JP7187438B2 - Aqueous polyurethane resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-based polyurethane resin composition, and more specifically, a urethane prepolymer composition comprising a urethane prepolymer obtained by reacting a polyisocyanate component, a polyol component and an anionic group-introducing agent, and a cationic curable substance. is dispersed in water to obtain a water dispersion, and the urethane prepolymer in the resulting water dispersion is reacted with a blocking agent and / or a chain extender, and can be used as an adhesive or an adhesive for optical films relates to a suitable aqueous polyurethane resin composition.

Water-based polyurethane resin compositions are useful because they can be used in various applications such as paints, adhesives, fiber sizing agents, leather, impregnation of substrates, and backings.

BACKGROUND ART Various optical films are used in liquid crystal displays used in televisions, personal computers, and the like, such as polarizer protective films, retardation films, viewing angle protective films, and the like. These optical films are composed of a substrate layer made of polyester resin, polycarbonate resin, or the like, and a layer made of energy ray-curable resin cured by ultraviolet rays or the like. Specifically, optical films described in Patent Documents 1 to 6 are known.

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

Patent Literature 1 describes an easily adhesive polyester film for optical use in which a water-based polyurethane resin composition is used as an adhesive layer. However, the water-based polyurethane resin composition described in this document cannot exhibit sufficient performance with respect to adhesion to a layer composed of an energy ray-curable resin cured by ultraviolet rays or the like.

Patent Document 2 describes a polarizing plate in which a cycloolefin resin film is laminated on a polarizing film made of a polyvinyl alcohol resin via an adhesive layer. In the polarizing plate, a water-based urethane resin composition containing an oxetane compound and an epoxy compound is used in the adhesive layer. However, when an oxetane compound or an epoxy compound is simply blended into a water-based urethane composition, sufficient storage stability cannot be obtained. When used as an adhesive for an optical film composed of a layer made of an energy ray-curable resin, sufficient adhesion cannot be imparted.

Cited Documents 3, 4, 5 and 6 describe combinations of water-based urethane resins and epoxy compounds such as β-methylglycidyl compounds, but the water-based resins described in these documents are polyester resins and the like. When used in a system consisting of a substrate layer and an energy ray-curable resin layer that is cured by ultraviolet rays or the like, only products with poor adhesion are obtained.

Therefore, the present inventors have found that the adhesive is useful as an adhesive for optical films, which is obtained by applying a layer made of an energy ray-curable resin that is cured by ultraviolet rays or the like to a substrate made of PET, PC, or the like. We have made every effort to obtain a water-based polyurethane resin composition.

As a result, the inventors have found that a water-based polyurethane resin composition containing specific components can solve the above problems, and have completed the present invention.

The present invention provides a urethane prepolymer comprising (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent, and (B) a cationic curable substance. A water-based polyurethane resin obtained by dispersing a polymer composition in water to obtain an aqueous dispersion, and reacting (A) a urethane prepolymer in the resulting aqueous dispersion with (C) a blocking agent and/or a chain extender. A composition is provided.

The water-based polyurethane resin composition of the present invention will be described in detail below.

In the present invention, (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent is used.
As the polyisocyanate component (a) used in the present invention, any known polyisocyanate component can be used without particular limitation. (a) The polyisocyanate component preferably contains a diisocyanate because the polyurethane molecules obtained and the coating film obtained therefrom are excellent in hydrolyzability. Examples of diisocyanates include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate. , dianisidine diisocyanate, tetramethylxylylene diisocyanate and the like; -hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexamethylene diisocyanate, and aliphatic diisocyanates such as lysine diisocyanate. Alicyclic diisocyanates are preferred, and isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate are more preferred, since they are excellent in hydrolyzability of the resulting coating film. These diisocyanates can be used alone, or two or more of them can be used in combination.
The above diisocyanates can be used in the form of modified products such as carbodiimide-modified, isocyanurate-modified and biuret-modified, and can be used in the form of blocked isocyanates blocked with various blocking agents.
The polyisocyanate component (a) used in the present invention may contain a polyisocyanate having three or more isocyanate groups in one molecule. Polyisocyanates having three or more isocyanate groups in one molecule include, for example, isocyanurate trimer, biuret trimer, and trimethylolpropane adduct of the above-exemplified diisocyanates; triphenylmethane triisocyanate, 1- Methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc., may be mentioned, and these isocyanate compounds may be used in the form of carbodiimide modification, isocyanurate modification, biuret modification, etc., and various blocking agents. can be used in the form of blocked isocyanates blocked by These can be used alone or in combination of two or more.
Here, in the polyisocyanate component which is the component (a), if the content of the diisocyanate is less than 50% by mass, the storage stability may decrease. preferable.

Furthermore, the polyisocyanate component (a) used in the present invention preferably contains an alicyclic diisocyanate. It is preferable that the polyisocyanate component (a) contains an alicyclic diisocyanate to improve the performance of the coating film, such as solvent resistance and alkali resistance.

Examples of the polyol component (b) used in the present invention include low-molecular-weight polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, silicone polyols, polyester polyols, and polyester carbonate polyols. These can be used alone or in combination of two or more.

Examples of the low-molecular-weight polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane. diol, 1,4-butanediol, neopentyl glycol, 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 , 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol and other aliphatic diols; cyclohexanedimethanol, cyclohexanediol and other cycloaliphatic diols trihydric or higher alcohols such as trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, pentaerythritol and tetramethylolpropane.

The polycarbonate polyol is obtained by reacting a carbonate ester and/or phosgene with the above-exemplified low-molecular-weight polyols. Examples of the carbonic acid ester include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, and phenylnaphthyl carbonate.

As the above polyester polyols, direct esterification of the above-exemplified low-molecular-weight polyols and polyvalent carboxylic acids in an amount less than the stoichiometric amount of the polyols or ester-forming derivatives such as esters, anhydrides, and halides thereof Examples include those obtained by reaction and/or transesterification reaction. Examples of polycarboxylic acids or ester-forming derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 2-methylsuccinic acid. , 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as 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- Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-dicarboxymethylencyclohexane, nadic acid, methylnadic acid; trimellitic acid, trimesic acid, Polycarboxylic acids such as tricarboxylic acids such as castor oil fatty acid trimers, acid anhydrides of these polycarboxylic acids, chlorides of these polycarboxylic acids, halides such as bromides, methyl esters of these polycarboxylic acids, Lower esters such as ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester and amyl ester; , γ-butyrolactone and the like.

Examples of polyether polyols include water, ethylene oxide and/or propylene oxide adducts of the above low-molecular-weight polyols, and polytetramethylene glycol.

Examples of silicone polyols include silicone oils having hydroxyl groups at the ends and having siloxane bonds in the molecule.

Polycarbonate diol is preferably contained in the polyol component (b) used in the present invention, and among polycarbonate diols, those having an average molecular weight of 500 to 5,000 are preferably used. If the average molecular weight is less than 500, the adhesion of the coating film to the substrate may not be sufficiently obtained, and if it exceeds 5000, the storage stability and impact resistance of the product may be deteriorated.
The content of the polycarbonate diol in the polyol component (b) is preferably 50% by mass or more, more preferably 70% by mass in the polyol component (b).

In addition, the polyol component (b) contains a small amount of polyfunctional polyol such as trimethylolpropane (less than 10% by mass in the polyol component (b)) to improve durability. can be done.

Examples of the anionic group-introducing agent that is the component (c) used in the present invention include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, and dimethylolvaleric acid; Examples include polyols containing sulfonic acid groups such as -butanediol-2-sulfonic acid, and polyols containing carboxyl groups, particularly dimethylolpropionic acid, are preferred. These can be used alone or in combination of two or more.

In general, when producing a urethane prepolymer 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, the polyol and the anion The terminal structure of the resulting urethane prepolymer varies depending on the ratio of the hydroxyl group-introducing agent to the total hydroxyl equivalent (OH).
Since the urethane prepolymer used in the present invention preferably has an isocyanate group at the end, it is preferable to adjust the NCO/OH to be greater than 1.0, more preferably 1.1 to 2.5. , more preferably 1.2 to 2.0. When NCO/OH is 1.0 or less, particularly less than 1.1, the resulting urethane prepolymer has a high molecular weight and a reduced water dispersibility, and reacts with the blocking agent and/or chain extender. The number of NCO groups for this may decrease, and the storage stability of the resulting water-based polyurethane resin composition may be adversely affected. If the NCO/OH ratio is greater than 2.0, the isocyanate group reacts with water when the resulting prepolymer is dispersed in water to generate carbon dioxide, which causes problems during production such as rapid foaming. It is not preferable because there is a risk of deterioration in performance such as adhesion to the substrate even when it is made into a water-based polyurethane resin composition.

In addition, the usage ratio (mass ratio) of the polyol as the component (b) and the anionic group-introducing agent as the component (c) is the former/latter in the range of 99.9/0.1 to 70/30. It can be selected as appropriate.

Here, when the water-based polyurethane resin composition of the present invention is used as an adhesive for optical films, the acid value of the urethane prepolymer as the component (A) affects the blocking performance. The acid value of the urethane prepolymer as the component (A) is set preferably in the range of 20-90 mgKOH/g, more preferably 30-80 mgKOH/g, particularly preferably 40-70 mgKOH/g. The amount of the anionic group-introducing agent as component (c) is adjusted so as to achieve such a range.
The acid value of the urethane prepolymer, component (A), is a theoretical value determined from the amount of the reactive component of the urethane prepolymer, component (A). As described later, when an inert solvent is used in the production of the urethane prepolymer as component (A), the measured acid value of the resulting urethane prepolymer as component (A) varies from the above theoretical value. do. The following relationship exists between the theoretical values, the measured values, and the theoretical values described above.
Acid value (theoretical value) = acid value (measured value) x [(a) + (b) + (c) + solvent: total mass] / [(a) + (b) + (c): total mass]

In the production of the urethane prepolymer, component (A) of the present invention, a catalyst can be used as necessary. Examples of such catalysts include 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"-pentamethyldipropylenetriamine, 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, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1- tertiary amines such as dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; Quaternary ammonium salts such as alkylammonium organic acid salts; stanus diacetate, stanus dioctoate, stanus dioleate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin Organometallic catalysts such as dilaurate, lead octanoate, lead naphthenate, nickel naphthenate and cobalt naphthenate. These catalysts can be used alone or in combination of two or more.
Although the amount of these catalysts used is not limited, it is preferably 0.001 to 1% by mass, more preferably 0.01 to 0%, based on the total amount of components (a), (b) and (c). .1 mass %.

When producing the urethane prepolymer which is the component (A) of the present invention, a cross-linked structure can be introduced using a cross-linking agent. As the cross-linking agent, a cross-linking agent commonly used in the production of urethane prepolymers can be used. Examples of such cross-linking agents include melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, methylated methylolmelamine, butylated methylolmelamine, and melamine resins. can be used. Among these cross-linking agents, melamine is preferable because it has excellent compatibility with polyurethane and is inexpensive.
When these crosslinking agents are used, the amount used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polyol as the component (a). be.

The urethane prepolymer as the component (A) used in the present invention comprises a polyisocyanate as the component (a), a polyol as the component (b) and an anion group introducing agent as the component (c), and optional components. It can be obtained by heat-reacting a catalyst and/or a cross-linking agent in the presence of an arbitrary inert solvent. Conditions for the heating reaction are not particularly limited, and known conditions can be employed.
Examples of inert solvents used here include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, etc., which have a high affinity for water.
When a solvent having a boiling point of 100° C. or less is used, it is preferable to remove the solvent by distillation under reduced pressure or the like after producing the aqueous polyurethane resin composition of the present invention.
The amount of the solvent to be used is not particularly limited, but is preferably 3 to 200 parts by mass with respect to 100 parts by mass of the total amount of raw materials for the component (A) urethane prepolymer.

The cationically curable substance, component (B) used in the present invention, is a compound that undergoes polymerization or cross-linking reaction by a cationic polymerization initiator that is activated by irradiation with energy rays such as ultraviolet rays or by heating. Examples of cationic curable substances as the component (B) include oxetane compounds and epoxy compounds. Oxetane compounds and β-alkylglycidyl compounds are preferred because of their excellent storage stability when used as aqueous polyurethane resin compositions. is mentioned as a more preferable compound. These can be used alone or in combination of two or more.

Examples of the oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3 -(phenoxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy)methyl]oxetane, monofunctional oxetane compounds such as oxetanylsilsesquioxane; 1,4-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]benzene, 4,4'-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl, 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, tri Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,3,5-tris[6-(3-ethyloxetan-3-yl oxycarbonylamino)hexyl]-s-triazine-2,4,6-trione, polyfunctional oxetane compounds such as phenol novolak oxetane, and the like.

As the oxetane compound, commercially available products containing an oxetane compound as a main component can be used. -212 (manufactured by Toagosei Co., Ltd.), Ethanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.), and the like.

Among the above oxetane compounds, 3-ethyloxetanylmethyl)ether, 1,3,5-tris[6-(3-ethyloxetane-3-yloxycarbonylamino)hexyl]-s-triazine-2,4,6-trione , 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] biphenyl) by using a compound having two or more oxetanyl groups, energy ray curable cured by ultraviolet rays or the like This is preferable because it provides a water-based polyurethane resin composition having excellent adhesion to the resin.

Examples of the epoxy compounds include aliphatic epoxy compounds, aromatic epoxy compounds, and alicyclic epoxy compounds.

Examples of the aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl ether of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids; polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof; Examples include polyfunctional epoxy compounds such as polyglycidyl esters of 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 diglycidyl ether, triglycidyl ether of glycerin. , triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, and hydrogenated bisphenol A. , and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, and epoxidized polybutadiene.

Commercially available products can be used as the above-mentioned aliphatic epoxy compounds. 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 ChemteX Corporation); 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 (manufactured by Kyoeisha Chemical Co., Ltd.), ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T, ADEKA RESIN EP-4088S (ADEKA company).

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring. Specific examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or polyhydric phenols thereof. Mono/polyglycidyl-etherified products of alkylene oxide adducts, such as bisphenol A, bisphenol F, or glycidyl-etherified compounds obtained by further adding alkylene oxides to these compounds, and epoxy novolac resins; two or more phenols such as resorcinol, hydroquinone, and catechol mono/polyglycidyl etherified compounds of aromatic compounds having an alcoholic hydroxyl group; glycidyl etherified compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; phthalic acid, terephthalic acid, triglycidyl Examples include glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as mellitic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide and divinylbenzene.

Commercially available aromatic epoxy compounds 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 ChemteX Co., Ltd.) ); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemicals); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Toto Kasei Co., Ltd.) YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC); 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.); Adekaresin EP-4000, Adekaresin EP-4005, Adekaresin EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by Printec) and the like.

The above-mentioned alicyclic epoxy compound refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a spacer. Specific examples of the alicyclic epoxy compound include at least one alicyclic ring. cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. 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-methylcyclohexanecarboxylate, 3,4-epoxy-5 -methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxy cyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxy cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, and the like.

As the alicyclic epoxy compound, commercially available products can be used, and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel).

The β-alkylglycidyl compound, which is mentioned as the preferable epoxy compound, has a structure obtained by condensing β-alkylepahydrin and a hydroxy compound. However, the β-alkylglycidyl compound used in the present invention is not limited by its production method.

Examples of the β-alkylepahydrin include β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, β-ethylepichlorohydrin, β-ethylepibromohydrin. Phosphorus, β-ethylepifluorohydrin, β-propylepichlorohydrin, β-propylepibromohydrin, β-propylepifluorohydrin, β-butylepichlorohydrin, β-butylepibromohydrin, β-butyl epiphlohydrin and the like can be mentioned.

Examples of the hydroxy compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, hydroquinone, resorcinol, pyrocatechol, phloroglucinol, dihydroxynaphthalene. , biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxydichloromethane) 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, resorcinol novolak, terpene phenol, dicyclopentadiene/phenol polyadduct, ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol , thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A ethylene oxide and/or propylene oxide adducts, tricyclodecanedimethanol, and the like.

Among the β-alkylglycidyl compounds, a compound having two or more β-methylglycidyl groups, such as bisphenol A diβ-methylglycidyl ether, is used to achieve adhesion with the energy ray-curable resin layer cured by ultraviolet rays or the like. It is preferable because a water-based polyurethane resin composition having excellent properties can be obtained.

In the present invention, a urethane prepolymer composition containing a urethane prepolymer as component (A) and a cationic curable material as component (B) is prepared. In the present invention, the ratio (mass ratio) of the urethane prepolymer as component (A) and the cationic curable material as component (B) is the former:the latter, preferably 100:1-50. When the use ratio of the component (B) is less than 1, there is a possibility that the effect of use such as adhesion may not be obtained, and when it exceeds 50, the storage stability may deteriorate, which is not preferable. The method for preparing the urethane prepolymer composition is not particularly limited, and known methods can be employed.

In the present invention, a water dispersion is obtained by dispersing a urethane prepolymer composition containing a urethane prepolymer as component (A) and a cationic curable material as component (B) in water. Although the method for dispersing the urethane prepolymer composition in water is not particularly limited, for example, a prepolymer mixing method and a phase inversion method can be used.

The prepolymer mixing method is a method in which a prepolymer composition obtained by mixing components (A) and (B) is dispersed in water. Here, the anionic group-neutralizing agent and/or emulsifier can be added to the prepolymer composition and can be added to water.

The phase inversion method is a method of dispersing by adding water to a prepolymer composition obtained by mixing components (A) and (B). Here, the anionic group-neutralizing agent and/or emulsifier can be added to the prepolymer composition and can be added to water.

The anionic group-neutralizing agent is, for example, a basic compound that reacts with an anionic group to form a hydrophilic salt. For example, trialkylamines such as trimethylamine, triethylamine and tributylamine, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, 1-dimethylamino-2-methyl-2 - N,N-dialkylalkanolamines such as propanol, tertiary amine compounds such as trialkanolamines such as triethanolamine; ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. be done.
These can be used alone or in combination of two or more.
From the viewpoint that the dry product of the aqueous polyurethane resin composition of the present invention has good weather resistance and water resistance, it is preferable to use a highly volatile anionic group-neutralizing agent that is easily dissociated by heat. Trimethylamine and triethylamine are particularly preferred.

The amount of the anionic group-neutralizing agent used is determined from the viewpoint of the storage stability of the water-based polyurethane resin composition obtained by the present invention, and the mechanical properties such as strength and performance such as water resistance of products obtained using the same. Seeing, it is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, relative to 1 equivalent of anionic group.

A known surfactant can be used as the emulsifier. For example, well-known general anionic surfactants, nonionic surfactants, cationic surfactants, double-faced surfactants, polymeric surfactants, reactive surfactants, and the like can be used.

Examples of the above anionic surfactants include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoleate; alkali metal salts of sulfonated paraffin; Alkyl sulfonates such as the ammonium salt of paraffinic paraffin; Fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine abietate; naphthalenesulfonic acid formalin condensate; dialkylsulfosuccinate; polyoxyethylene alkyl sulfate; polyoxyethylene alkylaryl sulfate; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate; Salt; N-acylmethyl taurine salt and the like.

Examples of the nonionic surfactants include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerol fatty acid esters; alcohols having 1 to 18 carbon atoms. ethylene oxide and/or propylene oxide adducts of alkylphenol; ethylene oxide and/or propylene oxide adducts of alkylene glycol and/or alkylenediamine;

Examples of the alcohol having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, amyl alcohol, isoamyl alcohol, tert-amyl alcohol. , hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like. Butylphenol, 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, etc. Examples of alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl -1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentane diols, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. Examples of alkylenediamines include those obtained by substituting an amino group for the alcoholic hydroxyl group of the above alkylene glycol. . Ethylene oxide adducts and propylene oxide adducts may also be random adducts or block adducts.

Examples of the cationic surfactant include primary to tertiary amine salts; alkylpyridinium salts such as pyridinium salts such as alkylpyridinium bromide; imidazolinium salts such as imidazolinium laurate; lauryltrimethylammonium chloride; Quaternary ammonium salts such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkyl halide quaternary ammonium salts, and the like.

Examples of the above-mentioned amphoteric surfactants include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, and lauroylamidoethyl. Betaine-type amphoteric surfactants such as hydroxyethyl carboxymethyl betaine and metal salts of hydroxypropyl phosphate; amino acid-type amphoteric surfactants such as metal salts of β-laurylaminopropionic acid; sulfate ester-type amphoteric surfactants; sulfonic acid type amphoteric surfactants.

The amount of the emulsifier used is not particularly limited, but from the viewpoint of performance such as water resistance of the cured product obtained from the aqueous polyurethane resin composition of the present invention, the total solid content of the urethane prepolymer composition is 100 parts by mass. , preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass.

The water-based polyurethane resin composition of the present invention can be obtained by adding a blocking agent and/or a chain extender, which is the component (C), as a solution to the water-dispersed urethane prepolymer composition, if necessary. It is obtained by blocking and/or chain-extending the urethane prepolymer, which is the component (A) contained in the composition, in water. There are no particular restrictions on the reaction conditions between the water-dispersed urethane prepolymer composition and the blocking agent and/or chain extender as component (C), and known conditions can be employed.

Examples of blocking agents used in the present invention include alcohols such as methanol and ethanol; dialkylamines such as diethylamine, dimethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, didodecylamine and distearylamine; diarylamines such as diphenylamine; secondary amino group-containing heterocyclic compounds such as morpholine, piperidine, pyrrole, pyrrolidine, pyrazole and imidazole;
Among these, water-soluble secondary amines, particularly diethylamine, are preferred.

Chain extenders used in the present invention include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl- 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 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, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, and other aliphatic diols; cyclohexanedimethanol, cyclohexanediol, etc. alicyclic diols; 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 - aliphatic diamines such as methyl-1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine; polyether diamines such as polyoxypropylenediamine and polyoxyethylenediamine; diethylenetriamine, triethylenetetramine, polyalkylene polyamines such as tetraethylenepentamine; Alicyclic diamines such as (3-aminopropyl)2,4,8,10-tetraoxaspiro(5.5)undecane; m-xylenediamine, α-(m/p-aminophenyl)ethylamine, m- phenylenediamine, diaminodiamine Aromatic diamines such as phenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene; hydrazine dicarboxylic acid dihydrazides such as adipic acid dihydrazide, sebatic acid dihydrazide, and phthalic acid dihydrazide; 1,6-hexamethylenebis(N,N-dimethylsemicarbazide), 1,1,1′,1′-tetramethyl-4, semicarbazides such as 4′-(methylene-di-p-phenylene)disemiccarbazide; hydrazine hydrate; and water.
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 a blocking agent is used alone as the component (C), the amount of the blocking agent used is included in the blocking agent with respect to the isocyanate group equivalent contained in the urethane prepolymer that is the component (A) before blocking. It is preferable to set the amount so that the ratio of isocyanate-reactive group equivalents is in the range of 0.1 to 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 based on the isocyanate group equivalent contained in the urethane prepolymer which is the component (A) before chain extension. It is preferable to set the amount so that the ratio of isocyanate-reactive group equivalents contained in the agent is in the range of 0.1 to 1.0.
In the present invention, when a blocking agent and a chain extender are used as the component (C), the amount of the blocking agent and the chain extender used is the isocyanate contained in the urethane prepolymer which is the component (A) before the blocking and chain extension. It is preferable to set the amount so that the ratio of the isocyanate-reactive group equivalent contained in the blocking agent and the chain extender to the group equivalent is in the range of 0.1 to 1.0.

The aqueous polyurethane resin composition of the present invention contains a specific polyurethane as a main component. The polyurethane contained in the aqueous polyurethane resin composition of the present invention comprises (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent, and (B) ) is obtained by reacting a cationic curable substance with (C) a blocking agent and/or a chain extender in the presence of water. Therefore, the repeating unit of the polyurethane contained in the water-based polyurethane resin composition of the present invention is not uniform, and its structure and repetition are rich in variety. Therefore, the structure of the polyurethane contained in the aqueous polyurethane resin composition of the present invention is very complicated. For this reason, the present situation is that the structure of the polyurethane contained in the present invention cannot be uniformly represented by a certain general formula, and this is the technical common sense of those skilled in the art. Moreover, if the structure is not specified, the characteristics of the substance that are determined according to the structure cannot be easily understood, so it is impossible to express them by characteristics. Therefore, in the present invention, the invention "aqueous polyurethane resin composition" characterized by containing such a polyurethane is defined as "(a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent. A urethane prepolymer composition containing (A) a urethane prepolymer and (B) a cationically curable substance is prepared, and then the urethane prepolymer composition is dispersed in water to obtain a water dispersion. It must be defined by the expression "water-based polyurethane resin composition obtained by reacting (A) a urethane prepolymer in water dispersion with (C) a blocking agent and/or a chain extender". In other words, with respect to the water-based polyurethane resin composition of the present invention, there are circumstances where it is impossible or almost impractical to "directly specify the water-based polyurethane resin composition by its structure or properties at the time of filing".

In the aqueous polyurethane resin composition of the present invention, the solid content [1 g of the aqueous polyurethane resin composition was weighed into an aluminum cup and calculated from the weight before and after drying for 1 hour in a constant temperature bath at 150°C. ] is not particularly limited, and any value can be selected. The solid content of the water-based polyurethane resin composition of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, because of good dispersibility and paintability.

The weight-average molecular weight of the polyurethane dispersed in the water-based polyurethane resin composition of the present invention is not particularly limited, and can be selected within a range that provides dispersibility and a good coating film as a water-based paint. The weight average molecular weight is preferably 5,000 to 2,000,000, more preferably 10,000 to 100,000. Also, the hydroxyl value is not particularly limited. This value is usually 1 to 100 in terms of KOH consumption (mg) per 1 g of resin.

The state of the aqueous polyurethane resin composition of the present invention is emulsion, suspension, colloidal dispersion, aqueous solution, and the like. The particle size of emulsions, suspensions, and colloidal dispersions in which particles are dispersed in water (measured using a dynamic scattering device) is not particularly limited, but is 1 μm or less because a good dispersion state can be maintained. is preferred, 500 nm or less is more preferred, and 100 nm or less is particularly preferred.

Further, in the water-based polyurethane resin composition of the present invention, if necessary, various commonly used additives can be used. Examples of such additives include hindered amine light stabilizers, ultraviolet absorbers, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, pigments, dyes, film-forming aids, curing agents, and cross-linking agents. , silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, defoaming agents, anti-gelling 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, anticorrosive agents, cationic polymerization initiators and the like.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidylmethyl methacrylate, 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-piperidyl) 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-di-tert-butyl-4-hydroxybenzyl)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-pentamethyl) -4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-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-tetraaza Dodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)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 and the like.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone 2-hydroxybenzophenones such as; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5 -di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5- dicumylphenyl)benzotriazole, 2,2′-methylenebis(4-tert-octyl-6-benzotriazolylphenol), 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole polyethylene glycol ester, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5- tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyl oxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert- tributyl-5-(2-methacryloyloxyethyl)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-( 2-Hydroxyphenyl)benzotriazoles;2 -(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-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-(2-(2- -hydroxyphenyl)-4,6-diaryl-1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate , octyl-3,5-di-tert-butyl-4-hydroxybenzoate, dodecyl-3,5-di-tert-butyl-4-hydroxybenzoate, tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl -benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and behenyl-3,5-di-tert-butyl-4-hydroxybenzoate 2-ethyl-2'-ethoxy oxanilide, 2-ethoxy-4'-dodecyl oxanilide and other substituted oxanilides; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3 - cyanoacrylates such as methyl-3-(p-methoxyphenyl) acrylate; various metal salts or metal chelates, especially nickel or chromium salts or chelates;

Examples of the phosphorus antioxidant include 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 , diphenyldecylphosphite, diphenyloctylphosphite, bis(nonylphenyl)pentaerythritolphosphite, phenyldiisodecylphosphite, tributylphosphite, tris(2-ethylhexyl)phosphite, tridecylphosphite, trilaurylphosphite, dibutyl Acid phosphite, dilauryl acid phosphite, trilauryltrithiophosphite, bis(neopentylglycol).1,4-dicyclohexanedimethyldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite Phyto, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra( C12-15 mixed alkyl)-4,4-isopropylidene diphenyl phosphite, bis[2,2'-methylenebis(4,6-diamylphenyl)] isopropylidene diphenyl phosphite, tetratridecyl 4,4' -butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl) 1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite, tetrakis (2,4-di-tert-butylphenyl)biphenylenediphosphonite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphos phen-6-yl)oxy]ethyl)amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol 2,4,6 - tri-tert-butylphenol monophosphite and the like.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4- hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 4,4′-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-tert-butyl -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′-butylidenebis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis [2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di- tributyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-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-tert-butyl -5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra(β-dodecylmercaptopropionate). β-alkylmercaptopropionates of.

When various additives are used in the water-based polyurethane resin composition of the present invention, the amount used can be appropriately selected. For example, in the case of using a weather resistance imparting agent such as the hindered amine light stabilizer, ultraviolet absorber, phosphorus antioxidant, phenolic antioxidant, or sulfur antioxidant, the amount used is the amount specified in the present invention. If it is less than 0.001 part by mass relative to 100 parts by mass of the solid content of the water-based polyurethane resin composition, a sufficient effect may not be obtained. 0.001 to 10 parts by mass is preferable, and 0.01 to 5 parts by mass is more preferable.
The methods of adding these various additives include a method of adding to the polyol component, a method of adding to the prepolymer, a method of adding to the aqueous phase during water dispersion, and a method of adding after water dispersion. method can be selected.

The aqueous polyurethane resin composition of the present invention can be used in various applications such as paints, adhesives, fiber sizing agents, leather, impregnation of substrates, and backings. The water-based polyurethane resin composition of the present invention is particularly suitable for use in a cationic curing composite system using energy such as heat or ultraviolet rays. It can be used suitably for the application.

An optical film to which the aqueous polyurethane resin composition of the present invention can be applied has an optically anisotropic layer containing a liquid crystalline compound laminated on one side of a support and a hard coat layer laminated on the opposite side. It is a laminate with Examples of such optical films include polarizer protective films, retardation films, viewing angle compensation films, light diffusion films, reflective films, antireflection films, antiglare films, conductive films for touch panels, and prism sheets. Among these, the water-based urethane composition of the present invention can be suitably used for a polarizer protective film, a retardation film, and a viewing angle protective film.

For example, these optical films are produced by adhering a coating layer obtained from a photocurable resin monomer and a polymerization initiator to a sheet-shaped plastic substrate. The water-based polyurethane resin composition of the present invention is suitable as a binder, ie, an easy-adhesion layer, interposed between a plastic substrate and a layer obtained from a photocurable resin and a photopolymerization initiator.

Examples of the plastic substrate include polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane- Polyester resins such as 4,4'-dicarboxylate and polybutylene terephthalate; Silicone resins; Acrylic resins such as polymethyl methacrylate and polyacrylate; Epoxy resins; Fluorine resins, polystyrene, polyvinyl chloride, and polyvinyl fluoride vinyl compounds such as; polycarbonate, (PC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), cycloolefin polymer (COP); Cellulose esters such as butyryl cellulose, acetylpropionyl cellulose, nitrocellulose; Polyamide; Polyimide; Polyurethane; Polyolefins such as polyethylene, polypropylene, polymethylpentene; Polyvinyl acetate; Polysulfone; polyoxyethylene; norbornene resin; cycloolefin polymer (COP) and the like. PET is preferably used because it is available at low cost.
The plastic base material can be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and blasting treatment.

Here, in the method of curing the energy ray-curable resin by irradiation with energy rays, the energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequency rays, and the like, and ultraviolet rays are economically most preferable. Ultraviolet light sources include ultraviolet lasers, mercury lamps, xenon lasers, metal halide lamps, and the like.

The method of applying the aqueous polyurethane resin composition of the present invention to a plastic substrate is not particularly limited. Examples of such coating methods include roll coating, baking, air knife coating, spin coating, curtain coating, die coating, dip coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, and curtain roll coating. , dip coating, rod coating, and doctor plate coating.

As the energy ray curable resin such as ultraviolet rays, there are a radical curable resin and a cationic curable resin. Cationic curable resins using monomers and/or oligomers for cationically curable resins and cationic polymerization initiators are preferred because the products are suitable for use in cationic curable systems.

Examples of the monomers or oligomers for cationic curable resins include aliphatic, aromatic or alicyclic epoxy compounds, oxetane compounds, vinyl ether compounds and oligomers thereof.

Examples of the aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl ether of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids; polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof; Examples include polyfunctional epoxy compounds such as polyglycidyl esters of 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 diglycidyl ether, triglycidyl ether of glycerin. , triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, and hydrogenated bisphenol A. , and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, and epoxidized polybutadiene.
As the aliphatic epoxy compound, a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because it improves viscosity, coatability and reactivity.

Commercially available products can be used as the above-mentioned aliphatic epoxy compounds. 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 ChemteX Corporation); 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 (manufactured by Kyoeisha Chemical Co., Ltd.), ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T, ADEKA RESIN EP-4088S (ADEKA company).

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring. Specific examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or polyhydric phenols thereof. Mono/polyglycidyl-etherified products of alkylene oxide adducts, such as bisphenol A, bisphenol F, or glycidyl-etherified compounds obtained by further adding alkylene oxides to these compounds, and epoxy novolac resins; two or more phenols such as resorcinol, hydroquinone, and catechol mono/polyglycidyl etherified compounds of aromatic compounds having an alcoholic hydroxyl group; glycidyl etherified compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; phthalic acid, terephthalic acid, triglycidyl Examples include glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as mellitic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide and divinylbenzene.

Commercially available aromatic epoxy compounds 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 ChemteX Co., Ltd.) ); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemicals); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Toto Kasei Co., Ltd.) YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC); 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.); Adekaresin EP-4000, Adekaresin EP-4005, Adekaresin EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by Printec) and the like. As the aromatic epoxy compound, a polyfunctional compound is preferable because of its excellent curability.

The above-mentioned alicyclic epoxy compound refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a spacer. Specific examples of the alicyclic epoxy compound include at least one alicyclic ring. cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. 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-methylcyclohexanecarboxylate, 3,4-epoxy-5 -methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxy cyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxy cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, and the like.
Alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, It is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound, commercially available products can be used, and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel).

Examples of the oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3 -(phenoxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy)methyl]oxetane, monofunctional oxetane compounds such as oxetanylsilsesquioxane; 1,4-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]benzene, 4,4'-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl, 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, tri Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,3,5-tris[6-(3-ethyloxetan-3-yl oxycarbonylamino)hexyl]-s-triazine-2,4,6-trione, polyfunctional oxetane compounds such as phenol novolak oxetane, and the like.

As the oxetane compound, commercially available products containing a cationic curable monomer as a main component can be used. Aron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), ethanecol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like.

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-cyclohexanedimethanol divinyl ether and the like.

The cationic polymerization initiator may be any compound that can release a substance that initiates cationic polymerization by energy beam irradiation or heating. A double salt, or a derivative thereof, which is an onium salt that releases Typical examples of such compounds include the following general formula,
[A] ^r+ [B] ^r-
Salts of cations and anions represented by can be mentioned.

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example, the following general formula,
[(R ² ) _a Q] ^r+
can be expressed as

Furthermore, R ² is an organic group having 1 to 60 carbon atoms and which may contain atoms other than carbon atoms. a is an integer from 1 to 5; Each a R ² is independently the same or different. Moreover, at least one is preferably an organic group having an aromatic ring as described above. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N=N. Further, when the valence of Q in the cation [A] ^r+ is q, it is necessary that the relationship r=a−q holds true (however, N=N is treated as valence 0).

Further, the anion [B] ^r- is preferably a halide complex, and its structure is represented by, for example, the following general formula,
[LY _b ] ^r−
can be expressed as

Furthermore, here, L is a metal or semimetal (Metalloid) that 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 from 3 to 7; Further, when the valence of L in the anion [B] ^r- is p, it is necessary that the relationship r=bp holds true.

Specific examples of the anion [LY _b ] ^r- in the above general formula include tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate (BF ₄ ) ⁻ , Hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ⁻ and the like can be mentioned.

Further, the anion [B] ^r- is represented by the following general formula,
[LY _b-1 (OH)] ^r
A structure represented by can also be preferably used. L, Y and b are the same as above. Other usable anions include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate and the like.

Among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be used in combination.

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

(b) Diaryls such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, and tolylcumyliodonium tetrakis(pentafluorophenyl)borate iodonium salt

(C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimony ion, hexafluorophosphate ion, tetrakis(pentafluorophenyl)borate ion, etc.

Other preferred examples include (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]-iron - Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehyde)aluminum, and silanols such as triphenylsilanol thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts and the like; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino -alicyclic polyamines such as 3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; Polyepoxy addition-modified products produced by reacting various epoxy resins such as glycidyl ethers such as bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid in a conventional manner; Amidated modified products produced by reacting polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid in a conventional manner; Mannichiated modified products produced by reacting phenols having at least one aldehyde-reactive site in the nucleus, such as tributylphenol and resorcinol, in a conventional manner; Polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid , glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyl Aliphatic dicarboxylic acids such as octanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; Aromatic dicarboxylic acids; cyclohexanedicarboxylic acid alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid and castor oil fatty acid trimers; acid anhydrides such as tetracarboxylic acids such as pyromellitic acid; Sulfonic acid esters, amine imides, and the like can be mentioned.

Among these, it is preferable to use aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes from the viewpoint of practical use and improvement of photosensitivity. ) is more preferably contained in an amount of at least 0.1% by mass or more based on 100% by mass.

Here, 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, the number of carbon atoms represents an alkyl group ^having 1 to 10 carbon atoms, an alkoxy group ^having 1 to ¹⁰ carbon atoms or an ester group having 2 ^to 10 carbon atoms; represents an atom or an alkyl group having 1 to 10 carbon atoms, and R ²⁵ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any one selected from the following chemical formulas (A) to (C) represents a substituent, An ^q- represents a q-valent anion, and p represents a coefficient that renders the charge neutral.

Here, in the formula, ^{R11 , R12} , ^R13 , ^R14 , R15, ^R16 , ^R17 , ^R18 , ^R19 , ^R20 , ^R21 , ^R22 , ^R23 , ^R24 , ^R26 , 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, or 1 1 to 10 alkoxy groups or 2 to 10 carbon atom ester groups, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or a C 1 to 10 represents an alkyl group of

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} , ^R24 , ^R25 , ^{R26 , R27} , R28, ^R29 , ^R30 , ^R31 , ^R32 , ^R33 , ^R34 , ^R35 , ^R36 , ^R37 , ^R38 and ^R39 Examples of halogen atoms used include fluorine, chlorine, bromine, and iodine.

^R11 , ^{R12 , R13} , ^R14 , ^R15 , ^R16 , ^R17 , ^R18 , ^R19 , R20, ^R21 , ^R22 , ^R23 , ^R24 , ^R25 , ^R26 , ^R27 , 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 as an alkyl group having 1 to 10 carbon atoms, is 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, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl , bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl , methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, 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-butoxy carbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, 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 Examples include loxybutyl, 1,2-dihydroxyethyl and the like.

^R11 , ^{R12 , R13 , R14} , ^R15 , ^R16 , ^R17 , R18, ^R19 , R20, ^R21 , ^R22 , ^R23 , ^R24 , ^R26 , ^R27 , ^R28 , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ as alkoxy groups having 1 to 10 carbon atoms, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, 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 and the like.

^R11 , ^{R12 , R13 , R14} , ^R15 , ^R16 , ^R17 , R18, ^R19 , R20, ^R21 , ^R22 , ^R23 , ^R24 , ^R26 , ^R27 , ^R28 , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyl oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

The ratio of the cationic polymerization initiator to the cationic curable component is 0.001 to 15 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the cationic curable resin component. . If the amount is too small, curing tends to be insufficient, and if the amount is too large, physical properties such as water absorption and strength of the cured product may be adversely affected.

Examples of sensitizers and auxiliary sensitizers include anthracene-based compounds and naphthalene-based compounds.

Examples of the anthracene-based compound include those represented by the following formula (IIIa).

(wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ¹¹ is a hydrogen atom or a represents an alkyl group of ~6.)

Specific examples of the anthracene-based compound represented by the above 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-dipropoxyanthracene,
2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene,
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.

Examples of the naphthalene-based compound include those represented by the following formula (IIIb).

(wherein R ¹² and R ¹³ each independently represent an alkyl group having 1 to 6 carbon atoms)

Specific examples of the naphthalene compound represented by the above 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 and the like.

The use ratio of the sensitizer and the sensitizing aid is not particularly limited, and can be used in a generally normal use ratio within a range that does not impede the purpose of the present invention. From the viewpoint of improving the curability, the amount of each of the sensitizer and the sensitizing aid is preferably 0.1 to 3 parts by mass or more per 100 parts by mass.

As a process for producing a prism sheet, for example, a thermoplastic resin is heated and melted, the thermoplastic resin extruded by a single-screw or twin-screw extruder is made into a film by a stretching machine, and then an adhesive layer is formed on the surface of the thermoplastic resin. There is a method in which a photo-curing resin is adhered thereon.

Next, the method for producing the aqueous polyurethane resin composition of the present invention will be described.
In the method for producing an aqueous polyurethane resin composition of the present invention, (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent are reacted to obtain (A) a urethane prepolymer. A urethane prepolymer composition containing the obtained (A) urethane prepolymer and (B) a cationic curable substance is prepared. Then, the above urethane prepolymer composition is dispersed in water to obtain a water dispersion. Then, (A) the urethane prepolymer in the resulting water dispersion is reacted with (C) a blocking agent and/or a chain extender.
The raw materials, reaction conditions, and the like used in the method for producing the aqueous polyurethane resin composition of the present invention are as described above.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Production of water-based polyurethane resin composition U-1]
185.23 g of isophorone diisocyanate, 227.99 g of ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Industries, number average molecular weight: 2000), trimethylolpropane were placed in a 5-neck separable round-bottomed flask equipped with a Dimroth, a stirring blade, and a nitrogen line. 6.69 g of dimethylolpropionic acid, 49.16 g of dimethylolpropionic acid, and 0.55 g of ADEKA STAB OT-1 (dioctyltin laurate manufactured by ADEKA Corporation) were added to 202.98 g of methyl ethyl ketone and reacted at 80° C. for 6 hours to obtain a urethane prepolymer. rice field. The ratio of the total isocyanate group equivalents (NCO) of isophorone diisocyanate to the total hydroxyl group equivalents (OH) of polycarbonate diol, trimethylolpropane and dimethylolpropionic acid, NCO/OH, was 1.5. The obtained urethane prepolymer had an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content.
The resulting urethane prepolymer (including methyl ethyl ketone) was cooled to 60° C., and 27.78 g of triethylamine and 49.69 g of Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd., bis(3-ethyloxetanylmethyl)ether) were added. After addition, stirring was performed for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and Aron oxetane OXT-221 in the urethane prepolymer composition was 90/10.
1020.0 g of water at 40° C. and Adecanate B-1016 (antifoaming agent manufactured by ADEKA Corporation) were added to a 2 L disposable cup, stirred for 5 minutes with a disper, and then 620 g of the above urethane prepolymer composition was added for 2 minutes. was added over time and stirred for 30 minutes. After that, 80.8 g of diethylamine/water (1/3 mass ratio) aqueous solution was added, and the mixture was further stirred for 30 minutes. Thereafter, the mixture was heated to 40° C. and methyl ethyl ketone was removed under reduced pressure to obtain a water-based polyurethane resin composition U-1 having a solid content of 30% by mass. The ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 2 [Production of water-based polyurethane resin composition U-2]
A urethane prepolymer composition was obtained in the same manner as in Example 1.
1020.0 g of water at 40° C. and Adecanate B-1016 (antifoaming agent manufactured by ADEKA Corporation) were added to a 2 L disposable cup, stirred for 5 minutes with a disper, and then 620 g of the resulting urethane prepolymer composition was added. Add over 2 minutes and stir for 30 minutes. After that, 33.6 g of an ethylenediamine/water (1/3 mass ratio) aqueous solution was added, and the mixture was further stirred for 30 minutes. Thereafter, the mixture was heated to 40° C. and methyl ethyl ketone was removed under reduced pressure to obtain a water-based polyurethane resin composition U-2 having a solid content of 30% by mass. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 3 [Production of Waterborne Polyurethane Resin Composition U-3]
A urethane prepolymer (including methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content, obtained in the same manner as in Example 1, was cooled to 60°C. 27.78 g of triethylamine and 49.69 g of 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino)hexyl]-s-triazine-2,4,6-trione After addition, stirring was performed for 30 minutes to obtain a urethane prepolymer composition. Combination of urethane prepolymer and 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino)hexyl]-s-triazine-2,4,6-trione in urethane prepolymer composition The mass ratio was 90/10.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition U-3 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 4 [Production of water-based polyurethane resin composition U-4]
A urethane prepolymer (containing methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content obtained in the same manner as in Example 1 was cooled to 60°C. , 27.78 g of triethylamine and 49.69 g of ETERNACOLLOXBP (manufactured by Ube Industries, Ltd., 4,4'-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl) were added and stirred for 30 minutes. A urethane prepolymer 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.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition U-4 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 5 [Production of water-based polyurethane resin composition U-5]
A urethane prepolymer (containing methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content obtained in the same manner as in Example 1 was cooled to 60°C. , 27.78 g of triethylamine and 49.69 g of bisphenol A diβ-methylglycidyl ether were added and stirred for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and bisphenol A diβ-methylglycidyl ether in the urethane prepolymer composition was 90/10.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition U-5 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 6 [Production of Waterborne Polyurethane Resin Composition U-6]
A urethane prepolymer (containing methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content obtained in the same manner as in Example 1 was cooled to 60°C. , 27.78 g of triethylamine and 49.69 g of Celoxide 2021P (3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate manufactured by Daicel Co., Ltd.) were added and stirred for 30 minutes to form a urethane prepolymer composition. got The mass ratio of urethane prepolymer and 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate in the urethane prepolymer composition was 90/10.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition U-6 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 7 [Production of Waterborne Polyurethane Resin Composition U-7]
A urethane prepolymer (containing methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content obtained in the same manner as in Example 1 was cooled to 60°C. , 27.78 g of triethylamine 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 triglycidyl isocyanurate in the urethane prepolymer composition was 90/10.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition U-7 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 8 [Production of water-based polyurethane resin composition U-8]
144.31 g of isophorone diisocyanate, 177.63 g of ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Industries, number average molecular weight: 2000), trimethylolpropane were placed in a 5-neck separable round-bottomed flask equipped with a Dimroth, a stirring blade, and a nitrogen line. 5.21 g of dimethylolpropionic acid, 38.30 g of dimethylolpropionic acid, and 0.55 g of Adekastab OT-1 (octyltin laurate manufactured by ADEKA Corporation) were added to 158.14 g of methyl ethyl ketone and reacted at 80° C. for 6 hours. A urethane prepolymer having an acid value of 4.98% by mass in terms of minutes and a solid content of 43.85 mgKOH/g was obtained. The ratio of the total isocyanate group equivalents (NCO) of isophorone diisocyanate to the total hydroxyl group equivalents (OH) of polycarbonate diol, trimethylolpropane and dimethylolpropionic acid, NCO/OH, was 1.5.
The resulting urethane prepolymer was cooled to 60° C., 28.83 g of triethylamine and 197.14 g of Aronoxetane OXT-221 (manufactured by Toagosei Co., Ltd., bis(3-ethyloxetanylmethyl) ether) were added, and the mixture was stirred for 30 minutes. Agitation was performed to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and Aron oxetane OXT-221 in the urethane prepolymer composition was 50/50.
Using the urethane prepolymer composition obtained here, a solid content of 30 was obtained through the same water dispersion step as in Example 1 except that the amount of the diethylamine/water (mass ratio 1/3) aqueous solution added was 62.8 g. % by mass of water-based polyurethane resin composition HU-8 was obtained. The ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 9 [Production of water-based polyurethane resin composition U-9]
A urethane prepolymer composition was obtained in the same manner as in Example 1.
1020.0 g of water at 40° C. and Adecanate B-1016 (antifoaming agent manufactured by ADEKA Corporation) were added to a 2 L disposable cup, stirred for 5 minutes with a disper, and then 620 g of the resulting urethane prepolymer composition was added. Add over 2 minutes and stir for 30 minutes. Then, 97.2 g of an aqueous adipic acid dihydrazide/water (1/3 mass ratio) aqueous solution was added, and the mixture was further stirred for 30 minutes. Thereafter, the mixture was heated to 40° C. and methyl ethyl ketone was removed under reduced pressure to obtain an aqueous polyurethane resin composition U-9 having a solid content of 30% by mass. The ratio of the isocyanate reactive group equivalent contained in the adipic acid dihydrazide to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Comparative Example 1 [Production of water-based polyurethane resin composition HU-1]
A urethane prepolymer (containing methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mgKOH/g in terms of solid content obtained in the same manner as in Example 1 was cooled to 60°C. , and 27.78 g of triethylamine were added and stirred for 30 minutes to obtain a urethane prepolymer composition.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition HU-1 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 1. The ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.62.

Comparative Example 2 [Production of Waterborne Polyurethane Resin Composition HU-2]
A urethane prepolymer obtained in the same manner as in Example 1 has an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mg KOH/g in terms of solid content. was added and stirred for 30 minutes to obtain a urethane prepolymer composition.
Using the urethane prepolymer composition obtained here, a water-based polyurethane resin composition HU-2 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2. The ratio of the isocyanate reactive group equivalent contained in the ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.63.

Comparative Example 3 [Production of water-based polyurethane resin composition HU-3]
185.23 g of isophorone diisocyanate, 227.99 g of ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Industries, number average molecular weight: 2000), trimethylolpropane were placed in a 5-neck separable round-bottomed flask equipped with a Dimroth, a stirring blade, and a nitrogen line. 6.69 g, 49.16 g of dimethylolpropionic acid, and 0.55 g of Adekastab OT-1 (octyltin laurate manufactured by ADEKA Co., Ltd.) were added to 202.98 g of methyl ethyl ketone and allowed to react at 80° C. for 6 hours. A urethane prepolymer having a solid content of 4.98% by mass and an acid value of 43.85 mgKOH/g in solid content was obtained.
The resulting urethane prepolymer was cooled to 60° C. and stirred with 27.78 g of triethylamine for 30 minutes to obtain a urethane prepolymer composition.
1020.0 g of water at 40° C. and Adecanate B-1016 (antifoaming agent manufactured by ADEKA Corporation) were added to a 2 L disposable cup, stirred for 5 minutes with a disper, and then 558 g of the above urethane prepolymer composition was added for 2 minutes. was added over time and stirred for 30 minutes. After that, 80.8 g of diethylamine/water (1/3 mass ratio) aqueous solution was added, and the mixture was further stirred for 30 minutes. Furthermore, 62 g of Aron oxetane OXT-221 (Bis(3-ethyloxetanylmethyl)ether manufactured by Toagosei Co., Ltd.) was added and stirred for 30 minutes. After that, the mixture was heated to 40° C. and the methyl ethyl ketone was removed under reduced pressure.

Evaluation 1 (storage stability)
The water-based urethane resin composition was placed in a closed container and stored at 40° C. for up to one week, and precipitation and gelation were observed to evaluate storage stability. The table shows the number of days for precipitation and gelation in less than one week.

Evaluation 2 (substrate adhesion)
A water-based polyurethane resin composition was applied to the corona-treated PET surface using a bar coater so that the film thickness after drying was about 1 μm. got
The obtained test piece was cut into 100 squares using a cutter guide with a gap interval of 1 mm. After that, a cellophane tape was attached, rubbed to make it adhere, and then vigorously peeled off three times. A part of the mass that was peeled off was regarded as a peeled mass. Evaluation criteria are as follows.
A: 100 remaining, B: 99-90 remaining, C: 89-80 remaining, D: 79-70 remaining, E: 69-50 or less remaining, F: 50 or less remaining

Evaluation 3 (adhesion with topcoat ultraviolet curable resin paint)
Using a bar coater, 30 parts by mass of 1,6-hexanediol diglycidyl ether, 3′,4′- 30 parts by mass of epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 40 parts by mass of bisphenol A diglycidyl ether, and 5% by mass of a 50% by mass solution of triphenylsulfonium in propylene carbonate. Then, using a metal halide lamp, UV irradiation was performed at an intensity of 600 mW/cm ² and an integrated amount of light of 1000 mJ/cm ² for curing to obtain a test piece.
The obtained test piece was cut into 100 squares using a cutter guide with a gap interval of 1 mm. After that, a cellophane tape was attached, rubbed to make it adhere, and then vigorously peeled off three times. A part of the mass that was peeled off was regarded as a peeled mass. Evaluation criteria are as follows.
A: 100 remaining, B: 99-90 remaining, C: 89-80 remaining, D: 79-70 remaining, E: 69-50 or less remaining, F: 50 or less remaining

The results of evaluations 1 to 3 are shown in [Table 1] and [Table 2] below.

As is clear from the examples, the water-based polyurethane resin composition according to the present invention has excellent storage stability and adhesion to substrates, particularly adhesion to an ultraviolet curable resin layer used as a topcoat. and is suitable as an adhesive for optical films.

The water-based polyurethane resin composition of the present invention has excellent storage stability and adhesion to various substrates. Since it has excellent adhesion to other layers, it can be suitably used as an adhesive for optical films.

Claims (4)

A urethane prepolymer composition comprising (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent, and (B) a cationic curable substance A water-based polyurethane resin composition obtained by dispersing in water to obtain a water dispersion, and reacting (A) the urethane prepolymer in the obtained water dispersion with (C) a blocking agent and/or a chain extender. hand,
(A) the NCO/OH ratio during production of the urethane prepolymer is 1.2 to 2.0;
(A) the urethane prepolymer and (B) the cationic curable substance have a usage ratio (mass ratio) of 100:1 to 50;
(A) the ratio of the isocyanate reactive group equivalent contained in the (C) blocking agent and/or chain extender to the isocyanate group equivalent contained in the urethane prepolymer is 0.1 to 1.0;
The cationically curable substance as component (B) is bis[(3-ethyl-3-oxetanyl)methyl]ether, 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino) at least one oxetane compound selected from hexyl]-s-triazine-2,4,6-trione, 4,4′-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl) A water-based polyurethane resin composition. 2. The aqueous polyurethane resin according to claim 1 , wherein the chain extender as component (C) is at least one selected from water-soluble amine compounds having two or more active hydrogens and water-soluble dicarboxylic acid dihydrazide compounds. Composition. 3. The aqueous polyurethane resin composition according to claim 1 or 2 , wherein the blocking agent as component (C) is a water-soluble secondary amine compound. A urethane prepolymer composition comprising (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component and (c) an anionic group-introducing agent, and (B) a cationic curable substance A method for producing a water-based polyurethane resin composition comprising: dispersing in water to obtain a water dispersion; and reacting (A) the urethane prepolymer in the obtained water dispersion with (C) a blocking agent and/or a chain extender. ,
(A) the NCO/OH ratio during production of the urethane prepolymer is 1.2 to 2.0;
(A) the urethane prepolymer and (B) the cationic curable substance have a usage ratio (mass ratio) of 100:1 to 50;
(A) the ratio of the isocyanate reactive group equivalent contained in the (C) blocking agent and/or chain extender to the isocyanate group equivalent contained in the urethane prepolymer is 0.1 to 1.0;
The cationically curable substance as component (B) is bis[(3-ethyl-3-oxetanyl)methyl]ether, 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino) at least one oxetane compound selected from hexyl]-s-triazine-2,4,6-trione, 4,4′-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl) A method for producing a water-based polyurethane resin composition.