KR102573164B1 - Water-based polyurethane resin composition - Google Patents

Abstract

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 cation-curable substance is dispersed in water and dispersed in water An aqueous polyurethane resin composition obtained by obtaining and reacting (A) the urethane prepolymer in the obtained water dispersion with (C) a blocking agent and/or a chain extender. The water-based polyurethane resin composition of the present invention has excellent storage stability and adhesion to various substrates, in particular, adhesion to a layer made of an energy ray cured resin composition cured by ultraviolet rays or the like, especially a cationic light curable resin composition. Since it is excellent, it can be suitably used as an adhesive for optical films.

Description

Water-based polyurethane resin composition

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

The water-based polyurethane resin composition is useful because it can be used for various purposes such as paint, adhesive, fiber bundling agent, leather, substrate impregnation, and backing.

BACKGROUND ART Various optical films are used in liquid crystal displays used for televisions, PCs, and the like, and for example, polarizer protective films, retardation films, viewing angle protective films, and the like are used. These optical films are composed of a substrate layer made of a polyester resin, polycarbonate resin, or the like, and a layer made of an energy ray-curable resin cured by ultraviolet light or the like. Specifically, the optical films described in Patent Literatures 1 to 6 are known.

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

Patent Literature 1 describes an easily-adhesive polyester film for optics using a water-based polyurethane resin composition for an adhesive layer. However, the water-based polyurethane resin composition described in the same document cannot exhibit sufficient performance with respect to adhesion to a layer made of an energy ray curable resin cured by ultraviolet rays or the like.

Patent Literature 2 describes a polarizing plate formed by laminating a cycloolefin-based resin film on a polarizing film made of polyvinyl alcohol-based resin via an adhesive layer. In the polarizing plate, an aqueous urethane resin composition obtained by blending an oxetane compound and an epoxy compound in an adhesive layer is used. However, when only an oxetane compound or an epoxy compound is blended into an aqueous urethane composition, it is not possible to obtain a product with sufficient storage stability, and the aqueous urethane composition is a base layer such as a polyester resin and an energy ray cured resin cured by ultraviolet rays. When used as an adhesive for an optical film constituted by a layer composed of a layer formed of the above, sufficient adhesiveness cannot be imparted.

Cited Documents 3, 4, 5 and 6 describe a combination of an aqueous urethane resin and an epoxy compound such as a β-methylglycidyl compound. When used in a system composed of an energy ray-curable resin layer cured by the like, only those with poor adhesion are obtained.

Therefore, the present inventors have made great efforts to obtain a water-based polyurethane resin composition useful as an adhesive for an optical film 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. .

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

Dispersion of a urethane prepolymer composition comprising (A) a urethane prepolymer formed by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent, and (B) a cation curable substance in water It is to provide an aqueous polyurethane resin composition obtained by obtaining an aqueous dispersion and reacting (A) urethane prepolymer in the obtained aqueous dispersion with (C) a blocking agent and/or a chain extender.

Hereinafter, the aqueous polyurethane resin composition of the present invention is described in detail.

In the present invention, (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) component used in the present invention, a known polyisocyanate component may be used without particular limitation. (a) The polyisocyanate component preferably contains diisocyanate because the polyurethane molecules obtained and the coating film obtained therefrom are excellent in hydrolysis. Examples of diisocyanates include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, and 3,3'-dimethyl aromatic diisocyanates such as diphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, and norbornene diisocyanate; and aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Particularly, these diisocyanates Among them, alicyclic diisocyanates are preferable, and isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate are more preferable because the polyurethane molecules obtained and the coating film obtained therefrom are excellent in hydrolysis. These diisocyanates may be used alone or in combination of two or more.

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

In addition, the polyisocyanate component as component (a) used in the present invention may contain polyisocyanate having three or more isocyanate groups in one molecule. Examples of the polyisocyanate having three or more isocyanate groups in one molecule include isocyanurate trimer, burette trimer, and trimethylolpropane adduct of the above-exemplified diisocyanate; triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and the like, and these isocyanate compounds are carbodiimide-modified, isocyanurate-modified, biuret-modified, etc. It may be used in the form of, or it can be used in the form of blocked isocyanate blocked by various blocking agents. These may be used independently or may be used in combination of 2 or more types.

Here, in the polyisocyanate component as component (a), since the storage stability may deteriorate when the content of diisocyanate is smaller than 50% by mass, 50% by mass or more is preferable, and 70% by mass or more is more preferable.

Furthermore, it is preferable that the polyisocyanate component, which is component (a) used in the present invention, contains an alicyclic diisocyanate. Since performance, such as solvent resistance and alkali resistance of a coating film, improves when the polyisocyanate component which is (a) component contains alicyclic diisocyanate, it is preferable.

Examples of the polyol component (b) component 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 may be used independently or may be used in combination of 2 or more types.

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

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

As the polyester polyol, a direct esterification reaction of the low molecular weight polyol exemplified above with an ester-forming derivative such as a polyhydric carboxylic acid or an ester, anhydride or halide thereof in an amount smaller than the stoichiometric amount of the polyol and/or Or what is obtained by transesterification reaction is mentioned. Examples of polyhydric carboxylic 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, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane2 aliphatic dicarboxylic acids such as acids, hydrogenated dimer acids, and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane alicyclic dicarboxylic acids such as dicarboxylic acid, 1,4-dicarboxylmethylenecyclohexane, nadic acid, and methyl nadic acid; Polyhydric carboxylic acids such as tricarboxylic acids such as trimellitic acid, trimesic acid, and trimers of castor oil fatty acids, acid anhydrides of these polycarboxylic acids, halides such as chlorides and bromides of the polyvalent carboxylic acids, and Lower esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester and amyl ester of polyhydric carboxylic acid, γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl- and lactones such as ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

Examples of the polyether polyol include water, an ethylene oxide and/or propylene oxide adduct of the above low molecular weight polyol, and polytetramethylene glycol.

Examples of the silicone polyol include silicone oils having a siloxane bond in the molecule and having a hydroxyl group at the terminal.

It is preferable to contain polycarbonate diol in the polyol component (b) component used in the present invention, and among polycarbonate diols, it is preferable to use one having an average molecular weight of 500 to 5000. If the average molecular weight is less than 500, there is a risk that sufficient adhesion of the coating film to the substrate may not be obtained, and if it exceeds 5000, storage stability or impact resistance when made into a product may decrease.

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 as component (b) can aim at improving durability by using a small amount [less than 10% by mass in the polyol component as component (b)] of polyfunctional polyols such as trimethylolpropane.

Examples of the anionic group-introducing agent as component (c) used in the present invention include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, and dimethylolvaleric acid; and polyols containing sulfonic acid groups such as 1,4-butanediol-2-sulfonic acid. Polyols containing carboxyl groups, particularly dimethylolpropionic acid, are preferred. These may be used independently or may be used in combination of 2 or more types.

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

Since the terminal of the urethane prepolymer used in the present invention is preferably an isocyanate group, it is preferable to adjust the NCO/OH to be greater than 1.0, more preferably in the range of 1.1 to 2.5, and even more preferably in the range of 1.2 to 2.0. Adjust. When NCO / OH is 1.0 or less, particularly less than 1.1, the resulting urethane prepolymer has a high molecular weight, lowers its water dispersibility, and reduces NCO groups for reacting with the blocking agent and / or chain extender, resulting in a water-based polyurethane resin to be obtained There is a possibility of adversely affecting the storage stability of the composition. When NCO/OH is greater than 2.0, carbon dioxide is generated due to the reaction between isocyanate groups and water during aqueous dispersion of the obtained prepolymer, which may cause problems during production such as rapid foaming. This is not preferable because there is a risk of deterioration in performance such as adhesiveness with.

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

Here, when the water-based polyurethane resin composition of the present invention is used as an adhesive for an optical film, the acid value of the urethane prepolymer as component (A) affects the blocking performance. The acid value of the urethane prepolymer as component (A) is set in the range of preferably 20 to 90 mgKOH/g, more preferably 30 to 80 mgKOH/g, and particularly preferably 40 to 70 mgKOH/g. The amount of the anionic group introducing agent used as component (c) is adjusted so as to fall within such a range.

On the other hand, the acid value of the urethane prepolymer as the above-mentioned component (A) is a theoretical value determined from the compounding amount of the reactive components of the urethane prepolymer as component (A). As described later, when an inert solvent is used for the production of the urethane prepolymer as component (A), the measured acid value of the urethane prepolymer as component (A) to be obtained varies from the above theoretical value. There is the following relationship between the above-mentioned theoretical value and measured value.

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

In the production of the urethane prepolymer as component (A) of the present invention, a catalyst can be used as needed. Such catalysts include, for example, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N "-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylene Triamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo [5.4 .0] undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'- Dimethylpiperazine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, N,N-dimethyllaurylamine, 1-methylimidazole , tertiary amines such as 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; quaternary ammonium salts such as tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salts, and tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate; stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltindilaurate, dibutyltindichloride, Organometallic catalysts, such as dioctyl tin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate, etc. are mentioned. These catalysts can be used alone or in combination of two or more.

The amount of these catalysts used is not limited, but is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.1% by mass relative to the total amount of component (a), component (b) and component (c).

When producing the urethane prepolymer which is component (A) of the present invention, a crosslinking structure can be introduced using a crosslinking agent. As the crosslinking agent, a crosslinking agent commonly used in the manufacture of urethane prepolymers may be used. Examples of such a crosslinking agent include melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, methylated methylolmelamine, butylated methylolmelamine, A melamine resin etc. can be used. Among these crosslinking agents, melamine, which is excellent in compatibility with polyurethane and inexpensive, is preferable.

The usage amount in the case of using these crosslinking agents 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 component (a).

The urethane prepolymer as component (A) used in the present invention includes polyisocyanate as component (a), polyol as component (b), and anionic group introducing agent as component (c), catalyst and/or crosslinking agent as optional components, It is obtained by carrying out a heating reaction in the presence of an inert solvent of The conditions for the heating reaction are not particularly limited, and known conditions can be employed.

Examples of the inert solvent used herein include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone, which have a high affinity for water.

When using a solvent having a boiling point of 100°C or less, it is preferable to remove the solvent by distillation under reduced pressure or the like after preparing the water-based polyurethane resin composition of the present invention.

Although the amount of the solvent used is not particularly limited, it is preferably 3 to 200 parts by mass relative to 100 parts by mass of the total amount of the raw material of the urethane prepolymer (A) component.

The cation-curable substance as component (B) used in the present invention is a compound that undergoes a polymerization or crosslinking reaction by a cationic polymerization initiator activated by irradiation with energy rays such as ultraviolet rays or heating. Examples of the cation-curable substance as component (B) include oxetane compounds and epoxy compounds, and since they are excellent in storage stability when used as aqueous polyurethane resin compositions, oxetane compounds and β-alkyl glycols A cydyl compound is mentioned as a more preferable compound. These may be used independently or may be used in combination of 2 or more types.

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

As the oxetane compound, a commercially available product containing an oxetane compound as a main component can be used. -212 (product of Toagosei Co., Ltd.), Etanacol OXBP, OXTP (product of Ube Kosan Co., Ltd.), etc. are mentioned.

Among the above oxetane compounds, 3-ethyloxetanylmethyl ether, 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino)hexyl]-s-triazine-2,4 By using a compound having two or more oxetanyl groups such as ,6-trione, 4,4'-bis[{(3-ethyl-3-oxetanyl)methoxy}methyl]biphenyl, This is preferable because an aqueous polyurethane resin composition excellent in adhesion to the cured energy ray-curable resin can be obtained.

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

Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, and polyglycidyls of aliphatic polyhydric alcohols or their alkylene oxide adducts. and polyfunctional epoxy compounds such as etherified compounds and polyglycidyl esters of aliphatic long-chain polybasic acids. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycoldi Glycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, poly Diglycidyl ether of propylene glycol, glycidyl ether of polyhydric alcohols such as dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, hydrogenated bisphenol A, etc. The polyglycidyl ether compound of polyether polyol obtained by adding a species or two or more types of alkylene oxide, and the diglycidyl ester of an aliphatic long-chain dibasic acid are mentioned. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized polybutadiene, and the like are exemplified.

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

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or alkylene oxide adducts thereof. mono/polyglycidyl ether compounds such as bisphenol A, bisphenol F, or glycidyl ether compounds of compounds obtained by adding an alkylene oxide to them, or epoxy novolak resins; mono/polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide or divinylbenzene, and the like.

As said aromatic epoxy compound, the thing of a commercial item can be used, For example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-711, Denacol EX-147 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 ( manufactured by Nagase Chemicals Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Doto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Maproof G-0105SA, Maproof G-0130SP (manufactured by Nichiyu Co., Ltd.); 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.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (made by ADEKA); TECHMORE VG-3101L (product of Printec) etc. are mentioned.

The alicyclic epoxy compound refers to a compound in which an oxirane ring is directly bonded to a saturated ring without passing through a spacer, and specific examples of the alicyclic epoxy compound include polyglycidyl of a polyhydric alcohol having at least one alicyclic ring. and cyclohexene oxide or cyclopentene ring-containing compounds obtained by epoxidizing an etherified product 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-methyl Cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis( 3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), 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 said alicyclic epoxy compound, the thing of a commercial item can be used, For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel) etc. are mentioned.

As a (beta)-alkyl glycidyl compound mentioned as said preferable epoxy compound, it has a structure obtained by condensing (beta)-alkyl epihydrin and a hydroxy compound. However, the β-alkyl glycidyl compound used in the present invention is not limited by its manufacturing method.

Examples of the β-alkylepihydrin include β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, β-ethylepichlorohydrin, β-ethyl Epibromohydrin, β-ethylepifluorohydrin, β-propylepichlorohydrin, β-propylepibromohydrin, β-propylepifluorohydrin, β-butylepichlorohydrin, β -Butyl epibromohydrin, β-butyl epifluorohydrin, etc. are mentioned.

Examples of the hydroxy compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, hydroquinone, resorcin, pyrocatechol , phloroglucinol, dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), Tetrabromobisphenol A, 1,3-bis(4-hydroxydicumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane , 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, dihydroxynaphthalene, phenol novolac, butylphenol novolac, octylphenol novolac, resorcinol Rockfish, terpene phenol, dicyclopentadiene/phenol polyadduct, ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol Aethylene oxide and/or propylene oxide adducts, tricyclodecane dimethanol, and the like.

Among the above β-alkyl glycidyl compounds, by using a compound having two or more β-methylglycidyl groups such as bisphenol Adi β-methylglycidyl ether, adhesion to the energy ray-curable resin layer cured by ultraviolet rays or the like is improved. This is preferable because an excellent water-based polyurethane resin composition can be obtained.

In the present invention, a urethane prepolymer composition containing a urethane prepolymer as component (A) and a cationic curable substance as component (B) is prepared. In the present invention, the use 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 to 50. When the proportion of component (B) is less than 1, there is a fear that the use effect such as adhesion may not be obtained, and when the proportion exceeds 50, storage stability may decrease, which is not preferable. The preparation method of the urethane prepolymer composition is not particularly limited, and a known method 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 substance as component (B) in water. The method of dispersing the urethane prepolymer composition in water is not particularly limited, but, for example, a prepolymer mixing method or an inversion method can be used.

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

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

The anionic group neutralizing agent is, for example, a basic compound that reacts with anionic groups 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- tertiary amine compounds such as N,N-dialkyl alkanolamines such as 2-methyl-2-propanol and trialkanolamines such as triethanolamine; Ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are mentioned.

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

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

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

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

Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoleate; alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abietate; alkylaryl sulfonates such as sodium benzene sulfonate and alkali metal sulfates of alkylphenol hydroxyethylene; high alkyl naphthalene sulfonic acid salts; Naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate; N-acylamino acid salts; The N-acylmethyl taurine salt etc. are mentioned.

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

Examples of alcohols having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol , hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like, examples of the alkyl phenol include phenol, methyl phenol, 2,4-ditert-butylphenol, 3,5-ditertiary butylphenol, 4-(1,1,3,3-tetramethylbutyl)phenol, 4-isooctylphenol, 4-nonylphenol, 4-tertiary octylphenol, 4-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, 4-(3,5-dimethylheptyl)phenol, naphthol, bisphenol A, bisphenol F, etc. are mentioned, and 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, neopentylglycol, 1,5- pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, and the like, and alkylene diamines include the above alkylene glycols. Examples include those in which the alcoholic hydroxyl group of was substituted with an amino group. In addition, ethylene oxide adducts and propylene oxide adducts may be random adducts or may be block adducts.

Examples of the above cationic surfactants include primary to tertiary amine salts; Alkyl pyridinium salts, such as pyridinium salts, such as an alkyl pyridinium bromide; imidazolinium salts such as imidazolinium laurate; Quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, and alkyl quaternary ammonium salts can be heard

Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, lauryl betaine type amphoteric surfactants such as hydroxysulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine, and metal salts of hydroxypropyl phosphoric acid; amino acid type amphoteric surfactants such as metal salts of β-laurylaminopropionic acid; sulfuric acid ester type amphoteric surfactants; A sulfonic acid type amphoteric surfactant etc. are mentioned.

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

The water-based polyurethane resin composition of the present invention is obtained by adding a blocking agent and/or a chain extender as a component (C) as a solution to the urethane prepolymer composition in a water-dispersible state, as necessary, to obtain (A) contained in the urethane prepolymer composition It is obtained by blocking and/or chain-extending the urethane prepolymer as a component in water. The reaction conditions between the urethane prepolymer composition in a water-dispersed state and the blocking agent and/or chain extender as component (C) are not particularly limited, and known conditions can be employed.

Examples of the blocking agent 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; and secondary amino group-containing heterocyclic compounds such as morpholine, piperidine, pyrrole, pyrrolidine, pyrazole, and imidazole.

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

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-pentane diol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1, aliphatic diols such as 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, and triethylene glycol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; Ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,3-propanediamine, 2-butyl-2-ethyl-1,3-propanediamine, 1,4-butanediamine, Neopentanediamine, 3-methyl-2,4-pentanediamine, 2,4-pentanediamine, 1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-2,4-pentanediamine , 2,4-diethyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 3,5-heptanediamine, 1,8-octanediamine, 2-methyl-1,8 - Aliphatic diamines such as octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; Mensendiamine, isophoronediamine, norbornendiamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, 3,9-bis(3-amino alicyclic diamines such as propyl) 2,4,8,10-tetraoxaspiro (5.5) undecane; m-xylenediamine, α-(m/p-aminophenyl)ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldi aromatic diamines such as phenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene; hydrazine; dicarboxylic acid dihydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; 1,6-Hexamethylenebis(N,N-dimethylsemicarbazide), 1,1,1',1'-tetramethyl-4,4'-(methylene-dip-phenylene) disemicarbazide, etc. of semicarbazides; hydrated hydrazine; water etc. are mentioned.

Among these chain extenders, water-soluble amine compounds having two or more active hydrogens such as ethylenediamine or water-soluble dicarboxylic acid dihydrazide are preferred.

In the present invention, when the blocking agent is used alone as component (C), the amount of the blocking agent is the ratio of the isocyanate reactive group equivalent contained in the blocking agent to the isocyanate group equivalent contained in the urethane prepolymer, which is component (A) before sealing. It is preferable to set to an amount that is in the range of 0.1 to 1.0.

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

In the present invention, when using a blocking agent and a chain extending agent as component (C), the amount of the blocking agent and chain extending agent is contained in the isocyanate group equivalent contained in the urethane prepolymer, which is the component (A) before blocking and chain extension. It is preferable to set the ratio of isocyanate reactive equivalents contained in the agent and the chain extender to an amount in the range of 0.1 to 1.0.

The water-based polyurethane resin composition of the present invention contains a specific polyurethane as a main component. The polyurethane contained in the water-based polyurethane resin composition of the present invention is (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent, and (B) cation curing properties. It is obtained by reacting a 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 the same, and its structure and repetition are rich in diversity. Therefore, the structure of the polyurethane included in the water-based polyurethane resin composition of the present invention is quite complicated. For this reason, it is currently impossible to uniformly represent the structure of polyurethane included in the present invention by any kind of general formula, which is the common technical knowledge of those skilled in the art. In addition, if the structure is not specified, it is impossible to express it as a property because the properties of the material determined accordingly cannot be easily known. Therefore, in the present invention, the "aqueous polyurethane resin composition" of the invention comprising such a polyurethane is "(a) a polyisocyanate component, (b) a polyol component, and (c) formed by reacting an anionic group introducing agent" A urethane prepolymer composition containing (A) a urethane prepolymer and (B) a cation-curable substance is prepared, and then the urethane prepolymer composition is dispersed in water to obtain a water dispersion, and (A) urethane prepolymer in the obtained water dispersion is (C) It cannot be defined as the expression “water-based polyurethane resin composition obtained by reacting with a blocking agent and/or a chain extender.” That is, with respect to the water-based polyurethane resin composition of the present invention, there exists a situation where "directly specifying the water-based polyurethane resin composition by its structure or characteristics at the time of application" is impossible or almost impractical.

In the water-based polyurethane resin composition of the present invention, the solid content [calculated from the weight before and after weighing 1 g of the water-based polyurethane resin composition in an aluminum cup and drying in a thermostat at 150 ° C. for 1 hour] is not particularly limited, You can choose any value. The solid content of the water-based polyurethane resin composition of the present invention is preferably 10 to 70% by mass, since dispersibility and coating properties are good, and 20 to 60% by mass is more preferable.

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 a range that gives a good coating film and dispersibility as a water-based paint can be selected. About a weight average molecular weight, 5000-2000000 are preferable and 10000-100000 are more preferable. In addition, 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 water-based polyurethane resin composition of the present invention is emulsion, suspension, colloidal dispersion, aqueous solution and the like. The particle size of an emulsion, suspension, or colloidal dispersion in which particles are dispersed in water (measured using a dynamic scattering device) is not particularly limited, but is preferably 1 µm or less, and 500 nm or less, because a good dispersion state can be maintained. is more preferable, and 100 nm or less is particularly preferable.

In addition, various commonly used additives may be used in the water-based polyurethane resin composition of the present invention, if necessary. Examples of the additives include hindered amine light stabilizers, ultraviolet absorbers, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, pigments, dyes, film forming aids, curing agents, crosslinking agents, and silane coupling agents. , antiblocking agent, viscosity modifier, leveling agent, antifoaming agent, antigelling agent, dispersion stabilizer, radical scavenger, heat resistance imparting agent, inorganic and organic filler, plasticizer, lubricant, antistatic agent, reinforcing agent, catalyst, thixotropic agent, antibacterial agent, antifungal agent , 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-piperidylbenzoate, 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-piperidylmethylmethacrylate, 2,2,6,6-tetra Methyl-4-piperidylmethylmethacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis( 1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-p peridyl) 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-dizee 3butyl-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-tri Azin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis(N-butyl-N-(2,2,6,6-tetra Methyl-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-tetra oxyspiro [5.5] undecane; and the like.

Examples of the UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis. (2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tertiary Octylphenyl) benzotriazole, 2-(2-hydroxy-3,5-ditert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tertiary octyl-6-benzotriazolylphenol), Polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloxyethyl)-5-methylphenyl] Benzotriazole, 2-[2-hydroxy-3-(2-methacroyloxyethyl)-5-tertiary butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacroyloxyethyl) yloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole , 2-[2-hydroxy-5-(2-methacroyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tertiary butyl-5-(2-methacroyloxyethyl) ) Phenyl] benzotriazole, 2-[2-hydroxy-3-tertiary amyl-5-(2-methacryloxyethyl)phenyl] benzotriazole, 2-[2-hydroxy-3-tertiary Butyl-5-(3-methacroyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(methacroyloxymethyl)phenyl]benzotriazole, 2-[2 -Hydroxy-4-(3-methacryloxy-2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloxypropyl)phenyl]benzotriazole 2-(2-hydroxyphenyl)benzotriazoles such as 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-acroyloxyethoxy)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 such as ,4,6-(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine ,3,5-triazines; Phenyl salicylate, resorcinol monobenzoate, 2,4-ditertbutylphenyl-3,5-ditertertbutyl-4-hydroxybenzoate, octyl-3,5-ditertertbutyl-4-hydroxy Benzoate, dodecyl-3,5-ditertbutyl-4-hydroxybenzoate, tetradecyl-3,5-ditertertbutyl-4-hydroxybenzoate, hexadecyl-3,5-ditertertbutyl- benzoates such as 4-hydroxybenzoate, octadecyl-3,5-ditertbutyl-4-hydroxybenzoate, and behenyl-3,5-ditertertbutyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and various metal salts or metal chelates, particularly salts or chelates of nickel or chromium.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, tris(2,4-ditert-butylphenyl) phosphite, tris(2,5-ditert-butylphenyl) phosphite, and tris(nonylphenyl)phosphite. , tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditertiary butylphenyl) octyl phosphite, di Phenyldecyl phosphite, diphenyloctyl phosphite, bis(nonylphenyl)pentaerythritol phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, tri Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis(neopentyl glycol) 1,4-dicyclohexanedimethyl diphosphite, bis(2,4-diase) 3butylphenyl) pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, distearylpenta Erythritol diphosphite, tetra(C12-15 mixed alkyl)-4,4-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] isopropylidenedi Phenylphosphite, tetratridecyl/4,4'-butylidenebis(2-tertiary butyl-5-methylphenol) diphosphite, hexa(tridecyl)/1,1,3-tris(2-methyl- 5-tert-butyl-4-hydroxyphenyl)butane/triphosphite, tetrakis(2,4-ditert-butylphenyl)biphenylenediphosphonite, tris(2-[(2,4,8,10 -tetrakistert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 9,10-dihydro-9-oxa-10-phosphaphe Nanthrene-10-oxide, 2-butyl-2-ethylpropanediol/2,4,6-triztert-butylphenol monophosphite, and the like are exemplified.

Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditertertbutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, T O-diethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4, 6-bis(3,5-ditert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3 -bis(4-hydroxy-3-tertiary butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis(6-tertiary butyl-3-methylphenol), 1,1,3- Tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, bis[2-tertiary butyl-4-methyl-6-(2-hydroxy-3-tertiary butyl-5-methylbenzyl ) Phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-diase) 3-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3, 5-tris[(3,5-ditertbutyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-ditertertbutyl-4'- Hydroxyphenyl) propionate] methane, 2-tertiary butyl-4-methyl-6- (2-acroyloxy-3-tertiary 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 [beta-(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] etc. are mentioned.

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

In the case of using various additives in the water-based polyurethane resin composition of the present invention, the amount of each additive can be appropriately selected. For example, when a weather resistance imparting agent such as the hindered amine-based light stabilizer, ultraviolet absorber, phosphorus-based antioxidant, phenol-based antioxidant, or sulfur-based antioxidant is used, the amount used is the amount of the water-based polyurethane resin composition of the present invention If the solid content is less than 0.001 parts by mass for 100 parts by mass, sufficient addition effect may not be obtained, and if it is greater than 10 parts by mass, dispersibility or coating film properties may be affected, so 0.001 to 10 parts by mass is preferable, and 0.01 to 10 parts by mass 5 mass parts is more preferable.

In addition, the method of adding these various additives includes a method of adding to a polyol component, a method of adding to a prepolymer, a method of adding to a water phase at the time of water dispersion, a method of adding after water dispersion, and the like. you can choose a way

The water-based polyurethane resin composition of the present invention can be used for various purposes such as paint, adhesive, fiber bundling agent, leather, substrate impregnation, and backing. The water-based polyurethane resin composition of the present invention is particularly suitable for use in a cationic curing complex system by energy such as heat or ultraviolet rays, and for example, it can be suitably used for optical film applications using energy ray curable resins cured by ultraviolet rays. can

An optical film to which the water-based polyurethane resin composition of the present invention can be applied is a laminate in which an optically anisotropic layer containing a liquid crystalline compound is laminated on one side of a support and a hard coating layer is laminated on the opposite side. Such an optical film is, for example, a polarizer protective film, a retardation film, a viewing angle protective film, a light diffusing film, a reflective film, an antireflection film, an antiglare film, a conductive film for a touch panel, a prism sheet, and the like. Among these, the water-based urethane composition of 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 aqueous polyurethane resin composition of the present invention is suitable as a binder through a layer obtained from a plastic substrate, a photocurable resin, and a photopolymerization initiator, that is, an easily adhesive layer.

Examples of the plastic substrate include polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2 - Polyester resins such as diphenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; silicone resin; acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; epoxy resin; vinyl compounds such as fluorine-based resins, polystyrene, polyvinyl chloride, and polyvinyl fluoride; polycarbonate (PC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), cycloolefin polymer (COP); cellulose esters such as triacetyl cellulose (TAC), diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamide; polyimide; Polyurethane; polyolefins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl acetate; polysulfone; polyethersulfone; polyether ketone; polyetherimide; polyoxyethylene; norbornene resin; A cycloolefin polymer (COP) etc. are mentioned. PET is suitably used because of its low cost availability.

On the other hand, surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, blast treatment, etc. may be performed on the plastic substrate.

Here, in the method of curing the energy ray-curable resin by irradiation with energy rays, examples of the energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are economically most preferable. An ultraviolet light source includes an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, and the like.

A method of applying the water-based polyurethane resin composition of the present invention to a plastic substrate is not particularly limited. Such coating methods include, for example, roll coating, baking, air knife, spin coating, curtain coating, die coating, immersion coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, Curtain roll coating, dip coating, rod coating, doctor blade coating and the like may be mentioned.

The ultraviolet-ray curable resin includes a radical curable resin and a cationic curable resin. The cationic curable resin has better durability and adhesiveness, and the water-based polyurethane resin composition of the present invention is a cationic curable resin. Since it is suitable for use, cation-curable resins using monomers and/or oligomers for cation-curing resins and cationic polymerization initiators are preferred.

Examples of the monomer or oligomer for cation-cured resins include aliphatic, aromatic, or alicyclic epoxy compounds, oxetane compounds, vinyl ether compounds, or oligomers thereof.

Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, and polyglycidyls of aliphatic polyhydric alcohols or their alkylene oxide adducts. and polyfunctional epoxy compounds such as etherified compounds and polyglycidyl esters of aliphatic long-chain polybasic acids. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycoldi Glycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, poly Diglycidyl ether of propylene glycol, glycidyl ether of polyhydric alcohols such as dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, hydrogenated bisphenol A, etc. The polyglycidyl ether compound of polyether polyol obtained by adding a species or two or more types of alkylene oxide, and the diglycidyl ester of an aliphatic long-chain dibasic acid are mentioned. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized polybutadiene, and the like are exemplified.

As the aliphatic epoxy compound, a glycidyl ether compound of an aliphatic alcohol or a polyglycidyl ether compound of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coatability and reactivity are improved.

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

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or alkylene oxide adducts thereof. mono/polyglycidyl ether compounds such as bisphenol A, bisphenol F, or glycidyl ether compounds of compounds obtained by adding an alkylene oxide to them, or epoxy novolak resins; mono/polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide or divinylbenzene, and the like.

Commercially available products can be used as the aromatic epoxy compound, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, and 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 product of Chemutex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Doto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Maproof G-0105SA, Maproof G-0130SP (manufactured by Nichiyu Co., Ltd.); 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.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (made by ADEKA); TECHMORE VG-3101L (product of Printec) etc. are mentioned. As the aromatic epoxy compound, a polyfunctional one is preferable because it has excellent curing properties.

The alicyclic epoxy compound refers to one in which an oxirane ring is directly bonded to a saturated ring without passing through a spacer, and specific examples of the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring. and cyclohexene oxide or cyclopentene ring-containing compounds obtained by epoxidizing a cargo 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-methyl Cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis( 3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), 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, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate A boxylate is preferable from the viewpoint of improving adhesion.

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

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

As the oxetane compound, a commercially available product containing a cation-curable monomer as a main component can be used. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Seki) Yuga Chemical Co., Ltd.); Aaron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (product of Toagosei Co., Ltd.), Etanacol OXBP, OXTP (product of Ube Kosan Co., Ltd.), etc. are mentioned. .

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

The cationic polymerization initiator may be any compound capable of releasing a substance that initiates cationic polymerization when irradiated with energy rays or heated, but is preferably a double salt that is an onium salt that releases a Lewis acid when irradiated with energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula,

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

and salts of cations and anions represented by

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

Further, R ² is an organic group having 1 to 60 carbon atoms and possibly containing atoms other than carbon atoms. a is an integer from 1 to 5; a number of R ² 's are each independent, the same or different. Moreover, it is preferable that at least one of the above organic groups has an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. In addition, when the valence of Q in the cation [A] ^r+ is q, it is necessary that the relationship r = aq be established (however, N = N is treated as valence 0).

In addition, it is preferable that the anion [B] ^r- is a halide complex, and its structure is, for example, the following general formula;

[LY _b ] ^r-

can be expressed as

Moreover, where L is a metal or metalloid that is a central atom of a halide complex, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co, etc. Y is a halogen atom. b is an integer from 3 to 7. In addition, when the valence of L in the anion [B] ^r- is set to p, it is necessary that the relationship r = bp is established.

Specific examples of the anion [LY _b ] ^r- of the general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ^- , Hexafluorophosphate (PF ₆ ) ^- , Hexafluoroantimonate (SbF ₆ ) ^- , Hexafluoroarsenate (AsF ₆ ) ^- , Hexachloroantimonate (SbCl ₆ ) ^-, etc. can be heard

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

[LY _b-1 (OH)] ^r

A structure represented by can also be preferably used. L, Y, b are the same as above. In addition, as other anions that can be used, perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate anion, trinitro Benzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, etc. are mentioned.

Among such onium salts, it is particularly effective to use aromatic onium salts of (a) to (c) below. Among these, 1 type can be used individually or in mixture of 2 or more types.

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

(B) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyl iodo Diaryliodonium salts such as niumtetrakis(pentafluorophenyl)borate

(c) Sulfonium salts such as sulfonium cations represented by the following group I or group II, hexafluoroantimony ions, hexafluorophosphate ions, and tetrakis(pentafluorophenyl)borate ions

In addition, preferably, (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl)benzene]- Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylicaldehyde)aluminum, and triphenylsilanol mixtures of silanols such as the like; salts such as thiophenium salts, thioranium salts, benzylammonium salts, pyridinium salts, and hydrazinium salts; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; The above polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids polyepoxy addition-modified products produced by reacting various epoxy resins, such as molasses, by a conventional method; modified amidation products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a conventional method; Mannichization prepared by reacting the above polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reaction site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. by a conventional method metamorphoses; Polyhydric 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-methyladip acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, etc. Aliphatic dicarboxylic acids; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Trimellitic acid, trimesic acid, pima acid anhydrides of tricarboxylic acids such as trimers of free fatty acids; tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.

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

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 are each independently a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms. represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a halogen atom or 1 carbon atom Represents an alkyl group of ~ 10, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (A) to (C), and An ^q- is q of Represents an anion, and p represents a coefficient that neutralizes an electric charge.

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

In the compound represented by Formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R 18 , R ¹⁹ , R ²⁰ , R ²¹ , ^{R 22 ,} R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R 31 , R ^{32 , R 33 ,} R ³⁴ , R ³⁵ , R ³⁶ , ^{R 37 ,} R ³⁸ and R ³⁹ as halogen atoms may include fluorine, chlorine, bromine, iodine and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , 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 The alkyl group having 1 to 10 carbon atoms represented by ^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, difluoro Romethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoro Ethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, Methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclo Hexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxy Carbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl, 1,2-dihydroxyethyl, etc. are mentioned.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , 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-butyl Oxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2 -Methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy, etc. are mentioned.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ ester groups having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, and phenoxycarbonyl. Nyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy, etc. there is.

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, of the cationic polymerization initiator per 100 parts by mass of the cationic curable resin component. If it is too small, curing tends to be insufficient, and if it is too large, physical properties such as water absorption and strength of the cured product may be adversely affected.

Examples of the sensitizer and sensitizer include anthracene-based compounds and naphthalene-based compounds.

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

(In the formula, 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 carbon atom having 1 to 6 carbon atoms. represents an alkyl group.)

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

9,10-dimethoxyanthracene;

9,10-diethoxyanthracene;

9,10-dipropoxyanthracene;

9,10-diisopropoxyanthracene;

9,10-dibutoxyanthracene;

9,10-dipentyloxyanthracene;

9,10-dihexyloxyanthracene;

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

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

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

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

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

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

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

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

(In the formula, R ¹² and R ¹³ each independently represent an alkyl group having 1 to 6 carbon atoms.)

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

4-methoxy-1-naphthol;

4-ethoxy-1-naphthol;

4-propoxy-1-naphthol;

4-butoxy-1-naphthol;

4-hexyloxy-1-naphthol;

1,4-dimethoxynaphthalene;

1-ethoxy-4-methoxynaphthalene;

1,4-diethoxynaphthalene;

1,4-dipropoxynaphthalene;

1,4-dibutoxynaphthalene and the like.

The use ratio of the sensitizer and sensitizer is not particularly limited, and can be used in generally normal usage ratios within a range that does not impair the object of the present invention. For example, 100 parts by mass of the total amount of the cation-curable resin component On the other hand, it is preferable from the viewpoint of improving the curability that the sensitizer and the sensitizer are each 0.1 to 3 parts by mass or more.

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 filmed by a stretching machine, and then an adhesive layer is coated on the surface of the thermoplastic resin. A method of adhering a photocurable resin on top is exemplified.

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

In the method for producing an aqueous polyurethane resin composition of the present invention, (A) a urethane prepolymer is obtained by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent. A urethane prepolymer composition containing the obtained (A) urethane prepolymer and (B) cation curable substance is prepared. Then, the urethane prepolymer composition is dispersed in water to obtain a water dispersion. Then, (A) urethane prepolymer in the obtained aqueous dispersion is reacted with (C) a blocking agent and/or a chain extender.

Raw materials and reaction conditions used in the method for producing the water-based polyurethane resin composition of the present invention are as described above.

Example

Next, the present invention will be described in more detail by examples, but the present invention is not limited in any way by these examples.

Example 1 [Preparation of water-based polyurethane resin composition U-1]

In a five-necked round-bottom flask equipped with a Dimroth, stirring blade, and nitrogen line, 185.23 g of isophorone diisocyanate, ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Kosan Co., Ltd., number average molecular weight 2000) 227.99 g, 6.69 g of trimethylolpropane, 49.16 g of dimethylolpropionic acid, and 0.55 g of Adeka Stave OT-1 (dioctyl tin laurate manufactured by Adeka Co., Ltd.) were added to 202.98 g of methyl ethyl ketone, followed by 6 hours at 80°C. The reaction was performed to obtain a urethane prepolymer. 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 isocyanate content of the obtained urethane prepolymer was 4.98% by mass in terms of solid content, and the acid value was 43.85 mgKOH/g in terms of solid content.

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

In a 2-liter disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (a defoamer manufactured by ADEKA Co., Ltd.) were added, and after stirring for 5 minutes with a disper, 620 g of the urethane prepolymer composition was added in 2 minutes. It was added over and stirred for 30 minutes. Then, 80.8g of diethylamine/water (mass ratio 1/3) aqueous solution was added, and also stirring was performed 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-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 [Preparation of water-based polyurethane resin composition U-2]

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

In a 2-liter disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (a defoaming agent manufactured by ADEKA Co., Ltd.) were added, and after stirring for 5 minutes with a disper, 620 g of the obtained urethane prepolymer composition was added in 2 minutes. It was added over and stirred for 30 minutes. Then, 33.6g of ethylenediamine/water (mass ratio 1/3) aqueous solution was added, and also stirring was performed 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-2 having a solid content of 30% by mass. The ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 3 [Preparation of water-based 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., and 27.78 g of triethylamine was obtained. and 49.69 g of 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino)hexyl]-s-triazine-2,4,6-trione were added, and 30 Stirring was performed for a minute to obtain a urethane prepolymer composition. Mass ratio of urethane prepolymer and 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino)hexyl]-s-triazine-2,4,6-trione in the urethane prepolymer composition was 90/10.

Using the urethane prepolymer composition obtained here, 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 4 [Preparation of water-based polyurethane resin composition U-4]

The isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value of a urethane prepolymer (including methyl ethyl ketone) having a solid content of 43.85 mgKOH/g was cooled to 60 ° C. 49.69 g of ETERNACOLLOXBP (4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] biphenyl manufactured by Ube Industries Co., Ltd.) was added, stirred for 30 minutes, and a urethane prepolymer was obtained. 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, 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.

Example 5 [Preparation of water-based polyurethane resin composition U-5]

The isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value of a urethane prepolymer (including methyl ethyl ketone) having a solid content of 43.85 mgKOH/g was cooled to 60 ° C. , 49.69 g of bisphenol Adiβ-methylglycidyl ether was added, and stirring was performed for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer in the urethane prepolymer composition to bisphenol Adi β-methylglycidyl ether was 90/10.

Using the urethane prepolymer composition obtained here, 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 6 [Preparation of water-based polyurethane resin composition U-6]

The isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value of a urethane prepolymer (including methyl ethyl ketone) having a solid content of 43.85 mgKOH/g was cooled to 60 ° C. 49.69 g of Celloxide 2021P (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate manufactured by Daicel Co., Ltd.) was added, and stirring was performed for 30 minutes to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate in the urethane prepolymer composition was 90/10.

Using the urethane prepolymer composition obtained here, 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 7 [Preparation of water-based polyurethane resin composition U-7]

The isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value of a urethane prepolymer (including methyl ethyl ketone) having a solid content of 43.85 mgKOH/g was cooled to 60 ° C. 49.69 g of TEPIC-VL (triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.) was added, and stirring was performed 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, 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.

Example 8 [Preparation of water-based polyurethane resin composition U-8]

In a five-necked separable round-bottom flask equipped with a Dimroth, stirring blade, and nitrogen line, 144.31 g of isophorone diisocyanate, ETERNACOLL UH-200 (polycarbonate diol manufactured by Ube Kosan Co., Ltd., number average molecular weight: 2000) 177.63 g, trimethyl 5.21 g of all propane, 38.30 g of dimethylol propionic acid, and 0.55 g of Adeka Stave OT-1 (made by ADEKA Co., Ltd. octyl tin laurate) were added to 158.14 g of methyl ethyl ketone and reacted at 80 ° C. for 6 hours. Isocyanate content 4.98 mass % and acid value obtained the urethane prepolymer which is 43.85 mgKOH/g in solid content in conversion of silver solid content. 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 was cooled to 60°C, and 28.83 g of triethylamine and 197.14 g of Aaronoxetane OXT-221 (bis(3-ethyloxetanylmethyl)ether manufactured by Toagosei Co., Ltd.) were added, followed by 30 minutes Stirring was performed to obtain a urethane prepolymer composition. The mass ratio of the urethane prepolymer and Aaronoxetane OXT-221 in the urethane prepolymer composition was 50/50.

Using the urethane prepolymer composition obtained here, except that the addition amount of the diethylamine/water (mass ratio 1/3) aqueous solution was 62.8 g, an aqueous polyurethane resin composition having a solid content of 30% by mass was subjected to the same water dispersion step as in Example 1 Got U-8. 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 [Preparation of water-based polyurethane resin composition U-9]

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

In a 2-liter disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (foamer manufactured by ADEKA Co., Ltd.) were added, and after stirring for 5 minutes with a disper, 620 g of the obtained urethane prepolymer composition was added in 2 minutes. It was added over and stirred for 30 minutes. Then, 97.2g of adipic acid dihydrazide/water (mass ratio 1/3) aqueous solution was added, and stirring was performed for further 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 [Preparation of water-based polyurethane resin composition HU-1]

The isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value of a urethane prepolymer (including methyl ethyl ketone) having a solid content of 43.85 mgKOH/g was cooled to 60 ° C., and 27.78 g of triethylamine It was added and stirred for 30 minutes to obtain a urethane prepolymer composition.

Using the urethane prepolymer composition obtained here, an aqueous 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 [Preparation of water-based polyurethane resin composition HU-2]

The isocyanate content obtained in the same manner as in Example 1 was 4.98 mass% in terms of solid content, and the acid value of a urethane prepolymer having a solid content of 43.85 mgKOH/g was cooled to 60 ° C., 27.78 g of triethylamine was added, and stirring was performed for 30 minutes Thus, a urethane prepolymer composition was obtained.

Using the urethane prepolymer composition obtained here, an aqueous 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 ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.63.

Comparative Example 3 [Preparation of water-based polyurethane resin composition HU-3]

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

The obtained urethane prepolymer was cooled to 60°C, and stirred with 27.78 g of triethylamine for 30 minutes to obtain a urethane prepolymer composition.

In a 2-liter disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (a defoaming agent manufactured by ADEKA Co., Ltd.) were added, and after stirring for 5 minutes with a disper, 558 g of the urethane prepolymer composition was added in 2 minutes. It was added over and stirred for 30 minutes. Then, 80.8g of diethylamine/water (mass ratio 1/3) aqueous solution was added, and also stirring was performed for 30 minutes. Further, 62 g of Aronoxetane OXT-221 (bis(3-ethyloxetanylmethyl)ether manufactured by Toagosei Co., Ltd.) was added, and the mixture was stirred for 30 minutes. Thereafter, when the mixture was heated to 40°C and methyl ethyl ketone was removed under reduced pressure conditions, a uniform dispersion was not obtained, and the water-based polyurethane resin composition HU-3 could not be produced.

Evaluation 1 (storage stability)

The water-based urethane resin composition was placed in an airtight container, stored at 40°C for up to one week, and sedimentation and gelation were observed to evaluate storage stability. Those precipitated and gelated in less than one week in the table indicate the number of days, those that precipitated and gelled in less than one day were rated as ×, and those that did not precipitate and gel for more than one week were marked as ○.

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, and then dried at room temperature for 30 minutes and at 120 ° C. for 10 minutes to obtain a test piece.

The obtained test piece was cut into 100 sheets using a cutter guide with a gap interval of 1 mm. Thereafter, cellophane tape was attached, rubbed, and then peeled off vigorously three times, and then the adhesiveness was determined by counting the number of remaining masses. In addition, what was partially exfoliated among the masses was accepted as an exfoliated mass. The evaluation criteria are as follows.

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

Evaluation 3 (adhesion with top coat UV curable resin paint)

30 parts by mass of 1,6-hexanediol diglycidyl ether, 3',4'-epoxycyclohexyl using a bar coater so that the film thickness after curing is 3 μm on the urethane film side of the test piece obtained in the above evaluation 2 Applying an ultraviolet curable resin paint obtained from 30 parts by mass of methyl 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 with an intensity of 600 mW/cm 2 and a cumulative light amount of 1000 mJ/cm 2 was cured to obtain a test piece.

The obtained test piece was cut into 100 sheets using a cutter guide with a gap interval of 1 mm. Thereafter, cellophane tape was applied and rubbed to adhere, followed by a vigorous peeling operation three times, and then the top coat UV adhesion was determined by counting the number of remaining masses. In addition, what was partially exfoliated among the masses was accepted as an exfoliated mass. The evaluation criteria are as follows.

A: 100 remaining, B: 99-90 remaining, C: 89-80 remaining, D: 79-70 remaining, E: 69-50 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, excellent adhesion to a substrate, particularly an ultraviolet curable resin layer used as a top coat paint, and an adhesive for optical films. is appropriate as

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

Claims (7)

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 cation-curable substance is dispersed in water and dispersed in water As an aqueous polyurethane resin composition obtained by obtaining and reacting (A) urethane prepolymer in the obtained aqueous dispersion with (C) a blocking agent and / or a chain extender,
The cation-curable substance as component (B) is bis[(3-ethyl-3-oxetanyl)methyl]ether, 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino) ) Hexyl] -s-triazine-2,4,6-trione, 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] at least one selected from among biphenyls An oxetane compound of, an aqueous polyurethane resin composition. According to claim 1,
A water-based polyurethane resin composition in which the chain extender as component (C) is at least one selected from water-soluble amine compounds and water-soluble dicarboxylic acid dihydrazide compounds having two or more active hydrogens. According to claim 1 or 2,
(C) An aqueous polyurethane resin composition in which the blocking agent as component 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 cation-curable substance is dispersed in water and dispersed in water A method for producing an aqueous polyurethane resin composition, in which (A) urethane prepolymer in the obtained aqueous dispersion is reacted with (C) a blocking agent and / or a chain extender,
The cation-curable substance as component (B) is bis[(3-ethyl-3-oxetanyl)methyl]ether, 1,3,5-tris[6-(3-ethyloxetan-3-yloxycarbonylamino) ) Hexyl] -s-triazine-2,4,6-trione, 4,4'-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] at least one selected from among biphenyls A method for producing a water-based polyurethane resin composition, which is an oxetane compound of delete delete delete