WO2011013663A1

WO2011013663A1 - Actinic-energy-ray-curable adhesive composition for plastic film or sheet

Info

Publication number: WO2011013663A1
Application number: PCT/JP2010/062619
Authority: WO
Inventors: 一樹大房
Original assignee: 東亞合成株式会社
Priority date: 2009-07-28
Filing date: 2010-07-27
Publication date: 2011-02-03
Also published as: KR20120039053A; JP5761299B2; TW201109405A; TWI493005B; CN102471642A; JP5633514B2; CN102471642B; JP2014028976A; KR101713003B1; JPWO2011013663A1

Abstract

Provided is an adhesive composition curable with actinic energy rays which is for plastic films or the like and which has low viscosity and excellent curability, has excellent adhesion to various plastic films or the like, in particular, hydrophilic plastic films or the like, and has sufficient performance even in applications where extreme durability is required. The adhesive composition curable with actinic energy rays, which is for use in plastic films or sheets, is a composition comprising curable components and a polymerization initiator, wherein the curable components comprise component (A), which is a compound having two or more epoxy groups (10-80 wt.% of the curable components), and component (B), which is a compound having an ethylenically unsaturated group (20-90 wt.%), and contains substantially no cationically polymerizable compound containing a (meth)acryloyl group, and the polymerization initiator comprises component (C), which is a cationic photopolymerization initiator (0.1-20 wt.%), and component (D), which is a free-radical photopolymerization initiator (0.1-20 wt.%). Also provided is a process for producing the adhesive composition.

Description

Active energy ray-curable adhesive composition for plastic film or sheet

The present invention relates to an active energy ray-curable adhesive composition capable of adhering various plastic films or sheets by irradiation with active energy rays such as electron beams or ultraviolet rays, and the composition of the present invention. Is suitable for use in the production of various optical films or sheets used for liquid crystal display elements, etc. It can be used in the field.
In the present specification, acrylate and / or methacrylate is represented by (meth) acrylate, acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. .
In the following description, unless otherwise specified, a plastic film or sheet is collectively expressed as “plastic film or the like”, and a film or sheet is collectively expressed as “film or the like”.

Conventionally, in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film is bonded to a thin-layer adherend made of another material, an ethylene-vinyl acetate copolymer is used. A solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like. The dry laminating method for pressure bonding is mainly performed.
The adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem. In addition, the adhesive composition is a thin layer in a post-processing step such as a heat seal for bonding the obtained laminate film and a ruled line step for engraving grooves immediately after the thin layer adherend is bonded. There is a problem that the adherends are separated from each other.
As an adhesive composition for solving these problems, a solventless adhesive composition has been studied.

As the solventless adhesive composition, a two-component adhesive composition and an adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
As the two-component adhesive composition, a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent. However, the composition has a drawback that it takes a long time to cure, and thus there is a problem in productivity such as being unable to enter a post-processing step such as a ruled line step immediately after laminating the thin layer adherend. .
On the other hand, the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and has recently attracted attention.

On the other hand, liquid crystal display devices are widely used in navigation systems for automobiles, small electronic devices such as mobile phones and PDAs, screens of word processors and personal computers, and even television receivers because of their features such as thinness, light weight, and low power consumption. is doing.
In recent years, an active energy ray-curable adhesive has been used for bonding various optical films and the like used in the liquid crystal display element.

Examples of the optical film include a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an antireflection film, an antiglare film, a lens sheet, and a diffusion sheet, and various types of plastics are used. It has been.

Among these plastics, polyvinyl alcohol and triacetyl cellulose are particularly used as polarizing plates. These plastics contain a hydroxyl group and are characterized by being very hydrophilic compared to ordinary plastics.

Active energy ray curable adhesive compositions for polarizing plates include photo radical polymerization compositions using photo radical polymerization, photo cation polymerization compositions using photo cation polymerization, and photo radical polymerization and photo cation polymerization. Hybrid type compositions using a combination of these are known.

As a photo radical polymerization type composition, a composition containing a radical polymerizable compound containing a polar group such as a hydroxyl group or a carboxyl group and a radical polymerizable compound not containing a polar group (Patent Document 1) is known. ing.
However, the composition has a large shrinkage during curing, and depending on the type of adherend, it has been difficult to obtain sufficient peel strength due to the generation of stress at the interface.
In order to solve this problem, a composition containing urethane (meth) acrylate having a large molecular weight has been studied (for example, Patent Document 2).
However, since the viscosity increases, the composition has a problem that thin film coating cannot be performed depending on the coating apparatus. It is also possible to reduce the shrinkage stress during curing by improving the flexibility of the adhesive composition. However, since such a means lowers the heat resistance and water resistance of the adhesive, There is a problem that defects such as peeling, foaming, and cracks occur in applications that require high performance.

As a photocationic polymerization type composition, a composition containing an epoxy resin containing no aromatic ring as a main component (Patent Document 3) or a composition containing an aliphatic epoxy and an alicyclic epoxy and / or oxetane (Patent Document 4). ) Etc. are known.
The composition has an advantage that the generation of stress at the interface can be suppressed because the shrinkage at the time of curing is relatively small compared to the radical photopolymerization type composition.
However, photocationic polymerization is generally known to cause polymerization inhibition due to moisture and basic substances. In high humidity environments, substrates with a lot of moisture, and substrates with a basic surface. It was difficult to obtain sufficient peel strength. In addition, by using a composition containing a polyfunctional epoxy resin as a main component, it is possible to reduce the effect of curability reduction due to polymerization inhibition, but such a composition increases the viscosity, Depending on the coating apparatus, there is a problem that thin film coating is not possible.

As a hybrid type composition, a 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 5), having two or more epoxy groups An epoxy resin in which at least one of these groups is an alicyclic epoxy group, an epoxy resin having two or more epoxy groups and no alicyclic epoxy group, a photocationic polymerization initiator and polymerization Composition containing a reactive monomer (Patent Document 6), a compound having two or more (meth) acryl groups, a compound having a hydroxyl group and one (meth) acryl group, a cationic polymerizable compound having a (meth) acryl group, light A composition including a radical polymerization initiator and a photocationic polymerization initiator (Patent Document 7) is known.

These compositions are intended to solve the problem of shrinkage during curing and polymerization inhibition due to moisture by hybridization, but according to the study of the present inventors, it has been found that there are the following problems.

The composition disclosed in Patent Document 5 contains a (meth) acrylate compound having an isocyanuric ring skeleton as an essential component, but according to the study of the present inventors, the composition having two or more (meth) acryloyl groups. When a large amount of (meth) acrylate is contained in the composition, the shrinkage at the time of curing is not so small that stress generation at the interface cannot be suppressed. For this reason, it is difficult to obtain sufficient peel strength depending on the substrate. It turned out to be.

Although the composition disclosed in Patent Document 6 includes a hybridized composition as a concept, only the invention of the superordinate concept is described. In the examples, the composition is composed only of a photocationically polymerizable monomer. Only the prepared composition is shown and lacks specificity.

The composition disclosed in Patent Document 7 contains a cationic polymerizable compound having a (meth) acrylic group as an essential component at a specific ratio, but according to the study of the present inventors, the compound is often contained in the composition. If it is included, the shrinkage at the time of curing is not so small that stress generation at the interface cannot be suppressed. For this reason, it has been found that it is difficult to obtain a sufficient peel strength depending on the substrate.

JP 2008-009329 A (Claims) JP 2007-177169 A (Claims) JP 2004-245925 A (Claims) JP 2008-134384 A (Claims) JP 2008-233279 A (Claims) JP 2008-257199 A (Claims) JP 2008-260879 A (Claims)

The present invention has been made in view of the above problems, has low viscosity and excellent curability, has excellent adhesion to various plastic films, particularly hydrophilic plastic films, etc., and is sufficient for applications that require strict durability. It is an object of the present invention to provide an active energy ray-curable adhesive composition for plastic films and the like having excellent performance.

As a result of various studies, the inventors of the present invention include a compound having two or more epoxy groups in a molecule and a compound having one ethylenically unsaturated group in a molecule as a curable component (meta ) An active energy ray-curable adhesive composition that does not substantially contain a cation polymerizable compound having an acryloyl group and contains a photo radical polymerization initiator and a photo cation polymerization initiator as a polymerization initiator is various plastic films, etc. In particular, the present invention has been completed by finding that it has excellent adhesion to hydrophilic plastic films and the like, has low viscosity, and has sufficient performance even in applications requiring severe durability.
Hereinafter, the present invention will be described in detail.

The composition of the present invention is low in viscosity and excellent in coating properties, and can maintain high adhesive force on various plastic films and the like, particularly hydrophilic plastic films and the like even under high temperature and high humidity conditions. It is effective for adhesion of a thin layer adherend such as a film, and can be suitably used for producing an optical film used particularly for a liquid crystal display device or the like.

The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets comprising the following curable components and a polymerization initiator.
The curable component includes (A) component: a compound having two or more epoxy groups in the molecule (10 to 80% by weight in the curable component), and (B) component: one ethylenic group in the molecule. It contains a compound having a saturated group (20 to 90% by weight in the curable component) and substantially free of a cationically polymerizable compound having a (meth) acryloyl group.
Polymerization initiators are component (C): photocationic polymerization initiator (0.1 to 20% by weight based on the total amount of curable components), and component (D): radical photopolymerization initiator (total amount of curable components). 0.1 to 20% by weight).
Hereinafter, components (A) to (D) that are essential components of the composition will be described.

1. Component (A) The component (A) is a compound having two or more epoxy groups in the molecule, and various compounds can be used as long as the compound has two or more epoxy groups in the molecule.
As the component (A), for example, a compound having two or more epoxy groups and an aromatic ring skeleton in the molecule (hereinafter referred to as “aromatic epoxy compound”), 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 forming an epoxide between two adjacent carbon atoms constituting the ring). (Hereinafter referred to as “alicyclic epoxy compound”), a compound having two or more epoxy groups in the molecule and not containing an aromatic ring (hereinafter referred to as “aliphatic epoxy compound”). And so on).

Examples of aromatic epoxy compounds include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of brominated bisphenol A, diglycidyl ether of brominated bisphenol F, brominated Bisphenol-type epoxy resin such as diglycidyl ether of bisphenol S, diglycidyl ether of rubber-modified bisphenol A, di- or polyglycidyl ether of bisphenolfluorene or its alkylene oxide adducts; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bromine Phenol novolac epoxy resin, brominated cresol novolac epoxy resin, dicyclopentadiene-phenol novolac epoxy Novolak-type epoxy resins such as styrene resins; naphthalene-type epoxy resins; alkyldiphenol-type epoxy resins; naphthol-type epoxy resins; biphenyl-type epoxy resins; hydroquinone diglycidyl ethers; resorcin diglycidyl ethers; terephthalic acid diglycidyl ethers; Glycidyl ether; epoxidized product of styrene-butadiene copolymer; epoxidized product of styrene-isoprene copolymer; addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin; N, N, N ′, N′-tetraglycidyl -M-xylenediamine and the like.
In addition to these, the document “Epoxy Resin-Recent Advances” (Shojodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Vol. 9, Volume 22 Epoxy Resin (Polymer Publishing) Compounds published on pages 4 to 6, 9 to 16, and 29 to 55 of the Society, published in 1978.
Here, the epoxy resin means a compound or polymer having an average of two or more epoxy groups in the molecule and cured by reaction. In accordance with the custom in this field, in the present specification, any compound having two or more curable epoxy groups in the molecule may be referred to as an epoxy resin.

As aromatic epoxy compounds other than these, Epicoat 5050, 5051, 1031S, 1032H60, 604, 630, 871, 872, 191P, YX310, 545, YL6810, YX8800, YL980 [above, manufactured by Japan Epoxy Resins Co., Ltd.] Etc.

Examples of alicyclic epoxy compounds include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, bis (3,4 -Epoxycyclohexylmethyl) adipate and the like.
In addition to these, the document “Epoxy Resin-Recent Advances” (Shojodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Vol. 9, Volume 22 Epoxy Resin (Polymer Publishing) Compounds published on pages 7 and 18 to 20 of the Society).

Specific examples of the aliphatic epoxy compound include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylene glycols such as diglycidyl ethers of polyethylene glycol and polypropylene glycol Diglycidyl ether of dipentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; dimethylidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts, and pentaerythritol and Polyglycidides of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of the alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.
In addition to these, the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, can be mentioned.

Other aliphatic epoxy compounds include Denalex R-45EPT (manufactured by Nagase ChemteX Corp.), Epofriend AT501, CT310, Epolide PB3600 (above, Daicel Chemical Industries, Ltd.), KL-630 (Kuraray ( Co., Ltd.], Tetrad C [Mitsubishi Gas Chemical Co., Ltd.], TEPIC [Nissan Chemical Industry Co., Ltd.], and the like.

As the component (A), a compound having 2 to 10 epoxy groups is preferable because heat resistance and adhesiveness can be increased. The component (A) is preferably a low molecular weight compound because it can reduce the viscosity, specifically a compound having a molecular weight of 2,000 or less, and more preferably a compound having a molecular weight of 200 to 1,000.
As the component (A), an aromatic epoxy compound and an alicyclic epoxy compound are preferable because the composition has low viscosity and excellent curability, and the cured product has excellent adhesiveness. Specific examples include bisphenol type epoxy resin, naphthalene type epoxy resin, resorcin diglycidyl ether, limonene dioxide, and 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate.

As the component (A), only one kind of the aforementioned compounds can be used, or two or more kinds can be used in combination.

The ratio of the component (A) is 10 to 80% by weight, preferably 30 to 70% by weight in the curable component. By making the ratio of the component (A) 10% by weight or more, the cured product has excellent heat resistance and water resistance, and by making it 80% by weight or less, the composition has low viscosity and excellent coating properties. It becomes a thing and it becomes the thing excellent in the adhesive force of hardened | cured material.

2. Component (B) The component (B) is a compound having one ethylenically unsaturated group in the molecule, and examples thereof include a compound having a (meth) acryloyl group, a vinyl compound, and an allyl compound.

Examples of the vinyl compound include compounds having one vinyl group. Specifically, styrene, vinyl toluene, N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexane dimethanol monovinyl ether And vinyl monomers such as diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and the like.
Examples of the allyl compound include compounds having one allyl group. Specific examples include allyl alcohol.

Examples of the compound having a (meth) acryloyl group include (meth) acrylamide and (meth) acrylate.
Examples of (meth) acrylamide include compounds having one (meth) acrylamide group. Specifically, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, 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 (meth) acrylate include a compound having one (meth) acryloyl group (hereinafter referred to as monofunctional (meth) acrylate). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, carbon number 1 Alkyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , Ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxy Ethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy Polypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyl-octyl (meth) aliphatic acrylates such as (meth) acrylate;
Isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) ) Alicyclic (meth) acrylates such as acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate,
Phenyl (meth) acrylate, phenol derivative (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, cresol alkylene oxide modified (meth) acrylate , (Meth) acrylate of p-cumylphenol alkylene oxide modification, (meth) acrylate of nonylphenol alkylene oxide modification, (meth) acrylate of o-phenylphenol alkylene oxide modification, alkylene of p-phenylphenol Oxide modified (meth) acrylate, tribromophenol alkylene oxide modified (meth) acrylate, neopentyl glycol (meth) acrylic acid Aromatic ester (meth) aromatic acrylates (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meta) ) Acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meta) ) Acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl 2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate the hydroxyl group-containing (meth) acrylate and the like;
(Meth) acrylic acid, (meth) acrylic acid dimer, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid Carboxylic acid-containing (meth) acrylates such as ω-carboxypolycaprolactone (meth) acrylate;
Imides (meth) such as N- (meth) acryloyloxyethylhexahydrophthalimide, 2- (1,2-cyclohex-1-enedicarboximido) ethyl (meth) acrylate, funcryl FA-502A (manufactured by Hitachi Chemical) Acrylate;
Phosphoric acid (meth) acrylates such as 2- (meth) acryloyloxyethyl acid phosphate;
Is mentioned.
(B) A component can use only 1 type of an above described compound, and can also use 2 or more types together.

As the component (B), since the composition has low viscosity and excellent adhesiveness, a compound having one ethylenically unsaturated group and an aromatic ring skeleton or alicyclic skeleton [hereinafter, (b1 ) Component] is preferred.
As the component (b1), the above-described alicyclic (meth) acrylates and aromatic (meth) acrylates are preferable. Among them, isobornyl (meth) acrylate and dicyclopenta are preferable because heat resistance and adhesiveness can be increased. Nyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, alkylene oxide modification of phenol Of these, (meth) acrylate, N- (meth) acryloyloxyethylhexahydrophthalimide, 2- (1,2-cyclohex-1-enecarboximido) ethyl (meth) acrylate and the like are preferable.

As the component (B), a compound having one ethylenically unsaturated group and a hydroxyl group [hereinafter referred to as component (b2)] is preferable.
As the component (b2), (meth) acrylate having one hydroxyl group is preferable, and specific compounds are as described above. Among them, the composition has a low viscosity and is excellent in adhesiveness. Therefore, a compound having a molecular weight of less than 200 is preferable. Examples of the compound that satisfies the molecular weight include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Furthermore, as the component (B), a combination of the component (b1) and the component (b2) is more preferable. When used in combination, the weight ratio of the component (b1) to the component (b2) is, for example, 80:20 to 10:90, preferably 30:70 to 70:30.

The proportion of component (B) is 20 to 90% by weight, preferably 20 to 89% by weight, more preferably 30 to 70% by weight in the curable component. By making the proportion of the component (B) 20% by weight or more, the composition can have a low viscosity, can be excellent in coating properties, and can be excellent in adhesive strength, By setting it to 90% by weight or less, the cured product can be made excellent in heat resistance and water resistance.

3. (C) Component (C) component is a photocationic polymerization initiator. That is, it is a compound that generates a cation or a Lewis acid by irradiation with active energy rays and initiates polymerization of the component (A) which is a photocationically polymerizable compound.
Specific examples of the component (C) include sulfonium salts, iodonium salts, diazonium salts, and the like.

Examples of sulfonium salts include, for example:
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,
4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
Examples include triarylsulfonium salts such as 4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate.

Examples of iodonium salts include, for example:
Diphenyliodonium tetrakis (pentafluorophenyl) borate diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Di (4-t-butylphenyl) iodonium hexafluorophosphate,
Di (4-t-butylphenyl) iodonium hexafluoroantimonate,
Trilcumyl iodonium tetrakis (pentafluorophenyl) borate,
(4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,
Di (4-nonylphenyl) iodonium hexafluorophosphate,
Di (4-alkylphenyl) iodonium hexafluorophosphate,
And diaryl iodonium salts.

Examples of diazonium salts include benzenediazonium hexafluoroantimonate,
Examples thereof include benzenediazonium hexafluorophosphate.

Commercially available products of component (C) include Adekaoptomer SP-100, 150, 152, 170, 172 (manufactured by ADEKA Corporation), Photoinitiator 2074 (manufactured by Rhodia), Kayrad PCI-220, 620 [Japan Kayaku Co., Ltd.], Irgacure 250 (BASF Japan Ltd.), CPI-100P, 101A, 200K, 210S (San Apro Co., Ltd.), WPI-113, 116 (Wako Pure Chemical Industries, Ltd.) , BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 (manufactured by Midori Chemical Co., Ltd.) and the like.
Among these, triarylsulfonium salts and diaryliodonium salts are preferred because of their excellent active energy ray curability, cured films having excellent water resistance and no coloring, and diaryliodonium salts are particularly preferred because of their excellent curability. preferable.
Among the above-mentioned triarylsulfonium salts, triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable. Among the diaryl iodonium salts, among those mentioned above, tricumyl iodonium tetrakis (pentafluorophenyl) borate (Photoinitiator 2074; manufactured by Rhodia Japan KK), diphenyliodonium hexafluorophosphate, (4-methylphenyl) [4 -(2-Methylpropyl) phenyl] -hexafluorophosphate (Irgacure 250; manufactured by BASF Japan Ltd.), di (4-t-butylphenyl) iodonium hexafluorophosphate and WPI-113 (Wako Pure Chemical Industries, Ltd.) Product)) is preferred.

(C) As a component, an above described compound may be used independently, or 2 or more types may be used.
The proportion of component (C) is 0.1 to 20% by weight, preferably 1 to 10% by weight, more preferably 2 to 7% by weight, based on the total amount of curable components. When the proportion of the component (C) is 0.1% by weight or more, the active energy ray curability of the composition can be made sufficient and the adhesiveness can be made excellent, while it is made 20% by weight or less. As a result, the internal curability of the adhesive layer can be improved and the adhesiveness can be improved.

In using the component (C), a sensitizer may be used in combination in order to enhance the photocationic curability of the component (C).
Examples of the sensitizer include anthracene compounds, 4-methoxy-1-naphthol, fluorene, pyrene, and stilbene.
Examples of the anthracene compound include 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.
Among these, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dipropoxyanthracene are preferable from the viewpoint of excellent solubility in the composition and high sensitizing action of the component (C). .
Commercially available products of these sensitizers include Anthracure UVS-1331, 1221, 1101, and ET-2111 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.).

The proportion of the sensitizer is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the total amount of the curable components.
When a sulfonium salt is used as the component (C), an anthracene compound is preferably used as a sensitizer.

4). (D) Component (D) A component is a radical photopolymerization initiator. That is, it is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of component (B), which is a compound having an ethylenically unsaturated group. Further, depending on the type of the component (D), there are some which function as a sensitizer for enhancing the photocationic curability of the component (C).

Specific examples of the component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4- 1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2 -Methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4- Aromatic ketone compounds such as yl-phenyl) -butan-1-one, Adekaoptoma-N-1414 (Asahi Denka), phenylglyoxylic acid methyl ester, ethyl anthraquinone and phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis Benzophenone series 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, 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)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-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- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxy 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer; and acridines such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane Derivatives and the like.

Among these, a thioxanthone compound is preferable in that not only the polymerization initiation of the component (B) but also the sensitizing effect of the component (C) is exhibited and the effect is high. Among the thioxanthone compounds, 2,4-diethylthioxanthone and isopropylthioxanthone are more preferable from the viewpoint of excellent active energy ray curability and no coloration of the cured film.

As the component (D), the above-described compounds may be used alone, or two or more kinds may be used.

The proportion of the component (D) is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the curable component. By making the proportion of the component (D) 0.1 weight or more, the active energy ray curability of the composition can be made sufficient and the adhesiveness can be made excellent. Thus, the internal curability of the adhesive layer can be made good and the adhesiveness can be made excellent.

5. Component (E) and / or Component (F) The composition of the present invention comprises the components (A) to (D) as essential components, and various components may be further blended depending on the purpose. it can.
In order to further improve heat resistance, water resistance, adhesion, etc., a compound having two or more ethylenically unsaturated groups in the molecule [hereinafter referred to as component (E)] and / or a silane coupling agent [hereinafter referred to as (F) Component)] can be blended. This will be specifically described below.

Component (E) The component (E) is a compound having two or more ethylenically unsaturated groups in the molecule, and examples thereof include a compound having a (meth) acryloyl group, a vinyl compound, and an allyl compound.

Examples of vinyl compounds include compounds having two or more vinyl groups. Specifically, divinylbenzene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, etc. Can be mentioned.

Examples of allyl compounds include compounds having two or more allyl groups. Specific examples include diallyl phthalate, triallyl isocyanurate, triallyl cyanurate and the like.

Examples of (meth) acrylates include compounds having two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylates”).
Specific examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 3-methyl-1 , 5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-nonanediol diacrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) polyol poly (meth) acrylates such as acrylate;
Di (meth) acrylate of neopentyl glycol alkylene oxide adduct, di (meth) acrylate of 1,6-hexanediol alkylene oxide adduct, tri (meth) acrylate of glycerin alkylene oxide adduct, trimethylolpropane alkylene oxide Poly (meth) acrylates of alkylene oxide adducts of polyols such as tri (meth) acrylates of adducts, tri (meth) acrylates of pentaerythritol alkylene oxide adducts;
Glycol modified polyol poly (meth) acrylate such as neopentyl glycol modified trimethylolpropane di (meth) acrylate;
Caprolactone-modified polyol poly (meth) acrylates such as caprolactone-modified dipentaerythritol hexa (meth) acrylate;
Alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate;
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate;
Di (meth) acrylates of alicyclic diols such as tricyclodecane dimethylol di (meth) acrylate and dicyclopentanyl di (meth) acrylate;
Di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol F alkylene oxide adduct and di (meth) acrylate of bisphenol S alkylene oxide adduct (Meth) acrylate;
Di (meth) acrylates of hydrogenated bisphenol compounds such as di (meth) acrylate of alkylene oxide adducts of hydrogenated bisphenol A and di (meth) acrylates of alkylene oxide adducts of hydrogenated bisphenol F;
Poly (meth) acrylates of isocyanuric acid such as di (meth) acrylate of isocyanuric acid alkylene oxide adduct, tri (meth) acrylate of isocyanuric acid alkylene oxide adduct, tri (meth) acrylate of isocyanuric acid caprolactone adduct;
Di (meth) acrylates of ester diols such as neopentyl glycol hydroxypivalic acid di (meth) acrylate and hydroxypivalic acid neopentyl glycol di (meth) acrylate;
Di (meth) acrylates of caprolactone-modified ester diols such as caprolactone-modified neopentyl glycol hydroxypivalic acid di (meth) acrylate;
Fatty acid-modified dipentaerythritol penta (meth) acrylate and fatty acid-modified dipentaerythritol tetra (meth) acrylate obtained by reacting a polyol with (meth) acrylic acid and a fatty acid having 2 to 4 carbon atoms;
Triacrylformal; and aromatic polyfunctional (meth) acrylates such as trimethylolpropane (meth) acrylic acid benzoate, Ogsol EA-0200, 0500, 1000 (fluorene acrylate, manufactured by Osaka Gas Chemical).
Examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.

In addition to these, there are compounds such as those described in pages 53 to 56 of the document “Latest UV Curing Technology” [Printing Information Association, Inc., 1991].

Examples of the oligomer include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate. These oligomers are compounds having two (meth) acryloyl groups, but are simply referred to as (meth) acrylates unless otherwise specified.

Examples of the polyester (meth) acrylate include a dehydration condensate of polyester polyol and (meth) acrylic acid.

Here, examples of the polyester polyol include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.
Polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and their alkylene oxide adducts Etc.
As the carboxylic acid or anhydride thereof, dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, or anhydrides thereof Thing etc. are mentioned.
Examples of polyester poly (meth) acrylates other than these include compounds described on pages 74 to 76 of the above-mentioned document “UV / EB Curing Material”.

Urethane (meth) acrylates can be obtained by three-way reaction of polyhydric alcohol, polyhydric isocyanate and hydroxy (meth) acrylate compound, or polyhydric isocyanate and hydroxy (meth) acrylate without using polyhydric alcohol. What is obtained by two-way reaction with a compound is mentioned.

Examples of the polyhydric alcohol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reaction of the polyhydric alcohol and the polybasic acid, the polyhydric alcohol, the polybasic acid, and ε-caprolactone. And caprolactone polyol obtained by the above reaction, and polycarbonate polyol (for example, polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate).

Examples of the polyvalent isocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate. As the urethane (meth) acrylate used in the present invention, those obtained by the above three reactions or those obtained by the two reactions may be used alone, or both may be used in combination. .

Examples of hydroxy (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl And hydroxyalkyl (meth) acrylates such as (meth) acrylate, pentaerythritol tri, di- or mono (meth) acrylate, and trimethylolpropane di- or mono (meth) acrylate.

These can be obtained by heating and stirring the organic isocyanate to be used and a polyol component in the presence of an addition catalyst such as dibutyltin dilaurate, and further adding a hydroxyalkyl (meth) acrylate, heating and stirring, and causing the addition reaction.

Examples of urethane poly (meth) acrylates other than these include compounds as described on pages 70 to 74 of the document “UV / EB curable material” [CMC, 1992]. .

Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin, and examples thereof include compounds as described on pages 74 to 75 of the above-mentioned document “UV / EB Curing Material”. .

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; phenol novolac type epoxy resin and cresol novolac type Examples thereof include novolak-type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
In addition to these, the document “Epoxy Resin-Recent Advances” (Shojodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Volume 9, Volume 22 Special Issue Epoxy Resin [Polymer Publications, Compounds published on pages 4 to 6 and pages 9 to 16 of 1973.

Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts; Of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.
In addition to these, the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, can be mentioned.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Chemical Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.], etc., can be mentioned. Examples thereof include compounds described in pages 289 to 296 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

Polyether (meth) acrylate oligomers Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylates, including polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di ( And (meth) acrylate.

As the polymer, a (meth) acrylic polymer having a (meth) acryloyloxy group, a (meth) acrylic polymer having a functional group, and a (meth) acryloyl group introduced into the side chain, the above-mentioned document “UV” -Compounds such as those described on pages 78 to 79 of "EB Curing Material".

(E) A component can use only 1 type of an above described compound, or can also use 2 or more types together.

In the component (A) of the present invention, a phenomenon called so-called dark reaction, in which the reaction proceeds and cures even after the active energy ray irradiation is completed, may cause problems depending on the application. For example, in the case of producing a laminate using the composition of the present invention for adhesion of a film-like substrate, when the film laminate is wound after irradiation with active energy rays, the dark reaction proceeds and the film is wound as it is. There was a problem that the shape remained, and marks such as undulations and dents on the film were easily attached.
In order to prevent such a problem, it is very effective to add the component (E) in which the elastic modulus of the adhesive layer becomes high immediately after irradiation with the active energy ray. In addition, the heat resistance is improved by increasing the crosslinking density.
As the component (E), among the above-mentioned compounds, polyalkylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, bisphenol in terms of preventing problems due to dark reaction and improving heat resistance. Preferred is an alkylene oxide modified di (meth) acrylate of A, an alkylene oxide modified di (meth) acrylate of bisphenol F, and an alkylene oxide modified triacrylate of isocyanuric acid, and can maintain adhesive strength with a hydrophilic plastic. Polyalkylene glycol di (meth) acrylate is particularly preferable.

When the component (E) is contained in the composition, the proportion of the component (E) is preferably 1 to 20% by weight, more preferably 1 to 15% by weight in the curable component.
By making the ratio of the component (E) 1% by weight or more, it is possible to prevent problems due to dark reaction and to improve heat resistance, and by making it 20% by weight or less, the curing shrinkage of the composition is suppressed. , It can be excellent in adhesive strength.

Component (F) The component (F) is a silane coupling agent that can improve the interfacial adhesive strength between the adhesive layer and the hydrophilic plastic. The silane coupling agent used in the present invention is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

Specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2 -(Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3- Aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Examples include trimethoxysilane.

Among these silane coupling agents, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meta) from the viewpoint of storage stability and adhesive strength of the composition. ) Acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are preferred.

(F) A component can use only 1 type of an above described compound, and can also use 2 or more types together.
When the composition contains the component (F), the proportion of the component (F) is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight in the composition. By making the ratio of (F) component 0.1% by weight or more, the effect of improving the adhesive strength of the composition is made sufficient, and by making it 20% by weight or less, the storage stability of the composition is excellent. Can be.

6). Other components In addition to the above, the composition of the present invention may contain other components usually used in adhesive compositions.

Specifically, inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifier resins, leveling agents, antifoaming agents, plasticizers, organic solvents, dyes, pigments, treating agents, and UV blockers Inactive ingredients such as can be blended. Examples of the tackifying resin include rosins such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, and petroleum resin.
These are preferably blended in the composition in an amount of 20% by weight or less.

7). As a method for producing an active energy ray-curable adhesive composition for plastic films or sheets , the above components (A) to (D) are mixed and, if necessary, other components are stirred and mixed according to a conventional method. Can be manufactured. In this case, heating can be performed as necessary. The heating temperature may be appropriately set according to the composition to be used, the substrate, the purpose, etc., but is preferably 30 to 80 ° C.
Moreover, the composition of this invention is a composition which does not contain the cationically polymerizable compound which has the (meth) acryloyl group disclosed by patent document 7 as a sclerosing | hardenable component. Thereby, the shrinkage stress at the time of hardening can be made small and adhesive force can be improved.
Here, “the curable component is substantially free of a cationic polymerizable compound having a (meth) acryloyl group” means that the content of the cationic polymerizable compound having a (meth) acryloyl group in the curable component is It means less than 15% by weight, preferably 10% by weight or less, more preferably 5% by weight or less, particularly preferably 1% by weight or less, and most preferably 0% by weight.

The viscosity of the composition is preferably 10 to 1000 mPa · s from the viewpoint of excellent coatability on the substrate.

The composition of the present invention can be used for adhesion between plastic films and the like, and adhesion between plastic films and the like and various other substrates (hereinafter referred to as “other substrates”). That is, it can be used for bonding two substrates, at least one of which is a plastic film or the like. In the following, when simply described as “base material”, it means a general term for plastic films and other base materials.
Other examples of the substrate include paper and metal.
As a method of use, a conventional method may be used, and examples include a method of applying to a base material, pasting with another base material, and irradiating active energy rays.

Examples of the material in the plastic film include polyvinyl chloride resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, triacetyl cellulose, cycloolefin polymer, Examples include polymethyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer, and chlorinated polypropylene.
Examples of the paper include imitation paper, fine paper, craft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, water resistant paper, glassine paper, and corrugated paper.
Examples of the metal foil include aluminum foil.

Coating on the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.
The coating thickness of the composition of the present invention may be selected according to the substrate used and the application, but is preferably 0.1 to 100 μm, more preferably 1 to 25 μm.

Examples of the active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
Various light sources can be used as the light source when cured by ultraviolet rays, and examples thereof include a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED.
In the case of curing with an electron beam, various devices can be used as an EB irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device. Those having an energy of 1000 eV are preferred, and more preferably 100 to 300 eV.

The composition of the present invention is suitable for bonding a thin layer adherend as a substrate. The method of use for adhering the thin-layer adherend may be in accordance with a method usually used in the production of laminates.
For example, a method in which the composition is applied to a first thin-layer adherend, dried as necessary, and then a second thin-layer adherend is bonded thereto and irradiated with active energy rays. Is mentioned.

Examples of the thin layer adherend include plastic film, paper, metal foil, and the like.
The plastic film or the like 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 use, but preferably the thickness is 0.2 mm or less. is there.

Among these thin layer adherends, the composition of the present invention is preferably used for adhesion between plastic films and the like, and can be suitably used for hydrophilic plastics, specifically, polyvinyl alcohol and triacetyl cellulose. .

Also, before bonding the adherend, an activation treatment can be performed on one or both surfaces in order to increase the interlayer adhesion. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment and etching treatment, and flame treatment, and these may be used in combination.

Coating on the thin layer adherend may be performed according to a conventionally known method, and examples thereof include the same method as described above.
The coating thickness of the composition of the present invention may be selected according to the thin layer adherend to be used and the application, but the same coating thickness as described above is preferable.

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

By the above method, a laminate composed of a plastic film / cured product of the composition of the present invention / plastic film and a laminate composed of a plastic film / cured product of the composition of the present invention / other substrates are produced. The
Laminates such as a laminate film obtained from the composition of the present invention are excellent in adhesive strength under high temperature and high humidity conditions. Therefore, optical films such as polarizing plates, protective films and retardation films used in liquid crystal display devices, etc. It can be suitably used for a film.
Especially the composition of this invention can be preferably used for manufacture of a polarizing plate and a polarizing plate with retardation film. Hereinafter, the manufacturing method of a polarizing plate is demonstrated.

In the present specification, a polarizer means a film or film having a polarizing function described later, and a polarizing plate means a polarizer with a protective layer in which one side or both sides of the polarizer are protected by a film or film. Represents that. Moreover, a polarizing plate with a retardation film represents a polarizer or a polarizing plate in which a retardation film is bonded or a film having a retardation function is formed by coating.

8). Production method of polarizing plate As described above, the composition of the present invention can be preferably used for adhesion of hydrophilic plastics. In the production of a polarizing plate, polyvinyl alcohol used as a polarizer and tri-layer used as a protective film for a polarizer. Acetyl cellulose corresponds to a hydrophilic plastic.

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

A polarizer has a function of selectively transmitting linearly polarized light in one direction from natural light.
Specific examples of polarizers include iodine polarizers in which iodine is adsorbed and oriented on a polyvinyl alcohol film, dichroic dyes in which dichroic dye is adsorbed and oriented on a polyvinyl alcohol film, and (lyotropic) liquid crystal Examples thereof include a coating type polarizer coated with a dye in a state, oriented and fixed.
These iodine-based polarizers, dye-based polarizers, and coating-type polarizers have the function of selectively transmitting one direction of linearly polarized light from natural light and absorbing the other direction of linearly 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.

Examples of protective films used in the protective layer include cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose, acrylic resin films, polyester resin films, polyarylate resin films, polyethersulfone resin films, and cyclic rings such as norbornene. Examples thereof include cyclic polyolefin resin films containing olefin as a monomer.

Next, the composition of this invention can also be used for adhesion | attachment of a polarizing plate and retardation film.
In this case, a polarizing plate having a protective layer on one side or both sides can be used. In this case, the protective layer may be one obtained by bonding the protective film or a protective film formed by coating. In a polarizing plate provided with a protective layer only on one side, the surface to be bonded to the retardation film may be a surface with a protective layer or a surface without a protective layer.

Various types of retardation films can be used. Optical films that have been subjected to processing such as uniaxial or biaxial stretching, or liquid crystal compounds are applied to a substrate, and processed to be oriented and fixed. An optical film or the like is used, and the magnitude relationship (refractive index ellipsoid) of the three-dimensional refractive index is controlled in accordance with the use conditions. It is mainly used to compensate for coloration of the liquid crystal layer of a liquid crystal display and to compensate for changes in phase difference due to viewing angle.

Specific examples of retardation films include optical film materials that are subjected to processing such as stretching, such as polyolefins such as polyethylene, polypropylene, and cyclic polyolefins, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polyarylate. And polyamide.
The above-mentioned cyclic polyolefin is a general generic name for resins obtained from cyclic olefins such as norbornene, tetracyclododecene, and derivatives thereof. For example, JP-A-3-14882 and JP-A-3-122137. Etc. are mentioned.
Specifically, a cyclic olefin ring-opening polymer, a cyclic olefin addition polymer, a random copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene, or these are modified with an unsaturated carboxylic acid or a derivative thereof. Examples of such graft-modified products can be given. Furthermore, these hydrides are mentioned. Examples of the products include ZEONEX and ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, and TOPAS manufactured by TICONA.

In addition, as optical films coated with liquid crystalline compounds, etc., and oriented and fixed, "WV film" (Fuji Photo Film Co., Ltd.), "LC film", "NH film" “[All manufactured by Nippon Oil Corporation]” and the like.

The manufacturing method of a polarizing plate or a polarizing plate with a retardation film will be described using the composition of the present invention.
Examples of the production method include a method including the following steps [1] to [3].
[1] A process of applying the composition of the present invention to an adherend (base material) selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film to be an adherend. ,
[2] On the adherend (base material) coated with the composition, another adherend selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film is attached. Process of combining, and
[3] A step of irradiating the bonded adherend (laminate) with active energy rays, particularly a step of irradiating the composition with active energy rays through the bonded adherend (laminate).
When the protective film or retardation film is bonded to only one side, a polarizing plate or a polarizing plate with a retardation film can be produced by the above procedure, but when bonding to both sides, the steps [1] and [2 ] May be performed twice, and then step [3] may be performed, 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 performed by the same method as described above.
Moreover, it can also adhere | attach in a curved surface state as mentioned above using said manufacturing method.

When using a polarizing plate with a retardation film as a circularly polarizing plate, in order to obtain a circularly polarized state over a wide band, a retardation film having a different retardation is further pasted on the retardation film side of the polarizing plate with a retardation film. It can also be combined.
Specifically, there is a method in which a retardation film having a ½ wavelength with respect to each wavelength is bonded to a polarizing film, and a retardation film having a ¼ wavelength is bonded to each wavelength. . In this case, step [3] may be performed after steps [1] and [2] are repeated three times, or steps [1], [2] and [3] may be repeated three times.
In addition, the literature quoted in this specification is referred as reference.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

Examples 1 to 8 and Comparative Examples 1 to 5
The components (A) to (F) shown in Table 1 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable adhesive composition. The numbers in parentheses in Table 1 mean parts by weight.

Abbreviations in Table 1 are as follows.
(A) component jER: diglycidyl ether of bisphenol A, manufactured by Japan Epoxy Resins Co., Ltd., trade name jER-828
CEL: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, manufactured by Daicel Chemical Industries, Ltd., trade name Celoxide 2021P:
(B) Component BzA: benzyl acrylate, Osaka Organic Chemical Co., Ltd. Biscoat # 160
IBXA: Isobornyl acrylate, light acrylate IB-XA manufactured by Kyoeisha Chemical Co., Ltd.
ACMO: acryloylmorpholine, manufactured by Kojin Co., Ltd. PEA: phenoxyethyl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate PO-A
M-145: 2- (1,2-cyclohex-1-enedicarboximide) ethyl acrylate, Aronix M-145 manufactured by Toagosei Co., Ltd.
HPA: 2-hydroxypropyl acrylate, Kyoeisha Chemical Co., Ltd. light ester HOP-A
・ HBA: 2-hydroxybutyl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate HOB-A
-HEM: 2-hydroxyethyl methacrylate, Kyoeisha Chemical Co., Ltd. light ester HOP
Component (C) Irg: Irgacure 250: Iodonium salt photocationic initiator (manufactured by BASF Japan)
CPI: CPI-100P: 50% by weight propylene carbonate solution of sulfonium salt photocation initiator (manufactured by San Apro)
Component (D) DETX: 2,4-diethylthioxanthone, Nippon Kayaku Co., Ltd. DETX-S
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF Japan Darocur TPO
(E) Component M203S: Tricyclodecane dimethanol diacrylate, Aronix M-203S manufactured by Toagosei Co., Ltd.
M211B: Bisphenol A (EO modified ≈ 2) diacrylate, Aronix M-211B manufactured by Toagosei Co., Ltd.
M315: isocyanuric acid EO-modified triacrylate, Aronix M-315 manufactured by Toagosei Co., Ltd.
M325: ε-caprolactone modified tris (acryloxyethyl isocyanurate, Aronix M-325 manufactured by Toagosei Co., Ltd.)
M-270: Polypropylene glycol (n≈12) diacrylate, Aronix M-270 manufactured by Toagosei Co., Ltd.
Component (F) KBM: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.
Other components OX211: 3-ethyl-3-phenoxymethyloxetane, Aron Oxetane OXT-211 manufactured by Toagosei Co., Ltd.
SM100: 3,4-epoxycyclohexylmethyl methacrylate, cyclomer M-100: (manufactured by Daicel Chemical Industries)
M1310: Urethane acrylate, Aronix M-1310 manufactured by Toagosei Co., Ltd.
・ M1200: Urethane acrylate, Aronix M-1200 manufactured by Toagosei Co., Ltd.
M1600: Urethane acrylate, Aronix M-1600 manufactured by Toagosei Co., Ltd.
DBA: anthracure UVS-1331: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei)
The obtained composition was evaluated according to the following test method. The results are shown in Table 2.

Test example 1 (25 degreeC viscosity)
The viscosity of the active energy ray-curable adhesive composition at 25 ° C. was measured using an E-type viscometer. In the case of thin film coating with a coater, the lower the 25 ° C. viscosity, the better.
○: Less than 100 mPa · s △: 100 to 200 mPa · s
×: Over 200 mPa · s

Test Example 2 (Model experiment for manufacturing polarizing plate)
Assuming that a polarizer and a protective layer, which are hydrophilic plastics, are bonded to produce a polarizing plate, the following model experiment was conducted using triacetyl cellulose, which is a hydrophilic plastic, as a base material for the adhesion test.

(T peel strength)
On a triacetylcellulose film containing a UV absorber with a thickness of 80 μm (trade name: Fujitac, manufactured by Fuji Film Co., Ltd., hereinafter referred to as “FTAC”), corona treatment (polydyne 1 manufactured by Navitas, output 0.1 kW, The processing speed was 1 second / cm).
Thereafter, the composition obtained above was applied on a film to a thickness of 5 μm by a bar coater. After laminating the same corona-treated FTAC, it was cured at a conveyor speed of 5 m / min using a 160 W / cm condensing metal halide lamp (30 cm from the focal length), and a laminate film as a test specimen Manufactured. The ultraviolet intensity was 150 mW / cm ² and the integrated light quantity was 400 mJ / cm ² (both values at 365 nm).

The obtained specimen was allowed to stand at room temperature for 30 minutes or more, and then the peel strength was measured with a tensile tester (Instron 5564 manufactured by Instron Japan Company Limited) under the following conditions (initial peel strength). The results are shown in Table 2.
-Test piece: 25 mm x 100 mm
Test method: T-shaped peeling / peeling speed: 200 mm / min
Next, the obtained specimen was subjected to a high temperature test and a high humidity test under the following conditions, and then peel strength was measured by the same method and conditions as described above. The results are shown in Table 2.
・ After high temperature test: 96 hours at 85 ° C./After high humidity test: 96 hours at 60 ° C. and 90% RH The peel strength value of 1 N / 25 mm or more was evaluated as good, and the specimen did not peel and the material was destroyed (Table 2), it was evaluated that it was more excellent.

Test Example 3 (dark reaction inhibitory property)
Similar to the T peel strength test, film lamination to UV curing were performed. The film was cut into a width of 50 mm and a length of 100 mm, and attached to a 3-inch paper tube using cello tape (registered trademark). Then, after leaving at room temperature for 24 hours, the film was removed and placed on a horizontal desk to observe the film appearance. If the dark reaction is likely to proceed, the shape at the time of winding on the paper tube remains, so that the warp height of the film end increases. The warp height at the corners of the four corners of the film was measured with a ruler, and the average value (mm) was used as an indicator of dark reaction inhibition. Smaller is better.
The results are shown in Table 2.

The composition of the present invention has a low viscosity, excellent initial peel strength, and excellent peel strength after a high temperature test and a high humidity test.
On the other hand, although it is a photocationic polymerization type composition which does not contain the (B) and (D) component of this invention (Comparative Example 1) and a hybrid type composition, the composition which does not contain the (A) component of this invention The product (Comparative Example 2) and the photoradical composition (Comparative Example 2) that does not contain the components (A) and (C) of the present invention are insufficient in both the initial peel strength and the peel strength after the high humidity test. It was a thing.

The composition of the present invention can be used as an adhesive for various plastic films, especially as an adhesive for hydrophilic plastics, and is particularly suitable for the production of optical films such as liquid crystal display devices, particularly for the production of polarizing plates. Can be used.

Claims

A composition comprising a curable component and a polymerization initiator,
The curable component includes (A) component: a compound having two or more epoxy groups in the molecule (10 to 80% by weight in the curable component), and (B) component: one ethylenic group in the molecule. A compound having a saturated group (20 to 90% by weight in the curable component) and substantially free of a cationically polymerizable compound having a (meth) acryloyl group;
Polymerization initiators are component (C): photocationic polymerization initiator (0.1 to 20% by weight based on the total amount of curable components), and component (D): radical photopolymerization initiator (total amount of curable components). 0.1 to 20% by weight)
An active energy ray-curable adhesive composition for a plastic film or sheet.
The active energy ray-curable adhesive composition for plastic film or sheet according to claim 1, wherein the component (A) comprises a compound having two or more epoxy groups and an aromatic ring skeleton or an alicyclic skeleton.
The active energy ray-curable adhesive for plastic film or sheet according to claim 1 or 2, wherein the component (B) comprises a compound having one ethylenically unsaturated group and an aromatic ring skeleton or alicyclic skeleton. Agent composition.
The active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 3, wherein the component (B) comprises a compound having one ethylenically unsaturated group and a hydroxyl group. object.
Furthermore, (E) the compound which has a 2 or more ethylenically unsaturated group in a molecule | numerator is contained as a sclerosing | hardenable component, and the ratio which shows (A), (B) and (E) component below in a sclerosing | hardenable component The active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 4, which is contained in
Component (A): 10 to 80% by weight in the curable component,
Component (B): 20 to 89% by weight in the curable component,
Component (E): 1 to 20% by weight in the curable component,
However, the proportions of the components (A), (B), and (E) mean the proportion that the total amount is 100% by weight.
The active energy ray-curable adhesive composition for plastic film or sheet according to claim 5, wherein the component (E) comprises polyalkylene glycol di (meth) acrylate.
The plastic film or sheet active energy ray according to any one of claims 1 to 6, further comprising (F) a silane coupling agent in a proportion of 0.1 to 20% by weight in the composition. A curable adhesive composition.
The active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 7, wherein either one or both of the plastic film or sheet is a hydrophilic plastic.
The active energy ray-curable adhesive composition for producing a polarizing plate according to any one of claims 1 to 7, wherein the plastic film or sheet is a polyvinyl alcohol polarizing film.
A laminate comprising a plastic film or sheet, a cured product of the composition according to any one of claims 1 to 7, and another substrate or a plastic film or sheet.
A polarizing plate comprising a plastic film or sheet, a cured product of the composition according to any one of claims 1 to 7, and another substrate or a plastic film or sheet.
A method for producing an active energy ray-curable adhesive composition for a plastic film or sheet,
Component (A): Compound having two or more epoxy groups in the molecule (10 to 80% by weight in the curable component), and Component (B): Compound having one ethylenically unsaturated group in the molecule A curable component containing (20 to 90% by weight in the curable component) and substantially free of a cationic polymerizable compound having a (meth) acryloyl group; and (C) component: a photocationic polymerization initiator (cured) And (D) component: a polymerization initiator containing a radical photopolymerization initiator (0.1 to 20% by weight with respect to the total amount of the curable component),
A manufacturing method characterized by mixing.
10. Adhering two substrates, at least one of which is a plastic film or sheet, using the composition according to any one of claims 1 to 9, and irradiating the substrate with active energy rays. A characteristic bonding method.
10. Adhering two substrates, at least one of which is a plastic film or sheet, using the composition according to any one of claims 1 to 9, and irradiating the substrate with active energy rays. The manufacturing method of the laminated body characterized.