JP5516163B2 - Active energy ray-curable adhesive composition - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition capable of bonding various substrates, particularly plastic films or sheets, by irradiation with active energy rays such as electron beams or ultraviolet rays. The composition of the invention is suitably used for the adhesion of thin-layer adherends including plastic films or sheets, and further suitably used for the production of various optical films or sheets used for liquid crystal display elements and the like. And can be used in these technical fields.
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 and a thin-layer adherend made of another material are bonded together, 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. . In addition, the composition has a drawback in that it is difficult to form a single solution because the urethanization reaction of a hydroxyl group and an isocyanate group proceeds after mixing the two solutions, and the viscosity is increased by increasing the molecular weight.
On the other hand, the active energy ray-curable adhesive composition has a high curing rate and is excellent in productivity because it can be made into one liquid, 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. 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 triacetylcellulose are particularly used. These plastics contain a hydroxyl group and are characterized by being very hydrophilic compared to ordinary plastics.

  In Patent Document 1, (A) 5 to 30% by mass of urethane (meth) acrylate having a molecular weight of 4000 or less for adhering a hydrophobic resin and a hydrophilic resin, (B) 60 to 95% by mass of a radical polymerizable compound, (C) The radiation curable liquid resin composition for adhesives which consists of 0.1-10 mass% of photoinitiators is disclosed.

  Patent Document 2 discloses a photocurable adhesive composition for bonding a polyvinyl alcohol polarizing film and a thermoplastic norbornene resin film, wherein the photocurable adhesive composition is (a) urethane. 30 to 50% by weight of (meth) acrylate, (b) 13 to 40% by weight of hydroxyalkyl (meth) acrylate and (c) 0 to 30% by weight of acrylamide derivative, and (b) hydroxyalkyl (meth) acrylate and (C) A photocurable adhesive composition in which the total amount of acrylamide derivatives is 20 to 60% by weight is disclosed.

  Patent Document 3 discloses a urethane (meth) acrylate obtained from a polyisocyanate, a polyol and a hydroxyl group-containing (meth) acrylate, a substrate penetrating monomer and a photopolymerization initiator that are permeable to a polarizing plate protective film. An adhesive for a polyvinyl alcohol polarizing plate is disclosed.

  Patent Document 4 discloses a urethane (meth) acrylate obtained from polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a polyol (meth) acrylate obtained from a polyol and a hydroxyl group-containing (meth) acrylate or a hydroxyl group-containing (meth) acrylate. An adhesive for a polarizing plate containing is disclosed.

JP 2007-169580 A (Claims) JP 2007-177169 A (Claims) JP 2008-063527 A (Claims) JP 2008-250260 A (Claims) Japanese Patent Application No. 2009-105659

  However, when a plastic film or the like is bonded with the adhesive composition described in the above patent document, the adhesive may be insufficient. More specifically, there was a problem that the laminate was peeled off under high temperature and high humidity conditions. The invention described in Patent Document 4 was excellent in adhesive properties, but peeling occurred in a more severe hot water resistance test.

  The inventors of the present invention have an active energy ray-curable composition that excels in adhesives to various substrates, and further has an adhesive force to plastic films and the like, particularly hydrophilic plastic films and the like, under high temperature and high humidity conditions. In the water test, in order to find an active energy ray-curable adhesive composition excellent in adhesiveness, intensive studies were conducted.

As a result, the present inventors have found that the active energy ray-curable adhesive composition comprising a compound having an ethylenically unsaturated group and an isocyanate group adheres to various substrates, particularly plastic films, particularly hydrophilic plastic films. It has been found that the adhesive laminate is excellent in strength and does not cause peeling even under high temperature and high humidity conditions, and even in a hot water test (Patent Document 5).
However, the composition of Patent Document 5 is excellent in adhesive strength, particularly peel strength, but may be insufficient under more severe conditions, and the present invention aims to further improve this point. It is what.

As a result of various studies, the present inventors have found that a composition in which an ethylenically unsaturated compound having a maleimide group is further blended with a compound having an ethylenically unsaturated group and an isocyanate group has a peel strength in addition to the above performance. The present invention was completed by finding out that it would be superior.
Hereinafter, the present invention will be described in detail.

The composition of the present invention has high adhesion to various substrates. Furthermore, the composition of the present invention can maintain excellent adhesion to plastic films and the like, particularly hydrophilic plastic films and the like under high temperature and high humidity conditions, and even in a hot water test, and has a peel strength. It will be better.
Therefore, the composition of the present invention is effective for adhesion of thin-layer adherends such as various plastic films, and can be suitably used for the production of optical films used particularly for liquid crystal display devices.

The present invention includes (A) a compound having an ethylenically unsaturated group and an isocyanate group [hereinafter referred to as “component (A)”], (B) a compound having an ethylenically unsaturated group other than a maleimide group and a maleimide group , “Component (B)”, and (C) a compound having one or more ethylenically unsaturated groups other than the components (A) and (B), which is reactive with the isocyanate group of component (A). The present invention relates to an active energy ray-curable adhesive composition containing a compound that does not contain [hereinafter referred to as “component (C)”].
Hereinafter, the essential components (A) to (C) will be described.

1. Ingredients
1-1. (A) component (A) A component is a compound which has an ethylenically unsaturated group and an isocyanate group.

Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group, and a (meth) acryloyl group is preferable in terms of easy production.
As the number of ethylenically unsaturated groups in the component (A), there are one compound and one or more compounds, and one ethylenically unsaturated group is used because it is easy to control the adhesion of the cured product. The compound which has is preferable.

  As the number of isocyanate groups in the component (A), there are a compound having one and a compound having two or more, and a compound having one isocyanate group is preferable because the storage stability of the viscosity of the composition is excellent.

In the component (A), examples of the skeleton connecting the ethylenically unsaturated group and the isocyanate group include various ones as long as they can bond the ethylenically unsaturated group and the isocyanate group, and include, for example, a hetero atom. And a saturated hydrocarbon skeleton (an alkylene skeleton, an oxyalkylene skeleton, etc.), an aromatic hydrocarbon skeleton, and the like.
As the component (A), any of a low molecular weight compound and a high molecular weight compound can be used.

In the component (A), specific examples of the low molecular weight compound include the following compounds.
As a compound having one ethylenically unsaturated group and one isocyanate group, examples of the compound in which these two groups are linked by an alkylene skeleton include (meta) such as 2- (meth) acryloyloxyethyl isocyanate. ) Acryloyloxyalkyl isocyanate and the like, and examples of compounds in which these two groups are linked by an oxyalkylene skeleton include (meth) acryloyloxyalkoxyalkyl isocyanates such as 2- (meth) acryloyloxyethoxyethyl isocyanate, and Examples of the compound in which these two groups are linked by an aromatic hydrocarbon skeleton include 2- (meth) acryloyloxyphenyl isocyanate.
As a compound having one isocyanate group having two ethylenically unsaturated groups, examples of compounds in which these two groups are linked by a branched saturated hydrocarbon skeleton include 1,1-bis [(meta ) Acrylyloxymethyl] ethyl isocyanate.

Moreover, as (A) component, the reaction material of polyisocyanate and a hydroxyl-containing (meth) acrylate is mentioned.
Examples of the polyisocyanate include diisocyanate and triisocyanate.
Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate and naphthalene diisocyanate; isophorone diisocyanate, 4,4 ′. -Cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate, norbornene diisocyanate and hydrogenated xylene diisocyanate.
Examples of the triisocyanate include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.
In the case of a reaction product of a polyisocyanate and a hydroxyl group-containing (meth) acrylate, the reaction ratio of the polyisocyanate and the hydroxyl group-containing (meth) acrylate can be varied as long as the (meth) acryloyl group and the isocyanate are present in the reaction product. In terms of molar ratio, (hydroxyl group in hydroxyl group-containing (meth) acrylate) :( total of isocyanate groups in polyisocyanate) = 1: 1.2 to 1: 4.0 is preferable.

Examples of the high molecular weight compound in the component (A) include polymers of hydroxyalkyl (meth) acrylate and diisocyanate.
The said compound is marketed, BASF LamarerLR9000 etc. which are a polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate are mentioned.

As described above, the molecular weight of the component (A) can be used from a low molecular weight material to a high molecular weight material. However, the composition can have a low viscosity and is low in terms of excellent curability of the composition. Molecular compounds are preferred.
That is, in a compound having one ethylenically unsaturated group and one isocyanate group, a compound in which these two groups are linked by an alkylene skeleton, a compound in which these two groups are linked by an oxyalkylene skeleton, and , A compound in which these two groups are linked by an aromatic hydrocarbon skeleton, and more specifically, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxyethoxyethyl isocyanate and 2- ( (Meth) acryloyloxyphenyl isocyanate is preferred.

As the component (A), among these compounds, the composition becomes liquid without crystallizing, and (meth) acryloyloxyalkyl isocyanate is used because there is no deformation of the substrate due to heat generation during curing. Is preferred.
(A) A component can use only 1 type and can also use 2 or more types together.

1-2. Component (B) The component (B) is a compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group.
The maleimide group in component (B) is preferably a group represented by the following general formula (1).

[However, in General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R ¹ and R ² are combined to form 5 or The hydrocarbon group which forms a 6-membered ring is represented. ]

As the alkyl group, an alkyl group having 4 or less carbon atoms is preferable.
As the alkenyl group, an alkenyl group having 4 or less carbon atoms is preferable.
A phenyl group etc. can be mentioned as an aryl group.
Examples of the hydrocarbon group that forms a 5-membered ring or 6-membered ring together include a group —CH ₂ CH ₂ CH ₂ —, a group —CH ₂ CH ₂ CH ₂ CH ₂ — and the like, and an unsaturated hydrocarbon. Examples of the group include a group —CH═CHCH ₂ — and a group —CH ₂ CH═CHCH ₂ —. In the unsaturated hydrocarbon group, in order for the maleimide group to undergo a dimerization reaction, it is necessary to select a finally obtained 5-membered or 6-membered ring having no aromaticity. The hydrocarbon group is preferably a saturated hydrocarbon group.

  Preferred specific examples of the maleimide group in the general formula (1) are shown in the following formulas (3) to (8). In the formula (7), X represents a chlorine atom or a bromine atom. Moreover, Ph in Formula (8) represents a phenyl group.

As R ¹ and R ² , one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R ¹ and R ² are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle Saturated hydrocarbon groups are preferred.

  Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group, and a (meth) acryloyl group is preferable in terms of easy production.

Examples of the component (A) include compounds in which an ethylenically unsaturated group and a maleimide group are bonded to a skeleton such as an ether skeleton, an ester skeleton, or a urethane skeleton.
As the component (A), maleimide (meth) acrylate represented by the following general formula (2) is preferable because it can be easily produced.

[However, in General formula (2), R < ¹ > and R < ² > is synonymous with said Formula (1). R ³ represents a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]

  Among the compounds represented by the general formula (2), compounds represented by the following general formulas (9) to (11) are more preferable, and a compound represented by the following general formula (9) is particularly preferable.

[However, in the general formula (9), R ⁴ and R ⁵ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6. ]

[However, in the general formula (10), R ⁴ and R ⁵ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6. ]

[However, in the general formula (11), R ⁴ and R ⁵ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6. ]

1-3. Component (C) Component (C) is a compound having one or more ethylenically unsaturated groups other than the components (A) and (B) and having no reactivity with the isocyanate group of component (A). It is.
As the component (C), various compounds can be used as long as they are compounds other than the components (A) and (B) and have no reactivity with the isocyanate group of the component (A). Specifically, any compound having no hydroxyl group or acidic group and having an ethylenically unsaturated group is optional.

(C) As an ethylenically unsaturated group in a component, the group similar to what was illustrated by the said (A) component is mentioned.
(C) A component can use only 1 type and can also use 2 or more types together.
(C) As a component, a monomer, an oligomer, and a polymer can be mentioned.

1-3-1. Examples of monomer monomers include vinyl compounds and allyl compounds as examples of compounds having a vinyl group as an ethylenically unsaturated group, and examples of compounds having a (meth) acryloyl group as an ethylenically unsaturated group include: Examples include (meth) acrylamide, (meth) acrylate, (meth) acrylic acid, and (meth) acryloylmorpholine.

Examples of vinyl compounds include styrene, vinyl toluene, N-vinyl formamide, N-vinyl pyrrolidone and N-vinyl caprolactone.
Examples of allyl compounds include allyl alcohol.

  As (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like can be mentioned.

  As (meth) acrylate, a compound having one (meth) acryloyl group (hereinafter referred to as monofunctional (meth) acrylate) and a compound having two or more (meth) acryloyl groups (hereinafter referred to as polyfunctional (meth) acrylate). ).

  Monofunctional (meth) acrylates include alkyl (meth) acrylates such as isooctyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclo Alicyclic (meth) acrylates such as pentenyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethylhexyl carbitol Alkoxy such as (meth) acrylate and ethoxyethoxyethyl (meth) acrylate; Aromatic (meth) acrylates of acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N- (meth) acryloyloxyethyl tetrahydrophthalimide and N- (meth) acryloyloxyethylhexa And hydrophthalimide.

Polyfunctional (meth) acrylates include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxypivalic acid Di (meth) acrylate, alkylene oxide modified neopentyl glycol di (meth) acrylate, alkylene oxide modified 1,6-hexanediol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, dicyclopentanyl di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, C2-C5 aliphatic modified dipentaerythritol penta (meth) acrylate, C2-C5 aliphatic modified dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl ] Isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate and the like.
In addition to these, compounds such as those described in pages 53 to 56 of the document “Latest UV Curing Technology” [Printing Information Association, 1991] are listed.

1-3-2. Examples of the oligomer include urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, and polyether (meth) acrylate oligomer.

  The urethane (meth) acrylate oligomer is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

  Examples of the polyol include a low molecular weight polyol, a polyether polyol, a polycarbonate polyol, and a polyester polyol.

Examples of the low molecular weight polyol include polyols having at least two hydroxyl groups having a molecular weight of about 50 to 300, and specific examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, and 1,6-hexanediol. 2-methyl-1,8-octanediol, nonanediol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, and the like.
Examples of the polyether polyol include polyalkylene glycol having 3 or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polycarbonate polyol include a reaction product of carbonate and diol. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the diol include the low molecular weight polyol described above.
Examples of the polyester polyol include a reaction product of at least one selected from the group consisting of these low molecular weight polyols, polyether polyols, and polycarbonate polyols with an acid component. Examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof. Moreover, the ring-opening reaction product of polycarbonate diol and caprolactone is also mentioned.

Examples of the organic polyisocyanate include diisocyanate and triisocyanate.
Examples of the diisocyanate include aromatic diisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate and naphthalene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate, 4,4 ′. -Cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate, norbornene diisocyanate and hydrogenated xylene diisocyanate.
Examples of the triisocyanate include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. Among these, the resulting compound has a low viscosity and is easy to handle. Therefore, diisocyanate is preferable.

  Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and pentaerythritol tri, di or mono (meth) acrylate, And a reaction product of a polyol such as trimethylolpropane di or mono (meth) acrylate and (meth) acrylic acid. As the hydroxyl group-containing (meth) acrylate, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

The urethane (meth) acrylate oligomer may be a compound obtained by reacting a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate according to a conventional method.
Specifically, in the presence of urethanization such as dibutyltin dilaurate, if necessary, in the presence of a reaction solvent, a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate can be heated and stirred to be urethanized. it can.
In this case, even if the polyol, the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate are prepared all at once, after the polyol and the organic polyisocyanate are reacted to produce the isocyanate group-containing prepolymer, the hydroxyl group-containing (meth) It may be produced by adding acrylate.

As a weight average molecular weight of a urethane (meth) acrylate oligomer, 2,000-100,000 are preferable, More preferably, it is 20,000-60,000.
A urethane (meth) acrylate oligomer having a weight average molecular weight in the above preferred range is preferable because a cured product of the resulting composition is superior in peel strength.
In the present invention, the weight average molecular weight is a value obtained by converting the weight average molecular weight obtained by gel permeation chromatography into polystyrene.

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

Here, examples of the polyester polyol oligomer 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 the polyester poly (meth) acrylate other than these include compounds described on pages 74 to 76 of the above-mentioned document “UV / EB Curing Material”.

  The epoxy (meth) acrylate oligomer 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”. It is done.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adducts; phenol novolac type epoxy resin and cresol novolac Novolak type epoxy resins such as epoxy resin; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
In addition to these, Chapter 2 of the document “Epoxy Resin-Recent Advances” (published by Shosodo, 1990) and Appendix “Polymer Processing”, Vol. 9, Volume 22, Epoxy Resin [Polymer Publishing Society, Compounds published on pages 4 to 6 and pages 9 to 16 of "Showa 48".

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; polyglycerides such as diglycidyl ethers of polyethylene glycol and polypropylene glycol. Diglycidyl ether of alkylene glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di- or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct, and penta Polyglycerides of polyhydric alcohols such as di, tri or tetraglycidyl ethers of erythritol 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. Examples thereof include compounds as described on 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.

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

1-3-3. As the polymer polymer, a (meth) acrylic polymer having a (meth) acryloyloxy group, a (meth) acrylic polymer having a functional group, a (meth) acryloyl group introduced into the side chain, Examples thereof include compounds described on pages 78 to 79 of “UV / EB Curing Material”.

1-3-4. As a preferable compound (C) component, a urethane (meth) acrylate oligomer is preferable because it is excellent in adhesion, more specifically, peel strength among the above-described compounds . As described above, the urethane (meth) acrylate oligomer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 20,000 to 60,000.
As a ratio of the urethane (meth) acrylate oligomer in (C) component, 3 to 100 weight% is preferable in (C) component, and 3 to 60 weight part is more preferable.

  Moreover, the compound which has one ethylenically unsaturated group and a heterocyclic ring, and the compound which has one ethylenically unsaturated group and an amide group are preferable at the point which can improve the adhesive force with a plastic.

In the compound having one ethylenically unsaturated group and a heterocyclic ring, preferable heterocyclic rings include cyclic ether, morpholine, pyrrolidone, caprolactam, cyclic imide and the like.
Examples of the compound having a cyclic ether include tetrahydrofurfuryl (meth) acrylate, examples of the compound having morpholine include (meth) acryloylmorpholine, and examples of the compound having pyrrolidone include N-vinylpyrrolidone. Examples of the compound having caprolactam include N-vinylcaprolactam.

  Examples of the compound having one ethylenically unsaturated group and an amide group include N-vinylformamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide.

Among these compounds, it is preferable to use acrylate because it is more excellent in curability of the composition.
Furthermore, among acrylates, acryloylmorpholine, tetrahydrofurfuryl acrylate, and N-acryloyloxyethyl hexahydrophthalimide are preferable.

Moreover, it is preferable to mix | blend long chain alkyl (meth) acrylate or / and an aromatic monofunctional (meth) acrylate at the point which can provide water resistance to the hardened | cured material of a composition.
Examples of the long-chain alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 6 to 20 carbon atoms such as isooctyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
As aromatic monofunctional (meth) acrylate, phenyl (meth) acrylate, p-cumylphenyl (meth) acrylate, o-phenylphenyl (meth) acrylate, m-phenylphenyl (meth) acrylate, p-phenylphenyl (meth) Acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, p-phenylphenoxyethyl (meth) acrylate, etc. Is mentioned.

1-4. Other components In addition to the essential components (A) to (C), other components usually used in an adhesive composition can be blended with the composition of the present invention.

1-4-1. Photopolymerization initiator When the composition of the present invention is cured with visible light or ultraviolet light, it is preferable to incorporate a photopolymerization initiator (hereinafter referred to as component (D)).
In addition, when hardening the composition of this invention with an electron beam etc., it is not always necessary to mix | blend (D) component.

As component (D), benzyldimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-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-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methyl-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- ON, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, Adekaoptomer N-1414 (manufactured by Asahi Denka), phenyl Aromatic ketone compounds such as glyoxylic 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 Benzophenones such as (diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone Compound;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2, 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.
These compounds may be used alone or in combination of two or more.
Among these, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, 2-chlorothioxanthone, 2, 4-Diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone are preferable from the viewpoints of adhesive strength, heat resistance, and storage stability.

When adhering a base material containing an ultraviolet absorber, it is preferable to use a photopolymerization initiator having absorption on the long wavelength side (400 nm or more). In particular, a protective film for a polarizer often contains an ultraviolet absorber, and therefore can be preferably used for the production of a polarizing plate.
Specific examples of the compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2- (4-methyl-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, acylphosphinoxide compounds, thioxanthone compounds, and the like.

  These photopolymerization initiators can be used alone, and in order to further increase the reactivity, photopolymerization of aliphatic amines or aromatic amines such as diethylaminophenone, dimethylaminobenzoic acid ethyl, dimethylaminobenzoic acid isoacyl is initiated. It can also be added as an auxiliary agent.

(D) As a mixture ratio of a component, 0.01 to 10 weight% is preferable in a composition, More preferably, it is 0.1 to 5 weight%.
By setting the blending ratio of the component (D) to 0.01% by weight or more, the composition can be cured with an appropriate amount of ultraviolet light, and the productivity can be improved. The cured product is excellent in weather resistance and transparency.

1-4-2. Specifically, other components other than the component (D) include inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifier resins, leveling agents, antifoaming agents, plasticizers. Inactive ingredients such as agents, dyes, pigments, treating agents and UV blockers can be incorporated.
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.
Moreover, a silane coupling agent can also be mix | blended in order to improve adhesiveness with a base material.
Further, when the curability of the composition is insufficient, a urethanization catalyst can be blended. Examples of the urethanization catalyst include metal catalysts and amine catalysts. Examples of the metal-based catalyst include a tin-based catalyst, an iron-based catalyst, and a zinc-based catalyst, and examples of the tin-based catalyst include dibutyltin dilaurate. Examples of the amine catalyst include primary amines such as alkylamines and (dialkylamino) alkylamines, secondary amines such as dialkylamines, dialkoxyalkylamines and diallylamines, tertiary amines such as trialkylamines and DABCO, and the like. .
These are preferably blended in an amount of 100 parts by weight or less with respect to 100 parts by weight of the total of components (A) to (C).

2. Energy ray curable adhesive composition TECHNICAL FIELD This invention relates to the active energy ray curable adhesive composition which contains the said (A)-(C) component as an essential component.
As a manufacturing method of a composition, it can manufacture by stirring and mixing said (A)-(C) component and another component as needed according to a conventional method.
Since the component (A) is easily decomposed by water or the like, the obtained composition may have insufficient storage stability. In this case, there is a method in which a composition containing the components (B) and (C) is first produced in advance, and the component (A) is added to the composition immediately before use, followed by stirring and mixing. preferable.

  As a blending ratio of the components (A) to (C), in the total amount of the components (A) to (C), the component (A) is 5 to 50% by weight, the component (B) is 5 to 50% by weight, and (C). The component is preferably 20 to 90% by weight. By making the proportion of the component (A) 5% by weight or more, the adhesive strength of the adherend at a high temperature can be improved, and on the other hand, by making it 50% by weight or less, the viscosity of the composition The storage stability of can be improved. Moreover, the impact resistance of a to-be-adhered thing can be made favorable by the ratio of (B) component being 5 to 50 weight%. Moreover, the base-material permeability at the time of coating of a composition can be made favorable by the ratio of (C) component being 20 weight% or more.

  As a viscosity of a composition, 10-1000 mPa * s is preferable at the point which is excellent in the coating property with respect to a base material.

3. Method of Use The method of using the composition of the present invention may be a conventional method, such as a method in which the composition is applied to a substrate and then bonded to another substrate and irradiated with active energy rays.

The composition of the present invention can be used for adhesion of various substrates.
Examples of the substrate include plastic, paper, and metal.
Examples of the plastic 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, chlorinated polypropylene and the like.
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, curtain coater and the like.
Moreover, what is necessary is just to select the application | coating thickness of the composition of this invention according to the base material to be used and a use, However, Preferably it is 0.1-100 micrometers, More preferably, it is 1-25 micrometers.

Examples of the active energy ray include 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. What has the energy of 1000 eV is preferable, More preferably, it is 100-300 eV.

3-1. Adhesion of Plastic Film, etc. The composition of the present invention can be suitably used for adhesion between plastic films and the like, adhesion of plastic films and the like to various other substrates (hereinafter referred to as other substrates), It can be suitably used as an active energy ray-curable adhesive composition for plastic films or sheets.
In the following description, when simply described as “base material”, it means a general term for plastic films and the like and other base materials.
Other examples of the substrate include paper and metal.

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 suitably used for bonding plastic films and the like, and can be suitably used for hydrophilic plastics.
Hydrophilic plastic in the present invention, moisture permeability 200g / m ² · 24hr or more in thickness 100 [mu] m (in particular, 200 to 2000 g / m about ² · 24 hr or) means a plastic with.
Specific examples of hydrophilic plastics include plastics produced by molding and processing polymers containing hydrophilic sites such as hydroxyl groups, carboxyl groups, phosphate groups, sulfonate groups, amino groups and amide bonds. Can do. Preferable examples of the polymer containing a hydrophilic part include polyvinyl alcohol, triacetyl cellulose, polyvinyl acetal, polyamide and the like.
In addition, it is also possible to use a polymer which has been subjected to hydrophilic treatment after molding a polymer having no hydrophilic portion. Specifically, a plastic or the like in which a hydrophilic group is introduced into a polymer having no hydrophilic portion by corona treatment, plasma treatment, flame treatment, primer treatment of a hydrophilic portion-containing polymer, or the like can be given. Preferable specific examples include polyethylene terephthalate primer-treated with polyamide.
As the hydrophilic plastic, a plastic produced by molding a polymer containing a hydrophilic part is preferable, and polyvinyl alcohol and triacetyl cellulose are more preferably used as the polymer containing a hydrophilic part.

  Further, 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.

Adhesion of a plastic film or the like is not limited to a flat state, but can be performed in a curved state.
That is, a method of bending a plastic film or the like into a concave state or a convex state, applying the composition of the present invention in this state, bonding the other plastic film or the like, and irradiating with an active energy ray for adhesion. It is done.
As another method, the composition of the present invention is applied in a flat state on a plastic film or the like, the other plastic film or the like is bonded together, bent into a concave state or a convex state, and irradiated with active energy rays to be bonded. A method is mentioned.
What is necessary is just to follow an above-described method as a method of coating a composition in a planar state. Examples of the method for applying the composition in a curved surface include a method using a spray coater, a bar coater, a micro gravure 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 this 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 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 film in which a retardation film is bonded to a polarizer or a polarizing plate, or a film having a retardation function is formed by coating.

3-2. 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 bonding 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, polyether sulfone 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, ring-opening polymers of cyclic olefins, addition polymers of cyclic olefins, random copolymers of cyclic olefins and α-olefins such as ethylene and propylene, and these are modified with unsaturated carboxylic acids or their derivatives. 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 processed for orientation and fixation, "WV film" (Fuji Photo Film Co., Ltd.), "LC film", "NH film" (Both made by Nippon Oil Corporation).

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 step of applying the composition of the present invention to any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film as an adherend.
[2] A step of laminating one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film as the other adherend to the film coated with the composition
[3] After bonding the film, when the process protective film or retardation film that irradiates the active energy ray through the substrate coated with the composition of the present invention is bonded only to one side, the polarization is performed according to the above procedure. A plate or a polarizing plate with a retardation film can be produced, but when pasting on both sides, [1] [2] may be repeated twice and then [3] may be carried out. 2] [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.
Also in this case, it can be bonded in a curved state as described above.

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, [3] may be performed after repeating [1] [2] three times, or [1] [2] [3] may be repeated three times.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “parts” means parts by weight.

○ Production Example 1 [Production of component (C)]
In a 500 mL reaction vessel equipped with a stirrer, 24 g (0.11 mol) of isophorone diisocyanate (hereinafter referred to as IPDI), 198 g of isobornyl acrylate as a diluent, 0.16 g of dibutyltin dilaurate (hereinafter referred to as DBTDL) as a catalyst, 0.10 g of 2,6-di-t-butyl-4-methylphenol (hereinafter referred to as BHT) was added as a polymerization inhibitor, and the liquid temperature was kept under stirring in an atmosphere of nitrogen containing 5% by volume of oxygen. Was heated to 70 ° C.
169 g (0.086 mol) of polyester polyol (P-2010, Kuraray Co., Ltd., esterified product of adipic acid and 3-methyl-1,5-pentanediol) having a hydroxyl value of 57 mgKOH / g was added to the reaction solution for 2 hours. It was dripped over. The internal temperature was raised to 80 ° C. and the reaction was further continued for 2 hours. Then, 0.67 g (0.011 mol) of ethylene glycol was added and further 2 hours, and 4.46 g of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was added. 038 mol) was added, and the mixture was further reacted for 2 hours. The spectrum was measured by an infrared absorption spectrum apparatus (FT-IR Spectrum 100 manufactured by Perkin Elmer), and it was confirmed that the isocyanate group was completely consumed.
As a result of measuring the obtained urethane acrylate by gel permeation chromatography (solvent: tetrahydrofuran, column: HSPgel HR MB-L manufactured by Waters), Mw in terms of polystyrene was 34,000.

○ Production Example 2 [Production of Component (C)]
A 500 mL reaction vessel equipped with a stirrer was charged with 20.5 g (0.092 mol) of IPDI, 0.044 g of BHT as a polymerization inhibitor, and 0.035 g of DBTDL as a catalyst, and nitrogen containing 5% by volume of oxygen. While stirring them, the solution was heated to 70 ° C. under an atmosphere.
To the reaction solution, 150 g (0.074 mol) of a polyether polyol (EXCENOL2020 manufactured by Asahi Glass Co., Ltd.) having a hydroxyl value of 55 mgKOH / g was added dropwise over 2 hours. The internal temperature was raised to 80 ° C. and the reaction was further continued for 2 hours, and 5.14 g (0.044 mol) of HEA was added and the reaction was continued for another 2 hours. The spectrum was measured in the same manner as in Production Example 1 to confirm that the isocyanate groups were completely consumed.
As a result of measuring the obtained urethane acrylate in the same manner as in Production Example 1, the Mw in terms of polystyrene was 42,000.

○ Examples 1 to 3 and Comparative Examples 1 to 4
The components (B) to (D) shown in Table 1 below are dissolved by heating and stirring at 60 ° C. for 1 hour. After cooling to room temperature, the component (A) is added, and stirring is further performed for 30 minutes to cure the active energy ray. A mold adhesive composition was produced.
The viscosity of the resulting composition was measured with an E-type viscometer at 25 ° C.

・ Manufacture of film laminate (model experiment for manufacturing polarizing plate)
The obtained composition was applied to a polyvinyl acetate film (Solbron EF # 30, manufactured by Aicello, hereinafter referred to as PVA film) to a thickness of 3 μm by a bar coater, and a triacetyl cellulose film (Lonza, thickness 100 μm, hereinafter referred to as TAC). Film). The composition was similarly applied to the PVA film side of this laminate, and a TAC film was laminated. From both sides of this laminate, using a 160 W / cm condensing metal halide lamp (30 cm from the focal length), the composition is cured by irradiating ultraviolet rays under the condition of a conveyor speed of 5 m / min, and a film laminate is obtained. Obtained.
About the obtained laminated body, the water immersion test and the peeling strength measurement were performed according to the following test method. The results are shown in Table 2.

[60 ° C water immersion test]
The obtained film laminate was cut into a width of 20 mm and a length of 50 mm, and immersed in flowing water at 60 ° C. for 3 hours to confirm the presence or absence of peeling of the film.

[Peel strength measurement]
The obtained film laminate was cut into a width of 25 mm and a length of 100 mm, and a peeling test (peeling speed 100 mm / min) was performed under the condition of 25 ° C.

The abbreviations in Table 1 mean the following.
AOI: 2-acryloyloxyethyl isocyanate, Karenz AOI manufactured by Showa Denko K.K.
M145: a compound represented by the following formula (9), Aronix M-145 manufactured by Toagosei Co., Ltd.

THFA: Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. Biscoat # 150
POA: 2-phenoxyethyl acrylate, light acrylate PO-A manufactured by Kyoeisha Chemical Co., Ltd.
ACMO: acryloylmorpholine IBXA: isobornyl acrylate UA1: polyester urethane acrylate UA2 obtained in Production Example 1: polyether urethane acrylate obtained in Production Example 2 M240: polyethylene glycol diacrylate, Aronix M manufactured by Toagosei Co., Ltd. -240
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Darocur TPO manufactured by Ciba Japan Co., Ltd.

The compositions of Examples 1 to 3 corresponding to the composition of the present invention did not peel off after the 60 ° C. water immersion test, and were excellent in peel strength.
On the other hand, the composition of Comparative Example 1 that does not contain the component (A) and the component (B) of the present invention was peeled after the 60 ° C. water immersion test and further had insufficient peel strength.
Further, the composition of Comparative Example 2 which does not contain the component (B) of the present invention was peeled off at the end after the 60 ° C. water immersion test, and the peel strength was insufficient. The compositions of Comparative Examples 3 and 4 (corresponding to the invention of Patent Document 5) that do not contain the component (B) of the present invention but contain urethane acrylate oligomers (corresponding to the invention of Patent Document 5) do not peel off at the end after the 60 ° C. water immersion test. However, the peel strength was insufficient compared to the examples.

  The composition of the present invention can be used as an adhesive for various substrates, preferably as an adhesive for plastic films and the like, and particularly as an adhesive for hydrophilic plastics and the like. In particular, the composition of the present invention can be suitably used for the production of optical films such as liquid crystal display devices, particularly for the production of polarizing plates.

Claims (17)

(A) Compound having ethylenically unsaturated group and isocyanate group, (B) Compound having ethylenically unsaturated group other than maleimide group and maleimide group, and (C) 1 other than components (A) and (B) An active energy ray-curable adhesive composition comprising a compound having at least one ethylenically unsaturated group and having no reactivity with the isocyanate group of component (A). The active energy ray-curable adhesive composition according to claim 1, wherein the component (A) is a compound having one ethylenically unsaturated group and one isocyanate group. The active energy ray-curable adhesive composition according to claim 2, wherein the component (A) is (meth) acryloyloxyalkyl isocyanate. The maleimide group in (B) component is group represented by following General formula (1), The active energy ray hardening-type adhesive composition in any one of Claims 1-3.

[However, in General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R ¹ and R ² are combined to form 5 or The hydrocarbon group which forms a 6-membered ring is represented. ] The active energy ray-curable adhesive composition according to claim 4, wherein the component (B) is a compound represented by the following general formula (2).

[However, in General formula (2), R < ¹ > and R < ² > is synonymous with said Formula (1). R ³ represents a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ] The active energy ray hardening-type adhesive composition in any one of Claims 1-5 in which (C) component contains a urethane (meth) acrylate oligomer. The urethane (meth) acrylate oligomer is a weight average molecular weight 20,000 to 60,000 according to claim 6 active energy ray-curable adhesive composition. The active energy ray hardening-type adhesive composition in any one of Claims 1-7 in which (C) component contains the compound which has one ethylenically unsaturated group and a heterocyclic ring. 5 to 50% by weight of component (A), 5 to 50% by weight of component (B) and 20 to 90% by weight of component (C) based on the total amount of components (A) to (C). The active energy ray hardening-type adhesive composition in any one of Claims 1-8. (D) The active energy ray hardening-type adhesive composition in any one of Claims 1-9 which further contains a photoinitiator. The active energy ray hardening-type adhesive composition of Claim 10 which contains 0.01-10 weight% of (D) component in a composition. The active energy ray hardening-type adhesive composition for plastic films or sheets containing the composition in any one of Claims 1-11. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 12, wherein either one or both of the plastic film or sheet is a hydrophilic plastic. The active energy ray hardening-type adhesive composition for polarizing plate manufacture containing the composition in any one of Claims 1-11. (B) a compound having an ethylenically unsaturated group other than a maleimide group and a maleimide group, and (C) a compound having one or more ethylenically unsaturated groups other than the components (A) and (B) ( The manufacturing method of the active energy ray hardening-type adhesive composition which manufactures the mixture of the compound which does not have a reactivity with A) component, and mix | blends the compound which has (A) ethylenically unsaturated group and an isocyanate group at the time of use. A laminate comprising a plastic film or sheet, a cured product of the composition according to any one of claims 1 to 11, and another substrate or a plastic film or sheet. The polarizing plate comprised from the plastic film or sheet, the hardened | cured material of the composition in any one of Claims 1-11, and another base material, or a plastic film or sheet.