JP7006226B2 - Active energy ray-curable adhesive composition and laminate - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is an active energy ray capable of adhering a hydrolyzable plastic film or a sheet (hereinafter referred to as "hydrolytable plastic film") by irradiation with an active energy ray such as ultraviolet rays, visible light, or an electron beam. The present invention relates to a curable adhesive composition and a laminate having a hydrolyzable plastic film as a base material.

Various displays such as liquid crystal displays and organic EL displays are thin, lightweight, and have low power consumption, so mobile devices equipped with touch panels such as smartphones, tablets, and car navigation systems, as well as personal computers, televisions, digital signage, etc. Widely used in medium- and large-sized image display devices.
Various optical films are used for the display, and the optical films include a hard coat film having functionality such as anti-fingerprint and anti-glare, a front plate of a touch panel, a polarizing plate, a retardation film, and a viewing angle compensation. Examples thereof include a film, a brightness improving film, an antireflection film, an antiglare film, a lens sheet and a diffusion sheet.

These optical films include a variety of cellulose ester films such as triacetyl cellulose, polyester films such as polyethylene terephthalate, (meth) acrylic films or sheets such as polymethylmethacrylate, and carbonate films or sheets such as polycarbonate. It is often used by laminating various types of plastic films. For bonding the plastic films to each other, an active energy ray-curable adhesive is widely used because the curing speed is high and the productivity is excellent.

In recent years, mobile devices equipped with touch panels such as smartphones and tablets are often used as car navigation systems, and the active energy ray-curable adhesive used in the manufacture of optical films has a high degree of moisture resistance and heat resistance for in-vehicle use. It is requested.

Conventionally, an active energy ray-curable composition having excellent moisture and heat resistance has been proposed.

Patent Document 1 discloses a curable composition containing a curable component composed of a (meth) acrylate monomer containing a polyfunctional (meth) acrylate and a carbodiimide compound.

Patent Document 2 describes a curable composition containing a curable component composed of a (meth) acrylate monomer containing a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate, and a carbodiimide compound. A curable composition comprising a monofunctional (meth) acrylate in which the monofunctional (meth) acrylate has a phenoxybenzyl group is disclosed.

Japanese Unexamined Patent Publication No. 2014-185336 Japanese Unexamined Patent Publication No. 2014-185337

The cured product of the curable composition described in Patent Documents 1 and 2 was excellent in moisture resistance and heat adhesion. However, the curable composition contains urethane (meth) acrylate as a polyfunctional (meth) acrylate component, and at least one of the two types of substrates of the optical film is a hydrolyzable plastic film such as a cellulose ester film. In a harsh moist heat environment (for example, temperature 85 ° C., relative humidity 85%) assuming in-vehicle use, the hydrolyzable plastic film and / or the other base material becomes fragile, and the hydrolyzable plastic film is adhered. There has been a problem of causing deterioration such as white turbidity and yellowing of the laminated film having (hereinafter referred to as "deterioration of the laminated film").
The present invention has been made in view of the above circumstances, and is an active energy ray-curable adhesive which has excellent adhesive strength in a harsh moist heat environment and can suppress deterioration of a laminate having a hydrolyzable plastic film as a base material. It is an object of the present invention to provide a composition.

According to the present inventors, the deterioration of the laminate is caused by the promotion of hydrolysis of the hydrolyzable plastic film by the metal catalyst derived from urethane (meth) acrylate in the curable composition. It was presumed that the acid deteriorates the hydrolyzable plastic film itself, or the carboxylic acid is transferred from the hydrolyzable plastic film to the other base material and weakens the other base material.
Therefore, as a result of diligent studies to solve the above problems, an active energy ray-curable adhesive composition containing a urethane (meth) acrylate and an acid scavenger has excellent adhesive strength in a harsh moist heat environment and can be used as a base material. The present invention has been completed by finding that deterioration of a laminate having a hydrolyzable plastic film can be suppressed.

The present invention is as follows.
[1] The urethane (meth) acrylate and an acid trapping agent are contained, the urethane (meth) acrylate contains a polycarbonate-based urethane (meth) acrylate, and the acid trapping agent contains at least one of a carbodiimide compound or a hydrotalcite calcined product. , Active energy ray-curable adhesive composition for hydrolyzable plastic films or sheets.
[ 2 ] The active energy ray-curable adhesive composition for a hydrolyzable plastic film or sheet according to [1 ], which further contains a hydroxyl group-containing (meth) acrylate.
[ 3 ] The active energy ray-curable adhesive composition for a hydrolyzable plastic film or sheet according to [1] or [ 2], wherein the hydrolyzable plastic film or sheet is a cellulose ester film or sheet.
[ 4 ] Consists of a substrate, a cured product of the hydrolyzable plastic film according to any one of [1] to [ 3 ], or an active energy ray-curable adhesive composition for a sheet, and the other substrate. It ’s a laminate,
A laminate in which both or one of the substrate and the other substrate is a hydrolyzable plastic film or sheet.

According to the active energy ray-curable adhesive composition of the present invention, it is possible to suppress deterioration of a laminate having a hydrolyzable plastic film as a base material, which has excellent adhesive strength in a severe moist heat environment.

Hereinafter, various embodiments of the techniques disclosed in the present specification will be described in detail. In the present specification, the acrylic film and / or the methacrylic film is a (meth) acrylic film, the acrylate and / or methacrylate is a (meth) acrylate, and the acryloyl group and / or the methacryloyl group is a (meth) acryloyl. The group and acrylic acid and / or methacrylic acid are referred to as (meth) acrylic acid.

The present invention relates to an active energy ray-curable adhesive composition for a hydrolyzable plastic film, which comprises a urethane (meth) acrylate and an acid scavenger.
Hereinafter, urethane (meth) acrylate, an acid scavenger, an active energy ray-curable adhesive composition for a hydrolyzable plastic film, a method of use, and a laminate and a method for producing the same will be described in detail.

1. 1. Urethane (meth) acrylate The urethane (meth) acrylate in the present invention is a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and is a (meth) acrylate compound having a urethane bond.
The raw material compound of urethane (meth) acrylate and the production method will be described below.

1-1. Raw Material Compounds Polyols, organic polyisocyanates, hydroxyl group-containing (meth) acrylates and metal catalysts are used as raw material compounds for urethane (meth) acrylates.

Specific examples of the polyol include a polyether polyol, a polycarbonate polyol, a polyester polyol and the like.
Examples of the polyether polyol include polyalkylene glycol having two or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polycarbonate polyol include reaction products of carbonate and diol. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and the like. Examples of the diol include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, nonanediol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1, Examples thereof include 5-pentanediol and hydroxypivalic acid neopentyl glycol ester (hereinafter referred to as "low molecular weight diol").
Examples of the polyester polyol include a reaction product of at least one selected from the group consisting of the above-mentioned low molecular weight diols, polyether polyols and polycarbonate polyols and an acid component. Specific examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof, and ring-opening reaction products of polycarbonate diol and caprolactone. And so on.
As the above-mentioned polyol, only one kind may be used, or two or more kinds may be used in combination.

Examples of the organic polyisocyanate include diisocyanate and triisocyanate.
Specific examples of the diisocyanate include aromatic diisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate and naphthalenedi isocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4. Examples thereof include alicyclic diisocyanates such as'-dicyclohexylmethane diisocyanate, norbornene diisocyanate and hydrogenated xylene diisocyanate.
Specific examples of the triisocyanate include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate.
The organic polyisocyanate may be used alone or in combination of two or more.

Specific examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
As the hydroxyl group-containing (meth) acrylate, only one type may be used, or two or more types may be used in combination.

Specific examples of the metal catalyst include tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and dibutyltin diacetylacetonate, and bismuth compounds such as bismuth dioctate.
As the metal catalyst, only one kind may be used, or two or more kinds may be used in combination.

A preferred embodiment of the urethane (meth) acrylate is that a polyether urethane (meth) acrylate using a polyether polyol as a raw material polyol and a polycarbonate polyol as a raw material polyol are used because deterioration of the laminate in a moist heat environment can be suppressed. The polycarbonate-based urethane (meth) acrylate that has been used is preferable, and the polycarbonate-based urethane (meth) acrylate is more preferable.

1-2. Production method Urethane (meth) acrylate can be produced by heating and stirring polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate in the presence of a metal catalyst and, if necessary, in the presence of a reaction solvent to form urethane. can.
In this case, the polyol, the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate can be charged together and reacted (hereinafter referred to as "one-step reaction"), and the polyol and the organic polyisocyanate are reacted to form an isocyanate group-containing prepolymer. Can also be added with a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “two-step reaction”).

The ratio of the polyol to the organic polyisocyanate may be appropriately set according to the structure of the urethane (meth) acrylate to be finally obtained. Specifically, it is organic with respect to 1 mol of the total amount of hydroxyl groups in the polyol. The total amount of isocyanate groups in the polyisocyanate is preferably 1.05 to 2 mol.
The ratio of the hydroxyl group-containing (meth) acrylate is preferably such that the isocyanate group does not remain in the obtained urethane (meth) acrylate.
In the case of producing by the above-mentioned two-step reaction, the hydroxyl group-containing (meth) acrylate is preferably 1.0 to 1.5 mol with respect to the total isocyanate group amount of 1 mol of the isocyanate group-containing prepolymer.
In the case of producing by the above-mentioned one-step reaction, with respect to 1 mol of the total amount of isocyanate groups remaining in the isocyanate group-containing prepolymer calculated based on the structure of the urethane (meth) acrylate to be finally obtained. A ratio of 1.0 to 1.5 mol of the hydroxyl group-containing (meth) acrylate is preferable.
Further, in this case, the ratio of the total amount of hydroxyl groups of the polyol and the acid group-containing (meth) acrylate is preferably 1.0 to 1.5 mol with respect to the total amount of isocyanate groups of 1 mol of the organic polyisocyanate.

When the molecular weight of the urethane (meth) acrylate produced by this reaction is high, the reaction mixture becomes highly viscous and stirring may be difficult. Therefore, a reaction solvent can be added to the reaction components.
The reaction solvent is preferably one that does not participate in the urethanization reaction, and examples thereof include aromatic solvents such as toluene and xylene, and organic solvents such as ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
When an organic solvent is used, the blending amount may be appropriately set according to the viscosity of the urethane (meth) acrylate to be produced, but is preferably set to 0 to 70% by weight in the reaction solution.
Here, the reaction solution means the total amount of the raw material compounds when only the raw material compounds are used, and means the total amount including these when the reaction solvent or the like is used in addition to the raw material compounds. Specifically, it is used to mean a solution containing a polyol, an organic polyisocyanate, a hydroxyl group-containing (meth) acrylate, a reaction solvent used as necessary, and the like.

As the reaction solvent, a (meth) acrylate compound other than urethane (meth) acrylate and urethane (meth) acrylate used as a component of the composition together with or in place of the above organic solvent (hereinafter, “other (meth) acrylate”). ") Can also be blended. As the other (meth) acrylate, those described as other components described later can be used. When the urethanization reaction is carried out by blending other (meth) acrylates and the obtained urethane (meth) acrylate is blended in the active energy ray-curable adhesive composition, the composition is different from the case where the organic solvent is blended. It is preferable because it does not need to be dried after applying the substance.
When the other (meth) acrylate is blended in the reaction component, the blending amount may be appropriately set according to the ratio of the other (meth) acrylate finally blended in the composition. For example, 10 to 10 to 10 in the reaction solution. It is preferably set to 70% by weight, more preferably 10 to 50% by weight.

The blending amount of the metal catalyst may be a catalyst amount, for example, 0.01 to 1,000 wtppm, more preferably 0.1 to 1,000 wtppm, and more preferably 0.1 to 1,000 wtppm with respect to the reaction solution. When the blending amount of the metal compound is 0.01 wtppm or more, the urethanization reaction can proceed preferably, and when it is 1,000 wtppm or less, the coloring of the obtained urethane (meth) acrylate can be suppressed. can.

In the case of a one-step reaction, the metal catalyst can be added at the time of charging the polyol, the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate, and in the case of the two-step reaction, it can be added at the time of charging the polyol and the organic polyisocyanate.

In the urethanization reaction, a small amount of a chain extender can be added for the purpose of adjusting the molecular weight.
As the chain extender, those usually used in the urethanization reaction can be used, and the same ones as those of the above-mentioned low molecular weight polyols can be mentioned.

In the urethanization reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing the polymerization of the (meth) acryloyl group of the raw material or the product, and further, an oxygen-containing gas may be introduced into the reaction solution.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone and phenothiazine. Examples thereof include organic polymerization inhibitors such as copper chloride and inorganic polymerization inhibitors such as copper sulfate, and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate. The polymerization inhibitor may be used alone or in combination of two or more. The ratio of the polymerization inhibitor is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm in the reaction solution.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

The reaction temperature may be appropriately set according to the raw material used, the structure and molecular weight of the target urethane (meth) acrylate, and the like, but is usually preferably 25 to 150 ° C, more preferably 30 to 120 ° C. The reaction time may be appropriately set according to the raw material to be used, the structure and molecular weight of the target urethane (meth) acrylate, and the like, but is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

The weight average molecular weight (hereinafter referred to as “Mw”) of the urethane (meth) acrylate in the present invention is usually about 3,000 to 100,000, preferably 5,000 to 50,000.

In the present invention, Mw is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene, and means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: 40 ° C
・ Eluent: Tetrahydrofuran ・ Molecular weight standard: Polystyrene

The content ratio of urethane (meth) acrylate is when the curable component is 100 parts by mass.
In terms of improving the adhesive strength, 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, and 15 parts by mass or more is particularly preferable. 50 parts by mass or less is preferable, 40 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable.
The curable component is an unsaturated group-containing component that is cured by active energy rays, and when other (meth) acrylate described later is blended, it means urethane (meth) acrylate and other (meth) acrylate.

2. 2. Acid Scavenger The acid scavenger in the present invention is not particularly limited as long as it can capture carboxylic acid, and captures carboxylic acid generated from a hydrolyzable plastic film under moist heat conditions, and the hydrolyzable plastic film. And / or by suppressing the weakening of the other base material, it plays a role of suppressing the deterioration of the laminated body.

Examples of the acid scavenger include carbodiimide compounds, hydrotalcite calcined products, bismuth hydroxide compounds, tertiary amine compounds, epoxy compounds, oxazoline compounds and the like.
Among these, it is preferable to contain at least one selected from the group consisting of a carbodiimide compound, a hydrotalcite calcined product, a tertiary amine compound and an epoxy compound, and the carbodiimide is highly effective in suppressing deterioration of the laminate. It is more preferable to contain at least one selected from the group consisting of compounds, hydrotalcite calcined products and tertiary amine compounds. It is particularly preferable to contain at least one of the carbodiimide compound and the hydrotalcite calcined product in that even a relatively small amount of addition has a large effect of suppressing deterioration of the laminate.
2-1. Carbodiimide compound

The carbodiimide compound is a compound having a carbodiimide group (-N = C = N-) in the molecule, and is a monocarbodiimide compound (a compound having one carbodiimide group) and a polycarbodiimide compound (a compound having two or more carbodiimide groups). Can be mentioned.
Among these, a polycarbodiimide compound is preferable because it has a large effect of suppressing deterioration of the laminate.

Examples of the monocarbodiimide compound include an aliphatic monocarbodiimide compound, an alkylaralkylcarbodiimide compound, an alicyclic monocarbodiimide compound, and an aromatic monocarbodiimide compound.
Specific examples of the aliphatic monocarbodiimide compound include 1,3-dimethylcarbodiimide, 1,3-diisopropylcarbodiimide, 1-isopropyl-3-t-butylcarbodiimide, 1,3-dihexylcarbodiimide, and 1,3-dioctylcarbodiimide. Examples thereof include 1-isopropyl-3-dodecylcarbodiimide, 1,3-dioctyldecylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
Specific examples of the alkylaralkylcarbodiimide compound include benzylisopropylcarbodiimide and the like.
Specific examples of the alicyclic monocarbodiimide compound include 1,3-dicyclohexylcarbodiimide and the like.
Specific examples of aromatic monocarbodiimide compounds include N, N'-diphenylcarbodiimide, N, N'-dio-tolylcarbodiimide, N, N'-bis (2,6-dimethylphenyl) carbodiimide, N, N'. -Bis (2,4,6-trimethylphenyl) carbodiimide, N, N'-bis (2,6-diethylphenyl) carbodiimide, N, N'-bis (2-ethyl-6-isopropylphenyl) carbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-bis (2,4,6-triisopropylphenyl) carbodiimide, N, N'-bis (2-isobutyl-6-isopropylphenyl) carbodiimide , N, N'-bis (2,6-dit-butylphenyl) carbodiimide, N-phenyl-N'-tolylcarbodiimide, N, N'-di-β-naphthylcarbodiimide, N, N'-di (p) Examples thereof include -nitrophenyl) carbodiimide, N, N'-di (p-aminophenyl) carbodiimide, N, N'-di (p-hydroxyphenyl) carbodiimide and N-tolyl-N'-cyclohexylcarbodiimide.

Examples of the polycarbodiimide compound include an aliphatic polycarbodiimide compound, an alicyclic polycarbodiimide compound, and an aromatic polycarbodiimide compound.
Specific examples of the aliphatic polycarbodiimide compound include polyhexamethylene carbodiimide and the like.
Specific examples of the alicyclic polycarbodiimide compound include poly (4,4'-dicyclohexylmethanecarbodiimide and the like.
Specific examples of aromatic polycarbodiimide compounds include polym-phenylenecarbodiimide, polyp-phenylenecarbodiimide, polytrilencarbodiimide, poly (diisopropylphenylenecarbodiimide), poly (methyldiisopropylphenylenecarbodiimide) and poly (4,4'-. Diphenylmethane carbodiimide) and the like.
Examples of commercially available polycarbodiimide compounds include carbodilite LA-01, carbodilite V-05, carbodilite V-02B, and carbodilite V-04K manufactured by Nisshinbo Chemical Co., Ltd.
The polycarbodiimide compound is preferably one that does not contain an isocyanate group from the viewpoint of excellent storage stability.
As the shape of the polycarbodiimide compound, a liquid is preferable because it has excellent solubility and can lower the initial haze of the cured product.
The above carbodiimide compound may be used alone or in combination of two or more.

The content ratio of the carbodiimide compound is preferably 0.5 to 100 parts by mass, more preferably 2 to 30 parts by mass, when the curable component is 100 parts by mass, in that deterioration of the laminate in a moist heat environment can be suppressed. 3 to 20 parts by mass is particularly preferable.
2-2. Hydrotalcite fired product

The hydrotalcite calcined product is a compound obtained by calcining a hydrotalcite compound at about 400 ° C. or higher.

The hydrotalcite compound has the formula (1).
M ²⁺ аM ³⁺ _b (OH- ⁾ _c (A ^n- ) _d・ nH ₂ O
It is a layered compound represented by (M ²⁺ represents a divalent metal, M ³⁺ represents a trivalent metal, and An − represents an anion, and a, b, c, d, and ⁿ are positive numbers).
Specific examples of the hydrotalcite compound include Zn _4.5 Al ₂ (OH) ₁₃ CO ₃・ 3.5H ₂ O, Ni _4.5 Al ₂ (OH) ₁₃ CO ₃・ 3.5H ₂ O and Mg _4.5 Fe ₂ (OH). ) ₁₃ CO ₃・ 3.5H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・ 3.5H ₂ O, Mg ₅ Al _1.5 (OH) _12.5 CO ₃・ 3.5H ₂ O, Mg ₆ Al ₂ ( OH) ₁₆ CO _{3.4H 2} O, Mg _4.3 Al ₂ (OH) _12.6 CO _{3.4H 2} O and the like.

In the hydrotalcite calcined product, anions in the structure are desorbed by calcining the hydrotalcite compound.
M ²⁺ _x M ³⁺ _y O _Z
It is a substance represented by (M ²⁺ represents a divalent metal, M ³⁺ represents a trivalent metal, and x, y, and z are positive numbers).
Specific examples of hydrotalcite fired products include Zn _0.7 Al _0.3 O _1.15 , Ni _0.7 Al _0.3 O _1.15 , Mg _0.7 Al _0.3 O _1.15 , Mg _0.7 Fe _0.3 O _1.15 , Mg _0.8 Al _0.24 O _1.16 , and Mg _0.9 Al _0.3 . Examples include O _1.35 , Mg _0.6 Al _0.3 O _1.05 , and the like.
The hydrotalcite fired product may be used alone or in combination of two or more.

Among these, Mg _0.7 Al _0.3 O _1.15 , Mg _0.8 Al _0.24 O _1.16 , Mg _0.9 Al _0.3 O _1.35 , and Mg _0.6 Al _0.3 O _1.05 are preferable because they have a great effect of suppressing deterioration of the laminated body.

The content ratio of the hydrotalcite calcined product is preferably 0.5 to 5 parts by mass, preferably 1 to 5 parts by mass, when the curable component is 100 parts by mass, in that deterioration of the laminated body can be suppressed in a moist heat environment. Is more preferable, and 2 to 5 parts by mass is particularly preferable.
2-3. 3rd grade amine compound

Examples of the tertiary amine compound include known tertiary amine compounds (excluding photoinitiators), polyfunctional (meth) acrylates, and tertiary amino groups which are Michael adducts of primary and / or secondary amine compounds. Examples thereof include (meth) acrylate having (hereinafter referred to as "amine-modified (meth) acrylate").
Among these, amine-modified (meth) acrylates are preferable because they are incorporated into the crosslinked structure and are difficult to bleed out or erode the substrate.
As the tertiary amine compound, only one kind may be used, or two or more kinds may be used in combination.

Specific examples of polyfunctional (meth) acrylate, which is a raw material compound for amine-modified (meth) acrylate, include pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, and dipentaerythritol tetra, penta and hexa (meth). ) Polypoly (meth) acrylates such as acrylates; as well as tetra (meth) acrylates of pentaerythritol alkylene oxide adducts, tetra (meth) acrylates of diglycerin alkylene oxide adducts, tetra, penta and dipentaerythritol alkylene oxide adducts. Examples thereof include poly (meth) acrylate of a polyol alkylene oxide adduct such as hexa (meth) acrylate.
The polyfunctional (meth) acrylate may be used alone or in combination of two or more.
Among these, poly (meth) acrylate of a polyol alkylene oxide adduct is preferable because it has a high effect of exhibiting the adhesive strength of the active energy ray-curable adhesive composition.

Specific examples of the primary amine compound which is a raw material compound of an amine-modified (meth) acrylate include aliphatic monoamines such as n-propylamine, n-butylamine and n-hexylamine; and aromatic monoamines and monoamines such as benzylamine. Examples thereof include hydroxylmonoamines such as ethanolamine and 2- (2-aminoethoxy) ethanol.
Can be mentioned.
As the primary amine compound, only one kind may be used, or two or more kinds may be used in combination.
Among these primary amine compounds, hydroxylmonoamine is preferable because it does not easily erode the substrate.

Specific examples of the secondary amine compound which is the raw material compound of the amine-modified (meth) acrylate include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, morpholine, piperazine and 1. -Adioxide monoamines such as methylpiperazine; and hydroxylmonoamines such as N-methylethanolamine, N-acetylethanolamine and diethanolamine can be mentioned.
As the secondary amine compound, only one kind may be used, or two or more kinds may be used in combination.
Among these secondary amine compounds, hydroxyl monoamines are preferable because they do not easily erode the substrate.

As a method for producing an amine-modified (meth) acrylate, a conventional method may be followed. Specifically, a polyfunctional (meth) acrylate and a primary and / or a secondary amine compound are used at room temperature to about 50 ° C. for 1 hour. As mentioned above, a method of causing a Michael addition reaction and the like can be mentioned.

In the method for producing an amine-modified (meth) acrylate, it is preferable to use a polymerization inhibitor for the purpose of preventing the polymerization of the (meth) acryloyl group of the raw material or the product, and further, an oxygen-containing gas is introduced into the reaction solution. You may.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, and 4-tert. -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamineammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salts such as dibutyldithiocarbamate copper and N-nitroso-N-phenylhydroxylamine aluminum salt. Polymerization inhibitors can be mentioned. The polymerization inhibitor may be used alone or in combination of two or more. The ratio of the polymerization inhibitor is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm in the reaction solution.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

The (meth) acrylic equivalent of the amine-modified (meth) acrylate is preferably 90 to 250 g / eq, more preferably 110 to 230 g / eq, in terms of excellent curability and adhesive strength.
In the present invention, the (meth) acrylic equivalent means a value (unit: g / eq) converted into g number of the mixture of (meth) acrylate per 1 mol of (meth) acryloyl group, and the bromine value (sample). It means the value measured by g number of bromine added to the unsaturated component in 100 g).

The amine-modified (meth) acrylate is a mixture containing a compound having a tertiary amino group, and its tertiary amine value is preferably 5 to 140 mgKOH / g, preferably 5 to 80 mgKOH / g, because it is excellent in low yellowing of the cured product. g is more preferable.

The amine-modified (meth) acrylate preferably has a hydroxyl group because it does not easily erode the substrate, and the hydroxyl value is preferably 1 to 500 mgKOH / g, more preferably 20 to 500 mgKOH / g.

The Mw of the amine-modified (meth) acrylate is preferably 250 to 2,000, more preferably 250 to 1,500 in that it has a high effect of exhibiting the adhesive strength of the active energy ray-curable adhesive composition. ..

The viscosity of the amine-modified (meth) acrylate at 25 ° C. is preferably 2 to 15,000 mPa · s, preferably 50 to 12,000 mPa · s, in that the viscosity of the active energy ray-curable adhesive composition can be adjusted. Is more preferable.
In the present invention, the viscosity means a value measured at 25 ° C. using an E-type viscometer.

The content ratio of the tertiary amine compound is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, when the curable component is 100 parts by mass, in that deterioration of the laminate in a moist heat environment can be suppressed. 10 to 30 parts by mass is particularly preferable.
When the tertiary amine compound contains an amine-modified (meth) acrylate, the content ratio of the amine-modified (meth) acrylate is 1 when the curable component excluding the amine-modified (meth) acrylate is 100 parts by mass. It is preferably up to 30 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 10 to 30 parts by mass.
2-4. Epoxy compound

Examples of the epoxy compound include aromatic epoxy compounds, polyglycidyl ethers, and compounds having an alicyclic epoxy group.
Among these, aromatic epoxy compounds are preferable because they are less likely to bleed out or erode the substrate.

Further, it is preferable to include a catalyst such as tetrabutylammonium bromide in that the effect of promoting the reaction between the carboxylic acid and the epoxy compound and suppressing the deterioration of the laminate can be improved.

Specific examples of the aromatic epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A, bisphenol F and epichlorohydrin polycondensed epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A. Examples thereof include novolak type epoxy resin and bisphenol F novolak type epoxy resin.
Specific examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and cyclohexanedi. Methylol diglycidyl ether, 1,9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcin diglycidyl ether , Trimethylol propanediglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, dipentaerythritol polyglycidyl ether and the like.
And so on.
Specific examples of the compound having an alicyclic epoxy group include 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4-epoxycyclohexylmethyl) adipate. , 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate caprolactone modified, polyvalent carboxylic acid and 3,4-epoxycyclohexylmethyl alcohol esterified or caprolactone modified, dicyclopentadiendioxide, limonene Dioxide and the like can be mentioned.
In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxidized polybutadiene, and double bond of styrene-butadiene copolymer are partially epoxidized. Compounds [eg, "Epofriend" manufactured by Daicel Chemical Industries, Ltd.] and compounds in which the isoprene unit of the block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (eg, manufactured by KRATON). "L-207") and the like.
The epoxy compound may be used alone or in combination of two or more.

The content ratio of the epoxy compound is preferably 0.5 to 5 parts by mass, more preferably 1 to 5 parts by mass, when the curable component is 100 parts by mass, in that deterioration of the laminate in a moist heat environment can be suppressed. 2 to 5 parts by mass is particularly preferable.

3. 3. Other Ingredients The active energy ray-curable adhesive composition for hydrolyzable plastic films of the present invention contains urethane (meth) acrylate and an acid scavenger as essential ingredients, but various other ingredients may be used depending on the purpose. Can be blended.

Specific examples of the other components include other (meth) acrylates, photoradical polymerization initiators and the like.
In addition to these, photosensitizers, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, silane coupling agents, polymers, tackifiers, fillers, metals, as long as the effects of the present invention are not impaired. Examples thereof include fine particles, metal oxide fine particles, ion trapping agents, defoaming agents, leveling agents, dyes and pigments.
Hereinafter, these components will be described.
As the other components described later, only one of the exemplified compounds may be used, or two or more of them may be used in combination.
3-1. Other (meth) acrylate

Other (meth) acrylates include a compound having one (meth) acryloyl group in the molecule [hereinafter referred to as “monofunctional (meth) acrylate”] and two or more (meth) acryloyl groups in the molecule. Examples include compounds [hereinafter referred to as "polyfunctional (meth) acrylates"]. However, the amine-modified (meth) acrylate is excluded from the other (meth) acrylate.
Among these, monofunctional (meth) acrylate is preferably contained because the effect of diluting urethane (meth) aclate is large.

Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-. Aliphatic alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. ;
Alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate;
Addition of benzyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, (meth) acrylate of o-phenylphenol alkylene oxide adduct and nonylphenol alkylene oxide adduct. Aromatic (meth) acrylates such as (meth) acrylates of things;
2-Hydroxyethyl (meth) acrylicate, 2-hydroxypropyl (meth) acrylicate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, pentanediol mono (meth) Acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol Mono (meth) acrylate, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3-butoxypropyl (meth). Hydroxyl-containing (meth) acrylates such as acrylates;
Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and ethoxyethoxyethyl (meth) acrylate;
An imide group-containing (meth) acrylate such as N- (meth) acryloyloxyethyl hexahydrophthalimide and N- (meth) acryloyloxyethyl tetrahydrophthalimide;
An alkoxysilyl group-containing (meth) acrylate such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyldimethoxymethylsilane and 3- (meth) acryloyloxypropyltriethoxysilane; and tetrahydrofurfuryl. (Meta) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2-isobutyl-2-methyl-1) , 3-Dioxolan-4-yl) methyl (meth) acrylate, (1,4-dioxaspiro [4,5] decane-2-yl) methyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl Methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, allyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid , 2- (meth) acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate and the like.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1 , 6-Hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate and 1,9 -Di (meth) acrylate of an aliphatic diol such as nonan diol di (meth) acrylate;
Di (meth) acrylates of alicyclic diols such as cyclohexanedimethylol di (meth) acrylates and tricyclodecanedimethylol di (meth) acrylates;
Alkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate;
Esterification reaction products of neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid;
Di (meth) acrylate of alkylene oxide adduct of bisphenol compound such as di (meth) acrylate of bisphenol A alkylene oxide adduct;
Di (meth) acrylate of hydrogenated bisphenol compound such as di (meth) acrylate of hydrogenated bisphenol A;
Polyolpoly (meth) acrylates such as trimethylolpropane tri (meth) acrylates, ditrimethylolpropane tetra (meth) acrylates, pentaerythritol di, tri or tetra (meth) acrylates, dipentaerythritol penta or hexa (meth) acrylates;
Tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tetra (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as penta or hexa (meth) acrylates;
Epoxy (meth) acrylate; and polyester (meth) acrylate may be mentioned.
The polyester (meth) acrylate may be a dendrimer type (meth) acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Among these, aromatic monofunctional (meth) acrylates are preferable because they have excellent adhesive strength.
Preferred examples of aromatic monofunctional (meth) acrylates include benzyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, and o-phenylphenol. Examples thereof include (meth) acrylates of alkylene oxide adducts and (meth) acrylates of nonylphenol alkylene oxide adducts.

On the other hand, a hydroxyl group-containing (meth) acrylate is preferable because it has a large effect of suppressing deterioration of the laminate, and the hydroxyl group-containing (meth) acrylate includes a hydroxyl group-containing monofunctional (meth) acrylate and a hydroxyl group-containing polyfunctional (meth) acrylate. Can be mentioned.
Preferred examples of hydroxyl group-containing monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylicate, 2-hydroxypropyl (meth) acrylicate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3. -Phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate and the like can be mentioned.
Preferred examples of the hydroxyl group-containing polyfunctional (meth) acrylate include pentaerythritol di or tri (meth) acrylate, dipentaerythritol pentaacrylate, and epoxy (meth) acrylate.

3-2. Photoradical Polymerization Initiator The active energy ray-curable adhesive composition for a hydrolyzable plastic film of the present invention preferably contains a photoradical polymerization initiator.
When ultraviolet rays and visible light are used as the active energy rays, it is preferable that the active energy ray-curable adhesive composition of the present invention further contains a photoradical polymerization initiator from the viewpoint of ease of curing and cost.
Further, when an electron beam is used as the active energy ray, the active energy ray-curable adhesive composition of the present invention may be cured without containing a photoradical polymerization initiator, but the curability is improved. Therefore, it can be contained in a small amount if necessary.

Specific examples of the photoradical polymerization initiator include benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy). Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-Hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpho Renopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-) Acetphenone compounds such as morpholin-4-yl-phenyl) butane-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4-methoxy-4' -Benzophenone compounds such as dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Acylphosphine oxide compounds; as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2. -Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, methyl phenylglycite, ethylanthraquinone, phenanthrenequinone, camphorquinone and the like.

Among these compounds, the photoradical polymerization initiator preferably contains an acylphosphine oxide-based compound in that the composition is excellent in curability and the cured product is excellent in low yellowing.

When it is necessary to increase the thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, or when an ultraviolet absorber or a pigment is used in combination. For the purpose of improving the curability of the composition, it is preferable to use a plurality of kinds of compounds selected from an acylphosphine oxide compound, a thioxanthone compound and an α-aminoalkylphenone compound in combination.
Preferred examples of the compound in this case include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl- (2,) as the acylphosphine oxide compound. 4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, and examples of the thioxanthone-based compound include 2,4-diethylthioxanthone. , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like, and examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane. -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-) 4-Il-phenyl) -butane-1-one and the like can be mentioned.

The content ratio of the photoradical polymerization initiator is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the curable components. By setting the ratio of the photoradical polymerization initiator to 0.1 parts by mass or more, the photocurability of the composition can be improved and the adhesion can be improved, and by setting the ratio to 15 parts by mass or less, the composition can be cured. The internal curability of the object can be improved, and the adhesion to the substrate can be improved.

4. Active energy ray-curable adhesive composition for hydrolyzable plastic film The active energy ray-curable adhesive composition of the present invention contains the urethane (meth) acrylate and an acid scavenger.

As a method for producing the active energy ray-curable adhesive composition of the present invention, a conventional method may be followed, and the urethane (meth) acrylate and the acid scavenger are further stirred as necessary with other components according to a conventional method. -Can be manufactured by mixing. In this case, it can be heated or heated as needed.

The viscosity of the active energy ray-curable adhesive composition of the present invention may be appropriately set according to the purpose of use.
In order to obtain a coated surface having excellent coatability, that is, smoothness, which can be used in the manufacturing process of a laminate using a hydrolyzable plastic film, the viscosity at 25 ° C. is preferably 3,000 mPa · s or less. , 50 to 2,000 mPa · s is more preferable, and 50 to 700 mPa · s is particularly preferable.

The active energy ray-curable adhesive composition of the present invention is used for adhesion between hydrolyzable plastic films and adhesion between the hydrolyzable plastic film and various other substrates (hereinafter referred to as "other substrates"). can do. That is, it can be used to bond two substrates, one of which is a hydrolyzable plastic film. In the following, when the term "base material" is simply used, it means a general term for hydrolyzable plastic films and other base materials.

In the present invention, the hydrolyzable plastic film is a plastic having an ester group such as a cellulose ester film or sheet, a (meth) acrylic film or sheet and a polyester film or sheet, and generating carboxylic acid by hydrolysis. Means film or sheet.
Specific examples of the cellulose ester-based film or sheet include a triacetyl cellulose film or sheet, a cellulose acetate butyrate film or sheet, and the like.
Specific examples of the (meth) acrylic film or sheet include a polymethylmethacrylate film or sheet.
Specific examples of the polyester-based film or sheet include a polyethylene terephthalate film or sheet.

Examples of other substrates include polycarbonate films or sheets, plastic films or sheets such as polyvinyl alcohol films or sheets, glass, metal oxides, metals, wood, paper and the like.
Examples of the metal oxide include tin oxide, indium oxide, titanium oxide, zinc oxide and the like. Examples of the metal include gold, silver, copper, aluminum, iron, nickel, titanium and the like. Of these, when a transparent thin film formed by vapor deposition, sputtering, or the like is a substrate, transparency, which is one of the characteristics of the active energy ray-curable adhesive composition of the present invention, is required. Since there are many, it is more preferably applied.

When the hydrolyzable plastic film or the like is a poorly adhesive material, one or both surfaces may be activated before applying the active energy ray-curable adhesive composition of the present invention. can. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical liquid treatment, roughening treatment and etching treatment, flame treatment, and the like, and these may be used in combination.

5. Usage method The active energy ray-curable adhesive composition of the present invention may be used according to a conventional method. After the composition is applied to a base material, it is bonded to the other base material to generate active energy rays. Examples include a method of irradiating.
The active energy ray-curable adhesive composition of the present invention is suitable for adhering a thin-layer adherend as a base material. The method of use when adhering the thin-layer adherend may follow the method usually used in the production of a laminate. For example, a method of applying the composition to the first thin-layer adherend, attaching the second thin-layer adherend to the composition, and irradiating the active energy rays with the composition can be mentioned.

Coating on the substrate may follow conventionally known methods, including natural coaters, knife belt coaters, floating knives, knife overrolls, knife-on blankets, sprays, dips, kiss rolls, squeeze rolls, reverse rolls, and air blades. , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater and the like.

The coating thickness of the active energy ray-curable adhesive composition of the present invention may be selected depending on the substrate to be used and the intended use, but is preferably 5 to 100 μm, more preferably 10 to 50 μm. ..

Examples of the active energy ray include visible light, ultraviolet light, X-ray and electron beam, but ultraviolet light is preferable because an inexpensive device can be used.

As the light source for curing by ultraviolet rays, various light sources can be used, and examples thereof include pressurized or high pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps and LEDs. Among these, high-pressure mercury lamps and metal halide lamps are particularly preferable. The irradiation amount of ultraviolet rays is preferably 200 to 2,000 mJ / cm ² in the UV-A region (near 365 nm), and more preferably 300 to 1,500 mJ / cm ² .

When curing with an electron beam, various devices can be used as the EB irradiation device that can be used, and examples thereof include Cockcroft-Walton type, Van de Graaff type, and resonance transformer type devices.
The absorbed dose of the electron beam is preferably 1 to 200 kGy, more preferably 10 to 100 kGy.
The acceleration voltage of the electron beam may be appropriately set in the range of 80 to 300 kV depending on the film thickness of the substrate, and 200 kV is preferable when the film thickness of the substrate is 100 μm.
The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

6. Laminated body and method for producing the same The laminated body of the present invention is a laminated body containing a hydrolyzable plastic film as a base material. The structure of the laminate is a laminate composed of a base material, a cured product of the above-mentioned composition, and the other base material, and both or one of the base material and the other base material is hydrolyzed. It is a sex plastic film.
As the hydrolyzable plastic film, at least one of them is preferably a cellulose ester-based film or a sheet because it has a great effect of suppressing deterioration of the laminated body.
Specifically, as a method for producing a laminate, the above-mentioned composition is coated on a base material, the other base material is bonded to the coated surface, and either the above-mentioned base material or the other base material is attached. A method of irradiating the active energy ray from the side of the surface can be mentioned.
The coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy rays, and the like are also as described above.

Applications of the obtained laminate include various optical films used in liquid crystal displays, organic EL displays, etc., and specifically, hard coat films and touch panels having functionality such as anti-fingerprint and anti-glare. Examples thereof include a front plate, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness improving film, an antireflection film, an antiglare film, a lens sheet and a diffusion sheet.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

1. 1. Manufacturing example
1) Production Example 1 (Urethane (meth) acrylate)
1,220 g of polycarbonate diol (1,6-hexanediol and caprolactone base, Ethanacole UHC-200 manufactured by Ube Kosan Co., Ltd.) in a 4-port flask with a 2 L side tube equipped with a thermometer, agitator and a reflux tube. Add 33 g of hydroxypivalic acid neopentiglycol ester (HPN manufactured by BASF Japan Co., Ltd.), 360 mg of dibutyltin dilaurate as a catalyst, and 920 mg of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor, and 5 volumes. Under the atmosphere of nitrogen containing% oxygen, the mixture was heated with stirring until the liquid temperature reached 70 ° C. 350 g of isophorone diisocyanate was added to the reaction solution in a batch, and the mixture was reacted for 2 hours.
Then, 210 g of 2-hydroxypropyl acrylate was added and reacted for 3 hours, and the spectrum was measured by an infrared absorption spectroscope (FT-IR Spectrum 100 manufactured by PerkinElmer), and it was confirmed that the isocyanate group was completely consumed, and urethane was used. A (meth) acrylate (Mw 20,000, 25 ° C. viscosity 13,100 mPa · s) was obtained. Hereinafter, it is referred to as "UA1".
◆ Mw (GPC measurement conditions)
・ Equipment: Waters Co., Ltd. GPC system name 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Showa Denko Co., Ltd. Shodex KFG (8 μm 4.6 x 10 mm), 2 types of this column Waters Co., Ltd. stylel HR 4E THF (7.8 x 300 mm) + stylel HR 1 THF (7.8 x 300 mm)
-Column temperature: 40 ° C
-Eluent composition: Tetrahydrofuran (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min-Molecular weight standard substance: Polystyrene
◆ Viscosity
The viscosity was measured at 25 ° C. using an E-type viscometer.

2) Production Example 2 (amine-modified (meth) acrylate)
(1) Production of raw material polyfunctional (meth) acrylate A 4-port flask with a 2 L side tube equipped with a thermometer, a stirrer and a reflux tube is provided with an EO4 mol addition of diglycerin [Kao Co., Ltd., Emargen G2E-4. , 625 mgKOH / g] 500 g, acrylic acid 518 g, p-toluenesulfonic acid monohydrate 41 g, cupric chloride 1.59 g, hydroquinone monomethyl ether 1.59 g and toluene 550 g were added.
While blowing the oxygen-containing gas into the flask, the mixture was heated and stirred under the conditions of a reaction solution temperature of 80 to 100 ° C. and a reaction system pressure of 400 to 760 Torr. A dehydration esterification reaction was carried out for 7 hours while removing water generated as the reaction proceeded to the outside of the system with a Dean-Stark apparatus.
After completion of the reaction, the obtained reaction solution is added to a separating funnel, washed and separated with pure water, then the organic layer is further washed and separated with an aqueous sodium hydroxide solution, and the organic layer is further washed with pure water. After washing and separating the liquid with, and allowing it to stand, the lower layer was removed. The organic phase in the upper layer was heated under reduced pressure to distill off toluene.
The obtained reaction product was a mixture containing triacrylate and tetraacrylate (Mn1,218, 25 ° C. viscosity 440 mPa · s, hydroxyl value 14 mgKOH / g). Hereinafter, it is referred to as "mixture (а1)".
The Mn and viscosity of the mixture (а1) were measured according to the above method, and the hydroxyl value was measured according to the method described later.
(2) Production of amine-modified (meth) acrylate
In a 500 mL 4-necked flask with a side tube equipped with a thermometer, a stirrer and a reflux tube, 250 g (0.205 mol) of the mixture (а1) was placed and 14.1 g (0.134 mol, mixture (а1) 1) of diethanolamine was placed. After adding 0.66 mol) to the mol at room temperature, the reaction was carried out at 50 ° C. for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen. The obtained reaction product was a mixture containing a Michael adduct of diethanolamine (acrylic equivalent 204 g / eq, tertiary amine value 28 mgKOH / g, hydroxyl value 70 mgKOH / g, Mw1290, 25 ° C. viscosity 698 mPa · s). Hereinafter, it is referred to as "amine-modified (meth) acrylate DEA".
The acrylic equivalent of the amine-modified (meth) acrylate DEA, the tertiary amine value and the hydroxyl value were measured according to the method described below, and Mw and the viscosity were measured according to the above method.
◆ Acrylic equivalent
The bromine value of acrylate (the number of g of bromine added to the unsaturated component in 100 g of the sample) measured based on JIS K 2605 is converted into the number of g of acrylate per mol of acryloyl group (unit: g). / Eq).
◆ Tertiary amine value
5 ml of acetic anhydride was added to 0.2 g of a sample and 50 g of acetone, and the mixture was reacted at room temperature for 30 minutes, and then titrated with 0.01N perchloric acid by a potentiometric titration method. A blank test was carried out in the same manner, and the tertiary amine value was calculated from the following formula.
Tertiary amine value = {(AB) x f x 0.01 x 56.11} / C
A: Consumption of 0.01N perchloric acid required for sample titration (ml)
B: Consumption of 0.01N perchloric acid required for titration of blank test (ml)
f: 0.01N Perchloric acid factor C: Amount of sample (g)
◆ Hydroxy group value
It represents the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample, which is measured based on JIS K 0070-1992.

2. 2. Examples 1 to 16, Comparative Examples 1 and 2
1) Preparation of active energy ray-curable adhesive composition The compounds shown in Table 1 below were stirred and mixed at the ratios shown in Table 1 to produce an active energy ray-curable adhesive composition.
Using the obtained composition of Table 1, the evaluation described later was performed. The results are shown in Table 1.

The numbers in Table 1 mean parts by mass.
The abbreviations in Table 1 mean the following.

◆ Urethane (meth) acrylate・ UA1: Polycarbonate urethane acrylate (Production Example 1)

◆ Other (meth) acrylate・ THFA: Tetrahydrofurfuryl acrylate (25 ℃ viscosity 2.8mPa ・ s), Viscote # 150 manufactured by Osaka Organic Chemical Industry Co., Ltd.
-POA: Phenoxyethyl acrylate (25 ° C viscosity 8.7 mPa · s), Viscoat # 192 manufactured by Osaka Organic Chemical Industry Co., Ltd.
-M140: N-acryloyloxyethyl hexahydrophthalimide (25 ° C. viscosity 490 mPa · s), Aronix M-140 manufactured by Toagosei Co., Ltd.
-M5700: 2-Hydroxy-3-phenoxypropyl acrylate (25 ° C. viscosity 170 mPa · s), Aronix M-5700 manufactured by Toagosei Co., Ltd.

◆ Acid scavenger <carbodiimide compound>
-V04K: Polycarbodiimide compound (carbodiimide equivalent 336 g / eq), carbodilite V-04K manufactured by Nisshinbo Chemical Co., Ltd.
-V02B: Polycarbodiimide compound (carbodiimide equivalent 603 g / eq), carbodilite V-02B manufactured by Nisshinbo Chemical Co., Ltd.
<Hydrotalcite fired product>
・ MAO: Mg _0.7 Al _0.3 O _1.15
<Primary amine compound>
EBE80: Amine-modified polyether acrylate (hydroxyl value 58 mgKOH / g), EBECRYL 80 manufactured by Daicel Ornex Co., Ltd.
DEA: Amine-modified (meth) acrylate DEA (Production Example 2)
<Epoxy compound>
-JER1001: Bisphenol A type diglycidyl ether (solid type, epoxy equivalent 470 g / eq), jER-1001 manufactured by Mitsubishi Chemical Corporation

◆ Other ingredients・ TBAB: Tetrabutylammonium bromide

◆ Photo-radical polymerization initiator・ TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Lucillin TPO manufactured by BASF Japan Ltd.

2) Production of laminate Using a bar coater on a triacetyl cellulose film (thickness 80 μm, Fujitac TD 80UL, manufactured by FUJIFILM Corporation), the thickness of the active energy ray-curable adhesive composition shown in Table 1 is applied. It was applied at 15 μm and laminated with a polycarbonate film (thickness 100 μm, Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Company, Inc.).
Next, a conveyor-type ultraviolet irradiation device manufactured by Eye Graphics Co., Ltd. (100 W / cm metal halide lamp, lamp height 29 cm, irradiation intensity in the UV-A region 250 mW / cm ² (measured value of UV POWER PUCK manufactured by Heleus Co., Ltd.) )) Was used to irradiate the UV-A region with ultraviolet rays having an irradiation energy of 800 mJ / cm ² from the polycarbonate film side of the laminated film by passing through a 5.0 m / min conveyor once.
Further, the active energy ray-curable adhesive composition shown in Table 1 is applied to the exposed surface of the triacetyl cellulose film to a thickness of 15 μm using a bar coater, and a polycarbonate film (thickness 100 μm, Iupylon NF-2000) is applied. , Mitsubishi Gas Chemical Co., Ltd.) was laminated.
Next, from the newly laminated polycarbonate film side, under the same conditions as described above (metal halide lamp, irradiation intensity 250 mW / cm ² in the UV-A region, irradiation energy 800 mJ / cm ² in the UV-A region), the laminated film Ultraviolet irradiation was performed from the polycarbonate film side to obtain a laminate having triacetyl cellulose on both sides of the polycarbonate film.
The obtained laminate was evaluated according to the following method.

3) Evaluation method of laminated body
(1) Initial evaluation
◆ Adhesive strength The laminate obtained in 2.2) above was cut out to a width of 1 inch and a length of 10 cm to obtain a test piece, and then a T-peeling test (peeling speed of 200 mm / min) was performed to obtain a polycarbonate film and triacetyl. The peel strength between the cellulose films was measured. The results are shown in Table 1.

◆ Haze The haze of the laminate obtained in 2.2) above was measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 1.

◆ YI (Yellow Index)
The YI of the laminated body obtained in 2.2) was measured using a high-speed integrating sphere type spectral transmittance measuring device DOT-3C (manufactured by Murakami Color Technology Research Institute). The results are shown in Table 1.

(2) Evaluation of moisture and heat resistance
◆ Adhesive strength The laminate obtained in 2.2) above is cut into pieces 1 inch wide and 10 cm long, and after obtaining test pieces, they are placed in a constant temperature and humidity machine with a temperature of 85 ° C and a relative humidity of 85% for 300 hours. did.
After 300 hours, the test piece was taken out from the constant temperature and humidity chamber, and the peel strength between the polycarbonate film and the triacetyl cellulose film was measured by a T peel test (peeling speed 200 mm / min) and evaluated at the following four levels. .. If the adhesive strength after this moisture resistance test is 0.1 N / inch or more, it is a practical level. The results are shown in Table 1.
◎: 0.6 N / inch or more ○: 0.1 N / inch or more and less than 0.6 N / inch ×: 0.1 N / inch or less × ×: Measurement is not possible because the deterioration of the base material has become extremely brittle.

◆ Haze The laminated body subjected to the above initial evaluation is put into a constant temperature and humidity chamber having a temperature of 85 ° C. and a relative humidity of 85%, and the haze of the laminated body measured by the same method as described above reaches 50%. The time until was measured, and the evaluation was performed according to the following three levels. It means that the longer the time is, the greater the effect of suppressing the white turbidity of the laminated body. The results are shown in Table 1.
◎: 500 hours or more ○: 350 hours or more and less than 500 hours ×: 350 hours or less

◆ YI (Yellow Index)
The laminate subjected to the initial evaluation was placed in a constant temperature and humidity chamber having a temperature of 85 ° C. and a relative humidity of 85%, and the time required for the YI of the laminate to reach 10 measured by the same method as described above was set. It was measured and evaluated at the following three levels. The longer the time is, the greater the effect of suppressing yellowing of the laminated body is. The results are shown in Table 1.
◎: 500 hours or more ○: 350 hours or more and less than 500 hours ×: 350 hours or less

4) Evaluation Results As is clear from the results of Examples 1 to 16, when the active energy ray-curable adhesive composition of the present invention is used, the white turbidity and yellowing of the laminate are suppressed under a severe moist heat environment. The effect was great and the adhesive strength was at a practical level.
Among these, Examples 1 and 2 containing phenoxyethyl acrylate, which is an aromatic monofunctional (meth) acrylate, as the other (meth) acrylate, had particularly excellent adhesive strength. In addition, Examples 3 to 16 containing 2-hydroxy-3-phenoxypropyl acrylate, which is a hydroxyl group-containing monofunctional (meth) acrylate, were particularly excellent in the effect of suppressing white turbidity and yellowing of the laminate.
Further, in a comparison in which the composition of the curable component is constant, Examples 3 to 9 containing a carbodiimide compound as an acid scavenger, Examples 10 to 11 containing a hydrotalcite calcined product, and Example 12 containing a tertiary amine compound. Nos. 14 were more effective in suppressing white turbidity and yellowing of the laminate than in Examples 15 to 16 containing the epoxy compound. In particular, Examples 3 to 5, 9 and 10 to 11 had a great effect of suppressing white turbidity and yellowing of the laminate even when the amount of the acid scavenger added was relatively small. Further, Examples 12 and 13 containing an amine-modified (meth) acrylate as the tertiary amine compound had higher adhesive strength in a harsh moist heat environment than Example 6 containing the same mass part of the carbodiimide compound.
On the other hand, in Comparative Examples 1 and 2 containing no acid scavenger, the base material deteriorated so that the adhesive strength could not be measured under a severe moist heat environment, which was far from the practical level.

The active energy ray-curable adhesive composition of the present invention can be used for producing a laminate having a hydrolyzable plastic film as a base material, and in particular, various optics used for liquid crystal displays, organic EL displays and the like. It can be suitably used for producing a film or a sheet.

Claims (4)

Hydrolyzed, comprising urethane (meth) acrylate and acid trapping agent, said urethane (meth) acrylate comprising polycarbonate urethane (meth) acrylate, said acid trapping agent comprising at least one of a carbodiimide compound or a hydrotalcite calcined product. Active energy ray-curable adhesive composition for sex plastic films or sheets. The active energy ray-curable adhesive composition for a hydrolyzable plastic film or sheet according to claim 1 , further comprising a hydroxyl group-containing (meth) acrylate. The active energy ray-curable adhesive composition for a hydrolyzable plastic film or sheet according to claim 1 or 2, wherein the hydrolyzable plastic film or sheet is a cellulose ester film or sheet. A laminate composed of a base material, a cured product of the biodegradable plastic film or the active energy ray-curable adhesive composition for a sheet according to any one of claims 1 to 3 , and the other base material. And
A laminate in which both or one of the substrate and the other substrate is a hydrolyzable plastic film or sheet.