JP7427854B1 - Active energy ray polymerizable resin composition and laminate - Google Patents

Abstract

An object of the present invention is to provide an active energy ray polymerizable resin composition and a laminate that have excellent adhesive strength in a wide temperature range from high to low temperatures and can form a laminate with excellent heat resistance and moist heat resistance. [Solution] The problem of the present application is to solve the following problems: an ethylenically unsaturated double bond-containing compound (A) having a hydroxyl group, an ethylenically unsaturated double bond-containing compound (B) having no hydroxyl group, and a radical polymerization initiator ( The problem is solved by an active energy ray polymerizable resin composition containing E), which satisfies any of the following (1) to (4). (1) Further contains a metal salt of an organic acid (C) and a boric acid compound (F). (2) Further contains an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000. (3) It further contains a metal salt of an organic acid (C) and an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000. (4) Further contains an amino group-containing compound (D) and a boric acid compound (F) having a number average molecular weight of 500 to 40,000. [Selection diagram] None

Description

The present invention relates to an active energy ray polymerizable resin composition suitable for adhesives and a laminate thereof.

Active energy ray-polymerizable resin compositions have excellent properties such as high polymerization rate and generally can be used without solvents, so they have excellent workability and require extremely low energy during polymerization. Examples of active energy ray polymerizable resin compositions include radical, cationic, or combination (hybrid) active energy ray polymerizable resin compositions, such as adhesives and coating agents. Used in a wide range of fields.

Polarizers used in fields related to liquid crystal displays are usually manufactured by uniaxially stretching polyvinyl alcohol (PVA) with iodine or dye adsorbed thereon. This polyvinyl alcohol polarizer shrinks due to heat and moisture, resulting in a decrease in polarization performance. Therefore, a PVA-based polarizer with a protective film attached to the surface is used as a polarizing plate.

Water-based adhesives and active energy ray polymerizable resin compositions are used to bond PVA-based polarizers and protective films, but the versatility of the base materials used for protective films and the efficiency of production From the viewpoint of energy saving, the use of active energy ray polymerizable resin compositions as adhesives is progressing.
The active energy ray polymerizable resin composition has sufficient adhesion for bonding the PVA polarizer and the protective film, as well as heat resistance, moisture resistance, water resistance, etc. to suppress the deterioration of the polarizing performance of the PVA polarizer. Performance is required.

Patent Document 1 discloses that in order to solve problems such as the adhesive strength of a polarizing plate using a film such as a norbornene-based resin film that has lower moisture permeability than triacetyl cellulose as a protective film, a method using an epoxy resin that does not contain aromatic rings as the main component is disclosed. A cationic active energy ray polymerizable adhesive is disclosed.

Patent Document 2 describes 2-hydroxybutyl acrylate and 1,3-bis(N,N-diglycidyl) as adhesives that firmly bond not only norbornene resins but also acrylic resins and triacetyl cellulose films. A hybrid active energy ray-polymerizable adhesive using a combination of (aminomethyl) cyclohexane is disclosed.

Patent Document 3 discloses a radical active energy ray polymerizable adhesive that uses acryloylmorpholine and an alkyl acrylate having 10 to 20 carbon atoms in combination to address issues such as water resistance.

Compared to liquid crystal display devices for indoor use or mobile use, liquid crystal display devices for automotive use require stricter heat resistance, heat and humidity resistance, and good adhesive strength in a wide temperature range from high to low temperatures. However, conventional adhesives have insufficient adhesive strength at high and low temperatures, and have not been able to satisfy the required quality in terms of heat resistance and moist heat resistance.

Japanese Patent Application Publication No. 2004-245925 Japanese Patent Application Publication No. 2010-018722 Japanese Patent Application Publication No. 2017-194572

An object of the present invention is to provide an active energy ray polymerizable resin composition and a laminate that have excellent adhesive strength even at high and low temperatures and can form a laminate with excellent heat resistance and heat-and-moisture resistance.

As a result of extensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned goals can be achieved with the active energy ray polymerizable composition shown below, and have completed the present invention.

The present invention relates to an ethylenically unsaturated double bond-containing compound (A) having a hydroxyl group (excluding (D)), an ethylenically unsaturated double bond-containing compound (B) having no hydroxyl group (however, , excluding (D)) and a radical polymerization initiator (E), the active energy ray polymerizable resin composition comprising:
The present invention relates to an active energy ray polymerizable resin composition that satisfies any of the following (1) to (4).
(1) Further contains a metal salt of an organic acid (C) and a boric acid compound (F).
(2) Further contains an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000.
(3) It further contains a metal salt of an organic acid (C) and an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000.
(4) Further contains an amino group-containing compound (D) and a boric acid compound (F) having a number average molecular weight of 500 to 40,000.

The present invention also provides an ethylenically unsaturated double bond-containing compound (A) having a hydroxyl group, an ethylenically unsaturated double bond-containing compound (B) having no hydroxyl group, and a metal salt of an organic acid (C). , an active energy ray polymerizable resin composition comprising an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000, a radical polymerization initiator (E), and a boric acid compound (F).

Furthermore, in the present invention, in 100% by mass of the active energy ray polymerizable resin composition, the compound (A) is 10 to 60% by mass, the compound (B) is 30 to 89% by mass, and the compound (C) is 0.01 to 0.01% by mass. 5% by mass, 0.1 to 20% by mass of compound (D), 0.1 to 10% by mass of compound (E), and 0.1 to 7% by mass of compound (F). The present invention relates to a resin composition.

Moreover, the present invention provides that the ethylenically unsaturated double bond group-containing compound (B) having no hydroxyl group is
A compound (b1) having a weight average molecular weight of 1,000 to 60,000 and having a urethane structure and two ethylenically unsaturated double bond groups and having no hydroxyl group and two ethylenically unsaturated double bond groups. The present invention relates to the active energy ray-polymerizable resin composition containing at least one of the compounds (b2) (excluding (b1)) having at least one hydroxyl group and having no hydroxyl group.

Further, the present invention provides the active energy ray polymerizable resin composition containing 1 to 20 mass % of the compound (b1) and 9 to 69 mass % of the compound (b2) in 100 mass % of the active energy ray polymerizable resin composition. relating to things.

The present invention also relates to a laminate including a first base material (G1), a resin composition layer made of the active energy ray polymerizable resin composition, and a second base material (G2) in this order.

In addition, in the present invention, the base material (G1) and the base material (G2) are polyacetyl cellulose film, polynorbornene film, polypropylene film, polyacrylic film, polycarbonate film, polyester film, polyvinyl alcohol film. The present invention relates to the laminate, which is any one selected from the group consisting of a film, a polyimide film, and a glass film. .

According to the present invention, it is possible to provide an active energy ray polymerizable resin composition and a laminate that have excellent adhesive strength even at high and low temperatures and can form a laminate with excellent heat resistance and heat-and-moisture resistance.

Preferred embodiments of the present invention will be described below. In this specification, when it is written as "(meth)acrylic", it means "acrylic or methacrylic", respectively, unless otherwise specified. In addition, the active energy ray polymerizable resin composition is referred to as a resin composition, the ethylenically unsaturated double bond group-containing compound (A) having a hydroxyl group is referred to as a compound (A), and the ethylenically unsaturated double bond group having no hydroxyl group is referred to as a compound (A). The containing compound (B) is compound (B), the metal salt of an organic acid (C) is compound (C), the amino group-containing compound (D) with a number average molecular weight of 500 to 40,000 is compound (D), and the boric acid compound (F) is may be abbreviated as compound (F).
Furthermore, in this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are the weight average molecular weight and number average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) measurement.

In this specification, unless otherwise specified, a numerical range specified using "-" shall include the numerical values written before and after "-" as the range of lower and upper limits.
Further, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.
In addition, unless otherwise noted, the various components appearing in this specification may be used individually or in combination of two or more.

<Ethylenically unsaturated double bond group-containing compound (A) having a hydroxyl group>
Compound (A) is a compound having a hydroxyl group and an ethylenically unsaturated double bond group. By including the compound (A) in the resin composition, hydrogen bonds are formed with the hydrophilic functional groups of the base material, and the adhesive strength is improved. Compound (A) preferably has a weight average molecular weight of less than 1,000. When the weight average molecular weight of the compound (A) is less than 1,000, the viscosity of the resin composition does not become too high, making it easy to control the film thickness during coating. Moreover, it is preferable that the compound (A) has one ethylenically unsaturated double bond group from the viewpoint of adhesive strength.
In this application, if the number average molecular weight of an ethylenically unsaturated double bond-containing compound having an amino group is 500 to 40,000, it will be treated as an amino group-containing compound (D) described below even if it has a hydroxyl group. .

The content of compound (A) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When the content is 10 to 60% by mass, the balance between low-temperature adhesive strength and high-temperature adhesive strength is improved.

The compound (A) is not particularly limited as long as it has a hydroxyl group and an ethylenically unsaturated double bond group, and the following compounds can be used.

For example, 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxy(meth)acrylate Butyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxy (meth)acrylate Octyl, cyclohexanedimethanol mono(meth)acrylic acid ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl (meth)acrylate-α-(hydroxymethyl), or the above hydroxyl group A (meth)acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to a compound having an ethylenically unsaturated double bond group, or a compound having an ethylenically unsaturated double bond group containing the hydroxyl group. Hydroxyl group-containing aliphatic (meth)acrylic esters, such as alkylene oxide-added (meth)acrylic esters, which are obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to a compound;

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

For example, (meth)allyl alcohol, isopropenyl alcohol, dimethyl (meth)allyl alcohol, hydroxyethyl (meth)allyl ether, hydroxypropyl (meth)allyl ether, hydroxybutyl (meth)allyl ether, hydroxyhexyl (meth)allyl ether , hydroxyoctyl (meth)allyl ether, hydroxydecyl (meth)allyl ether, hydroxydodecyl (meth)allyl ether, hydroxyoctadecyl (meth)allyl ether, glyceryl (meth)allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide. Hydroxyl group-containing aliphatic (meth)allyl alcohols or (meth)allyl ethers such as alkylene oxide addition type (meth)allyl ether having a hydroxyl group at the end of which is repeatedly added;

For example, compounds having an ethylenically unsaturated double bond group having multiple hydroxyl groups such as propene diol, butene diol, heptene diol, octenediol, and glycerol di(meth)acrylate;
For example, N-hydroxyethyl (meth)acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as "N-hydroxyethyl (meth)acrylamide." Same below. ], hydroxyl group-containing (meth)acrylamides such as N-hydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, N-hydroxyhexyl (meth)acrylamide, and N-hydroxyoctyl (meth)acrylamide;

Examples include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may be used alone or in combination.

As the compound (A), acrylic esters of diols having 1 to 6 carbon atoms are preferred from the viewpoint of adhesion to the substrate, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate. and 4-hydroxybutyl (meth)acrylate are particularly preferred.

<Ethylenically unsaturated double bond group-containing compound (B) having no hydroxyl group>
Compound (B) is an ethylenically unsaturated double bond-containing compound that does not have a hydroxyl group. Including the compound (B) in the resin composition improves the heat and humidity resistance. In this application, when the number average molecular weight of the ethylenically unsaturated double bond-containing compound having an amino group is 500 to 40,000, it is treated as an amino group-containing compound (D) described below.

The content of compound (B) is preferably 30 to 89% by mass, more preferably 40 to 71% by mass based on 100% by mass of the active energy ray polymerizable resin composition. If it is 30% by mass or more, the heat and humidity resistance is further improved, and if it is 89% by mass or less, the adhesive strength is further improved.

Compound (B) has a weight average molecular weight of 1,000 to 60,000, has a urethane structure and two ethylenically unsaturated double bond groups, and has no hydroxyl group and compound (b1), which has an ethylenically unsaturated double bond group. Compounds (b2) that have two or more double bond groups and no hydroxyl groups (excluding (b1)), compounds that have one ethylenically unsaturated double bond group and no hydroxyl groups ( It can be classified as b3). Compound (B) preferably contains at least one of compound (b1) and compound (b2), and more preferably contains both compound (b1) and compound (b2). Inclusion of compound (b1) improves adhesive strength at low and high temperatures, and inclusion of compound (b2) improves heat and humidity resistance.

[Compound (b1)]
Compound (b1) is a compound generally called urethane acrylate and does not have a hydroxyl group. Compound (b1) has a highly polar urethane bond and has a weight average molecular weight of 1,000 to 60,000, so it has excellent coating film toughness and has excellent adhesion to substrates at low and high temperatures. improves. The weight average molecular weight of the compound (b1) is particularly preferably in the range of 5,000 to 50,000 from the viewpoint of compatibility, viscosity, and adhesive strength of the polymerized coating film.

The content of compound (b1) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass based on 100% by mass of the active energy ray polymerizable resin composition. If it is 1% by mass or more, the adhesive strength will be further improved, and if it is 20% by mass or less, the viscosity will not become too high, making it easier to control the film thickness during coating.

Compound (b1) is a compound obtained by reacting a compound having two or more isocyanate groups with compound (A), or a compound obtained by reacting a compound having two or more isocyanate groups with a polyhydric alcohol. Examples include compounds obtained by reacting a urethane prepolymer with terminal isocyanate groups and compound (A).

Compound (b1) is preferably a compound obtained by reacting a compound having two or more isocyanate groups, a polyhydric alcohol, and compound (A) at a molar ratio of 2:1:2. By reacting at the above ratio, the structure theoretically has acrylate groups at both ends of one molecule, which has a good balance between flexibility and crosslink density, and has excellent adhesion to the substrate and toughness, so it has adhesive strength over a wide temperature range. This is because the condition becomes better.

Examples of the compound having two or more isocyanate groups include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

More specifically, the aromatic polyisocyanate includes, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate. Isocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, Examples include 4,4',4''-triphenylmethane triisocyanate.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

As the aromatic aliphatic polyisocyanate, ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

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

In addition, a 2-methylpentane-2,4-diol adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. can also be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanates of these, and the like can be used. As the polyisocyanate modified product, a carbodiimide group, a uretdione group, a uretoimine group, a buret group reacted with water, an isocyanurate group, or a modified product having two or more of these groups can be used. Reactants of polyols and diisocyanates can also be used as compounds having at least two isocyanate groups.

The compound having an isocyanate group is preferably an aliphatic diisocyanate or an alicyclic diisocyanate compound from the viewpoint of adhesive strength.
Examples of polyhydric alcohols include low molecular weight polyols with a number average molecular weight (Mn) of about 50 to 500, and high molecular weight polyols with a number average molecular weight (Mn) of 500 to 30,000. , can be used without any particular restrictions.

More specifically, the low molecular weight polyols include, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4- Diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition 10 or less moles), polyoxypropylene glycol (10 or less added moles), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadienedimethanol, dimer diol, etc. aliphatic or cycloaliphatic diols;
1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4, 4'-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, addition type bisphenol with alkylene oxide added to bisphenol. Aromatic diols such as

Examples of the raw material bisphenol for addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

More specific examples of high molecular weight polyols include polyether polyols, polyester polyols, polyamide polyols, polycarbonate polyols, and polyurethane polyols. Polycarbonate polyols are obtained by reacting the above-mentioned low molecular weight diols with carbonates or phosgene.

Examples of commercially available polyester polyols include the Bylon series manufactured by Toyobo Co., Ltd., the Kuraray Polyol P series manufactured by Kuraray Co., Ltd., and the Kyowa Pol series manufactured by Kyowa Hakko Chemical Co., Ltd.
As a commercially available polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd., etc. can be used.
Examples of commercially available polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray Polyol PMHC series and Kuraray Polyol C series manufactured by Kuraray.

Commercially available polyurethane polyols include, for example, Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value < 3), manufactured by Mitsui Chemicals Polyurethane Co., Ltd., Takelac E551T (hydroxyl value = 30, acid value <3) and Takelac Y2789 (hydroxyl value=10, acid value<2).
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly(β-methyl-γ-valerolactone) diol, and polyvalerolactone diol are also included in high molecular weight polyols.

The polyhydric alcohol is preferably a high molecular weight polyether diol or a high molecular weight polyester diol from the viewpoint of adhesion.

[Compound (b2)]
Compound (b2) is a compound having two or more ethylenically unsaturated double bond groups other than (b1) and having no hydroxyl group. By including the compound (b2) in the resin composition, the crosslinking density of the cured composition coating film increases and the heat and humidity resistance improves. Compound (b2) preferably has a weight average molecular weight of less than 1,000. When the weight average molecular weight is less than 1,000, the viscosity of the resin composition does not become too high, making it easy to control the film thickness during coating. Moreover, it is preferable that the ethylenically unsaturated double bond group of (b2) contains one or more (meth)acryloyl groups.

The content of compound (b2) is preferably 9 to 69% by mass, more preferably 20 to 60% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When the content is 9 to 69% by mass, the balance between heat and humidity resistance, low temperature adhesive strength, and high temperature adhesive strength is improved.

As the compound (b2), any compound having two or more ethylenically unsaturated double bond groups and no hydroxyl group can be used without particular limitation. Examples of compounds having two ethylenically unsaturated double bond groups and no hydroxyl group include pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,4-butane diol di(meth)acrylate. Alkyl such as diol di(meth)acrylate, 2,2-dimethylpropane-1,3-diol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, nonanediol di(meth)acrylate, etc. di(meth)acrylate of diol;
Ethylene oxide modified pentanediol di(meth)acrylate, propylene oxide modified pentanediol di(meth)acrylate, tetramethylene oxide modified pentanediol di(meth)acrylate, ethylene oxide modified 2,2-dimethylpropane-1,3-diol di( meth)acrylate, propylene oxide-modified 2,2-dimethylpropane-1,3-diol di(meth)acrylate, tetramethylene oxide-modified 2,2-dimethylpropane-1,3-diol di(meth)acrylate, ethylene oxide-modified hexanediol Di(meth)acrylate, Propylene oxide modified hexanediol di(meth)acrylate, Tetramethylene oxide modified hexanediol di(meth)acrylate, Ethylene oxide modified heptanediol di(meth)acrylate, Propylene oxide modified heptanediol di(meth)acrylate , alkylene glycol-modified alkyl diol di(meth)acrylates such as tetramethylene oxide-modified heptanediol di(meth)acrylates;
Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, One type of alkylene glycol such as propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. di(meth)acrylate having;
Two types: ethylene glycol-propylene glycol di(meth)acrylate, diethylene glycol-propylene glycol di(meth)acrylate, diethylene glycol-dipropylene glycol di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, etc. di(meth)acrylate having an alkylene glycol;
Bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, ethoxylated Di(meth)acrylates having a benzene ring such as propoxylated bisphenol F di(meth)acrylate, 4,4'-bis(meth)acryloxymethylbiphenyl;
Hydrogenated biphenol A di(meth)acrylate, EO modified hydrogenated biphenol A (meth) diacrylate, dimethyloldicyclopentane di(meth)acrylate, 1,3-adamantyldiol di(meth)acrylate, 3-hydroxy-1 , di(meth)acrylate having an alicyclic structure such as 5-adamantyl di(meth)acrylate;
Examples include vinyl ether compounds such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, and triethylene glycol divinyl ether.

Examples of compounds having three or more ethylenically unsaturated double bond groups and no hydroxyl group include isocyanuric acid, ethylene oxide-modified tri(meth)acrylate, isocyanuric acid, propylene oxide-modified tri(meth)acrylate, and isocyanuric acid. Acid butyl oxide modified tri(meth)acrylate;
Trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tetramethylene oxide modified trimethylolpropane tri(meth)acrylate;
Ditrimethylolpropane tetra(meth)acrylate, ethylene oxide modified ditrimethylolpropane tetra(meth)acrylate, propylene oxide modified ditrimethylolpropane tetra(meth)acrylate, tetramethyleoxide modified ditrimethylolpropane tetra(meth)acrylate;
Glycerin tri(meth)acrylate, ethylene oxide modified glycerin tri(meth)acrylate, propylene oxide modified glycerin tri(meth)acrylate, tetramethylene oxide modified glycerin tri(meth)acrylate;
Examples include pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate, and tetramethylene oxide-modified pentaerythritol tetra(meth)acrylate.

Among the above compounds (b2), from the viewpoint of achieving both heat and humidity resistance and adhesion, compounds having two ethylenically unsaturated double bond groups and no hydroxyl group are selected from triethylene glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate (Meth)acrylate is preferred, and examples of compounds having three or more ethylenically unsaturated double bond groups and no hydroxyl group include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate and isocyanuric acid ethylene oxide modified tri(meth)acrylate are preferred.

Compound (b2) is a compound having two ethylenically unsaturated double bond groups and no hydroxyl group, and a compound having three or more ethylenically unsaturated double bond groups and no hydroxyl group. It is preferable that the compound contains a compound having two ethylenically unsaturated double bond groups and no hydroxyl group, and a compound having three or more ethylenically unsaturated double bond groups and having a hydroxyl group. (compounds with two ethylenically unsaturated double bond groups and no hydroxyl group/compounds with three or more ethylenically unsaturated double bond groups and no hydroxyl group) ) is more preferably 4/1 to 1/2 (mass ratio).

The resin composition of the present application can contain a compound (b3) having one ethylenically unsaturated double bond group and no hydroxyl group. By including the compound (b3), the resin composition can be made to have a low viscosity and has excellent low-temperature adhesive strength. Compound (b3) preferably has a weight average molecular weight of less than 1,000. When the weight average molecular weight of compound (b3) is less than 1,000, the viscosity of the resin composition will not become too high, and the film thickness during coating will be easily controlled.

The content of compound (b3) is preferably 0 to 30% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When the content is 0 to 30% by mass, low-temperature adhesive strength will be improved.

Examples of the compound (b3) having one ethylenically unsaturated double bond group and no hydroxyl group include n-octyl (meth)acrylate, isooctyl (meth)acrylate, and di(meth)acrylate. - Ethylhexyl, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and ( (meth)acrylic acid alkyl esters such as isostearyl meth)acrylate;
Having a terminal alkyl (poly)ethylene glycol and one acryloyl group, such as 2-methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. (meth)acrylic acid ester;
Benzyl (meth)acrylate, phenyl (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate, nonylphenol propylene oxide modified (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, etc. (meth)acrylic acid ester having an aromatic ring and one acryloyl group;
For example, cyclohexyl (meth)acrylate, 1-methyl-1-cyclopentyl (meth)acrylate, and 2-(meth)acryloyloxyethyl hexahydrophthalate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ) acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl ( (meth)acrylic acid ester having an alicyclic structure and one acryloyl group, such as meth)acrylate;
Tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alcohol acrylic acid polymer ester, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Examples include (meth)acrylic acid esters having a heterocycle and one acryloyl group, such as methyl acrylate and cyclic trimethylolpropane formal (meth)acrylate.

Compound (b3) is preferably dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, or isobornyl (meth)acrylate because they improve low-temperature adhesive strength.

<Metal salt of organic acid (C)>
Compound (C) is a salt formed from an organic acid and a metal ion. Including the compound (C) in the resin composition improves heat resistance. In a polarizing plate using a resin composition, it is thought that the acid component contained in the resin composition bleeds into the PVA polarizer under heating conditions, causing a color change. It is thought that the heat resistance of the compound (C) is improved by neutralizing the acid component derived from the monomer, the impurity of the monomer, and the acid component contained as a decomposition product.

The content of compound (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When the content is 0.01 to 5% by mass, heat resistance is excellent.

Compound (C) is formed from an organic acid that does not have an active energy ray polymerizable functional group and a metal ion (c1), and (c1) is formed from an organic acid that has an active energy ray polymerizable functional group and a metal ion. It can be classified as c2). (c2) is preferred because it has excellent curability and can easily achieve both heat resistance and heat-and-moisture resistance.

Examples of organic acids that do not have active energy ray polymerizable functional groups include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, Monobasic acids such as stearic acid; dibasic acids such as oxalic acid, succinic acid, adipic acid, phthalic acid, oxaloacetic acid, glutaric acid; lactic acid, glycolic acid, tartaric acid, malic acid, citric acid, gluconic acid, glyceric acid, etc. Acidic amino acids such as 2-oxoglutamic acid and aspartic acid; Keto acids such as pyruvic acid, acetoacetic acid, and levulinic acid; Aromatic carboxylic acids such as benzoic acid and salicylic acid; Polycarboxylic acids such as ethylenediaminetetraacetic acid; Other examples include isocitric acid, malonic acid, glutaric acid, and glucuronic acid.

Examples of organic acids having active energy ray polymerizable functional groups include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and 3-carboxypropyl (meth)acrylate. , 4-carboxybutyl (meth)acrylate, (meth)acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, glutaconic acid, citraconic acid, mesaconic acid , itaconic acid, tiglic acid, angelic acid, senecioic acid, crotonic acid, isocucrotonic acid, sorbic acid, muconic acid, penicylic acid, gellanic acid, citronel acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2-(meth) ) Acryloyloxyethylsuccinic acid, mono(meth)acryloyloxyethyl phthalate, mono(meth)acryloyloxyethyl hexahydrophthalate, mono(meth)acryloyloxypropyl phthalate, mono(meth)acryloyloxybutyl phthalate, etc. Polylactone-based (meth)acrylic acid ester having a carboxyl group at the end by ring-opening addition of a lactone ring, mono(meth)acrylic acid ω-carboxypolycaprolactone ester, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Examples include carboxyl group-containing unsaturated double bond-containing carboxylic acids such as benzoic acid and 4-isopropenylbenzenecarboxylic acid, and acid anhydrides thereof.

Examples of metal ions include ions such as Li, Na, K, Be, Mg, Ca, Sr, Ba, Ti, Zr, Cu, Ag, Zn, Cd, Al, Ga, In, and Sn. .

In particular, sodium (meth)acrylate, potassium (meth)acrylate, magnesium di(meth)acrylate, and zinc di(meth)acrylate are preferred as (c2) because they have excellent heat resistance and moist heat resistance.

<Amino group-containing compound (D) having a number average molecular weight of 500 to 40,000>
Compound (D) is a compound containing an amino group and having a number average molecular weight of 500 to 40,000. Including the compound (D) in the resin composition improves heat resistance. In a polarizing plate using a resin composition, it is thought that the acid component contained in the resin composition bleeds into the PVA polarizer under heating conditions, causing a color change. Compound (D) is thought to improve heat resistance by neutralizing acid components derived from monomers, impurities of monomers, and acid components contained as decomposition products.
The number average molecular weight of compound (D) is preferably 1,000 to 5,000. When it is 1000 to 5000, it has excellent heat resistance and moist heat resistance.

The content of compound (D) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When the content is 0.1 to 20% by mass, heat resistance is excellent.

Compound (D) can be classified into a compound (d1) not containing an ethylenically unsaturated double bond group and a compound (d2) containing an ethylenically unsaturated double bond group.
Examples of the compound (d1) include polyethyleneimine, polyallylamine, polyetheramine, melamine resin, guanamine resin, amino group-containing acrylic resin, amino group-containing acrylamide resin, amino group-containing polyester, amino group-containing vinyl resin, etc. It will be done.

Compound (d2) is a compound called an amine-modified oligomer. It is also a compound called amine-modified acrylate, acrylic-modified amine, reactive amine co-initiator, reactive amine catalyst, acrylate-modified amine catalyst, etc.

Compound (d2) can be used without any structural limitations as long as it contains an amino group and an ethylenically unsaturated double bond group and has a number average molecular weight of 500 to 40,000. As a manufacturing method, for example, after obtaining an amino group-containing dicarboxylic acid by a Michael addition reaction between a primary amine and acrylic acid, a polyester with a terminal hydroxyl group or a terminal carboxylic acid is synthesized with an amino group-containing dicarboxylic acid and a diol, and then It can be produced by acrylic-modifying the ends of the obtained polyester. At this time, if the terminal of the polyester is a hydroxyl group, (meth)acrylic modification can be performed by reacting an isocyanate group with a compound having a (meth)acryloyl group. When the polyester has a carboxylic acid terminal, it can be modified to (meth)acrylic by reacting a compound having a glycidyl group and a (meth)acryloyl group.

There are many commercially available compounds (d2). For example, Arkema's CN371NS, CN373, and CN550;
PHOTOCRYL A104, Miramer AS1000, Miramer AS2010, and Miramer SC9610 manufactured by MIWON;
Ebecryl80, Ebecryl81, Ebecryl83, and Ebecryl7100 manufactured by Daicel Allnex;
Etercure 6410, Etercure 6412, Etercure 6417, and Etercure 6410-TF manufactured by Choko Materials Industry Co., Ltd.;
Examples include GU8100W manufactured by Kokusei Chemical Co., Ltd.

Compound (D) is preferably compound (d2) in terms of heat resistance, low temperature adhesive strength, and high temperature adhesive strength.

<Radical polymerization initiator (E)>
The radical polymerization initiator (E) is a compound that generates radicals using active energy rays. By using the radical polymerization initiator (E), the radical polymerization reaction can be promoted.

The radical polymerization initiator (E) can be arbitrarily selected from known ones, and specific examples include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, and benzaldehyde. , anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like. Commercially available products include, for example, Irgacure-184,907,651,1700,1800,819,369,261, Darocure-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF), Omnirad819 ( Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) Darocure-1173 (manufactured by Merck & Co., Ltd.), Ezacure-KIP150, TZT (manufactured by Nippon Siberhegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Schiebelhegner), IGM Resins B.V. (manufactured by Kayakusha), etc.
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred because it has photobleaching properties.

The content of the radical polymerization initiator (E) is preferably 0.1 to 10% by mass based on 100% by mass of the active energy ray polymerizable resin composition.

<Boric acid compound (F)>
Compound (F) is boric acid or a compound having one or more B-O-H bonds in one molecule, or a boron-containing compound that can be hydrolyzed in the presence of water to form one or more B-O-H bonds. It is. The boric acid derivatives described below are classified as boric acid compounds. Compound (F) interacts with the hydroxyl group derived from compound (A) and the surface functional group of the base material, thereby improving adhesiveness or adhesion.

Boric acid derivatives include boron oxides (e.g. B ₂ O ₃ );
Derivatives obtained by the reaction of boric acid with alcohol or phenol, such as trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, triisopropyl borate , tri-t-amyl borate, triphenyl borate, trimethoxyboroxine, tri-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropylamine borate, mannitol borate, glycerol borate, and boric acid. Examples include boric acid esters such as acid triisopropanolamine.
Boric acid derivatives include derivatives of boronic acids, such as alkyl or alkenylboronic acids such as methylboronic acid, ethylboronic acid, butylboronic acid, and cyclohexylboronic acid;
Examples include arylboronic acids such as phenylboronic acid, naphthaleneboronic acid, and anthraceneboronic acid, and substituted arylboronic acids having arbitrary substituents on their aryl groups.

Furthermore, other amino group-containing borates and tertiary amine salts of boric acid are also preferred. For example, 2-(β-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborolane, 2-(β-diethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane , 2-(β-dimethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane, 2-(β-diisopropylaminoethoxy)-1,3,2-dioxabonaline, 2-(β- diisopropylaminoethoxy)-4-methyl-1,3,2-dioxaborinane, 2-(γ-dimethylaminopropoxy)-1,3,6,9-tetrapxa-2-boracycloundecane, and 2-(β-dimethyl Examples include aminoethoxy)-4,4-(4-hydroxybutyl)-1,3,2-dioxaborinane.

Further, as the boric acid derivative, organic oligomers and polymer compounds containing a boron-containing moiety can also be used. For example, a polymeric borate ester (e.g., an active hydrogen-containing polymer (e.g., a hydroxyl functional group-containing acrylic polymer or a polysiloxane polymer)) having boric acid ester groups is reacted with boric acid or a boric acid ester. Examples include polymers.
As the polymer serving as a raw material for the polymer borate ester, any known active hydrogen-containing polymer can be used, such as an acrylic polymer, a polyester polymer, a polyurethane polymer, a polyether polymer, and the like.

The boric acid compound (F) described so far is preferably boric acid, boric acid ester, or tertiary amine salt of boric acid because it dissolves well in the resin composition. preferable.
Moreover, it is preferable that the boric acid derivative has three or more hydroxyl groups. Examples of boric acid derivatives having three or more hydroxyl groups include 1,4-benzenediboronic acid (4 hydroxyl groups), tetrahydroxydiborane (4 hydroxyl groups), and boric acid triethanolamine salt (3 hydroxyl groups). It will be done. Note that boric acid and boric acid derivatives can be used alone or in combination.

The content of the boric acid compound (F) is preferably 0.1 to 7% by mass, more preferably 0.3 to 3% by mass based on 100% by mass of the active energy ray polymerizable resin composition. When 0.1 to 7% by mass of the boric acid compound (F) is used, the adhesiveness and solution stability of the active energy ray polymerizable resin composition are further improved. In the present invention, a case where the active energy ray polymerizable resin composition does not contain a solvent is also referred to as a solution.

<Other ingredients>
(Active energy ray sensitizer (G))
In order to improve the reactivity of the radical polymerization initiator (E), an active energy ray sensitizer (G) may be used in combination. Examples of the sensitizer (G) include thioxanthone compounds, anthracene compounds, naphthalene compounds, aminobenzoate compounds, carbazole compounds, perylene, phenothiazine, and rose bengal.

Examples of the sensitizer (G) include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxythioxanthone, 2-acetoxythioxanthone, and 2-propoxythioxanthone. Thioxanthone compounds;
Anthracene compounds such as 9,10-dimethoxyanthracene, 9,10-ethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene;
Examples include naphthalene compounds such as 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, and 1,4-dibutoxynaphthalene.

(Cationic polymerizable compound (H))
The resin composition of the present invention can further contain a cationically polymerizable compound (H) (hereinafter also referred to as compound (H)).

Compound (H) is a compound having an epoxy group which is a 3-membered ring ether, a compound having an oxetanyl group which is a 4-membered ring ether, and a compound having a cyclic carbonate group as a cationically polymerizable functional group. Compounds having an ethylenically unsaturated double bond group and a cationically polymerizable functional group are included in compound (H).

Examples of the compound having an epoxy group (epoxy compound) include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, and epoxy group-containing silane coupling agents.

Aromatic epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diglycidyl ether of propylene oxide adduct, and phenol novolac epoxy. , cresol novolac epoxy, biphenyl type epoxy, resorcin diglycidyl ether, phenyl glycidyl ether, phenol ethylene oxide glycidyl ether, t-butylphenyl glycidyl ether and the like.

The aliphatic epoxy compounds are preferably aliphatic monoalcohols, aliphatic polyalcohols, and glycidyl ethers of alkylene oxide adducts thereof.
Aliphatic epoxy compounds include, for example, 2-ethyl-hexyl glycidyl ether, diglycidyl ether of 1,4-butanediol, diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,6-hexanediol, and diglycidyl ether of glycerin. One or more types for aliphatic polyhydric alcohols such as triglycidyl ether, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, polypropylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by adding alkylene oxides (ethylene oxides and polypropylene oxides).

Examples of the compound having an ethylenically unsaturated double bond group and a cationically polymerizable functional group include glycidyl (meth)acrylate, glycidyl vinyl ether, and glycidyl allyl ether.

Alicyclic epoxy compounds include, for example, 1,2-epoxy-4-vinylcyclohexane, 1,2:8,9 diepoxylimonene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6- Examples include methylcyclohexylmethyl)adipate.

Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Examples include silane, 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, and 5,6-epoxyhexyltriethoxysilane.

Compounds having an oxetanyl group include, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, di(1-ethyl-3-oxetanyl)methyl Ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethyl-hexyloxymethyl)oxetane, phenol novolak oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) Examples include methyl}oxetane and the like.

Examples of the cyclic carbonate compound include ethylene carbonate and propylene carbonate.

<Photoacid generator (I)>
When the resin composition of the present invention contains the cationic polymerizable compound (H), it contains the photoacid generator (I).
The acid generator (I) generates an acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, or electron beams, and acts catalytically to initiate a polymerization reaction of silane compounds and cationically polymerizable compounds. This is the start of the process. Examples of acid generators include onium salt acid generators such as sulfonium salt acid generators, iodonium salt acid generators, diazonium salt acid generators, ammonium salt acid generators, and phosphonium salt acid generators. etc. can be mentioned.

Among these, sulfonium salt-based acid generators and iodonium salt-based acid generators are preferred from the viewpoint of producing an active energy ray polymerizable resin composition with excellent photodecomposition efficiency and more excellent curability.

[Sulfonium salt acid generator]
Examples of the sulfonium salt acid generator include triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium tetrakis(pentafluorophenyl)borate, and the like.

Commercially available sulfonium salt acid generators include, for example, triarylsulfonium hexafluorophosphate (CPI-110P, manufactured by San-Apro) and UVACURE 1590 (manufactured by Daicel Cytec).

[Iodonium salt acid generator]
Iodonium salt-based acid generators include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (4-tert-butylphenyl)iodonium hexafluorophosphate, -methylphenyl)(4-isopropylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis(pentafluoro)borate, and the like.

Commercially available iodonium salt-based acid generators include, for example, bis(4-tert-butylphenyl)iodonium hexafluorophosphate (WPI-170, manufactured by Wako Pure Chemical Industries, Ltd.), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.). ), IK-1 (manufactured by San-Apro), (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate (Omnicat250, IGM resins), and the like.

The active energy ray-polymerizable resin composition of the present invention may contain additives in addition to the above-mentioned components as long as they do not impair the effects of the present invention. For example, organic or inorganic fillers are added to reduce polymerization cure shrinkage, thermal expansion, dimensional stability, elastic modulus, viscosity adjustment, thermal conductivity, strength, toughness, coloring, etc. can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, etc. can be used, and the shape is not particularly limited, such as particulate or fibrous. In addition, when blending the above polymers, softeners, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy agents, dispersion stabilizers, flowability agents, and Foaming agents and the like can also be dissolved, semi-dissolved or microdispersed in the active energy ray polymerizable resin composition not as a filler but as a polymer blend or polymer alloy.

The active energy ray polymerizable resin composition of the present invention preferably does not substantially contain water or organic solvents in terms of drying equipment and drying energy. However, if the radical polymerization initiator (E), active energy sensitizer (G), or acid generator (I) becomes poorly soluble in compound (A) or compound (B) or becomes highly viscous, may contain a small amount of organic solvent to dissolve the radical polymerization initiator (E). In that case, the content of the organic solvent in the active energy ray polymerizable resin composition is within 5% by mass. There are no particular limitations on the organic solvents that can be used, but specific examples include methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbons. The viscosity of the active energy ray polymerizable resin composition can be adjusted by further adding an organic solvent such as a system solvent or water, or the viscosity can be lowered by heating the active energy ray polymerizable resin composition. You can also do it.

≪Active energy ray polymerizable resin composition≫
The active energy ray polymerizable resin composition of the present invention is any one of the following compositions (1) to (4).
(1) Compound (A), compound (B), compound (C), radical initiated polymerization agent (E) and compound (F) (2) Compound (A), compound (B), compound (D) and (3) Compound (A) containing radical polymerization initiator (E), compound (B), compound (C), compound (D) and (4) compound (A) containing radical polymerization initiator (E), compound (B), compound (D), radical polymerization initiator (E), and compound (F). By using a resin composition with such a composition, it has excellent adhesive strength in a wide temperature range from high to low temperatures. Therefore, a laminate with excellent heat resistance and heat and humidity resistance can be formed.

The resin composition of the present invention is more preferably a composition containing a compound (A), a compound (B), a compound (C), a compound (D), a radical polymerization initiator (E), and a compound (F).
By including the six components (A) to (F), it is possible to form a laminate that has particularly excellent adhesive strength in a wide temperature range from high to low temperatures, and has particularly excellent heat resistance and moist heat resistance.

≪Laminated body≫
The laminate of the present invention is a laminate including a first base material (G1), a resin composition layer made of an active energy ray polymerizable resin composition, and a second base material (G2) in this order. A laminate in which a plurality of base materials are laminated like base material (G1)/resin composition layer/base material (G2)/resin composition layer/base material (G3) may be used. For the base materials (G1), (G2), and (G3), the same type of base material can be used, or different types of base materials can be used.

The laminate can be obtained, for example, as follows.
Another transparent film is bonded to the film formed by coating an active energy ray polymerizable resin composition on one side of a transparent film that is a film-like base material, and then active energy ray polymerization is applied to one or both sides of this laminate. A laminate can be obtained by coating the transparent resin composition and further laminating it on another transparent film, glass, or transparent molded body. It goes without saying that the laminate of the present invention is not limited to the above-mentioned laminate structure.

The thickness of the resin composition layer formed from the active energy ray polymerizable resin composition in the present invention is not particularly limited, and can be adjusted as appropriate depending on the intended use. Adjustment of the viscosity and coating of the resin composition according to these embodiments can be easily carried out by adding a solvent to the active energy ray polymerizable resin composition, if necessary.

When the thickness of the resin composition layer is 0.1 to 6 μm, the viscosity is preferably 1 to 1500 mPa·s, more preferably 10 to 1300 mPa·s, and 20 to 1000 mPa·s. It is even more preferable that there be. If the viscosity is 1500 mPa·s or less, a thin film of 0.1 to 6 μm can be applied to a substrate, and the optical properties such as transmittance are also excellent. On the other hand, if the viscosity is 1 mPa·s or more, it is preferable because the thickness of the resin composition layer can be easily controlled.

Further, when the thickness of the resin composition layer is 6 to 300 μm, the viscosity is preferably 1,500 to 100,000 mPa·s, more preferably 3,000 to 50,000 mPa·s. preferable.

<Coating method>
The active energy ray polymerizable resin composition of the present invention can be applied using, for example, a Meyer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a microgravure coater, a lip coater, a comma coater, a curtain coater, a knife coater. Known coating methods such as , reverse coater, spin coater, etc. can be used.

<Base material>
The base material is not particularly limited, and may be a film base material, a glass plate, a processed paper product, or the like. On the other hand, when the active energy ray-polymerizable resin composition of the present invention is used as an adhesive for bonding two or more base materials together, in order to polymerize by irradiating the active energy rays, the active energy rays must be transmitted through the active energy rays. It is necessary to use a base material that is easy to use. In this case, it is preferable to use a transparent film or a transparent glass plate. In addition, one of the substrates to be laminated should be made of a substrate through which active energy rays do not easily pass, such as wood, metal plate, plastic plate, paper processed product, etc., and the other should be a transparent film or transparent glass plate. Polymerization and curing can also be performed by irradiating from the transparent glass plate side.

In the laminate of the present invention, it is preferable to use a film-like base material among the base materials. Examples of the film-like base material include film-like base materials such as cellophane, various plastic films, and synthetic paper, but it is preferable to use various transparent plastic films. Further, as the film-like base material, as long as it is transparent, it may be a single layer, or a multilayer film formed by laminating a plurality of base materials can be used.

In the laminate, in order to bond the resin composition and the base material, a polymerization reaction of the resin composition by irradiation with active energy rays is required. The active energy ray polymerization reaction progresses by irradiating the resin composition with active energy rays when coating or laminating the resin composition, or even after laminating the layers. It is preferable.

<Active energy rays>
The active energy ray-polymerizable resin composition of the present invention is applied onto a substrate and polymerized and cured by irradiating the formed film with active energy rays. Irradiation light sources for active energy rays mainly include light in the wavelength range of 150 to 550 nm, including low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gallium lamps, chemical lamps, black light lamps, Examples include microwave-excited mercury lamps, LED lamps, xenon lamps, and the like. In addition, semiconductor lasers, electron beams, etc. can also be used as active energy rays.

The irradiation intensity of ultraviolet rays is preferably 10 to 3000 mW/cm ² . When the irradiation intensity satisfies the above range, rapid curing becomes easy and deterioration of the base material can be suppressed to a minimum. The cumulative irradiation amount expressed as the product of irradiation intensity and irradiation time is preferably 50 to 20,000 mJ/cm ² . When the cumulative irradiation amount satisfies the above-mentioned cumulative irradiation amount, short-time curing becomes easier and productivity is further improved.

<Laminated body for optical elements>
The laminate of the present invention is preferably used as an optical laminate, more preferably an optical element laminate. The laminated structure of the optical laminate is preferably a sheet-like laminate in which multiple layers are laminated, such as transparent film/adhesive layer/transparent film, transparent film/adhesive layer/transparent film/adhesive layer/transparent film, etc. . Moreover, it is also possible to replace a part of the transparent film with glass or an optical member such as an optical molded body.

When using the laminate of the present invention as a laminate for optical elements, it is necessary to use an optical film as a base material.
The transparent film that can be used as the optical film is preferably a thermoplastic resin that has excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like. The transparent film is also called a plastic film or a plastic sheet, and includes, for example, polyolefin films such as polyvinyl alcohol film, polytriacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer; polyethylene terephthalate, and polyethylene terephthalate. Polyester films such as butylene terephthalate; polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, polyoxiranes type films, glass films, and the like.
Because of their particularly excellent transparency, the group consisting of polyacetyl cellulose films, polynorbornene films, polypropylene films, polyacrylic films, polycarbonate films, polyester films, polyvinyl alcohol films, polyimide films, and glass films are used. Preferably, it is one selected from the following.

When the transparent film is used as a laminate, each film may be used alone or two or more types may be used in combination. 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 determined as appropriate, but is generally about 1 to 500 μm, preferably 1 to 300 μm, and 5 to 200 μm from the viewpoint of strength, workability such as handling, and thin layer property. The thickness is more preferably 5 to 150 μm.

Note that when transparent films are provided on both sides of the polarizer of a polarizing plate film, which is an optical film, transparent films made of the same polymer material may be used on the front and back sides, or transparent films made of different polymer materials, etc. may be used on the front and back sides. .

When using the laminate of the present invention for an optical element, it is preferable to use an optical film as the base material. The optical film is a film obtained by coating the transparent film described above with a coating liquid having an optical function. Optical functions include light transmission, light diffusion, light collection, refraction, scattering, HAZE, and the like. Optical films include, for example, hard coat films, antistatic coated films, antiglare coated films, polarizing films, retardation films, elliptical polarizing films, antireflection films, light diffusion films, brightness enhancement films, and prism films (also referred to as prism sheets). ), and a light guide film (also referred to as a light guide plate). These may be used alone or in combination of two or more depending on the purpose.

The above-mentioned polarizing film is also called a polarizing plate, and both sides of a polyvinyl alcohol polarizer are covered with two polyacetyl cellulose films, such as a polytriacetyl cellulose protective film (hereinafter referred to as "TAC film") or a polyvinyl alcohol polarizer. A sheet-like optical film with a multilayer structure in which one or both sides of a polarizer are laminated with a polynorbornene film such as a polycycloolefin film, a polyacrylic film, a polycarbonate film, a polyester film, etc. via an adhesive. It is. As the adhesive, 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 can be applied to glass plates of liquid crystal display devices, touch panel modules, organic EL modules, etc., and transparent films such as the various plastic films described above. It is preferable that the active energy ray polymerizable resin composition is further laminated and adhered to be used as 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 is preferably produced, for example, by any of the following methods (I) to (III).

(I) Coating an active energy ray polymerizable adhesive on one side of a protective film that is a first transparent film to form a first polymerizable adhesive layer;
Coating an active energy ray polymerizable adhesive on one side of a second protective film, which is a transparent film, to form a second active energy ray polymerizable adhesive layer,
Next, the first active energy ray-polymerizable adhesive layer surface and the second active energy ray-polymerizable adhesive layer surface are simultaneously/or sequentially superimposed on each surface of the polyvinyl alcohol polarizer, and then active energy rays A method of manufacturing by irradiating and polymerizing and curing the first active energy ray polymerizable adhesive layer and the second active energy ray polymerizable adhesive layer,

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

(III) The end where the protective film that is the first transparent film and the polyvinyl alcohol polarizer are overlapped, and the end where the second protective film is overlaid on the side of the polyvinyl alcohol polarizer that does not have the first protective film. After applying the active energy ray-polymerizable adhesive, the adhesive is passed between rolls to spread the adhesive between each layer. Next, there is a method of manufacturing by irradiating active energy rays and polymerizing and curing the active energy ray polymerizable adhesive, but the method is not particularly limited.

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. Furthermore, in the Examples and Comparative Examples below, "parts" and "%" represent "parts by mass" and "% by mass", respectively, and "RH" means relative humidity.
Further, the blending amounts in the table are parts by mass, and values other than the solvent are nonvolatile content equivalent values. In addition, a blank column in the table indicates that it is not blended.

<Measurement method of weight average molecular weight and number average molecular weight>
"Weight average molecular weight" is a value measured using gel permeation chromatography "HLC-8220GPC" manufactured by Tosoh Corporation, and separation column: "TSK-GELSUPER H5000", "TSK-GELSUPER H4000" manufactured by Tosoh Corporation. , "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" were connected in series, using tetrahydrofuran at a temperature of 40°C as the mobile phase, and measured at a flow rate of 0.6 ml/min. Weight in terms of polystyrene. Average molecular weight and number average molecular weight.

<Method for measuring hydroxyl value>
The measurement of hydroxyl value is as follows. Accurately weigh approximately 1 g of the sample into a stoppered Erlenmeyer flask, add 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture to dissolve it, and then add an acetylating agent (25 g of acetic anhydride). Exactly 5 ml of a solution (dissolved with pyridine to make the volume 100 ml) was added and stirred for about 1 hour. To this, a phenolphthalein test solution was added as an indicator, and stirring was continued for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until it turned pale pink, and the hydroxyl value was determined by the following formula. The hydroxyl value was the value of the resin in a dry state (unit: mgKOH/g).
Hydroxyl value (mgKOH/g) = [{(ba) x F x 28.25}/S]/(nonvolatile content concentration/100) + D
However, S: Amount of sample collected (g)
a: Consumption amount (ml) of 0.1N alcoholic potassium hydroxide solution
b: Consumption amount (ml) of 0.1N alcoholic potassium hydroxide solution in blank experiment
F: Titer of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH/g)

The materials used in the examples and comparative examples are as follows.
<Compound (A) having an ethylenically unsaturated double bond group having a hydroxyl group>
4HBA: 4-Hydroxybutyl acrylate CHDMMA: Cyclohexane dimethanol monoacrylate ester <Ethylenically unsaturated double bond group-containing compound (B) having no hydroxyl group>
[Compound (b1) with a weight average molecular weight of 1,000 to 60,000, having a urethane structure and two ethylenically unsaturated double bond groups, and having no hydroxyl group]
b1-1: Urethane acrylate 1 produced by the following method was used.
b1-2: Urethane acrylate 2 produced by the following method was used.

<Production of urethane acrylate 1>
Polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.: PTG850, hydroxyl value 127.1 mgKOH/g) was placed in a 5-neck separable flask equipped with a stirrer, reflux condenser, gas introduction tube, thermometer, and dropping funnel. 81.6 parts and 41.4 parts of isophorone diisocyanate were charged, and the temperature was raised to 60° C. while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the mixture was reacted 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 separable flask over 1 hour. After the dropwise addition was completed, stirring was continued at 80° C. for 3 hours, and then it was confirmed by infrared absorption spectrum that there was no absorption peak of isocyanate groups, and the reaction was terminated to obtain urethane acrylate 1. Its weight average molecular weight was 4,000.

<Production of urethane acrylate 2>
A compound in which 2 mol of ε-caprolactone was added to 1 mol of 2-hydroxyethyl acrylate (manufactured by Daicel Chemical: Plaxel 113.4 parts of FA2D (hydroxyl value: 163.0 mgKOH/g), 36.6 parts of isophorone diisocyanate, and 0.15 parts of hydroquinone monomethyl ether were charged, and the temperature was raised to 60° C. while introducing dry air. 0.04 part of dibutyltin dilaurate was added thereto, and the temperature was raised to about 80° C. for 3 hours to react. The reaction was terminated when it was confirmed that there was no absorption peak of isocyanate groups in the infrared absorption spectrum, and urethane acrylate 2 was obtained. Its weight average molecular weight was 1,300.

[Compound (b2) having two or more ethylenically unsaturated double bond groups and no hydroxyl group]
TPGDA: tripropylene glycol diacrylate INATA: isocyanuric acid ethylene oxide (EO) modified triacrylate

[Compound (b3) having one ethylenically unsaturated double bond group and no hydroxyl group]
IBXA: Isoboronyl acrylate

<Metal salt of organic acid (C)>
[Metal salt of an organic acid (c1) formed from an organic acid that does not have an active energy ray polymerizable functional group and a metal ion]
potassium stearate

[Metal salt of an organic acid (c2) formed from an organic acid having an active energy ray polymerizable functional group and a metal ion]
Potassium acrylate Zinc diacrylate

<Compound (D) having an amino group with a number average molecular weight of 500 to 40,000>
[Compound (d1) having an amino group without an ethylenically unsaturated double bond group]
<Production of polyesters (d1-1) to (d1-4) having amino groups without ethylenically unsaturated double bonds>
(Production of polyester (d1-1) having an amino group)
A 5-neck separable flask equipped with a stirrer, reflux condenser, distillation device, gas introduction tube, thermometer, and dropping funnel was charged with 61.1 parts of hexylamine and 144.1 parts of acrylic acid, and dry air was introduced. The reaction was continued at 80° C. for 4 hours. It was confirmed that there was no absorption peak of the acrylic group in the infrared absorption spectrum. Then, while introducing nitrogen gas, 236.3 parts of 1,6-hexanediol and 0.34 parts of a solution of tetra-n-butoxytitanium diluted in 1,6-hexanediol to a concentration of 1 w% were added, and the mixture was stirred. At the same time, the temperature was raised to 150°C. At the start of dehydration, the temperature was increased by 20° C. per hour, and when it reached 220° C., the temperature was kept constant to allow reaction. The reaction was terminated when the acid value was confirmed to be 3 mgKOH/g or less, and a polyester (d1-1) having amino groups was obtained. Its number average molecular weight was 440. (dicarboxylic acid/diol = 1/2)

(Production of polyester (d1-2) having amino groups)
A 5-neck separable flask equipped with a stirrer, reflux condenser, distillation device, gas introduction tube, thermometer, and dropping funnel was charged with 61.1 parts of hexylamine and 144.1 parts of acrylic acid, and dry air was introduced. The reaction was continued at 80° C. for 4 hours. It was confirmed that there was no absorption peak of the acrylic group in the infrared absorption spectrum. Then, while introducing nitrogen gas, 177.3 parts of 1,6-hexanediol and 0.34 parts of a solution of tetra-n-butoxytitanium diluted in 1,6-hexanediol to a concentration of 1 w% were added, and the mixture was stirred. At the same time, the temperature was raised to 150°C. At the start of dehydration, the temperature was increased by 20° C. per hour, and when it reached 220° C., the temperature was kept constant to allow reaction. The reaction was terminated when the acid value was confirmed to be 3 mgKOH/g or less, and a polyester (d1-2) having an amino group was obtained. Its number average molecular weight was 770. (Dicarboxylic acid/diol = 2/3)

(Production of polyester (d1-3) having amino groups)
A 5-neck separable flask equipped with a stirrer, reflux condenser, distillation device, gas introduction tube, thermometer, and dropping funnel was charged with 61.1 parts of hexylamine and 144.1 parts of acrylic acid, and dry air was introduced. The reaction was continued at 80° C. for 4 hours. It was confirmed that there was no absorption peak of the acrylic group in the infrared absorption spectrum. Then, while introducing nitrogen gas, 147.7 parts of 1,6-hexanediol and 0.34 parts of a solution of tetra-n-butoxytitanium diluted in 1,6-hexanediol to a concentration of 1 w% were added, and the mixture was stirred. At the same time, the temperature was raised to 150°C. At the start of dehydration, the temperature was increased by 20° C. per hour, and when it reached 220° C., the temperature was kept constant to allow reaction. The reaction was terminated when the acid value was confirmed to be 3 mgKOH/g or less, and a polyester (d1-3) having an amino group was obtained. Its number average molecular weight was 1,400. (dicarboxylic acid/diol = 4/5)

(Production of polyester (d1-4) having an amino group)
A 5-neck separable flask equipped with a stirrer, reflux condenser, distillation device, gas introduction tube, thermometer, and dropping funnel was charged with 61.1 parts of hexylamine and 144.1 parts of acrylic acid, and dry air was introduced. The reaction was continued at 80° C. for 4 hours. It was confirmed that there was no absorption peak of the acrylic group in the infrared absorption spectrum. Then, while introducing nitrogen gas, 132.9 parts of 1,6-hexanediol and 0.34 parts of a solution of tetra-n-butoxytitanium diluted in 1,6-hexanediol to a concentration of 1 w% were added, and the mixture was stirred. At the same time, the temperature was raised to 150°C. At the start of dehydration, the temperature was increased by 20° C. per hour, and when it reached 220° C., the temperature was kept constant to allow reaction. The reaction was terminated when the acid value was confirmed to be 3 mgKOH/g or less, and an amino group-containing polyester (d1-4) was obtained. Its number average molecular weight was 2,700. (dicarboxylic acid/diol = 8/9)

<Acrylic resins having amino groups (d1-5) to (d1-6)>
The following poly[2-(dimethylamino)ethyl methacrylate] manufactured by Tokyo Kasei Co., Ltd. was used.
・d1-5: Poly[2-(dimethylamino)ethyl methacrylate], number average molecular weight 25,000
・d1-6: Poly[2-(dimethylamino)ethyl methacrylate], number average molecular weight 50,000

[Compound (d2) having an ethylenically unsaturated double bond group and an amino group]
The following amine-modified acrylate manufactured by Daicel Allnex was used.
・Ebecryl7100: Amine-modified acrylate, number average molecular weight: 1180, number of acrylic groups: 2
・Ebecryl80: Amine-modified acrylate, number average molecular weight: 1300, number of acrylic groups: 4

<Production of compound (d2-1) having an ethylenically unsaturated double bond group and an amino group>
In a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, TETRAD-X (N,N,N',N',-tetraglycidyl) manufactured by Mitsubishi Gas Chemical Co., Ltd. 360.5 parts of -m-xylene diamine and 288.2 parts of acrylic acid were charged and reacted at 80°C for 4 hours while introducing dry air.It was confirmed that there was no absorption peak of epoxy groups in the infrared absorption spectrum. A compound (d2-1) having four acryloyl groups, four hydroxyl groups, and two amino groups was obtained.The number average molecular weight was 640.

<Production of acrylic resin (d2-2) having an ethylenically unsaturated double bond group and an amino group>
50.6 parts of ethyl acetate, 180 parts by mass of N,N-diethylaminoethyl methacrylate, and 20 parts by mass of 2-hydroxyethyl methacrylate were charged into a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and nitrogen After raising the temperature to 50°C while replacing the mixture, 2.3 parts of 1-thioglycerol was added, and the temperature was raised to 70°C. 16.8 parts by mass of ethyl acetate and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were placed in a dropping tank.
After adding parts by mass and stirring until uniform, the mixture was added dropwise to the reaction tank over 7 hours.The reaction was then continued at the same temperature for 1 hour, and it was confirmed by solid content measurement that 95% or more had reacted. Next, the inside of the flask was purged with air, 32.8 parts by mass of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part by mass of hydroquinone were charged, and a reaction was carried out at 70° C. for 4 hours. After confirming the disappearance of the peak at 2270 cm ^-1 based on isocyanate groups by FTIR, the reaction solution was cooled to obtain a solution of acrylic resin (d2-2) having an ethylenically unsaturated double bond group and an amino group. . Its number average molecular weight was 22,000. The portion to be used was dried by heating at 180° C. for 20 minutes before use.

<Radical initiator (E)>
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO manufactured by IGM resins B.V.)

<Boric acid compound (F)>
Boric acid 1,4-benzenediboronic acid

<Active energy ray sensitizer (G)>
2-ITX: 2-isopropylthioxanthone

[Example 1]
40 parts of 4HBA as compound (A), 5 parts of b1-1 (urethane acrylate 1) as compound (B), 36 parts of TPGDA, 15 parts of INATA, 1 part of potassium stearate as compound (C), radical polymerization 2 parts of TPO as the initiator (E) and 1 part of boric acid as the compound (F) were placed in a 300 ml glass bottle shielded from light, thoroughly stirred with a disper, thoroughly degassed, and activated energy rays were added. A polymerizable resin composition was obtained.

[Examples 2 to 64, Comparative Examples 1 to 8]
As shown in Tables 1 to 5, active energy ray polymerizable resin compositions were obtained in the same manner as in Example 1, except that the composition and blending amount (parts by mass) were changed.

<Evaluation of laminate>
The following laminate X1 was produced using the obtained active energy ray polymerizable resin composition, and the laminate was evaluated by the following method. The results are shown in Tables 1 to 5.

<Manufacture of laminate X1 (polarizing plate)>
As the transparent film (1), a 40 μm thick ultraviolet absorber-containing polytriacetyl cellulose (hereinafter abbreviated as TAC) film was used, and as the transparent film (2), a 20 μm thick TAC film containing no ultraviolet absorber was used. . Corona treatment was performed on the surface of one side of the transparent films (1) and (2) at a discharge rate of 300 W min/m ² , and within 1 hour thereafter, an active energy ray polymerizable adhesive shown in Tables 1 to 3 was applied. A coating was formed on the corona-treated surface of each film using a wire bar coater to a thickness of 2 μm. A polyvinyl alcohol-based (hereinafter abbreviated as PVA) polarizer is sandwiched between the active energy ray polymerizable adhesive layer formed on the transparent films (1) and (2), and the transparent film (1)/adhesive layer/PVA A laminate consisting of polarizer/adhesive layer/transparent film (2) was obtained. This laminate was fixed on all sides with cellophane tape so that the transparent film (1) was in contact with the tin plate, and then fixed to the tin plate.
Laminated body X1 (polarizing plate) was created by irradiating ultraviolet rays with a maximum illuminance of 300 mW/cm ² and a cumulative light amount of 300 mJ/cm ² from the transparent film (2) side using an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation). .

<Low temperature adhesive strength>
The obtained laminate X1 (polarizing plate) was cut into a size of 25 mm x 150 mm using a cutter to prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the surface of the transparent film (2) of the sample, and it was attached onto a metal plate using a laminator to obtain a laminate of a polarizing plate and a metal plate. The obtained laminate was used as a laminate for measuring adhesive strength. A peeling trigger was provided in advance between the transparent film (2) and the polarizer on the polarizing plate, and the laminate for measurement was pulled at a 90° angle at a speed of 300 mm/min at 0°C. It was peeled off and used as peeling force. At this time, the peeling force between the PVA polarizer and the transparent film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
[Evaluation criteria]
◎: Not peelable or polarizing plate destroyed, very good ○: Peeling possible without destroying the polarizing plate, peeling force 2.0 (N/25mm) or more, excellent △: Peeling force 1.0 ( N/25mm) or more and less than 2.0 (N/25mm), practically possible ×: Peeling force is less than 1.0 (N/25mm), not practical

<Room temperature adhesive strength>
The obtained laminate X1 (polarizing plate) was cut into a size of 25 mm x 150 mm using a cutter to prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the surface of the transparent film (2) of the sample, and it was attached onto a metal plate using a laminator to obtain a laminate of a polarizing plate and a metal plate. The obtained laminate was used as a laminate for measuring adhesive strength. A peeling trigger was provided in advance between the transparent film (2) and the polarizer on the polarizing plate, and the laminate for measurement was pulled at a 90° angle at a speed of 300 mm/min at 25°C. It was peeled off and used as peeling force. At this time, the peeling force between the PVA polarizer and the transparent film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
[Evaluation criteria]
◎: Not peelable or polarizing plate destroyed, very good ○: Peeling possible without destroying the polarizing plate, peeling force 2.0 (N/25mm) or more, excellent △: Peeling force 1.0 ( N/25mm) or more and less than 2.0 (N/25mm), practically possible ×: Peeling force is less than 1.0 (N/25mm), not practical

<High temperature adhesive strength>
The obtained laminate X1 (polarizing plate) was cut into a size of 25 mm x 150 mm using a cutter to prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the surface of the transparent film (2) of the sample, and it was attached onto a metal plate using a laminator to obtain a laminate of a polarizing plate and a metal plate. The obtained laminate was used as a laminate for measuring adhesive strength. A peeling trigger was provided in advance between the transparent film (2) and the polarizer on the polarizing plate, and the laminate for measurement was pulled at a 90° angle at a speed of 300 mm/min at 80°C. It was peeled off and used as peeling force. At this time, the peeling force between the PVA polarizer and the transparent film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
[Evaluation criteria]
◎: Not peelable or polarizing plate destroyed, very good ○: Peeling possible without destroying the polarizing plate, peeling force 2.0 (N/25mm) or more, excellent △: Peeling force 1.0 ( N/25mm) or more and less than 2.0 (N/25mm), practically possible ×: Peeling force is less than 1.0 (N/25mm), not practical

<Heat resistance test and moist heat resistance test (optical property evaluation) of polarizing plate>
The obtained laminate X1 (polarizing plate) was cut into a size of 40 mm x 40 mm and used as a test sample for the heat resistance test and the moist heat resistance test. Optical properties were evaluated before and after the test, and the difference was used as the evaluation result. . The optical properties were evaluated using an ultraviolet-visible spectrophotometer V-730 manufactured by JASCO Corporation with an optional accessory for polarizing plate measurement. The degree of polarization and the b value of the single hue were used to evaluate the optical properties.

<Heat resistance test>
The test sample was tested at 110°C for 500 hours, and the difference in b value before and after the test was evaluated.
Difference in b value (Δb) = (b value after test) - (b value before test)
[Evaluation criteria]
◎: Δb is 0.00 or more and less than 2.00, very excellent ○: Δb is 2.00 or more and less than 4.00, excellent △: Δb is 4.00 or more and 6.00 or less, practical ×: Δb is 6 Greater than .00, impractical

<Moisture heat resistance test>
The test sample was tested at 65° C. and 95% RH for 500 hours, and the difference in polarization degree before and after the test was evaluated.
Difference in polarization degree (ΔP) = (Polarization degree P after test) - (Polarization degree P before test)
[Evaluation criteria]
◎: ΔP is -0.50 or more and 0.00 or less, very excellent ○: ΔP is -1.00 or more and less than -0.50, excellent △: ΔP is -2.00 or more and less than -1.00, practical ×: ΔP is less than -2.00, not practical

Claims (7)

Ethylenically unsaturated double bond group-containing compound (A) having a hydroxyl group (excluding (D)), ethylenically unsaturated double bond group-containing compound (B) not having a hydroxyl group (however, (D) An active energy ray polymerizable resin composition comprising a radical polymerization initiator (E) and a radical polymerization initiator (E),
An active energy ray polymerizable resin composition for forming a laminate that satisfies any of the following (1) to (4).
(1) Further contains a metal salt of an organic acid (C) and a boric acid compound (F).
(2) Furthermore , a compound (d2) containing an ethylenically unsaturated double bond group is contained as an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000.
(3) It further contains a metal salt of an organic acid (C) and an amino group-containing compound (D) having a number average molecular weight of 500 to 40,000.
(4) Further contains an amino group-containing compound (D) and a boric acid compound (F) having a number average molecular weight of 500 to 40,000. Ethylenically unsaturated double bond-containing compound (A) having a hydroxyl group, ethylenically unsaturated double bond-containing compound (B) not having a hydroxyl group, metal salt of an organic acid (C), number average molecular weight 500~ An active energy ray polymerizable resin composition comprising a 40,000 amino group-containing compound (D), a radical polymerization initiator (E), and a boric acid compound (F). In 100% by mass of the active energy ray polymerizable resin composition, 10 to 60% by mass of compound (A), 30 to 89% by mass of compound (B), 0.01 to 5% by mass of compound (C), The active energy ray polymerizable resin composition according to claim 2, containing 0.1 to 20% by mass of D), 0.1 to 10% by mass of compound (E), and 0.1 to 7% by mass of compound (F). thing. The ethylenically unsaturated double bond group-containing compound (B) having no hydroxyl group is
A compound (b1) having a weight average molecular weight of 1,000 to 60,000 and having a urethane structure and two ethylenically unsaturated double bond groups and having no hydroxyl group and two ethylenically unsaturated double bond groups. The active energy ray polymerizable resin composition according to any one of claims 1 to 3, which contains at least one compound (b2) (excluding (b1)) having at least one hydroxyl group. The active energy ray polymerizable resin composition according to claim 4, which contains 1 to 20 mass % of the compound (b1) and 9 to 69 mass % of the compound (b2) in 100 mass % of the active energy ray polymerizable resin composition. A laminate comprising a first base material (G1), a resin composition layer comprising the active energy ray polymerizable resin composition according to claim 5, and a second base material (G2) in this order. The base material (G1) and the base material (G2) each independently include a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacrylic film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film. The laminate according to claim 6, which is any one selected from the group consisting of a glass film and a glass film.