KR101988922B1 - Resin composition for uv-curable pressure sensitive adhesive, pressure sensitive adhesive and laminate - Google Patents

Abstract

A problem to be solved by the present invention is to provide a resin composition for an ultraviolet-curable pressure-sensitive adhesive which has both an adhesive force and a holding force excellent in level that does not cause peeling at a time with respect to a substrate made of various materials or shapes. The present invention relates to a urethane (meth) acrylate resin (A), a (meth) acrylic monomer (B) obtained by reacting a polyol (a), a polyisocyanate (b) and a hydroxyl group- (Meth) acrylic monomer (B) capable of forming a homopolymer having a glass transition temperature of 50 占 폚 or higher, wherein the (meth) acrylic monomer (B) is a 1) capable of forming a homopolymer having a glass transition temperature of -20 占 폚 or lower and a (meth) acrylic monomer (b-2) capable of forming a homopolymer having a glass transition temperature of -20 占 폚 or less. (B-1) / (b-2) = 20/80 to 60/40. The present invention also provides a resin composition for an ultraviolet curable pressure-sensitive adhesive.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for an ultraviolet curable pressure-sensitive adhesive, a pressure-sensitive adhesive, and a laminate,

The present invention relates to a resin composition, a pressure-sensitive adhesive and a laminate for an ultraviolet curable pressure-sensitive adhesive excellent in adhesion and retention.

BACKGROUND ART [0002] In optical-related products including a touch panel and a liquid crystal display, a large number of optical members having various kinds of materials and shapes have been used along with their high functionality.

In the past, a pressure-sensitive adhesive has been used for bonding the optical member as described above, but in the industry, a pressure-sensitive adhesive having excellent adhesive force is required regardless of the material and shape of the component.

In addition, in the production scenes of the above-mentioned optical related products, improvement of the productivity of the final products has become a big problem in recent years. This is because the pressure sensitive adhesive conventionally used usually contains a solvent such as a solvent or water and therefore the pressure sensitive adhesive is applied to the surface of a base material or the like and then subjected to a process for removing the solvent contained in the pressure sensitive adhesive for a long time , Which is a cause of lowering the production efficiency of the final product.

As a pressure-sensitive adhesive capable of improving the production efficiency of the product, an ultraviolet curable pressure-sensitive adhesive is known. Since the ultraviolet curing type pressure-sensitive adhesive usually does not contain a solvent such as a solvent or water, it does not require a step of removing the solvent when forming the pressure-sensitive adhesive layer.

As a pressure-sensitive adhesive capable of improving the production efficiency of a final product as compared with the prior art, for example, a pressure-sensitive adhesive having a urethane bond at 100 parts with respect to 100 parts of a monomer having an unsaturated double bond , And further contains 5 parts by mass or more and 200 parts by mass or less of a high molecular weight substance having a weight average molecular weight of 20,000 or more having an unsaturated double bond at the terminal of the polymer (for example, refer to Patent Document 1 Reference).

However, the pressure-sensitive adhesive composition may not exhibit sufficient adhesive force for practical use depending on the material of the base material and the like. Depending on the material and the shape of the base material, the pressure-sensitive adhesive composition may be peeled off in a time- There is a case where the base material is displaced with respect to a force in the lateral direction which is parallel to the surface of the base material.

Japanese Patent Application Laid-Open No. 2006-104296

A problem to be solved by the present invention is to provide a resin composition for an ultraviolet curing type pressure-sensitive adhesive which has both an adhesive force and a holding force excellent in level that does not cause peeling at a time with respect to a substrate made of various materials and shapes.

The inventors of the present invention proceeded with intensive studies in order to solve the above problems by studying a (meth) acrylic monomer used in combination with a urethane (meth) acrylate resin.

However, when a single (meth) acrylic component was used as the (meth) acrylic monomer, a pressure-sensitive adhesive capable of achieving both adhesion and retention was not obtained.

Therefore, the inventors of the present invention paid attention to the control of the cohesion force due to the glass transition temperature of the (meth) acrylic monomer, and conducted intensive studies.

As a result, it has been found that (meth) acrylic monomers having a specific glass transition temperature, a (meth) acrylic monomer using a combination of a nitrogen-containing (meth) acrylic monomer having a specific glass transition temperature with And found that a pressure-sensitive adhesive capable of achieving excellent adhesive force and holding force can be obtained when used in combination, and thus the present invention has been accomplished.

That is, the present invention relates to a urethane (meth) acrylate resin (A), a (meth) acrylic monomer (B) obtained by reacting a polyol (a), a polyisocyanate (b) and a hydroxyl group- ) And a photopolymerization initiator (C), wherein the (meth) acrylic monomer (B) is a nitrogen-containing (meth) acrylic monomer capable of forming a homopolymer having a glass transition temperature of 50 ° C or higher (b-1) capable of forming a homopolymer having a glass transition temperature of -20 占 폚 or lower and a (meth) acrylic monomer (b-2) capable of forming a homopolymer having a glass transition temperature of- (B-1) / (b-2) = 20/80 to 60/40, wherein the ratio of (b-1) /

The resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention comprises a urethane (meth) acrylate resin (A) obtained by reacting a polyol (a), a polyisocyanate (b) and a hydroxyl group- (Meth) acrylic monomer (B) and a photopolymerization initiator (C), wherein the (meth) acrylic monomer (B) (Meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of -20 占 폚 or lower, wherein the (meth) acrylic monomer (b- (b-1) / (b-2) = 20/80 to 60/40, the mass ratio of the pressure-sensitive adhesive to the pressure-sensitive adhesive (b-2) The pressure-sensitive adhesive comprising the resin composition for an ultraviolet curable pressure-sensitive adhesive of the present invention can be suitably used as a pressure-sensitive adhesive for use in an optical member. In particular, it can be suitably used for manufacturing liquid crystal touch panels, liquid crystal displays, plasma displays, organic ELs and the like.

The resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention is a resin composition containing a urethane (meth) acrylate resin (A), the (meth) acrylic monomer (B), the photopolymerization initiator (C) will be.

The resin composition for an ultraviolet-curable pressure-sensitive adhesive is characterized in that the urethane (meth) acrylate resin (A), the (meth) acrylic monomer (B), the photopolymerization initiator (C), and additives are contained in an organic solvent or an aqueous medium (Meth) acrylate resin (A), the photopolymerization initiator (C) and the like are dissolved or dispersed in the (meth) acrylic monomer (B) The step of removing the solvent contained in the pressure-sensitive adhesive is not required when the laminate is manufactured, and the production efficiency of the laminate can be improved.

Next, the urethane (meth) acrylate resin (A) used in the present invention will be described.

The urethane (meth) acrylate resin (A) can be obtained by reacting the polyol (a), the polyisocyanate (b) and the hydroxyl group-containing (meth) acrylic compound (c).

The urethane (meth) acrylate resin (A) has a (meth) acryl group for promoting radical polymerization by light irradiation or heating. The equivalent weight of the (meth) acrylic group is preferably in the range of 4000 to 9000, from the viewpoint of being able to form a pressure-sensitive adhesive layer having both excellent adhesive force and holding force and having good transparency, Is more preferable. The equivalent weight of the (meth) acrylic group is preferably such that the total mass of the polyol (a), the polyisocyanate (b) and the hydroxyl group-containing (meth) acrylic compound (c) (Meth) acrylic group present in the resin (A).

As the urethane (meth) acrylate resin (A), those having a weight average molecular weight of 1,000 to 50,000 can be used from the viewpoints of both excellent adhesive force and holding force and capable of imparting good coating workability More preferably from 10,000 to 25,000, and particularly preferably from 12,000 to 25,000. The weight average molecular weight of the urethane (meth) acrylate resin (A) is a value obtained by styrene conversion using gel permeation chromatography (GPC).

The polyol (a) is not particularly limited, but a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyacryl polyol, or the like may be used, and these may be used alone or in combination of two or more. Among them, it is preferable to use a polyether polyol from the viewpoints of both excellent adhesive force and holding force, and from the viewpoint of improving the durability, particularly the hydrolysis resistance, of the pressure-sensitive adhesive film.

Examples of the polyether polyol usable in the polyol (a) include, for example, one or more kinds of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, with addition polymerization of a compound having two or more active hydrogen Polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, modified polytetramethylene glycol obtained by copolymerizing tetrahydrofuran and alkyl-substituted tetrahydrofuran, or a copolymer of neopentyl glycol and tetrahydrofuran And modified polytetramethylene glycol.

Examples of the compound having two or more active hydrogens include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl- -Methyl-1,8-octanediol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, pentaerythritol, Dipentaerythritol, sorbitol, saccharose, ethylenedia 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, Diethylenetriamine, phosphoric acid, acidic phosphate and the like can be used.

In addition to these, polyether polyols having an alicyclic structure may be used.

Among these, aliphatic polyether polyols are more preferably used from the viewpoint of imparting good adhesive property, and it is particularly preferable to use polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran.

As the polyol (a), other active hydrogen-containing chain (chain) extender may be used in combination with the above-mentioned polyester polyol, polyether polyol, polycarbonate polyol, polyacrylic polyol and the like.

Examples of other active hydrogen-containing chain extender include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, Cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, 1,4-cyclohexanedimethanol, Polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylol propane, sorbitol and hydroquinone diethylol ether; aliphatic alcohols such as ethylenediamine, propylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, -Dicyclohexylmethanediamine, diaminocyclohexane, methyldiaminocyclohexane, norbornenediamine, and the like can be used singly or in combination of two or more.

The polyol (a) preferably has a weight average molecular weight in the range of 500 to 2,000 from the viewpoint of imparting good cohesive strength and flexibility to the pressure-sensitive adhesive layer, and has a weight average molecular weight in the range of 500 to 1,500 It is more preferable to use the one. The weight average molecular weight of the polyol (a) is a value determined by gel permeation chromatography (GPC) by styrene conversion.

Examples of the polyisocyanate (b) include aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate, and aromatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclo Aliphatic or aliphatic cyclic structure-containing diisocyanates such as hexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanatomethylcyclohexane, and tetramethylxsilylene diisocyanate; More than one species can be used in combination. Among them, use of a diisocyanate containing an alicyclic cyclic structure is preferable from the viewpoints of both excellent adhesion and retention, and from the viewpoint of improving heat resistance yellowing, 4,4'-dicyclohexylmethane diisocyanate , Isophorone diisocyanate, cyclohexane diisocyanate, and diisocyanatomethylcyclohexane are more preferably used.

As the hydroxyl group-containing (meth) acrylic compound (c), those containing a hydroxyl group capable of reacting with an isocyanate group are used for introducing a (meth) acrylic group into the urethane (meth) acrylate resin .

Examples of the hydroxyl group-containing (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl (Meth) acrylates such as trimethylolpropane di (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl acrylate, trimethylolpropane di (Meth) acrylate, dipentaerythritol penta (meth) acrylate and the like, polyfunctional (meth) acrylate, polyethylene glycol monoacrylate, and polypropylene glycol monoacrylate. Among them, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferably used from the viewpoint of easiness of raw material availability, curability, and good adhesive property.

Examples of the method for producing the urethane (meth) acrylate resin (A) include a method of charging the polyol (a) and the hydroxyl group-containing (meth) acrylic compound (c) into a reaction system under a solvent- (a) and the polyisocyanate (b) are reacted under a solventless condition to obtain an urethane prepolymer having an isocyanate group at the molecular terminal, and subsequently reacting the polyisocyanate (b) with the hydroxyl group Containing (meth) acrylic compound (c), and mixing and reacting the same. It is preferable that the above reaction is carried out at a temperature of 20 to 120 캜 for about 30 minutes to 24 hours.

The urethane (meth) acrylate resin (A) may be prepared in the presence of an organic solvent or an aqueous medium. In place of the organic solvent or the aqueous medium, it may be produced in the presence of a (meth) acrylic monomer (B) described later. Among them, in the production of the laminate, the removal of the organic solvent and the aqueous medium is unnecessary, and the production process can be simplified. Therefore, from the viewpoint of suppressing viscosity in a solvent or in a reaction system, .

The reaction of the polyol (a) with the polyisocyanate (b) and the hydroxyl group-containing (meth) acrylic compound (c) is carried out in such a manner that the hydroxyl group of the polyol (a) (Isocyanate group / hydroxyl group)] = 0.75 to 1.00 in the case where the urethane (meth) acrylate resin (A) obtained has a molecular weight of And is more preferably in the range of 0.79 to 0.95. In this case, for the purpose of inactivating the terminal isocyanate group of the urethane (meth) acrylate resin (A), an alcohol such as methanol may be used for the purpose of deactivating the terminal isocyanate group of the urethane (meth) acrylate resin . In this case, the total amount of the hydroxyl group of the polyol (a) and the hydroxyl group of the hydroxyl group of the hydroxyl group-containing (meth) acrylic compound (c) and the alcohol is preferably in the range of the equivalent ratio of the polyisocyanate group [isocyanate group / hydroxyl group Is within the above-mentioned range.

Examples of the alcohol which can be used for the purpose of deactivating the terminal isocyanate group of the urethane (meth) acrylate resin (A) include monofunctional alcohols such as methanol, ethanol, propanol and butanol, Bifunctional alcohols composed of primary and secondary hydroxyl groups such as propylene glycol and 1,3-butylene glycol may be used.

When the urethane (meth) acrylate resin (A) is produced, a polymerization inhibitor or an urethanization catalyst may be used if necessary.

Examples of the polymerization inhibitor include 3,5-bis tert-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), para tert- butyl catechol methoxyphenol , 2,6-ditert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene and the like can be used.

Examples of the urethanization catalyst include nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine, metal salts such as potassium acetate, zinc stearate and tin octylate, and dibutyl tin laurate Organic metal compounds and the like can be used.

Next, the (meth) acrylic monomer (B) used in the present invention will be described.

(Meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of 50 DEG C or higher and a (meth) acrylic monomer capable of forming a homopolymer having a glass transition temperature of- And contains the monomer (b-2).

As the nitrogen-containing (meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of 50 DEG C or higher, a homopolymer having a glass transition temperature of 55 to 160 DEG C (Meth) acrylic monomer capable of forming a nitrogen-containing (meth) acrylic monomer is preferable, and a nitrogen-containing (meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of 140 to 160 캜 is more preferable.

Examples of the nitrogen-containing (meth) acrylic monomer usable in the above (b-1) include (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N, (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt, (meth) acryloylmorpholine, isopropyl ) Acrylamide, N- (meth) acryloyloxyethylhexahydrophthalimide, and hydroxyethyl (meth) acrylamide. These may be used alone or in combination of two or more.

Among these, from the viewpoint of improving the curability, it is preferable to use a nitrogen-containing acrylic monomer, and from the viewpoint of being able to further improve both adhesion and holding force, acryloylmorpholine, dimethyl acrylamide, dimethylamino Propyl acrylamide, N-acryloyloxyethylhexahydrophthalimide is more preferably used, and it is particularly preferable to use acryloylmorpholine.

As the (meth) acrylic monomer (b-2) capable of forming a homopolymer having a glass transition temperature of -20 占 폚 or lower, a glass transition temperature of -25 to -80 占 폚 (Meth) acrylic monomer capable of forming a homopolymer of a (meth) acrylic monomer.

Examples of the (meth) acrylic monomer usable in the above (b-2) include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, Hexyl acrylate, n-heptyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl acrylate, n-lauryl methacrylate, tridecyl methacrylate, isomyristyl acrylate, 2-ethylhexyl acrylate 2-methylbutyl acrylate, 2-methylpentyl acrylate, 2-methoxyethyl acrylate, 3-methoxypropyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2- Ethoxypropyl, 2-ethoxybutyl acrylate, etc. These may be used alone or in combination of two or more.

Of these, from the viewpoint of enhancing the curability, it is preferable to use an acrylic monomer, and from the viewpoint of being able to further improve both the good adhesive force and the holding force, it is preferable to use n-butyl acrylate or 2-ethylhexyl acrylate More preferable.

(B-1) / (b-2) = 20/80 to 60/40 in the mass ratio of the (meth) acrylic monomer to the (b-1) A pressure-sensitive adhesive having both adhesive force and holding force can be obtained. (B-1) / (b-2) = 30/70 to 50 (b-2) from the viewpoint that the excellent adhesion and holding force can be further improved, / 50 is more preferable. When the mass ratio of (b-1) in the mass ratio of (b-1) to (b-2) is less than 20 (lower) The hardness is increased by the high cohesive force, and the pressure-sensitive adhesive can not be obtained.

The (meth) acrylic monomers to be used in the present invention may be used in combination with other vinyl monomers other than the above-mentioned (b-1) and (b-2) so long as the effect of the present invention is not impaired.

Examples of the other vinyl monomer include (meth) acrylic acid, dimethylaminoethyl (meth) acrylate, N-methylol acrylamide, N-vinylpyrrolidone, acrylonitrile, N- vinylformamide, (Meth) acrylate, methyl (meth) acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl (meth) acrylate, Butyl methacrylate, isobutyl methacrylate, t-butyl (meth) acrylate, n-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, methacryl (Meth) acrylate, isobutyl methacrylate, n-heptyl methacrylate, isoheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, cyclohexyl (Meth) acrylate dodecyl, phenyl methacrylate, methacrylate 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-methylpropyl (meth) acrylate 2 Perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, difluoromethyl methyl (meth) acrylate, 2- (perfluoroethyl) Perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate, etc. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate having a hydroxyl group such as pentaerythritol tri (meth) acrylate, , There may be mentioned vinyl monomers such as styrene, p- methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, p-tert- butyl styrene, such as styrene-based monomers, vinyl acetate, vinyl propionate, vinyl pivalate.

The amount of the (meth) acrylic monomer (B) to be used is preferably in the range of from 30 to 200 parts by mass in view of being able to achieve both good adhesive force and holding force for 100 parts by mass of the urethane (meth) acrylate resin (A) More preferably in a range of 40 to 150 parts by mass, and particularly preferably in a range of 50 to 100 parts by mass.

Next, the photopolymerization initiator (C) used in the present invention will be described.

The photopolymerization initiator (C) generates a radical by light irradiation or heating to initiate radical polymerization of the urethane (meth) acrylate resin (A) or the (meth) acrylic monomer (B).

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- 2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl - [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone; Benzoins such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 3,3'-dimethyl- Currents; Thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxane Thioxanthones such as santone and 2,4-diisopropylthioxanthone; (4-aminobenzophenone,? -Acyloxime ester, benzyl, methylbenzoylformate ("Baia Cure 55"), 2, 4'-dimethylaminothioxanthone - anthraquinones such as ethyl anthraquinone; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucillin TPO") and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE819" ; 3,3 ', 4,4'-tetra (tert-butyloxycarbonyl) benzophenone ("BTTB" manufactured by NOF Corporation), and acrylated benzophenone.

As the photopolymerization initiator, it is possible to achieve both excellent adhesive force and holding force, to prevent discoloration of the pressure-sensitive adhesive layer over time, and to improve the compatibility with the specific (meth) acrylic monomer used in the present invention From the viewpoint of improving the curability, it is preferable to use 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, It is preferable to use bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Among them, one or two of the above-mentioned 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1-hydroxycyclohexylphenylketone and 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and combinations thereof.

Further, one or two of the above-mentioned 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenylketone and 2,4,6-trimethylbenzoyldiphenylphosphine (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide is used in combination, the compatibility with the specific (meth) acrylic monomer used in the present invention Hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenylketone, and from the viewpoint of further improving the curability, , 6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide in a weight ratio of 20/80 to 80/20 And more preferably 45/55 to 65/35.

The amount of the photopolymerization initiator (C) to be used is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the urethane (meth) acrylate resin (A) More preferable.

When a pressure sensitive adhesive comprising a resin composition for an ultraviolet curable pressure sensitive adhesive of the present invention is used for an optical member, it is preferable that the ultraviolet curable pressure sensitive adhesive composition of the present invention further contains a light stabilizer (D) .

The light stabilizer (D) is a substance that captures radicals generated by photodegradation (deterioration). Examples of the light stabilizer (D) include radical scavengers such as thiol, thioether and hindered amine compounds, And ultraviolet absorbers such as an ultraviolet absorber compound and the like can be used. Among them, a hindered amine-based compound is preferably used from the viewpoint of maintaining compatibility between excellent adhesive force and holding power, and further improving compatibility with a specific (meth) acrylic monomer used in the present invention and light stability .

Examples of the hindered amine compound include cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5 (Product name: Tinuvin (registered trademark) 152 (manufactured by BASF Japan)), decanedioic acid bis (2,2,6,6-tetramethyl- The reaction product of 1,1-dimethylethyl hydroperoxide and octane, such as 1- (octyloxy) -4-piperidinyl ester (trade name: Tinuvin (registered trademark) 123 (Trade name: Hostavin < (R) >) (trade name: N-acetyl-3-dodecyl) -1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine- N-acetyl-type hindered amine compounds such as N-acetyl-type hindered amine compounds such as N-acetyl- 4,7-bis (1,1-dimethylpyridyl) benzoate (trade name: SANOL LS765, manufactured by BASF Japan K.K.)), bis (1,2,2,6,6, ) -4-hydroxyphenyl] methyl} butyl malonate (trade name: Tinuvin (registered trademark) 144 (manufactured by BASF Japan)), dimethyl succinate and 4-hydroxy-2,2,6,6- Propane di [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-tetrahydronaphthalene-1-yl) N-alkyl-based hindered amine compounds such as 6-pentamethyl-4-piperidyl ester (trade name: Hostavin (registered trademark) PR-31 (manufactured by Client Japan K.K.)). Among them, from the viewpoint of maintaining compatibility between excellent adhesive force and holding force and further improving the compatibility with the specific (meth) acrylic monomer used in the present invention and the stability against light, the hindered It is particularly preferable to use an amine compound.

The amount of the light stabilizer (D) to be used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate resin (A) from the viewpoint of imparting heat resistance yellowing of the pressure- And more preferably 0.1 to 5 parts by mass.

When the pressure-sensitive adhesive comprising the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention is used for an optical member, it is preferable that the ultraviolet-curable pressure-sensitive adhesive composition of the present invention further contains an antioxidant (E) .

The antioxidant (E) refers to a hindered phenol-based compound (primary antioxidant) that is caught by radicals generated by thermal degradation and a phosphorus-based or sulfur-containing compound (secondary antioxidant) that decomposes peroxides generated by thermal degradation. These can be used alone or in combination.

Examples of the hindered phenol compound include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 245 (Trade name: IRGANOX (registered trademark) 1010 (manufactured by BASF Japan Co., Ltd.)), pentaerythritoltetrakis [3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionate (Trade name: IRGANOX (registered trademark) 1076 (manufactured by BASF Japan)), octadecyl [3- (3,5-di-tert- (Trade name: IRGANOX (registered trademark) 1035 (manufactured by BASF Japan)), benzenepropanetetraacetic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy--C ₇ -C ₉ branched alkyl ester (trade name: IRGANOX (TM) 1135 (BASF jyapan (Ltd.))), 4,6 -Bis (dodecylthiomethyl) -o-cresol (trade name: IRGANOX (registered trademark) 1726 (manufactured by BASF Japan), N-phenylbenzeneamine and 2,4,4-trimethylpentene Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-tert-butoxycarbonylamino- Methylphenyl acrylate (trade name: Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.)), 3,9-bis [2- [3- (t- butyl- Oxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., 2,6-di-tert-butyl-4-methylphenol (trade name: Knockarac 200 (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2,2'- Butylphenol) (trade name: Knockarak NS-6 (manufactured by Ouchi Shinko Chemical Industries, Ltd.)), 2,5-di-tert-amylhydroquinone (trade name: Knockarak DAH Ltd.)) and the like.

Examples of the phosphorus compound include triphenylphosphine, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethylphosphite, triphenylphosphite, trisnonylphenylphosphite, Tris (2,4-dibutylphenyl) phosphite, tris (2,4-dibutyl-5-methylphenyl) phosphite, tris [2- tert- (Methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) (2,6-dibutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tributylphenyl) pentaerythritol diphosphite, ) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite , Tetra (tridecyl) -4,4'-n-butylidenebis (2-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3- (2,4-dibutylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphoperanthrene- 2-ethylhexylphosphite, 2,2'-methylenebis (4,6-butylphenyl) -octadecylphosphite, 2,2'-methylenebis Tris (2 - [(2,4,8,10-tetrakisbutyldibenzo [d, f] [1,3,2-dioctylphenyl] fluorophosphite, ] Dioxyphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and a phosphite of 2,4,6-tributylphenol.

Examples of the sulfur compounds include, but are not limited to, didodecyl-3,3'-thiopropionate, dilauryl-3,3'-thiodipropionate, lauryldithiothionate, Thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate 3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, bis [2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide,? -Laurylthiopropionate, 2- mercaptobenzoimidazole, 2- mercapto- Dioctadecyl-3,3'-thiodipropionate, and the like.

Among them, from the viewpoints of maintaining both excellent adhesion and holding force and further improving the compatibility with the specific (meth) acrylic monomer used in the present invention and the heat resistance to sulfur, it is preferable to use a phosphorus compound (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite, pentaerythritol tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate is particularly preferably used.

The amount of the antioxidant (E) to be used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate resin (A), from the viewpoint of imparting good heat- , And more preferably 0.1 to 5 parts by mass.

When the pressure sensitive adhesive comprising the resin composition for an ultraviolet curable pressure sensitive adhesive of the present invention is used in the production of an optical member, in particular, a liquid crystal touch panel, metal corrosion of indium tin oxide (hereinafter abbreviated as ITO) It is preferable to further contain a rust inhibitor (F) in the ultraviolet-curing pressure-sensitive adhesive composition of the present invention from the viewpoint of preventing (rust-inhibiting)

As the rust preventive (F), for example, triazole-based compounds, organic carboxylic acid amine salts, nitrite amine salts, phosphoric acid amine salts, carbonic acid amines, heterocyclic amines and the like may be used. From the viewpoints of maintaining compatibility with excellent adhesive force and holding force and further improving the compatibility with the specific (meth) acrylic monomer used in the present invention and the rustproofing property without impairing the light resistance stability and the heat resistance yellowing resistance , Triazole-based compounds are preferably used.

Examples of the triazole compound include 1- [bis (2-ethylhexyl) aminomethyl] benzotriazole, methylbenzotriazole, dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethyl Benzotriazole, unsubstituted benzotriazole, 5-methyl-1H-benzotriazole, N, N-bis (2-ethylhexyl) - (4 or 5) , A triazole compound represented by the following general formula (1), and the like can be used.

(Wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 7 to 13 carbon atoms An aryl group having 6 to 10 carbon atoms, or a hydroxyl group)

As the triazole compound represented by the general formula (1), N, N-bis (2-ethylhexyl) - [(1,2,4-triazol-1-yl) methyl] have.

As the triazole compound, commercially available products such as "IRGAMET (registered trademark) 30" and "IRGAMET (registered trademark) 38S" (manufactured by BASF Japan) can be used.

The amount of the rust preventive (F) to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the urethane (meth) acrylate resin (A), which is capable of imparting good rust- , And more preferably in a range of 0.01 to 2 parts by mass.

Next, the resin composition for an ultraviolet curable pressure-sensitive adhesive of the present invention will be described.

The resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention can be obtained by, for example, preparing a urethane (meth) acrylate resin (A) alone and then using a (meth) acrylic monomer (B), a photopolymerization initiator A method of mixing the light stabilizer (D), the antioxidant (E) and the rust preventive (F) or a method of mixing the urethane (meth) acrylate resin (A) in the presence of a part or the whole of the (meth) acrylic monomer (B) (D), an antioxidant (E) and an antirusting agent (F), if necessary.

The resin composition for an ultraviolet curable pressure-sensitive adhesive obtained by the above method is not particularly limited, but is preferably 500 to 20,000 mPa · s, more preferably 1,000 to 10,000 mPa · s, from the viewpoints of good coatability and good handling of the pressure- . In addition, the viscosity shows a value measured by a B-type viscometer at 25 캜.

The resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention may contain other additives in addition to those described above.

Examples of other additives include additives such as a thixo imparting agent, a sensitizer, a polymerizable metal material, a curing agent, a curing accelerator, a leveling agent, a tackifier, a wax, a heat stabilizer, a fluorescent brightener, a foaming agent, a thermoplastic resin, A water-repellent agent, a hollow foam, a crystal water-containing compound, a flame retardant, an absorbent, a moisture absorbent, a deodorant, a defoaming agent, a defoaming agent, an antifoaming agent, an antistatic agent, Antifungal agents, antiseptics, antiblocking agents, hydrolysis inhibitors, organic and inorganic water-soluble compounds, and the like can be used.

Examples of the sensitizer include biphenyls, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, anthracene, 9,10-diphenylanthracene, 9,10-dimethoxy Anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, benzophenone, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, Benzaldehyde and the like can be used.

Examples of the curing agent include polyisocyanate compounds represented by tolylene diisocyanate, adducts derived from hexamethylene diisocyanate and the like, and nylon, polyfunctional epoxy compounds, melamine compounds, metal chelates, and the like.

INDUSTRIAL APPLICABILITY The resin composition for an ultraviolet curable pressure-sensitive adhesive of the present invention can be cured by irradiation with an energy ray such as ultraviolet rays.

As a method of curing the resin composition for an ultraviolet curable pressure-sensitive adhesive of the present invention, a known ultraviolet light irradiation apparatus such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, Of ultraviolet rays.

The irradiation of the ultraviolet ray is preferably in the range of 50 to 5000 mJ / cm 2, more preferably 100 to 3000 mJ / cm 2, and particularly preferably 300 to 1500 mJ / cm 2. The ultraviolet irradiation dose was based on a value measured in a wavelength range of 300 to 390 nm using UV Checker UVR-N1 (manufactured by GS Yuasa).

When the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention contains the above other additives, the curing may be further promoted by heating to about 40 to 80 캜 after irradiation with ultraviolet light, if necessary.

The pressure-sensitive adhesive comprising the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention can be suitably used as a pressure-sensitive adhesive for use in an optical member, since it has both excellent adhesive force and holding force. In particular, it can be suitably used for manufacturing liquid crystal touch panels, liquid crystal displays, plasma displays, organic EL displays and the like.

As a preferred use of the pressure-sensitive adhesive comprising the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention, for example,

In the liquid crystal touch panel, a plastic substrate, a flexible printed substrate, a glass substrate, a pressure-sensitive adhesive for bonding graphen as a transparent conductive material, a substrate obtained by depositing ITO,

In a liquid crystal display, a transparent substrate made of glass or plastic, a pressure-sensitive adhesive for sticking a polarizing plate constituting the outermost part of the liquid crystal panel,

In the liquid crystal display, a transparent protective substrate made of glass or plastic, and a pressure-sensitive adhesive used in a gap called an air gap provided between the liquid crystal panel and the like can be given.

The pressure sensitive adhesive comprising the resin composition for an ultraviolet ray curable pressure sensitive adhesive of the present invention can be applied to a plastic substrate, a flexible print substrate, a glass substrate, or a glass substrate or graphen, which is a transparent conductive material, A flexible printed substrate and a glass substrate are laminated on both surfaces of at least a layer (i) formed by using a pressure sensitive adhesive comprising a resin composition for an ultraviolet curable pressure sensitive adhesive of the present invention, and ITO (indium tin oxide Oxide) is deposited on the surface of the substrate (ii).

Here, the layer (i) can be formed using a pressure sensitive adhesive comprising the resin composition for an ultraviolet curable pressure sensitive adhesive of the present invention. The thickness of the layer (i) varies depending on the field in which the liquid crystal touch panel is used, It is preferable that the thickness is approximately 10 to 500 mu m, more preferably 50 to 500 mu m.

The layer (ii) is composed of one kind of substrate selected from the group consisting of a plastic substrate, a flexible print substrate, a glass substrate, and a substrate formed by depositing ITO on these substrates, Separate substrates may be used.

Examples of the plastic substrate include a substrate made of a generally used acrylic resin or the like, a substrate made of polycarbonate (PC), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether) (Polyethyleneterephthalate), COP (cycloolefin polymer), TAC (triacetylcellulose), an antireflection film or sheet, an antifouling film or sheet, or a film or sheet of a transparent conductive film constituting a touch panel .

As a method for producing the laminate, for example, a method of producing a laminate of one type of substrate selected from the group consisting of a plastic substrate forming the layer (ii), a flexible print substrate, a glass substrate, or a substrate obtained by depositing ITO on these substrates The laminate of the present invention can be obtained after applying the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention to the surface, irradiating the ultraviolet ray, immediately placing the other substrate on the applied surface, and leaving. When the substrate is light-transmissive, the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention is applied to the surface of the substrate, the other substrate is placed on the surface of the substrate, Whereby the laminate of the present invention can be obtained.

When the resin composition for an ultraviolet-curable pressure-sensitive adhesive of the present invention contains the above other additives, it may be heated to about 40 to 80 캜, if necessary, after irradiation with ultraviolet rays.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

In the present invention, " part (s) " and "% "

[Synthesis Example 1]

<Synthesis of urethane (meth) acrylate resin (A-1)>

465.9 parts by mass of polytetramethylene glycol (weight average molecular weight 1000), 9.6 parts by mass of 2-hydroxyethyl acrylate, 2, 6-di-tert-butyldimethylsilyl methacrylate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, 1.7 parts by mass of tert-butyl-cresol and 0.3 parts by mass of p-methoxyphenol were added. After the temperature in the reaction vessel was raised to 40 占 폚, 101.5 parts by mass of isophorone diisocyanate was added. Thus, 0.06 parts by mass of dioctyltin dinneodecanoate was added, and the temperature was elevated to 80 ° C over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all the isocyanate groups were lost, and then cooled to obtain a urethane acrylate resin as (A-1). The urethane acrylate resin (A-1) thus obtained had an equivalent weight of 7,000 and an average molecular weight of 18,000.

[Example 1]

&Lt; Adjustment of Resin Composition for UV-

100 parts by mass of the urethane (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 30 parts by mass of n-butyl acrylate and 30 parts by mass of acryloylmorpholine were added to a vessel equipped with a stirrer, a reflux condenser and a thermometer The mixture was stirred at a temperature of 80 deg. C in a vessel until the mixture became homogeneous. Thereafter, the mixture was cooled to room temperature, and 4 parts by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 3 parts by mass of 2,4,6-trimethoxybenzoyldiphenylphosphine oxide And the mixture was stirred until homogeneous. Thereafter, the mixture was filtered with a 200-mesh netting mesh to obtain a resin composition for an ultraviolet curable pressure-sensitive adhesive.

[Examples 2 to 7 and Comparative Examples 1 to 4]

Except that the kind and amount of the component (b-1) used, the amount of the component (b-2), and the amount of the photopolymerization initiator (C) used were changed as shown in Tables 1 to 3, A resin composition for a curable pressure-sensitive adhesive was obtained.

[Production method of adhesive film]

The resin composition for an ultraviolet-curable pressure-sensitive adhesive composition obtained in Examples and Comparative Examples was applied onto the surface of a polyethylene terephthalate film (release PET 50) having a thickness of 50 占 퐉, which had been subjected to release treatment on the surface, And on the application side, a release type PET 50 different from the above was applied.

Subsequently, ultraviolet rays were irradiated from the upper side of the release-type PET 50 using a UV irradiation apparatus to produce an adhesive film in which two release-type PETs 50 were laminated via the pressure-sensitive adhesive layer. The irradiation of the ultraviolet rays was performed under the condition that the accumulated light quantity of 300 to 390 nm of the wavelength after passing through the above-mentioned modified PET 50 was 1000 mJ / cm 2.

[Measurement method of adhesive strength]

One of the release-type PETs 50 constituting the pressure-sensitive adhesive film was peeled off, and polyethylene terephthalate (PET75) having a thickness of 75 占 퐉 was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet cut into a width of 25 mm was used as a test piece used for measuring the adhesive force.

2 kg rolls were applied to an SUS304 stainless steel plate (surface treatment BA (after cold rolling, bright heat treatment)), a polycarbonate plate and a glass plate in an atmosphere of 23 ° C and 50% RH Two reciprocations were applied to each adherend. One hour after the attachment, the 180 degree peel strength was measured in an atmosphere of 23 DEG C and 50% RH to obtain an adhesive force.

In addition, in the case where an adhesive was not obtained and an adhesive was obtained, measurement of the 180 degree peel strength was not performed.

[Measurement of Retentivity]

The specimens prepared in the same manner as the test pieces used for the measurement of the tack strength were laminated to a specularly finished stainless steel plate so as to have an adhesive area of 25 mm x 25 mm, The rolls were compounded by making two reciprocations.

Subsequently, a load of 1 kg was applied to the test piece attached to the stainless steel plate in an atmosphere of 40 占 폚 over the stainless steel plate in the direction of 0 占 (shearing direction), when the test piece fell from the stainless steel plate Was measured, and the holding time was referred to as holding power. In addition, when it was maintained after 24 hours, the holding time was set to 24 hours or more, and the deviation width from the initial attachment position was measured and described.

In addition, the measurement of the retention force was not performed in the case where the adhesive became an adhesive without obtaining a pressure-sensitive adhesive.

[Table 1]

[Table 2]

[Table 3]

The abbreviations in Tables 1 to 3 will be described.

"ACMO"; Acryloylmorpholine

"BA"; N-butyl acrylate

"(C-1)"; 2-hydroxy-2-methyl-1-phenylpropan-1-

"(C-2)"; 2,4,6-trimethoxybenzoyldiphenylphosphine oxide

"M-140"; N-acryloyloxyethyl hexahydrophthalimide

"DMAA"; Dimethylacrylamide

"DMAPAA"; Dimethylaminopropylacrylamide

"DMAEA"; Dimethylaminoethyl acrylate

"N-VP"; N-vinylpyrrolidone

[Example 8]

&Lt; Adjustment of Resin Composition for UV-

100 parts by mass of the urethane (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 60 parts by mass of n-butyl acrylate and 30 parts by mass of acryloylmorpholine were placed in a vessel equipped with a stirrer, a reflux condenser and a thermometer The mixture was stirred at a temperature of 80 deg. C in a vessel until the mixture became homogeneous. Thereafter, the mixture was cooled to room temperature, and 3 parts by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1 part by weight of an acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester ("Tinuvin (registered trademark) 123", produced by BASF Japan) 1 part by mass of phenylphosphine and 0.1 part by mass of 1-bis (2-ethylhexyl) aminomethyl-1,2,4-triazole ("IRGAMET (registered trademark) 30", manufactured by BASF Japan) And stirred until uniform. Thereafter, the resultant was filtered through a mesh of 200 meshes to obtain a resin composition for an ultraviolet curable pressure-sensitive adhesive.

[Examples 9 to 11]

A resin composition for an ultraviolet-curable pressure-sensitive adhesive was obtained in the same manner as in Example 5, except that the kind and amount of the antioxidant (E) used were changed as shown in Table 4.

[Evaluation method of light stability]

One of the releasing PETs 50 constituting the pressure-sensitive adhesive film obtained by the above-described method was peeled off, the surface of the pressure-sensitive adhesive layer was attached to a glass plate, and the other releasing PET 50 was peeled off. The test piece was irradiated with ultraviolet rays directly on the adhesive surface in an ultraviolet carbon arc lamp, a black panel temperature of 63 占 폚, and an ultraviolet fade meter "U48" (manufactured by Suga Shikeki Co., Ltd.) in accordance with JIS A 1415, I left it. Thereafter, the test piece was irradiated with a light yellow hue (b * (UV) light according to JIS K 7105 with a light source C, a visual field 2 °, and a "CM-5000d" spectrometer side colorimeter (manufactured by Konica Minolta Sensing Co., )) Was measured.

[Evaluation method of heat resistance yellowing resistance]

A test piece was obtained in the same manner as described above, and the test piece was exposed for 250 hours under the conditions of 85 ° C and 85% RH. Thereafter, the test piece was measured with a light source C, a visual field 2 °, a spectroscopic colorimetry CM-5000d (manufactured by Konica Minolta Sensing Co., Ltd.), a yellow color change (b *) by heat in accordance with JIS K 7105 did.

[Evaluation method of rust resistance]

One of the release-type PETs 50 constituting the pressure-sensitive adhesive film was peeled off, and polyethylene terephthalate (PET75) having a thickness of 75 占 퐉 was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet cut into a size of 40 mm x 50 mm was used as a test piece used for evaluation of rust-preventive properties.

The other piece of releasing PET 50 was peeled off from the test piece, and the piece was allowed to stand in an atmosphere of 60 ° C x 90% RH for 150 hours. Thereafter, the surface of the copper foil was visually observed to evaluate the rust resistance as described below.

"○": No rust occurred.

"X": rust occurred.

[Table 4]

The abbreviations in Table 4 will be described.

Irgafos38: Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite

&Quot; IrganoxPS800FD &quot;: didodecyl-3,3'-thiopropionate

"Irganox1010": pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate

[Example 12]

(Preparation of laminate)

The resin composition for an ultraviolet-curable pressure-sensitive adhesive obtained in Example 5 was subjected to the above-mentioned method to obtain a pressure-sensitive adhesive film having a thickness of 175 탆. Thereafter, one of the release type PET 50 films was peeled off and bonded to the polycarbonate film.

Thereafter, the other releasable PET film was peeled off and attached to a glass plate to obtain a laminate.

Claims (14)

(Meth) acrylate resin (A), (meth) acrylic monomer (B) and a photopolymerization initiator (B) obtained by reacting a polyol (a), a polyisocyanate (b) and a hydroxyl group- (C) is contained in the resin composition for an ultraviolet-curable pressure-sensitive adhesive,
Wherein the (meth) acrylic monomer (B) is a mixture of a nitrogen-containing (meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of 50 ° C or higher and a homopolymer capable of forming a homopolymer having a glass transition temperature of- (B-1) / (b-2) = 20/80 to 60 / (b-2) 40,
The resin composition for an ultraviolet-curable pressure-sensitive adhesive, wherein the polyol (a) is a polyether polyol. The method according to claim 1,
Wherein the nitrogen-containing (meth) acrylic monomer (b-1) capable of forming a homopolymer having a glass transition temperature of 50 ° C or higher is a nitrogen-containing (meth) acrylic monomer capable of forming a homopolymer having a glass transition temperature of 55 to 160 ° C, / RTI &gt; 3. The method of claim 2,
Wherein the nitrogen-containing (meth) acrylic monomer capable of forming a homopolymer having a glass transition temperature of 55 to 160 ° C is at least one selected from the group consisting of acryloylmorpholine, dimethyl acrylamide, dimethylaminopropylacrylamide, and N-acryloyloxyethylhexahydrophthalate (Meth) acrylate and (meth) acrylate. The method according to claim 1,
Wherein the photopolymerization initiator (C) is at least one compound selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. The resin composition for an ultraviolet-curable pressure-sensitive adhesive according to claim 1, The method according to claim 1,
And further contains a light stabilizer (D). The method according to claim 1,
And further contains an antioxidant (E). The method according to claim 1,
And further contains an antirust agent (F). 6. The method of claim 5,
Wherein the light stabilizer (D) is a hindered amine compound. The method according to claim 6,
Wherein the antioxidant (E) is a phosphorus compound. 8. The method of claim 7,
Wherein the rust preventive (F) is a triazole-based compound. The method according to claim 1,
(Equivalent amount of isocyanate group / hydroxyl group) of the total amount of the hydroxyl group of the polyol (a) and the hydroxyl group of the hydroxyl group-containing (meth) acrylic compound (c) and the isocyanate group of the polyisocyanate (b) 0.75 to 1.00. &Lt; / RTI &gt; A pressure-sensitive adhesive comprising the resin composition for an ultraviolet-curable pressure-sensitive adhesive according to any one of claims 1 to 11. 13. The method of claim 12,
Wherein the pressure-sensitive adhesive is used for an optical member. A pressure-sensitive adhesive composition comprising a plastic substrate, a flexible print substrate, a glass substrate, and a laminate comprising a layer (i) formed by using a pressure sensitive adhesive comprising the resin composition for an ultraviolet curable pressure sensitive adhesive according to any one of claims 1 to 11, And a layer (ii) comprising one kind of substrate selected from the group consisting of a substrate on which tin oxide is deposited.