JP2018070878A - Polyurethane resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin aqueous dispersion which is excellent in chemical resistance and can provide a coating film excellent in adhesion to a base material.SOLUTION: The polyurethane resin aqueous dispersion is provided that is a polyurethane resin aqueous dispersion (Q) containing: a polyurethane resin (U) formed by reaction of an active hydrogen component (A) and an organic polyisocyanate component (B); and an aqueous medium, wherein: the (A) contains a component (a1) composed of a compound having 3 to 6 groups of at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group value and a thiol group in the molecule; an amine value based on the primary amino group and the secondary amino group of (U) is 0-40 mgKOH/g; a hydroxyl value of (U) is 5-40 mgKOH/g; a thiol value of (U) is 0-40 mgKOH/g; and the total value of an amine value, a hydroxyl value and a thiol value based on the primary amino group and the secondary amino group of (U) is 5-100 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous polyurethane resin dispersion.

  Polyurethane resin aqueous dispersions are used in paints, adhesives, textile processing agents, paper treatment agents, inks, etc. as highly functional aqueous dispersions because of their excellent film properties obtained by drying. However, from the viewpoint of environmental protection, resource saving, safety, etc., it is thought that the importance will increase more and more. Conventionally, solvent-based urethanes dissolved in organic solvents have been used in these applications. However, due to the disadvantages of organic solvent toxicity, fire hazard, environmental pollution, etc. The switch to the dispersion is spurring.

  However, since the polyurethane resin is dissolved in the solvent in the solvent-based urethane, the film-forming property is good regardless of the heating temperature, whereas the polyurethane resin aqueous dispersion has a particle shape, Since the film is formed by fusing, the film forming property is inferior to that of the solvent-based urethane, so that there is a problem that the adhesion of the obtained film to the substrate is lowered.

  In order to improve the affinity of the urethane film to the substrate, an aqueous polyurethane resin dispersion (see Patent Document 1) having a tertiary amino group in the molecular side chain has been proposed. As a result, the required level of adhesion has increased, and further improvements in adhesion to the substrate and chemical resistance have been demanded.

International Publication No. 2012/111360

  The subject of this invention is providing the polyurethane resin aqueous dispersion which is excellent in chemical-resistance and excellent in the adhesiveness to a base material.

  As a result of intensive studies, the present inventors have found an aqueous polyurethane resin dispersion that can solve the above problems. That is, the present invention is an aqueous polyurethane resin dispersion comprising a polyurethane resin (U) obtained by reacting an active hydrogen component (A) and an organic polyisocyanate component (B) and an aqueous medium, wherein (A) Contains a component (a1) consisting of a compound having 3-6 at least one active hydrogen-containing group selected from the group consisting of primary amino group, secondary amino group, hydroxyl value and thiol group in the molecule And the amine value based on the primary amino group and the secondary amino group of (U) is 0 to 40 mgKOH / g, the hydroxyl value of (U) is 5 to 40 mgKOH / g, ) Has a thiol group value of 0 to 40 mgKOH / g, and the total value of the amine value, hydroxyl value and thiol group value based on the primary amino group and secondary amino group of (U) is 5 to 100 mgKOH / g g An aqueous polyurethane resin dispersion (Q); an aqueous coating material containing the aqueous polyurethane resin dispersion (Q); an aqueous adhesive containing the aqueous polyurethane resin dispersion (Q); and an aqueous polyurethane resin dispersion (Q). It is an aqueous fiber processing agent to be contained.

  The aqueous polyurethane resin dispersion (Q) of the present invention can provide a film having excellent chemical resistance and excellent adhesion to a substrate.

The aqueous polyurethane resin dispersion (Q) of the present invention is an aqueous polyurethane resin dispersion comprising a polyurethane resin (U) obtained by reacting an active hydrogen component (A) and an organic polyisocyanate component (B) and an aqueous medium. Wherein the active hydrogen component (A) contains at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl value, and a thiol group in the molecule 3-6. The polyurethane resin (U) contains a component (a1) composed of a compound having a number of compounds, and the polyurethane resin (U) further has a primary amino group, a secondary amino group and / or a thiol group as necessary.
Each component will be described below.

[Polyurethane resin (U)]
<Active hydrogen component (A)>
The active hydrogen in the present invention means a hydrogen atom that is bonded to oxygen, nitrogen, sulfur or the like and has a high reactivity with an isocyanate group. The group having this active hydrogen (active hydrogen-containing group) is a hydroxyl group, A primary amino group, a secondary amino group, a thiol group, etc. are mentioned. In the present invention, the carboxyl group is not included in the active hydrogen-containing group.

  As the active hydrogen component (A), at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl value, and a thiol group as essential components is contained in the molecule. Examples thereof include a component (a1) composed of 6 compounds and a component (a2) composed of a compound having 2 active hydrogen-containing groups as optional components in the molecule. (A1) and (a2) may be used alone or in combination of two or more.

  By using the component (a1) comprising a compound having 3 to 6 at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group. The cross-linked structure is introduced into the polyurethane resin (U), and the chemical resistance is improved.

  Component (a1) includes a compound (a11) having only 3 to 6 primary amino groups and secondary amino groups in the molecule as active hydrogen-containing groups, primary amino group and / or active hydrogen-containing groups Or a compound (a12) having only 3 to 6 secondary amino groups and hydroxyl groups in the molecule, a compound (a13) having only 3 to 6 thiol groups and hydroxyl groups in the molecule as active hydrogen-containing groups, and containing active hydrogen Examples thereof include a compound (a14) having only 3 to 6 hydroxyl groups in the molecule as a group and a compound (a15) having only 3 to 6 thiol groups in the molecule as an active hydrogen-containing group.

  Examples of the compound (a11) having only 3 to 6 primary amino groups and secondary amino groups in the molecule as active hydrogen-containing groups include polyalkylene polyamines [diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine. , Poly (n = 2 to 5) alkylene (carbon number 2 to 6) poly (n = 3 to 6) amine] such as tetraethylenepentamine and pentaethylenehexamine] and the like.

  Examples of the compound (a12) having 3 to 6 primary amino groups and / or secondary amino groups and hydroxyl groups in the molecule as active hydrogen-containing groups include dialkanolamines (diethanolamine and diethanolamine having 4 to 20 carbon atoms). Isopropanolamine etc.), 2- (2-aminoethylamino) ethanol and 3,6-diazaoctane-1,8-diol.

  Examples of the compound (a13) having only 3 to 6 thiol groups and hydroxyl groups in the molecule as active hydrogen-containing groups include thioglycerol.

  As the compound (a14) having only 3 to 6 hydroxyl groups in the molecule as the active hydrogen-containing group, a 3 to 6-valent alcohol having 3 to 20 carbon atoms (glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, Diglycerin and dipentaerythritol, etc.) and trialkanolamines having 6 to 20 carbon atoms (such as triethanolamine and tripropanolamine) are preferred. From the viewpoint of chemical resistance, trivalents having 3 to 20 carbon atoms are preferred. Alcohol, especially trimethylolpropane.

  Examples of the compound (a15) having only 3 to 6 thiol groups in the molecule as active hydrogen-containing groups include methanetrithiol, ethane-1,1,1-trithiol, 1,1,1-tris (mercaptomethyl) ethane. 1,2,3-propanetristhiol, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,1,1-butanetrithiol, 1,3,5-tris (mercaptomethyl) benzene, Examples include methanetetrathiol, tetrakis (mercaptomethyl) methane, 3,3′-thiobis (propane-1,2-dithiol) and 2,2′-thiobis (propane-1,3-dithiol).

  The component (a2) comprising a compound having two active hydrogen-containing groups in the molecule contains at least one active hydrogen selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group. Examples thereof include a component (a21) comprising a compound having two groups in the molecule and a compound (a22) having an anionic group and / or a cationic group and two active hydrogen-containing groups.

  The component (a21) comprising a compound having at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group in the molecule includes active hydrogen A compound (a211) having a primary amino group and a hydroxyl group in the molecule as a group, a compound (a212) having only two hydroxyl groups in the molecule as an active hydrogen-containing group, a primary or Examples thereof include a compound having only two secondary amino groups in the molecule (a213) and a compound having only two thiol groups in the molecule as active hydrogen-containing groups (a214).

  As the compound (a211) having one primary amino group and one hydroxyl group in the molecule as the active hydrogen-containing group, monoalkanolamine having 2 to 20 carbon atoms (monoethanolamine, monopropanolamine, monobutanolamine, etc.) Etc.

  As the compound having only two hydroxyl groups in the molecule as the active hydrogen-containing group (a212), a diol having a number average molecular weight (hereinafter abbreviated as Mn) or a chemical formula weight of less than 300 (a2121) and a diol having an Mn of 300 or more (2122 ).

Mn of (a212) can be measured, for example, under the following conditions by gel permeation chromatography.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation)”
Sample solution: 0.25 wt% tetrahydrofuran solution solution injection amount: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polyethylene glycol

  Mn or diol (a2121) having a chemical formula amount of less than 300 includes a dihydric alcohol having 2 to 20 carbon atoms and a carbon of divalent alcohol or bisphenol (such as bisphenol A, bisphenol S and bisphenol F) having 2 to 20 carbon atoms. Examples of the alkylene oxide (hereinafter abbreviated as AO) adduct having 2 to 12 are Mn or those having a chemical formula amount of less than 300.

  Examples of the dihydric alcohol having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohol having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5- Directly such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and tetraethylene glycol Chain alcohols; 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2- Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexa Diol, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl- Branched alcohols such as 1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7 -Norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, 1,4 Bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; aromatic aliphatic dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylenediol, bis (hydroxyethyl) benzene And bis (hydroxyethoxy) benzene, etc.].

  As AO having 2 to 12 carbon atoms in the present invention, ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3- or Examples include 2,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, α-olefin oxide, and epichlorohydrin.

  Among Mn or diol (a2121) having a chemical formula amount less than 300, from the viewpoint of chemical resistance and adhesiveness, a linear or branched aliphatic dihydric alcohol having 2 to 12 carbon atoms is more preferable. Are ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol.

  Examples of the diol (2122) having Mn of 300 or more include polyether diol and polyester diol.

  Examples of the polyether diol include aliphatic polyether diols and aromatic-containing polyether diols.

  Examples of the aliphatic polyether diol include AO adducts having 2 to 12 carbon atoms of the dihydric alcohol having 2 to 20 carbon atoms and having Mn of 300 or more.

  Specific examples of the aliphatic polyether diol include polyethylene glycol, polypropylene glycol, poly (oxyethylene / propylene) glycol, and poly (oxytetramethylene) glycol. Commercial products of aliphatic polyether diol include PTMG1000. [Min = 1,000 poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [Mn = 2,000 poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Corporation], PTMG3000 [Mn = 3,000 (poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Corporation)] and PTMG4000 (Mn = 4,000 poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Corporation).

  As the aromatic-containing polyether diol, the carbon number of the AO adduct having 2 to 12 carbon atoms and the bisphenol compounds (bisphenol A, bisphenol B, bisphenol S and bisphenol F) of the araliphatic dihydric alcohol having 8 to 20 carbon atoms. Examples thereof include 2 to 12 AO adducts having Mn of 300 or more.

  Examples of the polyester diol include condensed polyester diol, polylactone diol, and polycarbonate diol.

The condensed polyester diol is a polyester diol of the Mn or diol (2121) having a chemical formula amount less than 300 and a divalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
Among the Mn or diol (2121) having a chemical formula of less than 300 used in the condensed polyester diol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol are preferred. , EO or PO low molar adducts of bisphenol A and combinations thereof.

  Examples of divalent carboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof used in condensed polyester diols include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc. ), Alicyclic dicarboxylic acids (dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), their anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, etc.), these Examples thereof include acid halides (such as adipic acid dichloride), low molecular weight alkyl esters thereof (such as dimethyl succinate and dimethyl phthalate), and combinations thereof.

  Specific examples of the condensed polyester diol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene seba Kate diol and polyneopentyl terephthalate diol That.

  As a commercially available product of condensed polyester diol, Kuraray polyol P-1010 [poly (3-methylpentylene adipate) diol of Mn = 1,000, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-2010 [Mn = 2, 000 poly (3-methylpentylene adipate) diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-3010 [Mn = 3,000 poly (3-methylpentylene adipate) diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-4010 [poly (3-methylpentylene adipate) diol with Mn = 4,000, manufactured by Kuraray Co., Ltd.], Sanester 2610 [polyethylene adipate diol with Mn = 1,000, Sanyo Chemical Industries, Ltd. Manufactured by], Sanester 4620 [polytetramethylene adipate di having Mn = 2,000 Lumpur, and polyethylene adipate diol San Esther 2620 [Mn = 2,000, Sanyo Chemical Industries, Ltd.], and the like.

The polylactone diol is a polyaddition product of a lactone to the dihydric alcohol having 2 to 20 carbon atoms. Examples of the lactone include lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). ) And the like.
Specific examples of the polylactone diol include polycaprolactone diol and polyvalerolactone diol.

  Examples of the polycarbonate diol include the dihydric alcohol having 2 to 20 carbon atoms and a low-molecular carbonate compound (for example, an alkylene carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and carbon). And polycarbonate diol produced by condensing a diaryl carbonate having an aryl group of several 6 to 9 with a dealcoholization reaction. Two or more divalent alcohols having 2 to 20 carbon atoms and alkylene carbonates may be used in combination.

  Specific examples of the polycarbonate diol include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane. And a diol obtained by condensing a diol with a dialkyl carbonate while causing a dealcoholization reaction).

  Commercially available products of polycarbonate diol include Nipponol 980R [polyhexamethylene carbonate diol with Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.], Kuraray polyol C-1090 [poly (3-methyl- with Mn = 1,000) 5-pentanediol / hexamethylene) carbonate diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol C-2090 [Mn = 2,000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, Kuraray Co., Ltd. )], Kuraray polyol C-3090 [poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol of Mn = 3,000, manufactured by Kuraray Co., Ltd.], Kuraray polyol C-4090 [Mn = 4 000 poly (3-methyl-5-pentanedio Le / hexamethylene) carbonate diol, Kuraray Co., Ltd.], and T4672 [Mn = 2,000 Poly (tetramethylene / hexamethylene) carbonate diol include Asahi Kasei Chemicals Co., Ltd.] or the like.

  Of the diols (2122) having an Mn of 300 or more, polyether diols are preferable from the viewpoint of adhesion of the resulting film, aliphatic polyether diols are more preferable, and poly (oxytetra) is more preferable. Methylene) glycol.

  Examples of the compound (a213) having only two primary or secondary amino groups in the molecule as active hydrogen-containing groups include aliphatic diamines having 2 to 36 carbon atoms (such as ethylenediamine and hexamethylenediamine), and carbon numbers 6 -20 alicyclic diamine (1,3- or 1,4-diaminocyclohexane, 4,4'- or 2,4'-dicyclohexylmethane diamine, isophorone diamine, etc.), C6-C20 aromatic diamine ( 1,3- or 1,4-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4'- or 2,4'-methylenebisaniline, etc.), C8-20 aromatic fat Group diamine [1,3- or 1,4-xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene, bis (aminobutyl) benzene, etc.] Fine heterocyclic diamine [2,4-diamino-1,3,5-triazine, piperazine, and N-(2-aminoethyl) piperazine, etc.] having a carbon number of 3 to 20, and the like.

  Examples of the compound having only two thiol groups in the molecule as active hydrogen-containing groups (a214) include methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 2-methyl-1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2- or 1,4-cyclohexanedithiol and 1,2-, 1,3-or Examples include 1,4-bis (mercaptomethyl) benzene.

  As the compound (a22) having an anionic group and / or a cationic group and two active hydrogen-containing groups, a compound (a221) having an anionic group and two active hydrogen-containing groups and a cationic group And a compound (a222) having two active hydrogen-containing groups.

  As the compound (a221) having an anionic group and two active hydrogen-containing groups, for example, a compound having a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (for example, 2, 2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (eg glycine, alanine and valine)], anions A compound having a sulfonic acid group as a functional group and having 2 to 16 carbon atoms [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester, etc.], anionic A compound having a sulfamic acid group as a group and having 2 to 10 carbon atoms [N, N-bis (2-hydroxylethyl Like sulfamic acid] and the like as well as salts neutralized with a neutralizing agent to these compounds.

Examples of the neutralizing agent used in the salt of (a221) include ammonia, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide, and lithium hydroxide).
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine and methylpropanolamine. Examples include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

  As the neutralizing agent used for the salt of (a221), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the resulting polyurethane resin aqueous dispersion and the chemical resistance of the resulting film. From this point of view, the neutralizing agent used in the salt of (a221) is preferably ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine or dimethylethylamine, more preferably ammonia or monoethylamine. Dimethylamine and diethylamine, particularly preferred is ammonia.

  Among (a221), 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof are preferable from the viewpoint of the resin physical properties of the obtained film and the dispersion stability of the aqueous polyurethane resin dispersion. More preferred are neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms.

  Examples of the compound (a222) having a cationic group and two active hydrogen-containing groups include a tertiary amino group-containing diol having 1 to 20 carbon atoms [N-alkyl dialkanolamine (for example, N-methyldiethanolamine, N- Propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamine (for example, N, N-dimethylethanolamine) and the like] and the like, and the like, and the like. It is done.

Examples of the neutralizing agent used in (a222) include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, benzyl chloride, and the like. .
As the neutralizing agent used for (a222), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the aqueous dispersion of the polyurethane resin to be produced and the chemical resistance of the resulting film. From such a viewpoint, the neutralizing agent used in (a222) is preferably a monocarboxylic acid having 1 to 10 carbon atoms and carbonic acid, more preferably formic acid and carbonic acid, and particularly preferably carbonic acid.

  The neutralizing agent used in (a221) and (a222) is added before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. However, from the viewpoint of the stability of the polyurethane resin (U) and the stability of the aqueous dispersion, it is preferably added before or during the water dispersion step.

The amount of (a22) used is such that the content of the hydrophilic group in (U) is preferably 0.01 to 5% by weight, more preferably 0.1 to 4% by weight, based on the weight of (U). %, Particularly preferably 0.5 to 3% by weight.
The content of the hydrophilic group in the present invention means the weight percent of the unneutralized cationic group or anionic group, and does not include the weight of the counter ion. For example, the content of the hydrophilic group in (a221) is such that, in the case of triethylamine salt of 2,2-dimethylolpropionic acid, the weight percentage of the carboxyl group (—COOH) is 3- (2,3-dihydroxypropoxy). In the case of triethylamine salt of -1-propanesulfonic acid, it means the weight percent of the sulfo group (—SO ₃ H). Further, the content of the hydrophilic group in (a222) means the weight% of only the nitrogen atom in the tertiary amino group.

<Organic polyisocyanate component (B)>
As the organic polyisocyanate component (B), an aromatic polyisocyanate having 8 to 26 carbon atoms (b1) having 2 or 3 or more isocyanate groups, an aliphatic polyisocyanate having 4 to 22 carbon atoms (b2), Examples thereof include alicyclic polyisocyanates having 8 to 18 carbon atoms (b3), araliphatic polyisocyanates having 10 to 18 carbon atoms (b4), and modified products (b5) of these organic polyisocyanates.

  Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as tolylene diisocyanate as TDI). Abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl Cyanate and the like.

  Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  Examples of the alicyclic polyisocyanate having 8 to 18 carbon atoms (b3) include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, Mention may be made of methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the C10-18 araliphatic polyisocyanate (b4) include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). It is done.

  (B1) to (b4) modified organic polyisocyanate (b5) include urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group, or oxazolidone of the polyisocyanate. Group-containing modified products [for example, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, biuret modified HDI, isocyanurate modified HDI and isocyanurate modified IPDI].

  Of the organic polyisocyanate component (B), (b2) and (b3) are preferable from the viewpoint of mechanical properties and weather resistance of the resulting film, more preferably (b3), and particularly preferably IPDI and hydrogenated. MDI.

  The polyurethane resin (U) in the present invention has a hydroxyl group as an essential active hydrogen-containing group, and can further have a primary amino group, a secondary amino group and / or a thiol group as the active hydrogen-containing group. When the polyurethane resin (U) has these active hydrogen-containing groups, the polyurethane resin is excellent in film adhesion. Moreover, the film | membrane excellent in mechanical physical property and chemical-resistance can be obtained by reaction with the below-mentioned crosslinking agent (C).

The amine value based on the primary amino group and the secondary amino group of the polyurethane resin (U) is 0 to 40 mgKOH / g, preferably 10 to 30 mgKOH / g, from the viewpoint of film adhesion and chemical resistance. More preferably, it is 15 to 25 mg KOH / g. The amine value based on the primary amino group and the secondary amino group can be calculated by subtracting the tertiary amine value from the total amine value of (U).
The hydroxyl value of the polyurethane resin (U) is 5 to 40 mgKOH / g, preferably 10 to 30 mgKOH / g, and more preferably 15 to 25 mgKOH / g, from the viewpoint of film adhesion and chemical resistance.
The thiol value of the polyurethane resin (U) is 0 to 40 mgKOH / g, preferably 10 to 30 mgKOH / g, and more preferably 15 to 25 mgKOH / g, from the viewpoint of film adhesion and chemical resistance. The thiol value in the present invention is defined by “milligrams of potassium hydroxide equivalent to the active hydrogen-containing group in 1 g of the sample” in the same manner as the hydroxyl value, and is defined in the hydroxyl group measurement method (JIS K 0070-1992). It can be measured accordingly.

  The total value of the amine value based on the primary amino group and the secondary amino group of the polyurethane resin (U), the hydroxyl value and the thiol group value is 5 to 100 mgKOH / g, preferably 5 to 70 mgKOH / g, More preferably, it is 20-50 mgKOH / g. When the total value of the amine value based on the primary amino group and the secondary amino group, the hydroxyl value, and the thiol group value is less than 5 mgKOH / g, the adhesion to the substrate is not sufficient, and the active hydrogen value is 100 mgKOH. If it exceeds / g, the chemical resistance becomes insufficient.

The swelling ratio of the polyurethane resin (U) with ethanol at 25 ° C. (hereinafter referred to as the ethanol swelling ratio) is a measure of the crosslinking amount of (U), and is a film forming property, adhesion of the resulting film, and resistance to resistance. From the viewpoint of chemical properties, it is preferably 0.1 to 300% by weight, more preferably 1 to 280% by weight, and particularly preferably 5 to 250% by weight with respect to the weight of (U). When the ethanol swelling ratio is 0.1% by weight or more, the film-forming property and adhesion are good, and when it is 300% by weight or less, the chemical resistance is good.
The swelling ratio of the polyurethane resin (U) in ethanol in the present invention is calculated from the change in weight of the urethane film before and after being immersed in ethanol as described in the examples.
In order to bring the ethanol swelling ratio of the polyurethane resin (U) into a desired range, the trifunctional or higher functional component [component (a1) and the organic polyisocyanate component (B) having a trifunctional or higher functionality, etc.] used in (U). What is necessary is just to adjust usage-amount suitably.

The Mn of the polyurethane resin (U) is preferably 5000 or more, more preferably 10,000 or more, from the viewpoints of mechanical properties, durability, chemical resistance, abrasion resistance, and the like of the resulting film.
When the Mn of the polyurethane resin (U) is 5000 or more, the mechanical properties, durability, chemical resistance and abrasion resistance of the film are excellent.

Mn of the polyurethane resin (U) in the present invention can be measured by gel permeation chromatography, for example, under the following conditions.
Apparatus: “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn α” + “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: Dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

[Polyurethane resin aqueous dispersion (Q)]
The polyurethane resin aqueous dispersion (Q) of the present invention can be produced by the following method (1) or (2).
(1) A method in which the active hydrogen component (A) and the organic polyisocyanate component (B) are mixed together and dispersed in an aqueous medium after the urethanization reaction, or the mixture is dispersed in water and then subjected to the urethanization reaction.
(2) A urethane prepolymer (P) having an isocyanate group at the terminal obtained by reacting the active hydrogen component (A) with the organic polyisocyanate component (B) and a neutralizing agent are mixed at a predetermined weight ratio. A method in which (P) is subjected to an extension reaction with a chain extender after being dispersed in water, and a termination reaction is performed with a reaction terminator if necessary.

  In the case of the above method (1), the polyurethane resin (U) is activated by using an active hydrogen component in such an amount that the number of moles of the active hydrogen-containing group in (A) exceeds the number of moles in the isocyanate group in (B). Hydrogen-containing groups can be introduced.

  In the method (1), the reaction system becomes highly viscous by using the component (a1) composed of a compound having 3 to 6 active hydrogen-containing groups in the molecule, so that a homogeneous polyurethane resin (U) is obtained. From the viewpoint, the method (2) is preferable.

  As the active hydrogen component (A) for producing the prepolymer (P), it is preferable to contain a compound (a22) having an anionic group and / or a cationic group and two active hydrogen-containing groups. By using (a22), an aqueous polyurethane resin dispersion having excellent dispersion stability and chemical resistance of the film can be obtained. Further, from the viewpoint of the mechanical properties, chemical resistance and adhesion of the film, it is preferable to use a compound (a212) having only two hydroxyl groups in the molecule as active hydrogen-containing groups, and in particular, a diol having a Mn of 300 or more ( 2122) and Mn or a diol (2121) having a chemical formula weight of less than 300 are preferably used in combination.

  As the chain extender, a component composed of a compound having 3 to 6 at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group in the molecule ( a1), a component (a21) comprising a compound having at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group in the molecule, and water More preferably, the compound (a11) having only 3 to 6 primary amino groups and secondary amino groups in the molecule as active hydrogen-containing groups, primary amino groups and / or active hydrogen-containing groups, and Alternatively, a compound (a12) having 3 to 6 secondary amino groups and hydroxyl groups in the molecule and a compound (a213) having only two primary or secondary amino groups in the molecule as active hydrogen-containing groups Particularly preferred are polyalkylene polyamines, aliphatic diamines having 2 to 36 carbon atoms and 2- (2-aminoethylamino) ethanol, and most preferred is polyethylene polyamines and ethylene diamine.

  The reaction terminator includes a compound (a12) having only 3 to 6 primary amino groups and / or secondary amino groups and hydroxyl groups in the molecule as active hydrogen-containing groups, and primary amino groups as active hydrogen-containing groups. A compound (a211) having one group and one hydroxyl group in the molecule is preferable, and more preferable are a dialkanolamine having 4 to 20 carbon atoms and a monoalkanolamine having 2 to 20 carbon atoms.

As a method of introducing an active hydrogen-containing group into the polyurethane resin (U), a method of introducing an amino group by reacting the urethane prepolymer (P) with only water, and containing an active hydrogen from the number of moles of the isocyanate group in (P). Examples include a method using an active hydrogen component in an amount in which the number of moles of the group is excessive and a method using the above-mentioned reaction terminator. However, since more active hydrogen-containing groups can be efficiently introduced, the above-mentioned reaction terminator The method using is preferable.
When a thiol group is introduced as an active hydrogen-containing group, thioglycerol is used to react only the hydroxyl group of thioglycerol with a prepolymer reaction using the difference in reactivity between the hydroxyl group and the thiol group. After obtaining the urethane prepolymer in which the groups coexist, a method in which the urethane prepolymer is dispersed in water and subjected to a chain elongation reaction is preferably used.
Moreover, when introducing a hydroxyl group as an active hydrogen-containing group, as described above, it is preferable to use the compounds (a12) and (a211) as the reaction terminator, but two or more of the compounds (a12) as the chain extender It is also preferable to use a compound having a primary or secondary amino group and a hydroxyl group [2- (2-aminoethylamino) ethanol and 3,6-diazaoctane-1,8-diol, etc.].

  In the aqueous polyurethane resin dispersion (Q) of the present invention, from the viewpoint of the dispersibility of (U) and the stability of the aqueous dispersion, the urethane prepolymer (P) is optionally added in the presence of a dispersant (J). Can be dispersed.

  Examples of the dispersant (J) include a nonionic surfactant (j1), an anionic surfactant (j2), a cationic surfactant (j3), an amphoteric surfactant (j4), and other emulsifying dispersants (j5). ). (J) may be used alone or in combination of two or more.

  Examples of (j1) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. As the AO addition type, EO addition product of aliphatic alcohol having 10 to 20 carbon atoms, EO addition product of phenol, EO addition product of nonylphenol, EO addition product of alkylamine having 8 to 22 carbon atoms, and EO addition of polypropylene glycol. Examples of the polyhydric alcohol type include fatty acid (carbon number 8-24) esters (for example, glycerin monostearate, glycerin) of polyhydric (3 to 8 valence or higher) alcohol (2 to 30 carbon atoms). Monooleate, sorbitan monolaurate, sorbitan monooleate and the like) and alkyl (carbon number 4 to 24) poly (degree of polymerization 1 to 10) glycosides.

  (J2) is, for example, an ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [sodium lauryl ether acetate and (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl ether acetate, etc.]; Sulfate ester or ether sulfate ester having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl sulfate, (poly) oxyethylene (addition) Mole number 1 to 100) lauryl sulfate triethanolamine and (poly) oxyethylene (addition mole number 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; sulfonate having a hydrocarbon group having 8 to 24 carbon atoms [Sodium dodecylbenzenesulfonate, etc.]; carbon number 8-2 Sulfosuccinates having 1 or 2 hydrocarbon groups; phosphate esters or ether phosphate esters having 8 to 24 carbon atoms and their salts [sodium lauryl phosphate and (poly) oxyethylene ( Addition mole number 1-100) sodium lauryl ether phosphate, etc.]; fatty acid salt having a hydrocarbon group having 8-24 carbon atoms [sodium laurate, triethanolamine laurate, etc.]; and hydrocarbon having 8-24 carbon atoms Acylated amino acid salts having a group [coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl- Sodium L-glutamate and lauroylmethyl β- alanine sodium, etc.] and the like.

  Examples of (j3) include quaternary ammonium salt types [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.] and amine salt types [diethylaminoethyl stearate. Amide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Examples of (j4) include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxy Sulfobetaine and lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl phosphate sodium etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate etc.].

  Examples of (j5) include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, and carboxyl group-containing (co) polymers such as sodium polyacrylate and US Pat. No. 5,906,704. And emulsifying dispersants having the urethane group or ester group described above [for example, polycaprolactone polyol and polyether diol linked with polyisocyanate] and the like.

  The dispersant (J) is used before the urethanization reaction of the urethane resin (U), during the urethanization reaction, after the urethanization reaction, before the water dispersion step of (U), during the water dispersion step, or after water dispersion. Although it may be added, it is preferably added before or during the water dispersion step from the viewpoint of the dispersibility of (U) and the stability of the aqueous dispersion.

  The amount of (J) used is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the total weight of (P). is there.

  The urethane prepolymer (P) in the present invention is obtained by heating and reacting the active hydrogen component (A) and the organic polyisocyanate component (B) with a heatable facility. For example, the raw material (P) is charged in a container and uniformly stirred, and then heated without stirring in a heating dryer or heating furnace, a simple pressure reactor (autoclave), Kolben, uniaxial or biaxial kneading. And a method of reacting by heating with stirring or kneading in a machine, a plast mill or a universal kneader. Among them, the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained (P), and the mechanical properties, durability, chemical resistance, wear resistance, etc. of the obtained film are higher. This is preferable because it tends to be excellent.

  When producing the urethane prepolymer (P), it is preferable to react the active hydrogen component (A) and the organic polyisocyanate component (B) in the presence of an organic solvent from the viewpoint of obtaining homogeneous (P). Further, from the viewpoint of VOC reduction, the organic solvent used in the reaction of (P) is distilled off in a step after the reaction step of (P) (for example, during or after the extension step with a chain extender). It is preferable.

  Examples of the organic solvent include ketone solvents (for example, acetone and methyl ethyl ketone), ester solvents (for example, ethyl acetate), ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethylformamide and N-methylpyrrolidone), Examples include alcohol solvents (for example, isopropyl alcohol), aromatic hydrocarbon solvents (for example, toluene), and acetone is particularly preferable. The aqueous medium in the present invention means water or a mixture of water and the above organic solvent.

  The reaction temperature for producing the urethane prepolymer (P) is preferably 60 to 120 ° C., more preferably 60 to 110 ° C., from the viewpoint of suppressing the formation of allophanate groups and burette groups of (P). Preferably it is 60-100 degreeC. The time for producing (P) can be appropriately selected depending on the equipment to be used, but is generally preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours, particularly preferably. 5 minutes to 20 hours. If it is this range, (P) which can fully exhibit the effect of the present invention will be obtained.

  In order to control the urethanization reaction rate, known reaction catalysts (such as tin octylate and bismuth octylate) and reaction retarders (such as phosphoric acid) can be used. The addition amount of these catalysts or reaction retarders is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0.01 to 1% by weight based on the weight of (P). %.

  As a device for dispersing the urethane prepolymer (P) in water, any device having a dispersion ability can be used. From the viewpoint of temperature adjustment, supply of granular or block resin and dispersion ability, etc., rotary dispersion It is preferable to use a mixing device, an ultrasonic dispersing device, or a kneader, and more preferable is a rotary dispersion mixing device having particularly excellent dispersing ability.

  The main dispersion principle of the rotary dispersion mixing apparatus is to apply a shearing force to the processed material from the outside by rotation of the drive unit or the like to make fine particles and disperse them. The rotary dispersion mixing apparatus can be operated under normal pressure, reduced pressure, or increased pressure.

  Examples of the rotary dispersion mixing device include a mixing device having general stirring blades such as Max blend and a helical blade, TK homomixer [manufactured by Primics Co., Ltd.], Claremix [manufactured by MTechnic Co., Ltd.], fill mix [Primics Co., Ltd.], Ultra Turrax [IKA Co., Ltd.], Ebara Milder [Ebara Seisakusho Co., Ltd.], Cavitron (Eurotech Co., Ltd.), Biomixer [Nihon Seiki Co., Ltd.], etc. Is exemplified.

  From the viewpoint of dispersion capability, the number of rotations when the urethane prepolymer (P) is dispersed using a rotary dispersion mixer is preferably 10 to 30000 rpm, more preferably 20 to 20000 rpm, and particularly preferably 30 to 10000 rpm. is there.

  The main dispersion principle of the ultrasonic dispersion apparatus is to apply energy from the outside to the processed material by vibration of the drive unit to form fine particles and disperse them. The ultrasonic dispersion apparatus can be operated under normal pressure, reduced pressure, or increased pressure.

  As the ultrasonic dispersion device, an ultrasonic dispersion device commercially available from Ikemoto Rika Kogyo Co., Ltd., Cosmo Bio Co., Ltd., and Ginsen Co., Ltd. can be used.

  The frequency when the urethane prepolymer (P) is dispersed using an ultrasonic dispersion device is preferably 1 to 100 kHz, more preferably 3 to 60 kHz, and particularly preferably 10 to 30 kHz from the viewpoint of dispersion capability. is there.

  The main dispersion principle of the kneader is that the processed material is kneaded in the rotating part of the kneader to give energy to make fine particles and disperse. The kneader can be operated under normal pressure, reduced pressure or increased pressure.

  As a kneader, a twin screw extruder [Ikegai Co., Ltd. PCM-30 etc.], a kneader [Kurimoto Kiko KRC Kneader etc.], a universal mixer [Primics Co., Ltd. Hibismix etc.] and Examples include plast mill [labor plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.] and the like.

  The number of rotations when the urethane prepolymer (P) is dispersed using a kneader is preferably 1 to 1000 rpm, more preferably 3 to 500 rpm, and particularly preferably 10 to 200 rpm from the viewpoint of dispersion ability.

  The weight ratio of the urethane prepolymer (P) and water supplied to the dispersing apparatus is appropriately selected according to the resin component content of the target aqueous dispersion, but preferably (P) / water = 10/2 to 10/100, more preferably 10/5 to 10/50.

  Moreover, the time which processes (P) and water with a dispersing device is from a dispersible viewpoint, Preferably it is 10 second-10 hours, More preferably, it is 1 minute-3 hours, Most preferably, it is 10-60 minutes.

  When dispersing with a dispersing device, one kind of additive selected from a pH adjuster, an antifoaming agent, an antifoaming agent, an antioxidant, an anti-coloring agent, a plasticizer, a mold release agent, etc. The above can be added. Moreover, you may perform solvent removal, concentration, dilution, etc. after dispersion | distribution as needed.

  The apparatus for reacting the chain extender and, if necessary, the reaction terminator after dispersing the urethane prepolymer (P) is not particularly limited, but it is preferable to carry out the reaction while mixing with the dispersing apparatus or the static mixer.

The aqueous polyurethane resin dispersion (Q) of the present invention has at least one active hydrogen-containing group selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group and a thiol group that the polyurethane resin (U) has. The crosslinking agent (C) which has two or more reactive groups in a molecule | numerator which can react with can be contained. By using (C) in combination, the chemical resistance and mechanical properties of the coating are improved. In addition, when a polyurethane resin (U) has a carboxyl group, a crosslinking agent (C) can also carry out a crosslinking reaction with the carboxyl group.
In the aqueous polyurethane resin dispersion (Q) of the present invention, the mixture of the polyurethane resin (U) and the crosslinking agent (C) may form one particle, and (U) and (C) are different. It may exist in the state of particles.

  As the crosslinking agent (C), blocked isocyanate compound (c1), melamine compound (c2), oxazoline compound (c3), carbodiimide compound (c4), aziridine compound (c5), epoxy compound (c6) and hydrazine compound (c7) Etc. A crosslinking agent (C) may be used individually by 1 type, or may use 2 or more types together.

  The blocked isocyanate compound (c1) is not particularly limited as long as it has two or more blocked isocyanate groups in the molecule. For example, the polyisocyanate compound exemplified as the organic polyisocyanate component (B) is a known blocking agent [ Phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalimides, lactams, active methylene compounds (malonic acid dialkyl esters, etc.), pyrazole compounds (Such as pyrazole and 3,5-dimethylpyrazole) and acidic sodium sulfite] and the like.

  As commercial products of (c1), Duranate series (Duranate 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-70E, E402 manufactured by Asahi Kasei Chemicals Corporation. -B80B and WM44-L70G).

  The melamine compound (c2) is not particularly limited as long as it is a methylolated melamine compound or a methoxymethylolated melamine compound having two or more methylol groups or methoxymethylol groups in the molecule. For example, Uban series manufactured by Mitsui Chemicals, Inc. [Uban 120, 20HS, 2021, 2028, 228, 2860, and 22R, etc.], Cymel series manufactured by Nippon Cytec Co., Ltd. (Symel 202, 232, 235, 238, 254, 266, 267, 272, 285, 301, 303, 325, 327, 350, 370, 701, 703, 736, 738, 771, 114, 1156 and 1158, etc.) and Sumitomo Chemical Co., Ltd.'s Sumimar series (Sumimar M-30W, M-50W, M- 55, M-66B, 50B, etc.).

  The oxazoline compound (c3) is not particularly limited as long as it is a compound having two or more oxazoline groups (oxazoline skeletons) in the molecule, such as 2,2′-isopropylidenebis (4-phenyl-2-oxazoline). Compounds having two or more oxazoline groups; (co) polymers of polymerizable oxazoline compounds such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2-oxazoline; The polymerizable oxazoline compound and a copolymerizable monomer that does not react with the oxazoline group [methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate and polyethylene glycol (meth) acrylate ( (Meth) acrylic esters, (meth) acrylic acid amide vinyl acetate, steel Copolymers of emissions and α- methylstyrene sodium styrenesulfonate, etc.]; and the like. Examples of the commercially available product (c3) include “Epocross K-2010E”, “Epocross K-2020E”, and “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.

  The carbodiimide compound (c4) is not particularly limited as long as it is a compound having two or more carbodiimide groups in the molecule. For example, the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms and the aliphatic having 4 to 22 carbon atoms. Aliphatic polycarbodiimide [poly (hexamethylene) obtained by polymerizing polyisocyanate (b2), alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms or aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms Carbodiimide) etc.], alicyclic polycarbodiimide [poly (4,4'-dicyclohexylmethanecarbodiimide) etc.] and aromatic polycarbodiimide [poly (p-phenylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide) and poly (Diisopropylphenylcarbodiimide) etc. . The commercially available products of (c4) include “Carbodilite V-01”, “Carbodilite V02”, “Carbodilite V-03”, “Carbodilite V-04”, “Carbodilite V-05”, “Carbodilite” manufactured by Nisshinbo Co., Ltd. V-07 "," Carbodilite V-09 "," Carbodilite E-02 "," Carbodilite E-03A "," Carbodilite E-04 "and the like.

  The aziridine compound (c5) is not particularly limited as long as it is a compound having two or more aziridinyl groups in the molecule. For example, tetramethylol methanetris (β-aziridinylpropionate) and trimethylolpropane tris (β-azizin). Lysinyl propionate).

  The epoxy compound (c6) is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule. For example, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Examples include polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and polypropylene glycol diglycidyl ether.

  Examples of the hydrazine compound (c7) include hydrazine and a compound having two or more hydrazine groups (hydrazine skeleton) in the molecule [for example, dicarboxylic acid dihydrazide having 2 to 10 carbon atoms (oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutar Acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide) and C2-C10 alkylene dihydrazine (ethylene dihydrazine, 1,3-propylene dihydrazine and 1,4 -Butylene hydrazine and 1,6-hexylene dihydrazine, etc.)].

  The amount of the crosslinking agent (C) used is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the solid content weight of the polyurethane resin aqueous dispersion (Q).

  The solid content concentration (content of components other than volatile components) of the aqueous polyurethane resin composition dispersion (Q) is preferably 20 to 65% by weight, more preferably 25, from the viewpoint of easy handling of the aqueous dispersion. ~ 55% by weight. The solid concentration was about 1 g of an aqueous dispersion thinly stretched on a Petri dish, weighed accurately, then weighed the weight after heating at 130 ° C for 45 minutes using a circulating constant temperature dryer, and before weighing, It can be obtained by calculating the ratio (percentage) of the remaining weight after heating to the weight.

The viscosity of the aqueous polyurethane resin dispersion (Q) is preferably 10 to 100,000 mPa · s, more preferably 10 to 5,000 mPa · s. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.
The pH of the aqueous polyurethane resin dispersion (Q) of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH can be measured at 25 ° C. with pH Meter M-12 [manufactured by Horiba, Ltd.].

  The volume average particle size (Dv) of the particles in the polyurethane resin composition aqueous dispersion (Q) of the present invention is preferably 0.01 to 1 μm, more preferably from the viewpoint of the handling property and dispersion stability of (Q). It is 0.02 to 0.7 μm, particularly preferably 0.03 to 0.4 μm. When (Dv) is 0.01 μm or more, the viscosity is appropriate and the handling property is good, and when it is 1 μm or less, the dispersion stability is good. (Dv) is measured using a light scattering particle size distribution analyzer [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

  The aqueous polyurethane resin dispersion (Q) of the present invention comprises an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for nonwoven fabrics, a sizing agent for reinforcing fibers). Composition, binder composition for antibacterial agent and raw material composition for artificial leather / synthetic leather, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, antifouling coating composition, etc.), aqueous paper treatment agent Although it can be used for a composition, a water-based ink composition, etc., its water-based coating composition, water-based adhesive composition, and water-based fiber processing agent composition are particularly preferred because of its excellent chemical resistance, adhesion and film-forming properties. Can be suitably used.

  When used in these applications, other additives such as coating forming auxiliary resins, crosslinking agents, catalysts, pigments, pigment dispersants, viscosity modifiers, antifoaming agents, leveling agents, preservatives, anti-degradation are necessary. One, two or more agents, stabilizers, antifreezing agents and the like can be added.

[Water-based paint]
Hereinafter, the preparation of an aqueous paint using the aqueous polyurethane resin dispersion (Q) of the present invention will be described.
For water-based paints, other than the polyurethane resin (U) in the aqueous polyurethane resin dispersion (Q) of the present invention, other water-dispersible resins or water-soluble resins are used as necessary for the purpose of coating film formation and improving the binder function. A resin may be used in combination.

  Examples of other water-dispersible resins or water-soluble resins used in combination with water-based paints include water-dispersible or water-soluble polyurethane resins other than the polyurethane resin (U) in the present invention, polyacrylic resins, and polyester resins. . These other resins can be appropriately selected from those commonly used in each application for each application of the water-based paint.

The solid content of the aqueous polyurethane resin dispersion (Q) of the present invention in the aqueous paint is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight, based on the weight of the aqueous paint.
The content of the other resin in the water-based paint is preferably 60% by weight or less, more preferably 50% by weight or less based on the weight of the water-based paint.

  The water-based paint may further contain one or more of a crosslinking agent, a pigment, a pigment dispersant, a viscosity modifier, an antifoaming agent, an antiseptic, a deterioration preventing agent, a stabilizer, an antifreezing agent, water, and the like. it can.

  Examples of the crosslinking agent used in the water-based paint include those similar to the crosslinking agent (C), and the amount used is preferably 30% by weight or less based on the solid content weight of the polyurethane resin aqueous dispersion (Q). More preferably, it is 0.1 to 20% by weight.

  Examples of the pigment include inorganic pigments having a solubility in water of 1 or less (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, purple pigment and metallic pigment) and organic pigments ( For example, natural organic pigment synthetic organic pigments, nitroso pigments, nitro pigments, pigment dye-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes , Anthraquinone lake, pigments from vat dyes and phthalocyanine pigments). The pigment content is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous paint.

  Examples of the pigment dispersant include the above-described dispersant (J), and the content of the pigment dispersant is preferably 20% by weight or less, more preferably 15% by weight or less based on the weight of the pigment.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose viscosity modifiers (such as methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose with Mn of 20,000 or more), proteins System viscosity modifiers (casein, casein soda, casein ammonium, etc.), acrylics (such as sodium polyacrylate and ammonium polyacrylate with Mn of 20,000 or more) and vinyl viscosity modifiers (Mn of 20,000 or more) Polyvinyl alcohol).
Examples of antifoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone).

Examples of the preservative include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.
Deterioration inhibitors and stabilizers (such as UV absorbers and antioxidants) include hindered phenol, hindered amine, hydrazine, phosphorus, benzophenone or benzotriazole degradation inhibitors and stabilizers. .
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The contents of the viscosity modifier, antifoaming agent, antiseptic, deterioration preventing agent, stabilizer and antifreezing agent are each preferably 5% by weight or less, more preferably 3% by weight or less, based on the weight of the aqueous paint. is there.

  A solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying. Examples of the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (such as methanol, ethanol and propanol), glycols having 1 to 20 carbon atoms (such as ethylene glycol, propylene glycol and diethylene glycol), and 3 having 1 to 20 carbon atoms. Alcohols having higher valences (such as glycerin) and cellosolves having 1 to 20 carbon atoms (such as methyl and ethyl cellosolve) can be used. The content of the solvent to be added is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the aqueous paint.

The aqueous paint using the polyurethane resin aqueous dispersion (Q) of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion (Q) of the present invention and each of the components described above. When mixing, all the components may be mixed at the same time, or each component may be added stepwise and mixed.
The solid content concentration of the water-based paint is preferably 10 to 70% by weight, more preferably 15 to 60% by weight.

[Water-based adhesive]
The aqueous adhesive using the polyurethane resin aqueous dispersion (Q) of the present invention will be described below.
As the resin used for the water-based adhesive, the urethane resin (U) in the polyurethane resin aqueous dispersion (Q) of the present invention may be used alone, but other than the urethane resin represented by SBR latex resin and acrylic resin. A water-dispersible or water-soluble resin can be used in combination. When used in combination, the ratio of the polyurethane resin (U) to the total weight of the resin is preferably 1% by weight or more, more preferably 10% by weight or more.

  Furthermore, the auxiliary materials and additives preferably used for the adhesive, such as a cross-linking agent, a plasticizer, and a tackifier, as long as the cohesiveness of the adhesive containing the aqueous polyurethane resin dispersion (Q) of the present invention is not inhibited. It is also possible to use agents, fillers, pigments, thickeners, antioxidants, ultraviolet absorbers, surfactants, flame retardants, and the like.

[Aqueous fiber processing agent]
Hereinafter, the preparation of an aqueous fiber processing agent using the aqueous polyurethane resin dispersion (Q) of the present invention will be described. The fiber processing agent containing the polyurethane resin aqueous dispersion (Q) of the present invention may include known antifoaming agents, wetting agents, various resin aqueous dispersions (polyurethane aqueous dispersions other than the present invention, acrylic aqueous dispersions, if necessary). Body and SBR latex) and softeners can be blended. In the case of an aqueous resin dispersion, these blending amounts are preferably 30% by weight or less, particularly preferably 20% by weight or less based on the weight of the polyurethane resin (U) in terms of solid content, and in the case of other additives, respectively. It is preferably 1% by weight or less, particularly preferably 0.1 to 0.5% by weight. Moreover, a pH adjuster can also be added as needed. Examples of pH adjusters include alkaline substances such as salts of strong bases (alkali metals, etc.) and weak acids (acids with pKa exceeding 2.0, such as carbonic acid and phosphoric acid) (sodium bicarbonate, etc.) or acidic substances (acetic acid, etc.). Can be mentioned. The amount of the pH adjusting agent is preferably 0.01 to 0.3% by weight based on the weight of the polyurethane resin (U).

  The solid content (nonvolatile content) concentration of the aqueous fiber processing agent of the present invention is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 45% by weight. The viscosity (25 ° C.) is preferably 10 to 100,000 mPa · s.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.

<Production Examples 1-5>
The raw materials listed in Table 1 were charged into a simple pressure reactor equipped with a stirrer and a heating device, and stirred at 85 ° C. for 10 hours to conduct a urethanization reaction. Urethane prepolymers (P-1) to (P- 5) Acetone solution was prepared.

<Production Examples 6-7>
Each raw material shown in Table 1 is charged into a simple pressure reactor equipped with a stirrer and a heating device, and cooled by performing a urethanization reaction at 85 ° C. until the reaction between the hydroxyl group and isocyanate group of thioglycerol is completed. By this, acetone solutions of urethane prepolymers (P-6) to (P-7) in which thiol groups and isocyanate groups coexist were produced. In addition, when producing an aqueous polyurethane resin dispersion using these urethane prepolymers, the polyurethane resin aqueous dispersion described later immediately after the production of the urethane prepolymer in order to avoid the reaction of thiol groups and isocyanate groups over time. The body was manufactured.

In addition, the content of diol (a2122) whose Mn in Table 1 is 300 or more is as follows.
PTMG2000: Polytetramethylene ether glycol (Mitsubishi Chemical Corporation) with Mn = 2,004 and Mw / Mn = 1.1
Kuraray polyol P-2010: poly (3-methylpentylene adipate) diol [manufactured by Kuraray Co., Ltd.] with Mn = 1,997 and Mw / Mn = 1.1
Kuraray polyol C-2090: poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol [manufactured by Kuraray Co., Ltd.] with Mn = 2,000 and Mw / Mn = 1.1

<Example 1>
Each raw material shown in Table 2 was charged into a simple pressure reactor equipped with a stirrer and a heating reactor as follows. Acetone solution of 500.00 parts of urethane prepolymer (P-1) obtained in Production Example 1 was added and stirred at 40 ° C., 152.26 parts of acetone as an organic solvent, and 14.40 of triethylamine as a neutralizing agent. The mixture was homogenized at 60 rpm for 30 minutes, and then emulsified by gradually adding 648.52 parts of ion-exchanged water while stirring at 500 rpm while maintaining the temperature at 60 ° C., and then triethylene as a chain extender. 0.37 parts of tetramine and 23.04 parts of ethylenediamine and 1.99 parts of diethanolamine as a reaction terminator were added, and acetone was distilled off at 65 ° C. under reduced pressure for 12 hours to obtain an aqueous polyurethane resin dispersion (Q-1 )

<Examples 2 to 19 and Comparative Examples 1 to 4>
Except for using the raw materials listed in Table 2 or 3, in the same manner as in Example 1, the polyurethane resin aqueous dispersions (Q-2) to (Q-19) and the comparative polyurethane resin aqueous dispersion (Q′- 1) to (Q′-4) were obtained.

  Various physical property values of polyurethane resin aqueous dispersions (Q-1) to (Q-19) and (Q'-1) to (Q'-4) obtained in Examples 1 to 19 and Comparative Examples 1 to 4 The evaluation results are shown in Tables 2 and 3. In addition, the measuring method and evaluation method of various physical property values in the present invention are as follows.

<Method for measuring Mn of polyurethane resin (U)>
Add the aqueous polyurethane dispersion in dimethylformamide so that the concentration of the polyurethane resin is 0.125 wt%, stir and dissolve at room temperature for 1 hour, and then filter through a filter with a pore size of 0.3 μm for gel permeation. Mn of the polyurethane resin (U) was measured by chromatography (GPC) under the following conditions.
When the solubility of the polyurethane resin in dimethylformamide was less than 90%, it was difficult to accurately measure Mn, and “measurement impossible” was displayed.
<GPC measurement conditions>
Apparatus: “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn α” + “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: dimethylformamide Solution injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

[Evaluation method]
<Dispersion stability of aqueous polyurethane resin dispersion>
The aqueous polyurethane resin dispersion was allowed to stand at 25 ° C. for 12 hours, and the occurrence of sediment was visually evaluated. The case where no sediment was generated was marked as ◯, and the case where sediment was generated was marked as x.

<Chemical resistance of polyurethane resin aqueous dispersion film (swelling ratio by ethanol)>
Pour a polyurethane resin aqueous dispersion in an amount of 200 μm into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying at room temperature for 12 hours, The film obtained by heating and drying for 3 hours was cut into 2 cm × 8 cm to prepare test pieces, and the weight (W0) was measured with an electronic balance capable of weighing up to 4 digits after the decimal point. The test piece was dipped in ethanol, dipped at 25 ° C. for 24 hours and then taken out, and after the ethanol adhering to the surface was wiped off, the weight (W1) was measured. The ethanol swelling ratio was calculated by the following formula using the obtained numerical values.
Ethanol swelling rate (%) = 100 × [(W1) − (W0)] / (W0)
W0: Weight of urethane film before ethanol immersion W1: Weight of urethane film after ethanol immersion

<Evaluation of film adhesion of aqueous polyurethane resin dispersion>
A polyurethane resin aqueous dispersion is applied to a hot-dip galvanized steel sheet so that the film thickness after drying is 50 μm, and is dried in an atmosphere of 25 ° C. and a relative humidity of 50% for 7 days. The film was cured under conditions of 10% relative humidity, and a cellophane tape peeling test with 100 grids was performed under conditions of a temperature of 5 ° C. and a relative humidity of 10% to evaluate the adhesion to the steel sheet. Conditions other than temperature and humidity were based on JIS K5600-5-6, and cellophane adhesive tape [manufactured by Nichiban Co., Ltd.] was used. The case where 100 cells were not peeled was rated as ◎, the case where 90 to 99 cells were not peeled off was marked as ◯, and the case where there were less than 90 cells were not marked as ×.

<Example 20> (Evaluation as water-based paint)
45 parts of ion-exchanged water, 35 parts of thickener [“Biseriser AP-2”, manufactured by Sanyo Chemical Industries, Ltd.], 5 parts of pigment dispersant [“Caribbon L-400”, manufactured by Sanyo Chemical Industries, Ltd.] Then, 70 parts of titanium oxide [“CR-93”, manufactured by Ishihara Sangyo Co., Ltd.], carbon black [“FW200P”, manufactured by Degussa Co., Ltd.], and 80 parts of calcium carbonate were mixed and dispersed for 30 minutes using a paint conditioner. Here, 10 parts of 1-nonanol, 100 parts of an acrylic water dispersion [“Polytron Z330”, manufactured by Asahi Kasei Co., Ltd.] and 100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4 were charged for 10 minutes. Mixed and dispersed. Furthermore, it adjusted so that the viscosity in 25 degreeC might be set to 150 mPa * s using ion-exchange water, and the water-based coating material (W-1) was obtained. The viscosity was measured at a rotational speed of 60 rpm using a rotary viscometer manufactured by TOKIMEC.

<Examples 21 to 23> (Evaluation as water-based paint)
45 parts of ion-exchanged water, 35 parts of thickener [“Biseriser AP-2”, manufactured by Sanyo Chemical Industries, Ltd.], 5 parts of pigment dispersant [“Caribbon L-400”, manufactured by Sanyo Chemical Industries, Ltd.] Then, 70 parts of titanium oxide [“CR-93”, manufactured by Ishihara Sangyo Co., Ltd.], carbon black [“FW200P”, manufactured by Degussa Co., Ltd.], and 80 parts of calcium carbonate were mixed and dispersed for 30 minutes using a paint conditioner. Here, 3 parts of the crosslinking agent (C) listed in Table 4, 10 parts of 1-nonanol, 100 parts of an acrylic water dispersion [“Polytron Z330”, manufactured by Asahi Kasei Co., Ltd.] and the polyurethane resin water dispersion obtained in Example 4 100 parts of the body (Q-4) was charged and mixed and dispersed for 10 minutes. Furthermore, it adjusted so that the viscosity in 25 degreeC might be set to 150 mPa * s using ion-exchange water, and the water-based coating materials (W-2)-(W-4) were obtained. The viscosity was measured at a rotational speed of 60 rpm using a rotary viscometer manufactured by TOKIMEC.

<Comparative Example 5> (Evaluation as water-based paint)
A comparative water-based paint (W′-1) was obtained in the same manner as in Example 20, except that the polyurethane resin water dispersion (Q′-4) was used instead of the polyurethane resin water dispersion (Q-4). .

The obtained water-based paints (W-1) to (W-4) and the comparative water-based paint (W′-1) were evaluated on the water resistance of the coating film and the film-forming property of the paint based on the following test methods. The results are shown in Table 4.
<Water resistance evaluation method of coating film>
A water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 120 ° C. for 10 minutes to prepare a coating film having a thickness of 20 μm. The coated steel sheet was immersed in ion exchange water at 80 ° C. for 14 days, and then taken out and the surface was lightly wiped. The surface of the coating film was visually evaluated according to the following evaluation criteria.
○: There is no change in the coating film surface before and after immersion.
X: After immersion, a part of the paint is peeled off.

<Method for evaluating film-forming properties of paint>
A water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to produce a coating film having a thickness of 20 μm. This coated steel sheet was immersed in 25 ° C. ion-exchanged water for 10 minutes, then taken out, gently wiped with a cloth, and visually evaluated according to the following evaluation criteria.
○: Color does not transfer to the cloth.
X: Color transfer is observed on the cloth.

<Example 24> (Evaluation as a water-based adhesive)
To 100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4, a thickener (“SN Thickener A—manufactured by San Nopco” was added so that the viscosity at 25 ° C. was 4,000 to 5,000 mPa · s. 803 ") to obtain an aqueous adhesive (X-1).

<Examples 25-27> (Evaluation as a water-based adhesive)
100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4 was mixed with 3 parts of the crosslinking agent (C) shown in Table 5 as a curing agent, and the viscosity at 25 ° C was 4,000 to 4,000. It adjusted with the thickener ("SN thickener A-803" by San Nopco) so that it might become 5,000 mPa * s, and the water-based adhesives (X-2)-(X-4) were obtained.

<Comparative example 6> (Evaluation as a water-based adhesive)
A comparative aqueous adhesive (X′-1) was obtained in the same manner as in Example 24 except that the polyurethane resin aqueous dispersion (Q′-4) was used instead of the polyurethane resin aqueous dispersion (Q-4). It was.

Table 5 shows the results of evaluating the adhesive strength and water resistance of the obtained aqueous adhesives (X-1) to (X-4) and the comparative aqueous adhesive (X′-1) based on the following test methods. Shown in
<Adhesive strength evaluation method of water-based adhesive>
The water-based adhesive was applied to a flexible urethane slab foam (length 100 mm × width 120 mm × thickness 5 mm, bulk specific gravity 0.05) so that the coating amount was 50 g / m ² . After drying at 80 ° C. for 2 minutes, another soft urethane slab foam (length 100 mm × width 120 mm × thickness 5 mm, bulk specific gravity 0.05) not coated with adhesive is pressure-bonded for 10 seconds under a load of 4 kg, and after pressure bonding The peel strength was measured by an autograph (crosshead speed 500 mm / min) using a test piece immediately cut to a width of 25 mm. When the peel strength was 25 mm, 200 g or more was defined as adhesive strength ◯, and less than 200 g as adhesive strength ×.

<Water-resistant adhesive evaluation method of water-based adhesive>
The peel strength was measured immediately after immersing a test piece prepared in the same manner as the above-described method for evaluating the adhesive strength in boiling water for 1 hour. When the peel strength was 25 mm, 100 g or more was regarded as water-resistant adhesion ○, and less than 100 g was regarded as water-resistant adhesion x.

<Example 28> (Evaluation as aqueous fiber processing agent)
A pigment printing paste was prepared using an aqueous polyurethane resin dispersion as follows. For 100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4, 8.9 parts of a viscoelasticity modifier [“SN thickener 618” manufactured by San Nopco Co., Ltd.], a silicon-based antifoaming agent [“ SN deformer 777 “San Nopco Co., Ltd.” 0.9 parts, water 35 parts, titanium oxide 44.6 parts and pigment [“NL Red FR3R-D” manufactured by Yamagata Kogyo Co., Ltd.] 18.9 parts were mixed. Thus, a pigment printing paste (Y-1) was obtained.

<Examples 29 to 31> (Evaluation as aqueous fiber processing agent)
For 100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4, 3 parts of the crosslinking agent (C) listed in Table 6 and a viscoelasticity modifier [“SN thickener 618” manufactured by San Nopco Co., Ltd. 8.9 parts, silicon-based antifoaming agent ["SN deformer 777" manufactured by San Nopco Co., Ltd.] 0.9 parts, water 35 parts, titanium oxide 44.6 parts and pigment ["NL Red FR3R-D" Yamagata [Products Co., Ltd.] 18.9 parts were mixed to obtain pigment printing pastes (Y-2) to (Y-4).

<Comparative Example 7>
A comparative pigment printing paste (Y′-1) was obtained in the same manner as in Example 28 except that the polyurethane resin aqueous dispersion (Q′-4) was used instead of the polyurethane resin aqueous dispersion (Q-4). It was.

With respect to the obtained pigment printing pastes (Y-2) to (Y-4) and the comparative pigment printing paste (Y′-1), the water resistance and pigment printing of the fiber cloths pigment-printed based on the following test methods The results of testing the film forming property of the paste are shown in Table 6.
<Method for evaluating water resistance of textile fabric printed with pigment>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried for 5 minutes with a tenter temperature-controlled at 140 ° C. to obtain a textile fabric printed with pigment. This pigment-printed fiber cloth was immersed in ion-exchanged water at 60 ° C. for 1 day, then taken out, and the surface was lightly wiped with a non-printed fiber cloth, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

<Method for evaluating film forming property of pigment printing paste>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried with a 120 ° C. tenter for 3 minutes to obtain a textile fabric printed with pigment. The surface of the textile fabric printed with the pigment was lightly wiped with a textile fabric not subjected to textile printing, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

  The aqueous polyurethane resin dispersion of the present invention comprises an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for nonwoven fabrics, a sizing agent composition for reinforcing fibers, Antibacterial agent binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, antifouling coating composition, etc.), aqueous paper treatment agent composition, and It can be suitably used for a water-based ink composition or the like.

Claims (17)

  A polyurethane resin aqueous dispersion comprising a polyurethane resin (U) obtained by reacting an active hydrogen component (A) and an organic polyisocyanate component (B) and an aqueous medium, wherein (A) is a primary amino acid. A component (a1) comprising a compound having 3 to 6 active hydrogen-containing groups selected from the group consisting of a group, a secondary amino group, a hydroxyl value and a thiol group in the molecule; ) Has an amine value based on a primary amino group and a secondary amino group of 0 to 40 mgKOH / g, the hydroxyl value of (U) is 5 to 40 mgKOH / g, and the thiol group value of (U) Is 0 to 40 mgKOH / g, and the total value of amine value, hydroxyl value and thiol value based on the primary amino group and secondary amino group in (U) is 5 to 100 mgKOH / g Fat-aqueous dispersion (Q).   The polyurethane resin aqueous dispersion according to claim 1, wherein the swelling ratio of the polyurethane resin (U) by ethanol at 25 ° C is 0.1 to 300% by weight based on the weight of the (U).   The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the active hydrogen component (A) contains a component (a2) comprising a compound having two active hydrogen-containing groups in the molecule.   Component (a21) wherein the component (a2) is a compound having at least one active hydrogen-containing group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a thiol group in the molecule (a21 The aqueous polyurethane resin dispersion according to claim 3, which contains   5. The component according to claim 1, wherein the component (a1) contains a compound (a11) having only 3 to 6 primary amino groups and secondary amino groups in the molecule as active hydrogen-containing groups. Polyurethane resin aqueous dispersion.   The component (a1) contains a compound (a12) having only 3 to 6 primary amino groups and / or secondary amino groups and hydroxyl groups in the molecule as active hydrogen-containing groups. The aqueous polyurethane resin dispersion according to any one of the above.   The aqueous polyurethane resin dispersion according to claim 5 or 6, wherein the compound (a11) is a polyalkylene polyamine.   The aqueous polyurethane resin dispersion according to claim 6 or 7, wherein the compound (a12) is dialkanolamine.   The polyurethane resin aqueous dispersion according to any one of claims 4 to 8, wherein the component (a21) contains a compound (a211) having one primary amino group and one hydroxyl group in the molecule as an active hydrogen-containing group.   The aqueous polyurethane resin dispersion according to claim 9, wherein the compound (a211) is a monoalkanolamine.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 10, wherein the component (a1) contains a compound (a14) having 3 to 6 hydroxyl groups in the molecule as active hydrogen-containing groups.   The polyurethane resin aqueous dispersion according to any one of claims 4 to 11, wherein the component (a21) contains a compound (a212) having only two hydroxyl groups in the molecule as active hydrogen-containing groups.   The aqueous polyurethane resin dispersion according to any one of claims 3 to 12, wherein the component (a2) contains a compound (a22) having an anionic group and / or a cationic group and two active hydrogen-containing groups.   Furthermore, it is selected from the group consisting of a blocked isocyanate compound (c1), a melamine compound (c2), an oxazoline compound (c3), a carbodiimide compound (c4), an aziridine compound (c5), an epoxy compound (c6), and a hydrazine compound (c7). The aqueous polyurethane resin dispersion according to any one of claims 1 to 13, comprising at least one crosslinking agent (C).   An aqueous paint containing the aqueous polyurethane resin dispersion according to claim 1.   The aqueous adhesive containing the polyurethane resin aqueous dispersion in any one of Claims 1-14.   The aqueous fiber processing agent containing the polyurethane resin aqueous dispersion in any one of Claims 1-14.