TW201100516A - Adhesive composition curable by high energy beam for use with hydrophilic plastic - Google Patents

Abstract

Provided is an adhesive composition that is curable by a high energy beam and that has excellent adhesiveness to hydrophilic plastic films and excellent adhesion properties even under high temperature, high humidity, and hot water conditions. The adhesive composition, which is curable by a high energy beam and is for use with hydrophilic plastic, comprises the following compounds (A) to (C): (A) a compound having an ethylenic unsaturated group and an isocyanate group; (B) a compound having one ethylenic unsaturated group, wherein the compound is not the compound in (A) and does not react with the isocyanate group in (A); and (C) a compound having two or more ethylenic unsaturated groups, wherein the compound is not the compound in (A) and does not react with the isocyanate group in (A).

Description

201100516 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an active energy ray-curable type which can be irradiated by an electron beam or an ultraviolet ray, followed by irradiation of an energy ray. The following composition, and the composition of the present invention is particularly suitable for use in a thin layer containing a plastic or a thin layer, which is more suitable for use in use.

The manufacture of various optical films or sheets in liquid crystal display elements and the like is well received in these technical fields. In the case of ° 儿 曰 ' 将 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 ' 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将The acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid. In the following description, the plastic film or sheet is collectively referred to as "plastic (four) or the like", and the film or thin (four) is indicated as "film or the like". BACKGROUND OF THE INVENTION In the past, in the lamination method of the viscous sigma, the thin layer of the four materials, the thin layer of the plastic film, and the thin layer of the adherend composed of the other materials, the dry stack is mainly used. a layer method in which a solvent-based adhesive composition containing a ethylene-vinyl acetate s copolymer or a polyamine-based polymer is applied onto a first thin layer body, dried, and then borrowed The second thin layer of adherend is crimped by the nip roll. 201100516 The composition of the adhesive used in the method generally contains a lot of solvent in order to make the coating amount-μ, so when the drying, a large amount of solvent vapor will be volatilized, and the safety and environmental pollution are = constitutes a problem. Further, after the thin layered body is adhered, the step towel is processed after the step of laminating the thin heat seal H groove, and the thin layer is peeled off from each other. The problem.

As an adhesive composition for solving such problems, the adhesive composition is currently reviewed. The ...M solventless adhesive composition is a two-liquid type adhesive composition widely used, and a subsequent composition which is hardened by ultraviolet rays or electron beam (4). The two-liquid type adhesive composition mainly uses a so-called polyaminocarbamic acid-based binder composition which has a polymer having a hydroxyl group at its terminal as a main component: and has a polyisotopic s of a different end. The compound is used as a hardener. However, the composition has a drawback that it takes a long time to harden. Therefore, there is a problem in productivity such as a processing step after the step of immediately entering the ruled line after the thin layer is adhered. Further, this composition is obtained by mixing the two liquids to carry out the secret reaction of the secret phase and the heterogeneous (four), and to increase the molecular weight. Therefore, since the viscosity is increased, it is disadvantageous in that single liquefaction is difficult. The active energy ray-curable adhesive composition is excellent in productivity because it has a fast hardening rate and is excellent in productivity, and has recently attracted attention. On the other hand, the liquid crystal display device is characterized by thin, lightweight, and power-saving power, such as a small electronic device such as a navigation system for a car, a mobile phone, and a PDA, or a personal computer, even 201100516. Popularized to TV cameras. In recent years, in the bonding of various optical films and the like used in the liquid crystal display element, an active energy ray-curable adhesive has been used. Examples of the optical film include a polarizing plate, a retardation film, a viewing angle compensation (four) film, a redundancy lifting film, an antireflection film, an antiglare film, a lens sheet, and diffusion, etc., and each of them is used in the material. Type of plastic. Among these plastics, those who are particularly used for re-use can be enumerated, for example, polyethylene glycol and an ethyl@夂, a truncated, a quasi-prime. The plastics such as βHei contain a warp group and are highly hydrophilic compared to ordinary plastics. Patent Document 1 discloses a radiation-curable liquid resin composition for an adhesive which is used for a hydrophobic resin and a hydrophilic resin, and an amino phthalate (hereinafter referred to as a molecular weight of 4,000 or less). Methyl) acrylate 5 篁% to 30 篁 ° /. (8) The radically polymerizable compound is composed of 6% by mass to 95% by mass and (C) a photopolymerization initiator 〇.1% by mass to 丨〇% by mass. Further, Patent Document 2 discloses a photocurable adhesive composition for adhering a polyvinyl alcohol-based polarizing film and a thermoplastic resin-reducing silicone resin film, and the photocurable adhesive composition. Containing (methic acid ester (meth) acrylate 30% by weight to 50% by weight, (b) hydroxyalkyl (indoyl) acrylate 13% by weight to 4% by weight and (homoacrylamide derivative) The weight of the material is from 3% by weight to 3% by weight, and (b) the total amount of the alkyl (meth) acrylate vinegar and the (4) acrylamide derivative is from 20% by weight to 6% by weight. Document 3 discloses an adhesive for a polyvinyl alcohol polarizing plate comprising a urethane (meth) acrylate obtained by polyisocyanate, a polyhydric alcohol, and a hydroxyl group-containing (f-based) acrylate. The substrate permeable single 201100516 is a permeable medium for a polarizing plate protective film; and a photopolymerization initiator. Further, Patent Document 4 discloses an adhesive for a polarizing plate, which contains an amine hydrazine. Acid ester (meth) acrylate, which is composed of polyisocyanate and hydroxyl group Manufactured from (meth) acrylate; and polyol (mercapto) acrylate, which is prepared from a polyol and a hydroxyl group-containing (meth) acrylate or a hydroxy group-containing (fluorenyl) acrylate. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-177169 (Application No.) [Patent Document 3] JP-A-2008-063527 (Patent Application) [Patent Document 4] JP-A-2008-250260 (Patent Application) [Summary of the contents of the invention] Summary of the Invention The object to be solved by the invention = and 'disclosed by the aforementioned patent documents When the composition of the adhesive = two or the like, there is a case where the adhesive force is insufficient, and more specifically, there is a problem that the laminated body occurs under high temperature and high humidity conditions (4). However, in the more stringent pair, the water-based test application will still peel off. ^This 'the purpose of the present invention is to provide an active energy line hardening type of agent set secret, which is hydrophilic (four) h ancient Ha film It is excellent in the strength of the pick-up, and it is excellent under the hot conditions, even under hot water conditions. The means to solve the problem is the result of careful study by the inventors of the present invention to solve the above problems. The active energy ray-curable adhesive composition composed of the ethylenically unsaturated group and the isocyanate group-containing compound has excellent adhesion to the hydrophilic plastic film, and is then laminated under high temperature and high humidity conditions, or even in hot water. In the test, no peeling occurs, and further investigation is carried out, and the present invention is completed. The present invention will be described in detail below. Effect of the Invention The composition of the present invention has high adhesion to a hydrophilic plastic film, and is high in south temperature and high. Under wet conditions, even in the hot water test, excellent adhesion can be maintained, which is effective in the subsequent adhesion of various plastic films and the like, and is particularly suitable for the production of optical films (which are used in liquid crystal display devices, etc.). . [Embodiment 3] The present invention relates to an active energy ray-curable adhesive composition for a hydrophilic plastic, comprising: (A) a compound having an ethylenically unsaturated group and an isocyanate group (hereinafter referred to as " (A) component"); (B) a compound having one ethylenically unsaturated group and being a compound other than the component (A) and having no reactivity with the isocyanate group of the component (A) (hereinafter referred to as a compound) r (B) component"; and 7 201100516 (C) A compound having two or more ethylenically unsaturated groups, which is a compound other than the component (A), and is not reactive with the isocyanate group of the component (A). The compound (hereinafter referred to as "(C) component"). Hereinafter, the components of the essential component contained in the composition of the present invention are described in order to the component (C), and other components ((D) component, etc.) which are blended as needed. 1. Incorporation of a component (A) Component (A) A component having an ethylenically unsaturated group and an isocyanate group. Examples of the 'ethylenically unsaturated group' of S include, for example, an ethylene group, a vinyl ether group, a (fluorenyl) acryl fluorenyl group, and a (fluorenyl) acrylamide group, and it is preferably (a) Base) propylene fluorenyl. The number of the ethylenically unsaturated groups in the component (A) is one or two or more, and if it is easy to control the adhesion of the cured product, it is preferably one or two, and more preferably, One. The number of isocyanate groups in the component (A) is one or two or more, and if it is excellent in storage stability depending on the viscosity of the composition, it is preferably one or two, and more preferably, 丨One. In the (βΑ) component, the skeleton linking the ethylenically unsaturated group and the isocyanate group may be any one as long as it is a bondable ethylenically unsaturated group or an isocyanate group. For example, a saturated hydrocarbon skeleton (a sub-alkyl skeleton, an oxygen sub-base skeleton, etc.) which may contain a hetero atom, an aromatic skeleton, or the like may be mentioned. 201100516 (A) component Any of a low molecular weight compound and a high molecular weight compound can be used. Specific examples of the low molecular weight compound in the component (A) include the following compounds: in a compound having one ethylenically unsaturated group and one isocyanate group, the two groups are linked by an alkylene skeleton. Examples of the compound include (meth)acryl oxime alkyl isocyanate such as 2-(meth)acryloyloxyethyl isocyanate. Examples of the compound in which the two groups are bonded by an oxyalkylene skeleton may, for example, be a (fluorenyl) propylene oxyalkyloxyalkyl group such as 2-(meth)acrylomethoxyethoxyethyl isocyanate. Isocyanate. Examples of the compound in which the two groups are linked by an aromatic skeleton are, for example, 2 (methyl) acrylonitrile phenyl isocyanate. Examples of the compound include, for example, ethyl isocyanate. a compound having two ethylenically unsaturated groups and one isocyanate group is bonded to U-bis[(indenyl)propenyloxy] by saturated smoke (especially a branched saturated hydrocarbon skeleton) The component (A) may, for example, be a reaction product of polyisocyanuric acid and a transalkyl group-containing (meth) acrylate. For example, the polyisocyanate may be exemplified by diisocyanate and triisocyanate. For example, i isocyanate (iv) is listed as: hexamethylene diisocyanate

201100516 rl rat acid from the purpose, 4,4,-dicyclohexylmethane diisocyanate _, decene diiso = slightly and hydrogenated xylene diisocyanate and other alicyclic diisocyanate temple. - A case of 5 bis of acid vinegar may be exemplified by ······················ The polyisocyanate is mixed with the (meth)acrylic acid-containing reactant, and the reaction ratio containing the (meth)acrylic acid is only present in the reaction. The ratio of acrylonitrile to isocyanic acid vinegar, including various ratios, and the molar ratio of Irmol, should be the content of 26-based polyisocyanic acid in the base of (meth)acrylic acid. In the total of the high-molecular weight compound, examples of the high-molecular-weight compound may be, for example, a polymer of a hydroxyalkyl (meth) acrylate and a diisocyanate. This compound is commercially available, and examples thereof include Laromer LR9® manufactured by BASF which is a polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate. As described above, the molecular weight of the component (A) can be used from a low molecular group to a polymer. However, it is preferably a low molecular weight based on the viewpoint that the composition can be made into a low viscosity and the composition is excellent in hardenability. Compound. Specifically, it is preferably 2-(methyl) propylene oxime oxyethyl lactic acid vinegar, 2-(indenyl) propylene oxyhexyloxyethyl isophthalic acid S, 2-(meth)acrylic acid Oxyphenyl phenyl isocyanate. Among these compounds, if the composition is not crystallized to form a liquid, and there is no deformation of the substrate due to heat generation during hardening, etc., the reason is that the composition of the shell is preferably (sulfenyl). Propylene oxyalkyl isocyanate (especially 2-(indenyl) propylene oxiranyl ethyl isocyanate). The (Α) component may be used alone or in combination of two or more. (Β) The component (Β) component is a compound having one ethylenically unsaturated group and is a compound other than the (Α) component, and is a compound which is not reactive with the isocyanate group of the (Α) component. The (Β) component is a compound which is not reactive with an isocyanate group of the (Α) component, specifically, a compound which does not have a hydroxyl group or an acidic group, and which has one ethylidene unsaturated group other than the (Α) component. The compound can be any. The (Β) component may be used alone or in combination of two or more. The ethylenically unsaturated group in the (Β) component may, for example, be the same as those exemplified in the above components, and examples thereof include a vinyl group, a (meth)acryl fluorenyl group and the like. Examples of the compound having a vinyl group include a vinyl compound and a dilute propylene compound. Examples of the compound having a (meth)acrylic acid group include, for example, (meth)acrylamide, (meth)acrylic acid vinegar, (meth)acrylic acid, and (meth)acryloquinone morpholine. Wait. Examples of the vinyl compound include styrene, vinyl toluene, N-vinylformamide, anthracene-vinylpyrrolidone, and mucocaprolactone. The allyl compound may, for example, be allyl alcohol or the like. Examples of the (meth) acrylamide include (meth) acrylamide, hydrazine-hydroxyindole (meth) acrylamide, hydrazine-methoxymethyl (meth) acrylamide, hydrazine methoxy Butyl (mercapto) acrylamide, hydrazine, hydrazine-dimethyl(fluorenyl) acrylamide, ν, Ν-diethyl 201100516 (meth) acrylamide, N-(2-hydroxyethyl) (Methyl) acrylamide, 2_(meth) acrylamide-2-methylpropane sulfonic acid, N-isopropyl (decyl) acrylamide, and the like. The (meth) acrylate may, for example, be a compound having one (meth) acrylonitrile group (hereinafter referred to as a monofunctional (fluorenyl) acrylate). Examples of the monofunctional (meth) acrylate include alkyl (meth) acrylates such as isooctyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Ester; cyclohexyl (meth) acrylate, tricyclic brothel (meth) acrylate, dicyclopentenyl (mercapto) acrylate, isodecyl (meth) acrylate s 曰 and adamantane An aliphatic cyclo (methyl) propionate such as a (meth)propionate; 2-methoxyethyl (mercapto) acrylate, methoxy triethylene glycol (meth) acrylate, 2 - alkoxylates such as ethylhexyl carbitol (meth) acrylate and ethoxy ethoxyethyl (meth) acrylate; epoxide modifications of benzyl (meth) acrylate and phenol derivatives (meth) acrylate and aromatic (meth) acrylate of 2-hydroxy-3-phenoxypropyl (meth) acrylate; tetrahydroindenyl (mercapto) acrylate; N-(fluorenyl) ) propylene oxiranyl ethyl tetrahydro quinone imine and group (methyl) propylene oxiranium hexahydro phthalimide. In the foregoing, if it is based on the point of the adhesion that can increase the adhesion to the hydrophilic plastic, the component (8) should be present! Ethylene unsaturated groups and heterocyclic compounds & and compounds having one ethylenically unsaturated group and an amine group. In the case of a compound having one ethylenically unsaturated group and a heterocyclic ring, a coating may be mentioned, for example, a cyclic ring, a phenanthrene group, a hydrazine ketone, a decylamine, a cyclic linoleic amine or the like. ρ has a cyclic compound, such as: tetrahydroindenyl (meth) acrylonitrile, etc. 'The compound having morphine can be exemplified by (meth) propylene morpholine, etc., 12 201100516 The compound of the ketone may, for example, be an N-ethylidene group, or the like, and the compound having a caprolactam may be, for example, N-ethene caprolactam or the like, and a compound having a cyclic quinone imine may be mentioned. Such as: Ν · (meth) propylene oxiranyl ethyl tetrachloro quinone imine and Ν - (meth) propylene oxiranyl ethyl hexahydro quinone imine, etc. has one ethylenically unsaturated group and decylamine The compound of the group may, for example, be fluorene-vinylformamide, hydrazine, hydrazine-dimethyl(meth) acrylamide, hydrazine, hydrazine-ethyl(methyl) acrylamide. Among the compounds If it is based on the viewpoint that the hardenability of the composition is more excellent, acrylic acid ester is preferably used. Further, in the acrylic acid ester, it is also preferable to be acrylonitrile, tetrahydrofurfuryl acrylate or hydrazine- Acetyloxyethyl hexahydroindenine, etc. Further, if based on the viewpoint of imparting water resistance to the cured product of the composition, blending long-chain alkyl (meth) Acid esters or/and aromatic monofunctional (meth) acrylates. Examples of long chain alkyl (meth) acrylates include isooctyl (meth) acrylate, lauryl (meth) acrylate and hard An alkyl (meth) acrylate having a carbon number of 6 to 20, such as a fatty alcohol (meth) acrylate. The aromatic monofunctional (meth) acrylate may, for example, be phenyl (meth) acrylate. Ester, ρ-isopropylphenyl phenyl (meth) acrylate, 〇 phenyl phenyl (meth) acrylate, m-phenyl phenyl (meth) acrylate, p - phenyl phenyl ( Methyl) acrylate, phenoxyethyl (meth) acrylate, p_ cumyl phenoxyethyl (meth) acrylate, fluorenyl-phenylphenoxyethyl (meth) acrylate, m _Phenylphenoxyethyl (meth) acrylate and P-phenylphenoxyethyl (f-) acrylate, etc. 13 201100516 (c) Component (C) component has two or more ethylenic unsaturation a compound other than the component (A) and a compound which is not reactive with the component (A). The component (C) is as long as (A) The compound which is not reactive with the isocyanate group is not particularly a compound having no hydroxyl group or an acidic group, and is a compound having two or more ethylenically unsaturated groups other than the component (A). The component (C) may be used alone or in combination of two or more. The component (C) is preferably a urethane (meth) acrylate oligomer (hereinafter referred to as a component (C-1)]. It is a reactant of a polyhydric alcohol, an organic polyisocyanuric acid, and a (meth) acrylate containing a trans group; and has two or more ethylenic groups other than the above (A) component and ((>1) component) The compound of a saturated group is a compound which is not reactive with the isocyanate group of the component (A) (hereinafter referred to as a component (c_2)). These components will be described below. (C-1) In the present invention, in the case of the hydrophilic plastic, in order to make the hot water resistant composition more excellent, the (C) component is preferably blended (cq), which is a polyol, a silk s The invention relates to a reaction product containing a methyl (meth) propyl group. The alcohol can be exemplified by a low molecular weight polyol, a polycarbonate polyol, a polyester polyol, etc. The low molecular weight polyol may, for example, be a polyol having at least two mesogenic groups, and the specific examples may be as follows: 2011-0516, propane, butanediol, L6-hexanediol, cyclohexanedimethanol, neopentyl glycol and Alcohol, propylene glycol, diethylene glycol, 2-mercapto-1,8-octanediol, decyl-3-methyl-1,5-pentanediol, etc. For example, polyether polyols can be enumerated For example, a polyalkylene glycol having three or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polybutanediol. For example, polycarbonate is opened more. station

Ο The alcohol can be exemplified by a reaction product of a carbonate and a glycol. Specifically, the sulphonate may, for example, be a diaryl carbonate such as diphenyl carbonate; or a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate. ^ > The decyl alcohol may, for example, be a low molecular weight polyol as described above. For example, the polystyrene of the polyester may be, for example, selected from the group consisting of the low molecular weight polyol, the polyether polyol, and the carbonate polyol to the reaction of ν _ and H. Things. For example, examples of the acid component include adipic acid, sebacic acid, tetanic acid, maleic acid, ugly acid, hexahydrononanoic acid, and a dibasic acid such as oleic acid or an anhydride thereof. Polycarbonate - diol and ring-opening reactants, etc. In the compound such as Hai, the polyol used in the polyol is more excellent in the adhesiveness of the polyol, and the hot water is particularly excellent, so it is preferable. Common causes S of the 'organic polyisocyanate triisocyanate (four) and so on. - Iso-acid 1 and as an example, the two-acid soda can be exemplified by: Azure 2,4'-di-p-decane diisocyanate, _ __ ^ ^ 曰, a methyl diisocyanate and naphthalene Diisocyanide 15 201100516 An aromatic diisocyanate such as an acid ester; an aliphatic diisocyanate such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; isophorone diisocyanate, 4, 4'-di An alicyclic diisocyanate such as cyclohexyldecane diisocyanate, decene diisocyanate or hydrogenated xylene diisocyanate. For example, examples of the triisocyanate include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylenetriisocyanate, and bicycloheptane triisocyanate. Among these, since the obtained (〇) component is low in viscosity and easy to handle, it is preferably a diisocyanate. For example, the hydroxyl group-containing (meth) acrylate may, for example, be a hydroxyl-based (meth)acrylic acid such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl ( decyl acrylate). An ester; and a reaction product of a polyol such as pentaerythritol tris, di or mono(indenyl) acrylate, trishydroxypropyl propane di or mono (meth) acrylate, and (meth)acrylic acid. The hydroxyl group-containing (meth) acrylate is preferably a spectrin alkyl (meth) acrylate, more preferably 2-hydroxyethyl (meth) acrylate. 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 usual method. Specifically, 'in the presence of a dibasic acid such as dibutyltin dilaurate, the polyol, the organic polyisocyanate, and the hydroxyl group-containing (meth) acrylate are heated as needed in the presence of a reaction solvent. It is produced by stirring and urethane. In this case, a polyol, an organic polyisocyanate, and a hydroxyl group-containing (mercapto) acrylate can be injected together to produce a precipitate containing an isocyanate group by reacting a polyhydric alcohol with an organic polyisocene 16 201100516 cyanate ester. After the polymer, a hydroxy group-containing (fluorenyl) acrylate is added to produce. The molecular weight of the component (C-1) is preferably 2, 〇〇〇 to 60, 〇〇〇, more preferably 3, 〇〇〇 to 40,000. (C-2) Component In the composition of the present invention, the component (C) may be blended with the compound having two or more ethylenically unsaturated groups other than the component (A) and the component (C-1). A compound which is not reactive with an isocyanate group of the component (A). The component (C-2) is a compound which is not reactive with the isocyanate group of the component (A). Specifically, it is a compound having no hydroxyl group or an acidic group, and is a component other than the component (A) and the component (C-1). Any compound having two or more ethylenically unsaturated groups may be used. For example, the ethylenically unsaturated group in the component (C-2) may, for example, be a vinyl group, a (fluorenyl) acrylonitrile group or the like. The component (C-2) may, for example, be a monomer, an oligomer or a polymer. The monomer monomer may, for example, be a compound having two or more (fluorenyl) acrylonitrile groups (hereinafter referred to as polyfunctional (meth) acrylate). For example, the polyfunctional (meth) acrylate may, for example, be neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol via the top three Diethyl (meth) acrylate, caprolactone modified neopentyl glycol hydroxytrimethyl acetic acid di(meth) acrylate, epoxide modified neopentyl glycol di (meth) acrylate Epoxide modified hydrazine, 6-hexanediol di(meth) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, polyethylene II 17 201100516 alcohol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethylol di(mercapto) acrylate, dicyclopentenyl di(meth) acrylate, trimethylolpropane tri Mercapto) acrylate, pentaerythritol tri(meth) acrylate, aliphatic modified diterpene tetraol penta (meth) acrylate having a carbon number of 2 to 5, aliphatic modification of carbon number 2 to 5 Dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, caprolactone modified dipentaerythritol hexa(methyl) acrylate, neopentyl alcohol tetra (meth) acrylate, gin[(meth) propylene methoxyethyl] isocyanate The caprolactone is modified with [(meth)acrylomethoxyethyl]trimeric isocyanate, ditrimethylolpropane tetra(meth)acrylate, and the like. In addition to these, examples thereof include compounds disclosed in pages 53 to 56 of the "Latest Technology" (Printing Information Association (Share), 1991). Examples of the oligomers include oligomeric (meth)acrylic acid vinegar oligomers, epoxy (meth)acrylic acid S oligomers, and poly-(meth)acrylic acid. Vinegar oligomers, etc. The poly (meth)acrylic acid vinegar oligomer may, for example, be a dehydrated condensate of a polyacetic polyol and (meth)acrylic acid. Here, examples of the polyacetal polyol include a reaction product of a polyhydric alcohol with (iv) or an anhydrous substance thereof. For example, the polyhydric alcohol may, for example, be ethylene glycol, diethylene glycol, triethylenyl alcohol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropanol, polypropylene glycol, butanediol. , polybutanediol 'butanediol, hexamethylene 18 201100516 diol, neopentyl glycol, cyclohexane dimethanol, 3-methyl-1,5-pentanediol, 1,6, hexanediol And a low molecular weight polyol such as trimethylolpropane 'glycerol, neopentyl alcohol, and dipentaerythritol; and the epoxide adducts and the like. For example, a carboxylic acid or an anhydride thereof may be exemplified by phthalic acid, isophthalic acid, p-citric acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrofurfuric acid and a dibasic acid such as benzenetricarboxylic acid or an anhydride thereof.

Examples of the polyester poly(meth)acrylate other than the above are, for example, those disclosed in pages 74 to 76 of the aforementioned "UV. EB hardening material". The epoxy (meth) acrylate oligomer is a compound obtained by adding a reaction of (meth)acrylic acid to a cycloolefin resin, and is exemplified by, for example, 74 pages of the "UV. EB hardening material". To the compounds disclosed in the pages and the like. Examples of the earth-oxygen resin include: an aromatic epoxy resin and an aliphatic epoxy tree J. ruthenium; a double epoxide; a double age, a double bismuth, a double s, a double material or an epoxide addition thereof; Body two-filament epoxy acrylic; _ varnish-type epoxy resin and varnish-type epoxy resin (four) varnish-type epoxy resin; epoxy propyl ugly imine; phthalic acid diglycidyl phthalate. — In addition to recent ==, etc., it can also be listed, for example, in the literature "Epoxy Resin _ = Near Age" (4) Hall, Howling Release 2) or Silk "Polymer Plus" Book 9. Volume 22 Supplementary issue of Epoxy Tree Years... Money _ Day [very published in the guild, 1973 ^ 41 er, 9 pages to 16 pages of compounds disclosed. Specifically, examples of the aliphatic epoxy resin include ethylene glycol, propylene glycol 19 201100516 alcohol, 1,4-butanediol, and 1,6-hexanediol, etc. a di-epoxy propyl ether of a polyalkylene glycol such as polyethylene glycol and a polypropylene glycol propylene glycol; a neopentyl glycol, a dibromo neopentyl glycol, and an epoxide thereof; Adult di-glycidyl ether; trishydroxylethane, trimethylolpropane, glycerol and its epoxide addition di- or tri-epoxypropyl ether' and neopentyl alcohol and its ring a polyepoxypropyl ether of a polyhydric alcohol such as a di-, tri- or tetra-epoxypropyl bond of an oxide adduct; a hydrogenation double-A and an epoxide adduct thereof or a polyepoxypropyl group Ether; dihydroepoxy propyl tetrahydrophthalate; hydroquinone diepoxypropyl bond, and the like. In addition to these, there may be mentioned, for example, the compounds disclosed in the above-mentioned publication "Polymer Processing", Epoxy Resin, pages 3 to 6. In addition to the aromatic epoxy resin and the aliphatic epoxy resin, for example, an epoxy compound having a triazine core in a skeleton, such as TEPIC (Chemical Co., Ltd.), Dinako (DENACOL) EX-310 (WAGASE), etc., can be exemplified by, for example, as disclosed in pages 289 to 296 of the above-mentioned document "Molecular Processing". Compounds, etc. In the above description, the epoxide of the epoxide adduct is preferably ethylene oxide or propylene oxide. For example, the polyether (meth) acrylate oligomer may, for example, be a polydecyl monool (fluorenyl) dithanoic acid vinegar, and specifically, for example, a polyethylene glycol methyl group) Acrylic acid 35, polypropylene glycol di(meth) propylene, and polybutanediol di(meth)acrylate. Polymer 20 201100516: (meth)acrylic acid in a (meth)acrylic polymer having a (meth)acrylic acid-based (meth)acrylic acid-based oxime having a functional group The base is introduced into your silk water; and, for example, the compounds disclosed in the above-mentioned document "υν. ΕΒ化化材料", pages 78 to 79, etc. Other Ingredients In the composition of the present invention, in addition to the components (4) to (c) which are essential components, other components which are usually used in the adhesive composition may be blended.组成 The composition of the present invention is blended with a photopolymerization initiator (hereinafter referred to as component (D)) when it is cured by visible light or ultraviolet light. Further, it is not necessary to blend the component (D) when the composition of the present invention is cured by an electron beam or the like. The component (D) may, for example, be benzyldimethylketone, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, hydrazine-hydroxycyclohexyl phenyl ketone, 2-hydroxy- 2-methyl-1-phenylpropanone, Bu [4_(2-hydroxyethoxy)-benzyl]-2-predyl-2-methyl-1-propanone-l-_, oligomeric [ 2_经基基2-methyl_1_[ 4-1-(methylethlyl)phenyl]propanyl, 2-hydroxy_1_ { 4_ [4-(2-trans-base_2-fluorenyl) Propionyl)_benzyl]-phenylindole-2-methylpropane+ ketone, methyl-1-[4-(methylthio)]phenyl]_2_morpholinpropanone, 2-benzyl-2- Dimethylamino-1-(4-morphinyl)butane-l-_j, 2-(4-methyl-benzyl-2-dimethylamino-1-(4-morpholinyl) butyl Alkan-1-one, 2-dimethylamino 2-(4-methylbenzyl)-1-(4-morphin-4-yl-phenyl)-butan-1-one, ADEKA ) OPTOMER N-1414 (made by Asahi Kasei), aromatic ketone compounds such as phenylglyoxylate, acetamidine and phenanthrenequinone; diphenyl ketone, 2-methyldiphenyl _, 3-methyldiphenyl styrene|, 4-methyl 21 201100516 diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, 4-phenyldiphenyl ketone, 4-(曱Phenylthio)phenyl benzene decane, decyl-2-diphenyl ketone, 1-[4-(4-benzylidenebenzoic acid) phenyl]-2-methyl-2-(4- Methylbenzene acid group) propyl-i-ketone, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, N, N'-tetramethyl-4,4'-diaminodiphenyl-, N,N'-tetraethyl-4,4'-diaminodiphenyl ketone and 4-decyloxy-4' a diphenyl ketone compound such as diammonium diphenyl ketone; bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine Oxide, ethyl-(2,4,6-trimethylbenzylidene)phenylphosphinate and bis(2,6-dioxabenzyl)-2,4,4-tridecylpentane a mercaptophosphine oxide compound such as a phosphine oxide; a thioxanthone, a 2-oxothioxanthone, a 2,4-diethylthioxanthone, an isopropylthioxanthone, a 1-gas-4-propyl group Thioxanthone, 3-[3,4-dimercapto-9-sideoxy-9H-thioxanthen-2-yl]oxy]-2-propyl-hydrazide, hydrazine, hydrazine-trimethylammonium chloride And thioxanthone-based compounds such as sulphonone; ketone ketone and 10-butyl-2-ketone ketone; etc.; U2-octanedione 1-[4-(phenylsulfonate) Base)-2-(0-benzyl肟)], ethyl ketone ι_[9_ethyl-6-(2-indolylbenzyl)-9Η-oxazol-3-yl]·丨_(〇_乙醯肟) and other esters, 2- (〇-chlorophenyl)-4,5-dibenzimidazole dimer, 2-(〇-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(〇 _fluorophenyl)_4,5-benzimidazole dimer, 2-(anthracene-methoxyphenyl)-4,5-dibenzimidazole dimer, 2-(p-nonyloxyphenyl)-4, 5--one 11 m '1 sit-polymer, 2,4-(p-nonyloxyphenyl)-5-benzene π m β sit dimer and 2-(2,4-dioxanthene benzene 2,4,5-triarylimidazole dimer of the group 4,5-diphenyl-salt dimer; and 22 201100516 9-benzoindole and 1,7_bis (9,9,_吖) An acridine derivative such as pyridyl)heptane or the like. These compounds may be used alone or in combination of two or more. In these cases, it is preferably 1-hydroxycyclohexyl phenyl ketone, bis(2,4,6-trimethylbenzylidene phenylphosphine oxide, 4- depending on the adhesion, heat resistance or preservation stability. Phenyldiphenyl ketone, 4_(mercaptophenylthio)phenyl benzene methane, chlorochlorothioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 1-gas-4- Propyl beta ketoxime.

In the case of a substrate to which an ultraviolet absorber is subsequently blended, it is preferred to use a photopolymerization initiator having absorption on a long wavelength side (40 Å or more). In particular, since the protective film of the polarizing member mostly contains an ultraviolet absorber, it is preferably used in the production of a polarizing plate. Specific examples of the compound include, for example, the aforementioned 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-nonanone, 2-(4-methyl-benzyl-2) · dimethylamino-1-(4-morpholinyl)butanone, fluorenylphosphine oxide compound, thioxanthone compound, etc. The photopolymerization initiators can also be used alone, in addition, in order to improve the reaction For example, an aromatic amine such as an aliphatic amine or diethylamino benzoate, dimethylamino benzoic acid ethyl ester or diammonium benzoic acid isodecyl ester may be added as a photopolymerization initiation aid. The blending ratio of the component (D) is preferably 〇.〇1% by weight to 1% by weight of the composition. More preferably 〇·1% by weight to 5% by weight. By blending the proportion of the component (D) In the above, the composition can be hardened by an appropriate amount of ultraviolet light, and the productivity can be improved. 23 201100516 In addition, by making 10% by weight or less, the cured product can be made resistant. It is excellent in climatic or transparency. Specifically, other components other than the component (D) can be blended, for example, inorganic fillers, softeners, antioxidants, and anti-aging agents. An inactive component such as a stabilizer, an adhesive resin, a leveling agent, an antifoaming agent, a plasticizer, a dye, a pigment, a treating agent, and a UV blocking agent. For example, the adhesive resin may be exemplified by citronellic acid, A rosin, a terpene resin, a sulphur phenol resin, an aromatic hydrocarbon resin, an aliphatic saturated hydrocarbon resin, a petroleum resin, etc., such as citronellic acid and citronellate, and the like, for the purpose of improving the adhesion to the substrate. Further, a decane coupling agent may be blended. Further, when the hardenability of the composition is insufficient, a urethanization catalyst may be blended. Examples of the amine phthalate catalyst include a metal catalyst and an amine catalyst. Examples of the metal-based catalyst include a tin-based catalyst, an iron-based catalyst, and a zinc-based catalyst. Examples of the tin-based catalyst include dibutyltin dilaurate. The amine-based catalyst may, for example, be an alkylamine or a dioxane. a primary amine such as a monoamine such as an alkylamine; a secondary amine such as a dialkylamine, a dialkoxyalkylamine or a diallylamine; a tertiary alkylamine such as a trialkylamine or DABCO; From (A) to (C) A total of 1 part by weight is blended in an amount of 100 parts by weight or less. 2. An energy ray-curable adhesive composition for a hydrophilic plastic. The present invention relates to an active energy ray-curable adhesive composition for a hydrophilic plastic. It contains the above-mentioned components (A) to (c) as essential components. The term "hydrophilic plastic" refers to the use of hydrophilic plastics and 24 201100516 for the subsequent use of hydrophilic plastics. The component (A) to the component (c) and other components as needed are stirred and mixed according to a usual method. Since the component (A) is easily decomposed by water or the like, the obtained composition is obtained. There is a case where the storage stability is insufficient. Therefore, the composition is produced by mixing the component (B) and the component (C), and blending the component (A) with the mixture. Specifically, it is preferably a method of first preparing a mixture containing the component and the component (C) in advance, and adding the component (a) to the mixture immediately before use, and by mixing and mixing. Manufacturing. The blending ratio of the component (A) to the component (C) is preferably a ratio of the following components (A) to (the total of the components of Q). (A) Component: preferably 5 weight ° / 〇 to 50% by weight, more preferably 5% by weight to 30% by weight. (B) Component: preferably from 20% by weight to 90% by weight, more preferably from 3% by weight to 90% by weight. (C) Ingredient: preferably 5 The weight% to 50% by weight is more preferably 5% by weight to 30% by weight. By setting the ratio of the component (A) to 5% by weight or more, the temperature resistance can be improved, and on the other hand, 50% by weight can be obtained. In the following, the storage stability of the viscosity of the composition can be made good. Further, by setting the ratio of the component (B) to 20% by weight or more, the substrate permeability at the time of application of the composition can be made good, and 90 can be made by When the weight ratio is less than 5% by weight, the impact resistance of the cured product can be improved. Further, by setting the ratio of the component (C) to 5% by weight or more, the adhesion at a high temperature can be improved, and 50% by weight or less can be produced. The adhesion to the substrate is good for 201100516. If it is excellent in the spreadability to the substrate, the composition is The degree is preferably from 10 mPa·s to 1000 mPa.s. 3. Method of use The method of using the composition of the present invention can be carried out according to a conventional method, and can be exemplified by: after being applied to a substrate, adhering to the substrate of the other substrate. The method of irradiating the active energy ray, etc. The present invention is an adhesive composition for a hydrophilic plastic. Therefore, one or both of the above-mentioned substrates are preferably hydrophilic plastics. In the present invention, the term "hydrophilic plastic" means having The plasticity in the film thickness of 1 〇〇μηι is 200 g/m 2 · 24 hr or more (particularly 2 〇〇 g / m 2 · 24 & to 2000 g / m 2 · 24 hr). Specifically, the hydrophilic plastic can be enumerated as : Polymerization of a hydrophilic moiety containing a hydroxyl group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, an amine group, and a guanamine bond

A plastic that is formed by forming. Preferable examples of the polymerization Z containing a hydrophilic portion include polyvinyl alcohol, cellulose triacetate, polyacetal acetal, and polyamine. Further, it is also possible to use a polymer which has been subjected to a shape treatment after a polymer having no hydrophilic portion. In the case of a corona treatment, a treatment, a flame treatment, and a treatment of a substance containing a hydrophilic portion, a polymer having no hydrophilic portion is introduced into a hydrophilic group or the like. Specific examples of the preferred examples include the polypyridyl phthalate which has been subjected to the pull-up treatment by the polystyrene. The hydrophilic plastic is preferably formed by molding a polymer containing a hydrophilic portion. The polymer of the method of 2011 201116 is used for the preparation of the polymer, and more preferably the surface water-based portion of polyvinyl alcohol and cellulose triacetate. On the other hand, in addition to the hydrophilic plastic, the substrate of the other is a water-based plastic, and a substrate other than a hydrophilic plastic is also exemplified. In other words, substrates other than hydrophilic plastics include, for example, hydrophilic plastic Z plastic, paper, and metal. For example, plastics other than hydrophilic plastics can be cited as m

Ο

Alkenyl resin, polyvinylidene ethylene, polyethylene, polypropylene, polystyrene, ABS resin, ? Wuyi, Polycarbonate, Polyurethane, Cycloolefin Polymer, Polymethylmethacrylate, Acrylic/Phenyl Ethylene Resin, Ethylene·Acetic Acid, and Vaporized Polypropylene. s For example, the paper can be exemplified by: mould paper, Daolin paper, kraft paper, art paint paper, coated paper, pure white roller paper, parchment paper, water resistant paper, cellophane and corrugated paper. For example, the metal foil may, for example, be an aluminum foil or the like. The application of the substrate can be carried out according to a conventional method, for example, an intrinsic coater, a doctor blade coater, a float knife, a roller blade, a knife blanket layer, a spray, a dip coating, a contact roller. , extrusion, reverse roll, air knife 'curtain coater, angle cutter coater, gravure coater, micro gravure coater, die cast coater, curtain coater and the like. Further, the coating thickness of the composition of the present invention can be selected in accordance with the substrate to be used and the use thereof. However, it is preferably 01_00 μm, more preferably ΐμηη to 25 μm. Examples of the active energy ray include ultraviolet rays, xenon rays, and electron beams. 27 201100516 However, since an inexpensive device can be used, ultraviolet rays are preferable. The light source which is hardened by ultraviolet rays can be used in various forms, and examples thereof include, for example, a plus or a south pressure mercury lamp, a metal halide lamp, a gas lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED. When hardened by electron rays, various EB irradiation apparatuses can be used, and examples thereof include, for example, a Kirklaw-Worthon type, a Van de Graaff type, and a resonance transformer type device. The electron beam is preferably one having an energy of 50 eV to 1000 eV, more preferably i ev to 300 eV. The plastic film or the like is preferably used in the form of a hydrophilic plastic film or the like, a plastic film, or the like, and various other substrates (hereinafter referred to as other substrates), that is, suitable for use as An active energy ray-curable adhesive composition is used for the plastic film or sheet. Further, in the following disclosure, when only referred to as "substrate", it means a general term for a plastic film or the like and other substrates. Examples of the other substrate include paper, metal, and the like. The composition of the present invention is suitable for the case where a thin layer of adherend is subsequently used as a substrate. The method of use of the thin layer of adherend can then follow the method typically performed in the manufacture of the laminate. For example, the following method may be used, that is, the composition is applied to the first thin layer adherend, and if necessary, dried, and then the second thin layer adherend is adhered thereto and irradiated with an active energy ray. Examples of the thin layer adherend include a plastic film, paper, metal foil, and the like. Plastic film and the like must be permeable to active energy rays. The film thickness can be selected according to the thin layer adhesive used and used in 28 201100516. However, it is desirable that the thickness is less than 2 mm (especially 0.05 mm to 0.2 mm). ). Among the thin layer adherends, the composition of the present invention is also suitable for use in a plastic film or the like. Further, in order to increase the adhesion between the layers before the adhesion, the activation treatment may be performed on the surface of one or both of them. The surface activation treatment may be, for example, a plasma treatment, a corona discharge treatment, a chemical liquid treatment, a roughening treatment, an etching treatment, a flame treatment, or the like, and these treatments may be used in combination. The application of the thin-layered adherend can be carried out according to a conventional method, and the same method as described above can be exemplified. Further, the coating thickness of the composition of the present invention can be selected in accordance with the use of the thin layer adhesive and the use thereof, however, it is preferably the same coating thickness as described above. In the case of the plastic film or the like, it is not limited to the planar state, and it can be carried out in the curved state. That is, a method of bending a plastic film or the like into a concave state or a convex state, and applying the composition of the present invention in this state, bonding the other plastic film or the like, and irradiating the active energy ray And proceed. Other methods include a method in which the plastic film is applied to the composition of the present invention in a plane state, and the other plastic film or the like is bonded, and is bent into a concave state or a convex state, and the active energy ray is irradiated. Go ahead. The method of applying the composition in a planar state can be carried out by the method described above, and the method of applying the composition in a curved state can be exemplified by a method using a spray coater, a bar coater, and a micro gravure coater. In the liquid crystal display device or the like An optical film such as a polarizing plate and a protective film or a retardation film. "Specially, the composition of the present invention is preferably used in the production of a polarizing plate and a polarizing plate having a phase difference." Hereinafter, a method of manufacturing a polarizing plate will be described. In the present specification, the term "polarizing member" is as follows. The so-called polarizing plate of the polarizing machine's 'phase or film' means that the single polarizing member of the polarizing member is protected by a film or a film. The X-phase has a phase difference and is provided by a polarizing plate. The polarizer or the polarizing plate is bonded to the retardation film or formed by coating to form a film having a phase difference function. The method for producing the polarizing plate is as described above. The composition of the present invention is an adhesive for a hydrophilic plastic, and In the manufacture of a polarizing plate, a cellulose triacetate (IV) using a polyvinyl ether as a polarizing member and a protective film as a polarizing member is equivalent to a hydrophilic plastic. The composition of the present invention can be used in connection with a polarizing member and a protective film. The polarizing plate is followed by the retardation film. The polarizing member refers to a function of selectively polarizing a certain direction from natural light. Specific examples of the polarizing member include adsorption and enthalpy. Redene (10) is a polarizing element; a dichroic dye is adsorbed and entangled in a polyvinyl alcohol-based dye-based polarizing member; a coating = liquid) a liquid crystal state pigment and oriented, and (4) a coating-type polarizing light Polarizing member, dye-based polarizing member, and coating-type polarizing member 30 201100516 There is a function of linearly polarizing light which can selectively transmit in one direction from natural light and absorb linear polarization in the other direction, and is called an absorption type polarizing member. In the iodine-based polarizer and the dye-based polarizer, a protective layer is usually provided on one or both sides thereof, and the composition of the present invention can be used next to the polarizer and the protective film.

For example, the protective film used in the protective layer may be, for example, a cellulose acetate resin film such as cellulose triacetate or cellulose diacetate, an acrylic resin film, a polyester resin film, a polyarylate resin film, and a poly The ether sulfone resin film, a cyclic polyolefin resin film which is a monomer such as a cyclic olefin of norbornene, or the like. Next, the composition of the present invention can also be used in the case of a polarizing plate and a retardation film. In the case of &, a 35-plate can be used for a protective layer on one or both sides. In this case, the protective film can be bonded to the protective film, and r is a protective film which has been formed by coating. Only single

The phase difference between the polarizing plates «and then w can be a layer having a (four) layer H which can be a non-protective layer. The retardation film can be used in various forms, and examples thereof include an optical film which has been reinforced by uniaxial or biaxial stretching, or a liquid crystal compound = coated on a substrate and processed in a fixed direction. The optical film is used exclusively, and the relationship between the three-dimensional refractive index (refractive index ellipsoid) is controlled in accordance with the use conditions. It is mainly used to compensate for the color difference of the liquid crystal layer of the liquid crystal display, or to compensate for the change of the phase difference caused by the viewing angle. Specific examples of the retardation film, materials for performing the processing of the optical film such as stretching can be exemplified by a polyolefin such as polyethylene, polypropylene, or cyclic polystyrene 31 201100516; or polycarbonate or polyvinyl alcohol. Polystyrene, polymethyl methacrylate, polyaryl ester and polyamine. The cyclic polyolefin is a general term for a resin obtained from a cyclic olefin such as norbornene, tetracyclododecene or the like, and is exemplified by, for example, U.S. Patent No. 3,184,882. Japanese Laid-Open Patent Publication No. Hei 3-122137, the disclosure of which is incorporated herein. Specifically, a ring-opening polymer of a cyclic olefin; an addition polymer of a cyclic olefin; a random copolymer of a cyclic olefin and an a-olefin of ethylene, propylene or the like; or A graft modified body or the like modified with a carboxylic acid or a derivative thereof. Further, a hydride such as these may be mentioned. Commodities include, for example, ZEONEX, ZEONOR, JSR (ARTON), and Ticona (TICONA) manufactured by Japan's Swiss (ΖΕΟΝ) (share) Manufactured by Topas (TOPAS), etc. In addition, examples of the optical film which is obtained by applying a liquid crystal compound or the like to a substrate and performing processing for orientation and immobilization include, for example, "WV film" (manufactured by Fuji Photo Film Co., Ltd.), "LC film", and "ΝΗ". Films (all manufactured by Shin Sakamoto Petroleum Co., Ltd.) and the like. A method of producing a polarizing plate or a polarizing plate having a retardation film will be described using the composition of the present invention. The production method may, for example, be a method comprising the following steps [1] to [3]. [1] The composition of the present invention is applied to an adhesive body (substrate) selected from the group consisting of a polarizing member, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film. Steps; 32 201100516 [2] Adhesive body (substrate) adhered to the pre-formed core (adhesive 2 substrate) and the adherend (substrate) is selected from the bias material 1 f, protection The steps of the film, the protective film, the retardation film and the retardation film; and "'[3] the shaft body (county body) of the industry peaks, especially the bonded body (the layer = irradiation activity) (4) (4).

Γ Γ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在On both sides, it can be carried out after the cover 2: the person is just [3], or it can be repeated twice (1), in the above step [1], the technique, the 1 miscellaneous material, the front ❹ _ The activity of this amount line irradiation method can be carried out by the same method as before. When a polarizing plate having a phase difference thinness is used as the circular polarizing plate, the phase difference may be different in the stepwise film side of the phase difference film having the phase difference _ in order to form a circular green state in the wide band region. The retardation film 0' specifically includes a method of bonding a polarizing film to a retardation film having a wavelength of 丨/2 wavelengths at each wavelength, and then bonding a phase difference film having a wavelength of ... for each wavelength. At this time, it can be repeated three times (1) and [re-implemented [3], or three times [1], [2], and [3]. In addition, the documents cited in the present specification are inserted as a reference. EXAMPLES Examples and comparative examples are listed below, and the present invention will be more specifically described. 33 201100516 In addition, "parts" in the following examples mean 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 or isodecyl acrylate (hereinafter referred to as "IBXA") was placed. 198 g as a diluent, dibutyltin dilaurate. 16 g as a catalyst, 0.10 g of 2,6-di-t-butyl-4-nonylphenol as a polymerization inhibitor, and a nitrogen atmosphere containing 5 vol% of oxygen Under a gas, the surfaces were stirred and the surface was warmed until the liquid temperature was 70 °C. It took 2 hours to drip a polyester polyol having a hydroxyl value of 5 7rngK〇H/g in the reaction solution (Kuraray) to make P_2〇l〇, adipic acid and 3-methyl-1,5 - ester of pentanediol) i69g (0.086 moles). The internal temperature was raised to 80 ° C 'reaction for 2 hours, and ethylene glycol ruthenium. 67 g (0.011 mol) was added, and then reacted for 2 hours', and 2-hydroxyethyl acrylate 4.46 g (0.038 mol) was added. Re-reaction for 2 hours. The spectrum was measured by an infrared absorption spectroscopy apparatus (FT-IR spectrum (Speetrum) 100 manufactured by Perkin Elmer), and it was confirmed that the isocyanate group was completely consumed. The resulting reaction product contained a mixture of 50 parts of a urethane acrylate oligomer (hereinafter referred to as "UA1") and 50 parts of IBXA. Further, in Table 1 to be described later, the components of the composition are disclosed separately by the ratio of UA1 to IBXA. The result of the obtained UA1 was measured by gel permeation chromatography (solvent: tetrahydroanion, column: HSPgel HRMB-L manufactured by Waters), and the Mw in terms of polystyrene was 34,000. Example 1 to the same Example 9, Comparative Example 1 to Comparative Example 3 34 201100516 The components (B) to (D) shown in Table 1 were heated and stirred at 60 ° C for 1 hour to dissolve them. After cooling to room temperature, the component (A) was added, and the mixture was further stirred for 30 minutes to produce an active energy ray-curable adhesive composition. The viscosity of the obtained composition was measured at 25 ° by means of an E-type viscometer. Test Example 1. Production of a film laminate 1 (model test for polarizing plate production) A polyvinyl alcohol film (SOLUBLON EF# 30, manufactured by AICELL(R) Co., Ltd., hereinafter referred to as "PVA" On the film 1"), the obtained composition was applied to a thickness of 3 μm by a bar coater, and laminated with a cellulose triacetate (manufactured by Lonza) having a thickness of 10 (^m, The following is a private "TAC film". The composition is applied to the PVA film 1 side of the laminate in the same manner and a TAC film is laminated. From both sides of the laminate, a 160 W/cm concentrating metal element is used. The lamp (focus distance from 3 〇cm) was irradiated with ultraviolet rays at a conveyor speed of 5 m/min to harden the composition, and a film laminate was obtained. The water immersion test was carried out in accordance with the following test method for the obtained laminate. Table 2 shows the results. [60 ° C water immersion test] The prepared film laminate was cut into a width of 2 mm, a length of 5 〇 mm ' and immersed in the running water for 3 hours to confirm the peeling of the film. Whether or not the film is peeled off is not peeled off in the entire area of the film laminate. The area percentage of the fraction (the next part) was evaluated as the remaining area. If the residual area was 80% or more, the evaluation was good. 35 201100516 Test Example 2 • Production of a thin film laminate 2 (model experiment for polarizing plate manufacturing) A film laminate was obtained by the same method as described above except that the polyvinyl alcohol film was changed to Solblon NP (manufactured by Aisle, hereinafter referred to as "PVA film 2"). The peeling strength by the peeling test was measured according to the following test method, and the adhesive strength was measured. The results are shown in Table 2. [Peel Strength Measurement] The obtained film laminate was cut into a width of 25 mm and adhered by adhesion. The sheet was fixed to a gas-filled vinyl plate (manufactured by Nippon Test Panel Co., Ltd., 彡篆 resin 291A) and was subjected to a tensile tester for 9 Torr. The peeling test was performed. The unit of peel strength was N/25 mm. For iN/25mm or more, the evaluation is good. 36 201100516 [Table 1] Composition viscosity (mPa * s) (A) (B) (C) (D) Example 1 AOI (30) THFA (10) POA C30) — M240 (20) TPO (1) 4 implementation 2 AOI (30) THFA (20) POA (30) Ml 600 (20) TPO (1) 16 Example 3 AOI (30) ACMO (20) POA (30) M1600 (20) TPO (1) 21 Example 4 AOI (30) M140 (20) POA (30) M1600 (20) TPO (1) 33 Example 5 AOI (30) POA (30) Ml 600 (20) M240 (20) TPO (1) 24 Example 6 MOI (10) THFA (40) POA (10) Ml 600 (20) TPO (7) 20 Example 7 LR9000 0〇) THFA (40) POA (30) M1600 (20) TPO (1) 25 Example 8 AOI (10) THFA (50) POA ( 20) IBXA il〇) UA1 (10) TPO (1) 36 Example 9 AOI (10) THFA (60) IBXA (25) UA1 (5) TPO (1) 28 Comparative Example 1 THFA (50) POA (30) Ml 600 (10) TPO (1) 18 Comparative Example 2 ACMO (50) POA (30) M1600 C20) TPO (1) 23 Comparative Example 3 AOI (30) M240 (70) TPO (1) 8 * The numbers in parentheses in Table 1 refer to the number of copies. The abbreviations in Table 1 refer to the following. (A) ingredients

AOI : 2-Propylene Oxide Ethyl Isocyanate, Showa Denko Co., Ltd. manufactures KARENZ AOI

MOI : 2-Methyl propylene oxirane ethyl isocyanate, Showa Denko Co., Ltd. Manufacture of Kallenz MOI LR9000: Polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate, manufactured by BASF in Laromo (9) (B) Ingredients: THFA: Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. VISCOAT # 15〇37 201100516 ACMO: Propylene morpholine

POA : 2-Phenoxyethyl acrylate, Kyung Shing Chemical Co., Ltd. Manufactured by Light-Acrylate PO-A M140 : N-Propylene Oxyethyl Ethyl hexahydroimide, East Asia Synthesis (stock) Manufacture of ARONIX M-140 (C) Component M1600: Polyether urethane acrylate, East Asia Synthetic (Shares) Manufacture of Alstom M-1600 UA1: by Manufacturing Example 1 Polyurethane phthalate acrylate M240: polyethylene glycol diacrylate, manufactured by East Asia Synthetic Co., Ltd., manufactured by Aldos M-240 (D)

TPO: 2,4,6-trimethylbenzylidene diphenylphosphine oxide, Japan Ciba (CIBA) (share) manufacturing DAROCUR TPO

[Table 2] Test Example 1 Test Example 2 Residual area (%) of 60 ° C water immersion test Peel strength (N / 25 mm) Example 1 80 1.3 Example 2 100 2.0 Example 3 100 1.5 Example 4 100 1.7 Example 5 100 1.9 Example 6 100 2.1 Example 7 100 1.5 Example 8 100 2.5 Example 9 100 2.3 Comparative Example 1 0 0.3 Comparative Example 2 0 0.1 Comparative Example 3 70 0.8 38 201100516 Industrial Applicability The composition of the present invention can be As an adhesive for a hydrophilic plastic, an adhesive which is a hydrophilic plastic film or the like is used in particular. In particular, the composition of the present invention is suitably used for the production of an optical film such as a liquid crystal display device, particularly a polarizing plate. [Simple description of the diagram] (None) [Description of main component symbols] (none)

39

Claims (1)

201100516 VII. Patent application scope: 1. An active energy ray-curable adhesive composition for hydrophilic plastics, comprising the following components (A) to (c), namely: (A) having ethylenically unsaturated groups and isocyanates a compound having one ethylenically unsaturated group, which is a compound other than the component (A) and is a compound which is not reactive with the isocyanate group of the component (A); and (c) has 2 A compound having at least one ethylenically unsaturated group which is a compound other than the component (A) and which is not reactive with the isocyanate group of the component (A). The active energy ray-curable adhesive composition for a hydrophilic plastic according to the first aspect of the invention, wherein the component (A) is a compound having one ethylenically unsaturated group and one isocyanate group. 3) An active energy ray-curable adhesive composition for a hydrophilic plastic material according to the second aspect of the invention, wherein the component (A) is a (meth) propylene oxyalkylene isocyanate. 4. The active energy ray-curable adhesive composition for a hydrophilic plastic according to any one of claims 1 to 3, wherein the component (B) contains: a compound having one ethylenically unsaturated group and a heterocyclic ring . 5. The active property wire-curing adhesive composition for a hydrophilic plastic according to any one of claims 1 to 4, wherein the component (B) contains an aromatic monofunctional (fluorenyl) acrylate. 6. The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 1 to 5, wherein the component (C) contains an amine group 201100516 formic acid vinegar (meth)acrylic acid And the oligomer is a reactant of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate. 7. 8. Ο 9. 10. G 11. 12. The composition of the active energy ray-curable adhesive for hydrophilic plastics according to item 6 of the patent application, the urethane of the urethane (meth) acrylate The 'polyol in the oligomer is a polyester polyol. An active energy ray-curable adhesive composition for hydrophilic plastics according to claim 6 or 7, wherein the amino phthalate (meth) acrylate oligomer has a weight average molecular weight of 2, 〇〇 〇 to 6〇, 〇〇〇. The active energy ray-curable adhesive composition for hydrophilic plastics according to any one of claims 7 to 9, which is based on the total amount of the components (A) to (c) and contains 5 weights. % to 5〇 weight. /. (A) component, 20% by weight to 90% by weight of the cation component, and 5% by weight to 5% by weight of the (<:) component. The active monthly b linear hardening type adhesive composition for hydrophilic plastics according to any one of claims 1 to 9, which further comprises (D) a photopolymerization initiator. The active energy ray-curable adhesive composition for hydrophilic plastics according to claim 10, which further comprises from 0 to 10% by weight to 10% by weight of the bismuth component. The composition of the active-strength wire-curable adhesive for hydrophilic plastics according to any one of claims 1 to 11, wherein one or both of the adherends are hydrophilic plastics. For example, the active energy ray for hydrophilic plastics according to the scope of claim 12 is a composition of the adhesive composition, wherein the hydrophilic plastic is in the form of a film or a sheet. An adhesive composition for producing a polarizing plate, comprising the composition according to any one of claims 1 to 13. A method for producing a composition for an active energy ray-curable adhesive for plastics, comprising the following components (A) to (C), namely: (A) having a compound having an ethylenically unsaturated group and an isocyanate group; (B) a compound having one ethylenically unsaturated group which is a compound other than the component (A) and which is not reactive with the isocyanate group of the component (A) And (C) a compound having two or more ethylenically unsaturated groups, which is a compound other than the component (A), and is a compound which is not reactive with the isocyanate group of the component (A); and the method of production It is characterized in that: after mixing the component (B) and the component (C), the component (A) is blended in the obtained mixture. 16. A method of bonding a substrate and a substrate, characterized by using a composition according to any one of claims 1 to 13, which one or both are hydrophilic plastics The substrates are adhered to each other and are then irradiated with active energy lines. 17. A method of producing a laminate, characterized in that: using a composition according to any one of claims 1 to 13, one or both of the substrates of the hydrophilic plastic are adhered to each other' The active energy line is illuminated. 42 201100516 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: