JP5633511B2 - Active energy ray-curable adhesive composition for hydrophilic plastics - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition capable of adhering a hydrophilic plastic by irradiation with an active energy ray such as an electron beam or an ultraviolet ray, and the composition of the present invention is particularly a plastic. It is preferably used for the adhesion of thin-layer adherends including films or sheets, and is also preferably used for the production of various optical films or sheets used for liquid crystal display elements, etc. It can be used.
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)

  However, when a plastic film or the like is bonded with the adhesive composition described in the above patent document, the adhesive force 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 strength, but peeled off in a more severe hot water resistance test.

  Therefore, the present invention provides an active energy ray-curable adhesive composition that is excellent in adhesion to a hydrophilic plastic film and has excellent adhesion under high temperature and high humidity conditions, and also under hot water conditions. With the goal.

As a result of intensive studies to solve the above problems, the present inventors have found that an active energy ray-curable adhesive composition comprising a compound having an ethylenically unsaturated group and an isocyanate group is a hydrophilic plastic film. It has been found that the adhesive laminate is excellent and the adhesive laminate does not peel off even under high temperature and high humidity conditions, and even in a heat-resistant water test, and further studies are made to complete the present invention. It was.
Hereinafter, the present invention will be described in detail.

  The composition of the present invention has high adhesive strength to hydrophilic plastic films, can maintain excellent adhesive strength under high temperature and high humidity conditions, and even in a heat resistant water test, and various plastic films, etc. It is effective for adhesion of the thin layer adherend, and can be suitably used for the production of an optical film particularly used for a liquid crystal display device or the like.

The present invention relates to compounds having one ethylenically unsaturated group and one isocyanate group [hereinafter referred to as "component (A)"],
(B) a compound having one ethylenically unsaturated group, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A) [hereinafter referred to as “component (B) And (C) a compound having two or more ethylenically unsaturated groups, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A) , , Including a urethane (meth) acrylate oligomer that is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate [hereinafter referred to as “component (C)”]
And an active energy ray-curable adhesive composition for hydrophilic plastics as defined below .
○ Hydrophilic plastic: a plastic produced by molding a polymer containing a hydrophilic moiety selected from hydroxyl group, carboxyl group, phosphoric acid group, sulfonic acid group, amino group and amide bond. The components (A) to (C), which are essential components, and other components (such as the component (D)) that are blended as necessary will be described in order.

1. Ingredients
Component (A) Component (A) is a compound having one ethylenically unsaturated group and one isocyanate group.

Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, a (meth) acrylamide group, and the like, and a (meth) acryloyl group is preferable in terms of easy production.
The number of ethylenically unsaturated groups in component (A), because of easy control of the adhesion of the cured product, is one.

The number of isocyanate groups in component (A), on the grounds that the storage stability of viscosity set Narubutsu excellent, is one.

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.
Among the compounds having one ethylenically unsaturated group and one isocyanate group, examples of the compound in which the two groups are connected by an alkylene skeleton include 2- (meth) acryloyloxyethyl isocyanate and the like ( And (meth) acryloyloxyalkyl isocyanate. Examples of the compound in which the two groups are linked by an oxyalkylene skeleton include (meth) acryloyloxyalkoxyalkyl isocyanate such as 2- (meth) acryloyloxyethoxyethyl isocyanate. Examples of the compound in which the two groups are linked with an aromatic skeleton include 2- (meth) acryloyloxyphenyl isocyanate.
Among compounds having two ethylenically unsaturated groups and one isocyanate group, examples of compounds in which the three groups are connected by a saturated hydrocarbon (particularly, a branched saturated hydrocarbon skeleton) are 1 , 1-bis [(meth) acryloyloxymethyl] ethyl isocyanate and the like.

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, the total of hydroxyl groups in the hydroxyl group-containing (meth) acrylate: isocyanate groups in the polyisocyanate = 1: 1.2 to 1: 4.0 is preferable.

Examples of the high molecular weight compound in the component (A) include a polymer of hydroxyalkyl (meth) acrylate and diisosonate.
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 has low curability of the composition. Molecular compounds are preferred. Specifically, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxyethoxyethyl isocyanate, and 2- (meth) acryloyloxyphenyl isocyanate are preferable.

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. (In particular, 2- (meth) acryloyloxyethyl isocyanate) is preferable.
(A) A component can use only 1 type and can also use 2 or more types together.

Component (B) Component (B) is a compound having one ethylenically unsaturated group, which is a compound other than component (A) and has no reactivity with the isocyanate group of component (A). is there.
The component (B) is a compound having no reactivity with the isocyanate group of the component (A), specifically, a compound having no hydroxyl group or acidic group, and one ethylenic component other than the component (A). Any compound having an unsaturated group may be used.
(B) A component can use only 1 type and can also use 2 or more types together.

  Examples of the ethylenically unsaturated group in the component (B) include the same groups as those exemplified for the component (A), such as a vinyl group and a (meth) acryloyl group.

  Examples of the compound having a vinyl group include vinyl compounds and allyl compounds. Examples of the compound having a (meth) acryloyl group 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.

  Examples of (meth) acrylates include compounds having one (meth) acryloyl group [hereinafter referred to as monofunctional (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.

  As the component (B), one ethylenically unsaturated group and a compound having a heterocyclic ring, and one ethylenically unsaturated group and an amide group can be used to improve the adhesive force with the hydrophilic plastic among the above-mentioned components. A compound having is preferred.

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, and examples of the compound having cyclic imide include N- (meth) acryloyloxyethyl tetrahydrophthalimide and N- (meth) acryloyloxyethyl hexahydrophthalimide.

  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, N-acryloyloxyethyl hexahydrophthalimide, and the like 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.

Component (C) The component (C) is a compound having two or more ethylenically unsaturated groups, which is a compound other than the component (A) and has no reactivity with the component (A).
Component (C) is a compound having no reactivity with the isocyanate group of component (A), specifically, a compound having no hydroxyl group or acidic group, and two or more ethylene other than component (A) Any compound having a polymerizable unsaturated group may be used.
(C) A component can use only 1 type and can also use 2 or more types together.

  As the component (C), a urethane (meth) acrylate oligomer (hereinafter referred to as the component (C-1)) which is a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and the above (A) and (C A compound having two or more ethylenically unsaturated groups other than the component -1) and having no reactivity with the isocyanate group of the component (A) [hereinafter referred to as the component (C-2)] is preferable. . Hereinafter, these components will be described.

(C-1) Component In the present invention, since it is superior in hot water resistance in the adhesion of hydrophilic plastics, the reaction product of polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate is used as component (C). in a (C-1) you blended ingredients.

  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.
Among these compounds, it is preferable to use polyester polyol among these compounds because it is excellent in the adhesiveness of the hydrophilic plastic and particularly excellent in hot water resistance.

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 obtained component (C-1) is low. Diisocyanates are preferred because they are easy to handle due to their viscosity.

  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 component (C-1) 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.

  The molecular weight of the component (C-1) is preferably 2,000 to 60,000, more preferably 3,000 to 40,000.

Component (C-2) In the composition of the present invention, the component (C) is a compound having two or more ethylenically unsaturated groups other than the component (A) and the component (C-1). (A) The compound which does not have the reactivity with the isocyanate group of a component can be mix | blended.
The component (C-2) is a compound that is not reactive with the isocyanate group of the component (A), specifically, a compound that does not have a hydroxyl group or an acidic group, and the components (A) and (C-1) Any compound having two or more ethylenically unsaturated groups other than the components is optional.

  Examples of the ethylenically unsaturated group in component (C-2) include a vinyl group and a (meth) acryloyl group.

  Examples of the component (C-2) include monomers, oligomers, and polymers.

Examples of the monomer monomer include compounds having two or more (meth) acryloyl groups (hereinafter referred to as polyfunctional (meth) acrylates).
Examples of the polyfunctional (meth) acrylate include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, and caprolactone-modified neopentyl glycol hydroxy. Pivalic 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 (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, C2-C5 aliphatic modified dipentaerythritol penta (meth) acrylate, C2-C5 aliphatic modified di Pentaerythritol 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, etc. It is.
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.

The oligomers oligomers include polyester (meth) acrylate oligomer, epoxy (meth) acrylate oligomer and polyether (meth) acrylate oligomer and the like.

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

Here, examples of the polyester polyol include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.
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, tetramethylene glycol, hexamethylene glycol. , Neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and other low molecular weight polyols, and their alkylene oxides Examples include adducts.
Examples of the carboxylic acid or anhydride thereof include 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. The anhydride 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. Specifically, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di ( And (meth) acrylate.

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”.

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.
When the composition of the present invention is cured with visible light or ultraviolet light, it is preferable to blend 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, 2 Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methyl-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, Adekaoptomer N-1414 (Asahi Denka), phenylglycone Aromatic ketone compounds such as oxylic 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 a UV 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, acylphosphinoxite compounds and thioxanthone compounds.

  These photopolymerization initiators can be used alone, and in order to further increase the reactivity, for example, an aliphatic amine or an aromatic amine such as diethylaminophenone, dimethylaminobenzoic acid ethyl, dimethylaminobenzoic acid isoacyl is photocatalyzed. It can also be added as a polymerization initiation aid.

(D) As a mixture ratio of a component, 0.01-10 weight% is preferable in a composition, More preferably, it is 0.1-5 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. Thus, the cured product can be excellent in weather resistance and transparency.

Specific examples of other components other than the component (D) include, for example, inorganic fillers, softeners, antioxidants, antioxidants, stabilizers, tackifier resins, leveling agents, antifoaming agents, and plasticizers. Inactive ingredients such as dyes, pigments, treating agents and UV screening agents can be blended.
Examples of the tackifying resin include rosins such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, and petroleum resin.
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 a total of 100 parts by weight of the components (A) to (C).

2. For the hydrophilic plastic energy ray-curable adhesive composition The present invention relates to the components (A) ~ (C) component comprises as essential components, a hydrophilic plastic for the active energy ray-curable adhesive composition. The term “for hydrophilic plastics” means those suitable for bonding hydrophilic plastics and used for bonding hydrophilic plastics.
As a manufacturing method of a composition, it can manufacture by stirring and mixing said (A) component-(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. Therefore, after mixing (B) component and (C) component, this composition mix | blends (A) component with this mixture, and is manufactured. Specifically, there is a method in which a mixture containing the component (B) and the component (C) is first manufactured in advance, and the component (A) is added to the mixture immediately before use, followed by stirring and mixing. preferable.

As a mixing ratio of the components (A) to (C), the ratio shown below is preferable based on the total amount of the components (A) to (C).
(A) component: 5 to 50 weight% is preferable, More preferably, it is 5 to 30 weight%.
(B) Component: 20 to 90 weight is preferable, More preferably, it is 30 to 90 weight%.
(C) component: 5 to 50 weight% is preferable, More preferably, it is 5 to 30 weight%.
By making the ratio of the component (A) 5% by weight or more, the hot water resistance can be made good, and on the other hand, by making it 50% by weight or less, the storage stability of the viscosity of the composition is good. Can be. Moreover, by making the ratio of (B) component 20 weight% or more, the base-material permeability at the time of the coating of a composition can be made favorable, and by making it into 90 weight% or less, it is hardened | cured material. The impact resistance can be improved. In addition, when the proportion of the component (C) is 5% by weight or more, the adhesive strength at high temperature can be improved, and when it is 50% by weight or less, the adhesion to the substrate is good. Can be.

  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 present invention is an adhesive composition for hydrophilic plastics. Therefore, it is preferable that one or both of the substrates is a hydrophilic plastic.
The hydrophilic plastic in the present invention, the moisture permeability thickness 100μm is 200g / m ² · 24hr or more (in particular, 200~2000g / m ² · 24hr) means a plastic with.
Hydrophilic plastic in the present invention, the water group and a carboxyl group, a phosphoric acid group, a sulfonic acid group is defined by a plastic produced by molding a polymer containing a hydrophilic moiety such as an amino group and an amide bond The 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.

On the other hand, the other base material that adheres to the hydrophilic plastic includes a base material other than the hydrophilic plastic in addition to the hydrophilic plastic. Specific examples of substrates other than hydrophilic plastics include plastics other than hydrophilic plastics, paper, and metals.
Examples of the plastic other than the hydrophilic plastic include polyvinyl chloride resin, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, ABS resin, polyester, polycarbonate, polyurethane, cycloolefin polymer, polymethyl methacrylate, acrylic / styrene resin, ethylene- Examples thereof include vinyl acetate copolymer and chlorinated polypropylene.
Examples of the paper include imitation paper, fine paper, craft paper, art coat paper, caster coat 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, for example, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, Examples include air blades, curtain flow coaters, comma coaters, gravure coaters, micro gravure coaters, die coaters, curtain coaters, 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.

Adhesion of Plastic Film, etc. The composition of the present invention can be suitably used for adhesion between hydrophilic plastic films and the like, and adhesion of plastic films and the like to various other substrates (hereinafter referred to as other substrates). That is, 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 application, but preferably the thickness is 0.2 mm or less ( In particular, it is 0.05 to 0.2 mm).

  Among these thin layer adherends, the composition of the present invention is suitably used for adhesion between plastic films and the like.

  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.

Laminates (laminate films and the like) obtained using the composition of the present invention are excellent in adhesive strength under high temperature and high humidity conditions, so that polarizing plates and protective films used for liquid crystal display devices, retardation films, etc. It can use suitably for optical films, such as.
Especially the composition of this invention can be preferably used for manufacture of a polarizing plate and a polarizing plate with retardation film. Hereinafter, the manufacturing method of a polarizing plate is demonstrated.

  In the present specification, a polarizer means a film or film having a polarizing function described later, and a polarizing plate is 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 polarizer or a polarizing plate in which a retardation film is bonded or a film having a retardation function is formed by coating.

Production method of polarizing plate As described above, the composition of the present invention is an adhesive for hydrophilic plastics. In the production of a polarizing plate, polyvinyl alcohol used as a polarizer, triacetyl used as a protective film for a polarizer. Cellulose or the like 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 crystal compounds, etc., and oriented and fixed, "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 an adherend (base material) selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film,
[2] Another adherend (base) selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film on the adherend (base material) coated with the composition. The process of bonding the material), and
[3] A step of irradiating the bonded adherend (laminate) with active energy rays, particularly a step of irradiating the composition with active energy rays over the bonded adherend (laminate).
For example, when a protective film or a retardation film is pasted only on one side of a polarizer, a polarizing plate or a polarizing plate with a retardation film can be produced by the above procedure, but when pasting on both sides of a polarizer. [1] and [2] may be repeated twice and then [3] may be performed, or [1], [2] and [3] may be repeated twice.

  The coating method in the step [1] and the active energy ray irradiation method in the step [3] may be performed by the same method as described above.

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] and [2] three times, or [1], [2] and [3] may be repeated three times.
In addition, the literature cited in this specification is inserted as reference.

  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-1)]
In a 500 mL reaction vessel equipped with a stirrer, 24 g (0.11 mol) of isophorone diisocyanate, 198 g of isobornyl acrylate (hereinafter referred to as “IBXA”) as a diluent, 0.16 g of dibutyltin dilaurate as a catalyst, and as a polymerization inhibitor 0.10 g of 2,6-di-t-butyl-4-methylphenol was added and heated under stirring in a nitrogen atmosphere containing 5% by volume of oxygen until the liquid temperature reached 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 (0.038 mol) of 2-hydroxyethyl acrylate was further added. The reaction was performed 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. The obtained reaction product was a mixture containing 50 parts of urethane acrylate oligomer (hereinafter referred to as “UA1”) and 50 parts of IBXA. In Table 1 below, the ratios of UA1 and IBXA are shown separately as components of the composition.
The obtained UA1 was measured by gel permeation chromatography (solvent: tetrahydrofuran, column: HSPgel HR MB-L manufactured by Waters), and as a result, the Mw in terms of polystyrene was 34,000.

Examples 1 to 7, Reference Example 1, 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 active energy rays. A mold adhesive composition was produced.
The viscosity of the resulting composition was measured with an E-type viscometer at 25 ° C.

Test example 1
・ Manufacture of film laminate 1 (model experiment for manufacturing polarizing plate)
The obtained composition was applied to a polyvinyl alcohol film (Solbron EF # 30, manufactured by Aicello, hereinafter referred to as “PVA film 1”) to a thickness of 3 μm with 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 1 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 was done 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. The degree of peeling of the film was evaluated as a percentage (remaining area;%) of the area of the film laminate where no peeling occurred (bonded part). If the remaining area was 80% or more, it was evaluated as good.

Test example 2
・ Manufacture of film laminate 2 (Model experiment for manufacturing polarizing plate)
A film laminate was obtained in the same manner as above except that the polyvinyl alcohol film was changed to Solvron NP (manufactured by Aicello, hereinafter referred to as “PVA film 2”).
About the obtained laminated body, according to the following test method, adhesive strength was evaluated by measuring the peel strength by a peel test. The results are shown in Table 2.
[Peel strength measurement]
The obtained film laminate was cut to a width of 25 mm, fixed to a polyvinyl chloride substrate (manufactured by Nippon Test Panel Industry Co., Ltd., Mitsubishi resin 291A specification) with an adhesive sheet, and subjected to a 90 ° peel test with a tensile tester. . The unit of peel strength was N / 25 mm, and it was evaluated as good if it was 1 N / 25 mm or more.

The abbreviations in Table 1 mean the following.
(A) Component AOI: 2-acryloyloxyethyl isocyanate, Karenz AOI manufactured by Showa Denko KK
MOI: 2-methacryloyloxyethyl isocyanate, Karenz MOI manufactured by Showa Denko KK
LR9000: a polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate, BASF Laromer LR9000
(B) component THFA: Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. biscoat # 150
ACMO: acryloylmorpholine POA: 2-phenoxyethyl acrylate, light acrylate PO-A manufactured by Kyoeisha Chemical Co., Ltd.
M140: N-acryloyloxyethylhexahydrophthalimide, Aronix M-140 manufactured by Toagosei Co., Ltd.
(C) Component M1600: polyether urethane acrylate, Aronix M-1600 manufactured by Toagosei Co., Ltd.
UA1: Polyester urethane acrylate obtained in Production Example 1 M240: Polyethylene glycol diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
(D) Component TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Darocur TPO manufactured by Ciba Japan Co., Ltd.

  The composition of the present invention can be used as an adhesive for hydrophilic plastics, particularly as an adhesive for hydrophilic plastic films 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 (15)

Active energy ray-curable adhesive composition for hydrophilic plastics as defined below, including the following components (A) to (C):
(A) a compound having one ethylenically unsaturated group and one isocyanate group,
(B) a compound having one ethylenically unsaturated group, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A), and (C) two or more compounds A compound having an ethylenically unsaturated group, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A), which contains a polyol, an organic polyisocyanate and a hydroxyl group ( A urethane (meth) acrylate oligomer that is a reaction product of (meth) acrylate is included .
○ Hydrophilic plastic: A plastic produced by molding a polymer containing a hydrophilic part selected from hydroxyl, carboxyl, phosphate, sulfonate, amino and amide bonds The active energy ray-curable adhesive composition for hydrophilic plastics according to claim 1 , wherein the component (A) is (meth) acryloyloxyalkyl isocyanate. (B) The active energy ray hardening-type adhesive composition for hydrophilic plastics of Claim 1 or Claim 2 in which a component contains the compound which has one ethylenically unsaturated group and a heterocyclic ring. The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 1 to 3 , wherein the component (B) contains an aromatic monofunctional (meth) acrylate. In the urethane (meth) acrylate oligomer, the polyol is a polyester polyol. The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 1 to 4 . The urethane (meth) acrylate oligomer, claim 1 hydrophilic plastic for the active energy ray-curable adhesive composition according to any one of claims 5 which is 2,000 to 60,000 in weight-average molecular weight. 5 to 50% by weight of component (A), 20 to 90% by weight of component (B), and 5 to 50% by weight of component (C) based on the total amount of components (A) to (C) claims 1 to hydrophilic plastic for the active energy ray-curable adhesive composition according to any one of claims 6. The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 1 to 7 , further comprising (D) a photopolymerization initiator in the composition. The active energy ray hardening-type adhesive composition for hydrophilic plastics of Claim 8 which contains 0.01-10 weight% of (D) component in a composition. One or both of the adherends are hydrophilic plastics, The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 1 to 9 . The active energy ray-curable adhesive composition for hydrophilic plastics according to claim 10 , wherein the hydrophilic plastics are in the form of a film or a sheet. Polarizing plates prepared adhesive composition comprising a composition according to any one of claims 1 to 11. A method for producing an active energy ray-curable adhesive composition for hydrophilic plastics as defined below, comprising the following components (A) to (C):
(A) a compound having one ethylenically unsaturated group and one isocyanate group,
(B) a compound having one ethylenically unsaturated group, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A), and (C) two or more compounds A compound having an ethylenically unsaturated group, which is a compound other than the component (A) and has no reactivity with the isocyanate group of the component (A), which contains a polyol, an organic polyisocyanate and a hydroxyl group ( Including a urethane (meth) acrylate oligomer that is a reaction product of (meth) acrylate ;
(B) After mixing (B) component and (C) component, (A) component is mix | blended with the obtained mixture, The manufacturing method characterized by the above-mentioned.
○ Hydrophilic plastic: A plastic produced by molding a polymer containing a hydrophilic part selected from hydroxyl, carboxyl, phosphate, sulfonate, amino and amide bonds A method of bonding substrates together, one or both substrates to each other is a hydrophilic plastic, bonded using a composition according to any of claims 1 to 11, to which the active An adhesion method comprising irradiating energy rays. Laminate characterized in that one or both of the substrates are hydrophilic plastics are pasted together using the composition according to any one of claims 1 to 11 and irradiated with active energy rays. Body manufacturing method.