H>

A polyacrylic film containing no ultraviolet absorber manufactured by Mitsubishi Rayon Co., Ltd. was used as an optical film under the trade name "HBD-002: 50 μm" (thickness: 50 μm). For the surface of the optical film at 300W. The discharge amount of min/m ² was subjected to corona treatment, and the resin composition shown in Table 9-1, Table 9-2, Table 10-1, and Table 10-2 was used as the active energy within 1 hour after the surface treatment. The linear polymerizable coating agent was applied so as to have a film thickness of 4 μm using a wire bar coater to form a coating agent layer.

The periphery of the laminate was fixed to the tinplate by a cellophane tape so that the optical film was in contact with the tinplate.

After replacing the inside of the UV irradiation device (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) with dry nitrogen gas, the maximum illuminance at a wavelength of 365 nm of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² were irradiated from the coating agent layer side. A laminate having a coating agent layer was produced.

The adhesion and heat resistance of the obtained laminate were determined by the following methods, and the results are shown in Table 9-1, Table 9-2, Table 10-1, and Table 10-2 in the same manner.

"Close Relay"

The grid peel test was carried out in accordance with JIS K5400. The number of peeled cells in 100 blocks was evaluated in four levels, and the adhesion was determined as the adhesion. In the case of evaluation of ◎, ○, and Δ, there is no particular problem in actual use.

(evaluation benchmark)

◎: 0 grids

○: 1~10 grids

△: 11~30 grids

×: 31 or more squares

Heat resistance

The laminate obtained in each of the examples and the comparative examples was cut into a size of 50 mm × 40 mm, and exposed to light at 80 ° C - dry for 1000 hours. After exposure, by visual inspection, The presence or absence of peeling of the end portion of the laminate was evaluated in the following three levels. In the case of evaluation of ○ and Δ, there is no particular problem in actual use.

(evaluation benchmark)

○: No peeling at all

△: there is peeling less than 1mm

×: There is a peel of 1 mm or more

(the second aspect)

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

The activities of Examples 601 to 630 and Comparative Examples 601 to 602 were obtained in the same manner as in Example 101 and the like, and the compositions and ratios (parts by weight) shown in Table 11-1 and Table 11-2. An energy ray polymerizable resin composition. With respect to the obtained resin composition, a layered body H was produced in the same manner as in the first aspect of the above-mentioned coating agent. In addition, the abbreviations in Table 11-1 and Table 11-2 are the same as Tables 6 and 7.

With respect to the obtained laminate, the adhesion and heat resistance were evaluated in the same manner as in the first aspect of the coating agent. The results are shown in Table 11-1 and Table 11-2.

Table 11-2

(3rd aspect)

[Example 701 to Example 725, Comparative Example 701]

Active energy ray polymerization properties of Examples 701 to 725 and Comparative Example 701 were obtained in the same manner as in Example 201 and the like, and the compositions and ratios (parts by weight) shown in Tables 12-1 and 12-2. Resin composition. With respect to the obtained resin composition, a layered body H was produced in the same manner as in the first aspect of the coating agent. Further, the abbreviations in Table 12-1 and Table 12-2 are the same as those in Table 8.

With respect to the obtained laminate, the adhesion and heat resistance were evaluated in the same manner as in the first aspect of the coating agent. The results are shown in Table 12-1 and Table 12-2.

In the present invention, as a representative example of the optical film, the exemplified compounds are specifically shown in the above Tables 9 to 12, but are not limited to these compounds. Further, the expression of the exemplary film is represented by TAC: TAC 50μ manufactured by Fujifilm Commercial Supply Co., Ltd., polytrimethylene cellulose film (having a thickness of 50 μm) containing no ultraviolet absorber; ZF: Japan ZEON ZF-14 manufactured by the company, polynorbornene film without UV absorber (thickness: 100μm); HBD: HBD-002 manufactured by Mitsubishi Rayon Co., Ltd., polyacrylic film without UV absorber (thickness is 50 μm); R140: R-140 manufactured by Kaneka Co., Ltd., polycarbonate film without UV absorber (thickness: 43 μm); Embett: Embed S manufactured by Unitika A polyester film containing a UV absorber (thickness: 50 μm); TUX: TUX-HZ manufactured by Tohcello Co., Ltd., a polyethylene film containing a UV absorber (thickness: 50 μm).

In the case of using the resin composition of the present invention as a coating agent, Examples 503 to 536, Examples 602 to 605, Examples 607 to 612, Examples 616 to 623, and Examples 626 to 630, 702 to 718, and 720 to 725 are not particularly problematic. Further, in Example 501, Example 502, Example 601, Example 606, Example 613 to Example 615, Example 624, Example 625, Example 701, and Example 719, although adhesion or heat resistance was observed. The level is low but can be used. On the other hand, in Comparative Examples 501 to 525, Comparative Example 601, Comparative Example 602, and Comparative Example 701, it was found that the adhesion or the heat resistance was particularly inferior.

Claims (21)

An active energy ray-polymerizable resin composition comprising a polymerizable compound, and a boric acid and/or a boric acid derivative, and the polymerizable compound is selected from a compound containing an α,β-ethylenically unsaturated double bond group (M) And at least one of the group consisting of the cationically polymerizable compound (K). The active energy ray-polymerizable resin composition according to claim 1, wherein the polymerizable compound is a compound (M) containing an α,β-ethylenically unsaturated double bond group. The active energy ray-polymerizable resin composition according to claim 1 or 2, further comprising a radical polymerization initiator (RE). The active energy ray-polymerizable resin composition according to any one of claims 1 to 3, further comprising a cationic polymerization initiator (KE). The active energy ray-polymerizable resin composition according to claim 1, wherein the polymerizable compound is a cationically polymerizable compound (K) and further contains a cationic polymerization initiator (KE). The active energy ray-polymerizable resin composition according to claim 1, wherein the polymerizable compound is a compound (M) containing an α,β-ethylenically unsaturated double bond group and a cationically polymerizable compound (K). The active energy ray-polymerizable resin composition according to claim 6, which further comprises a radical polymerization initiator (RE). The active energy ray-polymerizable resin composition according to claim 6 or 7, further comprising a cationic polymerization initiator (KE). The active energy ray-polymerizable resin composition according to any one of claims 1 to 4, wherein the α,β-ethylenically unsaturated double bond group is contained. The compound (M) contains the compound (X) containing a hydroxyl group-containing α,β-ethylenically unsaturated double bond group. The active energy ray-polymerizable resin composition according to any one of claims 1 to 4, wherein the α,β-ethylenically unsaturated double bond group is contained. The compound (M) contains the compound (Y) containing an amino group-containing α,β-ethylenically unsaturated double bond group. The active energy ray-polymerizable resin composition according to any one of claims 1 to 4, wherein the α,β-ethylenically unsaturated double bond group is contained. The compound (M) contains the compound (C) containing an α,β-ethylenically unsaturated double bond group, and the compound (C) includes a cycloalkane skeleton and/or a cyclic olefin skeleton having two or more ring structures. The active energy ray-polymerizable resin composition according to any one of claims 1 to 4, wherein the α-bonding group-containing compound (M) comprises a weight average An oligomer (D) having a molecular weight of 300 to 30,000. The active energy ray-polymerizable resin composition according to any one of claims 5 to 8, wherein the cationically polymerizable compound (K) contains an oxirane compound (k1). The active energy ray-polymerizable resin composition according to claim 13, wherein the oxirane compound (k1) comprises an oxirane compound (k1-1) having an aromatic ring. The active energy ray-polymerizable resin composition according to any one of claims 1 to 14, wherein the boric acid derivative has three or more hydroxyl groups in one molecule. The active energy ray-polymerizable resin composition according to any one of the first aspect of the invention, wherein the active energy ray-polymerizable resin composition comprises 0.1 part by weight to 20 parts by weight per 100 parts by weight of the active energy ray-polymerizable resin composition. The boric acid and/or boric acid derivative. An adhesive comprising the active energy ray-polymerizable resin composition according to any one of claims 1 to 16. A coating agent comprising the active energy ray-polymerizable resin composition according to any one of claims 1 to 16. A laminated body comprising a laminated layer of the active energy ray-polymerizable resin composition according to any one of claims 1 to 16 on one or both sides of the substrate (F). a layered body. The laminate according to claim 19, wherein the substrate (F) is selected from the group consisting of a polyethylene-based cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, and a polycarbonate. At least one of a group consisting of an ester film, a polyester film, a polyvinyl alcohol film, and a polyimide film. A laminate for an optical element, which is obtained by using the laminate according to claim 19 or 20.