WO2020105569A1

WO2020105569A1 - Aqueous composite resin dispersion and method for producing aqueous composite resin dispersion

Info

Publication number: WO2020105569A1
Application number: PCT/JP2019/045001
Authority: WO
Inventors: 将浩渡辺; 増美山根
Original assignee: 三洋化成工業株式会社
Priority date: 2018-11-21
Filing date: 2019-11-18
Publication date: 2020-05-28
Also published as: CN113166289A; JPWO2020105569A1; CN113166289B; JP7266045B2

Abstract

The present invention is an aqueous composite resin dispersion which contains composite resin particles that contain a polyurethane resin (U) and a vinyl resin (V) within each particle, and which is configured such that: the polyurethane resin (U) is a reaction product of an active hydrogen component (A), an organic isocyanate component (B) and a chain extender (E); at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a tri- or higher functional compound; and a film obtained by drying this aqueous composite resin dispersion satisfies all of the requirements (1)-(3) described below. (1) The gel fraction with respect to N, N-dimethylformamide is 35-100%. (2) The elongation at break is 200-1,000%. (3) The storage elastic modulus E' at 25°C is 100-3,000 MPa.

Description

Composite resin aqueous dispersion and method for producing composite resin aqueous dispersion

The present invention relates to a composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin in the same particle, and a method for producing the same.

In recent years, aqueous resin dispersions have been widely used from the viewpoint of environmental issues and safety. Among them, an acrylic resin aqueous dispersion is generally used for a coating agent or the like which requires mechanical strength, weather resistance, water resistance and the like. When an acrylic resin aqueous dispersion is used, the film is generally inferior in flexibility, and therefore a method of using the acrylic resin aqueous dispersion and the polyurethane resin aqueous dispersion in combination has been proposed as a method for improving flexibility. (For example, see Patent Document 1). However, in general, the acrylic resin and the polyurethane resin have poor compatibility, so when the acrylic resin aqueous dispersion and the polyurethane resin aqueous dispersion are used in combination, the flexibility of the film, the mechanical strength, the flexibility, and the transparency and There is a problem that the performance such as gloss is deteriorated.

Japanese Patent Laid-Open No. 06-192616

An object of the present invention is to include composite resin particles containing a polyurethane resin and a vinyl resin in the same particle, which are excellent in flexibility, mechanical strength, storage stability, flexibility, hardness, transparency and glossiness. An object of the present invention is to provide a composite resin aqueous dispersion and a method for producing the same.

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.
That is, the present invention is a composite resin aqueous dispersion containing composite resin particles containing the polyurethane resin (U) and the vinyl resin (V) of the first invention in the same particle, wherein the polyurethane resin (U) Is a reaction product of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E), and among the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E), A composite resin aqueous dispersion containing at least one compound having a functionality of 3 or more and having a dried composite resin aqueous dispersion satisfying all of the following (1) to (3):
(1) The gel fraction relative to N, N-dimethylformamide is 35 to 100%;
(2) The breaking elongation is 200 to 1,000%;
(3) The storage elastic modulus E ′ at 25 ° C. is 100 to 3,000 MPa.

A second invention is a method for producing a composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particle, which comprises the following step (1): To (6), wherein at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a trifunctional or higher functional compound. Is.
Step (1): reacting the active hydrogen component (A) and the organic isocyanate component (B) in the presence of a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. To produce a urethane prepolymer (P) having an isocyanate group at the end;
Step (2): an optional step carried out between the step (1) and the following step (3), which is a monofunctional vinyl-based monomer having no hydroxyl group, amino group, imino group or thiol group. A step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous when the step (2) is carried out. Dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): Step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with a chain extender (E);
Step (5): an optional step performed between the step (4) and the following step (6), in which a monofunctional vinyl-based monomer (M1) is added;
Step (6): a step of polymerizing the vinyl-based monomer (M11) in the aqueous dispersion (α) or the vinyl-based monomer (M11) and the monofunctional vinyl-based monomer (M1) when the step (5) is performed. ..

The composite resin aqueous dispersion of the present invention is excellent in flexibility, mechanical strength, storage stability, flexibility, hardness, transparency and gloss, and according to the production method of the present invention, flexibility, mechanical A composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin, which are excellent in dynamic strength, storage stability, flexibility, hardness, transparency and glossiness, in the same particle can be obtained.

First, the composite resin aqueous dispersion which is the first invention will be described.
The composite resin aqueous dispersion of the present invention is a composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particle, wherein the polyurethane resin (U) is It is a reaction product of an active hydrogen component (A), an organic isocyanate component (B) and a chain extender (E), and is at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E). A composite resin aqueous dispersion, one of which contains a trifunctional or higher functional compound, and a film obtained by drying the composite resin aqueous dispersion satisfies all of the following (1) to (3):
(1) The gel fraction relative to N, N-dimethylformamide is 35 to 100%;
(2) The breaking elongation is 200 to 1,000%;
(3) The storage elastic modulus E ′ at 25 ° C. is 100 to 3,000 MPa.

In the present invention, the polyurethane resin (U) is a reaction product of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E).
As the active hydrogen component (A), a high molecular polyol (a1) having a number average molecular weight (hereinafter abbreviated as Mn) of 300 or more, a low molecular weight polyol (a2) having Mn or a chemical formula amount of less than 300, and an ionic group and active Examples thereof include a compound (a3) having a hydrogen atom and a reaction terminator (a4).

Examples of the polymer polyol (a1) having Mn of 300 or more include polyester polyol, polyether polyol, polyether ester polyol, castor oil-based polyol, and the like. The polymer polyol (a1) may be used alone or in combination of two or more.

Examples of the polyester polyol having Mn of 300 or more include condensation type polyester polyol, polylactone polyol, and polycarbonate polyol.

Examples of the condensed polyester polyol having Mn of 300 or more include Mn or a low molecular weight polyol (a2) having a chemical formula of less than 300 and a polyvalent carboxylic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof [acid anhydride, lower ( And the like, which are obtained by condensation with an alkyl ester having 1 to 4 carbon atoms and an acid halide, and the like.

Examples of the low molecular weight polyol (a2) having Mn or a chemical formula of less than 300 include polyhydric alcohols having 2 to 20 carbon atoms; alkylene oxides having 2 to 12 carbon atoms of polyhydric alcohols having 2 to 20 carbon atoms (hereinafter referred to as AO). (Abbreviation) an adduct having an Mn or a chemical formula amount of less than 300; an AO adduct of bisphenol (bisphenol A, bisphenol S, bisphenol F, etc.) having 2 to 12 carbon atoms and having an Mn or a chemical formula amount of less than 300 Examples thereof include bis (2-hydroxyethyl) terephthalate and an AO adduct thereof having 2 to 12 carbon atoms and having Mn or a chemical formula amount of less than 300.

Examples of the AO having 2 to 12 carbon atoms in the present invention include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, 3-methyl Tetrahydrofuran, styrene oxide, α-olefin oxide, epichlorohydrin and the like can be mentioned.

As the polyhydric alcohol having 2 to 20 carbon atoms, a linear or branched aliphatic dihydric alcohol having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5- Direct addition of pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and tetraethylene glycol. Chain alcohol; 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-hexanediol, 3-methyl-1,6-hexanediol, 2-methyl-1,7- Heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl-1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyl Branched alcohols such as octanediol, etc .; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, 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 .; Aroaliphatic dihydric alcohols having 8 to 20 carbon atoms [m- or p-xylylenediol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, etc. ]; C3-C20 trihydric alcohol [aliphatic triols (glycerin, trimethylolpropane, etc.)]; C5-C20 4-8 octavalent alcohol [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan , Diglycerin, dipentaerythritol, etc.); saccharides (sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives)]; and the like.

Examples of the polycarboxylic acid having 2 to 20 carbon atoms or its ester-forming derivative include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, fumaric acid and Maleic acid, etc.), alicyclic dicarboxylic acid (dimer acid, etc.), aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyl) Dicarboxylic acids, etc.), trivalent or higher polycarboxylic acids (such as trimellitic acid and pyromellitic acid), their anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), these Acid halides (such as adipic acid dichloride), low molecular weight alkyl esters thereof (such as dimethyl succinate and dimethyl phthalate), and combinations thereof. Preferred among these are aliphatic dicarboxylic acids and their ester-forming derivatives. The polycarboxylic acids may be used alone or in combination of two or more.

As the polylactone polyol having Mn of 300 or more, a lactone monomer having 3 to 12 carbon atoms (β-propiolactone, γ-butyrolactone, γ-valerolactone, ε) is prepared by using the polyhydric alcohol having 2 to 20 carbon atoms as an initiator. -Caprolactone, η-caprylolactone, 11-undecanolactone, 12-dodecanoid, etc.) and the like. The lactone monomers may be used alone or in combination of two or more.

As the polycarbonate polyol, one or more polyhydric alcohols having 2 to 20 carbon atoms (preferably aliphatic dihydric alcohol having 3 to 9 carbon atoms, more preferably 4 to 6 carbon atoms) and low molecular weight While carrying out a dealcoholization reaction from a carbonate compound (for example, a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms) Polycarbonate polyols produced by condensation are mentioned.

Examples of the polyether polyol having Mn of 300 or more include compounds obtained by adding AO having 2 to 12 carbon atoms to the above Mn or low molecular weight polyol (a2) having a chemical formula of less than 300. One type of AO may be used alone or two or more types may be used in combination. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a combination of these may be used.

The addition of AO to Mn or the low-molecular-weight polyol (a2) having a chemical formula weight of less than 300 is carried out, for example, without catalyst or in the presence of a catalyst (alkali catalyst, amine-based catalyst, acidic catalyst, etc.) (particularly the latter half stage of AO addition). In step 1) under normal pressure or under pressure in one step or multiple steps.

Specific examples of the polyether polyol include poly (oxyethylene) polyol, poly (oxypropylene) polyol, poly (oxytetramethylene) polyol, poly (oxy-3-methyltetramethylene) polyol, and tetrahydrofuran / ethylene oxide copolymer polyol. And tetrahydrofuran / 3-methyltetrahydrofuran copolymer polyol and the like. Among these, poly (oxytetramethylene) polyol is preferable from the viewpoint of tensile strength and elongation.

As the polyether ester polyol having Mn of 300 or more, one or more kinds of the above polyether polyols and one kind of polyvalent carboxylic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof as a raw material of the above condensation type polyester polyol. Examples thereof include those obtained by polycondensation of the above.

Examples of the castor oil-based polyol include castor oil, a castor oil fatty acid and a polyester polyol of a polyhydric alcohol having 2 to 20 carbon atoms or a polyoxyalkylene polyol (castor oil fatty acid mono- or diglyceride, castor oil fatty acid and trimethylol). Mono-, di- or triester from propane and mono- or diester from castor oil fatty acid and polyoxypropylene glycol), castor oil added with AO having 2 to 12 carbon atoms and two kinds thereof The above mixture and the like can be mentioned.

From the viewpoint of tensile strength and elongation, the Mn of the polymer polyol (a1) is preferably 300 or more, more preferably 1,000 to 5,000, and particularly preferably 1,500 to 3,000.

The Mn of the polyol in the present invention can be measured by gel permeation chromatography, for example, under the following conditions.
Device: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolumn Super HL" (one), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation) are connected one by one"
Sample solution: Tetrahydrofuran solution solution of 0.25 wt% Injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

Examples of the compound (a3) having an ionic group and an active hydrogen atom include a compound (a31) containing an anionic group and an active hydrogen atom, and a compound (a32) containing a cationic group and an active hydrogen atom. As the compound (a3), one type may be used alone, or two or more types may be used in combination.

Examples of the compound (a31) containing an anionic group and an active hydrogen atom include a compound containing a carboxyl group as an anionic group, a hydroxyl group as an active hydrogen atom, and a carbon number of 2 to 10 [dialkylol alkane]. Acids (eg 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) Etc.]], a compound having a sulfonic acid group as an anionic group, a hydroxyl group as an active hydrogen atom, and a carbon number of 2 to 16 [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and Sulfoisophthalic acid di (ethylene glycol) ester, etc.], a compound containing a sulfamic acid group as an anionic group, a hydroxyl group as an active hydrogen atom, and a carbon number of 2 to 10 [N, N-bis (2-hydroxyl) Ethyl) sulfamic acid, etc.] and salts of these compounds neutralized with a neutralizing agent.

Examples of the neutralizing agent used for the salt of the compound (a31) containing an anionic group and an active hydrogen atom include ammonia, amine compounds having 1 to 20 carbon atoms or alkali metal hydroxides (sodium hydroxide, potassium hydroxide). And lithium hydroxide).
Examples of amine compounds having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, and secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine and diisopropanolamine, methylpropanolamine. Examples thereof include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

As the neutralizing agent used for the salt of the compound (a31) containing an anionic group and an active hydrogen atom, a vapor pressure at 25 ° C. may be used from the viewpoint of the drying property of the resulting composite resin aqueous dispersion and the water resistance of the dry film. Compounds with high values are preferred. From this point of view, as the neutralizing agent used for the salt of the compound (a31) containing an anionic group and an active hydrogen atom, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine can be used. Is preferred.

Of the compound (a31) containing an anionic group and an active hydrogen atom, 2,2-dimethylolpropionic acid and 2,2-dimethylolpropionic acid are preferable from the viewpoints of mechanical strength of the obtained film and dispersion stability of the composite resin aqueous dispersion. 2,2-Dimethylolbutanoic acid and salts thereof, more preferably 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are neutralized with ammonia or an amine compound having 1 to 20 carbon atoms. It is salt.

As the compound (a32) containing a cationic group and an active hydrogen atom, a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, for example, containing a tertiary amino group having 1 to 20 carbon atoms Diols [N-alkyldialkanolamines (eg N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg N, N-dimethylethanolamine ) Etc.] and other compounds are neutralized with a neutralizing agent.

As the neutralizing agent used for the salt of the compound (a32) containing a cationic group and an active hydrogen atom, a monocarboxylic acid having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, Examples thereof include dimethyl sulfate, methyl chloride and benzyl chloride.
As the neutralizing agent used in the salt of the compound (a32) containing a cationic group and an active hydrogen atom, a vapor pressure at 25 ° C. may be used from the viewpoint of the drying property of the resulting composite resin aqueous dispersion and the water resistance of the dry film. Compounds with high values are preferred. From this point of view, the neutralizing agent used for the compound (a32) containing a cationic group and an active hydrogen atom is preferably a monocarboxylic acid having 1 to 10 carbon atoms and carbonic acid, and more preferably formic acid and carbonic acid. Particularly preferred is carbonic acid.

As the reaction terminator (a4), monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), monoamines having 1 to 20 carbon atoms (Mono- or di-alkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

Examples of the organic isocyanate component (B) in the present invention include aromatic polyisocyanates (b1) having 2 to 3 or more isocyanate groups and having 8 to 26 carbon atoms, and aliphatic polyisocyanates (b2) having 4 to 22 carbon atoms. ), 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, tolylene diisocyanate is referred to as TDI). Abbreviated), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Mention may be made of methanetriisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

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 may be mentioned.

Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms 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 araliphatic polyisocyanate having 10 to 18 carbon atoms (b4) include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Examples of the modified products (b5) of the organic polyisocyanates (b1) to (b4) include urethane groups, carbodiimide groups, alohanate groups, urea groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups or oxazolidones of the above polyisocyanates. Group-containing modified products [for example, modified MDI (urethane modified MDI, carbodiimide modified MDI and trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, HDI biuret form, HDI isocyanurate form and IPDI isocyanurate form] are mentioned.

Among these, from the viewpoint of weather resistance, preferred are aliphatic polyisocyanates having 4 to 22 carbon atoms (b2), alicyclic polyisocyanates having 8 to 18 carbon atoms (b3) and modified products thereof, and more preferred are HDI, IPDI, hydrogenated MDI, HDI isocyanurate and IPDI isocyanurate.
As the organic isocyanate component (B), one type may be used alone, or two or more types may be used in combination.

Examples of the chain extender (E) include water and Mn or a polyamine compound having a chemical formula amount of less than 500.
Examples of the polyamine compound having Mn or a chemical formula amount of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylenediamine such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepenta Polyalkylene polyamines having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms in an alkylene group such as amine, pentaethylene hexamine, and hexaethylene heptamine (poly (n = 2 to 6) alkylene (having 2 carbon atoms) To 6) poly (n = 3 to 7) amine}, etc.], and alicyclic polyamines having 6 to 20 carbon atoms (1,3- or 1,4-diaminocyclohexane, 4,4'- or 2,4'- Dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines having 6 to 20 carbon atoms (1,3- or 1,4-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4′- or 2,4'-methylenebisaniline etc.), araliphatic polyamines having 8 to 20 carbon atoms [1,3- or 1,4-xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (Aminobutyl) benzene etc.], heterocyclic polyamines having 3 to 20 carbon atoms [2,4-diamino-1,3,5-triazine, piperazine and N- (2-aminoethyl) piperazine etc.], hydrazine or the like. Examples thereof include derivatives (eg, dibasic acid dihydrazide such as adipic acid dihydrazide) and amino alcohols having 2 to 20 carbon atoms (eg, ethanolamine, diethanolamine, 2-amino-2-methylpropanol and triethanolamine).

In the composite resin aqueous dispersion of the present invention, the polyurethane resin (U) is a compound in which at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) is a trifunctional or higher functional compound. It is a reaction product of the contained raw materials. In the present invention, by using a trifunctional or higher functional compound for at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E), the polyurethane resin (U) has a crosslinked structure. To introduce.

Of the active hydrogen component (A), the trifunctional or higher functional compound used for the above purpose is preferably Mn or a trihydric alcohol having 3 to 20 carbon atoms in the low molecular weight polyol (a2) having a chemical formula amount of less than 300, It is a C4 to C4 tetrahydric alcohol and a saccharide, more preferred is a C3 to C20 trihydric alcohol, and particularly preferred is trimethylolpropane.

Among the organic isocyanate component (B), the trifunctional or higher functional compound used for the above purpose is preferably an HDI isocyanurate body and an IPDI isocyanurate body.

Among the chain extenders (E), the trifunctional or higher functional compound used for the above purpose is preferably a polyalkylene polyamine having a alkylene group having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms [poly (n = 2-6) alkylene (C2-6) poly (n = 3-7) amine], and more preferred are diethylenetriamine and triethylenetetramine.

From the viewpoint of the mechanical strength of the dry film, it is preferable to introduce a crosslinked structure into the polyurethane resin (U) by using a trifunctional or higher functional compound as the chain extender (E).

In the present invention, the vinyl-based monomer (M) constituting the vinyl-based resin (V) is a monofunctional vinyl monomer (M1) {monofunctional vinyl having no hydroxyl group, amino group, imino group or thiol group. -Based monomers (M11), monofunctional vinyl-based monomers (M12) having a hydroxyl group, amino group, imino group or thiol group}, and bifunctional or higher functional vinyl-based monomers (M2). You may use 1 type and may use 2 or more types together.
Examples of the vinyl-based monomer (M11) include the following vinyl-based monomers (m1) to (m7).
Examples of the monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group include the following vinyl-based monomers (m8) to (m10).

(1) Ester group-containing vinyl monomer (m1):
Esters of unsaturated alcohols or hydroxystyrene with monocarboxylic acids having 1 to 12 carbon atoms, such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, isopropenyl acetate, methyl-4-vinylbenzoate, vinyl methoxyacetate, Vinyl benzoate and acetoxy styrene; unsaturated carboxylic acid alcohol (carbon number 1 to 30) ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, cyclohexyl (meth) acrylate, methylnorbornene (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Acrylate, ethyl-α-ethoxy (meth) acrylate, di (cyclo) alkyl fumarate (two alkyl groups are linear or branched groups having 2 to 8 carbon atoms) and di (cyclo) alkylmale Ate (two alkyl groups are linear or branched groups having 2 to 8 carbon atoms); polyoxyalkylene (2 to 4 carbon atoms) monool unsaturated carboxylic acid ester having a polymerization degree of 5 to 50, For example, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate.

(2) Vinyl hydrocarbon (m2):
(2-1) Aliphatic vinyl hydrocarbons: alkenes having 2 to 20 carbon atoms such as ethylene, propylene, butene, isobutylene, pentene, heptene, octene, dodecene, octadecene and α-olefins other than the above.
(2-2) Alicyclic vinyl hydrocarbon: monocycloalkene such as cyclohexene.
(2-3) Aromatic vinyl hydrocarbon (C8 to C20): Styrene and its hydrocarbyl (alkyl and / or cycloalkyl) substituted product, for example, α-methylstyrene, vinyltoluene, 2,4-dimethyl Styrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene and vinylnaphthalene.

(3) Epoxy group-containing vinyl monomer (m3):
Glycidyl group-containing (meth) acrylates having 6 to 20 carbon atoms such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate; 4-vinyl-1,2-epoxycyclohexane and 5-vinyl-2,3-epoxy Alicyclic epoxy group-containing vinyl monomers having 6 to 20 carbon atoms such as norbornane.

(4) Carboxyl group-containing vinyl monomer (m4):
Unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids, their anhydrides and their monoalkyl (carbon atoms having 1 to 24) esters such as (meth) acrylic acid, (anhydrous) maleic acid, and monoalkyl maleates. Ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, citraconic acid, citraconic acid monoalkyl ester and cinnamic acid.

(5) Sulfo group-containing vinyl-based monomer (m5):
Alkene sulfonic acid having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid; styrene sulfonic acid and alkyl substituted products thereof having 1 to 24 carbon atoms, such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl (having 1 to 8 carbon atoms)-(meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyl Oxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid and 3- (meth) acrylamido-2-hydroxypropanesulfonic acid; alkyl (C3-18) (meth) allylsulfosuccinic acid Acid ester etc.

(6) Keto group-containing vinyl monomer (m6):
Any monomer having a double bond capable of polymerizing at least one keto group (excluding a keto group in a carboxyl group, an ester group and an amide group) in the molecule can be used without particular limitation, and examples thereof include: Diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, (meth) acryloxyalkylpropanal and diacetone (meth) acrylamide.

(7) Aldehyde group-containing vinyl monomer (m7):
Any monomer having at least one aldehyde group and a polymerizable double bond in the molecule can be used without particular limitation, and examples thereof include acrolein, formylstyrol, (meth) acrylamidopivalinaldehyde and acetoacetoxyethyl ( (Meth) acrylate.

As (M11), from the viewpoint of dispersion stability of the composite resin aqueous dispersion, (m1), (m4), (m5) and (m6) are preferable, and more preferable are methyl (meth) acrylate and ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and (meth) acrylic acid.

(8) The hydroxyl group-containing vinyl monomer (m8) includes alkenol having 2 to 12 carbon atoms, such as vinyl alcohol, (meth) allyl alcohol, 1-buten-3-ol and 2-buten-1-ol; 4 to 12 alkene diols such as 2-butene-1,4-diol; hydroxyl group-containing aromatic vinyl monomers such as hydroxystyrene; C5 to C8 hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and Hydroxypropyl (meth) acrylate; alkenyl ethers having 3 to 30 carbon atoms, such as 2-hydroxyethylpropenyl ether and sucrose allyl ether.

(9) The amino group- or imino group-containing vinyl monomer (m9) is an aminoalkyl (meth) acrylate having 5 to 20 carbon atoms, such as 7-amino-3,7-dimethyloctyl (meth) acrylate, monomethylaminoethyl. (Meth) acrylate, t-butylaminoethyl (meth) acrylate, t-octylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc .; N— having 5 to 20 carbon atoms Aminoalkyl (meth) acrylamides such as N- (2-aminoethyl) (meth) acrylamide, N- (1-methyl-2-aminoethyl) (meth) acrylamide, N- (3-aminopropyl) (meth) acrylamide , N- (4-aminobutyl) (meth) acrylamide, N- (5-aminopentyl) (meth) acrylamide, N- (6-aminohexyl) (meth) acrylamide, N- (3-methylaminopropyl) ( Examples thereof include (meth) acrylamide, N- (2-isopropylaminoethyl) (meth) acrylamide, N- (3-isopropylaminopropyl) (meth) acrylamide and N- (3-tert-butylaminopropyl) (meth) acrylamide. Be done.

(10) Examples of the thiol group-containing vinyl monomer (m10) include (meth) allyl mercaptan and a thiol group-containing (meth) acrylic acid ester [ethylene sulfide adduct of the above hydroxyl group-containing vinyl monomer (m8) {2- (2-mercaptoethoxy) ethyl (meth) acrylate and the like} and ethylene sulfide adduct to (meth) acrylic acid {2-mercaptoethyl (meth) acrylate and the like}] and the like.

Examples of the bifunctional or higher vinyl monomer (M2) include divinylbenzene, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate. , Ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 9,9-bis [4- ( 2- (meth) acryloyloxyethoxy) phenyl] fluorene, ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol poly (meth) acrylate, tripentaerythritol poly (meth) acrylate, polypentaerythritol poly (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) Examples thereof include acrylate, allyl (meth) acrylate, triallyl isocyanurate, diallyl iso (tere) phthalate, diallyl isocyanurate and diallyl maleate.

In the present invention, among the monomers constituting the vinyl resin (V), a hydroxyl group, an amino group, an imino group or a thiol covalently bonded to the bifunctional or higher functional vinyl monomer (M2) and the urethane resin (U). The total [(M2) + (M12 ')] of the monofunctional vinyl-based monomers (M12') having a group is 4% by weight or less based on the total weight of the monomers constituting the vinyl-based resin (V). Is more preferable, 3% by weight or less is more preferable, and 2% by weight or less is particularly preferable.
In order to reduce the above value, the weight ratio of the bifunctional or higher functional vinyl monomer (M2) in the vinyl monomer (M) constituting the vinyl resin (V) may be reduced. Further, the weight ratio of the monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group in the vinyl-based monomer (M) constituting the vinyl-based resin (V) is reduced, or a urethane resin After the production of (U), a monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group may be used at a stage where the isocyanate group is very small or scarcely left.
The weight ratio of the bifunctional or higher functional vinyl-based monomer (M2) and the monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group can be determined by thermal decomposition gas chromatography mass spectrometry. it can. The weight ratio of the monofunctional vinyl-based monomer (M12 ′) having a hydroxyl group, an amino group, an imino group or a thiol group “covalently bonded to the urethane resin (U)” is in accordance with JIS K1557-1. Hydroxyl value analyzed, total amine value analyzed according to JIS K1557-7, thiol group content and pyrolysis gas chromatograph mass spectrometry determined by DTNB method using "Redox Assay Thiol Quantitative Kit" manufactured by Metallogenics Co., Ltd. From the molecular weight of (M12) qualitatively determined by the method, the weight ratio of the monofunctional vinyl-based monomer having a hydroxyl group, an amino group, an imino group or a thiol group which is “not bonded to the urethane resin (U)” is obtained, It can be obtained by subtracting from the weight ratio.
Specifically as the pyrolysis gas chromatograph mass spectrometry, a composition containing a bifunctional or higher functional vinyl-based monomer (M2) and / or a monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group. Two or more known vinyl-based resins are analyzed by a pyrolysis gas chromatograph mass spectrometry, and a bifunctional or more-functional vinyl-based monomer (M2) and / or a monofunctional vinyl having a hydroxyl group, an amino group, an imino group or a thiol group. Using a calibration curve created from the integrated value of the peak of the system monomer (M12), a bifunctional or higher functional vinyl monomer (M2) and / or a hydroxyl group, an amino group in the pyrolysis gas chromatograph mass spectrometry of the resin whose composition is to be analyzed, Based on the integrated value of the peak of the monofunctional vinyl-based monomer (M12) having an imino group or a thiol group, a bifunctional or higher-functional vinyl-based monomer (M2) and / or a monofunctional vinyl monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group The weight ratio of the vinyl monomer (M12) can be calculated.
In the present invention, the weight ratio of the monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group is based on the total weight of the monomers constituting the vinyl resin (V). It is preferably 96% by weight or more, more preferably 98% by weight or more, and particularly preferably 100% by weight.

The weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V) in the composite resin aqueous dispersion according to the present invention is dispersion stability, flexibility of the dry film, and mechanical strength. From the viewpoint of storage stability, hardness, flexibility, transparency and glossiness, it is preferably 30:70 to 70:30, more preferably 40:60 to 60:40.

In the composite resin aqueous dispersion of the present invention, examples of the aqueous medium include water and a mixture of water and an organic solvent.
Examples of the organic solvent include ketone solvents (eg acetone and methyl ethyl ketone), ester solvents (eg ethyl acetate), ether solvents (eg tetrahydrofuran), amide solvents (eg N, N-dimethylformamide and N-methylpyrrolidone), Examples thereof include alcohol solvents (for example, isopropyl alcohol) and aromatic hydrocarbon solvents (for example, toluene). The organic solvent may be used alone or in combination of two or more.

The composite resin aqueous dispersion in the present invention may contain a crosslinking agent, a viscosity modifier, an antifoaming agent, an antiseptic agent, a weather resistance stabilizer, an antifreezing agent, and the like.

Examples of the cross-linking agent include water-soluble or water-dispersible compounds containing in the molecule two or more functional groups capable of reacting with the reactive functional groups of the polyurethane resin (U) and the vinyl resin (V). Specifically, when the polyurethane resin (U) has a carboxyl group, compounds such as a melamine compound, an oxazoline compound, a carbodiimide compound, an epoxy compound and an aziridine compound can be used as a crosslinking agent.
When the vinyl resin (V) has a hydroxyl group, an amino group, an imino group or a thiol group, a melamine compound, an oxazoline compound, an aziridine compound, an epoxy compound, a blocked isocyanate compound or the like can be used as a crosslinking agent.
The crosslinking agents may be used alone or in combination of two or more. The amount of these crosslinking agents used is 1.0 to 20% by weight, more preferably 1.5 to 10% by weight, based on the weight of the polyurethane resin (U).

Examples of the viscosity modifier include thickeners such as inorganic viscosity modifiers (sodium silicate and bentonite), cellulose viscosity modifiers (methyl cellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), protein viscosity. Modifiers (casein, casein soda, ammonium caseinate, etc.), acrylics (sodium polyacrylate and ammonium polyacrylate having Mn of 20,000 or more) and vinyl viscosity modifiers (polyvinyl alcohol having Mn of 20,000 or more) Etc.) can be mentioned.
Examples of the defoaming agent include long-chain alcohols (octyl alcohol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether modified silicone, etc.), and the like.

Examples of the preservatives include organic nitrogen-sulfur compound-based preservatives and organic sulfur halide-based preservatives.
Examples of weather resistance stabilizers include antioxidants (hindered phenol-based, sulfur-based, phosphorus-based, etc.), ultraviolet absorbers (benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, etc.), hindered amine-based light stabilizers, etc. A weathering stabilizer may be included. The amount of these weather stabilizers used is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the weight of the polyurethane resin (U).
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The amount of the viscosity modifier, defoaming agent, preservative, weathering stabilizer and antifreezing agent used is preferably 5% by weight or less, more preferably 3% by weight or less, based on the weight of the composite resin aqueous dispersion. is there.

The volume average particle diameter (Dv) of the particles in the composite resin aqueous dispersion in the present invention is preferably 0.01 to 1 μm, more preferably 0. 1 μm from the viewpoint of handling property and dispersion stability of the composite resin aqueous dispersion. The thickness is from 02 to 0.7 μm, particularly preferably from 0.03 to 0.4 μm. (Dv) is measured using a light scattering particle size distribution analyzer [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

The solid content concentration (content of components other than the volatile component) of the composite resin aqueous dispersion in the present invention is preferably 20 to 65% by weight, more preferably 25 to 55% from the viewpoint of easy handling of the aqueous dispersion. % By weight. The solid content concentration was about 1 g of the aqueous dispersion, which was thinly spread on a Petri dish and precisely weighed, and then the weight after heating for 45 minutes at 130 ° C. using a circulation type constant temperature dryer was precisely weighed. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight.

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

A film obtained by drying the composite resin aqueous dispersion of the present invention satisfies all of the following (1) to (3).
(1) The gel fraction relative to N, N-dimethylformamide is 35 to 100%;
(2) The breaking elongation is 200 to 1,000%;
(3) The storage elastic modulus E ′ at 25 ° C. is 100 to 3,000 MPa.
The film in the above (1) to (3) is obtained by drying the composite resin aqueous dispersion at 105 ° C. for 3 hours, and further by drying under reduced pressure at 105 ° C. and a pressure of 1.3 kPa for 1 hour. A film having a thickness of 200 μm is used.

The gel fraction with respect to N, N-dimethylformamide (DMF) in the above (1) can be determined, for example, by the following method.
The aqueous composite resin dispersion is applied to a polypropylene plate so that the dry film thickness is 200 μm, and dried at 105 ° C. to obtain a film. A sample is cut out from the obtained coating film, and the weight of the sample is measured to determine the “weight of the film before DMF immersion”. The weight of the sample is preferably 0.035 to 0.045 g. Then, the sample is put in 20 ml of DMF and immersed at 23 ° C. for 24 hours. After the immersion, DMF containing the sample is filtered using a tetrafluoroethylene resin (PTFE) filter. Further, the filter and the residue are dried at 105 ° C. for 3 hours and then cooled, and the “total weight of the filter and the residue after DMF immersion” is measured. The "gel weight before immersion in DMF", "weight of filter" and "total weight of filter and residue after immersion in DMF" are substituted into the following formula (1) to determine the gel fraction.
Gel fraction (%) = (“total weight of filter and residue after immersion in DMF” − “weight of filter”) / “weight of coating before immersion in DMF” × 100 (1)

The breaking elongation in (2) above is based on JIS K6251 and the test piece is dumbbell-shaped No. 3 and the autograph [Shimadzu Corporation “AGS-500D”] It is a value measured at 500 mm / min.

The storage elastic modulus E'in (3) above is a value measured at a frequency of 11 Hz using a storage elastic modulus measuring device [Rheogel E4000 {manufactured by UBM Co., Ltd.}].

The gel fraction relative to DMF is 35 to 100%, preferably 36 to 95%, more preferably 37 to 80%, particularly preferably 38 to 70%.
When the gel fraction with respect to DMF is less than 35%, the storage stability when blended in a paint or ink, the flexibility of the dry film, the mechanical strength and the elongation at break are poor.
The gel fraction with respect to DMF can be adjusted by the crosslink density and the weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V). Specifically, the gel fraction can be increased by increasing the crosslinking density by increasing the trifunctional or higher functional compound or increasing the weight ratio of the polyurethane resin (U).

The breaking elongation is 200 to 1,000%, preferably 210 to 800%, more preferably 220 to 650%.
If the breaking elongation is less than 200%, the flexibility is poor, and if it exceeds 1,000%, the hardness and strength are poor.
The elongation at break can be adjusted by the crosslink density and the weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V). Specifically, the breaking elongation can be increased by decreasing the cross-linking density by decreasing the trifunctional or higher functional compound used or by increasing the weight ratio of the polyurethane resin (U).

The storage elastic modulus E ′ is 100 to 3,000 MPa, preferably 150 to 2,000 MPa, more preferably 200 to 1,000 MPa.
If the storage elastic modulus E'is less than 100 MPa, the hardness and strength are poor, and if it exceeds 3,000 MPa, the flexibility is poor.
The storage elastic modulus E ′ can be adjusted by the urethane group and urea group contents of the polyurethane resin (U) and the glass transition point of the vinyl resin (V). Specifically, the storage elastic modulus E ′ can be increased by using a large amount of the organic isocyanate component (B) or by using a vinyl monomer having a high glass transition point.

In the composite resin aqueous dispersion of the present invention, the urethane group content of the polyurethane resin (U) is 0.9 based on the weight of the polyurethane resin (U) from the viewpoints of flexibility, hardness, mechanical strength and flexibility. It is preferably from 2.5 to 2.5 mmol / g, more preferably from 1.2 to 2.2 mmol / g, particularly preferably from 1.5 to 2.0 mmol / g.
The urethane group content can be calculated from the N atom content quantified by a nitrogen analyzer, the urethane group / urea group ratio quantified by ¹ H-NMR, and the alohanate group / biuret group content.

In the composite resin aqueous dispersion of the present invention, the urea group content of the polyurethane resin (U) is 0.15 based on the weight of the polyurethane resin (U) from the viewpoints of flexibility, hardness, mechanical strength and flexibility. It is preferably about 1.5 to 1.5 mmol / g, more preferably 0.18 to 1.3 mmol / g, and particularly preferably 0.2 to 1.1 mmol / g.
The urea group content can be calculated from the N atom content determined by a nitrogen analyzer, the urethane group / urea group ratio determined by ¹ H-NMR, and the alohanate group / biuret group content.

As the nitrogen analyzer, for example, a nitrogen analyzer [ANTEK7000 (manufactured by Antec Co.)] can be used.
^{The 1} H-NMR measurement is performed by the method described in “Structural Study of Polyurethane Resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”. That is, when ¹ H-NMR was measured and an aliphatic group was used, it was determined that a urea group was obtained from the ratio of the integrated amount of hydrogen derived from a urea group having a chemical shift of about 6 ppm and the integrated amount of hydrogen derived from a urethane group having a chemical shift of about 7 ppm. The weight ratio of urethane groups is calculated, and the urethane group and urea group contents are calculated from the weight ratio and the N atom content and the alohanate group and biuret group contents. When an aromatic isocyanate is used, the weight ratio of the urea group and the urethane group is calculated from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 8 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 9 ppm, The urea group content is calculated from the weight ratio and the above N atom content.

In the aqueous composite resin dispersion of the present invention, the glass transition point of the vinyl resin (V) is preferably −70 to 180 ° C., more preferably 0 to 180 ° C. from the viewpoint of flexibility, hardness, mechanical strength and flexibility. The temperature is 150 ° C., particularly preferably 30 to 120 ° C., most preferably 60 to 110 ° C.
In the composite resin aqueous dispersion of the present invention, the glass transition point Tg (K) when the vinyl resin (V) is composed of two-component monomers is calculated by theoretical calculation using the Fox equation of the following equation (2). It can be calculated.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ (2)
[Wherein, Tg ₁ and Tg ₂ are glass transition points (K) of homopolymers of Monomer 1 and Monomer 2 and W ₁ and W ₂ are weight fractions of Monomer 1 and Monomer 2]

The glass transition point Tg (K) when the vinyl resin (V) is composed of three-component monomers can be calculated by theoretical calculation using the Fox equation of the following equation (3).
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ (3)
[Wherein, Tg ₁ , Tg ₂ and Tg ₃ are glass transition points (K) of homopolymers of Monomer 1, Monomer 2 and Monomer 3, W ₁ , W ₂ and W ₃ are Monomer 1, Monomer 2 and Monomer 3) Weight fraction]

The composite resin aqueous dispersion of the present invention can be obtained by the method for producing the composite resin aqueous dispersion, which is the second invention described below, and the production methods (I) to (II) below. In addition, in (I) to (II), at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a trifunctional or higher functional compound.
In the present invention, as the method for producing the composite resin aqueous dispersion, the method for producing the composite resin aqueous dispersion which is the second invention is preferable from the viewpoints of flexibility, mechanical strength and flexibility.

(I) A production method including the following steps (1 ′) to (6 ′).
Step (1 '): In the presence of the vinyl-based monomer (M'), the active hydrogen component (A) and the organic isocyanate component (B) are reacted to produce a urethane prepolymer (P ') having an isocyanate group at the terminal. In the step of, the vinyl-based monomer (M ′) has a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group and hydroxyl group, amino group, imino group or thiol group. A monofunctional vinyl monomer (M12) and / or a bifunctional or higher functional vinyl monomer (M2), and the total weight ratio of (M12) and (M2) is 4 based on the weight of (M ′). A step of not more than wt%;
Step (2 ′): an optional step performed between step (1 ′) and the following step (3 ′), in which a vinyl-based monomer (M ′) is added;
Step (3 ′): The solution of the urethane prepolymer (P ′) obtained in the step (1 ′) or the urethane prepolymer (P ′ obtained in the step (2 ′) when the step (2 ′) is carried out Dispersing the solution of ') in an aqueous medium to obtain an aqueous dispersion (α');
Step (4 ′): Step of extending the urethane prepolymer (P ′) in the aqueous dispersion (α ′) with the chain extender (E);
Step (5 ′): an optional step performed between the step (4 ′) and the following step (6 ′), which is a monofunctional vinyl-based monomer (M11) or a monofunctional vinyl-based monomer (M12). ) And at least one selected from the group consisting of bifunctional or higher functional vinyl monomers (M2);
Step (6 ′): a step of polymerizing the vinyl monomers (M11), (M12) and (M2) in the aqueous dispersion (α ′).
In the production method of (I), when the step (1 ′) and the step (2 ′) are carried out, in the step (1 ′) and the step (2 ′), based on the weight of (M ′) (M11) By containing 96% by weight or more and less than 100% by weight, the crosslink density of (V) can be set in an appropriate range, and the dryness of the composite resin is excellent in flexibility, mechanical strength and flexibility. A dispersion is obtained.

In the production method of (I), the preferable conditions other than the vinyl-based monomer (M ′) are the second invention corresponding to the steps (1 ′) to (6 ′) in the following second invention {(I). This is the same as the steps (1) to (6) of the invention.

(II) A production method including the following steps (1 ″) to (4 ″).
Step (1 ″): In the absence of a vinyl monomer, the active hydrogen component (A) and the organic isocyanate component (B) are reacted to produce a urethane prepolymer (P ″) having an isocyanate group at the end. Process;
Step (2 ″): The solution of the urethane prepolymer (P ″) obtained in the step (1 ″) is dispersed in an aqueous medium to obtain an aqueous dispersion (αx), and then the urethane prepolymer (P ′). ') Is extended with a chain extender (E) to obtain an aqueous dispersion (α''), or the urethane prepolymer (P'') obtained in the step (1'') is added to the chain extender (E''). ) And then dispersing in an aqueous medium to obtain an aqueous dispersion (α ″);
Step (3 ″): a step of allowing the vinyl-based monomer (M ″) to coexist in the aqueous dispersion (α ″), wherein the vinyl-based monomer (M ″) is a hydroxyl group, an amino group, an imino group or Monofunctional vinyl-based monomer (M11) having no thiol group, and monofunctional vinyl-based monomer (M12) optionally having a hydroxyl group, amino group, imino group or thiol group, and / or bifunctional or more vinyl-based monomer A step of containing the monomer (M2), and the weight ratio of (M2) is 4% by weight or less based on the weight of (M ′);
Step (4 ″): A step of polymerizing the vinyl-based monomer (M ″) in the aqueous dispersion (α ″).

The correspondence between each step in the manufacturing method (II) and each step in the second invention is as follows.
Process (1 ''): Process (1)
Step (2 ''): Step (3) and Step (4)
Process (3 ''): Process (5)
Process (4 ''): Process (6)
Further, in the production method of (II), preferable conditions as the conditions other than producing the urethane prepolymer in the absence of the vinyl-based monomer in the step (1 ″) are the same as those in the step (1) in the second invention. is there. In step (2 ″), preferable conditions are the same as those in steps (3) and (4) in the second invention. In step (3 ″), preferable conditions are the same as those in step (5) in the second invention except that the vinyl-based monomer (M ″) is used. In step (4 ″), preferable conditions are the same as those in step (6) in the second invention.

A method for producing the composite resin aqueous dispersion which is the second invention will be described.
A method for producing a composite resin aqueous dispersion which is a second invention is a method for producing a composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particle. And the following steps (1) to (6), wherein at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a trifunctional or higher functional compound. It is a method for producing an aqueous resin dispersion.
Step (1): reacting the active hydrogen component (A) and the organic isocyanate component (B) in the presence of a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. To produce a urethane prepolymer (P) having an isocyanate group at the end;
Step (2): an optional step carried out between the step (1) and the following step (3), which is a monofunctional vinyl-based monomer having no hydroxyl group, amino group, imino group or thiol group. A step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous when the step (2) is carried out. Dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): Step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with a chain extender (E);
Step (5): an optional step performed between the step (4) and the following step (6), in which a monofunctional vinyl-based monomer (M1) is added;
Step (6): a step of polymerizing the vinyl-based monomer (M11) in the aqueous dispersion (α) or the vinyl-based monomer (M11) and the monofunctional vinyl-based monomer (M1) when the step (5) is performed. ..

When at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a trifunctional or higher functional compound, a crosslinked structure is introduced into the polyurethane resin (U), By polymerizing the vinyl monomer (M11) or (M11) and (M1) existing in the system at the time of forming the polyurethane resin (U), the vinyl resin (V It is possible to form a composite resin having a structure in which the molecular chain of (1) penetrates, and an aqueous composite resin dispersion having excellent flexibility, mechanical strength and flexibility of the dry film can be obtained.
Also, a monofunctional vinyl-based monomer is used to form a linear vinyl-based resin, and the vinyl-based monomer in steps (1) and (2) does not have any hydroxyl group, amino group, imino group or thiol group. By using a material such that the polyurethane resin (U) and the vinyl resin (V) do not form a covalent bond, the flexibility, mechanical strength and flexibility of the dry film can be further improved.

The active hydrogen component (A) used in the step (1) is the same as the active hydrogen component (A) in the first invention, and the preferred ones are also the same.

The organic isocyanate component (B) in the present invention is the same as the organic isocyanate component (B) in the first invention, and the preferred ones are also the same.

The monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group used in the step (1) is the same as the vinyl-based monomers (m1) to (m7) in the first invention. Is.

Among these, (m1), (m4), (m5) and (m6) are preferable from the viewpoint of solubility of the urethane prepolymer (P), and more preferable are methyl (meth) acrylate and ethyl (meth). ) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate and (meth) acrylic acid. The vinyl-based monomer (M11) used in the step (1) may be used alone or in combination of two or more kinds.

The urethane prepolymer (P) in step (1) contains an active hydrogen component (A) and an organic compound in the presence of a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. The isocyanate component (B) preferably has an equivalent ratio (isocyanate group / active hydrogen-containing group) of isocyanate groups to active hydrogen-containing groups (excluding carboxyl group, sulfo group and sulfamic acid group) of 1.01 to 3, It is preferably formed by a urethanization reaction at a ratio of 1.1 to 2.

Total weight of active hydrogen component (A) and organic isocyanate component (B) at the start of step (1) and weight of monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. The ratio [{(A) + (B)} :( M11)] is preferably 40:60 to 90:10, more preferably 50:50 to 80:20, and particularly preferably 55:45 to 75:25. is there.

The urethane prepolymerization reaction is preferably carried out at a reaction temperature of 20 to 150 ° C., more preferably 60 to 110 ° C., and a reaction time is preferably 2 to 30 hours. The urethane prepolymer preferably has 0.1 to 5% by weight of isocyanate groups.

A catalyst can be used as needed to accelerate the reaction during the urethane prepolymerization reaction. Specific examples of the catalyst include, for example, organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate, bismuth alkoxide and chelate compounds of compounds having a dicarbonyl group with bismuth), inorganic metal compounds (bismuth oxide, hydroxide). Bismuth, bismuth halide, etc.); amines (triethylamine, triethylenediamine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc.) and a combination of two or more thereof.

Also, it is preferable to use a radical scavenger in order to suppress an abnormal increase in the viscosity of the reaction system during the urethane prepolymerization reaction.

Radical scavengers include 2,6-di-t-butyl-4-methylphenol, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6 , 10-Tetra-butyldibenz [d, f] [1,3,2] dioxaphosphepine, 3-4′-hydroxy-3′-5′-di-t-butylphenyl) propionic acid-n-octadecyl , Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl ) Propionyloxy] -1,1dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4 , 4'butylidene bis (6-t-butyl-3-methylphenol), 3,6-dioxaoctamethylene = bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 4 , 4'-thiobis (2-t-butyl-5-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), thiodiethylenebis [3- (3,5-di- t-Butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) isocyanuric acid, 1,1,3-tris (2- Methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 1,3,5-trimethyl- Examples thereof include hindered phenol compounds such as 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl). The radical scavengers may be used alone or in combination of two or more.

The amount of the radical scavenger used is preferably 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on the weight of the vinyl-based monomer (M1) from the viewpoint of suppressing an abnormal increase in viscosity. ..

The step (2) in the present invention is an optional step performed between the step (1) and the step (3), and is a monofunctional vinyl having no hydroxyl group, amino group, imino group or thiol group. This is a step of adding a system monomer (M11).

In the step (1), from the viewpoint of the risk of a runaway reaction, many vinyl-based monomers (M11) cannot be used for the urethane prepolymer (P). Therefore, in the composite resin aqueous dispersion of the present invention, In some cases, it is necessary to add a vinyl-based monomer (M11) in order to bring the weight ratio of the polyurethane resin (U) and the vinyl-based resin (V) to a desired value. Step (2) is a step performed for this purpose.

The added vinyl-based monomer (M11) may be the same as or different from the vinyl-based monomer (M11) used in the step (1). The vinyl-based monomer (M11) used in the step (2) may be used alone or in combination of two or more.

Preferable examples of the vinyl-based monomer (M11) in the step (2) include the same ones as the preferable ones in the step (1).
Further, in the step (1), among the vinyl-based monomers (M11), the vinyl-based hydrocarbon (m2) is not listed as a preferred monomer because the solubility of the urethane prepolymer (P) is not so good. As the additional vinyl-based monomer (M11) in the step (2), in particular, an aromatic vinyl-based hydrocarbon having 8 to 20 carbon atoms (especially styrene) in (m2) is used from the viewpoint of mechanical strength of the dry film. It can be preferably used.

The step (3) in the present invention is a solution of the urethane prepolymer (P) obtained in the step (1) or the urethane prepolymer (P) obtained in the step (2) when the step (2) is carried out. In this step, the solution of (1) is dispersed in an aqueous medium to obtain an aqueous dispersion (α).

Examples of the aqueous medium used in the step (3) include water and a mixture of water and an organic solvent.
Examples of the organic solvent include ketone solvents (eg acetone and methyl ethyl ketone), ester solvents (eg ethyl acetate), ether solvents (eg tetrahydrofuran), amide solvents (eg N, N-dimethylformamide and N-methylpyrrolidone), Examples thereof include alcohol solvents (for example, isopropyl alcohol) and aromatic hydrocarbon solvents (for example, toluene). The organic solvent may be used alone or in combination of two or more.

When dispersing the reaction liquid in an aqueous medium, it is preferable to use a surfactant (C) from the viewpoint of dispersion stability. From the viewpoint of dispersion stability, it is preferable to use the compound (a3) having an ionic group and an active hydrogen atom as a constituent monomer of the polyurethane resin (U).

Examples of the surfactant (C) include a reactive surfactant (C1) having a radical reactive group and a non-reactive surfactant (C2), and one kind may be used alone, or a reaction may be performed. Two or more kinds may be used in combination, including the combination use of the surface active agent (C1) and the non-reactive surface active agent (C2). Among these, the reactive surfactant (C1) is preferable from the viewpoint of water resistance of the dry film.

The reactive surfactant (C1) is not particularly limited as long as it has radical reactivity, but specifically, Adecaria Soap [registered trademark, manufactured by ADEKA] SE-10N, SR-10, SR-20, SR-30, ER-20, ER-30, Aqualon [registered trademark, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] HS-10, KH-05, KH-10, KH-1025, Eleminol [registered trademark, Sanyo Chemical Industry Co., Ltd.] JS-20, Latemur [registered trademark, Kao Corporation] PD-104, PD-420, PD-430, Ionette [registered trademark, Sanyo Chemical Industry Co., Ltd. )) MO-200 and the like.

As the non-reactive surfactant (C2), nonionic surfactant (C21), anionic surfactant (C22), cationic surfactant (C23), amphoteric surfactant (C24) and other emulsion dispersions. An agent (C25) can be mentioned.

Examples of the nonionic surfactant (C21) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. Examples of the AO addition type include ethylene oxide (hereinafter abbreviated as EO) adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenol, EO adducts of nonylphenol, and EO of alkylamines having 8 to 22 carbon atoms. Examples thereof include adducts and EO adducts of poly (oxypropylene) glycol. As the polyhydric alcohol type, polyhydric (3 to 8 or higher) alcohol (C2 to C30) fatty acid (C8) To 24) esters (for example, glycerin monostearate, glycerin monooleate, sorbitan monolaurate and sorbitan monooleate) and alkyl (C4-24) poly (polymerization degree 1-10) glycosides.

Examples of the anionic surfactant (C22) include ethercarboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [sodium lauryl ether acetate and (poly) oxyethylene (additional mole number: 1 to 100) lauryl ether. Sodium acetate and the like]; sulfate ester or ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (additional mole number 1 to 100) sodium lauryl sulfate, (poly ) Oxyethylene (additional mole number 1 to 100) lauryl sulfate triethanolamine and (poly) oxyethylene (additional mole number 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; hydrocarbon group having 8 to 24 carbon atoms [Sodium dodecylbenzene sulfonate, etc.] having; sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms; phosphoric acid ester or ether having hydrocarbon group having 8 to 24 carbon atoms Phosphoric acid esters and salts thereof [sodium lauryl phosphate and sodium (poly) oxyethylene (additional mole number 1 to 100) sodium lauryl ether phosphate, etc.]; fatty acid salt having a hydrocarbon group having 8 to 24 carbon atoms [lauric acid Sodium and lauric acid triethanolamine, etc.]; acylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms [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-L-glutamate sodium, lauroylmethyl-β-alanine sodium, and the like].

Examples of the cationic surfactant (C23) include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride and lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate] and amine salts. Type [stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride and oleylamine lactate, etc.].

Examples of the amphoteric surfactant (C24) include betaine-type amphoteric surfactants [coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazole And sodium laurylhydroxysulfobetaine and lauroylamidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl phosphate] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate].

Other emulsifying dispersants (C25) include, for example, polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, and carboxyl group-containing (co) polymers such as sodium polyacrylate and US Pat. Emulsifying dispersants having urethane groups or ester groups described in the specification of 5906704 [for example, polycaprolactone polyol and polyether diol linked by polyisocyanate] and the like can be mentioned.

The amount of the surfactant (C) used is the weight of the vinyl-based monomer (M11) or the monofunctional vinyl-based monomer (M1) in the step (5) described below, from the viewpoint of water resistance and dispersion stability of the dry film. When used, it is preferably 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of (M11) and (M1).

When the compound (a3) having an ionic group and an active hydrogen atom is used as the active hydrogen component (A) in the step (1), the compound (a31) containing an anionic group and an active hydrogen atom and the cationic group and the active group The neutralizing agent used in the salt of the compound (a32) containing a hydrogen atom is, before the urethane prepolymerization reaction, during the urethane prepolymerization reaction, after the urethane prepolymerization reaction, and before the water dispersion step [step (3)]. Although it may be added at any time during or after the water dispersion step, it is preferably added before or during the water dispersion step from the viewpoint of the stability of the aqueous dispersion (α).
The temperature at which step (3) is carried out is preferably 0 to 100 ° C., and the time is preferably 1 to 180 minutes.

The step (4) in the present invention is a step of extending the urethane prepolymer (P) in the aqueous dispersion (α) obtained in the step (3) with a chain extender (E).

The chain extender (E) is the same as the chain extender (E) in the first invention, and the preferred ones are also the same.

As the chain extender (E), one type may be used alone, or two or more types may be used in combination.
The chain extender (E) can also be used as the active hydrogen component (A) in the step (1).
The temperature for carrying out step (4) is preferably 0 to 100 ° C., and the time is preferably 1 to 120 minutes.

The step (5) in the present invention is an optional step performed between the step (4) and the following step (6), and is a step of adding a monofunctional vinyl-based monomer (M1).

The vinyl-based monomer (M11) used in the step (1) needs to have no hydroxyl group, amino group, imino group or thiol group so that the ethylenically unsaturated bond group is not introduced into the polyurethane resin (U). However, as the vinyl-based monomer (M1) used in the step (5), a monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group can be used. By using these vinyl-based monomers, a hydroxyl group, an amino group, an imino group or a thiol group is introduced into the vinyl-based resin (V), the adhesion of the dry film to the substrate is improved, and the aqueous dispersion of the composite resin is improved. The mechanical strength of the dry film can be improved by using a cross-linking agent described below having reactivity with a hydroxyl group, an amino group, an imino group or a thiol group in the body.

Examples of the monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group include a hydroxyl group-containing vinyl monomer (m8), an amino group- or imino group-containing vinyl monomer (m9) in the first invention. And the thiol group-containing vinyl-based monomer (m10), and preferred ones are also the same.

As the vinyl-based monomer (M1), a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group may be used. In this case, it may be the same as or different from the vinyl-based monomer (M11) used in step (1). The vinyl-based monomer (M1) may be used alone or in combination of two or more.
The temperature for carrying out step (5) is preferably 0 to 100 ° C., and the time is preferably 1 to 180 minutes.

The step (6) in the present invention is a step of polymerizing the vinyl monomer (M11) in the aqueous dispersion (α) or the vinyl monomer (M11) and (M1) when the step (5) is carried out. ..

Examples of the polymerization initiator used in the polymerization in the step (6) include persulfate-based initiators such as sodium persulfate, potassium persulfate and ammonium persulfate; azo-based initiators such as azobisisobutyronitrile; Organic radicals such as benzoyl, cumene hydroperoxide, tert-butyl peroxybenzoate and tert-butyl hydroperoxide; hydrogen peroxide; and other general radical polymerization initiators can be used, and these can be used alone. They may be used, or two or more kinds may be mixed and used. Further, the amount of the polymerization initiator used is preferably 0.05 to 5% by weight based on the total weight of the vinyl monomers (M11) and (M1) used for the polymerization.
The required amount of these initiators may be used all at once at the start of polymerization, or may be divided and added at any time.

In polymerization, a reducing agent may be used together with the above-mentioned polymerization initiator, if necessary. Such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose and formaldehyde sulfoxylate metal salts, and reducing agents such as sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite. Examples thereof include inorganic compounds.

Further, in the polymerization, a chain transfer agent may be used if necessary. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and α-methylstyrene dimer. Be done.
Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate or the like can be used as a buffering agent, and polyvinyl alcohol, a water-soluble cellulose derivative, an alkali metal salt of polymethacrylic acid or the like can be used in an appropriate amount as a protective colloid.

The polymerization reaction is preferably carried out in the range of 20 ° C to 150 ° C, more preferably 40 ° C to 100 ° C. If the temperature is lower than 20 ° C, the polymerization rate may be slow. If the temperature exceeds 150 ° C, it may be difficult to control the polymerization reaction. The reaction time is preferably 1 minute to 50 hours. The polymerization reaction is preferably carried out in the presence of an inert gas.

The manufacturing apparatus used in steps (1) to (6) is not particularly limited, and any apparatus having a mixing / dispersing ability can be used, but from the viewpoint of temperature adjustment and mixing / dispersing ability, rotary mixing / It is preferable to use a dispersing device.
As the rotary mixing / dispersing device, for example, a mixing device having a general stirring blade such as Maxblend or a helical blade, TK Homomixer [manufactured by PRIMIX Co., Ltd.], CLEARMIX [manufactured by M Technique Co., Ltd.], fill Mix [Primix Co., Ltd.], Ultra Turrax [IKA Co., Ltd.], Ebara Milder [Ebara Corporation], Cavitron (Eurotech Co., Ltd.) and Biomixer [Nippon Seiki Co., Ltd.] Etc. are illustrated.

In the present invention, an organic solvent can be used in any of the manufacturing steps, and the solvent can be removed in the subsequent step.
The organic solvent is not particularly limited, and ketone solvents having 3 to 10 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents having 2 to 10 carbon atoms (ethyl acetate, butyl acetate, γ-butyrolactone, etc.) , Ether solvents having 4 to 10 carbon atoms (dioxane, tetrahydrofuran, ethyl cellosolve, diethylene glycol dimethyl ether, etc.), amide solvents having 3 to 10 carbon atoms (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl) -2-pyrrolidone and N-methylcaprolactam, etc.), sulfoxide solvents having 2-10 carbon atoms (dimethyl sulfoxide, etc.), alcohol solvents having 1-8 carbon atoms (methanol, ethanol, isopropyl alcohol, octanol, etc.), and carbon numbers Examples include 4 to 10 hydrocarbon solvents (cyclohexane, toluene, xylene, etc.). When an organic solvent is used, solvent removal may be performed in the subsequent step.

As described above, in the present invention, at least one of the active hydrogen component (A), the organic isocyanate component (B), and the chain extender (E) is a polyurethane resin (U Introducing a crosslinked structure into

Among the active hydrogen component (A), the organic isocyanate component (B), and the chain extender (E), the trifunctional or higher functional compound used for the above purpose is preferable as the trifunctional or higher functional compound in the first invention. Is the same as.

The weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V) in the aqueous composite resin dispersion of the present invention is dispersion stability and flexibility of the dry film, mechanical strength, From the viewpoint of flexibility, transparency and glossiness, it is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40.

The composite resin aqueous dispersion in the present invention may contain a crosslinking agent, a viscosity modifier, an antifoaming agent, an antiseptic, a weathering stabilizer, an antifreezing agent and the like, and specific examples are those in the first invention. The same applies to the preferable content.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, “part” means “part by weight”.

<Example 1> (Production method of the second invention)
In a simple pressure reactor equipped with a stirrer and a heating device, the types and amounts of active hydrogen component (A), organic isocyanate component (B), radical scavenger and vinyl monomer in step (1) shown in Table 1 ( After charging M11) and stirring at 80 ° C. for 10 hours to carry out a urethanization reaction to obtain a urethane prepolymer (P-1), the vinyl-based monomer (M11) in the step (2) is charged to homogenize by stirring. Thus, a solution of urethane prepolymer (P-1) was obtained.
According to the formulation shown in Table 2, 15.0 parts of triethylamine as a neutralizing agent and 500.0 parts of a solution of the obtained urethane prepolymer (P-1) and Eleminol JS- as a reactive surfactant (C1) were used. 20 [manufactured by Sanyo Chemical Industry Co., Ltd.] was added to 26.0 parts (solid content: 10.0 parts) to make a uniform solution, and 828.0 parts of ion-exchanged water was added thereto while stirring at 200 rpm (P- The solution of 1) was dispersed. To the obtained dispersion liquid, 4.7 parts of a 5.0 wt% aqueous solution of ethylenediamine as a chain extender (E) and 40.7 parts of a 5.0 wt% aqueous solution of diethylenetriamine were added, and a chain extension reaction was carried out at 25 ° C. The temperature was raised to 80 ° C. under a nitrogen stream, 8.0 parts of a 10% by weight aqueous solution of sodium persulfate as a polymerization initiator was added, and the mixture was polymerized at 80 ° C. for 3 hours to give a composite resin aqueous dispersion (Q-1) Obtained.

<Examples 2 to 4> (Production method of the second invention)
Using each raw material shown in Table 1, urethane prepolymers (P-2) to (P-4) solutions were produced in the same manner as in Example 1, and each raw material shown in Table 2 was used. Composite resin aqueous dispersions (Q-2) to (Q-4) were obtained in the same manner as in 1. In Example 2, the step (2) was omitted.

<Example 5> (Production method of the second invention)
A urethane prepolymer (P-5) solution was produced in the same manner as in Example 1 using each of the raw materials listed in Table 1. A solution of (P-5) was dispersed in the same manner as in Example 1 using each of the raw materials listed in Table 2, and then a chain extension reaction was performed. Then, 17.0 parts of hydroxyethyl methacrylate was added as the vinyl-based monomer (M12) in step (5), the temperature was raised to 80 ° C. under a nitrogen stream, and a 10 wt% aqueous solution of potassium persulfate as a polymerization initiator 11 0.0 parts was added and the mixture was polymerized at 80 ° C. for 3 hours to obtain an aqueous composite resin dispersion (Q-5).

<Example 6> (Production method of the second invention)
In a simple pressure reactor equipped with a stirrer and a heating device, the types and amounts of active hydrogen component (A), organic isocyanate component (B), radical scavenger, vinyl monomer in step (1) ( After charging M11) and an organic solvent and stirring at 80 ° C. for 10 hours to carry out a urethanization reaction to obtain a urethane prepolymer (P-6), the vinyl-based monomer (M11) in the step (2) is charged and stirred. By homogenizing, a solution of urethane prepolymer (P-6) was obtained.
According to the formulation shown in Table 2, 8.9 parts of triethylamine as a neutralizing agent and 500.0 parts of a solution of the obtained urethane prepolymer (P-6) and Eleminol JS- as a reactive surfactant (C1) were used. 20 [manufactured by Sanyo Chemical Industry Co., Ltd.] was added to 15.6 parts (solid content: 6.0 parts) to form a uniform solution, and 905.0 parts of ion-exchanged water was added thereto while stirring at 200 rpm (P- The solution of 6) was dispersed. 16.7 parts of a 5.0 wt% aqueous solution of diethylenetriamine as a chain extender was added to the obtained dispersion, and a chain extension reaction was carried out at 25 ° C. The temperature was raised to 80 ° C. under a nitrogen stream, 5.0 parts of a 10 wt% potassium persulfate aqueous solution as an initiator was added, and polymerization was carried out at 80 ° C. for 3 hours. Then, the organic solvent was distilled off under reduced pressure at 65 ° C. for 8 hours to obtain a composite resin aqueous dispersion (Q-6).

<Examples 7 to 9> (Production method of the second invention)
Using each raw material shown in Table 1, urethane prepolymers (P-7) to (P-9) solutions were produced in the same manner as in Example 1, and each raw material shown in Table 2 was used. Composite resin aqueous dispersions (Q-7) to (Q-9) were obtained in the same manner as in 1.

<Example 10> (Production method of (II))
A simple pressure reactor equipped with a stirrer and a heating device was charged with the active hydrogen component (A), organic isocyanate component (B), radical scavenger and organic solvent in the types and amounts shown in Table 1 at 80 ° C. A urethane reaction was carried out by stirring for a time to obtain a solution of a urethane prepolymer (P-10).
According to the formulation shown in Table 2, 7.1 parts of triethylamine as a neutralizing agent was added to 500.0 parts of the obtained solution of the urethane prepolymer (P-10) to form a uniform solution, which was then stirred at 200 rpm. 640.0 parts of ion-exchanged water was added to disperse the solution of (P-10). 95.5 parts of a 5.0 wt% aqueous solution of diethylenetriamine as a chain extender was added to the obtained dispersion, and a chain extension reaction was carried out at 25 ° C. Then, the organic solvent was distilled off under reduced pressure at 65 ° C. for 8 hours to obtain a urethane resin aqueous dispersion.
Separately, in a separable flask equipped with a dropping funnel for monomer dispersion, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, the entire amount of the urethane resin aqueous dispersion obtained was charged, and nitrogen was added. The mixture was stirred under a stream of air and heated to 70 ° C. Next, 122.5 parts of methyl methacrylate, 27.3 parts of n-butyl acrylate, 18.0 parts of Aqualon KH-1025 [Daiichi Kogyo Seiyaku Co., Ltd.] as a reactive surfactant (C1) (solid content: 4.5 parts) and 184.5 parts of ion-exchanged water were prepared and charged into a dropping funnel for monomer dispersion, and 5.0 parts of a 10 wt% potassium persulfate aqueous solution as an initiator solution was prepared. The monomer dispersion liquid and the initiator solution were added dropwise at a constant rate over 3 hours while the temperature in the reaction system was maintained at 70 ± 2 ° C. After that, stirring was continued at the same temperature for 90 minutes and then cooled to room temperature to obtain an aqueous composite resin dispersion (Q-10).

<Examples 11 and 12> (Production method of (I))
Using each raw material shown in Table 1, urethane prepolymer (P-11) and (P-12) solutions were produced in the same manner as in Example 1, and each raw material shown in Table 2 was used. Aqueous composite resin dispersions (Q-11) and (Q-12) were obtained in the same manner as in 1.

<Comparative Example 1>
A simple pressure reactor equipped with a stirrer and a heating device was charged with the active hydrogen component (A), organic isocyanate component (B), radical scavenger and organic solvent in the types and amounts shown in Table 1 at 80 ° C. A urethane reaction was carried out by stirring for a time to obtain a solution of urethane prepolymer (P'-1).
According to the formulation shown in Table 2, 8.9 parts of triethylamine as a neutralizing agent was added to 500.0 parts of the obtained solution of the urethane prepolymer (P′-1) to form a uniform solution, which was then stirred at 200 rpm. While adding 563.0 parts of ion-exchanged water, the solution of (P'-1) was dispersed. After adding 35.7 parts of a 5.0 wt% aqueous solution of diethylenetriamine as a chain extender to the obtained dispersion liquid and carrying out a chain extension reaction at 25 ° C, the organic solvent was distilled off under reduced pressure at 65 ° C for 8 hours. After that, an aqueous polyurethane resin dispersion (1) was obtained.
Separately, in a separable flask equipped with a dropping funnel for monomer dispersion, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer and a nitrogen introducing tube, 120.8 parts of ion-exchanged water and a reactive surfactant. Eleminol JS-20 (manufactured by Sanyo Chemical Industry Co., Ltd.) 1.3 parts (solid content: 0.5 part) as (C1) was charged, and the mixture was stirred under a nitrogen stream and heated to 70 ° C.
Next, 226.4 parts of ion-exchanged water, Eleminol JS-20 [manufactured by Sanyo Chemical Industry Co., Ltd.] as a reactive surfactant (C1), 24.7 parts (solid content: 9.5 parts), methyl methacrylate. A monomer dispersion liquid containing 301.5 parts, 143.7 parts of n-butyl acrylate, 50.0 parts of styrene and 7.7 parts of methacrylic acid was prepared and charged into a dropping funnel for the monomer dispersion liquid. Parts were added to a separable flask.
Next, 8.0 parts of a 10% by weight aqueous solution of sodium persulfate as an initiator was added to initiate polymerization, and the temperature of the reaction system was maintained at 70 ± 2 ° C. while maintaining the remaining monomer dispersion and initiator. The solution was added dropwise at a constant rate over 3 hours. After that, stirring was continued at the same temperature for 90 minutes and then cooled to room temperature to obtain an aqueous vinyl resin dispersion (1).
100 parts of the obtained polyurethane resin aqueous dispersion (1) and 100 parts of the vinyl resin aqueous dispersion (1) were uniformly mixed to obtain a composite resin aqueous dispersion (Q'-1).
The composite resin aqueous dispersion (Q'-1) of Comparative Example 1 was a mixture of the polyurethane resin aqueous dispersion (1) and the vinyl resin aqueous dispersion (1), and was produced by the production method of the present invention. Table 1 and Table 2 show the types of raw materials and the amounts used, although not necessarily.

<Comparative Examples 2 to 4>
A solution of urethane prepolymers (P'-2) to (P'-4) was produced in the same manner as in Example 1 using each raw material shown in Table 1, and each raw material shown in Table 2 was used. In the same manner as in Example 1, composite resin aqueous dispersions (Q′-2) to (Q′-4) were obtained.

The compositions of the raw materials represented by trade names in Table 1 are as follows.
-Nipporan 980R: polyhexamethylene carbonate diol with Mn = 2,000 [manufactured by Nippon Polyurethane Industry Co., Ltd.]
Kuraray polyol C-3090 [poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol with Mn = 3,000] [manufactured by Kuraray Co., Ltd.]
Duranol G4672: poly (tetramethylene / hexamethylene) carbonate diol with Mn = 2,000 [manufactured by Asahi Kasei Chemicals Corporation]
PTMG2000: poly (oxytetramethylene) glycol with Mn = 2,000 [manufactured by Mitsubishi Chemical Corporation]
-PTMG3000: poly (oxytetramethylene) glycol with Mn = 3,000 [manufactured by Mitsubishi Chemical Corporation]
Kuraray polyol P-2010: poly-3-methyl-1,5-pentane adipate diol with Mn = 2,000 [manufactured by Kuraray Co., Ltd.]
Duranate TKA-100: isocyanurate of hexamethylene diisocyanate [manufactured by Asahi Kasei Chemicals Corporation]
IRGANOX 1010: pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] [manufactured by BASF Japan Ltd.]
IRGANOX 245: 3,6-dioxaoctamethylene = bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] [manufactured by BASF Japan Ltd.]

Using the composite resin aqueous dispersions (Q-1) to (Q-12) of Examples 1 to 12 and the composite resin aqueous dispersions (Q'-1) to (Q'-4) of Comparative Examples 1 to 4, Physical properties of the dry film measured by the following methods (gel fraction with respect to DMF, storage modulus E ′ at 25 ° C., 100% stress, breaking strength and breaking elongation, ethanol swelling ratio, König hardness, 180 ° C. bending test), and Table 3 shows the evaluation results (haze and gloss) of the coated product.

<Weight ratio of bifunctional or higher vinyl monomer (M2) and monofunctional vinyl monomer (M12 ′) covalently bonded to polyurethane resin (U)>
○ Measurement of Hydroxyl Group of Vinyl Resin (V) The hydroxyl group value was determined according to JIS K1557-1.
Pyrolysis Gas Chromatography / Mass Spectroscopy Using the dry film obtained in the following "Production of dry film", all vinyl-based monomers (constituting vinyl resin (V) ( The weight ratio of each monomer of M) was determined.
[Pyrolysis gas chromatography mass spectrometry conditions]
Equipment: GCMS QP-2010PLUS [Shimadzu Corporation]
Column: Ultra Alloy-5 [manufactured by Frontier Lab. Ltd.]
Temperature: 480 ° C
From the results of the obtained hydroxyl value and the result of the thermal decomposition gas chromatography mass spectrometry, the monofunctional vinyl-based monomer (M12 ′) covalently bonded to the bifunctional or higher-functional vinyl-based monomers (M2) and (U). Was calculated.

<Physical properties of dry film>
[Production of dry film]
A polypropylene resin mold was gently poured into a polypropylene resin mold to have a solid content concentration of 20% by weight so that the film thickness after drying would be about 200 μm, and the mixture was spread so as to be uniform throughout, then at 25 ° C. for 24 hours. After standing still, it was dried at 105 ° C. for 3 hours using a circulating air drier, and further dried under reduced pressure at 105 ° C. and a pressure of 1.3 kPa for 1 hour to obtain a dried film.

[Measurement of gel fraction]
The sample obtained by cutting out the dried film obtained above to about 0.035 to 0.045 g was put in 20 ml of DMF and immersed at 23 ° C. for 24 hours. After the dipping, the DMF containing the sample was filtered using a tetrafluoroethylene resin (PTFE) filter (trade name: TOLAST Disc GLCTD-PTFE2522, manufactured by Shimadzu GC). Further, the above filter and the residue were dried at 105 ° C. for 3 hours and then cooled, and the “total weight of the filter and the residue after DMF immersion” was measured. The "gel weight before immersion in DMF", "weight of filter", and "total weight of filter and residue after immersion in DMF" were substituted into the following formula (1) to determine the gel fraction.
Gel fraction (%) = (“total weight of filter and residue after immersion in DMF” − “weight of filter”) / “weight of coating before immersion in DMF” × 100 (1)

[Storage elastic modulus E ']
The dry film obtained above was measured at a frequency of 11 Hz using a storage elastic modulus measuring device [Rheogel E4000 {manufactured by UBM Co., Ltd.]].

[100% stress, breaking strength and breaking elongation]
Based on JIS K6251, the dry film obtained above was used as a dumbbell-shaped No. 3 test piece, and an autograph [Shimadzu Corporation's "AGS-500D"] was used to pull at a speed of 500 mm / min. 100% stress, breaking strength and breaking elongation were measured. The composite resin aqueous dispersion obtained in Comparative Example 4 had a breaking elongation of less than 100%, so 100% stress could not be measured.

[Ethanol swelling rate]
The dried film obtained above was cut into 1 cm × 4 cm, immersed in ethanol, and allowed to stand at 25 ° C. for 24 hours. After that, the immersed film was taken out, and the ethanol adhering to the surface of the film was wiped off with a filter paper, and the “weight of the film after ethanol immersion” was measured. The film after immersion in ethanol was dried at 130 ° C. for 45 minutes, and the “weight of the film after drying” was measured. The swelling ratio of ethanol was calculated by the following formula (4).
Ethanol swelling rate (%) = (“weight of film after immersion in ethanol” − “weight of film after drying”) / “weight of film after drying” × 100 (4)

[König hardness]
The dry film obtained above was measured by a Pendrum hardness meter [manufactured by BYK Gardner Co., Ltd. {Pendulum Hardness Tester}] using a König-type pendulum according to ASTM D4366. The larger the numerical value of the measurement result, the higher the hardness.

[180 degree bending test]
The 180 ° bending test was repeated 10 times for the dried film obtained above, and the presence or absence of cracks was visually confirmed.

<Evaluation of coated objects>
[Haze]
The composite resin aqueous dispersion was applied onto a polyethylene terephthalate film (Lumirror L-38T60 [manufactured by Toray Industries, Inc.]) with a bar coater so that the film thickness after drying would be 25 μm, and heated at 105 ° C. for 60 minutes for coating. I made things. Based on JIS-K7136, the haze of the coated article was measured using a total light transmittance measuring device [trade name "haze-gardual" BYK gardner Co., Ltd.].

[Glossiness]
The composite resin aqueous dispersion was applied onto a polyethylene terephthalate film (Lumirror L-38T60 [manufactured by Toray Industries, Inc.]) with a bar coater so that the film thickness after drying would be 25 μm, and heated at 105 ° C. for 60 minutes for coating. I made things. The 60 ° glossiness of the coated surface was measured by a gloss meter (manufactured by BYK).

From the results of Table 3, the gel fraction is 35 to 100%, the elongation at break is 200 to 1,000%, and the storage elastic modulus E ′ at 25 ° C. is 100 to 3,000 MPa, so that the ethanol swelling ratio is 113. It can be seen that the storage stability is low when it is used as a paint or ink, which is as low as 0.1% or less. Moreover, the result of the bending test is also excellent, and it is understood that it is excellent in flexibility and flexibility. Further, it can be seen that the breaking strength is as high as 31 MPa or more and the König hardness is as high as 15 times or more, which is excellent in hardness and mechanical strength. Further, it can be seen that the haze is as small as 1.1% or less and the glossiness is as large as 78 or more, which is excellent in transparency and glossiness.

The composite resin aqueous dispersion of the present invention and the composite resin aqueous dispersion obtained by the production method of the present invention have constant quality, and storage stability, hardness, flexibility, mechanical strength, water resistance, and resistance Due to its excellent properties such as solvent resistance, transparency and gloss, paints, coating agents (anti-rust coating agents, waterproof coating agents, water repellent coating agents, anti-fouling coating agents, etc.), adhesives, textile processing agents (pigment printing) Binders, non-woven fabric binders, reinforcing fiber sizing agents, antibacterial agent binders, artificial leather / synthetic leather raw materials, etc.), paper treatment agents, inks, etc., especially water-based paints, water-based anticorrosion coatings It can be suitably used as a composite resin aqueous dispersion for an agent, an aqueous fiber processing agent and an aqueous adhesive.

Claims

A composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particle, wherein the polyurethane resin (U) is an active hydrogen component (A) and an organic isocyanate component. (B) and a chain extender (E), wherein at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) contains a trifunctional or higher functional compound. Then, the film obtained by drying the composite resin aqueous dispersion satisfies all of the following (1) to (3):
(1) The gel fraction relative to N, N-dimethylformamide is 35 to 100%;
(2) The breaking elongation is 200 to 1,000%;
(3) The storage elastic modulus E ′ at 25 ° C. is 100 to 3,000 MPa.
The composite resin aqueous solution according to claim 1, wherein the tri- or more-functional compound in the active hydrogen component (A) is a trihydric alcohol having 3 to 20 carbon atoms, a 4 to 8 alcohol having 5 to 20 carbon atoms and / or a saccharide. Dispersion.
The composite resin aqueous dispersion according to claim 1 or 2, wherein the trifunctional or higher functional compound in the organic isocyanate component (B) is an isocyanurate body of hexamethylene diisocyanate and / or an isocyanurate body of isophorone diisocyanate.
The tri- or higher-functional compound in the chain extender (E) is a polyalkylene polyamine having an alkylene group having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms. The composite resin aqueous dispersion described.
5. The weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V) in the aqueous composite resin dispersion is 30:70 to 70:30. The composite resin aqueous dispersion according to item 1.
Monomers having a hydroxyl group, an amino group, an imino group or a thiol group covalently bonded to a bifunctional or higher functional vinyl monomer (M2) and a urethane resin (U) among the monomers constituting the vinyl resin (V). The total [(M2) + (M12 ')] of the functional vinyl monomers (M12') is 4% by weight or less based on the total weight of the monomers constituting the vinyl resin (V). 6. The composite resin aqueous dispersion according to any one of 1 to 5.
A method for producing an aqueous composite resin dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particle, comprising the following steps (1) to (6): A method for producing a composite resin aqueous dispersion, wherein at least one of a hydrogen component (A), an organic isocyanate component (B) and a chain extender (E) contains a trifunctional or higher functional compound.
Step (1): reacting the active hydrogen component (A) and the organic isocyanate component (B) in the presence of a monofunctional vinyl-based monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. To produce a urethane prepolymer (P) having an isocyanate group at the end;
Step (2): an optional step carried out between the step (1) and the following step (3), which is a monofunctional vinyl-based monomer having no hydroxyl group, amino group, imino group or thiol group. A step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous when the step (2) is carried out. Dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): Step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with a chain extender (E);
Step (5): an optional step performed between the step (4) and the following step (6), in which a monofunctional vinyl-based monomer (M1) is added;
Step (6): a step of polymerizing the vinyl-based monomer (M11) in the aqueous dispersion (α) or the vinyl-based monomer (M11) and the monofunctional vinyl-based monomer (M1) when the step (5) is performed. ..
The production method according to claim 7, wherein the trifunctional or higher functional compound in the active hydrogen component (A) is a trihydric alcohol having 3 to 20 carbon atoms, a 4 to 8hydric alcohol having 5 to 20 carbon atoms, and / or a saccharide.
The method according to claim 7 or 8, wherein the tri- or more-functional compound in the organic isocyanate component (B) is an isocyanurate body of hexamethylene diisocyanate and / or an isocyanurate body of isophorone diisocyanate.
10. The trifunctional or higher functional compound in the chain extender (E) is a polyalkylene polyamine having an alkylene group having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms. The manufacturing method described.
Total weight of active hydrogen component (A) and organic isocyanate component (B) at the start of step (1) and weight of monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. The production method according to any one of claims 7 to 10, wherein the ratio [{(A) + (B)} :( M11)] is 40:60 to 90:10.
The production method according to any one of claims 7 to 11, wherein the step (1) is performed in the presence of a radical scavenger.
13. The weight ratio [(U) :( V)] of the polyurethane resin (U) and the vinyl resin (V) in the composite resin aqueous dispersion is 30:70 to 70:30. The method according to item 1.