KR101713003B1 - Actinic-energy-ray-curable adhesive composition for plastic film or sheet - Google Patents

Abstract

An object of the present invention is to provide an active energy ray for use in a plastic film having a low viscosity and excellent curability and having a sufficient adhesive property against various plastic films and particularly hydrophilic plastic films and having sufficient performance even in applications requiring strict durability A curable adhesive composition is provided.
(A): a compound having at least two epoxy groups (10 to 80% by weight in the curable component) and a component (B): an ethylenically unsaturated group-containing compound (20) (Meth) acryloyl group-containing cationic polymerizable compound, and the polymerization initiator is (C): a photocationic polymerization initiator (0.1 to 20% by weight) and Component (D): an active energy ray-curable adhesive composition for a plastic film or sheet comprising a photo-radical polymerization initiator (0.1 to 20% by weight) and a method for producing the same.

Description

Technical Field [0001] The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet,

The present invention relates to an active energy ray-curable adhesive composition capable of bonding various plastic films or sheets by irradiation with active energy rays such as electron beams or ultraviolet rays. The composition of the present invention is a thin layer It is most suitably used for adhering an adherend and is most suitably used in the production of various optical films or sheets used in liquid crystal display devices and the like and can be commercially used in these technical fields.

In the present specification, the term "acrylate" and / or "methacrylate" as used herein means an acrylate and / or a methacrylate as a (meth) acrylate, an acryloyl group and / or a methacryloyl group as a (Meth) acrylic acid.

In the following, in the case where it is not necessary to specify in detail, a plastic film or sheet is collectively referred to as "plastic film or the like", and the film or sheet is collectively represented as "film or the like".

BACKGROUND ART Conventionally, in a lamination method in which a thin layer adherend such as a plastic film or the like, or a thin layer adherend such as a plastic film and a thin layer adherend made of a different material are adhered, an ethylene- A dry lamination method in which a solvent-type adhesive composition is applied to a first thin layer adherend, followed by drying, and then a second thin layer adherend is pressed with a nip, a roller, or the like is mainly performed.

The adhesive composition used in this method generally contains a large amount of solvent in order to make the application amount of the composition uniform. Therefore, since a large amount of solvent vapor is volatilized during drying, toxicity, work safety and environmental pollution . In addition, the adhesive composition has a problem in that, in the post-processing step such as a heat seal for adhering the obtained laminate film and a ruled line process in which grooves are formed, immediately after the thin layer adherend is adhered, the thin layer adherends are peeled off I have.

As an adhesive composition for solving these problems, a solventless adhesive composition has been studied.

As a solvent-based adhesive composition, a two-pack type adhesive composition and an adhesive composition which is cured by an active energy ray such as ultraviolet rays or electron beams are widely used.

As the two-pack type adhesive composition, a so-called polyurethane-based adhesive composition is mainly used, in which a polyisocyanate compound having a terminal isocyanate group as a curing agent is mainly used as a polymer having a hydroxyl group at the terminal. However, such a composition has a drawback that a long time is required for curing, and therefore there is a problem in productivity such that it is not possible to enter a post-processing step such as a ruled line process immediately after adhering a thin layer adherend.

On the other hand, the active energy ray curable adhesive composition has attracted attention recently because of its high curing rate and excellent productivity.

On the other hand, the liquid crystal display device has been popularized in small-sized electronic devices such as navigation systems for automobiles, mobile phones, and PDAs, on screens of word processors, personal computers, and TV sets, .

2. Description of the Related Art In recent years, an active energy ray curable adhesive has been used to adhere various optical films used in liquid crystal display devices.

Examples of the optical film include a polarizing plate, a retardation film, a viewing angle compensating film, a luminance improving film, an antireflection film, an antiglare film, a lens sheet and a diffusion sheet, and various kinds of plastics are used for these.

Among these plastics, polyvinyl alcohol and triacetylcellulose are particularly used as the polarizing plate. These plastics contain a hydroxyl group and are characterized in that they are highly hydrophilic compared to ordinary plastics.

As the active energy ray curable adhesive composition for a polarizing plate, there are known a photo-radical polymerization type composition using photo radical polymerization, a photo-ion polymerization type composition using photo-ion polymerization, and a hybrid-type composition using light radical polymerization and photo-ion polymerization in combination.

As the photo-radical polymerization type composition, there is known a composition comprising a radical polymerizing compound containing a polar group such as a hydroxyl group or a carboxyl group and a radical polymerizing compound containing no polar group in a specific ratio (Patent Document 1).

However, the composition has a large shrinkage upon curing, and depending on the kind of the adherend, it is difficult to obtain sufficient peel strength by occurrence 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, etc.).

However, since the viscosity of the composition is increased, there is a problem that thin film coating can not be performed depending on the coating apparatus. It is also possible to alleviate the shrinkage stress at the time of curing by improving the flexibility of the adhesive composition. However, such a means lowers the heat resistance and water resistance of the adhesive. Therefore, in applications requiring strict durability, peeling, There was a problem that unreasoning occurred.

As the light-ionic polymerization type composition, a composition comprising an epoxy resin containing no aromatic ring as a main component (Patent Document 3), a composition comprising an aliphatic epoxy and an alicyclic epoxy and / or oxetane (Patent Document 4) have.

The composition has the advantage of suppressing the occurrence of stress at the interface because the shrinkage upon curing is relatively small for the photo-radical polymerization type composition.

However, it is generally known that the polymerization of Gwangyang ion causes polymerization inhibition by water or a basic substance, and it is difficult to obtain a sufficient peel strength in a substrate having a high temperature or a large amount of water or a basic surface . In addition, it is possible to reduce the effect of lowering the curability due to polymerization inhibition by using a composition containing a polyfunctional epoxy resin as a main component. However, such a composition has an increased viscosity, and therefore, And so on.

Examples of the hybrid composition include a composition comprising a (meth) acrylate having an isocyanurate skeleton, an alicyclic epoxy compound, a compound containing a hydroxyl group and a photoacid generator (Patent Document 5), a composition containing two or more epoxy groups (Patent Literature 6), (meth) acrylic acid ester-based compositions containing at least two epoxy resins, at least one of which is an alicyclic epoxy group, an epoxy resin having two or more epoxy groups and no alicyclic epoxy group, A composition comprising a compound having two or more acryl groups, a compound having a hydroxyl group and a (meth) acrylic group, a cationic polymerizable compound having a (meth) acrylic group, a photo radical polymerization initiator and a photo cationic polymerization initiator (Patent Document 7) It is known.

These compositions solve the problems of shrinkage upon curing and polymerization inhibition due to moisture by hybridization. The inventors of the present invention have found that there are problems as described below.

The composition disclosed in Patent Document 5 contains a (meth) acrylate compound having an isocyanatome skeleton as an essential component. According to the study of the inventors of the present invention, the (meth) acryloyl group having two or more ) Acrylate is contained in a large amount in the composition, the shrinkage at the time of curing is not so small that the occurrence of stress at the interface can not be suppressed, and it has been found that it is difficult to obtain sufficient peel strength depending on the base material .

Although the composition disclosed in Patent Document 6 conceptually includes the hybridized composition, only the composition comprising only the photocationic polymerizable monomer is shown in the examples in the description of the invention of the upper concept , Lack of specificity.

The composition disclosed in Patent Document 7 contains a cationic polymerizable compound having a (meth) acrylic group as an essential component in a specific ratio. According to the study by the present inventor, when the compound is contained in a large amount in the composition, shrinkage upon curing It is not possible to suppress the generation of stress at the interface. Therefore, it has been found that it is difficult to obtain a sufficient peel strength depending on the base material.

Patent Document 1: JP 2008-009329 A (claims) Patent Document 2: Japanese Patent Application Laid-Open No. 2007-177169 (claims) Patent Document 3: Japanese Patent Application Laid-Open No. 2004-245925 (claims) Patent Document 4: Japanese Patent Application Laid-Open No. 2008-134384 (claims) Patent Document 5: JP-A-2008-233279 (claims) Patent Document 6: JP 2008-257199 A (claims) Patent Document 7: Japanese Patent Application Laid-Open No. 2008-260879 (claims)

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a plastic having a low viscosity, excellent in hardenability, excellent in adhesion to various plastic films and the like, particularly hydrophilic plastic film and the like, Film adhesive composition for use as an active energy ray curable adhesive composition.

As a result of various studies, the present inventors have found that, as a curable component, a curable composition comprising a compound having two or more epoxy groups in a molecule and a compound having one ethylenic unsaturated group in the molecule, , An active energy ray curable adhesive composition comprising a photo radical polymerization initiator and a photo cation polymerization initiator as a polymerization initiator is excellent in adhesion to various plastic films and the like and hydrophilic plastic film among them and has a low viscosity, And has sufficient performance even in applications requiring strict durability, thereby completing the present invention.

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 a high adhesive force even under high temperature and high humidity conditions for various plastic films and especially hydrophilic plastic films and the like, And is most suitably used in the production of an optical film used for a liquid crystal display device or the like.

The present invention relates to an active energy ray curable adhesive composition for a plastic film or sheet comprising the following curable component and a polymerization initiator.

(A): a compound having two or more epoxy groups in the molecule (10 to 80% by weight in the curable component) and (B): a compound having one ethylenic unsaturated group in the molecule % By weight), and substantially does not contain a cationic polymerizable compound having a (meth) acryloyl group.

(C): a photocationic polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components) and (D): a photo radical polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components).

Hereinafter, components (A) to (D) which 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.

Examples of the component (A) include compounds having two or more epoxy groups and aromatic ring skeletons in the molecule (hereinafter referred to as " aromatic epoxy compounds "), two or more epoxy groups in the molecule, (Here, the alicyclic epoxy group means an alicyclic group which forms an epoxide between two neighboring carbon atoms constituting a ring) (hereinafter referred to as an " alicyclic epoxy compound "), 2 (Hereinafter referred to as " aliphatic epoxy compounds "), which have at least two epoxy groups and do not contain an aromatic ring.

Examples of the aromatic epoxy compound 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 Bisphenol-type epoxy resins such as diglycidyl ether of bisphenol S bromide, diglycidyl ether of rubber-modified bisphenol A, di- or polyglycidyl ether of bisphenol fluorene or alkylene oxide adduct thereof, and the like; Novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, cresol brominated cresol novolak type epoxy resin and dicyclopentadiene-phenol novolak type epoxy resin; Naphthalene type epoxy resin; Alkyl diphenol type epoxy resins; Naphthol type epoxy resin; Biphenyl type epoxy resins; Hydroquinone diglycidyl ether; Resorcine diglycidyl ether; Terephthalic acid diglycidyl ether; Phthalic acid diglycidyl ether; An epoxide of a styrene-butadiene copolymer; Epoxides of styrene-isoprene copolymers; An addition reaction product of a terminal carboxylic acid polybutadiene and a bisphenol A type epoxy resin; N, N, N ', N'-tetraglycidyl-m-xylenediamine and the like.

In addition, in addition to these, there are two other publications, "Epoxy Resin - Recent Progress" (published by Shokudo, 1990), and "Polymer Processing", Separate Volume 9, Vol. 22, Epoxy Resin (Polymer Publication Society, , Pages 4 to 6, pages 9 to 16, and pages 29 to 55.

Here, the epoxy resin refers to a compound or polymer having two or more epoxy groups on average in the molecule and curing by reaction. According to the convention in this field, in the present specification, even a monomer having two or more curable epoxy groups in a molecule may be referred to as epoxy resin.

As other aromatic epoxy compounds, Epikote 5050, 5051, 1031S, 1032H60, 604, 630, 871, 872, 191P, YX310, 545, YL6810, YX8800, YL980 (manufactured by Japan Epoxy Resin Co., Ltd.) .

Examples of the alicyclic epoxy compound include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, bis Epoxycyclohexylmethyl) adipate, and the like.

In addition, in addition to these, in addition to those described in the literature "Epoxy Resin - Recent Advances" (published by Shokudo, 1990) and in "Polymer Processing" Separate Vol. 9, Volume 22 Epoxy Resin (Polymer Publication, 1973) Page 7, pages 18 to 20, and the like.

Specific examples of the aliphatic epoxy compound include diglycidyl ether of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; Diglycidyl ethers of polyalkylene glycols such as diglycidyl ether of polyethylene glycol and polypropylene glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide adduct thereof; Trimethylol ethane, trimethylol propane, di- or triglycidyl ether of glycerin and its alkylene oxide adduct, and di- or tetraglycidyl ether of pentaerythritol and its alkylene oxide adduct, Glycidyl ether; Di- or polyglycidyl ethers of hydrogenated bisphenol A and its 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 " Polymer Processing "

Examples of the aliphatic epoxy compounds other than these may include, but are not limited to, Denarax R-45EPT (manufactured by Nagase ChemteX Corporation), Epofriend AT501, CT310, Epolide PB3600 (available from Daicel Chemical Industries, Ltd.), KL- Ltd.), Tetrade C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

As the component (A), a compound having from 2 to 10 epoxy groups is preferable because the heat resistance and adhesiveness can be enhanced. As the component (A), a compound having a low molecular weight is preferable because of its low viscosity, and specifically, a compound having a molecular weight of 2,000 or less and a compound having a molecular weight of 200 to 1,000 are preferable.

As the component (A), an aromatic epoxy compound and an alicyclic epoxy compound are preferable because the composition is low in viscosity and excellent in curability and the cured product is excellent in adhesiveness. Specific examples include bisphenol-type epoxy resins, naphthalene-type epoxy resins, resorcin diglycidyl ether, limonene dioxide, and 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate.

As the component (A), one kind or two or more kinds of the above-mentioned compounds may be used in combination.

The proportion of the component (A) is 10 to 80% by weight, preferably 30 to 70% by weight, in the curable component. When the proportion of the component (A) is 10% by weight or more, the cured product is excellent in heat resistance and water resistance, and when it is 80% by weight or less, the composition has a low viscosity and excellent coating property. do.

2. Component (B)

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

As the vinyl compound, a compound having one vinyl group can be mentioned. Specific examples include styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, n-propylvinylether, isopropylvinylether, n-butylvinylether, Cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl Ethyl vinyl ether, and 2-ethylhexyl vinyl ether.

As the allyl compound, there can be mentioned a compound having one allyl group. Specific examples thereof include allyl alcohol and the like.

Examples of the compound having a (meth) acryloyl group include (meth) acrylamide and (meth) acrylate.

As the (meth) acrylamide, a compound having one (meth) acrylamide group can be mentioned. Specific examples thereof include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid and N-isopropyl (meth) acrylamide.

As the (meth) acrylate, a compound having one (meth) acryloyl group (hereinafter referred to as a monofunctional (meth) acrylate) can be cited. Specific examples include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate, undecyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylates having 12 to 13 carbon atoms, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl Isomyristyl (meta) arc (Meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, (Meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl Aliphatic (meth) acrylates such as 7-dimethyloctyl (meth) acrylate;

(Meth) acrylate, isobornyl (meth) acrylate, boron (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyloxyethyl (Meta) acrylate such as phenyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (Meth) acrylate of an alkylene oxide modified product of an alkylene oxide modified product of an alkylene oxide, an alkylene oxide modified product of an alkylene oxide modified product of an alkylene oxide modified product of an alkylene oxide, (Meth) acrylate of an alkylene oxide modified product of an alkylene oxide modified product of o-phenylphenol, a (meth) acrylate of an alkylene oxide modified product of an alkylene oxide modified product of p-phenylphenol, an alkylene oxide modified product of a tribromophenol (Meth) acrylate of aromatic (meth) acrylate of neopentyl glycol (meth) acrylic acid benzoate ester;

Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono Polytetramethylene glycol mono (meth) acrylate, polyethyleneglycol-polypropylene glycol mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol mono Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- Hydroxyl group-containing (meth) acrylates such as hydroxyethyl phthalate and 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate;

(Meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, carboxylic acid-containing (meth) acrylates such as? -carboxypolycaprolactone (meth) acrylate;

(Meth) acryloyloxyethylhexahydrophthalimide, 2- (1,2-cyclohexa-1-endocarboximide) ethyl (meth) acrylate, Pancryl FA-502A (manufactured by Hitachi Kasei Kogyo Co., Imide (meth) acrylate;

(Meth) acrylate such as 2- (meth) acryloyloxyethyl acid phosphate;

.

The component (B) may be used alone or in combination of two or more of the above-mentioned compounds.

(B) is preferably a compound having one ethylenic unsaturated group and an aromatic ring skeleton or alicyclic skeleton (hereinafter referred to as component (b1)) since the composition has a low viscosity and an excellent adhesiveness Do.

As the component (b1), alicyclic (meth) acrylate and aromatic (meth) acrylate are preferable, and among them, isobornyl (meth) acrylate and dicyclopentyl Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (Meth) acrylate, an alkylene oxide-modified (meth) acrylate of phenol, N- (meth) acryloyloxyethylhexahydrophthalimide, 2- (1, 2-cyclohexa-1-endicarboxyimide ) Ethyl (meth) acrylate are preferable.

As the component (B), a compound having one ethylenic unsaturated group and a hydroxyl group [hereinafter referred to as a component (b2)) is preferable.

As the component (b2), a (meth) acrylate having one hydroxyl group is preferable, and specific compounds are the same as described above. Among them, the composition has a low viscosity and an excellent adhesive property. . Examples of the compound satisfying the molecular weight include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

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

(B) is 20 to 90% by weight, preferably 20 to 89% by weight, and more preferably 30 to 70% by weight in the curable component. (B) is 20% by weight or more, the composition can be made to have a low viscosity, and the coating can be made excellent. Further, the adhesive strength can be excellent, and 90% by weight or less, It can be made excellent in heat resistance and water resistance.

3. Component (C)

(C) is a photocationic polymerization initiator. That is, it is a compound which generates a cation or a Lewis acid by irradiation of an active energy ray and initiates polymerization of the component (A) as a photopolymerizable compound.

Specific examples of the component (C) include a sulfonium salt, an iodonium salt and a diazonium salt.

Examples of sulfonium salts include, for example,

Triphenylsulfonium hexafluorophosphate,

Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate,

Triphenylsulfonium tetrakis (pentafluorophenyl) borate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,

4, 4'-bis [diphenylsulfonio] diphenylsulfide bishexafluorophosphate,

4, 4'-bis [di (beta -hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate,

4, 4'-bis [di (? - hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,

7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,

7-di (p-toluyl) sulfonio] -2-isopropylthioxantonetetrakis (pentafluorophenyl) borate,

4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,

4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate,

And triarylsulfonium salts such as 4- (p-tert-butylphenylcarbonyl) -4'-di (p-tolyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) .

Examples of iodonium salts include, for example,

Diphenyl iodonium tetrakis (pentafluorophenyl) borate,

Diphenyl iodonium hexafluorophosphate,

Diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate,

Di (4-t-butylphenyl) iodonium hexafluorophosphate,

Di (4-t-butylphenyl) iodonium hexafluoroantimonate,

Tolylcumyl iodonium tetrakis (pentafluorophenyl) borate,

(4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,

Di (4-nonylphenyl) iodonium hexafluorophosphate,

Di (4-alkylphenyl) iodonium hexafluorophosphate,

And the like.

As an example of the diazonium salt, for example,

Benzene diazonium hexafluoroantimonate, benzene diazonium hexafluoroantimonate,

Benzene diazonium hexafluorophosphate,

And the like.

(C) are commercially available as ADEKA OPTOMA SP-100, 150, 152, 170 and 172 (manufactured by ADEKA), Photo Initiator 2074 (manufactured by Rhodia), Kayalard PCI-220 and 620 (manufactured by Nippon Kayaku WPI-113, 116 (manufactured by Wako Pure Chemical Industries, Ltd.), IRGACURE 250 (manufactured by BASF, Japan), CPI-100P, 101A, 200K, 210S BBI-102, BBI-103, TPS-102, TPS-103, DTS-102 and DTS-103 (manufactured by Midori Kagaku).

Of these, triarylsulfonium salts and diaryliodonium salts are preferred because of their excellent activity energy ray curability and excellent curability of the cured film against water resistance. In particular, diaryliodonium salts are preferred from the viewpoint of excellent curability .

As the triarylsulfonium salt, triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable among the above. Examples of the diaryliodonium salts include tolylcumyl iodonium tetrakis (pentafluorophenyl) borate (Photoinitiator 2074, produced by Rhodia Japan K.K.), diphenyliodonium hexafluorophosphate, (4-methylphenyl (4-t-butylphenyl) iodonium hexafluorophosphate and WPI-4 (2-methylpropyl) phenyl] -hexafluorophosphate (Irgacure 250, manufactured by BASF Japan) 113 (manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

As the component (C), the above-described compounds may be used alone, or two or more of them may be used.

(C) is 0.1 to 20% by weight, preferably 1 to 10% by weight, and more preferably 2 to 7% by weight based on the total amount of the curable component. By setting the ratio of the component (C) to 0.1% by weight or more, the composition can be made excellent in adhesive property by providing sufficient active energy ray curability. On the other hand, when it is 20% by weight or less, the adhesive layer has good internal curability, Can be made excellent.

Further, in the use of the component (C), a sensitizer may be used in combination with the component (C) in order to enhance the photocatalytic curing property 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, 9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 4'-nitrobenzyl-9,10-dimethoxyanthracene- Dimethoxyanthracene-2-sulfonate, and 4'-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate.

Of these, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 9,10-dipropoxyanthracene are preferred because they are excellent in solubility in the composition and high in the action of increasing and decreasing 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 from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the total amount of the curable component.

When a sulfonium salt is used as the component (C), an anthracene compound is preferably used in combination as a sensitizer.

4. Component (D)

(D) is a photoradical polymerization initiator. That is, it is a compound which generates radicals by irradiation of active energy rays and initiates polymerization of component (B), which is a compound having an ethylenic unsaturated group. Depending on the kind of the component (D), the component (C) also functions as a sensitizer for enhancing the photocatalytic curing property 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- Methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy- 1- [4- [4- (2- ] - phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) 1- (4-morpholin-4-yl-phenyl) -butan-l- , Adeka Optoma-N-1414 (Asahi Denka Co.), phenylglyoxylic acid methyl ester, Aromatic ketone compounds such as anthraquinone and phenanthrene-quinone;

Benzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2 (2-methylbenzophenone) (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzo Phenanone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl- Benzophenone-based compounds such as phenone and 4-methoxy-4'-dimethylaminobenzophenone;

Bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis 2, 6-dimethoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide;

2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl- -9H-thioxanthone-2-yl] oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanone;

Acridine-based compounds such as acridone and 10-butyl-2-chloroacridone;

(2-methylbenzoyl) -9H-carbazole-3 < / RTI > (O-acetyloxime), oxime esters such as 2- (o-chlorophenyl) -4,5-diphenylimidazole, 2- (o- Imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- (P-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole 2 2, 4, 5-triarylimidazole dimer such as dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer; And

Acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9'-acridinyl) heptane.

Among them, the thioxanthone compound is preferred because it not only initiates polymerization of the component (B) but also exhibits the effect of increasing and decreasing the component (C). Among the thioxanthone-based compounds, 2,4-diethylthioxanthone and isopropylthioxanthone are more preferable because of their excellent activity energy ray curability and lack of cohesion of the cured film.

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

(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. When the ratio of the component (D) is 0.1 wt% or more, the composition can exhibit sufficient activity-ray curability and excellent adhesive property. On the other hand, when the content is 20 wt% or less, the adhesive layer has good internal curability, Can be made excellent.

5. Component (E) and / or component (F)

The composition of the present invention contains the above components (A) to (D) as essential components, and various components can be further blended according to the purpose.

(Hereinafter referred to as component (E)) and / or a silane coupling agent (hereinafter referred to as component (F)) having two or more ethylenically unsaturated groups in the molecule for further improving heat resistance, water resistance, Can be blended. Hereinafter, this will be described in detail.

(E) 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 the vinyl compound include compounds having two or more vinyl groups. Specific examples include divinylbenzene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, (meth) acrylic acid 2- (2-vinyloxy Ethoxy) ethyl and the like.

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

As the (meth) acrylate, there may be mentioned a compound having two or more (meth) acryloyl groups (hereinafter referred to as "multifunctional (meth) acrylate").

Specific examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) (Meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2- (Meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hydroxypropyl (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, and other polyol poly (meth) acrylates Agent;

Di (meth) acrylate of a neopentyl glycol alkylene oxide adduct, di (meth) acrylate of a 1,6-hexanediol alkylene oxide adduct, tri (meth) acrylate of an alkylene oxide adduct of glycerin, trimethylolpropane Poly (meth) acrylates of alkylene oxide adducts of polyols such as tri (meth) acrylates of alkylene oxide adducts and tri (meth) acrylates of pentaerythritol alkylene oxide adducts;

Glycol-modified polyol poly (meth) acrylates such as neopentyl glycol-modified trimethylolpropane di (meth) acrylate;

Caprolactone-modified polyol (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 (meth) acrylate and dicyclopentanyl di (meth) acrylate;

Di (meth) acrylates of bisphenol A alkylene oxide adducts, di (meth) acrylates of bisphenol F alkylene oxide adducts, and di (meth) acrylates of bisphenol S alkylene oxide adducts. Di (meth) acrylate of water;

Di (meth) acrylates of di (meth) acrylates of alkylene oxide adducts of water-added bisphenol A and water-added bisphenol compounds such as di (meth) acrylates of alkylene oxide adducts of water-added bisphenol F; (Meth) acrylates of isocyanuric acid alkylene oxide adducts, tri (meth) acrylates of isocyanuric acid alkylene oxide adducts, tri (meth) acrylates of isocyanuric acid caprolactone adducts, (Meth) acrylate;

Di (meth) acrylates of ester diols such as neopentyl glycol hydroxypivalic acid di (meth) acrylate and neopentyl glycol di (meth) acrylate hydroxycarboxylate;

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;

Triacrylic form; And

(Meth) acrylic acid esters such as trimethylolpropane (meth) acrylic acid ester, and Ogrosol EA-0200, 0500, 1000 (fluorene acrylate, Osaka Gas Chemicals).

Examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.

In addition to these, compounds described in pages 53 to 56 of "Newest UV curing technology" (published by Printing Information Association of Japan, 1991) can be mentioned.

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

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

Examples of the polyester polyol include a reaction product with a carboxylic acid or its anhydride with a polyol.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, Low molecular weight polyols such as methylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, Alkylene oxide adducts, and the like.

Examples of the carboxylic acid or its anhydride include dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, malic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid or anhydrides thereof.

Examples of the polyester poly (meth) acrylates other than these include compounds described on pages 74 to 76 of the above-mentioned " UV / EB curing material ".

Urethane (meth) acrylate is obtained by a reaction of a polyhydric alcohol and a polyfunctional isocyanate and a hydroxy (meth) acrylate compound, but does not use a polyhydric alcohol and is obtained by reacting a polyfunctional isocyanate with a hydroxy (meth) And the like.

Examples of polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol; polyester polyols obtained by the reaction between the polyhydric alcohol and the polybasic acid; and caprolactone obtained by the reaction between the polyhydric alcohol and the polybasic acid and epsilon -caprolactone A lactone polyol and a polycarbonate polyol (e.g., a polycarbonate polyol obtained by the reaction of 1,6-hexanediol with diphenyl carbonate).

Examples of the polyvalent isocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4, 4'-diisocyanate, dicyclopentanyl diisocyanate and the like. The urethane (meth) acrylate used in the present invention may be either those obtained by the above-mentioned three-way reaction or those obtained by the two-way reaction, either alone or in combination.

Examples of the hydroxy (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (Meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate and trimethylolpropane di or mono Acrylate, and the like.

These are obtained by subjecting an organic isocyanate to be used and a polyol component to an addition reaction by heating with stirring in the presence of an addition catalyst such as dibutyltin dilaurate, adding hydroxyalkyl (meth) acrylate, and heating and stirring to carry out addition reaction Loses.

Examples of the urethane poly (meth) acrylates other than these are compounds as described in pages 70 to 74 of "UV · EB curing material" (published by SHM Co., Ltd., 1992).

The epoxy (meth) acrylate is a compound obtained by addition reaction of an epoxy resin with (meth) acrylic acid, and includes compounds described on pages 74 to 75 of the above-mentioned "UV / EB curing material".

Examples of the epoxy resin include an aromatic epoxy resin and an aliphatic epoxy resin.

Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; Di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or alkylene oxide adduct thereof; Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Glycidyl phthalimide; phthalic acid diglycidyl ester, and the like.

In addition to these, there are also other methods known in the art, such as those described in "Epoxy Resin - Recent Advances-" (published by Shokudo, 1990) or in "Polymer Processing" Sep. 9, Vol. 22, Epoxy Resin [Polymer Publication, 1973] 6, pages 9 to 16, and the like.

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 polyalkylene glycols such as diglycidyl ether of polyethylene glycol and polypropylene glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide adduct thereof; Trimethylol ethane, trimethylol propane, di- or triglycidyl ether of glycerin and its alkylene oxide adduct, and di- or tetraglycidyl ether of pentaerythritol and its alkylene oxide adduct, Glycidyl ether; Di- or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; Tetrahydrophthalic acid diglycidyl ether; And hydroquinone glycidyl ether.

In addition to these, the compounds described on pages 3 to 6 of the above-mentioned " Polymer Processing "

In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triarylamine skeleton such as TEPIC (Nissan Chemical Co., Ltd.) and Denacol EX-310 (Nagase Chemical Co., Ltd.) Further, the compounds described in the above " Polymer Processing " Separate Epoxy Resins, pages 289 to 296, and the like can be given.

In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

Examples of the polyether (meth) acrylate oligomer-polyether (meth) acrylate oligomer include polyalkylene glycol (meth) diacrylate and polyethylene glycol di (meth) acrylate, polypropylene glycol di And polytetramethylene glycol di (meth) acrylate.

As the polymer, a (meth) acryloyloxy group having a (meth) acryloyloxy group and a (meth) acryl-based polymer having a functional group introduced with a (meth) acryloyl group on the side chain, And compounds described on pages 78 to 79 of JP-A-10-19605.

The component (E) may be used alone or in combination of two or more of the above-mentioned compounds.

The component (A) of the present invention causes a phenomenon called so-called dark reaction, in which the reaction progresses and cures even after the completion of the active energy ray irradiation, so that unstability may occur depending on the application. For example, in the case of producing a laminate by using the composition of the present invention for adhering a film-like substrate, if the film laminate is wound after being subjected to active energy ray irradiation, There is a problem that traces of torsion or scratches are likely to remain.

In order to prevent such a problem, it is very effective to mix the component (E) in which the elastic modulus of the adhesive layer becomes high immediately after the irradiation with the active energy rays. In addition, the heat resistance is improved by increasing the crosslinking density.

Examples of the component (E) include polyalkylene glycol di (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, alkylene of bisphenol A Di (meth) acrylate of alkylene oxide modified product of bisphenol F, di (meth) acrylate of alkylene oxide modified product of bisphenol F, di (meth) acrylate of alkylene oxide modified product of isocyanuric acid, Polyalkylene glycol di (meth) acrylate is particularly preferred.

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.

When the ratio of the component (E) is 1% by weight or more, it is possible to prevent the unreasoning due to the dark reaction and to improve the heat resistance, and by setting the content to 20% by weight or less, it is possible to suppress the curing shrinkage of the composition.

(F) Component

(F) is a silane coupling agent capable of improving the interfacial adhesion 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 with a base material.

Specific examples include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- glycidoxypropyl tri (Meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Ropil tree and the like silane.

Among these silane coupling agents, from the viewpoint of storage stability and adhesion of the composition, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3- Propyl methyl dimethoxy silane, and 3- (meth) acryloxypropyl trimethoxy silane are preferable.

The component (F) may be used alone or in combination of two or more of the above-mentioned compounds.

When the component (F) is contained in the composition, the proportion of the component (F) is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, in the composition. (F) is 0.1% by weight or more, the effect of improving the adhesive strength of the composition is sufficient, and when it is 20% by weight or less, the storage stability of the composition is excellent.

6. Other ingredients

The composition of the present invention may be blended with other components usually used as an adhesive composition.

Specifically, inert components such as an inorganic filler, a softening agent, an antioxidant, an antioxidant, a stabilizer, a tackifier resin, a leveling agent, a defoamer, a plasticizer, an organic solvent, a dye, a pigment, a treating agent and a sunscreen agent may be added. Examples of the tackifier resin include rosins such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resins, terpene phenol resins, aromatic hydrocarbon resins, aliphatic saturated hydrocarbon resins and petroleum resins.

These are preferably blended in the composition in an amount of 20% by weight or less.

7. Active energy ray curable adhesive composition for plastic film or sheet

The composition may be produced by mixing the above components (A) to (D), if necessary, with other components in accordance with the conventional method by stirring and mixing. In this case, heating may be performed if necessary. The heating temperature may be suitably set in accordance with the composition to be used, the substrate and the purpose, and is preferably 30 to 80 캜.

The composition of the present invention is a composition which does not substantially contain a cationic polymerizable compound having a (meth) acryloyl group disclosed in Patent Document 7 as a curable component. As a result, the shrinkage stress at the time of curing can be reduced and the 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 15 wt% %, 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 from 10 to 1,000 mPa · s in view of excellent coatability to the substrate.

The composition of the present invention can be used for bonding between plastic films and the like, for bonding plastic films, and various other substrates (hereinafter referred to as " other substrates "). That is, at least one of them can be used for bonding two substrates such as a plastic film. In the following, in the case of simply "substrate", it means a general term of a plastic film or the like and other substrates.

Other substrates include paper, metal, and the like.

As a method of use, a method according to a conventional method may be used, and a method in which the composition is applied to a substrate and then attached to the other substrate to irradiate an active energy ray.

Examples of the material for the plastic film and the like include polyvinyl chloride resin, polyvinylidene chloride, cellulose resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol , Triacetyl cellulose, cycloolefin polymer, polymethyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer and chlorinated polypropylene.

Examples of the paper include imitation paper, high-gloss paper, kraft paper, art paper, castor coated paper, pure white paper, parchment paper, resin, grainy paper and corrugated paper.

Examples of the metal foil include aluminum foil and the like.

The coating on the substrate may be performed according to a conventionally known method and may be carried out by a known method such as a natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, , A comma coater, a gravure coater, a micro gravure coater, a die coater and a curtain coater.

The coating thickness of the composition of the present invention may be selected depending on the substrate and the application to be used, but is preferably from 0.1 to 100 탆, more preferably from 1 to 25 탆.

Examples of the active energy ray include visible ray, ultraviolet ray, X-ray and electron ray. Ultraviolet rays are preferable because a low-cost apparatus can be used.

As the light source for curing by ultraviolet rays, various materials 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.

In the case of curing by electron beam, various devices can be used as the EB irradiating device which can be used. Examples of the EB irradiating device include a COCROW WALTON type, a Bandegraph type and a resonant transformer type device. Preferably has an energy of 50 to 1000 eV, more preferably 100 to 300 eV.

The composition of the present invention is most suitable when a thin layer adherend is adhered as a base material. The method for adhering a thin layer adherend may be suitably selected according to a method usually employed in the production of a laminate.

For example, the composition may be applied to a first thin layer adherend, dried as required, and then a second thin layer adherend may be attached to the layer to conduct active energy ray irradiation.

Examples of the thin layer adherend include a plastic film, paper, metal foil and the like.

The plastic film or the like needs to be capable of transmitting an active energy ray. The film thickness may be selected depending on the thin layer adherend to be used and the intended use, but preferably the thickness is 0.2 mm or less.

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

In order to increase the interlaminar adhesive strength before the adherend is adhered, the activation treatment may be performed on one or both surfaces. Examples of the surface activation treatment include a plasma treatment, a corona discharge treatment, a chemical solution treatment, a roughening treatment, an etching treatment, a flame treatment, and the like, and they may be used in combination.

The coating of the thin layer adherend may be performed according to a conventionally known method, and the same method as described above may be used.

The coating thickness of the composition of the present invention may be selected depending on the thin layer adherend to be used and the application, but the same coating thickness as the above is preferable.

In this case, it is not limited to the planar state, and it is also possible to perform adhesion in a curved state. That is, there is a method in which the substrate is folded in a concave state or a convex state, the composition is applied in this state, and the other substrate is attached to irradiate the active energy ray.

As another method, a method of applying the composition of the present invention in a planar state to the substrate, folding the other substrate in a concave state or a convex state, and irradiating an active energy ray for bonding may be mentioned.

In this case, as a method of coating the composition in a planar state, the above-mentioned method may be employed. Examples of the method of coating the composition in a curved state include a method using a spray, a dip, a curtain float coater, a screen printing and a slot die coater.

In this way, a laminate composed of a plastic film / a laminate composed of a cured product / plastic film of the composition of the present invention, a plastic film / a cured product of the composition of the present invention / another substrate is produced.

Since a laminate such as a laminate film obtained from the composition of the present invention has excellent adhesion under high temperature and high humidity conditions, it can be most suitably used for an optical film such as a polarizing plate, a protective film and a retardation film used for a liquid crystal display device.

The composition of the present invention can be suitably used particularly in the production of a polarizing plate and a polarizing plate with a retardation film. Hereinafter, a method for producing a polarizing plate will be described.

In this specification, the term "polarizer" refers to a film or film having a polarizing function, which will be described later, and a polarizer refers to a polarizer with a protective layer, in which one side or both sides of the polarizer are protected with a film or a film. The polarizing plate with a retardation film means that a retarder film is attached to a polarizer or a polarizing plate, or a film having a retardation function is formed by coating.

8. Manufacturing method of polarizing plate

As described above, the composition of the present invention can be preferably used for bonding a hydrophilic plastic. In the production of a polarizing plate, polyvinyl alcohol used as a polarizer and triacetyl cellulose used as a protective film for a polarizer correspond to hydrophilic plastics .

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

The polarizer has a function of selectively transmitting linear polarized light in one direction from natural light.

Specific examples of the polarizer include a dye-based polarizer in which a dichroic dye is adsorbed and oriented on an oxo-based polarizer or a polyvinyl alcohol-based film obtained by adsorbing and orienting oxo on a polyvinyl alcohol-based film, a dye of a (lyotropic) And a coating type polarizer obtained by orienting and immobilizing the polarizer.

These oxo-based polarizers, dye-based polarizers, and coated polarizers have a function of selectively transmitting linear polarized light in one direction from natural light and absorbing linear polarized light in the other direction, and are called absorption-type polarizers.

In the above-mentioned oxo-based polarizer and dye-based polarizer, usually, a protective layer is provided on one side or both sides thereof. The composition of the present invention can be used for bonding a polarizer and a protective film.

Examples of the protective film used in the protective layer include cellulose acetate resin films such as triacetylcellulose and diacetylcellulose, acrylic resin films, polyester resin films, polyarylate resin films, polyether sulfone resin films, And cyclic polyolefin resin films using the same cyclic olefin as a monomer.

Next, the composition of the present invention may be used for bonding 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 the protective layer, the protective film may be attached or may be a protective film formed by coating. The polarizing plate provided with the protective layer only on one surface may be a surface having a protective layer or a surface having no protective layer to be adhered to the retardation film.

As the retardation film, various films can be used. Examples of the retardation film include an optical film on which an optical film or a liquid crystal compound subjected to processing such as uniaxial or biaxial stretching is applied to a base material and subjected to orientation and fixation. Dimensional refractive index (refractive index ellipsoid) according to the conditions of use. This is mainly used to compensate for the change in the retardation due to the coloring of the liquid crystal layer of the liquid crystal display or the viewing angle.

As specific examples of the retardation film, examples of the material of the optical film to be processed such as stretching include polyolefin such as polyethylene, polypropylene and cyclic polyolefin, polycarbonate such as polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyacrylate And polyamides.

The above-mentioned cyclic polyolefins are general generic names of resins obtained from cyclic olefins such as norbornene, tetracyclododecene and their derivatives, and they are disclosed, for example, in JP-A-3-14882, JP-A-3-122137 And the like.

Specific examples thereof include ring-opening polymers of cyclic olefins, addition polymers of cyclic olefins, random copolymers of cyclic olefins and? -Olefins such as ethylene and propylene, and graft-modified products obtained by modifying them with unsaturated carboxylic acids or their derivatives For example. And further, their hydrides. Examples of the products include Zeonex, Zeonor, Zoner, and Aton of JSR, Topas of TICONA, and the like.

As an optical film to which a liquid crystal compound or the like is applied to a substrate and subjected to orientation and immobilization, there can be mentioned "WV film" (manufactured by Fuji Photo Film Co., Ltd.), "LC film" (Manufactured by Nippon Petroleum K.K.).

A method of producing a polarizing plate or a polarizing plate with a retardation film using the composition of the present invention will be described.

Examples of the production method include the following steps [1] to [3].

[1] A process for coating an adherend (substrate) selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film and a retardation film as an adherend,

[2] A method for manufacturing a polarizing plate, comprising the steps of: adhering an adherend (substrate) coated with the composition onto a polarizer, a polarizing plate, a protective film, a protective film,

[3] A step of irradiating an adherend (laminate) adhered with an active energy ray, particularly a step of irradiating the composition with an active energy ray over the adherend (laminate) adhered thereto.

In the case where the protective film or the retardation film is attached to only one side, the polarizing plate or the polarizing plate with a retardation film can be manufactured by the above procedure. In the case of attaching the polarizing plate or the retardation film on both sides, the steps [1] and [2] [3] may be performed, and the steps [1], [2] and [3] may be repeated twice.

The coating method in the step [1] and the method of irradiating the active energy rays in the step [3] may be carried out in the same manner as described above.

Also, as described above, it may be bonded in a curved state using the above-described manufacturing method.

When the polarizing plate with a retardation film is used as a circularly polarizing plate, a retardation film having a retardation different from that of the retardation film side of the polarizing plate with a retardation film may be further attached to the circularly polarized state over a wide band.

Specifically, there is a method of attaching a retardation film having a half wavelength to each wavelength to the polarizing film, and attaching a retardation film having a quarter wavelength to each wavelength. In this case, step [3] may be performed after repeating steps [1] and [2] three times, or steps [1], [2] and [3] may be repeated three times.

Also, the documents cited in this specification are incorporated by reference.

(Example)

Hereinafter, the present invention will be described in more detail 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 were stirred and dissolved at 60 占 폚 for 1 hour to prepare an active energy ray curable adhesive composition. The numbers in parentheses in Table 1 mean weight parts.

(A) (B) (C) (D) (E) (F) Other (b1) (b2) Example 1 jER
(50) BzA
(50) Irg
(4) DETX
(One) KBM
(5) Example 2 jER
(50) BzA
(30) HPA
(20) Irg
(4) DETX
(One) Example 3 jER
(50) IBXA
(30) HPA
(20) Irg
(4) DETX
(One) Example 4 CEL
(50) BzA
(30) HPA
(20) Irg
(4) DETX
(One) Example 5 jER
(50) BzA
(20) HPA
(20) Irg
(4) DETX
(One) M203S
(10) Example 6 jER
(50) BzA
(20) HPA
(20) Irg
(4) DETX
(One) M211B
(10) Example 7 jER
(50) BzA
(20) HPA
(20) Irg
(4) DETX
(One) M315
(10) Example 8 jER
(50) BzA
(20)
M145
(10) HPA
(20) Irg
(4) DETX
(One) Example 9 jER
(45) IBXA
(20) HPA
(30) Irg
(4) DETX
(One) M-270
(5) Example 10 jER
(45) IBXA
(20) HPA
(30) CPI
(10) DETX
(One) M-270
(5) DBA
(2) Comparative Example 1 CEL
(50) Irg
(4) OX211
(50) Comparative Example 2 HBA
(40) Irg
(4) DETX
(One) M325
(20) SM100
(40) Comparative Example 3 PEA
(35)
ACMO
(30) HEM
(20) TPO
(One) M1310
(15) Comparative Example 4 PEA
(35)
ACMO
(30) HEM
(20) TPO
(One) M1200
(15) Comparative Example 5 PEA
(35)
ACMO
(30) HEM
(20) TPO
(One) M1600
(15)

The abbreviation symbols in Table 1 are as follows.

(A) Component

JER: diglycidyl ether of bisphenol A, manufactured by Japan Epoxy Resin Co., Ltd., trade name jER-828

CEL: 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, manufactured by Daicel Chemical Industries, Ltd., trade name: Celloxide 2021P

Component (B)

ㆍ BzA: Benzyl acrylate, Viscot # 160 made by Osaka Organic Chemical Industry Co., Ltd.

IBXA: isobornyl acrylate, light acrylate IB-XA manufactured by Kyoeisha Chemical Co., Ltd.

ㆍ ACMO: acryloylmorpholine, hogging agent

PEA: phenoxyethyl acrylate, light acrylate PO-A manufactured by Kyoeisha Chemical Co., Ltd.

M-145: 2- (1, 2-cyclohexa-1-endocarboximide) ethyl acrylate, Aronix M-145

ㆍ HPA: 2-hydroxypropyl acrylate, Light Ester HOP-A manufactured by Kyoeisha Chemical Co., Ltd.

HBA: 2-hydroxybutyl acrylate, light acrylate HOB-A manufactured by Kyoeisha Chemical Co., Ltd.

ㆍ HEM: 2-hydroxyethyl methacrylate, Light Ester HOP manufactured by Kyoeisha Chemical Co., Ltd.

(C) Component

Irg: Irgacure 250: iodonium salt based light ion initiator (manufactured by BASF, Japan)

CPI: CPI-100P: 50 wt% propylene carbonate solution of sulfonium salt-based Gwangyang ion initiator (acid-

(D) Component

DETX: 2,4-diethylthioxanthone, DETX-S (manufactured by Nippon Kayaku Co., Ltd.)

- TPO: 2,4,4-trimethylbenzoyldiphenylphosphine oxide (DARACURE TPO manufactured by BASF Japan)

(E) Component

M203S: tricyclodecane dimethanol diacrylate, ARONIX M-203S (trade name, manufactured by TOAGOSEI CO., LTD.)

M211B: bisphenol A (EO modification? 2) diacrylate, Aronix M-211B manufactured by Donga Synthesis Co., Ltd.

M315: isocyanuric acid EO-modified triacrylate, Aronix M-315 manufactured by Donga Seiyaku Co., Ltd.

M325:? -Caprolactone denatured tris (acryloxyethyl isocyanurate, Aronix M-325 manufactured by Donga Synthetic Co., Ltd.)

M-270: polypropylene glycol (n? 12) diacrylate, ARONIX M-270

(F) Component

KBM: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, KBM-303 manufactured by Shin-Etsu Chemical Co.,

Other components

OX211: 3-ethyl-3-phenoxymethyloxetane, AARON oxetane OXT-211

SM100: 3, 4-epoxycyclohexylmethyl methacrylate, Cyclomer M-100: (manufactured by Daicel Chemical Industries, Ltd.)

M1310: urethane acrylate, Aronix M-1310 manufactured by Donga Synthetic Co., Ltd.

M1200: urethane acrylate, Aronix M-1200 manufactured by Donga Synthetic Co., Ltd.

M1600: urethane acrylate, ARONIX M-1600 manufactured by Donga Synthetic Co., Ltd.

ㆍ DBA: Anthracure UVS-1331: 9,10-dibutoxyanthracene (Kawasaki Gasase)

The obtained composition was evaluated according to the following test methods. The results are shown in Table 2.

Test Example 1 (25 占 폚 viscosity)

The viscosity of the active energy ray-curable adhesive composition at 25 캜 was measured using an E-type viscometer. Since the lower the viscosity at 25 DEG C is, the better the viscosity is measured at the time of applying the thin film in the coater.

○: less than 100 mPa · s

?: 100 to 200 mPa 占 퐏

X: exceeding 200 mPa 占 퐏

Test Example 2 (Model test of polarizer production)

For the production of a polarizing plate, the following model test was conducted using triacetyl cellulose as a hydrophilic plastic as a base material of the adhesion test on the assumption that a polarizer and a protective layer, which are hydrophilic plastics, were bonded.

(T peel strength)

A UV absorber having a thickness of 80 占 퐉 was subjected to corona treatment (Polydyne 1 produced by Nautas Co., Ltd., output 0.1 kW, Processing speed 1 second / cm).

Thereafter, the above-obtained composition was applied on the film to a thickness of 5 탆 by a bar coater. Then, the same corona-treated FTAC was laminated and cured at a conveyer speed of 5 m / min using a metal halide lamp (30 cm from the focal distance) of a 160 W / cm light focusing type to produce a test chain laminate film. The ultraviolet intensity was 150 mW / cm 2, and the accumulated light quantity was 400 mJ / cm 2 (all values at 365 nm).

After the obtained test piece was allowed to stand at room temperature for 30 minutes or longer, the peel strength was measured by a tensile tester (Instron 5564 manufactured by Instron Japan Co., Ltd.) under the following conditions (initial peel strength). The results are shown in Table 2.

Test piece: 25 mm x 100 mm

ㆍ Test method: T-peeling

Peeling speed: 200 mm / min

Next, the obtained test piece was subjected to a high-temperature test and a high-humidity test under the following conditions, and then the peel strength was measured under the same conditions and conditions as those described above. The results are shown in Table 2.

ㆍ After high temperature test: 96 hours at 85 ℃

ㆍ After high humidity test: 96 hours at 60 ℃, 90% RH

It was evaluated that the value of the peel strength was better than 1 N / 25 mm and that the test piece was more excellent in the case where the material was broken (indicated as "rupture" in Table 2) without peeling.

Test Example 3 (dark reaction inhibiting property)

T peeling strength test was carried out from film lamination to UV curing. The film was cut into a width of 50 mm and a length of 100 mm, and was attached to a 3-inch paper tube using Cellotape (registered trademark). After that, the film was left to stand at room temperature for 24 hours, and then the film was peeled off and placed on a horizontal desk to observe the appearance of the film. If the dark reaction is likely to proceed, the warp height of the film end portion becomes large because the shape of the wound core tube remains. The bending height of the end portion of the film 4 corner was measured by regular measurement, and the average value (mm) was used as an index of the anti-darkness property. The smaller the better.

Table 2 shows the above results.

Test Example 1 Test Example 2 Test Example 3 25 ℃ Viscosity T peel strength (N / 25 mm) Dark reaction
Inhibitory
(Mm) (mPa 占 퐏) Judgment Early After 85 ° C × 96 hours 60 [deg.] C / 90% RH x 96 hours later Example 1 26 ○ 1.25 Repatriation Repatriation 26 Example 2 31 ○ Repatriation Repatriation Repatriation 25 Example 3 77 ○ Repatriation Repatriation Repatriation 23 Example 4 15 ○ Repatriation Repatriation Repatriation 0 Example 5 56 ○ Repatriation Repatriation Repatriation 0 Example 6 69 ○ Repatriation Repatriation Repatriation 0 Example 7 71 ○ Repatriation Repatriation Repatriation 0 Example 8 60 ○ Repatriation Repatriation Repatriation 24 Example 9 50 ○ Repatriation Repatriation Repatriation 0 Example 10 45 ○ 3.31 Repatriation Repatriation 0 Comparative Example 1 56 ○ 0.21 0.35 0.87 0 Comparative Example 2 18 ○ 0.13 0.54 0.76 0 Comparative Example 3 58 ○ 1.81 2.19 0.03 0 Comparative Example 4 30 ○ 0.50 0.89 0.02 0 Comparative Example 5 28 ○ 0.45 0.97 0.03 0

The composition of the present invention was low in viscosity, excellent in initial peel strength, and excellent in peel strength after high temperature test and high humidity test.

On the contrary, the composition of Comparative Example 1 which does not contain components (B) and (D) of the present invention (Comparative Example 1), the composition which does not contain the component (A) of the present invention 2), and the photo-radical type composition (Comparative Example 2) containing no components (A) and (C) of the present invention had insufficient initial peel strength and peel strength after high humidity test.

Industrial availability

The composition of the present invention can be used as an adhesive such as various plastic films, among others, as an adhesive such as a hydrophilic plastic. Particularly, it can be most suitably used for the production of an optical film such as a liquid crystal display device, particularly, a polarizing plate.

Claims (14)

A composition comprising a curable component and a polymerization initiator,
Component (A): a compound having at least two epoxy groups and an aromatic ring skeleton in the molecule (10 to 80% by weight in the curable component); (B) component: component (b1); A compound having one ethylenic unsaturated group and an aromatic ring skeleton or alicyclic skeleton and (b2) component; (20 to 89% by weight in the curing component) having one ethylenic unsaturated group in the molecule including a compound having one ethylenic unsaturated group and a hydroxyl group and (E) a compound having two or more ethylenically unsaturated groups in the molecule 1 to 20% by weight in the composition)
[Note that the ratio of the components (A), (B) and (E) means the ratio of the total amount thereof to 100% by weight.)
Further, it is preferable that the cationic polymerizable compound is substantially free of a cationic polymerizable compound having a (meth) acryloyl group,
Wherein the polymerization initiator comprises (C): a photocationic polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components) and (D): a photoradical polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components)
An active energy ray curable adhesive composition for a plastic film or sheet.
The method according to claim 1,
(B) is a component (b1); A compound having one ethylenic unsaturated group and an aromatic ring skeleton or alicyclic skeleton and (b2) component; A compound having one ethylenic unsaturated group and a hydroxyl group at a weight ratio of 80:20 to 10:90
An active energy ray curable adhesive composition for a plastic film or sheet.
3. The method according to claim 1 or 2,
(E) comprises a polyalkylene glycol di (meth) acrylate.
An active energy ray curable adhesive composition for a plastic film or sheet.
3. The method according to claim 1 or 2,
The composition further contains (F) a silane coupling agent in a proportion of 0.1 to 20% by weight
An active energy ray curable adhesive composition for a plastic film or sheet.
3. The method according to claim 1 or 2,
One or both of the plastic film or sheet is a hydrophilic plastic
An active energy ray curable adhesive composition for a plastic film or sheet.
3. The method according to claim 1 or 2,
When the plastic film or sheet is a polyvinyl alcohol polarizing film
An active energy ray curable adhesive composition for a plastic film or sheet.
A film or sheet made of a plastic, a cured product of the composition according to any of claims 1 or 2, and other substrates, or a film or sheet made of plastic
Laminates.
A film or sheet made of a plastic, a cured product of the composition according to any of claims 1 or 2, and other substrates, or a film or sheet made of plastic
Polarizer.
A process for producing an active energy ray-curable adhesive composition for a plastic film or sheet,
(A): a compound having at least two epoxy groups and an aromatic ring skeleton in the molecule (10 to 80% by weight in the curable component); (B) component: component (b1); A compound having one ethylenic unsaturated group and an aromatic ring skeleton or alicyclic skeleton and (b2) component; (20 to 89% by weight in the curing component) having one ethylenic unsaturated group in the molecule including a compound having one ethylenic unsaturated group and a hydroxyl group and (E) a compound having two or more ethylenically unsaturated groups in the molecule 1 to 20% by weight in the composition)
[Note that the ratio of the components (A), (B) and (E) means the ratio of the total amount thereof to 100% by weight.)
Further, a curable component that does not substantially contain a cationic polymerizable compound having a (meth) acryloyl group,
(C): A polymerization initiator comprising a photocationic polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components) and (D): a photoradical polymerization initiator (0.1 to 20% by weight based on the total amount of the curable components) .
Wherein at least one of the two substrates is a plastic film or sheet, which is adhered using the composition according to claim 1 or 2, and is irradiated with an active energy ray.
Wherein at least one of the two substrates is a plastic film or sheet, and the active energy ray is irradiated to the two substrates using the composition as described in claim 1 or 2. delete delete delete