JPWO2019177134A1 - Active energy ray-curable adhesive composition for plastic films or sheets, laminates and polarizing plates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable adhesive composition having excellent adhesive strength to various plastic films, particularly excellent adhesiveness between hydrophilic plastic films and adhesiveness between a hydrophobic plastic film and a hydrophilic plastic film, and laminating. Provision of body and polarizing plate. SOLUTION: A curable component is composed of the following (A) to (C), a polymerization initiator is composed of the following (D) and (E), and (A): a compound (B) having two or more epoxy groups. : Urethane (meth) acrylate (C): Hydro group-containing unsaturated compound (D): Photocation initiator (E): Photoradical initiator In 100% by mass (hereinafter,%) of the total amount of the curable component, (A) 15 (D) 0.1 to 10 parts, (E) with respect to 100 parts by mass (hereinafter referred to as "parts") of the total amount of the curable component containing ~ 80%, (B) 1 to 30%, (C) 5 to 55%. An active energy ray-curable adhesive composition for a plastic film or sheet containing 0.1 to 15 parts.

Description

The present invention relates to an active energy ray-curable adhesive composition, a laminate and a polarizing plate capable of adhering various plastic films or sheets by irradiation with active energy rays such as ultraviolet rays and electron beams.
In the following, unless otherwise specified, plastic films or sheets are collectively referred to as "plastic film", and films or sheets are collectively referred to as "film".

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 polarizing plates, retardation films, viewing angle compensation films, brightness improving films, antireflection films, antiglare films, lens sheets, diffusion films, and the like. Examples thereof include a hard coat film having functionality such as anti-fingerprint and anti-glare, and a front plate of a touch panel.

These optical films include various types such as polyvinyl alcohol-based films, cellulose ester-based films such as triacetyl cellulose, polyester-based films such as polyethylene terephthalate, acrylic films such as polymethyl methacrylate, and carbonate-based films such as polycarbonate. It is often used by sticking plastic films together. 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.

The active energy ray-curable adhesive composition includes a photoradical polymerization type composition using photoradical polymerization, a photocationic polymerization type composition using photocationic polymerization, and a hybrid in which photoradical polymerization and photocationic polymerization are used in combination. Mold compositions are known.

The photoradical polymerization type composition has an advantage that the polymerization rate is high, but has a drawback that the shrinkage at the time of curing is large and the adhesive force is lowered due to the generation of stress at the interface depending on the type of the adherend.
On the other hand, the photocationic polymerization type composition has a relatively small shrinkage during curing as compared with the photoradical polymerization type composition, and therefore has an advantage that stress generation at the interface can be suppressed and a decrease in adhesive strength can be suppressed. There is a drawback that the adhesive strength is lowered due to the inhibition of polymerization by water or a basic substance.

In recent years, a hybrid type composition has attracted attention as an active energy ray-curable adhesive composition that mutually complements the above-mentioned drawbacks of a photoradical polymerization type composition and a photocationic polymerization type composition.

Patent Document 1 discloses a hybrid composition containing a (meth) acrylate having an isocyanuric ring skeleton, an alicyclic epoxy compound, a compound containing a hydroxyl group, and a photoacid generator.

Patent Document 2 describes an epoxy resin having two or more epoxy groups and at least one of these groups being an alicyclic epoxy group, and having two or more epoxy groups and an alicyclic epoxy group. A hybrid composition containing a non-existent epoxy resin, a photocationic polymerization initiator and a polymerizable monomer is disclosed.

Patent Document 3 describes a compound having two or more (meth) acrylic groups, a compound having a hydroxyl group and one (meth) acrylic group, a cationically polymerizable compound having a (meth) acrylic group, a photoradical polymerization initiator, and light. A hybrid composition containing a cationic polymerization initiator is disclosed.

Patent Document 4 describes at least one compound selected from the group consisting of aromatic epoxy compounds containing two or more epoxy groups in the molecule, 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate, and two in the molecule. A hybrid composition containing at least an ethylenically unsaturated compound composed of the above compounds having an ethylenically unsaturated group and a photocationic polymerization initiator is disclosed.

Japanese Unexamined Patent Publication No. 2008-23279 Japanese Unexamined Patent Publication No. 2008-257199 Japanese Unexamined Patent Publication No. 2008-260879 International Publication No. 2012/173005

However, although the hybrid type compositions disclosed in Patent Documents 1 to 4 are excellent in adhesiveness between hydrophilic plastic films, according to the study of the present inventor, the adhesiveness between hydrophilic plastic films and the adhesiveness between hydrophilic plastic films are also excellent. It has been difficult to achieve a high level of adhesion between a hydrophobic plastic film such as polycarbonate and a hydrophilic plastic film.
In the present invention, a highly hydrophilic plastic film such as a polyvinyl alcohol-based film and a cellulose ester-based film is referred to as a "hydrophilic plastic film", and other plastic films are referred to as a "hydrophilic plastic film". The contact angle of water is used as an index of hydrophilicity, a plastic film having a water contact angle of less than 70 ° at 23 ° C is called a "hydrophilic plastic film", and a plastic film having a water contact angle of 70 ° or more is called a "hydrophilic plastic film". To do.

The present invention has been made in view of the above problems, and has excellent adhesive strength to various plastic films. In particular, the adhesiveness between hydrophilic plastic films such as polyvinyl alcohol-based films and cellulose ester-based films, and the polycarbonate-based films. It is an object of the present invention to provide an active energy ray-curable adhesive composition, a laminate and a polarizing plate having excellent adhesiveness between a hydrophobic plastic film and a hydrophilic plastic film.

As a result of diligent studies to solve the above problems, the present inventors have one each of a compound containing two or more epoxy groups in the molecule, urethane (meth) acrylate, and a hydroxyl group and an ethylenically unsaturated group in the molecule. The active energy ray-curable adhesive composition for plastic films, which contains a specific ratio of a compound containing more than one, a photocationic polymerization initiator and a photoradical polymerization initiator, has adhesiveness between hydrophilic plastic films and hydrophobicity. We have found that the adhesiveness between the sex plastic film and the hydrophilic plastic film is excellent, and completed the present invention.

The present invention is as follows.
[1] At least composed of a curable component and a polymerization initiator, the curable component is composed of at least the following components (A) to (C), and the polymerization initiator is at least composed of the following components (D) and (E). Configured
Component (A): Compound having two or more epoxy groups in the molecule (B) Component: Urethane (meth) acrylate (C) Component: Compound having one or more hydroxyl groups and ethylenically unsaturated groups in the molecule ( D) Component: Photocationic polymerization initiator (E) Component: Photoradical polymerization initiator The components (A) to (C) are contained in the total amount of 100% by mass of the curable component in the following proportions.
(A) Ingredient: 15-80% by mass
(B) Component: 1 to 30% by mass
(C) component: 5 to 55% by mass
An active energy ray-curable adhesive composition for a plastic film or sheet containing the components (D) and (E) in the following proportions with respect to 100 parts by mass of the total amount of curable components.
Component (D): 0.1 to 10 parts by mass (E) Component: 0.1 to 15 parts by mass [2] The component (B) is urethane (meth) having a weight average molecular weight of 1,000 to 50,000. ) The active energy ray-curable adhesive composition for a plastic film or sheet according to [1], which contains an acrylate.
[3] The active energy ray for a plastic film or sheet according to [1] or [2], wherein the component (B) contains a urethane (meth) acrylate having two (meth) acryloyl groups in the molecule. Curable adhesive composition.
[4] The plastic film or sheet according to any one of [1] to [3], wherein the component (C) contains a compound having one hydroxyl group and one ethylenically unsaturated group in the molecule. Active energy ray-curable adhesive composition for use.
[5] The component (C) contains at least one compound selected from the group consisting of 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , [4] The active energy ray-curable adhesive composition for a plastic film or sheet.
[6] The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of [1] to [5], wherein the component (D) contains a diaryliodonium salt.
[7] The method according to any one of [1] to [6], further comprising a (meth) acryloyl group-containing compound other than the component (G): component (B) and (C) as the curable component. Active energy ray-curable adhesive composition for plastic films or sheets.
[8] The active energy ray-curable adhesive composition for a plastic film or sheet according to [7], wherein the component (G) further contains a caprolactone-modified neopentyl glycol di (meth) acrylate.
[9] The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of [1] to [8], which further contains an ultraviolet absorber.
[10] The plastic film or sheet according to any one of [1] to [9], wherein the plastic film or sheet is a hydrophilic plastic film or sheet and is used for manufacturing a polarizing plate. Active energy ray-curable adhesive composition for use.
[11] The active energy ray-curable type for a plastic film or sheet according to [10], wherein the hydrophilic plastic film or sheet is a polyvinyl alcohol-based polarizing film or sheet and is used for producing a polarizing plate. Adhesive composition.
[12] A laminate in which a base material is arranged on both sides of a cured product layer formed from the composition according to any one of [1] to [11], and at least one of the base materials is a plastic. A laminate that is a film or sheet.
[13] A polarizing plate having substrates arranged on both sides of a cured product layer formed from the composition according to any one of [1] to [11], wherein one of the substrates is polyvinyl alcohol. A polarizing plate that is a system-polarized lighter film or sheet and the other of the base material is a plastic film or sheet.
[14] Two substrates, one of which is a plastic film or sheet, are attached using the composition according to any one of [1] to [11], and the composition is irradiated with active energy rays. A method for manufacturing a laminated body.

According to the active energy ray-curable adhesive composition of the present invention, it is possible to obtain a laminate and a polarizing plate having excellent adhesiveness between hydrophilic plastic films and adhesiveness between the hydrophobic plastic film and the hydrophilic plastic film. it can.

Hereinafter, various embodiments of the techniques disclosed in the present specification will be described in detail.
In the present specification, acrylate and / or methacrylate are referred to as (meth) acrylate, acryloyl group and / or methacrylic acid group is referred to as (meth) acryloyl group, and acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid and acrylamide. And / or methacrylamide is referred to as (meth) acrylamide.
The curable component means a cationically curable component containing the component (A) and a radical curable component containing the components (B) and (C) that are cured by active energy rays.
Further, "VV to XX mass%" which means the ratio of each component means VV mass% or more and XX mass% or less, and "YY to ZZ mass parts" means YY mass parts or more and ZZ mass. It means less than a part.

The present invention relates to an active energy ray-curable adhesive composition for a plastic film containing the components (A) to (E) in a specific ratio.
Hereinafter, the components (A) to (E), other components, an active energy ray-curable adhesive composition for a plastic film, a method of use, and a laminate and a method for producing the same will be described in detail.

1. 1. Component (A) Component (A) is an epoxy compound containing two or more epoxy groups in the molecule.
The component (A) has two or more epoxy groups in the molecule, a compound containing an aromatic ring (hereinafter, referred to as "aromatic epoxy compound"), and two or more epoxy groups in the molecule. , At least one of them is an alicyclic epoxy group (here, the alicyclic epoxy group represents an alicyclic group that forms an epoxide between two adjacent carbon atoms constituting a ring). (Hereinafter referred to as "alicyclic epoxy compound"), and compounds other than the above "alicyclic epoxy compound" having two or more epoxy groups in the molecule and not containing an aromatic ring (hereinafter referred to as "alicyclic epoxy compound"). , "Aromatic epoxy compound").

Specific examples of the aromatic epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and bromine. Bisphenol type epoxy resin such as diglycidyl ether of bisphenol S, diglycidyl ether of rubber-modified bisphenol A, di or polyglycidyl ether of bisphenol fluorene or its alkylene oxide adduct; phenol novolac type epoxy resin, cresol novolac type epoxy resin, Novolac type epoxy resin such as brominated phenol novolac type epoxy resin, brominated cresol novolac type epoxy resin, dicyclopentadiene-phenol novolac type epoxy resin; naphthalene type epoxy resin; alkyldiphenol type epoxy resin; naphthol type epoxy resin; biphenyl Epoxy resin; Hydroquinone diglycidyl ether; Resolcin diglycidyl ether; Diglycidyl terephthalate ether; Diglycidyl phthalate ether; Epoxy of styrene-butadiene copolymer; Epoxy of styrene-isoprene copolymer; Polybutadiene terminal carboxylate And bisphenol A type epoxy resin addition reactants; N, N, N', N'-tetraglycidyl-m-xylene diamine and the like.
Other aromatic epoxy compounds include Chapter 2 of the document "Epoxy Resin-Recent Advances-" (Shokodo, published in 1990) and the document "Polymer Processing", Separate Volume 9, Vol. 22, Special Issue Epoxy Resin. Compounds such as those described on pages 4 to 6, 9 to 16 and 29 to 55 of (Polymer Publishing Association, published in 1973) can be mentioned.
Here, the epoxy resin refers to a compound or polymer that has an average of two or more epoxy groups in the molecule and is cured by a reaction. According to the convention in the art, in the present specification, a compound having two or more curable epoxy groups in the molecule may be referred to as an epoxy resin even if it is a monomer.

Specific examples of the alicyclic epoxy compound include dicyclopentadiendioxide, limonendioxide, 4-vinylcyclohexendioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, and bis (3,). Examples thereof include 4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
In addition to these, Chapter 2 of the document "Epoxy resin-Recent progress-" (Shokodo, published in 1990) and the document "Polymer processing" separate volume 9 and 22 special issue Epoxy resin (Polymer publication) Examples of compounds as described on pages 7 and 18 to 20 of the Society, published in 1973) can be mentioned.

Specific examples of the aliphatic epoxy compound include diglycidyl ether of alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; and polyalkylene such as diglycidyl ether of polyethylene glycol and polypropylene glycol. Diglycidyl ether of glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct, and pentaerythritol. And polyglycidyl ethers of polyhydric alcohols such as di, tri or tetraglycidyl ethers of its alkylene oxide adducts; di or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; diglycidyl ethers of tetrahydrophthalates; hydroquinones. Examples thereof include diglycidyl ether.
Other aliphatic epoxy compounds include Denarex R-45EPT [manufactured by Nagase ChemteX Corporation], Epofriend AT501, CT310, Epolide PB3600 [above, manufactured by Daicel Chemical Industry Co., Ltd.], KL-630 [ Described on pages 3 to 6 of commercially available products such as Kuraray Co., Ltd.], Tetrad C [manufactured by Mitsubishi Gas Chemical Company], TEPIC [manufactured by Nissan Chemical Industry Co., Ltd.], and the separate volume epoxy resin of the above-mentioned document "Polymer processing". Can be mentioned.

Among the above-mentioned compounds, the component (A) is preferably an aromatic epoxy compound or an aliphatic epoxy compound, and more preferably an aromatic epoxy compound, in that the obtained composition has excellent adhesive strength.
Among the aromatic epoxy compounds, a bisphenol type epoxy resin is preferable, and a more preferable embodiment is diglycidyl ether of bisphenol A.

As the component (A), only one type may be used alone, or two or more types may be used in combination.

The content ratio of the component (A) is 15 to 80% by mass, more preferably 25 to 70% by mass, and further preferably 30 to 60% by mass of the component (A) in 100% by mass of the total amount of the curable component. %.
If the proportion of the component (A) is less than 15% by mass, the heat resistance and water resistance of the cured product of the composition are lowered, and if it exceeds 80% by mass, the composition becomes highly viscous and the coatability is improved. It will be reduced, and the adhesive strength of the cured product of the composition will be reduced.

2. Component (B) Component (B) is a urethane (meth) acrylate, which is a (meth) acrylate compound having a urethane bond.
As the component (B), a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate [hereinafter referred to as “(B-1) component”], and a reaction of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate. A thing (so-called urethane adduct) can be mentioned, and the component (B-1) is preferable from the viewpoint of adhesive strength.
The raw material compound of the component (B-1) and the production method will be described below.

2-1. Raw material compound
As the raw material compound of the component (B-1), a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate are used.

Specific examples of the polyol include polyether polyols, polycarbonate polyols, polyester polyols, diols having a polyene skeleton, 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 neopentiglycol ester of hydroxypivalic acid (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 diol, polyether polyol and polycarbonate polyol, 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.
Examples of the diol having a polyene skeleton include a diol having a polybutadiene skeleton, a diol having a polyisoprene skeleton, a diol having a hydrogenated polybutadiene skeleton, and a diol having a hydrogenated polyisoprene skeleton.
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 diisocyanides 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.

As a preferred embodiment of the component (B-1), urethane (meth) acrylate having two (meth) acryloyl groups in the molecule is preferable from the viewpoint of improving the adhesive strength. Further, in terms of further improving the adhesive strength, polyester-based urethane (meth) acrylate using a polyester polyol as a raw material polyol, polycarbonate-based urethane (meth) acrylate using a polycarbonate polyol as a raw material polyol is preferable, and polycarbonate-based urethane (meth) acrylate is preferable. Meta) acrylate is more preferred.

2-2. Production method
The component (B-1) can be produced by heating and stirring a polyol, an organic polyisocyanate, and a 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. ..
In this case, the polyol, the organic polyisocyanate, and the hydroxyl group-containing (meth) acrylate can be collectively charged 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”).

As the metal catalyst, those usually used in the urethanization reaction can be used.
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.

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, 1.0 to 1.5 mol of hydroxyl group-containing (meth) acrylate is preferable with respect to 1 mol of the total amount of isocyanate groups 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.
In this case, 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 1 mol of the total amount of isocyanate groups of the organic polyisocyanate.

When the molecular weight of the component (B-1) 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 component.
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 component (B-1) to be produced, but is preferably set to 0 to 70% by mass 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 using a reaction solvent or the like 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 a reaction solvent, a (meth) acrylate compound other than the component (B-1) and the component (B-1) used as a component of the composition together with or in place of the organic solvent (hereinafter, "other (meta)" ) Acrylate ”) can also be blended. As the other (meth) acrylate, those described as other components described later can be used. When the other (meth) acrylate is blended and the urethanization reaction is carried out, 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 is not necessary to dry 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 to be finally blended in the composition. For example, 10 to 10 in the reaction solution. It is preferable to set it to be 70% by mass and further 10 to 50% by mass.

The blending amount of the metal catalyst may be a catalytic amount, for example, 0.01 to 1,000 wtppm, 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 component (B) can be suppressed. ..

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

In the urethanization reaction, a small amount of 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 those similar to 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 copper sulfate, inorganic polymerization inhibitors such as copper chloride and 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 proportion 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 to be used, the structure of the target component (B-1), the molecular weight, 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.

As the component (B), only one type may be used alone, or two or more types may be used in combination.

The weight average molecular weight of the component (B) in the present invention (hereinafter referred to as “Mw”) is preferably 1,000 to 50,000, preferably 3,000, from the viewpoint of improving the coatability and adhesive strength of the composition. It is more preferably ~ 50,000, and even more preferably 7,000 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: Crosslinked polystyrene column-Column temperature: 40 ° C
・ Eluent: Tetrahydrofuran ・ Molecular weight standard substance: Polystyrene

The content ratio of the component (B) is 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass in 100% by mass of the total amount of the curable component.
If the proportion of the component (B) is less than 1% by mass, film curl after curing of the composition occurs, and the adhesive strength of the cured product of the composition decreases, and if it exceeds 30% by mass, The composition becomes highly viscous and the coatability is lowered.

3. 3. Component (C) Component (C) is a compound containing at least one hydroxyl group and one or more ethylenically unsaturated groups in the molecule.
The component (C) is a compound having one hydroxyl group and one ethylenically unsaturated group in the molecule, and a compound having one hydroxyl group and one (meth) acryloyl group [hereinafter, “hydroxyl-containing monofunctional (meth)”. It is called "acrylate". ], A compound having a hydroxyl group and two or more ethylenically unsaturated groups in the molecule, a compound having a hydroxyl group and two or more (meth) acryloyl groups [hereinafter referred to as "hydroxyl-containing polyfunctional (meth) acrylate" .. ], And hydroxyl group-containing (meth) acrylamide such as N- (2-hydroxyethyl) (meth) acrylamide.

Specific examples of the hydroxyl group-containing monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. Pentandiol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexene oxide (meth) acrylic acid adduct, diethylene glycol mono (meth) acrylate, triethylene Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Meta) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol mono (meth) acrylate , 2-Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, 2- (meth) acryloyloxyethyl -2-Hydroxypropyl phthalate and the like can be mentioned.

Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include di (meth) acrylate of trimethylolpropane, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of trimethylolpropane, and dipentaerythritol. Di, tri, tetra or penta (meth) acrylate, epoxy (meth) acrylate can be mentioned.

Examples of the epoxy (meth) acrylate include compounds obtained by addition-reacting (meth) acrylic acid to an epoxy resin, and compounds as described on pages 74 to 75 of the above-mentioned document "UV / EB curing material". Be done.
Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adduct di or polyglycidyl ether; phenol novolac type epoxy resin and cresol novolac type epoxy resin. Novolak type epoxy resin and the like; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like. In addition to these, Chapter 2 of the document "Epoxy resin-Recent progress-" (Shokodo, published in 1990) and the document "Polymer processing" separate volume 9 and 22 special issue Epoxy resin [Polymer publication The compounds as described on pages 4 to 6 and 9 to 16 of [Kai, published in 1973] can be mentioned.
Specific examples of the aliphatic epoxy resin include diglycidyl ether of alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; poly such as diglycidyl ether of polyethylene glycol and polypropylene glycol. Diglycidyl ether of alkylene glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct, and penta. Polyglycidyl ethers of polyhydric alcohols such as di, tri or tetraglycidyl ethers of erythritol and its alkylene oxide adducts; di or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; diglycidyl ethers of tetrahydrophthalates; Hydroquinone diglycidyl ether and the like can be mentioned. In addition to these, compounds described on pages 3 to 6 of the separate volume epoxy resin of the above-mentioned document "Polymer processing" can be mentioned.
In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus as a skeleton, for example, TEPIC [Nissan Kagaku Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.] and the like can be mentioned. Examples thereof include compounds as described on pages 289 to 296 of the separate volume epoxy resin of the above-mentioned document "Polymer processing".
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

Among the above, in order to make the composition low in viscosity and excellent in adhesiveness, a hydroxyl group-containing monofunctional (meth) acrylate is preferable, and a hydroxyl group-containing monofunctional (meth) acrylate having a molecular weight of less than 300 is more preferable.
Preferred specific examples of the hydroxyl group-containing monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , Cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid adduct of cyclohexene oxide, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like, 4-hydroxybutyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferable.

As the component (C), only one type may be used alone, or two or more types may be used in combination.

The content ratio of the component (C) is 5 to 55% by mass, more preferably 7 to 45% by mass, and further preferably 10 to 40% by mass in 100% by mass of the total amount of the curable component.
If the proportion of the component (C) is less than 5% by mass, the curability of the composition is lowered, or the adhesive strength of the cured product of the composition is lowered, and if it exceeds 55% by mass, the curing of the composition is lowered. The water resistance of the object is reduced.

4. Component (D) Component (D) is a photocationic polymerization initiator. That is, by irradiation with active energy rays, cations or Lewis acids and radicals are generated, and the polymerization of the photocationically polymerizable compound (A) component, the photoradical polymerizable compound (B) component and (C) is started. It is a compound that
Examples of the component (D) include sulfonium salt, iodonium salt, diazonium salt and the like.

Specific examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, and diphenyl-4. -(Phenylthio) phenylsulfonium hexafluoroantimonate, 4,4'-bis [diphenylsulfonio] diphenylsulfide bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bis Hexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate , 7- [di (p-toluyl) Sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-) Butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide Hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) Sulfonio-diphenylsulfide Tetrax (pentafluorophenyl) Examples thereof include triarylsulfonium salts such as borate.

Specific examples of the iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-t-butylphenyl) iodonium hexafluorophosphate, and di (4-t). -Butylphenyl) Iodonium Hexafluoroantimonate, Trilucmil Iodonium Tetrax (pentafluorophenyl) borate, Iodonium (4-methylphenyl) [4- (2-Methylpropyl) phenyl] -Hexafluoroophosphate, di (4-) Examples thereof include diaryliodonium salts such as nonylphenyl) iodonium hexafluorophosphate and di (4-alkylphenyl) iodonium hexafluorophosphate.

Specific examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate and the like.

Commercially available products of the component (D) include ADEKA PUTMER SP-100, 150, 152, 170, 172 [manufactured by ADEKA Corporation], Photoinitiator 2074 [manufactured by Rhodia], Kayarad PCI-220, 620 [Japan]. Chemicals Co., Ltd.], Irgacure 250 (manufactured by Ciba Japan), CPI-100P, 101A, 110P, 200K, 210S [manufactured by Sun Appro Co., Ltd.], WPI-113, 116, 170 [manufactured by Wako Pure Chemical Industries, Ltd.] ], BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [manufactured by Midori Kagaku Co., Ltd.], Speed Cure 938, 976 [manufactured by Rambuson Japan], TR-PAG- Examples thereof include 201, 202, 201S, 202S, 30101, 30201, 31102, 20008, 21108, 30208, 31108 [manufactured by DTS].

Among these, triarylsulfonium salt and diaryliodonium salt are preferable because they are excellent in active energy ray curability and the cured film is excellent in water resistance and adhesiveness, and diaryliodonium salt is particularly excellent in adhesiveness. preferable.
Among the above-mentioned salts, the triarylsulfonium salt is preferably triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate. Among the above-mentioned diaryliodonium salts, trilucmiliodonium tetrakis (pentafluorophenyl) borate (photoinitiator 2074; manufactured by Rhodia Japan Co., Ltd.), diphenyliodonium hexafluorophosphate, iodonium (4-methylphenyl) [ 4- (2-Methylpropyl) Phenyl] -Hexafluoroolophosphate (Irgacure 250; manufactured by BASF Japan Co., Ltd.), Di (4-t-Butylphenyl) Iodonium Hexafluorophosphate (Speed Cure 938; Rambuson Japan) (Manufactured by Wako Pure Chemical Industries, Ltd.) and WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

As the component (D), only one type may be used alone, or two or more types may be used in combination.

The ratio of the component (D) is 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount of the curable component.
When the ratio of the component (D) is less than 0.1 parts by mass, the active energy ray curability of the composition becomes insufficient, and the adhesiveness of the cured product of the composition is lowered, while 10 If it exceeds a mass portion, the internal curability of the cured product (adhesive layer) of the composition becomes poor, and the adhesiveness of the cured product of the composition is lowered.

Further, in using the component (D), a sensitizer may be used in combination in order to increase the photodecomposition efficiency of the component (D), and these are also included as the component (D). Examples of the sensitizer include anthracene compounds, 4-methoxy-1-naphthol, fluorene, pyrene, stilbene and the like.
Specific examples of the anthracene compound include, for example, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9. , 10-Diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 4'-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-diethoxyanthracene- 2-sulfonate and 4'-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate and the like can be mentioned.
Among these, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 9,10-dipropoxyanthracene are preferable because of their excellent solubility in the composition and high sensitizing effect of the component (D). ..
Examples of commercially available products of these sensitizers include Anthracure UVS-1331, 1221, 1101, and ET-2111 [manufactured by Kawasaki Kasei Chemicals Co., Ltd.].

The ratio of the sensitizer is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the curable component.
When the plastic film as an adherend absorbs a large amount of ultraviolet rays and a sulfonium salt is used as the component (D), it is preferable to use an anthracene compound as a sensitizer.

5. Component (E) Component (E) is a photoradical polymerization initiator. The component (E) is a compound that generates radicals by irradiation with active energy rays and initiates polymerization of the components (B) and (C), which are compounds having an ethylenically unsaturated group. Further, depending on the type of the component (E), there is also one that functions as a sensitizer that promotes photodecomposition of the component (D).

Specific examples of the component (E) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-. 1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- On, 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-morpholinopropane-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one , Adekaoptomer N-1414 (manufactured by Asahi Denka Co., Ltd.), phenylglioxylic acid methyl ester, ethylanthraquinone, phenanthrenquinone and other aromatic ketone compounds;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, 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 Benzophenones such as (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone Compound;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6) Acylphosphine oxide compounds such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone and 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Oxime esters such as -1- (O-acetyloxime), 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) 4,5-di (m-methoxy) Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-) Phenylphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) 4,5-diphenyl Examples thereof include 2,4,5-triarylimidazole dimer such as imidazole dimer; and acrydin derivatives such as 9-phenylaclydin and 1,7-bis (9,9'-acrydinyl) heptane.

Among these, aromatic ketone compounds and thioxanthone compounds are preferable because they have a high sensitizing effect on the component (D). Among aromatic ketone compounds and thioxanthone compounds, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1- are excellent in active energy ray curability and less colored in the cured film. On, 2,4-diethylthioxanthone and isopropylthioxanthone are more preferred.

As the component (E), only one type may be used alone, or two or more types may be used in combination.

The ratio of the component (E) is 0.1 to 15 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the total amount of the curable component.
When the ratio of the component (E) is less than 0.1 parts by mass, the active energy ray curability of the composition becomes insufficient, and the adhesiveness of the cured product of the composition is lowered, while 15 If it exceeds a mass portion, the internal curability of the cured product (adhesive layer) of the composition becomes poor, and the adhesiveness of the cured product of the composition is lowered.

6. Other Ingredients The active energy ray-curable adhesive composition for plastic films of the present invention contains components (A) to (E) as essential components, but various other components may be blended depending on the purpose. Can be done.

Other components include a cationic curable component other than the component (A) (hereinafter referred to as the component (F)), the component (B) and the component (C), which have one or more cationically polymerizable groups in the molecule. Examples thereof include a radical curable component (hereinafter referred to as (G) component), a polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, an antioxidant, and a surface modifier.

6-1. Component (F) Examples of the component (F) include an oxetane compound and a vinyl ether compound.

An oxetane compound is a compound having one or more oxetane rings in its molecule. Specific examples thereof include various oxetane compounds described in JP-A-8-85775 and JP-A-8-134405, and among these, compounds having one or more oxetane groups are preferable.
Specific examples of monofunctional oxetane are 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Examples thereof include ethyl-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane.
Specific examples of the bifunctional oxetane include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and bis {[1-ethyl (3-oxetanyl)] methyl} ether.

The vinyl ether compound is a compound having one or more vinyl ether groups in the molecule, and examples thereof include a monofunctional vinyl ether compound and a polyfunctional vinyl ether compound.
Specific examples of the monofunctional vinyl ether compound include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, and dodecyl vinyl ether. , Octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and the like.
Specific examples of the polyfunctional vinyl ether compound include polyfunctional vinyl ethers such as 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

As the component (F), a compound having a low molecular weight is preferable because the adhesive strength can be increased and the viscosity can be lowered, and specifically, a compound having a molecular weight of 2,000 or less is preferable.
Among the components (F), particularly preferable examples are 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, and bis (3-ethyl-3-oxetanylmethyl). Ether is mentioned.

As the component (F), only one type may be used alone, or two or more types may be used in combination.

The content ratio of the component (F) in the curable component is preferably 2 to 30% by mass, more preferably 5 to 20% by mass, based on 100% by mass of the total amount of the curable component. By setting the ratio of the component (F) to 2% by mass or more, the composition has a low viscosity and excellent coatability.
When the content is 30% by mass or less, the adhesive strength becomes excellent.

6-2. (G) component Examples of the (G) component include (meth) acryloyl group-containing compounds other than the (B) component and the (C) component, (meth) acrylamide compounds, vinyl compounds, and allyl compounds. Further, as the molecular weight thereof, various ones can be selected, and any of a monomer, an oligomer, and a polymer may be used.

Examples of the (meth) acryloyl group-containing compound 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. [Hereinafter referred to as “polyfunctional (meth) acrylate”].

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-. Ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenol alkylene oxide adduct (meth) acrylate, p-cumylphenol alkylene oxide adduct (meth) acrylate, (Meta) acrylate of o-phenylphenol alkylene oxide adduct, (meth) acrylate of nonylphenol alkylene oxide adduct, 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, alkylene oxide addition of 2-ethylhexyl alcohol (Meta) acrylates, tetrahydrofurfuryl (meth) acrylates, caprolactone-modified tetrahydrofurfuryl (meth) acrylates, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylates, (2-Isobutyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (1,4-dioxaspiro [4,5] decane-2-yl) methyl (meth) acrylate, glycidyl ( Meta) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, allyl (meth) acrylate, N- (Meta) Acryloyloxyethyl Hexahydrophthalimide, N- (Meta) Acryloyloxyethyl Tetrahydrophthalimide, 2- (Meta) Acryloyloxyethyl Hexahydrophthalic Acid, 2- (Meta) Acryloyloxyethyl Succinic Acid, ω-carboxy-Poly Caprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 3-( Examples thereof include meta) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyldimethoxymethylsilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 2- (meth) acryloyloxyethyl acid phosphate.
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 nonane diol di (meth) acrylate;
Di (meth) acrylates of alicyclic diols such as cyclohexanedimethylol di (meth) acrylate and tricyclodecanedimethylol di (meth) acrylate;
Diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as triethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate;
The esterification reaction product of neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid (hereinafter referred to as "hydroxypivalate neopentyl glycol di (meth) acrylate"), caprolactone-modified hydroxypivalate neopentyl glycol di (meth). ) Acrylate;
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;
Di (meth) acrylate of isocyanuric acid alkylene oxide adduct, tri (meth) acrylate of isocyanuric acid alkylene oxide adduct, di (meth) acrylate of caprolactone-modified isocyanuric acid alkylene oxide adduct, caprolactone-modified isocyanuric acid alkylene oxide adduct Poly (meth) acrylates of isocyanuric acid alkylene oxide adducts such as tri (meth) acrylates;
Polyester poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate;
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:
Urethane (meth) acrylate;
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.

Specific examples of the (meth) acrylamide compound include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, and N, N-diethyl (meth). ) Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like.

Examples of the vinyl compound include monofunctional vinyl compounds such as styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole and vinylpyridine, and polyfunctional vinyl compounds such as divinylbenzene.

Examples of the allyl compound include monofunctional allyl compounds such as allyl alcohol, and polyfunctional allyl compounds such as diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.

In addition to these, compounds and the like described on pages 53 to 56 of the document "Latest UV Curing Technology" [Printing Information Association, Inc., published in 1991] can be mentioned.

Among the components (G), tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-Hexanediol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, and caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylate are preferred, and caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylate is preferred. ) Acrylate (preferably 1 to 10 mol of caprolactone modification amount) is particularly preferable.

As the component (G), only one type may be used alone, or two or more types may be used in combination.

The content ratio of the component (G) in the curable component using the component (G) is preferably 5 to 79% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total amount of the curable component. Is. When the proportion of the component (G) is 5% by mass or more, the adhesive strength is excellent, and when it is 79% by mass or less, the composition has a low viscosity and excellent coatability.

6-3. Ultraviolet absorber The composition of the present invention can improve the adhesive strength by containing an ultraviolet absorber, and for unknown reasons, the curing rate is suppressed by blocking ultraviolet rays in the low wavelength region. It is presumed that this is because the residual stress at the bonding interface is reduced.

Specific examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
These can be used alone or in combination of two or more.

The content ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the curable component. 2 parts by mass. When the content ratio is 0.1 parts by mass or more, the adhesive strength can be increased, and when the content ratio is 5 parts by mass or less, the decrease in curability can be suppressed.

6-4. Polymerization inhibitor Examples of the polymerization inhibitor include an organic polymerization inhibitor, an inorganic polymerization inhibitor, and an organic salt polymerization inhibitor.
Specific examples of the organic polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-. Phenolic compounds such as tert-butylcatechol, quinone compounds such as benzoquinone, galbinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 Examples thereof include stable radicals such as −oxyl, phenothiazine, N-nitroso-N-phenylhydroxylamineammonium and the like.
Specific examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate and iron sulfate.
Specific examples of the organic salt-based polymerization inhibitor include nitroso compounds such as N-nitroso-N-phenylhydroxylamine / aluminum salt and ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.
These can be used alone or in combination of two or more.

Among these, stable radicals and nitroso compounds are preferable because the coloration of the adhesive is small, thickening and gelation of the composition can be prevented, and storage stability can be improved.
The content ratio of the polymerization inhibitor may be appropriately set according to the purpose, and is preferably 0.0001 to 1 part by mass, more preferably 0.0005 to 1 part by mass, based on 100 parts by mass of the total amount of the curable component. It is 0.5 parts by mass. When the content ratio is 0.0001 parts by mass or more, the thermal stability and photostability of the composition can be enhanced, and when it is 1 part by mass or less, the photocurability of the composition is excellent. Can be done.

6-5. Silane Coupling Agent Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. 3-glycidoxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane, 3- (meth) acrylic Loxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-amino Examples thereof include propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
These can be used alone or in combination of two or more.

6-6. Antioxidants Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like.
Specific examples of the phenolic antioxidant include hindered phenols such as dit-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.
Specific examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphine, and triaryl phosphine. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Specific examples of the sulfur-based antioxidant include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA CORPORATION.
These can be used alone or in combination of two or more. Preferred combinations of these antioxidants include a combination of a phenolic antioxidant and a phosphorus-based antioxidant, and a combination of a phenolic antioxidant and a sulfur-based antioxidant.

6-7. Surface modifiers Examples of surface modifiers include surface conditioners, surfactants, leveling agents, defoamers, slipperiness-imparting agents and antifouling agents, and these known surface modifiers are used. can do.
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferably mentioned.
Specific examples of the silicone-based surface modifier include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, and the like.
Specific examples of the fluorine-based surface modifier include a fluorine-based polymer and an oligomer having a perfluoroalkyl group and a polyalkylene oxide chain, and a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain. And so on.
Further, in order to improve durability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group in the molecule may be used.
These can be used alone or in combination of two or more.

7. Active Energy Ray Curable Adhesive Composition for Plastic Films The present invention is an active energy ray curable adhesive composition for plastic films containing the components (A) to (E) in a specific ratio.
The composition can be produced by mixing the above-mentioned components (A) to (E), further mixing other components as necessary, and stirring according to a conventional method.
In this case, it can be heated if necessary. The heating temperature may be appropriately set according to the composition to be used, the base material, the purpose, and the like, but is preferably 30 to 80 ° C.

The viscosity of the composition at 25 ° C. is preferably 10 to 1,000 mPa · s because it is excellent in coatability on a base material.

8. Method of Use The composition of the present invention can be used for adhering plastic films to each other and for adhering a plastic film to various other base materials (hereinafter referred to as other base materials). Examples thereof include a method of bonding with the other base material after coating and irradiating with active energy rays.
In the present invention, the term "base material" simply means a general term for plastic films and other base materials.
Examples of other base materials include paper and metal.

Examples of the plastic film include a hydrophilic plastic film and a hydrophobic plastic film.
Specific examples of the hydrophilic plastic film include a polyvinyl alcohol-based film and a cellulose ester-based film.
Specific examples of the hydrophobic plastic film include polycarbonate film, polyethylene terephthalate film, polyethylene naphthalate film, acrylic film, acrylic / styrene film, aliphatic polyamide (nylon) film, aromatic polyamide film, and the like. Polyarylate film, polyether sulfone film, polyurethane film, polyimide film, ethylene-vinyl acetate copolymer film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene film, polypropylene film, poly Cycloolefin-based film, polystyrene-based film, ABS-based film, chlorinated polypropylene-based film and the like can be mentioned.
Specific examples of the paper include imitation paper, high-quality paper, kraft paper, art-coated paper, caster-coated paper, pure white roll paper, parchment paper, water-resistant paper, glassin paper, corrugated paper and the like.
Specific examples of the metal include gold, silver, copper, aluminum, iron, nickel, titanium, stainless steel, chrome molybdenum steel and the like.

Coating on the substrate can be done according to conventionally known methods, such as natural coaters, knife belt coaters, floating knives, knife overrolls, knife-on blankets, sprays, dips, kiss rolls, squeeze rolls, reverse rolls, air blades. , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater and the like.
The coating thickness of the composition of the present invention may be selected depending on the substrate to be used and the intended use, but is preferably 0.1 to 100 μm, and more preferably 1 to 25 μm.

Examples of the active energy ray include visible light, ultraviolet light, X-ray, electron beam, and the like, 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 preferable, and metal halide lamps are particularly preferable. The dose of ultraviolet rays is in the range of UV-A (365 nm vicinity) is preferably ^{200~2,000mJ / cm 2, 300~1,500mJ / cm} 2 is more preferable.

In the case of curing with an electron beam, various devices can be used as the electron beam irradiation device that can be used, and examples thereof include a Cockloft Waldsin type device, a bandegraf type device, and a resonance transformer type device. 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 base material. For example, when the film thickness of the base material is 100 μm, 200 kV is preferable. The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

9. Laminated body and method for producing the same The laminated body of the present invention is a laminated body in which base materials are arranged on both sides of a cured product layer formed from the composition of the present invention, and at least one of the base materials is a plastic film. is there.
The composition of the present invention is suitable for adhering a thin-layer adherend as a base material, and the method of use for adhering a thin-layer adherend follows the method usually used in the production of laminates. Just do it. For example, a method in which the composition is applied to a first thin-layer adherend, dried if necessary, and then a second thin-layer adherend is attached thereto to irradiate the active energy rays. 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.

Examples of the thin-layer adherend include a plastic film, paper, metal leaf, and the like.
The plastic film needs to be capable of transmitting active energy rays, and the film thickness may be selected according to the thin-layer adherend to be used and the application, but the thickness is preferably 0.2 mm or less. ..

Among these thin-layer adherends, the composition of the present invention is suitably used for bonding plastic films to each other, and further for bonding hydrophilic plastic films to each other and bonding hydrophobic plastic films and hydrophilic plastic films. It can be preferably used.

Further, before adhering the adherend, one or both surfaces can be activated in order to increase the interlayer adhesive force. 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.

The coating on the thin layer adherend may be performed according to a conventionally known method, and the same method as described above can be mentioned.
The coating thickness of the composition of the present invention may be selected according to the thin-layer adherend to be used and the intended use, but the same coating thickness as described above is preferable.

Further, in this case, the bonding can be performed not only in a flat state but also in a curved state.
That is, there is a method in which the base material is bent into a concave state or a convex state, the composition is applied in this state, the other base material is bonded, and the active energy ray is irradiated.
As another method, the composition of the present invention is applied to the base material in a flat state, the other base material is bonded, bent into a concave state or a convex state, and irradiated with active energy rays to bond them. Can be mentioned.
In this case, as a method of applying the composition in a flat state, the above-mentioned method may be followed. Examples of the method of applying the composition in a curved surface state include a method of using a spray, a dip, a curtain flow coater, screen printing, a slot die coater and the like.

By the above method, from a plastic film / a cured product layer formed from the composition of the present invention / a laminate composed of a plastic film, a plastic film / a cured product layer formed from the composition of the present invention / other base material. The laminated body to be composed is manufactured.
The laminate of the laminated film obtained from the composition of the present invention has excellent adhesive strength under high temperature and high humidity conditions, and is therefore suitable for polarizing plates and protective films used for liquid crystal displays and the like, and optical films for retardation films. Can be used for.

(Preferable form)
The composition of the present invention can be particularly preferably used for producing a polarizing plate and a polarizing plate with a retardation film. Hereinafter, a method for manufacturing a polarizing plate will be described.

In the present specification, the polarizer refers to a film or film having a polarizing function, which will be described later, and the polarizing plate is a polarizing element with a protective layer in which one or both sides of the polarizing element are protected by the film or film. Represents that. Further, the polarizing plate with a retardation film represents a polarizing plate or a polarizing plate to which a retardation film is attached or a film having a retardation function is formed by coating.

As described above, the composition of the present invention can be preferably used for adhering hydrophilic plastic films to each other, and also for bonding hydrophobic plastic films and hydrophilic plastic films, and is a polyvinyl alcohol-based composition used as a polarizer in the production of polarizing plates. The polarizer film and the cellulose ester-based film used as the protector-protecting film correspond to the hydrophilic plastic film, and the polycarbonate-based film, the polyethylene terephthalate-based film, the acrylic film, the polycycloolefin-based film, etc. become the hydrophobic plastic film. Equivalent to.

The composition of the present invention can be used for bonding a polarizer and a protective film or for bonding a polarizing plate and a retardation film.

The polarizer has a function of selectively transmitting linearly polarized light in a certain direction from natural light.
Specific examples of the polarizer include an iodine-based polarizer in which iodine is adsorbed and oriented on a polyvinyl alcohol-based film, a dye-based polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based film, and a (riotropic) liquid crystal. Examples thereof include a coating type polarizer in which a state dye is coated, oriented, and immobilized.
These iodine-based polarizers, dye-based polarizers, and coating-type polarizers have a function of selectively transmitting linearly polarized light in one direction from natural light and absorbing linearly polarized light in the other direction, and absorb the polarized light. It is called a type polarizer.

In the iodine-based polarizer and the dye-based polarizer, a protective layer is usually provided on one side or both sides thereof, but the composition of the present invention can be used for adhesion between the polarizer and the protective film.

Specific examples of the protective film used in the protective layer include cellulose ester films such as triacetyl cellulose and diacetyl cellulose, polycarbonate films, polyethylene terephthalate films, acrylic films, polyarylate films, and polyether sulfone films. Examples thereof include a polycycloolefin-based film using a cycloolefin such as norbornene as a monomer, and an aliphatic polyamide (nylon) -based film.

Next, the composition of the present invention can also be used for adhering a polarizing plate and a retardation film.
In this case, as the polarizing plate, one having a protective layer on one side or both sides thereof can be used.
In this case, as a specific example of the protective layer, the protective film may be bonded or the protective film formed by coating may be used.
In a polarizing plate having a protective layer provided on only one surface, the surface to be adhered to the retardation film may be a surface with a protective layer or a surface without a protective layer.

Various retardation films can be used, and an optical film or a liquid crystal compound that has been subjected to processing such as uniaxial or biaxial stretching is applied to the base material, and the orientation and immobilization are processed. Examples include optical films, in which the magnitude relationship (refractive index elliptical body) of the three-dimensional refractive index is controlled according to the usage conditions. It is mainly used to compensate for the coloring of the liquid crystal layer of a liquid crystal display and the change in phase difference due to the viewing angle.

Specific examples of the retardation film include polyethylene-based film, polypropylene-based film, polycycloolefin-based film, polycarbonate-based film, polyvinyl alcohol-based film, and polystyrene as the material of the optical film to be subjected to processing such as stretching. Examples thereof include based films, acrylic films, polyarylate films, polyamide films and the like.
The above-mentioned polycycloolefin is a general general term for resins obtained from cycloolefins such as norbornene, tetracyclododecene, and derivatives thereof. For example, JP-A-3-14882 and JP-A-3-122137 are used. Examples thereof are those described in publications and the like.
Specifically, a ring-opening polymer of cycloolefin, an addition polymer of cycloolefin, a random copolymer of cycloolefin and α-olefin such as ethylene and propylene, and modification of these with unsaturated carboxylic acid or a derivative thereof. Examples thereof include a modified graft. Furthermore, these hydrides can be mentioned. Examples of commercially available products include Zeonex and Zeonoa manufactured by Zeon Corporation, Arton manufactured by JSR Corporation, and Topus manufactured by TICONA.

Further, as the optical film obtained by applying a liquid crystal compound or the like to a base material and processing the orientation and immobilization, "WV film" [manufactured by Fuji Film Co., Ltd.], "LC film", "NH film" Commercially available products such as [all manufactured by JX Nikko Nisseki Energy Co., Ltd.] can be mentioned.

A method for producing a polarizing plate or a polarizing plate with a retardation film using the composition of the present invention will be described below.
Examples of the manufacturing method include methods including the following steps [1] to [3].
[1] A step of applying the composition of the present invention to any of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film as an adherend.
[2] A step of adhering any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film to be the other adherend to the film coated with the composition.
[3] A step of irradiating an active energy ray through a base material coated with the composition of the present invention after laminating the films.
When a protective film or a retardation film is bonded to only one side, a polarizing plate or a polarizing plate with a retardation film can be manufactured by the above procedure, but when bonding to both sides, steps [1] and [2] ] May be repeated twice and then step [3] may be repeated, or steps [1], [2] and [3] may be repeated twice.

The coating method in the step [1] and the active energy ray irradiation method in the step [3] may be carried out in the same manner as described above.
Further, as described above, it is also possible to bond in a curved state.

When a polarizing plate with a retardation film is used as a circular polarizing plate, a retardation film having a different retardation is further attached to the retardation film side of the polarizing plate with a retardation film in order to achieve a circularly polarized state over a wide band. You can also match.
Specifically, a method of laminating a retardation film having a 1/2 wavelength for each wavelength to a polarizer film and further laminating a retardation film having a 1/4 wavelength for each wavelength is used. is there. In this case, the step [3] may be carried out after repeating the steps [1] and [2] three times, or the steps [1], [2] and [3] may be repeated three times.

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.
In addition, "part" in each of the following examples means a mass part.
1. 1. Manufacturing example
1) Production Example 1 [Production of component (B)]
23 g (0.10) of isophorone diisocyanate in a 500 mL reaction vessel equipped with a stirrer.
Mol), 194 g of tetrahydrofurfuryl acrylate (hereinafter referred to as "THFA") as a diluent, 0.16 g of dibutyltin dilaurate as a catalyst, and 2,6-di-t-butyl-4-methylphenol 0 as a polymerization inhibitor. .10 g was added and heated until the liquid temperature reached 70 ° C. while stirring in an atmosphere of nitrogen containing 5% by volume of oxygen.
167 g (0.082 mol) of a polyester polyol having a hydroxyl value of 55 mgKOH / g (polyester polyol HS 2F-233AN manufactured by Toyokuni Oil Co., Ltd., an esterified product of adipic acid and neopentyl glycol) was added dropwise to the reaction solution over 1 hour. did. The internal temperature is raised to 80 ° C., 0.93 g (0.01 mol) of 1,4-butanediol is added for an additional 12 hours, and 4.32 g (0.037 mol) of 2-hydroxyethyl acrylate is added for an additional 12 hours. It was reacted.
The spectrum was measured by the transmission method with an infrared absorption spectrum device (FT-IR Spectrum 100 manufactured by PerkinElmer), and it was confirmed that the isocyanate groups were completely consumed. The obtained reaction product was a mixture containing 50 parts of urethane acrylate (hereinafter referred to as "UA1") and 50 parts of THFA. In Table 1 below, the ratios of UA1 and THFA are shown separately as the components of the composition.
As a result of measuring the obtained UA1 by GPC (solvent: tetrahydrofuran, column: HSPgel HR MB-L manufactured by Waters), the polystyrene-equivalent Mw was 42,000.

2. Examples 1-16, Comparative Examples 1-3
1) Preparation of active energy ray-curable adhesive composition The components (A) to (E) and other components shown in Table 1 below are dissolved by heating and stirring at 60 ° C. for 1 hour to dissolve the active energy ray-curable adhesive. The composition was prepared.
Using the obtained composition of Table 1, the evaluation described later was performed. The results are shown in Table 1.

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

◆ (A) Ingredients・ EXA: Bisphenol A diglycidyl ether, Epicron EXA-850CRP manufactured by DIC Corporation
-SR14BJ: 1,4-butanediol diglycidyl ether, SR-14BJ manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
◆ (B) component・ UN9200A: Polycarbonate skeleton urethane acrylate (Mw15,000), Art resin UN-9200A manufactured by Negami Kogyo Co., Ltd.
-UN9000PEP: Polycarbonate skeleton urethane acrylate (Mw5,000), Art resin UN-9000PEP manufactured by Negami Kogyo Co., Ltd.
UA1: Polyester skeleton urethane acrylate produced in Production Example 1 (Mw42,000)
UN6202: Polyester skeleton urethane acrylate (Mw11,000), Art resin UN-6202 manufactured by Negami Kogyo Co., Ltd.
◆ (C) component・ 4HBA: 4-hydroxybutyl acrylate, Viscoat 4-HBA manufactured by Osaka Organic Chemical Industry Co., Ltd.
-HPA: 2-Hydroxypropyl acrylate, Light ester HOP-A manufactured by Kyoeisha Chemical Co., Ltd.
◆ (D) component・ 938: Diaryliodonium salt-based photocation initiator, Speed Cure 938 manufactured by Rambuson Japan Co., Ltd.
-CPI: Triarylsulfonium salt-based photocation initiator, CPI-110P manufactured by San-Apro Co., Ltd.
◆ Ingredient (E)・ DETX: 2,4-diethylthioxanthone, DETX-S manufactured by Nippon Kayaku Co., Ltd.
SBPI714: 1-Hydroxycyclohexylphenyl ketone, SB-PI714 manufactured by Soho Kogyo Co., Ltd.

◆ Other ingredients
(G) Ingredients -THFA: Tetrahydrofurfuryl acrylate, Viscoat # 150 manufactured by Osaka Organic Chemical Industry Co., Ltd.
-HX220: Caprolactone-modified neopentyl glycol diacrylate (caprolactone-modified amount: 2 mol), Kayacure HX-220 manufactured by Nippon Kayaku Co., Ltd.
-HX620: Caprolactone-modified neopentyl glycol diacrylate (caprolactone-modified amount: 6 mol), Kayacure HX-620 manufactured by Nippon Kayaku Co., Ltd.
Polymerization inhibitor・ TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl ・ Q1301: N-nitrosophenylhydroxylamine ・ aluminum salt, Wako Pure Chemical Industries, Ltd. Q-1301
UV absorber Ti900: Benzotriazole UV absorber, Tinubin 900 manufactured by BASF Japan Ltd.

2) Evaluation of active energy ray-curable adhesive composition The viscosity of the obtained composition at 25 ° C. was measured using an E-type viscometer. The results are shown in Table 1.
The viscosity of the compositions of Examples 1 to 16 after heating at 80 ° C. for 24 hours was less than twice the initial value, and the storage stability was excellent.

3) Manufacture of laminate (example of manufacture of polarizer)
A staining solution was prepared by dissolving 0.05 parts by mass of iodine and 0.5 parts by mass of potassium iodide in 100 parts by mass of water.
This dyeing solution was heated to 55 ° C., and a polyvinyl alcohol-based film having a thickness of 75 μm [Vinylon film VF-PS manufactured by Kuraray Co., Ltd.] was immersed for 1 minute, and then the film was stretched 6 times in one direction. Further, washing after dyeing is performed in an aqueous solution prepared by dissolving 4 parts by mass of boric acid and 6 parts by mass of potassium iodide in 90 parts by mass of water, and then dried to obtain a polarizer having a thickness of 30 μm [hereinafter, “PVA-”. It is called "P". ] Was prepared. The contact angle of water of PVA-P at 23 ° C. was measured using a contact angle measuring device (SCA20 manufactured by Eiko Seiki Co., Ltd.) at room temperature of 23 ° C. in a 50% RH environment and a dropping amount of 4 microliters. As a result, it was 57 °.

(Manufacturing of polarizing plate)
Triacetyl cellulose film with a thickness of 80 μm containing a UV absorber [Fujitac TD 80UL manufactured by Fuji Film Co., Ltd. Hereinafter, it is referred to as "TAC". ] Above, a corona treatment (Polydyne 1, Navitas, output 0.1 kW, processing speed 1 second / cm) was carried out as an easy-adhesion treatment. The contact angle of water at 23 ° C. of TAC was 66 ° as a result of measurement in the same manner as described above.
Subsequently, the active energy ray-curable adhesive composition was applied to the polarizer PVA-P obtained above with a bar coater to a thickness of 5 μm.
After laminating the corona-treated TAC on this, turn it over, apply the active energy ray-curable adhesive composition in the same manner, and apply a 125 μm-thick polycarbonate film [Teijin Co., Ltd. Panlite PC-2151. Hereinafter, it is referred to as "PC". ] Was laminated. The contact angle of water at 23 ° C. of the PC was 80 ° as a result of measurement in the same manner as described above.
After that, a conveyor-type ultraviolet irradiation device (160 W / cm metal halide lamp, UV-A region irradiation intensity 500 mW / cm ² , integrated light intensity 1,000 mJ / cm ² ) manufactured by Eye Graphics Co., Ltd., all manufactured by Heleus Co., Ltd. Using UV POWER PUCK (measured value), the front and back surfaces of the laminated film were irradiated with ultraviolet rays for 1 pass each and cured to obtain a polarizing plate.

4) Evaluation method of laminated body
◆ Peeling strength The polarizing plate obtained in 2.3) above is attached to glass via double-sided tape, and the peeling strength between TAC and the polarizer PVA-P and the peeling between the PC and the polarizer PVA-P are achieved. The intensities were measured under the following conditions. The results are shown in Table 1.
・ Tensile tester: Instron 5564 manufactured by Instron Japan Company Limited
-Test piece: Width 25 mm x 100 mm
-Test method: 90 ° peeling / peeling speed: 200 mm / min

5) 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 adhesiveness between hydrophilic plastic films (TAC and PVA-P), In addition, it was excellent in both the adhesiveness of the hydrophobic plastic film (PC) and the hydrophilic plastic film (PVA-P).
Among these, in addition to the components (A) to (E), a composition containing a caprolactone-modified neopentyl glycol diacrylate (Examples 6 and 7) and a composition containing an ultraviolet absorber. The product (Example 8) was excellent in adhesiveness to the extent that the material was broken in the measurement of the peel strength between the hydrophilic plastic films, and the adhesiveness between the hydrophobic plastic film and the hydrophilic plastic film was the most excellent.
Here, under certain conditions other than the component (B), the composition containing the polycarbonate skeleton urethane acrylate (Examples 1 and 11) and the composition containing the polyester skeleton urethane acrylate (Example 12) are the portel skeleton urethane. The adhesiveness between the hydrophilic plastic films was particularly excellent as compared with the composition containing acrylate (Example 13).
On the other hand, a composition in which the content ratio of the component (A) of the present invention is less than 15% by mass in 100% by mass of the curable component (Comparative Example 1), and a composition not containing the component (B) of the present invention. (Comparative Example 2) and the composition (Comparative Example 3) containing no component (C) of the present invention had very low adhesiveness between the hydrophobic plastic film and the hydrophilic plastic film.

The composition of the present invention can be used as an adhesive for various plastic films, especially between hydrophilic plastic films, and as an adhesive between a hydrophobic plastic film and a hydrophilic plastic film, such as a liquid crystal display and an organic EL display. It can be suitably used for various optical films used in. Specifically, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness improving film, an antireflection film, an antiglare film, a lens sheet, a diffusion film, a hard coat film having functionality such as anti-fingerprint and anti-glare, etc. Examples thereof include an optical film such as a front plate of a touch panel, which can be particularly preferably used for manufacturing a polarizing plate.

Claims (14)

It is composed of at least a curable component and a polymerization initiator, the curable component is composed of at least the following components (A) to (C), and the polymerization initiator is composed of at least the following components (D) and (E).
Component (A): Compound having two or more epoxy groups in the molecule (B) Component: Urethane (meth) acrylate (C) Component: Compound having one or more hydroxyl groups and ethylenically unsaturated groups in the molecule ( D) Component: Photocationic polymerization initiator (E) Component: Photoradical polymerization initiator The components (A) to (C) are contained in the total amount of 100% by mass of the curable component in the following proportions.
(A) Ingredient: 15-80% by mass
(B) Component: 1 to 30% by mass
(C) component: 5 to 55% by mass
An active energy ray-curable adhesive composition for a plastic film or sheet containing the components (D) and (E) in the following proportions with respect to 100 parts by mass of the total amount of curable components.
Component (D): 0.1 to 10 parts by mass (E) Component: 0.1 to 15 parts by mass The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 1, wherein the component (B) contains a urethane (meth) acrylate having a weight average molecular weight of 1,000 to 50,000. .. The active energy ray-curable adhesive for a plastic film or sheet according to claim 1 or 2, wherein the component (B) contains a urethane (meth) acrylate having two (meth) acryloyl groups in the molecule. Agent composition. The active energy for a plastic film or sheet according to any one of claims 1 to 3, wherein the component (C) contains a compound having one hydroxyl group and one ethylenically unsaturated group in the molecule. Line-curable adhesive composition. The claim that the component (C) contains at least one compound selected from the group consisting of 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 4. The active energy ray-curable adhesive composition for a plastic film or sheet according to 4. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 5, wherein the component (D) contains a diaryliodonium salt. The plastic film according to any one of claims 1 to 6, further comprising a (meth) acryloyl group-containing compound other than the component (G): component (B) and component (C) as a curable component. Alternatively, an active energy ray-curable adhesive composition for a sheet. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 7, which contains a caprolactone-modified neopentyl glycol di (meth) acrylate as a component (G). The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 8, further comprising an ultraviolet absorber. The active energy for a plastic film or sheet according to any one of claims 1 to 9, wherein the plastic film or sheet is a hydrophilic plastic film or sheet and is used for manufacturing a polarizing plate. Linear curable adhesive composition. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 10, wherein the hydrophilic plastic film or sheet is a polyvinyl alcohol-based polarizing film or sheet and is used for producing a polarizing plate. Stuff. A laminate obtained by arranging base materials on both sides of a cured product layer formed from the composition according to any one of claims 1 to 11, wherein at least one of the base materials is a plastic film or sheet. A laminate. A polarizing plate formed by arranging a base material on both sides of a cured product layer formed from the composition according to any one of claims 1 to 11, wherein one of the base materials is a polyvinyl alcohol-based polarizer film or A polarizing plate that is a sheet and the other of the base material is a plastic film or sheet. Two substrates, one of which is a plastic film or sheet, are attached to each other using the composition according to any one of claims 1 to 11, and the two substrates are irradiated with active energy rays. How to make a body.