KR20190123260A - Water-based Polyurethane Resin Composition - Google Patents

Abstract

(a) a urethane prepolymer composition comprising (a) a urethane prepolymer made by reacting a polyisocyanate component, (b) a polyol component and a (c) anionic group introducing agent, and (B) a cationically curable substance, in water and dispersed The aqueous polyurethane resin composition obtained by obtaining and obtaining the (A) urethane prepolymer in the obtained water dispersion with (C) blocking agent and / or chain extension agent. The water-based polyurethane resin composition of the present invention is excellent in storage stability and adhesiveness with respect to various substrates, in particular, with an energy ray-curable resin system cured by ultraviolet rays or the like, inter alia, a layer made of a cationic photocurable resin composition. Since it is excellent, it can be used suitably as an adhesive agent for optical films.

Description

Water-based Polyurethane Resin Composition

The present invention relates to an aqueous polyurethane resin composition, and in detail, a urethane prepolymer formed by reacting a polyisocyanate component, a polyol component, and an anionic group introducing agent and a urethane prepolymer composition containing a cation curable material are dispersed in water to disperse the water. It is obtained by reacting the urethane prepolymer in the obtained aqueous dispersion with a blocking agent and / or a chain extender, and relates to an aqueous polyurethane resin composition suitable for use as an adhesive or an adhesive for an optical film.

The aqueous polyurethane resin composition is useful because it can be used for various applications such as paints, adhesives, fiber binding agents, leathers, base impregnations, backings, and the like.

Various optical films are used for the liquid crystal display used for television, PC, etc., For example, a polarizer protective film, retardation film, a viewing angle protective film, etc. are used. These optical films are comprised from the base material layer which consists of polyester resin, a polycarbonate resin, etc., and the layer which consists of an energy-beam hardening type resin hardened | cured by ultraviolet-rays. Specifically, the optical film of patent documents 1-6 is known.

Japanese Laid-Open Patent Publication No. 2011-140139 Japanese Laid-Open Patent Publication No. 2005-181817 Japanese Patent Laid-Open No. 2001-55479 Japanese Laid-Open Patent Publication No. 2004-115670 Japanese Laid-Open Patent Publication No. 2004-300223 Japanese Laid-Open Patent Publication No. 2007-153958

Patent Literature 1 describes an easily-adhesive polyester film for optics using an aqueous polyurethane resin composition for an adhesive layer. However, the water-based polyurethane resin composition described in this same document cannot exhibit sufficient performance regarding adhesiveness with the layer which consists of energy-beam hardening-type resin hardened | cured by ultraviolet-rays etc ..

PTL 2 describes a polarizing plate in which a cycloolefin resin film is laminated on a polarizing film made of polyvinyl alcohol-based resin through an adhesive layer. In the said polarizing plate, the water-based urethane resin composition which mix | blends an oxetane compound and an epoxy compound with the adhesive bond layer is used. However, when only an oxetane compound and an epoxy compound are blended into the aqueous urethane composition, sufficient storage stability is not obtained, and the aqueous urethane composition is used as an energy ray cured resin cured by a base layer such as a polyester resin and ultraviolet rays. When used with the adhesive agent for optical films comprised from the layer which consists of, sufficient adhesiveness cannot be provided.

Citations 3, 4, 5, and 6 describe combinations of water-based urethane resins and epoxy compounds such as β-methylglycidyl compounds. The aqueous resins described in these documents include base layers such as polyester resins and ultraviolet rays. When used in the system which consists of an energy-beam hardening type resin layer hardened | cured by etc., only adhesiveness is inferior.

Therefore, the present inventors have made an intensive effort to obtain an aqueous polyurethane resin composition useful as an adhesive for an optical film obtained by applying a layer made of an energy ray curable resin cured by ultraviolet rays or the like to a substrate made of PET, PC or the like. .

As a result, it was found that the water-based polyurethane resin composition of a specific component could solve the said subject, and reached this invention.

This invention disperses in water the urethane prepolymer composition containing (A) urethane prepolymer formed by making (a) polyisocyanate component, (b) polyol component, and (c) anionic group introduction agent react, and (B) a cation-curable substance To obtain an aqueous dispersion, and to provide an aqueous polyurethane resin composition obtained by reacting the (A) urethane prepolymer in the obtained aqueous dispersion with a (C) blocking agent and / or a chain extender.

Hereinafter, the water-based polyurethane resin composition of this invention is explained in full detail.

In this invention, the (A) urethane prepolymer which makes (a) polyisocyanate component, (b) polyol component, and (c) anionic group introduction agent react is used.

As a polyisocyanate component which is (a) component used by this invention, a well-known polyisocyanate component can be used without a restriction | limiting in particular. Since the (a) polyisocyanate component is excellent in the hydrolyzability of the polyurethane molecule obtained and the coating film obtained from these, it is preferable to contain diisocyanate. As diisocyanate, for example, tolylene diisocyanate, diphenylmethane-4,4'- diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1, 5- naphthylene diisocyanate, 3,3'- dimethyl Aromatic diisocyanates such as diphenyl-4,4'-diisocyanate, dianisidine diisocyanate and tetramethylxylylene diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexyl methane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate; Aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like. Since it is excellent in the hydrolyzability of the polyurethane molecule obtained among these and the coating film obtained from these, alicyclic diisocyanate is preferable and isophorone diisocyanate and dicyclohexyl methane-4,4'- diisocyanate are more preferable. These diisocyanate may be used independently and may be used in combination of 2 or more type.

The diisocyanate can be used in the form of a modified product such as carbodiimide modification, isocyanurate modification, biuret modification, or the like, and can be used in the form of blocked isocyanate blocked by various blocking agents.

In addition, the polyisocyanate component which is (a) component used by this invention may contain the polyisocyanate which has three or more isocyanate groups in 1 molecule. As polyisocyanate which has three or more isocyanate groups in 1 molecule, For example, the isocyanurate trimer, the burette trimer, the trimethylolpropane adduct of a diisocyanate of the said example; Triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc., and these isocyanate compounds are carbodiimide modification, isocyanurate modification, biuret modification, etc. It may be used in the form of and may be used in the form of blocked isocyanate blocked by various blocking agents. These may be used independently and may be used in combination of 2 or more type.

Here, in the polyisocyanate component which is (a) component, when content of diisocyanate is less than 50 mass%, there exists a possibility that storage stability may fall, 50 mass% or more is preferable, and 70 mass% or more is more preferable.

Moreover, it is preferable that the polyisocyanate component which is (a) component used for this invention contains alicyclic diisocyanate. Since the polyisocyanate component which is (a) component contains alicyclic diisocyanate, since the performances, such as solvent-proof solvent resistance and alkali resistance, of a coating film improve, it is preferable.

As a polyol component which is (b) component used for this invention, a low molecular polyol, polycarbonate polyol, polyether polyol, polybutadiene polyol, silicone polyol, polyester polyol, polyester carbonate polyol is mentioned, for example. These may be used independently and may be used in combination of 2 or more type.

As the low molecular polyol, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Diol, 1,4-butanediol, neopentylglycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2- Methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol Aliphatic diols such as 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol and triethylene glycol; Alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; And trihydric or higher alcohols such as trimethylol ethane, trimethylol propane, hexitols, pentitols, glycerin, pentaerythritol, and tetramethylol propane.

As said polycarbonate polyol, it is obtained by making carbonate ester and / or phosgene react with the low molecular polyol exemplified above. Examples of the carbonate esters include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, and phenylnaphthyl carbonate.

As said polyester polyol, the direct esterification reaction of the low molecular polyol exemplified above with ester-forming derivatives, such as polyhydric carboxylic acid or its ester, anhydride, a halide, of less than the stoichiometric amount of the said polyol, and / Or what is obtained by a transesterification reaction is mentioned. Examples of the polycarboxylic acid or its ester-forming derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentane diacid, 2-methyloctane diacid, 3,8-dimethyldecane diacid, 3,7-dimethyldecane2 Aliphatic dicarboxylic acids such as acid, hydrogenated dimer acid and dimer acid; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acid, 1,4-dicarboxymethylenecyclohexane, nadic acid and methylnadic acid; Polyhydric carboxylic acids, such as tricarboxylic acids such as trimellitic acid, trimesic acid, and trimer of castor oil fatty acid, acid anhydrides of these polyvalent carboxylic acids, halides such as chlorides and bromide of the polyvalent carboxylic acids, Lower esters such as methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, and amyl esters of polyhydric carboxylic acids, γ-caprolactone, δ-caprolactone, ε-caprolactone, and dimethyl- and lactones such as ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

As a polyether polyol, water, the ethylene oxide and / or propylene oxide addition product of the said low molecular weight polyol, polytetramethylene glycol, etc. are mentioned, for example.

As silicone polyol, silicone oil etc. whose terminal which has a siloxane bond in a hydroxyl group are hydroxyl groups are mentioned.

It is preferable to contain polycarbonate diol in the polyol component which is (b) component used for this invention, and it is preferable to use the thing of average molecular weights 500-5000 among polycarbonate diol. If the average molecular weight is less than 500, there is a fear that sufficient adhesion of the coating film to the base may not be obtained. If the average molecular weight is more than 5000, the storage stability or impact resistance when used as a product may be lowered.

Content of the polycarbonate diol in the polyol component which is (b) component becomes like this. Preferably it is 50 mass% or more in polyol component which is (b) component, More preferably, it is 70 mass%.

Moreover, the polyol component which is (b) component can aim at the durability improvement by using small amount of polyfunctional polyols, such as a trimethylol propane [less than 10 mass% in the polyol component which is (b) component].

As an anionic group introduction agent which is (c) component used for this invention, For example, Polyol containing carboxyl groups, such as dimethylol propionic acid, dimethylol butanoic acid, dimethylol butyric acid, dimethylol valeric acid; And polyols containing sulfonic acid groups such as 1,4-butanediol-2-sulfonic acid. Polyols containing a carboxyl group, in particular, dimethylolpropionic acid are preferable. These may be used independently and may be used in combination of 2 or more type.

In general, when a urethane prepolymer is prepared by reacting a polyisocyanate, a polyol, and an anionic group introducing agent (as an anionic group-containing polyol), the total isocyanate group equivalent (NCO) of the polyisocyanate group and the total of the polyol and anionic group introducing agent The terminal structure of the urethane prepolymer obtained differs by the ratio of hydroxyl equivalent (OH).

Since the urethane prepolymer used in the present invention is preferably an isocyanate group, it is preferable to adjust NCO / OH to greater than 1.0, more preferably in the range of 1.1 to 2.5, and more preferably in the range of 1.2 to 2.0. Adjust When the NCO / OH is 1.0 or less, in particular less than 1.1, the obtained urethane prepolymer becomes high molecular weight to lower the water dispersibility, and the NCO group for reacting with the containment agent and / or the chain extender decreases, resulting in an aqueous polyurethane resin. There exists a possibility that it may adversely affect the storage stability of a composition. When NCO / OH is larger than 2.0, the isocyanate group and water react at the time of water dispersion of the obtained prepolymer, and carbon dioxide may be generated, which may cause problems in manufacturing such as rapid foaming. It is unpreferable because there exists a possibility of the performance deterioration, such as adhesiveness.

In addition, the use ratio (mass ratio) of the polyol which is (b) component and the anionic group introduction agent which is (c) component can be suitably selected in the range of 99.9 / 0.1-70/30 by the former / the latter.

Here, when using the water-based polyurethane resin composition of this invention as an adhesive for optical films, the acid value of the urethane prepolymer which is (A) component affects blocking performance. The acid value of the urethane prepolymer which is (A) component becomes like this. Preferably it is 20-90 mgKOH / g, More preferably, it is set in the range of 40-70 mgKOH / g, Especially preferably, it is 40-70 mgKOH / g. The usage-amount of the anionic group introduction agent which is (c) component is adjusted so that it may become such a range.

In addition, the acid value of the urethane prepolymer which is above-mentioned (A) component is a theoretical value calculated | required from the compounding quantity of the reaction component of the urethane prepolymer which is (A) component. When an inert solvent is used for preparation of the urethane prepolymer which is (A) component as mentioned below, the measured value of the acid value of the urethane prepolymer which is (A) component to be obtained changes from the above-mentioned theoretical value. There is the following relationship between the above theoretical value and measured value.

Acid value (theoretical value) = acid value (measured value) x [(a) + (b) + (c) + solvent: total mass] / [(a) + (b) + (c): total mass]

In manufacture of the urethane prepolymer which is (A) component of this invention, a catalyst can be used as needed. As such a catalyst, for example, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N ", N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylene Triamine, N, N, N ', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4 .0] undecene-7, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'- Dimethylpiperazine, N, N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, N, N-dimethyllaurylamine, 1-methylimidazole Tertiary amines such as 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-dimethylaminopropylimidazole; Quaternary ammonium salts such as tetraalkylammonium hydroxides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate; Stanus diacetate, Stanus dioctoate, Stanus dioleate, Stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, Organometallic catalysts such as dioctyl tin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate and cobalt naphthenate. These catalysts can be used independently and can use 2 or more types together.

Although there is no restriction | limiting in the usage-amount of these catalysts, Preferably it is 0.001-1 mass%, More preferably, it is 0.01-0.1 mass% with respect to the total amount of (a) component, (b) component, and (c) component.

When manufacturing the urethane prepolymer which is (A) component of this invention, a crosslinking structure can be introduce | transduced using a crosslinking agent. As a crosslinking agent, the crosslinking agent normally used at the time of manufacture of a urethane prepolymer can be used. As such a crosslinking agent, for example, melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, methylated methylolmelamine, butylated methylolmelamine, Melamine resin etc. can be used. Among these crosslinking agents, melamine which is excellent in compatibility with polyurethane and inexpensive is preferable.

The usage-amount in the case of using these crosslinking agents becomes like this. Preferably it is 0.01-10 mass parts with respect to 100 mass parts of polyols which are (a) component, More preferably, it is 0.1-5 mass parts.

The urethane prepolymer which is (A) component used for this invention is a polyisocyanate which is (a) component, the polyol which is (b) component, and the anionic group introduction agent which is (c) component, the catalyst and / or crosslinking agent which are arbitrary components, It is obtained by heating under the presence of an inert solvent. There is no restriction | limiting in particular in the conditions of a heating reaction, Well-known conditions can be employ | adopted.

As an inert solvent used here, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl- 2-pyrrolidone, etc. which have affinity for water are mentioned.

When using the solvent below boiling point 100 degreeC, after manufacturing the water-based polyurethane resin composition of this invention, it is preferable to remove the solvent by distillation under reduced pressure.

Although the usage-amount of a solvent does not have a restriction | limiting in particular, 3-200 mass parts is preferable with respect to 100 mass parts of total amounts of the raw material of the urethane prepolymer which is (A) component.

The cation curable material which is (B) component used for this invention is a compound which causes a polymerization or a crosslinking reaction by the cation polymerization initiator activated by energy-beam irradiation or heating, such as an ultraviolet-ray. Examples of the cationic curable material as the component (B) include an oxetane compound and an epoxy compound, and the oxetane compound and the β-alkylglycol are excellent because of the excellent storage stability when the aqueous polyurethane resin composition is used. A cylyl compound is mentioned as a more preferable compound. These may be used independently and may be used in combination of 2 or more type.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl ) Oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy) methyl] Monofunctional oxetane compounds such as oxetane and oxetanyl silsesquioxane; 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene, 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] ratio Phenyl, bis [(3-ethyl-3-oxetanyl) methyl] ether, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] propane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane , Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl Methyl) ether, 1,3,5-tris [6- (3-ethyloxetan-3-yloxycarbonylamino) hexyl] -s-triazine-2,4,6-trione, phenol novolac jade And polyfunctional oxetane compounds such as cetane.

As said oxetane compound, the thing of the commercial item which has an oxetane compound as a main component can be used, For example, Aaron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT -212 (product of Toagosei Co., Ltd.), Etanacol OXBP, OXTP (product made by Ube Koyama Co., Ltd.), etc. are mentioned.

Among the above oxetane compounds, 3-ethyloxetanylmethyl ether, 1,3,5-tris [6- (3-ethyloxetan-3-yloxycarbonylamino) hexyl] -s-triazine-2,4 By using a compound having two or more oxetanyl groups such as 6-trione and 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] biphenyl, Since the water-based polyurethane resin composition excellent in adhesiveness with hardened energy-beam curable resin is obtained, it is preferable.

As said epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, and an alicyclic epoxy compound are mentioned.

Examples of the aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl etherates of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, and polyglycidyls of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. And polyfunctional epoxy compounds such as polyglycidyl esters of ethers and aliphatic long-chain polybasic acids. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol di Glycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, poly Glycidyl ethers of polyhydric alcohols, such as diglycidyl ether of propylene glycol and dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, and hydrogenated bisphenol A. Of polyglycidyl ethers of polyether polyols and aliphatic long-chain dibasic acids obtained by adding a species or two or more alkylene oxides Glycidyl esters can be given dill. Moreover, monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene, etc. are mentioned.

As said aliphatic epoxy compound, a commercial item can be used, For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX -313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612 , Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Dena Call EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Kemutech Co., Ltd.); Epolite M-1230, epolite 40E, epolite 100E, epolite 200E, epolite 400E, epolite 70P, epolite 200P, epolite 400P, epolite 1500NP, epolite 1600, epolite 80MF, epolite 100MF ( Kyoeisha Chemical Co., Ltd.), Adeka Glycerol ED-503, Adeka Glycerol ED-503G, Adeka Glycerol ED-506, Adeka Glycerol ED-523T, Adeka Resin EP-4088S (Made by ADEKA Corporation), etc. are mentioned.

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenol or an alkylene oxide adduct having at least one aromatic ring such as phenol, cresol, and butylphenol. Mono / polyglycidyl ether compounds such as bisphenol A, bisphenol F, or glycidyl ether compounds or epoxy novolac resins of compounds in which alkylene oxide is added thereto; Mono / polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; Glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; And glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene, and the like.

As said aromatic epoxy compound, a commercial item can be used, For example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, oncoat EX-1020, oncoat EX-1030, oncoat EX-1040, oncoat EX-1050, oncoat EX-1051, oncoat EX-1010, oncoat EX-1011, oncoat 1012 Nagase Kemutekkusu company); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Toto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Mafruf G-0105SA, Mafruf G-0130SP (manufactured by Nichiyu Co., Ltd.); Epiclone N-665, Epiclone HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printech).

The alicyclic epoxy compound refers to the fact that an oxirane ring is directly bonded to a saturated ring without passing through a spacer. Specific examples of the alicyclic epoxy compound include polyglycidyl of a polyhydric alcohol having at least one alicyclic ring. And cyclohexene oxides and cyclopentene oxide-containing compounds obtained by epoxidizing ethers or cyclohexene or cyclopentene ring-containing compounds with oxidizing agents. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methyl Cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis ( 3,4-Epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthalic acid dioctyl, epoxy hexahydrophthalic acid di-2-ethylhexyl , 1-on When the like ethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxy-ethylcyclohexane, α- pinene oxide, limonene dioxide.

As said alicyclic epoxy compound, a commercial item can be used, For example, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000 (made by Daicel Corporation), etc. are mentioned.

The (beta) -alkylglycidyl compound mentioned as the said preferable epoxy compound has a structure obtained by condensing (beta) -alkyl epihydrin and a hydroxy compound. However, the (beta) -alkylglycidyl compound used for this invention is not restrict | limited by the manufacturing method.

As said β-alkyl epihydrin, for example, β-methyl epichlorohydrin, β-methyl epibromohydrin, β-methyl epifluorohydrin, β-ethyl epichlorohydrin, β-ethyl Epibromohydrin, β-ethyl epifluorohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin, β-propyl epifluorohydrin, β-butyl epichlorohydrin, β -Butyl epibromohydrin, (beta) -butyl epifluorohydrin, etc. are mentioned.

Examples of the hydroxy compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, hydroquinone, resorcin, pyrocatechol , Phloroglucinol, dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), Tetrabromobisphenol A, 1,3-bis (4-hydroxydicumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane , 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, dihydroxynaphthalene, phenol novolak, butylphenol novolak, octylphenol novolak, resorcinno Volac, Terpenephenol, Dicyclopentadiene / Phenol Additive, Ethyl Glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol Aethylene oxide and / or propylene oxide adduct, tricyclodecane dimethanol Can be mentioned.

Adhesiveness with the energy-beam curable resin layer hardened by ultraviolet-ray etc. by using the compound which has two or more (beta) -methylglycidyl groups, such as bisphenol Adi (beta) -methylglycidyl ether, among the said (beta) -alkylglycidyl compounds Since an excellent water-based polyurethane resin composition is obtained, it is preferable.

In this invention, the urethane prepolymer composition containing the urethane prepolymer which is (A) component and the cation curable substance which is (B) component is prepared. In this invention, the use ratio (mass ratio) of the urethane prepolymer which is (A) component and the cationically curable material which is (B) component is former: latter, Preferably it is 100: 1-50. When the use ratio of the component (B) is smaller than 1, the use effect such as adhesiveness may not be obtained, and when it exceeds 50, the storage stability may decrease, which is not preferable. There is no restriction | limiting in particular as a preparation method of a urethane prepolymer composition, A well-known method can be employ | adopted.

In this invention, the urethane prepolymer composition containing the urethane prepolymer which is (A) component and the cation curable substance which is (B) component is disperse | distributed in water, and water dispersion is obtained. Although it does not specifically limit about the method of disperse | distributing a urethane prepolymer composition in water, For example, the prepolymer mixing method and the phase inversion method can be used.

A prepolymer mixing method is a method of disperse | distributing the prepolymer composition obtained by mixing (A) component and (B) component in water. Here, the anionic group neutralizer and / or emulsifier may be added to the prepolymer composition, and may be added in water.

The phase inversion method is a method of adding and dispersing water to the prepolymer composition obtained by mixing the component (A) and the component (B). Here, the anionic group neutralizer and / or emulsifier may be added to the prepolymer composition, and may be added in water.

As said anionic group neutralizer, it is a basic compound which reacts with anionic group and forms a hydrophilic salt, for example. For example, trialkylamines such as trimethylamine, triethylamine and tributylamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1-dimethylamino- Tertiary amine compounds such as N, N-dialkylalkanolamines such as 2-methyl-2-propanol, and trialkanolamines such as triethanolamine; Ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are mentioned.

These may be used independently and may be used in combination of 2 or more type.

From the viewpoint of good weather resistance, water resistance and the like of the dried product of the water-based polyurethane resin composition of the present invention, use of a highly volatile anionic group neutralizing agent that is easily dissociated by heat is preferable. In particular, trimethylamine and triethylamine are preferable.

The amount of the anionic group neutralizing agent used per one equivalent of the anionic group in terms of the storage stability of the water-based polyurethane resin composition obtained by the present invention, and the performance of mechanical properties such as the strength of the product obtained using the same, and water resistance. Preferably it is 0.5-2.0 equivalent, More preferably, it is 0.8-1.5 equivalent.

A well-known surfactant can be used as said emulsifier. For example, well-known general anionic surfactant, a nonionic surfactant, a cationic surfactant, a double-sided surfactant, a high molecular type surfactant, a reactive surfactant, etc. can be used.

As said anionic surfactant, For example, alkyl sulfates, such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate; Sodium dodecyl polyglycol ether sulfate; Sodium sulforicinoleate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffin and ammonium salts of sulfonated paraffin; Fatty acid salts such as sodium laurate, triethanolamine oleate and triethanolamine abietate; Alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfates of alkyl phenol hydroxyethylene; High alkyl naphthalene sulfonates; Naphthalenesulfonic acid formalin condensate; Dialkylsulfosuccinates; Polyoxyethylene alkyl sulfate salts; Polyoxyethylene alkyl aryl sulfate salts; Polyoxyethylene ether phosphate; Polyoxyethylene alkyl ether acetate; N-acylamino acid salt; N-acylmethyl taurine salt etc. are mentioned.

As said nonionic surfactant, Fatty acid partial ester of polyhydric alcohols, such as sorbitan monolaurate and sorbitan monooleate; Polyoxyethylene glycol fatty acid esters; Polyglycerol fatty acid esters; Ethylene oxide and / or propylene oxide adducts of alcohols having 1 to 18 carbon atoms; Ethylene oxide and / or propylene oxide adducts of alkylphenols; And ethylene oxide and / or propylene oxide adducts of alkylene glycol and / or alkylenediamine.

Examples of the C1-C18 alcohol constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, amyl alcohol, isoamyl alcohol, and third amyl alcohol. , Hexanol, octanol, decanal alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and the like. Examples of the alkyl phenol include phenol, methyl phenol, 2,4-dithi butyl phenol, 3,5-dizeterylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F, and the like can be given. Examples of alkylene glycols include ethylene glycol and 1,2- Propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 1,4-butanediol, neopentylglycol, 1,5- Pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol etc. are mentioned, As alkylenediamine, the thing in which the alcoholic hydroxyl group of said alkylene glycol was substituted by the amino group is mentioned. In addition, the ethylene oxide adduct and the propylene oxide adduct may be random adducts and may be block adducts.

As said cationic surfactant, Primary-tertiary amine salt; Alkylpyridinium salts such as pyridinium salts such as alkylpyridinium bromide; Imidazolinium salts such as imidazolinium laurate; Quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, and halogenated alkyl quaternary ammonium salts; Can be mentioned.

Examples of the amphoteric surfactant include palm oil fatty acid amidopropyldimethyl acetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, and lauryl. Betaine type amphoteric surfactants, such as a hydroxysulfobibetaine, lauroyl amido ethylhydroxyethyl carboxymethyl betaine, and the metal salt of hydroxypropyl phosphoric acid; amino acid type amphoteric surfactants such as metal salts of β-laurylaminopropionic acid; Sulfate ester amphoteric surfactants; Sulfonic acid type amphoteric surfactants;

Although the usage-amount of the said emulsifier is not specifically limited, From a viewpoint of performance, such as water resistance of the hardened | cured material of the product obtained from the water-based polyurethane resin composition of this invention, with respect to 100 mass parts of total amounts of solid content of a urethane prepolymer composition, Preferably it is 0- It is 30 mass parts, More preferably, it is 0-20 mass parts.

The water-based polyurethane resin composition of this invention is contained in the said urethane prepolymer composition by adding the blocking agent and / or chain extension agent which are (C) component to a solution as needed to the urethane prepolymer composition of a water dispersion state, (A) It is obtained by blocking and / or chain elongating the urethane prepolymer which is a component in water. There is no restriction | limiting in particular in reaction conditions of the urethane prepolymer composition of the water dispersion state, and the blocking agent and / or chain extension agent which are (C) component, A well-known condition can be employ | adopted.

As a blocking agent used for this invention, For example, Alcohol, such as methanol and ethanol; Dialkylamines such as diethylamine, dimethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, didodecylamine and distearylamine; Diarylamines such as diphenylamine; And secondary amino group-containing heterocyclic compounds such as morpholine, piperidine, pyrrole, pyrrolidine, pyrazole, and imidazole.

Among these, water-soluble secondary amines, especially diethylamine are preferable.

Examples of the chain extender used in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1 , 3-propanediol, 1,4-butanediol, neopentylglycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1, Aliphatic diols such as 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol and triethylene glycol; Alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; Ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,3-propanediamine, 2-butyl-2-ethyl-1,3-propanediamine, 1,4-butanediamine, Neopentanediamine, 3-methyl-2,4-pentanediamine, 2,4-pentanediamine, 1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-2,4-pentanediamine , 2,4-diethyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 3,5-heptanediamine, 1,8-octanediamine, 2-methyl-1,8 Aliphatic diamines such as -octanediamine, 1,9-nonanediamine and 1,10-decanediamine; Polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; Mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino Alicyclic diamines such as propyl) 2,4,8,10-tetraoxaspiro (5.5) undecane; m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldi Aromatic diamines such as phenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, and α, α'-bis (4-aminophenyl) -p-diisopropylbenzene; Hydrazine; Dicarboxylic acid dihydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide; 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-dip-phenylene) diisemicarbazide, etc. Semicarbazides; Hydrated hydrazine; Water and the like.

Among these chain extenders, a water-soluble amine compound having two or more active hydrogens such as ethylenediamine or a water-soluble dicarboxylic acid dihydrazide is preferable.

In the present invention, when the blocking agent is used alone as the component (C), the amount of the blocking agent used is the ratio of the isocyanate reactor equivalents contained in the blocking agent to the equivalent of the isocyanate group contained in the urethane prepolymer which is the component (A) before the blocking. It is preferable to set to the quantity which becomes a range of 0.1-1.0.

In the present invention, when the chain extender is used alone as the component (C), the amount of the chain extender used is an isocyanate contained in the chain extender relative to the isocyanate group equivalent contained in the urethane prepolymer, which is the component (A) before chain extension. It is preferable to set it in the quantity which becomes a range of 0.1-1.0 of reactor equivalent.

In the present invention, when the blocking agent and the chain extension agent are used as the component (C), the amount of the blocking agent and the chain extension agent is used in terms of the isocyanate group equivalents contained in the urethane prepolymer which is the component (A) before the blocking and chain extension. It is preferable to set it in the quantity which the ratio of the isocyanate reactor equivalent contained in an agent and chain extension agent exists in the range of 0.1-1.0.

The water-based polyurethane resin composition of this invention contains a specific polyurethane as a main component. The polyurethane contained in the water-based polyurethane resin composition of the present invention comprises (A) a urethane prepolymer formed by reacting a (a) polyisocyanate component, (b) a polyol component, and (c) anionic group introducing agent, and (B) cationic curable The substance is obtained in water and reacted with the (C) blocking agent and / or chain extender. Therefore, the repeating unit of polyurethane contained in the water-based polyurethane resin composition of this invention is not the same, The structure and repetition become a thing rich in diversity. Therefore, the structure of the polyurethane contained in the water-based polyurethane resin composition of the present invention is quite complicated. For this reason, it is currently impossible to represent the structure of the polyurethane contained in this invention uniformly in any kind of general formula, and this is technical common sense of those skilled in the art. And if the structure is not specified, the properties of the material determined accordingly are not easily known, so it is hardly possible to express them as properties. Therefore, in the present invention, the invention "aqueous polyurethane resin composition" comprising such a polyurethane is made by reacting "(a) polyisocyanate component, (b) polyol component and (c) anionic group introducing agent. The urethane prepolymer composition comprising (A) a urethane prepolymer and (B) a cation curable material is adjusted, and then the urethane prepolymer composition is dispersed in water to obtain an aqueous dispersion, and the (A) urethane prepolymer in the obtained aqueous dispersion is (C) It must be defined by the expression "aqueous polyurethane resin composition obtained by reacting with a blocking agent and / or a chain extension agent." That is, with respect to the water-based polyurethane resin composition of the present invention, there is a situation where it is impossible or almost impractical to "specify the water-based polyurethane resin composition at the time of application directly by its structure or properties".

In the water-based polyurethane resin composition of the present invention, the solid content content (1 g of the water-based polyurethane resin composition was put in an aluminum cup and calculated from the weight before and after drying for 1 hour in a 150 ° C thermostat) is not particularly limited. You can choose any value. Solid content of the water-based polyurethane resin composition of this invention is preferable because 10-70 mass% has good dispersibility and paintability, and 20-60 mass% is more preferable.

There is no restriction | limiting in particular about the weight average molecular weight of the polyurethane disperse | distributed to the water-based polyurethane resin composition of this invention, The range which gives dispersibility as an aqueous coating material and a favorable coating film can be selected. About a weight average molecular weight, 5000-2 million are preferable and 10000-100000 are more preferable. In addition, the hydroxyl value is not particularly limited. This value is 1-100 in KOH consumption (mg) per 1g of resin normally.

The state of the water-based polyurethane resin composition of this invention is emulsion, suspension, colloidal dispersion, aqueous solution, etc. The particle diameters (measured using a dynamic scattering apparatus) of emulsions, suspensions and colloidal dispersions in which particles are dispersed in water are not particularly limited, but 1 µm or less is preferable, since a good dispersion state can be maintained. Is more preferable, and 100 nm or less is especially preferable.

In addition, the water-based polyurethane resin composition of this invention can use various additives generally used well as needed. Examples of the additives include hindered amine light stabilizers, ultraviolet light absorbers, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, pigments, dyes, film forming aids, curing agents, crosslinking agents, and silane coupling agents. , Antiblocking agents, viscosity modifiers, leveling agents, antifoaming agents, antigelling agents, dispersion stabilizers, radical scavengers, heat resistance imparting agents, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing agents, catalysts, thixotropic agents, antibacterial agents, antifungal agents , Preservatives, cationic polymerization initiators, and the like.

As the hindered amine light stabilizer, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl Stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sevacate, 1,2,2,6,6-pentamethyl-4-piperidylmethylmethacrylate, 2,2,6,6-tetra Methyl-4-piperidylmethylmethacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-pi Ferridyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-digeze 3-butyl-4- Idroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-pentamethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-penta Methyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiaryctylamino-s-triazine polycondensate, 1,5,8,12- [2,4-bis (N-butyl- N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5, 8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl 1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-pi) Ferridyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-) Pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- ( Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy) ethyl] -2,4,8,10-tetraoxyspiro [5.5] undecane, 3, 9-bis [1,1-dimethyl-2- (tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy) ethyl] -2,4, 8,10- tetraoxyspiro [5.5] undecane etc. are mentioned.

As said ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octoxy benzophenone, 5, 5'-methylenebis 2-hydroxybenzophenones such as (2-hydroxy-4-methoxybenzophenone), 2- (2-hydroxy-5-methylphenyl) benzotriazole, and 2- (2-hydroxy-5-third Octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dizetbutylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tertbutyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), Polyethylene glycol ester of 2- (2-hydroxy-3- tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] Benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tertbutylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3- tert-butyl-5- (2-Methacroyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2 -Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (methacryloyloxymethyl) phenyl] Benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacroyl 2- (2-hydroxyphenyl) benzotriazole such as oxypropyl) phenyl] benzotriazole; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5 -Triazine, 2- (2-high Oxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4 2- (2-hydroxyphenyl) -4,6-diaryl-1,3 such as, 6- (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine , 5-triazines; Phenylsalicylate, resorcinol monobenzoate, 2,4-dize-3butylphenyl-3,5-dize-3-butyl-4-hydroxybenzoate, octyl-3,5-dize-3-butyl-4-hydroxy Benzoate, dodecyl-3,5-dize-3-butyl-4-hydroxybenzoate, tetradecyl-3,5-dizethibutyl-4-hydroxybenzoate, hexadecyl-3,5-dizethibutyl- Benzoates, such as 4-hydroxybenzoate, an octadecyl-3, 5-dije 3 butyl- 4-hydroxy benzoate, and a behenyl-3, 5-dize- 3-butyl-4- hydroxy benzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; Various metal salts or metal chelates, in particular salts or chelates of nickel or chromium;

As said phosphorus antioxidant, for example, triphenyl phosphite, tris (2, 4- di- tert butylphenyl) phosphite, tris (2, 5- di- tert butylphenyl) phosphite, tris (nonylphenyl) phosphite , Tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di- tert-butylphenyl) octylphosphite, di Phenyldecyl phosphite, diphenyl octyl phosphite, bis (nonylphenyl) pentaerythritol phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tri Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithio phosphite, bis (neopentyl glycol), 1, 4- dicyclo hexane dimethyl diphosphite, bis (2, 4-digeze) 3butylphenyl) pentaerythritol diphosphite, bis (2,6- Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritoldiphosphite, distearylpentaerythritoldiphosphite, tetra (C12-15 mixed alkyl) -4, 4-isopropylidene diphenyl phosphite, bis [2,2'- methylenebis (4,6- diamylphenyl)] isopropylidene diphenyl phosphite, tetratridecyl 4,4'- butylidene Bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) .1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane trifoss Fight, tetrakis (2,4-dijetributylphenyl) biphenylenediphosphonite, tris (2-[(2,4,8,10-tetrakis tributyldibenzo [d, f] [1, 3,2] dioxaphosphine-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphazanthrene-10-oxide, 2-butyl-2-ethylpropanediol 2,4,6-tri 3 butyl phenol monophosphite etc. are mentioned.

Examples of the phenolic antioxidants include 2,6-dize-3-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol and stearyl (3,5-dize-3-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-dize-3-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-dize-3-butyl-4-hydroxybenzylthioacetate, tee Odyethylene bis [(3,5-dizethibutyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4, 6-bis (3,5-dijetbutyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3 -Bis (4-hydroxy-3- tert-butylphenyl) butyric acid] glycol ester, 4,4'- butylidene bis (6-tert-butyl-3-methylphenol), 1,1,3- Tris (2-methyl-4-hydroxy-5-tertbutylphenyl) butane, bis [2-tertbutyl-4-methyl-6- (2-hydroxy-3- tert-butyl-5-methylbenzyl ) Phenyl] terephthalate, 1,3,5-tris (2,6- Methyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (3,5-dize-3-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-dize-3-butyl-4-hydroxyphenyl ) Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4- Methyl-6- (2-acryloyloxy-3-tertbutyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyl Oxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tertbutyl-4-hydroxy-5-methylphenyl ) Propionate] and the like.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates and pentaerythritol tetra (β-dode) such as dilauryl, dimyristyl, myristyl stearyl, and distearyl ester of thiodipropionic acid. (Beta) -alkyl mercaptopropionic acid ester of polyol, such as a silmercaptopropionate).

When using various additives in the water-based polyurethane resin composition of this invention, the usage-amount can respectively be suitably selected. For example, when the weathering agent such as the hindered amine light stabilizer, ultraviolet absorber, phosphorus antioxidant, phenolic antioxidant or sulfur antioxidant is used, the amount thereof is used in the aqueous polyurethane resin composition of the present invention. When it is less than 0.001 mass part with respect to 100 mass parts of solid content, sufficient addition effect may not be acquired, and when it is larger than 10 mass parts, since it may affect dispersibility and coating-film property, 0.001-10 mass parts is preferable, and 0.01 ~ 5 mass parts is more preferable.

Moreover, the method of adding these various additives is a method of adding to a polyol component, the method of adding to a prepolymer, the method of adding to a water phase at the time of water dispersion, the method of adding after water dispersion, etc. You can choose the method.

The aqueous polyurethane resin composition of this invention can be used for various uses, such as a coating material, an adhesive agent, a fiber binding agent, leather, a base material impregnation, a backing. The water-based polyurethane resin composition of the present invention is particularly suitable for use in cationically cured complex systems by energy such as heat or ultraviolet rays, and for use in optical film applications using energy ray-curable resins cured by, for example, ultraviolet rays. Can be.

The optical film which can apply the water-based polyurethane resin composition of this invention is a laminated body in which the optically anisotropic layer containing a liquid crystalline compound is laminated | stacked on one side of a support body, and the hard-coat layer is laminated | stacked on the other side. Such an optical film is, for example, a polarizer protective film, a retardation film, a viewing angle protective film, a light diffusing film, a reflective film, an antireflection film, an antiglare film, a conductive film for a touch panel, a prism sheet, and the like. Among these, the water-based urethane composition of this invention can be used suitably for a polarizer protective film, a retardation film, and a viewing angle protective film.

For example, these optical films are produced by adhering the coating film layer obtained from the monomer for photocuring resins and a polymerization initiator to a sheet-like plastic base material. The water-based polyurethane resin composition of this invention is suitable as a binder, ie, an easily adhesive layer, through the layer obtained from a plastic base material, a photocuring resin, and a photoinitiator.

Examples of the plastic substrate include polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2 Polyester resins such as diphenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; Silicone resins; Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; Epoxy resins; Vinyl compounds such as fluorine resin, polystyrene, polyvinyl chloride, and polyvinyl fluoride; Polycarbonate (PC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), cycloolefin polymer (COP); Cellulose esters such as triacetyl cellulose (TAC), diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose and nitrocellulose; Polyamides; Polyimide; Polyurethane; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Polyvinyl acetate; Polysulfones; Polyethersulfones; Polyether ketones; Polyetherimide; Polyoxyethylene; Norbornene resins; Cycloolefin polymer (COP) etc. are mentioned. PET is suitably used in that it can be obtained inexpensively.

On the other hand, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, and blast treatment can be applied to the plastic substrate.

Here, in the method of hardening an energy ray curable resin by irradiation of an energy ray, an ultraviolet ray, an electron beam, an X ray, a radiation, a high frequency etc. are mentioned, An ultraviolet ray is the most economically preferable. As a light source of an ultraviolet-ray, an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, etc. are mentioned.

The method of apply | coating the water-based polyurethane resin composition of this invention to a plastic base material is not specifically limited. Such coating methods include, for example, roll coating, baking, air knife, spin coating, curtain coating, die coating, dip coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, Curtain roll coating, dip coating, rod coating, doctor blade coating, and the like.

The energy ray curable resins such as ultraviolet rays include radical curable resins and cationic curable resins, and the cation curable resins are more durable and adhesive, and the water-based polyurethane resin composition of the present invention Since it is suitable for use, the cation curing system resin which uses the monomer and / or oligomer for cation curing system resins, and a cationic polymerization initiator is preferable.

As said monomer or oligomer for cation curing type resin, an aliphatic, aromatic, or alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, or its oligomer is mentioned, for example.

Examples of the aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl etherates of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, and polyglycidyls of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. And polyfunctional epoxy compounds such as polyglycidyl esters of ethers and aliphatic long-chain polybasic acids. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentylglycol di Glycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, poly Glycidyl ethers of polyhydric alcohols, such as diglycidyl ether of propylene glycol and dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, and hydrogenated bisphenol A. Polyglycidyl ethers of polyether polyols obtained by adding one or two or more kinds of alkylene oxides, and di of aliphatic long chain dibasic acids. There may be mentioned the receiver deals ester. Moreover, monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene, etc. are mentioned.

As an aliphatic epoxy compound, the glycidyl etherate of an aliphatic alcohol or the polyglycidyl etherate of an aliphatic polyhydric alcohol or its alkylene oxide adduct is preferable because a viscosity, coating property, and reactivity are improved.

As said aliphatic epoxy compound, a commercial item can be used, For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX- 612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Kemutech Co., Ltd.); Epolite M-1230, epolite 40E, epolite 100E, epolite 200E, epolite 400E, epolite 70P, epolite 200P, epolite 400P, epolite 1500NP, epolite 1600, epolite 80MF, epolite 100MF ( Kyoeisha Chemical Co., Ltd.), Adeka Glycerol ED-503, Adeka Glycerol ED-503G, Adeka Glycerol ED-506, Adeka Glycerol ED-523T, Adeka Resin EP-4088S (Made by ADEKA Corporation) etc. are mentioned.

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenol or an alkylene oxide adduct having at least one aromatic ring such as phenol, cresol, and butylphenol. Mono / polyglycidyl ether compounds such as bisphenol A, bisphenol F, or glycidyl ether compounds or epoxy novolac resins of compounds in which alkylene oxide is added thereto; Mono / polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; Glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; And glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene, and the like.

As said aromatic epoxy compound, a commercial item can be used, For example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX -721, oncoat EX-1020, oncoat EX-1030, oncoat EX-1040, oncoat EX-1050, oncoat EX-1051, oncoat EX-1010, oncoat EX-1011, oncoat 1012 (Nagase Chemutekkus Co.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Toto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Mafruf G-0105SA, Mafruf G-0130SP (manufactured by Nichiyu Co., Ltd.); Epiclone N-665, Epiclone HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printech). As said aromatic epoxy compound, since polyfunctional thing is excellent in sclerosis | hardenability, it is preferable.

The alicyclic epoxy compound indicates that the oxirane ring is directly bonded to the saturated ring without passing through a spacer, and specific examples of the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring. The cyclohexene oxide and cyclopentene oxide containing compound obtained by epoxidizing a cargo or a cyclohexene and a cyclopentene ring containing compound with an oxidizing agent are mentioned. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methyl Cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis ( 3,4-Epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthalic acid dioctyl, epoxy hexahydrophthalic acid di-2-ethylhexyl , 1-on When the like ethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxy-ethylcyclohexane, α- pinene oxide, limonene dioxide.

As an alicyclic epoxy compound, 3, 4- epoxycyclohexyl methyl-3, 4- epoxy cyclohexane carboxylate or 3, 4- epoxy- 1-cyclocyclohexyl-3, 4- epoxy- 1-methyl-hexane-carbox A carboxylate is preferable from a viewpoint of adhesive improvement.

As said alicyclic epoxy compound, a commercial item can be used, For example, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000 (made by Daicel Corporation), etc. are mentioned.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl ) Oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy) methyl] Monofunctional oxetane compounds such as oxetane and oxetanyl silsesquioxane; 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene, 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] ratio Phenyl, bis [(3-ethyl-3-oxetanyl) methyl] ether, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] propane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane , Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl Methyl) ether, 1,3,5-tris [6- (3-ethyloxetan-3-yloxycarbonylamino) hexyl] -s-triazine-2,4,6-trione, phenol novolac jade And polyfunctional oxetane compounds such as cetane.

As said oxetane compound, the thing of the commercial item which has a cation-curable monomer as a main component can be used, For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Seki) Yugaku Co., Ltd.); Aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, OXTP (manufactured by Ube Kosan Co., Ltd.), etc. may be mentioned. .

Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, Ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1 , 4-butanediol divinyl ether, 1, 6-cyclohexane dimethanol divinyl ether, etc. are mentioned.

The cationic polymerization initiator may be any compound as long as it is a compound capable of releasing a substance for initiating cationic polymerization by energy ray irradiation or heating, but preferably a double salt which is an onium salt that releases Lewis acid by irradiation with energy ray, Or a derivative thereof. Typical examples of such compounds include the following general formulas,

[A] ^{r +} [B] ^r-

The salt of the cation and anion shown by these is mentioned.

It is preferable that cation [A] ^{r +} is onium here, The structure is a following general formula, for example,

[(R ² ) _a Q] ^{r +}

It can be represented as.

Moreover, R <^2> is an organic group in which carbon number is 1-60 here and may contain atoms other than a carbon atom. a is an integer of 1-5. a R ² are each independently, same or different. Moreover, it is preferable that at least 1 is group of the above organic which has an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. In addition, when the valence of Q in the cation [A] ^{r +} is q, it is necessary to establish a relationship of r = aq (where N = N is treated as 0).

Moreover, it is preferable that anion [B] ^r- is a halide complex, The structure is the following general formula, for example,

[LY _b ] ^r-

It can be represented as.

Furthermore, L is a metal or metalloid (Metalalloid) which is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co and the like. Y is a halogen atom. b is an integer of 3-7. In addition, when the valence of L in the anion [B] ^r- is p, it is necessary to establish a relationship of r = bp.

Specific examples of the anion [LY _b ] ^r- of the general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄₎ ^- or the like ^-, phosphate (PF ₆₎ ^hexafluoro-, antimonate hexafluorophosphate (SbF ₆₎ ^-, it is Senate hexafluorophosphate (AsF ^_6), hexachloro antimonate (SbCl ₆₎ Can be mentioned.

In addition, anion [B] ^r- is a following general formula,

[LY _b-1 (OH)] ^r

The structure represented by can also be used preferably. L, Y, and b are the same as above. Other anions that can be used include perchlorate ions (ClO ₄ ) ^- , trifluoromethylsulfite ions (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ions (FSO ₃ ) ^- , toluenesulfonic acid anions and trinitro Benzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraaryl borate, tetrakis (pentafluorophenyl) borate and the like.

It is especially effective to use the aromatic onium salt of following (A)-(C) among such onium salts. Among these, the 1 type can be used individually or in mixture of 2 or more types.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate

(B) Diphenyl iodonium hexafluoro antimonate, di (4-methylphenyl) iodonium hexafluoro phosphate, di (4-tert- butylphenyl) iodonium hexafluoro phosphate, tolyl cumyl iodo Diaryl iodonium salts, such as nium tetrakis (pentafluorophenyl) borate

(C) sulfonium salts such as sulfonium cations and hexafluoroantimony ions, hexafluorophosphate ions, and tetrakis (pentafluorophenyl) borate ions shown in the following Group I or Group II;

In addition, other preferable ones are (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene]- Iron complexes such as iron-hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and triphenylsilanol Mixtures of silanols such as these; Salts such as thiophenium salts, thioranium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; Polyalkyl polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophorone diamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; Glycidyl esters of the aforementioned polyamines, glycidyl ethers such as phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or carboxylic acid Polyepoxy addition modified substances produced by reacting various epoxy resins such as the above compounds by a conventional method; An amidated modified product produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; Manifination produced by reacting polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reactive site to a nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin by a conventional method Denaturate; Polyhydric carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, 2-methyl succinic acid, 2-methyl adipic acid Acids, 3-methyladipic acid, 3-methylpentane diacid, 2-methyloctane diacid, 3,8-dimethyldecane diacid, 3,7-dimethyldecane diacid, hydrogenated dimer acid, dimer acid, and the like. Aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid, castor Acid anhydrides such as tricarboxylic acids such as trimers of free fatty acids, tetracarboxylic acids such as pyromellitic acid, and the like; Dicyandiamide, imidazole, carboxylic acid ester, sulfonic acid ester, amine imide, etc. are mentioned.

Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, and an iron-arene complex from a practical viewpoint and a viewpoint of a light sensitivity improvement, and the aromatic sulfonium salt which has the following structure with respect to 100 mass% of cationic polymerization initiators (B). It is more preferable to contain at least 0.1 mass% or more.

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ^19, and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or a carbon atom 1 An alkyl group of ˜10, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or any substituent selected from the following formulas (A) to (C), and An ^q- is a q-valent An anion is shown and p represents the coefficient which makes a charge neutral.

Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 10 carbon atoms A group or an ester group having 2 to 10 carbon atoms is represented, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms.

In the compound represented by the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R Halogen atom represented by ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ Examples of the fluorine include fluorine, chlorine, bromine and iodine.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ^{27 Examples} of the alkyl group having 1 to 10 carbon atoms represented by R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ include methyl. , Ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluor Chloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoro Ethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl , Tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxy Methyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl -1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbon Carbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl , Hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxy And the like bitter naphthyl, 1,2-dihydroxy-ethyl.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ^38, and R ³⁹ include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, and s-butyl. Oxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2 -Methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy, etc. are mentioned.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ Examples of the ester group having 2 to 10 carbon atoms represented by R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl and phenoxycarbon Nilyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like. have.

The use ratio of the cationic polymerization initiator with respect to the said cationically curable component is 0.001-15 mass parts, Preferably it is 0.1-10 mass parts of cationic polymerization initiators with respect to 100 mass parts of cationically curable resin components. When too small, hardening will become inadequate easily, and when too large, it may adversely affect the physical properties, such as water absorption of hardened | cured material and hardened | cured material strength.

As an sensitizer and a sensitizer, anthracene type compound, a naphthalene type compound, etc. are mentioned.

As an anthracene type compound, what is represented by following formula (IIIa) is mentioned, for example.

(In formula, R <^9> and R <^10> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, or a C2-C12 alkoxyalkyl group, R <^11> represents a hydrogen atom or C1-C6 Alkyl group.)

Specific examples of the anthracene-based compound represented by the formula (IIIa) include the following compounds.

9,10-dimethoxyanthracene,

9,10-diethoxyanthracene,

9,10-dipropoxyanthracene,

9,10-diisopropoxyanthracene,

9,10-dibutoxyanthracene,

9,10-dipentyloxyanthracene,

9,10-dihexyloxyanthracene,

9,10-bis (2-methoxyethoxy) anthracene,

9,10-bis (2-ethoxyethoxy) anthracene,

9,10-bis (2-butoxyethoxy) anthracene,

9,10-bis (3-butoxypropoxy) anthracene,

2-methyl- or 2-ethyl-9,10-dimethoxyanthracene,

2-methyl- or 2-ethyl-9,10-diethoxyanthracene,

2-methyl- or 2-ethyl-9,10-dipropoxycanthracene,

2-methyl- or 2-ethyl-9,10-diisopropoxycanthracene,

2-methyl- or 2-ethyl-9,10-dibutoxyanthracene,

2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene,

2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like.

As a naphthalene type compound, what is represented by following formula (IIIb) is mentioned, for example.

(In formula, R <^12> and R <^13> represents a C1-C6 alkyl group each independently.)

Specific examples of the naphthalene compound represented by the formula (IIIb) include the following compounds.

4-methoxy-1-naphthol,

4-ethoxy-1-naphthol,

4-propoxy-1-naphthol,

4-butoxy-1-naphthol,

4-hexyloxy-1-naphthol,

1,4-dimethoxynaphthalene,

1-ethoxy-4-methoxynaphthalene,

1,4-diethoxynaphthalene,

1,4-dipropoxynaphthalene,

1,4-dibutoxynaphthalene etc.

Although the use ratio of the said sensitizer and a sensitizer is not specifically limited, It can be used in general use ratio within the range which does not impair the objective of this invention, For example, 100 mass parts of total amounts of a cation curable resin component It is preferable that it is 0.1-3 mass parts or more, respectively, from a viewpoint of sclerosis | hardenability improvement with respect to a sensitizer and a sensitizer.

As a process of manufacturing a prism sheet, for example, a thermoplastic resin is heat-melted, the thermoplastic resin extruded by a single screw or a twin screw extruder is filmed by a stretching machine, and then an adhesive layer is coated on the surface of the thermoplastic resin, The method of contact | adhering photocuring resin to the above is mentioned.

Next, the manufacturing method of the water-based polyurethane resin composition of this invention is demonstrated.

The manufacturing method of the water-based polyurethane resin composition of this invention reacts (a) polyisocyanate component, (b) polyol component, and (c) anionic group introduction agent, and obtains (A) urethane prepolymer. The urethane prepolymer composition containing the obtained (A) urethane prepolymer and (B) cation curable substance is prepared. The urethane prepolymer composition is then dispersed in water to obtain an aqueous dispersion. And the (A) urethane prepolymer in the obtained water dispersion is made to react with (C) blocking agent and / or chain extension agent.

The raw material, reaction conditions, etc. which are used by the manufacturing method of the water-based polyurethane resin composition of this invention are as above-mentioned.

Example

Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

Example 1 [Production of Water-Based Polyurethane Resin Composition U-1]

185.23 g of isophorone diisocyanate, ETERNACOLL UH-200 (polycarbonate diol made by Ube Kosan Co., Ltd., number average molecular weight 2000) in a 5-necked separate round bottom flask equipped with dimroth, stirring blades and nitrogen line 227.99 g, 6.69 g of trimethylolpropane, 49.16 g of dimethylol propionic acid, and 0.55 g of adekastat OT-1 (dioctyl tin laurate manufactured by ADEKA Co., Ltd.) were added to 202.98 g of methyl ethyl ketone, and the mixture was heated at 80 ° C for 6 hours. The reaction was carried out to obtain a urethane prepolymer. The ratio of the total isocyanate group equivalent (NCO) of isophorone diisocyanate, the total hydroxyl group equivalent (OH) of polycarbonate diol, trimethylolpropane, and dimethylol propionic acid, and NCO / OH was 1.5. The isocyanate content of the obtained urethane prepolymer was 4.98 mass% in solid content conversion, and the acid value was 43.85 mgKOH / g in solid content.

The obtained urethane prepolymer (containing methyl ethyl ketone) was cooled to 60 ° C, 27.78 g of triethylamine, and Aaron Oxetane OXT-221 (Toagosei Co., Ltd. bis (3-ethyloxetanylmethyl) ether) 49.69 g was added and stirred for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and the Aaronoxetane OXT-221 in the urethane prepolymer composition was 90/10.

Into a 2 L disposable cup, 1020.0 g of 40 ° C water and adecanate B-1016 (defoamer made by ADEKA Co., Ltd.) were added and stirred for 5 minutes with a disper, followed by 620 g of the urethane prepolymer composition in 2 minutes. It was added over and stirred for 30 minutes. Then, 80.8g of diethylamine / water (mass ratio 1/3) aqueous solution was added, and also it stirred for 30 minutes. Then, it heated up at 40 degreeC, removed the methyl ethyl ketone under reduced pressure conditions, and obtained the water-based polyurethane resin composition U-1 of 30 mass% of solid content. The ratio of the isocyanate reactor equivalents in diethylamine to the isocyanate group equivalents in the urethane prepolymer was 0.67.

Example 2 [Production of Water-Based Polyurethane Resin Composition U-2]

The urethane prepolymer composition was obtained in the same manner as in Example 1.

1020.0g of 40 degreeC water and the adecanate B-1016 (defoamer made by ADEKA Co., Ltd.) were added to a 2-liter disposable cup, and it stirred for 5 minutes with a disper, and then obtained 620g of urethane prepolymer compositions in 2 minutes. It was added over and stirred for 30 minutes. Thereafter, 33.6 g of an aqueous solution of ethylenediamine / water (mass ratio 1/3) was added, followed by further stirring for 30 minutes. Then, it heated up at 40 degreeC, removed the methyl ethyl ketone under reduced pressure conditions, and obtained the water-based polyurethane resin composition U-2 of 30 mass% of solid content. The ratio of the isocyanate reactor equivalents contained in ethylenediamine to the isocyanate group equivalents contained in the urethane prepolymer was 0.68.

Example 3 [Production of Water-Based Polyurethane Resin Composition U-3]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content conversion, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines And 49.69 g of 1,3,5-tris [6- (3-ethyloxetan-3-yloxycarbonylamino) hexyl] -s-triazine-2,4,6-trione are added, and 30 The mixture was stirred for a minute to obtain a urethane prepolymer composition. Mass ratio of urethane prepolymer and 1,3,5-tris [6- (3-ethyloxetan-3-yloxycarbonylamino) hexyl] -s-triazine-2,4,6-trione in the urethane prepolymer composition Was 90/10.

The water-based polyurethane resin composition U-3 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents contained in ethylenediamine to the isocyanate group equivalents contained in the urethane prepolymer was 0.68.

Example 4 [Production of Water-Based Polyurethane Resin Composition U-4]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines and And 49.69 g of ETERNACOLLOXBP (4,4'-bis ({(3-ethyl-3-oxetanyl) methoxy} methyl] biphenyl) made by Ube Kosan Co., Ltd.) were added, and it stirred for 30 minutes, and urethane prepolymer A composition was obtained. The mass ratio of the urethane prepolymer and 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] biphenyl in the urethane prepolymer composition was 90/10.

The water-based polyurethane resin composition U-4 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents contained in ethylenediamine to the isocyanate group equivalents contained in the urethane prepolymer was 0.68.

Example 5 [Production of Water-Based Polyurethane Resin Composition U-5]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines and 49.69 g of bisphenol Adi-methylglycidyl ether was added and stirred for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and bisphenol Adiβ-methylglycidyl ether in the urethane prepolymer composition was 90/10.

The water-based polyurethane resin composition U-5 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents in ethylenediamine to the isocyanate group equivalents in the urethane prepolymer was 0.67.

Example 6 [Production of Water-Based Polyurethane Resin Composition U-6]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines and And 49.69 g of ceoxide 2021P (3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate made by Daicel Co., Ltd.) were added, and stirred for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and the 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate in the urethane prepolymer composition was 90/10.

The water-based polyurethane resin composition U-6 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents in ethylenediamine to the isocyanate group equivalents in the urethane prepolymer was 0.67.

Example 7 [Production of Water-Based Polyurethane Resin Composition U-7]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines and And 49.69 g of TEPIC-VL (triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.) were added and stirred for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and the triglycidyl isocyanurate in the urethane prepolymer composition was 90/10.

The water-based polyurethane resin composition U-7 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents in ethylenediamine to the isocyanate group equivalents in the urethane prepolymer was 0.67.

Example 8 [Production of Water-Based Polyurethane Resin Composition U-8]

In a five-necked separate round bottom flask equipped with dimrose, stirring blades and nitrogen lines, 144.31 g of isophorone diisocyanate, ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Kosan Co., Ltd., number average molecular weight 2000), 177.63 g, trimethyl 5.21 g of all propane, 38.30 g of dimethylol propionic acid, and 0.55 g of adekastat OT-1 (octyl tin laurate manufactured by ADEKA Co., Ltd.) were added to 158.14 g of methyl ethyl ketone and reacted at 80 ° C for 6 hours to give an isocyanate content. The urethane prepolymer which is 4.98 mass% in conversion of silver solid content, and an acid value is 43.85 mgKOH / g in solid content was obtained. The ratio of the total isocyanate group equivalent (NCO) of isophorone diisocyanate, the total hydroxyl group equivalent (OH) of polycarbonate diol, trimethylolpropane, and dimethylol propionic acid, and NCO / OH was 1.5.

The obtained urethane prepolymer was cooled to 60 degreeC, 28.83 g of triethylamines, and 197.14 g of aron oxetane OXT-221 (made by Toagosei Co., Ltd. bis (3-ethyloxetanylmethyl) ether) were added for 30 minutes. Stirring was performed to obtain the urethane prepolymer composition. The mass ratio of the urethane prepolymer and the aroxoxane OXT-221 in the urethane prepolymer composition was 50/50.

Aqueous polyurethane resin composition having a solid content of 30% by mass through the same aqueous dispersion process as in Example 1, except that the amount of diethylamine / water (mass ratio 1/3) was added to 62.8 g using the urethane prepolymer composition obtained here. U-8 was obtained. The ratio of the isocyanate reactor equivalents in diethylamine to the isocyanate group equivalents in the urethane prepolymer was 0.67.

Example 9 [Production of Water-Based Polyurethane Resin Composition U-9]

The urethane prepolymer composition was obtained in the same manner as in Example 1.

To a 2 L disposable cup, 1020.0 g of 40 ° C. water and adecanate B-1016 (made by ADEKA antifoam) were added and stirred for 5 minutes with a disper, followed by 620 g of the obtained urethane prepolymer composition in 2 minutes. It was added over and stirred for 30 minutes. Then, 97.2g of adipic acid dihydrazide / water (mass ratio 1/3) aqueous solution was added, and also it stirred for 30 minutes. Then, it heated up at 40 degreeC, removed methyl ethyl ketone under reduced pressure conditions, and obtained the water-based polyurethane resin composition U-9 of 30 mass% of solid content. The ratio of the isocyanate reactor equivalents in adipic acid dihydrazide to the isocyanate group equivalents in the urethane prepolymer was 0.68.

Comparative Example 1 [Manufacture of Water-based Polyurethane Resin Composition HU-1]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content, the acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer (containing methyl ethyl ketone) is cooled to 60 degreeC, and 27.78 g of triethylamines are obtained. The mixture was added and stirred for 30 minutes to obtain a urethane prepolymer composition.

The aqueous polyurethane resin composition HU-1 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 1 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents in diethylamine to the isocyanate group equivalents in the urethane prepolymer was 0.62.

Comparative Example 2 [Manufacture of Water-based Polyurethane Resin Composition HU-2]

The isocyanate content obtained by carrying out similarly to Example 1 is 4.98 mass% in solid content conversion, and acid value is 43.85 mgKOH / g in solid content, The urethane prepolymer is cooled to 60 degreeC, 27.78 g of triethylamines are added, and it stirred for 30 minutes To obtain a urethane prepolymer composition.

The aqueous polyurethane resin composition HU-2 of 30 mass% of solid content was obtained through the water dispersion process similar to Example 2 using the urethane prepolymer composition obtained here. The ratio of the isocyanate reactor equivalents contained in ethylenediamine to the isocyanate group equivalents contained in the urethane prepolymer was 0.63.

Comparative Example 3 [Manufacture of Water-based Polyurethane Resin Composition HU-3]

In a five-neck separate round bottom flask equipped with dimrose, stirring blades and nitrogen line, 185.23 g of isophorone diisocyanate, ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Kosan Co., Ltd., number average molecular weight 2000) 227.99 g, trimethyl 6.69 g of all propane, 49.16 g of dimethylol propionic acid, 0.55 g of Adeka Stab OT-1 (Octyl tin laurate manufactured by ADEKA) was added to 202.98 g of methyl ethyl ketone, and reacted at 80 ° C for 6 hours, Isocyanate content obtained the urethane prepolymer which is 4.98 mass% in solid content conversion, and an acid value is 43.85 mgKOH / g in solid content.

The obtained urethane prepolymer was cooled to 60 degreeC, and it stirred for 30 minutes with 27.78 g of triethylamine, and obtained the urethane prepolymer composition.

To a 2 L disposable cup, 1020.0 g of 40 ° C. water and adecanate B-1016 (defoamer made by ADEKA Co., Ltd.) were added and stirred for 5 minutes with a disper, followed by 558 g of the urethane prepolymer composition in 2 minutes. It was added over and stirred for 30 minutes. Then, 80.8g of diethylamine / water (mass ratio 1/3) aqueous solution was added, and also it stirred for 30 minutes. Furthermore, 62 g of aron oxetane OXT-221 (Bio (3-ethyloxetanylmethyl) ether manufactured by Toagosei Co., Ltd.) was added, and it stirred for 30 minutes. Then, when heated to 40 degreeC and methyl ethyl ketone was removed under reduced pressure conditions, a uniform dispersion was not obtained and the aqueous polyurethane resin composition HU-3 could not be manufactured.

Evaluation 1 (preservation stability)

The aqueous urethane resin composition was placed in an airtight container and stored at 40 ° C. for up to one week, and precipitation and gelation were observed to evaluate storage stability. In the table, those precipitated and gelled in less than a week indicate the number of days, and precipitated and gelled in less than one day were ×, and those not precipitated or gelated for more than a week were set to ○.

Evaluation 2 (material adhesion)

The water-based polyurethane resin composition was apply | coated to the corona treated PET surface using the bar coater so that the film thickness after drying might be about 1 micrometer, Then, it dried at 30 degreeC and 120 degreeC for 10 minutes at room temperature, and obtained the test piece.

It cut into 100 masses using the cutter guide of clearance gap 1mm for the obtained test piece. Thereafter, the cellophane tape was attached, rubbed to adhere, and then washed off three times. After that, the remaining mass was counted to obtain adhesion. In addition, what peeled partially in the mass was taken as the peeled mass. Evaluation criteria are as follows.

A: 100 left, B: 99-90 left, C: 89-80 left, D: 79-70 left, E: 69-50 left, F: 50 left

Evaluation 3 (adhesiveness with the top coat ultraviolet curable resin paint)

30 parts by mass of 1,6-hexanediol diglycidyl ether, 3 ', 4'-epoxycyclohexyl using a bar coater on the urethane film side of the test piece obtained in the above evaluation 2 so that the film thickness after curing is 3 m. Applying the ultraviolet curable resin paint obtained from 30 mass parts of methyl 3, 4- epoxycyclohexane carboxylates, 40 mass parts of bisphenol A diglycidyl ether, and 5 mass% of the propylene carbonate 50 mass% solution of triphenylsulfonium Using the metal halide lamp, UV irradiation of intensity 600 mW / cm <2> and accumulated light quantity 1000mJ / cm <2> was carried out, and it hardened | cured, and the test piece was obtained.

It cut into 100 masses using the cutter guide of clearance gap 1mm for the obtained test piece. Then, after attaching and rubbing the cellophane tape and sticking it, the peeling operation was performed three times, and the number of remaining masses was counted to obtain the top coat UV adhesiveness. In addition, what peeled partially in the mass was taken as the peeled mass. Evaluation criteria are as follows.

A: 100 left, B: 99-90 left, C: 89-80 left, D: 79-70 left, E: 69-50 left, F: 50 left

The result of evaluation 1-3 was shown to the following [Table 1] and [Table 2].

As is clear from the examples, the water-based polyurethane resin composition according to the present invention is excellent in storage stability, excellent in adhesiveness to a substrate, in particular, an ultraviolet curable resin layer used as a top coat paint, and an adhesive for an optical film. It is suitable as.

The water-based polyurethane resin composition of the present invention is excellent in storage stability and adhesiveness with respect to various substrates, in particular, with an energy ray-curable resin system cured by ultraviolet rays or the like, inter alia, a layer made of a cationic photocurable resin composition. Since it is excellent, it can be used suitably as an adhesive agent for optical films.

Claims (7)

(a) a urethane prepolymer composition comprising (a) a urethane prepolymer made by reacting a polyisocyanate component, (b) a polyol component and a (c) anionic group introducing agent, and (B) a cationically curable substance, in water and dispersed The aqueous polyurethane resin composition obtained by obtaining and obtaining the (A) urethane prepolymer in the obtained water dispersion with (C) blocking agent and / or chain extension agent. The method of claim 1,
The water-based polyurethane resin composition whose cation curable material which is (B) component is at least 1 sort (s) chosen from an oxetane compound and an epoxy compound. The method of claim 2,
The aqueous polyurethane resin composition whose cation curable material which is (B) component is an oxetane compound. The method of claim 2,
The aqueous polyurethane resin composition whose cation curable material which is (B) component is a (beta) -alkylglycidyl compound. The method according to any one of claims 1 to 4,
The water based polyurethane resin composition whose chain extension agent (C) component is at least 1 sort (s) chosen from the water-soluble amine compound and water-soluble dicarboxylic acid dihydrazide compound which have two or more active hydrogens. The method according to any one of claims 1 to 4,
The aqueous polyurethane resin composition whose blocking agent which is (C) component is a water-soluble secondary amine compound. Dispersing in water the urethane prepolymer composition comprising (a) a urethane prepolymer comprising (a) a polyisocyanate component, (b) a polyol component and a (c) anionic group introducing agent, and (B) a cationically curable material The method for producing the aqueous polyurethane resin composition obtained by reacting the (A) urethane prepolymer in the obtained aqueous dispersion with the (C) blocking agent and / or chain extender.