JPWO2020105569A1 - Method for producing composite resin aqueous dispersion and composite resin aqueous dispersion - Google Patents

Abstract

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 particles, wherein the polyurethane resin (U) is an active hydrogen component (A). , A reaction product of the organic isocyanate component (B) and the chain extender (E), and at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E) is trifunctional or higher. The film containing the compound of the above and the dried composite resin aqueous dispersion is a composite resin aqueous dispersion satisfying all of the following (1) to (3): (1) Gel content with respect to N, N-dimethylformamide. The rate is 35 to 100%; (2) the elongation at break is 200 to 1,000%; (3) the storage elasticity E'at 25 ° C. is 100 to 3,000 MPa.

Description

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 particles, and a method for producing the same.

In recent years, aqueous dispersions of resins have been widely used from the viewpoint of environmental problems and safety. Among them, an acrylic resin aqueous dispersion is generally used as a coating agent or the like that 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, so a method of using an acrylic resin aqueous dispersion and a polyurethane resin aqueous dispersion in combination has been proposed as a method for improving the flexibility. (See, for example, Patent Document 1). However, since the compatibility between the acrylic resin and the polyurethane resin is generally not good, when the acrylic resin aqueous dispersion and the polyurethane resin aqueous dispersion are used in combination, the flexibility, mechanical strength, flexibility, transparency and transparency of the film are improved. There is a problem that performance such as glossiness is deteriorated.

Japanese Unexamined Patent Publication No. 06-192616

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

The present inventors have arrived at the present invention as a result of diligent 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) according to the first invention in the same particles, wherein the polyurethane resin (U) is used. Is a reaction product of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E), and is among the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E). At least one of them contains a trifunctional or higher functional compound, and the film obtained by drying the composite resin aqueous dispersion is a composite resin aqueous dispersion that satisfies all of the following (1) to (3):
(1) The gel fraction with respect to N, N-dimethylformamide is 35 to 100%;
(2) The elongation at break is 200 to 1,000%;
(3) The storage elastic modulus E'at 25 ° C. is 100 to 3,000 MPa.

The second invention is a method for producing an aqueous dispersion of a composite resin containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particles, according to the following step (1). A method for producing an aqueous dispersion of a composite resin containing ~ (6) and at least one of an active hydrogen component (A), an organic isocyanate component (B) and a chain extender (E) containing a trifunctional or higher functional compound. Is.
Step (1): The active hydrogen component (A) and the organic isocyanate component (B) are reacted in the presence of a monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. A step of producing a urethane prepolymer (P) having an isocyanate group at the terminal;
Step (2): A monofunctional vinyl-based monomer that is an arbitrary step carried out between the step (1) and the following step (3) and has neither a hydroxyl group, an amino group, an imino group, or a thiol group. Step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or, when the step (2) is carried out, the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous. Step of dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): A step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with the chain extender (E);
Step (5): An arbitrary 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 carried out. ..

The composite resin aqueous dispersion of the present invention is excellent in flexibility, mechanical strength, storage stability, flexibility, hardness, transparency and glossiness, and according to the production method of the present invention, flexibility and mechanical A composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin having excellent strength, storage stability, flexibility, hardness, transparency and glossiness in the same particles 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 particles, and the polyurethane resin (U) is It is a reaction product of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E), and is at least one of the active hydrogen component (A), the organic isocyanate component (B) and the chain extender (E). One type contains a trifunctional or higher functional compound, and the film obtained by drying the composite resin aqueous dispersion is a composite resin aqueous dispersion that satisfies all of the following (1) to (3):
(1) The gel fraction with respect to N, N-dimethylformamide is 35 to 100%;
(2) The elongation at break 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).
The active hydrogen component (A) includes a high molecular weight 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 of less than 300, an ionic group and activity. Examples thereof include a compound having a hydrogen atom (a3) and a reaction terminator (a4).

Examples of the polymer polyol (a1) having Mn of 300 or more include polyester polyols, polyether polyols, polyether ester polyols, castor oil-based polyols, 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 a condensed polyester polyol, a polylactone polyol, a polycarbonate polyol, and the like.

Condensation type polyester polyols 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 grade (acid anhydride, lower grade). Carbon number 1 to 4) Alkyl ester, acid halide, etc.] can be mentioned.

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

The AO having 2 to 12 carbon atoms in the present invention includes ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran and 3-methyl. Examples thereof include tetrahydrofuran, styrene oxide, α-olefin oxide and epichlorohydrin.

Examples of the polyhydric alcohol having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5- Directs of pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc. Chain alcohols; 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2- Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-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]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, 1,4-cycloheptandiol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane and 2 , 2-Bis (4-hydroxycyclohexyl) propane, etc.]; Aromatic aliphatic dihydric alcohols with 8 to 20 carbon atoms [m- or p-xylylenediol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, etc. ]; Trihydric alcohols with 3 to 20 carbon atoms [aliphatic triols (glycerin, trimethylolpropane, etc.), etc.]; 4 to 8-valent alcohols with 5 to 20 carbon atoms [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, etc.) , Diglycerin and dipentaerythritol, etc.); Sugars (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof)]; and the like.

Examples of the polyvalent carboxylic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, fumaric acid and Maleic acid, etc.), alicyclic dicarboxylic acid (dimeric 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 (trimellitic acid, pyromellitic acid, etc.), their anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), these Acid halides (dichloroide of adipate, etc.), these low molecular weight alkyl esters (dimethyl succinate, dimethyl phthalate, etc.), and their combined use can be mentioned. Of these, preferred are aliphatic dicarboxylic acids and ester-forming derivatives thereof. One type of polyvalent carboxylic acid may be used alone, or two or more types may be used in combination.

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) using the polyhydric alcohol having 2 to 20 carbon atoms as an initiator -Caprolactone, η-caprilolactone, 11-undecanolactone, 12-dodecanoid, etc.) are ring-opened and polymerized. One type of lactone monomer may be used alone, or two or more types may be used in combination.

As the polycarbonate polyol, one or more of the above polyhydric alcohols having 2 to 20 carbon atoms (preferably aliphatic dihydric alcohols having 3 to 9 carbon atoms, more preferably 4 to 6 carbon atoms) and low molecules. While dealcoholizing from a carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms of an alkyl group, 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). Examples thereof include polycarbonate polyols produced by condensation.

Examples of the polyether polyol having a Mn of 300 or more include the compound obtained by adding AO having 2 to 12 carbon atoms to the above-mentioned Mn or a small molecule 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, and in the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a combination system thereof may be used.

Addition of AO to Mn or a low molecular weight polyol (a2) having a chemical formula of less than 300 is carried out, for example, in the absence of a catalyst or in the presence of a catalyst (alkaline catalyst, amine-based catalyst, acidic catalyst, etc.) (particularly in the latter half of the AO addition). It is performed in one step or multiple steps under normal pressure or pressurization.

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 copolymerized polyol and the like. Of these, poly (oxytetramethylene) polyol is preferable from the viewpoint of tensile strength and elongation.

Examples of the polyether ester polyol having a Mn of 300 or more include one or more of the above-mentioned polyether polyols and one kind of polyvalent carboxylic acids having 2 to 20 carbon atoms or ester-forming derivatives thereof exemplified as raw materials for the above-mentioned condensed polyester polyols. Examples thereof include those obtained by polycondensing the above.

Examples of the castor oil-based polyol include polyester polyols (mono- or diglyceride of castor oil fatty acid, castor oil fatty acid and trimethylol) derived from castor oil, castor oil fatty acid and the above polyhydric alcohol or polyoxyalkylene polyol having 2 to 20 carbon atoms. Mono-, di- or triester from propane and mono- or diester from castor oil fatty acid and polyoxypropylene glycol), castor oil with AO of 2 to 12 carbon atoms added, and two of these Examples thereof include the above mixtures.

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 under the following conditions, for example.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: 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. The compound (a3) may be used alone or in combination of two or more.

Examples of the compound (a31) containing an anionic group and an active hydrogen atom include a compound having 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-dimethylolheptanic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (eg glycine, alanine and valine) ) Etc.], a compound containing a sulfonic acid group as an anionic group, having a hydroxyl group as an active hydrogen atom, and having 2 to 16 carbon atoms [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and Sulfoisophthalic acid di (ethylene glycol) ester, etc.], a compound containing sulfamic acid group as an anionic group, having a hydroxyl group as an active hydrogen atom, and having 2 to 10 carbon atoms [N, N-bis (2-hydroxyl) Ethyl) sulfamic acid, etc.] and salts obtained by neutralizing these compounds 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, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (sodium hydroxide, potassium hydroxide). And lithium hydroxide, etc.).
Examples of the amine compound 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 and methylpropanolamine. Examples thereof include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

The neutralizing agent used for the salt of the compound (a31) containing an anionic group and an active hydrogen atom is a vapor pressure at 25 ° C. from the viewpoint of the dryness of the resulting composite resin aqueous dispersion and the water resistance of the dry film. Compounds with a high value are suitable. From this point of view, the neutralizing agents used for the salt of the compound (a31) containing an anionic group and an active hydrogen atom include ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine. Is preferable.

Among the compounds (a31) containing an anionic group and an active hydrogen atom, 2,2-dimethylolpropionic acid and 2,2-dimethylolpropionic acid are preferable from the viewpoint of the mechanical strength of the obtained film and the 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 neutralized with ammonia or an amine compound having 1 to 20 carbon atoms. It is salt.

The compound (a32) containing a cationic group and an active hydrogen atom includes a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, for example, 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.], etc.] can be mentioned as a salt obtained by neutralizing a compound such as] with a neutralizing agent.

Examples of the neutralizing agent used for the salt of the compound (a32) containing a cationic group and an active hydrogen atom include monocarboxylic acids having 1 to 10 carbon atoms (formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, and the like. Examples thereof include dimethyl sulfate, methyl chloride and benzyl chloride.
The neutralizing agent used for the salt of the compound (a32) containing a cationic group and an active hydrogen atom is a vapor pressure at 25 ° C. from the viewpoint of the dryness of the resulting composite resin aqueous dispersion and the water resistance of the dry film. Compounds with a high value are suitable. From this point of view, as the neutralizing agent used for the compound (a32) containing a cationic group and an active hydrogen atom, monocarboxylic acid and carbonic acid having 1 to 10 carbon atoms are preferable, and formic acid and carbonic acid are more preferable. Carbonic acid is particularly preferable.

Examples of the reaction terminator (a4) include monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.) and monoamines having 1 to 20 carbon atoms. (Mono or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and mono or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine) can be mentioned.

The organic isocyanate component (B) in the present invention includes an aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 8 to 26 carbon atoms, and an aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms. ), An alicyclic polyisocyanate having 8 to 18 carbon atoms (b3), an aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms (b4), and a modified product (b5) of these organic polyisocyanates.

Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is referred to as TDI). (Omitted), crude TDI, 4,4'-or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4'-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenyl Examples thereof include methanetriisocyanate and m- or p-isocyanatophenylsulfonylisocyanate.

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-undecantryisocyanate, and 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-Diisocyanatohexanoate can 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), cyclohexene diisocyanate, and the like. Methylcyclohexylene diisocyanate, bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate can be mentioned.

Examples of the aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

Examples of the modified product (b5) of the organic polyisocyanate of (b1) to (b4) include urethane group, carbodiimide group, alohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone of the polyisocyanate. Group-containing modified products [for example, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, HDI biuret, HDI isocyanurate, and IPDI isocyanurate] can be mentioned.

Of these, from the viewpoint of weather resistance, aliphatic polyisocyanates having 4 to 22 carbon atoms (b2), alicyclic polyisocyanates having 8 to 18 carbon atoms (b3) and modified products thereof are preferable, and more preferable are them. 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 of less than 500.
Examples of Mn or polyamine compounds having a chemical formula of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylenediamines 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 alkylene groups such as min, pentaethierene hexamine and hexaethylene heptamin {poly (n = 2 to 6) alkylene (2 carbon atoms) ~ 6) Poly (n = 3-7) amine}, etc.], alicyclic polyamines with 6 to 20 carbon atoms (1,3- or 1,4-diaminocyclohexane, 4,4'-or 2,4'- Dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines with 6 to 20 carbon atoms (1,3- or 1,4-phenylenediamine, 2,4- or 2,6-tolylene diamine, 4,4'-or 2,4'-Methylenebisaniline, etc.), aromatic aliphatic polyamines having 8 to 20 carbon atoms [1,3- or 1,4-xylylene diamine, 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 its Examples thereof include derivatives (for example, dibasic acid dihydrazide such as adipate dihydrazide) and amino alcohols having 2 to 20 carbon atoms (for example, 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 trifunctional or higher. It is a reaction product of the raw material contained. In the present invention, a crosslinked structure is formed on the polyurethane resin (U) 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). Introduce.

Among the active hydrogen components (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 of less than 300. 4 to 8-valent alcohols and saccharides having 5 to 20 carbon atoms are more preferable, trihydric alcohols having 3 to 20 carbon atoms are particularly preferable, and trimethylolpropane is particularly preferable.

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

Among the chain extenders (E), the trifunctional or higher functional compound used for the above purpose is preferably a polyalkylene polyamine [poly (n) having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms in the alkylene group. = 2 to 6) alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amine], more preferably 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) {a monofunctional vinyl having neither a hydroxyl group, an amino group, an imino group or a thiol group. Examples thereof include a monofunctional vinyl monomer (M12) having a system monomer (M11), a hydroxyl group, an amino group, an imino group or a thiol group}, and a bifunctional or higher functional vinyl monomer (M2). One type may be used, or two or more types may be used in combination.
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-based monomer (m1):
Esters of unsaturated alcohols or hydroxystyrenes with monocarboxylic acids having 1 to 12 carbon atoms, such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, isopropenyl acetate, methyl-4-vinylbenzoate, vinylmethoxyacetate, Vinyl benzoate and acetoxystyrene; unsaturated carboxylic acid alcohol (1 to 30 carbon atoms) esters 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, ecocil (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 straight or branched groups with 2-8 carbon atoms) and di (cyclo) alkyl malee. Alate (two alkyl groups are linear or branched groups with 2 to 8 carbon atoms); polyoxyalkylene (2 to 4 carbon atoms) monool unsaturated carboxylic acid esters with a degree of polymerization of 5 to 50. For example, 10 mol additive (meth) acrylate of methyl alcohol ethylene oxide and 30 molar additive (meth) acrylate of lauryl alcohol ethylene oxide.

(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, for example, cyclohexene and the like.
(2-3) Aromatic vinyl hydrocarbons (8 to 20 carbon atoms): Styrene and its hydrocarbyl (alkyl and / or cycloalkyl) substituents such as α-methylstyrene, vinyltoluene, 2,4-dimethyl. Styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene and vinyl naphthalene.

(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-epoxide. An alicyclic epoxy group-containing vinyl monomer having 6 to 20 carbon atoms such as norbornane.

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

(5) Sulfonate-containing vinyl monomer (m5):
Alken sulfonic acid having 2 to 14 carbon atoms, for example vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid; styrene sulfonic acid and an alkyl substituent having 1 to 24 carbon atoms, for example, α-methylstyrene sulfonic acid, etc. Sulfo (hydroxy) alkyl (1-8 carbon atoms)-(meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyl Oxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid; alkyl (3-18 carbon atoms) (meth) allyl sulfosulfonic acid Acid ester etc.

(6) Keto group-containing vinyl monomer (m6):
Any monomer having a double bond polymerizable with 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 for example, it can be used. Diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, (meth) acrylic oxyalkylpropanal and diacetone (meth) acrylamide.

(7) Aldehyde group-containing vinyl monomer (m7):
Monomers having at least one aldehyde group in the molecule and a polymerizable double bond can be used without particular limitation, and for example, acrolein, formylstyrene, (meth) acrylamide pivalinaldehyde and acetoacetoxyethyl (meth). Meta) acrylate.

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

(8) Examples of the hydroxyl group-containing vinyl-based monomer (m8) include alkenols having 2 to 12 carbon atoms, such as vinyl alcohol, (meth) allyl alcohol, 1-butene-3-ol and 2-butene-1-ol; 4-12 alkene diols such as 2-butene-1,4-diol; hydroxyl group-containing aromatic vinyl monomers such as hydroxystyrene; hydroxyalkyl (meth) acrylates having 5-8 carbon atoms such as hydroxyethyl (meth) acrylate and Hydroxypropyl (meth) acrylate; alkenyl ethers having 3 to 30 carbon atoms, such as 2-hydroxyethylpropenyl ether and allyl ether of sucrose, and the like can be mentioned.

(9) Examples of the amino group- or imino group-containing vinyl-based monomer (m9) include aminoalkyl (meth) acrylates having 5 to 20 carbon atoms, such as 7-amino-3,7-dimethyloctyl (meth) acrylate and monomethylaminoethyl. (Meta) acrylate, t-butylaminoethyl (meth) acrylate, t-octylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc .; N- with 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 include meta) 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-based monomer (m10) include (meth) allyl mercaptan and a (meth) acrylic acid ester having a thiol group [ethylene sulfide adduct to the hydroxyl group-containing vinyl-based monomer (m8) {2- (2-Mercaptoethoxy) ethyl (meth) acrylate, etc.} and ethylene sulfide adduct to (meth) acrylic acid {2-mercaptoethyl (meth) acrylate, etc.}, etc.] 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, triethiolenglucol 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- (Meta) acryloyloxyethoxy) phenyl] fluorene, tri (meth) acrylate ethoxylated isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, Trimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Meta) acrylate, dipentaerythritol poly (meth) acrylate, tripentaerythritol poly (meth) acrylate, polypentaerythritol poly (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecanedimethanol 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 a bifunctional or higher functional vinyl monomer (M2) and a 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 preferable, more preferably 3% by weight or less, and particularly preferably 2% by weight or less.
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 monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group in the vinyl monomer (M) constituting the vinyl resin (V) is reduced, or the urethane resin is used. After producing (U), a monofunctional vinyl monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group may be used at a stage where there are very few or almost no isocyanate groups remaining.
The weight ratio of the bifunctional or higher functional vinyl monomer (M2) and the monofunctional vinyl monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group can be determined by pyrolysis gas chromatograph mass spectrometry. can. The weight ratio of the monofunctional vinyl monomer (M12') having a hydroxyl group, an amino group, an imino group or a thiol group "covalently bonded to the urethane resin (U)" is based on JIS K1557-1. Analyzed hydroxyl group value, total amine value analyzed according to JIS K1557-7, thiol group content determined by DTNB method using "Redox Assay Thiol Quantification Kit" manufactured by Metallogenix Co., Ltd., and thermal decomposition gas chromatograph mass analysis From the molecular weight of (M12) qualified 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 "not bonded to the urethane resin (U)" was determined, and the weight ratio of (M12) was determined. It can be obtained by subtracting from the weight ratio.
Specifically, as a thermal decomposition gas chromatograph mass analysis method, a composition containing a bifunctional or higher functional vinyl monomer (M2) and / or a monofunctional vinyl 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 thermal decomposition gas chromatograph mass analysis method, and a bifunctional or higher-functional vinyl-based monomer (M2) and / or a monofunctional vinyl having a hydroxyl group, an amino group, an imino group or a thiol group is used. Bifunctional or higher functional vinyl monomer (M2) and / or hydroxyl group, amino group in the thermal decomposition gas chromatograph mass analysis method of the resin whose composition is to be analyzed using the calibration line prepared from the integrated value of the peak of the system monomer (M12). From the integrated value of the peak of a 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 (M2) having a hydroxyl group, an amino group, an imino group or a thiol group The weight ratio of the vinyl-based monomer (M12) can be calculated.
In the present invention, the weight ratio of the monofunctional vinyl-based 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-based 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 aqueous dispersion of the composite resin in the present invention is the dispersion stability, the flexibility of the dry film, and the 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 (for example, acetone and methyl ethyl ketone), ester solvents (for example, ethyl acetate), ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethylformamide and N-methylpyrrolidone), and the like. Examples thereof include alcohol-based solvents (for example, isopropyl alcohol) and aromatic hydrocarbon-based solvents (for example, toluene). One type of organic solvent may be used alone, or two or more types may be used in combination.

The composite resin aqueous dispersion in the present invention can contain a cross-linking agent, a viscosity modifier, a defoaming agent, a preservative, a weather-resistant stabilizer, an antifreeze agent and the like.

Examples of the cross-linking agent include water-soluble or water-dispersible compounds containing two or more functional groups in the molecule capable of reacting with the reactive functional groups of the polyurethane resin (U) and the vinyl-based 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 cross-linking 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 and the like can be used as the cross-linking agent.
The cross-linking agent may be used alone or in combination of two or more. The amount of these cross-linking 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).

Viscosity adjusting agents include thickeners such as inorganic viscosity adjusting agents (sodium silicate and bentonite), cellulose viscosity adjusting agents (methyl cellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), and protein-based viscosities. Adjusters (casein, casein soda, ammonium casein, etc.), acrylics (sodium polyacrylate with Mn of 20,000 or more, ammonium polyacrylate, etc.) and vinyl viscosity adjusters (polyvinyl alcohol with Mn of 20,000 or more) Etc.).
Examples of the defoaming agent include long-chain alcohols (octyl alcohol and the like), sorbitan derivatives (sorbitan monooleate and the like) and silicone oils (polymethylsiloxane and polyether-modified silicones and the like).

Examples of the preservative include an organic nitrogen-sulfur compound-based preservative and an organic sulfur halide-based preservative.
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. It can contain a weather-resistant stabilizer. The amount of these weather-resistant 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 antifreeze agent include ethylene glycol and propylene glycol.
The amount of the viscosity modifier, antifoaming agent, preservative, weatherproof stabilizer and antifreeze agent used is preferably 5% by weight or less, more preferably 3% by weight or less, respectively, based on the weight of the composite resin aqueous dispersion. be.

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., from the viewpoint of handleability and dispersion stability of the composite resin aqueous dispersion. It is 02 to 0.7 μm, particularly preferably 0.03 to 0.4 μm. (Dv) is measured using a light scattering particle size distribution measuring device [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

The solid content concentration (content of components other than volatile components) 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 ease of handling of the aqueous dispersion. By weight%. For the solid content concentration, about 1 g of the aqueous dispersion was thinly spread on a Petri dish, weighed precisely, and then heated at 130 ° C. for 45 minutes using a circulating constant temperature dryer, and then weighed and weighed before heating. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight.

The viscosity of the aqueous dispersion of the composite resin in 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 aqueous dispersion of the composite resin in the present invention at 25 ° C. is preferably 2 to 12, and more preferably 4 to 10. The pH can be measured using a pH Meter M-12 [manufactured by HORIBA, Ltd.].

The 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 with respect to N, N-dimethylformamide is 35 to 100%;
(2) The elongation at break is 200 to 1,000%;
(3) The storage elastic modulus E'at 25 ° C. is 100 to 3,000 MPa.
The film thicknesses (1) to (3) above were obtained by drying the composite resin aqueous dispersion at 105 ° C. for 3 hours and then further drying the composite resin aqueous dispersion at 105 ° C. and a pressure of 1.3 kPa under reduced pressure for 1 hour. A film with a thickness of 200 μm is used.

The gel fraction with respect to N, N-dimethylformamide (DMF) in (1) above can be determined by, for example, the following method.
The composite resin aqueous 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 immersion in DMF". The weight of the sample is preferably 0.035 to 0.045 g. The sample is then placed in 20 ml DMF and soaked at 23 ° C. for 24 hours. After immersion, the 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 immersion in DMF" is measured. Substituting "weight of film before DMF immersion", "weight of filter", and "total weight of filter and residue after immersion in DMF" into the following formula (1), the gel fraction is obtained.
Gel fraction (%) = ("total weight of filter and residue after DMF immersion"-"weight of filter") / "weight of film before DMF immersion") x 100 ... (1)

The elongation at break in (2) above is based on JIS K6251, the shape of the test piece is dumbbell-shaped No. 3, and the tensile speed is increased using an autograph [“AGS-500D” manufactured by Shimadzu Corporation]. It is a value measured at 500 mm / min.

The storage elastic modulus E'in the above (3) 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 with respect to DMF is 35 to 100%, preferably 36 to 95%, more preferably 37 to 80%, and particularly preferably 38 to 70%.
If the gel fraction with respect to DMF is less than 35%, it is inferior in terms of storage stability when blended in paints and inks, flexibility of dry films, mechanical strength and elongation at break.
The gel fraction with respect to DMF can be adjusted by the crosslink density and the weight ratio of the polyurethane resin (U) to the vinyl resin (V) [(U): (V)]. Specifically, the gel fraction can be increased by increasing the number of trifunctional or higher functional compounds to increase the crosslink density or increasing the weight ratio of the polyurethane resin (U).

The elongation at break is 200 to 1,000%, preferably 210 to 800%, and more preferably 220 to 650%.
If the elongation at break is less than 200%, the flexibility is inferior, and if it exceeds 1,000%, the hardness and strength are inferior.
The elongation at break can be adjusted by the crosslink density and the weight ratio of the polyurethane resin (U) to the vinyl resin (V) [(U): (V)]. Specifically, the elongation at break can be increased by reducing the number of trifunctional or higher functional compounds used to reduce the crosslink density or 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, and more preferably 200 to 1,000 MPa.
If the storage elastic modulus E'is less than 100 MPa, the hardness and strength are inferior, and if it exceeds 3,000 MPa, the flexibility is inferior.
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-based 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 ~ 2.5 mmol / g, more preferably 1.2 to 2.2 mmol / g, and particularly preferably 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 ratio of urethane groups and urea groups quantified by 1} H-NMR, and the alohanate group and biuret group contents.

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 ~ 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 quantified by a nitrogen analyzer, ^{the ratio of urethane groups and urea groups quantified by 1} H-NMR, and the alohanate group and biuret group contents.

As the nitrogen analyzer, for example, a nitrogen analyzer [ANTEK7000 (manufactured by ANTEC)] can be used.
^{1 1} H-NMR measurement is carried out by the method described in "Structural Study of Polyurethane Resin by NMR: Takeda Research Institute Bulletin 34 (2), 224-323 (1975)". That is, when ¹ H-NMR is measured and an aliphatic is used, the urea group is derived from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 6 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 7 ppm. The weight ratio of the urethane group is calculated, and the urethane group and urea group contents are calculated from the weight ratio and the above N atom content and the alohanate group and biuret group contents. When aromatic isocyanate is used, the weight ratio of urea group to 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 composite resin aqueous dispersion of the present invention, the glass transition point of the vinyl resin (V) is preferably −70 to 180 ° C., more preferably 0 to 0, from the viewpoint of flexibility, hardness, mechanical strength and flexibility. It is 150 ° C., particularly preferably 30 to 120 ° C., and 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 formula of the following formula (2). Can be calculated.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ ... (2)
[In the formula, Tg ₁ and Tg ₂ are the glass transition points (K) of the homopolymers of the monomer 1 and the monomer 2, and W ₁ and W ₂ are the mass fractions of the monomer 1 and the 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 formula of the following formula (3).
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ ... (3)
[In the formula, Tg ₁ , Tg ₂ and Tg ₃ are the glass transition points (K) of the homopolymers of monomer 1, monomer 2 and monomer 3, and W ₁ , W ₂ and W ₃ are of 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 a composite resin aqueous dispersion which is the second invention described later and the following production methods (I) to (II). 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 aqueous dispersion of composite resin, the method for producing the aqueous dispersion of composite resin, which is the second invention, is preferable from the viewpoint of flexibility, mechanical strength and flexibility.

(I) A manufacturing method including the following steps (1') to (6').
Step (1'): In the presence of a 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 this step, the vinyl-based monomer (M') has a monofunctional vinyl-based monomer (M11) having neither a hydroxyl group, an amino group, an imino group or a thiol group, and a hydroxyl group, an amino group, an imino group or a thiol group. It contains a monofunctional vinyl-based monomer (M12) and / or a bifunctional or higher-functional vinyl-based monomer (M2), and the total weight ratio of (M12) and (M2) is 4 based on the weight of (M'). Steps of weight% or less;
Step (2'): An arbitrary step performed between the step (1') and the following step (3'), in which a vinyl-based monomer (M') is added;
Step (3'): A solution of the urethane prepolymer (P') obtained in step (1') or the urethane prepolymer (P') obtained in step (2') when step (2') was carried out. A step of dispersing the solution of') in an aqueous medium to obtain an aqueous dispersion (α');
Step (4'): A step of extending the urethane prepolymer (P') in the aqueous dispersion (α') with the chain extender (E);
Step (5'): An arbitrary step carried out between the step (4') and the following step (6'), which is a monofunctional vinyl-based monomer (M11) and 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-based monomers (M11), (M12) and (M2) in the aqueous dispersion (α').
In the production method (I), when the step (1') and the step (2') are carried out, in the step (1') and the step (2'), the weight of the (M') is used as a reference (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 aqueous composite resin having excellent flexibility, mechanical strength and flexibility of the dry film can be set. A dispersion is obtained.

In the production method of (I), preferable conditions other than the vinyl-based monomer (M') are the second ones corresponding to the steps (1') to (6') in the second invention described below {(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-based 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 terminal. Process;
Step (2 ″): The solution of the urethane prepolymer (P ″) obtained in the step (1 ″) was dispersed in an aqueous medium to obtain an aqueous dispersion (αx), and then the urethane prepolymer (P ′) was obtained. The step of extending') with a chain extender (E) to obtain an aqueous dispersion (α''), or the urethane prepolymer (P'') obtained in the step (1'') is used as a chain extender (E). ) And then dispersed in an aqueous medium to obtain an aqueous dispersion (α'');
Step (3 ″): A step of coexisting a vinyl-based monomer (M ″) in an aqueous dispersion (α ″), wherein the vinyl-based monomer (M ″) is a hydroxyl group, an amino group, an imino group or A monofunctional vinyl-based monomer (M11) having no thiol group, a monofunctional vinyl-based monomer (M12) having a hydroxyl group, an amino group, an imino group or a thiol group, and / or a bifunctional or higher-functional vinyl-based monomer. A step containing the monomer (M2) and having a weight ratio of (M2) of 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 production method (II) and each step in the second invention is as follows.
Process (1''): Process (1)
Step (2''): Step (3) and Step (4)
Step (3''): Step (5)
Step (4''): Step (6)
Further, in the production method (II), preferable conditions other than the production of the urethane prepolymer in the absence of the vinyl-based monomer in the step (1 ″) are the same as in the step (1) in the second invention. be. Further, in the step (2 ″), the preferable conditions are the same as those in the steps (3) and (4) in the second invention. In the step (3 ″), preferable conditions other than the use of the vinyl-based monomer (M ″) are the same as in the step (5) in the second invention. In step (4 ″), the preferred conditions are the same as in step (6) in the second invention.

The method for producing the composite resin aqueous dispersion, which is the second invention, will be described.
The method for producing a composite resin aqueous dispersion, which is the 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 particles. Including the following steps (1) to (6), 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. This is a method for producing a resin aqueous dispersion.
Step (1): The active hydrogen component (A) and the organic isocyanate component (B) are reacted in the presence of a monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. A step of producing a urethane prepolymer (P) having an isocyanate group at the terminal;
Step (2): A monofunctional vinyl-based monomer that is an arbitrary step carried out between the step (1) and the following step (3) and has neither a hydroxyl group, an amino group, an imino group, or a thiol group. Step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or, when the step (2) is carried out, the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous. Step of dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): A step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with the chain extender (E);
Step (5): An arbitrary 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 carried out. ..

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-based monomers (M11) or (M11) and (M1) that were present in the system when the polyurethane resin (U) was formed, the vinyl-based resin (V) was formed between the meshes of the polyurethane resin (U). ) Can be formed, and a composite resin aqueous dispersion having excellent flexibility, mechanical strength and flexibility of the dry film can be obtained.
Further, 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 preventing the polyurethane resin (U) and the vinyl-based resin (V) from forming 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 one is 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 one is 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.

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

The urethane prepolymer (P) in the step (1) contains an active hydrogen component (A) and an organic substance in the presence of a monofunctional vinyl-based monomer (M11) having neither a hydroxyl group, an amino group, an imino group or a thiol group. The equivalent ratio of isocyanate groups (isocyanate group / active hydrogen-containing group) to the active hydrogen-containing group (excluding carboxyl group, sulfo group and sulfamic acid group) of the isocyanate component (B) is preferably 1.01 to 3, and further. It is preferably formed by a urethanization reaction at a ratio of 1.1 to 2.

The total weight of the active hydrogen component (A) and the organic isocyanate component (B) at the start of the step (1) and the weight of the monofunctional vinyl monomer (M11) having neither a hydroxyl group, an amino group, an imino group or a 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. be.

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

In the urethane prepolymerization reaction, a catalyst can be used if necessary to promote the reaction. Specific examples of the catalyst include organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate, bismuth alkoxide, chelate compounds of bismuth with compounds having a dicarbonyl group, etc.), inorganic metal compounds (bismuth oxide, hydroxylation). Bismuth, bismuth halide, etc.); Amin (triethylamine, triethylenediamine and 1,8-diazabicyclo [5.4.0] -7-undecene, etc.) and a combination of two or more of these can be mentioned.

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

Examples of the radical trapping agent include 2,6-di-t-butyl-4-methylphenol and 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6. , 10-Tetra-butyldibenz [d, f] [1,3,2] dioxaphosfepine, 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] -1,1 dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4 , 4'butylidenebis (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-based compounds such as 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl). The radical scavenger 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. ..

Step (2) in the present invention is an arbitrary step carried out between step (1) and step (3), and is a monofunctional vinyl having neither a hydroxyl group, an amino group, an imino group or a thiol group. This is a step of adding the system monomer (M11).

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

The vinyl-based monomer (M11) to be added may be the same as or different from the vinyl-based monomer (M11) used in the step (1). Further, as the vinyl-based monomer (M11) used in the step (2), one type may be used alone or two or more types may be used in combination.

Preferred vinyl-based monomers (M11) in step (2) include those similar to those listed as preferred in step (1).
Further, in the step (1), among the vinyl-based monomers (M11), the vinyl-based hydrocarbon (m2) is not listed as a preferable monomer because the solubility of the urethane prepolymer (P) is not so good. As an additional vinyl monomer (M11) in the step (2), an aromatic vinyl hydrocarbon (particularly styrene) having 8 to 20 carbon atoms in (m2) is used from the viewpoint of the 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, when the step (2) is carried out, the urethane prepolymer (P) obtained in the step (2). This is a step of dispersing the solution of the above 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 (for example, acetone and methyl ethyl ketone), ester solvents (for example, ethyl acetate), ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethylformamide and N-methylpyrrolidone), and the like. Examples thereof include alcohol-based solvents (for example, isopropyl alcohol) and aromatic hydrocarbon-based solvents (for example, toluene). One type of organic solvent may be used alone, or two or more types may be used in combination.

When the reaction solution is dispersed in an aqueous medium, it is preferable to use a surfactant (C) from the viewpoint of dispersion stability. Further, from the viewpoint of dispersion stability, it is preferable to use a 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 radically reactive group and a non-reactive surfactant (C2), and one of them may be used alone or a reaction. Two or more kinds may be used in combination including the combination of the sex surfactant (C1) and the non-reactive surfactant (C2). Of 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 Corporation] SE-10N, SR-10, SR-20, SR-30, ER-20, ER-30, Aqualon [registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] HS-10, KH-05, KH-10, KH-1025, Eleminor [registered trademark, manufactured by Sanyo Kasei Kogyo Co., Ltd.] JS-20, Latemul [registered trademark, manufactured by Kao Co., Ltd.] PD-104, PD-420, PD-430, Ionet [registered trademark, manufactured by Sanyo Kasei Kogyo Co., Ltd.] )] MO-200 and the like.

Non-reactive activators (C2) include nonionic surfactants (C21), anionic surfactants (C22), cationic surfactants (C23), amphoteric surfactants (C24) and other emulsified dispersions. Agent (C25) can be mentioned.

Examples of the nonionic surfactant (C21) include an AO-added nonionic surfactant and a polyhydric alcohol-based nonionic surfactant. Examples of the AO addition type include ethylene oxide (hereinafter abbreviated as EO) adduct of an aliphatic alcohol having 10 to 20 carbon atoms, EO adduct of phenol, EO adduct of nonylphenol, and EO of alkylamine having 8 to 22 carbon atoms. Examples thereof include adducts and EO adducts of poly (oxypropylene) glycol, and examples of the polyhydric alcohol type include fatty acids (8 carbon atoms) of polyhydric (3 to 8 or more) alcohols (2 to 30 carbon atoms). -24) Esters (eg, glycerin monostearate, glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (4 to 24 carbon atoms) poly (polymerization degree 1 to 10) glycosides and the like can be mentioned.

Examples of the anionic surfactant (C22) include ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [lauryl ether sodium acetate and (poly) oxyethylene (additional molars 1 to 100) lauryl ether. Sodium acetate, etc.]; Sulfonate or ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (additional moles 1 to 100) sodium lauryl sulfate, (poly) ) Oxyethylene (additional moles 1 to 100) triethanolamine lauryl sulfate and (poly) oxyethylene (additional moles 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; hydrocarbon groups having 8 to 24 carbon atoms Sulfonate having (sodium dodecylbenzene sulfonate, etc.); sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms; phosphate ester or ether having a hydrocarbon group having 8 to 24 carbon atoms. Sulfonic acid ester and salts thereof [sodium lauryl phosphate and (poly) oxyethylene (additional moles 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 triethanolamine laurate, etc.]; Aylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms [sodium coconut oil fatty acid methyl taurine, sodium coconut oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N-palm Oil fatty acid acyl-L-glutamate triethanolamine, N-palm oil fatty acid acyl-L-sodium glutamate, sodium lauroylmethyl-β-alanine, etc.] can be mentioned.

Examples of the cationic surfactant (C23) include quaternary ammonium salt types [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid ethylsulfate fatty acid aminopropylethyldimethylammonium, etc.] and amine salts. Types [diethylaminoethylamide stearate, dilaurylamine hydrochloride, oleylamine, etc.] can be mentioned.

Examples of the amphoteric tenside agent (C24) include betaine-type amphoteric tenside agents [coconut oil fatty acid amidopropyldimethylaminoacetate betaine, lauryldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole. Nium betaine, lauryl hydroxysulfobetaine, lauroylamide ethyl hydroxyethyl carboxymethyl betaine sodium hydroxypropyl phosphate, etc.] and amino acid amphoteric tenside [β-lauryl aminopropionate, etc.] can be mentioned.

Other emulsifying dispersants (C25) include, for example, polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and US Patent No. Examples thereof include the emulsion dispersant having a urethane group or an ester group described in 5906704 (for example, a polycaprolactone polyol and a polyether diol linked with a polyisocyanate).

The amount of the surfactant (C) used is determined by the weight of the vinyl-based monomer (M11) or the monofunctional vinyl-based monomer (M1) in the step (5) described later 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 for 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 activity The neutralizing agent used for 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)]. , It may be added at any time during the water dispersion step or after the water dispersion step, but it is preferable to add it before the water dispersion step or during the water dispersion step from the viewpoint of the stability of the aqueous dispersion (α).
The implementation temperature of the step (3) 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 the chain extender (E).

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

The chain extender (E) may be used alone or in combination of two or more.
The chain extender (E) can also be used as the active hydrogen component (A) in the step (1).
The implementation temperature of the 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 arbitrary step carried out 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 composite resin is aqueously dispersed. The mechanical strength of the dry film can be improved by using a cross-linking agent described below having a reactivity with a hydroxyl group, an amino group, an imino group or a thiol group in combination with 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 the hydroxyl group-containing vinyl-based monomer (m8), the amino group- or imino group-containing vinyl-based monomer (m9) in the first invention. And the same as the thiol group-containing vinyl-based monomer (m10), and the preferred one is also the same.

As the vinyl-based monomer (M1), a monofunctional vinyl-based monomer (M11) having neither a hydroxyl group, an amino group, an imino group or a thiol group can also be used. In this case, it may be the same as or different from the vinyl-based monomer (M11) used in the step (1). As the vinyl-based monomer (M1), one type may be used alone or two or more types may be used in combination.
The implementation temperature of the 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-based monomer (M11) in the aqueous dispersion (α) or the vinyl-based monomer (M11) and (M1) when the step (5) is carried out. ..

As the polymerization initiator used for the polymerization in the step (6), a persulfate-based initiator such as sodium persulfate, potassium persulfate and ammonium persulfate; an azo-based initiator such as azobisisobutyronitrile; Organic peroxides such as benzoyl, cumene hydroperoxide, tert-butyl peroxybenzoate and tert-butyl hydroperoxide; hydrogen peroxide; etc. Common radical polymerization initiators can be used, and these can be used alone. It may be used, or two or more kinds may be mixed and used. The amount of the polymerization initiator used is preferably 0.05 to 5% by weight based on the total weight of the vinyl-based monomers (M11) and (M1) used for the polymerization.
These initiators may be used in a batch in a required amount at the start of polymerization, or may be divided and added at arbitrary time intervals.

In the 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 properties such as sodium thiosulfite, sodium sulfite, sodium bisulfite and sodium metabisulfite. Inorganic compounds and the like can be mentioned.

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-ethylhexylthioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, α-methylstyrene dimer and the like. Be done.
Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate and the like can be used as a buffer, and polyvinyl alcohol, a water-soluble cellulose derivative, an alkali metal salt of polymethacrylic acid and the like can be used as a protective colloid in an appropriate amount.

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 less than 20 ° C., the polymerization rate may slow down. Further, 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 equipment used in steps (1) to (6) is not particularly limited, and any equipment having mixing / dispersing ability can be used, but from the viewpoint of temperature adjustment, mixing / dispersing ability, etc., rotary mixing / dispersion / It is preferable to use a disperser.
Examples of the rotary mixing / dispersing device include a mixing device having general stirring blades such as Max Blend and helical blades, TK Homo Mixer [manufactured by Primix Corporation], Claire Mix [manufactured by M-Technique Co., Ltd.], and Phil. Mix [manufactured by Primix Corporation], Ultra Turlux [manufactured by IKA Co., Ltd.], Ebara Milder [manufactured by Ebara Corporation], Cavitron (manufactured by Eurotech Co., Ltd.) and Biomixer [manufactured by Nippon Seiki Co., Ltd.] Etc. are exemplified.

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

As described above, in the present invention, the polyurethane resin (U) is obtained 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). ) Introduce a crosslinked structure.

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 similar to.

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).

The weight ratio [(U): (V)] of the polyurethane resin (U) and the vinyl resin (V) in the aqueous dispersion of the composite resin in the present invention determines the dispersion stability, the flexibility of the dry film, and the 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 can contain a cross-linking agent, a viscosity modifier, a defoaming agent, a preservative, a weather-resistant stabilizer, an antifreeze agent, and the like, and specific examples thereof are those in the first invention. The same is true, and the preferred content is also the same.

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., from the viewpoint of handleability and dispersion stability of the composite resin aqueous dispersion. It is 02 to 0.7 μm, particularly preferably 0.03 to 0.4 μm. (Dv) is measured using a light scattering particle size distribution measuring device [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

The solid content concentration (content of components other than volatile components) 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 ease of handling of the aqueous dispersion. By weight%. For the solid content concentration, about 1 g of the aqueous dispersion was thinly spread on a Petri dish, weighed precisely, and then heated at 130 ° C. for 45 minutes using a circulating constant temperature dryer, and then weighed and weighed before heating. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight.

The viscosity of the aqueous dispersion of the composite resin in 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 aqueous dispersion of the composite resin in the present invention at 25 ° C. is preferably 2 to 12, and more preferably 4 to 10. The pH can be measured using a pH Meter M-12 [manufactured by HORIBA, Ltd.].

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following, the part represents the weight part.

<Example 1> (Manufacturing method of the second invention)
A simple pressurizing reaction device equipped with a stirrer and a heating device includes the types and amounts of the active hydrogen component (A), the organic isocyanate component (B), the radical trapping agent, and the vinyl-based monomer in the step (1) shown in Table 1. M11) is charged and stirred at 80 ° C. for 10 hours to carry out a urethanization reaction to obtain a urethane prepolymer (P-1), and then the vinyl monomer (M11) in the step (2) is charged to make the stirring uniform. As a result, a solution of urethane prepolymer (P-1) was obtained.
According to the formulation shown in Table 2, 15.7 parts of triethylamine as a neutralizing agent and eleminol JS- as a reactive surfactant (C1) were added to 500.0 parts of a solution of the obtained urethane prepolymer (P-1). 20 [Manufactured by Sanyo Chemical Industries, Ltd.] 26.0 parts (solid content: 10.0 parts) was added to make a uniform solution, and then 828.0 parts of ion-exchanged water was added while stirring at 200 rpm (P-). The solution of 1) was dispersed. 4.7 parts of an ethylenediamine 5.0% by weight aqueous solution and 40.7 parts of a diethylenetriamine 5.0% by weight aqueous solution as a chain extender (E) were 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, 8.0 parts of a 10 wt% aqueous solution of sodium persulfate as a polymerization initiator was added, and the mixture was polymerized at 80 ° C. for 3 hours to obtain a composite resin aqueous dispersion (Q-1). Obtained.

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

<Example 5> (Manufacturing method of the second invention)
Using each of the raw materials listed in Table 1, a urethane prepolymer (P-5) solution was produced in the same manner as in Example 1. Using each of the raw materials shown in Table 2, the solution of (P-5) was dispersed in the same manner as in Example 1, and then a chain extension reaction was carried out. Next, 17.0 parts of hydroxyethyl methacrylate was added as the vinyl-based monomer (M12) in the 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 part was added and polymerized at 80 ° C. for 3 hours to obtain a composite resin aqueous dispersion (Q-5).

<Example 6> (Manufacturing method of the second invention)
A simple pressurizing reaction device equipped with a stirrer and a heating device is provided with the types and amounts of the active hydrogen component (A), the organic isocyanate component (B), the radical trapping agent, and the vinyl-based monomer in the step (1) shown in Table 1. M11) and an organic solvent are charged and stirred at 80 ° C. for 10 hours to carry out a urethanization reaction to obtain a urethane prepolymer (P-6), and then 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 eleminol JS- as a reactive surfactant (C1) were added to 500.0 parts of the obtained urethane prepolymer (P-6) solution. 20 [Manufactured by Sanyo Chemical Industries, Ltd.] 15.6 parts (solid content: 6.0 parts) was added to make a uniform solution, and then 905.0 parts of ion-exchanged water was added 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% aqueous solution of potassium persulfate as an initiator was added, and the mixture was polymerized 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> (Manufacturing method of the second invention)
Urethane prepolymer (P-7) to (P-9) solutions were produced using each of the raw materials shown in Table 1 in the same manner as in Example 1, and each raw material shown in Table 2 was used in Examples. 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 pressurizing reaction device equipped with a stirrer and a heating device is charged with the types and amounts of the active hydrogen component (A), the organic isocyanate component (B), the radical scavenger and the organic solvent shown in Table 1 at 80 ° C. for 10 The urethanization reaction was carried out with stirring for a time to obtain a solution of urethane prepolymer (P-10).
According to the formulation shown in Table 2, 5.1 parts of triethylamine as a neutralizing agent was added to 500.0 parts of the obtained urethane prepolymer (P-10) solution to make a uniform solution, and then the mixture was 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, a separable flask equipped with a dropping funnel for a monomer dispersion liquid, a dropping funnel for an initiator solution, a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube is charged in its entirety with the obtained urethane resin aqueous dispersion in its entirety. The mixture was stirred under an air stream and the temperature was raised to 70 ° C. Next, 122.5 parts of methyl methacrylate, 27.3 parts of n-butyl acrylate, and Aquaron KH-1025 as a reactive surfactant (C1) [manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 18.0 parts (solid content: A monomer dispersion consisting of 4.5 parts) and 184.5 parts of ion-exchanged water was prepared and charged into a dropping funnel for the monomer dispersion, and 5.0 parts of a 10 wt% potassium persulfate aqueous solution as an initiator solution was added to the initiator solution. The mixture was charged into a dropping funnel, and the monomer dispersion and the initiator solution were dropped at a constant rate over 3 hours while maintaining the temperature in the reaction system at 70 ± 2 ° C. After that, stirring was continued at the same temperature for 90 minutes and then cooled to room temperature to obtain a composite resin aqueous dispersion (Q-10).

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

<Comparative example 1>
A simple pressurizing reaction device equipped with a stirrer and a heating device is charged with the types and amounts of the active hydrogen component (A), the organic isocyanate component (B), the radical scavenger and the organic solvent shown in Table 1 at 80 ° C. for 10 The urethanization reaction was carried out with 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 urethane prepolymer (P'-1) solution to make a uniform solution, and then the mixture was stirred at 200 rpm. While adding 563.0 parts of ion-exchanged water, the solution of (P'-1) was dispersed. 35.7 parts of a 5.0 wt% aqueous solution of diethylenetriamine as a chain extender was added to the obtained dispersion to carry out a chain extension reaction at 25 ° C., and then the organic solvent was retained under reduced pressure at 65 ° C. for 8 hours. The mixture was removed to obtain a polyurethane resin aqueous dispersion (1).
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, 120.8 parts of ion-exchanged water and a reactive surfactant Eleminol JS-20 [manufactured by Sanyo Kasei Kogyo Co., Ltd.] as (C1) was charged with 1.3 parts (solid content: 0.5 parts), stirred under a nitrogen stream, and heated to 70 ° C.
Next, 226.4 parts of ion-exchanged water, 24.7 parts (solid content: 9.5 parts) of eleminol JS-20 [manufactured by Sanyo Kasei Kogyo Co., Ltd.] as a reactive surfactant (C1), methyl methacrylate. A monomer dispersion consisting of 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 a monomer dispersion, of which 30.2. The part was added to a separable flask.
Next, 8.0 parts of a 10 wt% aqueous solution of sodium persulfate as an initiator was added to initiate polymerization, and the remaining monomer dispersion and initiator were maintained at 70 ± 2 ° C. in the reaction system. 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 the mixture was cooled to room temperature to obtain a vinyl-based resin aqueous dispersion (1).
A composite resin aqueous dispersion (Q'-1) was obtained by uniformly mixing 100 parts of the obtained polyurethane resin aqueous dispersion (1) and 100 parts of the vinyl resin aqueous dispersion (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. Although not the same, Tables 1 and 2 show the types and amounts of raw materials used.

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

The composition of the raw materials represented by the trade names in Table 1 is as follows.
-Nipporan 980R: Polyhexamethylene carbonate diol with Mn = 2,000 [manufactured by Nippon Polyurethane Industry Co., Ltd.]
-Kuraray polyol C-3090 [Mn = 3,000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol] [manufactured by Kuraray Co., Ltd.]
Duranol G4672: Poly (tetramethylene / hexamethylene) carbonate diol with Mn = 2,000 [manufactured by Asahi Kasei Chemicals Co., Ltd.]
-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-pentaneadipatediol with Mn = 2,000 [manufactured by Kuraray Co., Ltd.]
Duranate TKA-100: Hexamethylene diisocyanate isocyanurate [manufactured by Asahi Kasei Chemicals Co., Ltd.]
-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 method (gel fraction to DMF, storage elastic modulus E'at 25 ° C, 100% stress, breaking strength and breaking elongation, ethanol swelling rate, König hardness, 180 ° C bending test), and Table 3 shows the evaluation results (haze and glossiness) of the coated material.

<Weight ratio of bifunctional or higher functional vinyl monomer (M2) and monofunctional vinyl monomer (M12') covalently bonded to polyurethane resin (U)>
-Measurement of hydroxyl group of vinyl resin (V) The hydroxyl value was determined according to JIS K1557-1.
○ Pyrolysis gas chromatography mass analysis Using the dry film obtained in the following “Production of dry film”, all vinyl monomers constituting the vinyl resin (V) under the following pyrolysis gas chromatography mass analysis conditions ( The weight ratio of each monomer of M) was determined.
[Pyrolysis gas chromatography mass spectrometry conditions]
Equipment: GCMS QP-2010PLUS [manufactured by Shimadzu Corporation]
Column: Ultra Alloy-5 [manufactured by Frontier Lab Co., Ltd.]
Temperature: 480 ° C
From the results of the obtained hydroxyl value and the result of pyrolysis gas chromatography-mass spectrometry, a monofunctional vinyl monomer (M12') covalently bonded to a bifunctional or higher functional vinyl monomer (M2) and (U). The weight ratio of was calculated.

<Physical characteristics of dry film>
[Manufacturing of dry film]
A composite resin aqueous dispersion previously prepared to have a solid content concentration of 20% by weight is gently poured into a polypropylene mold so that the film thickness after drying becomes about 200 μm, spread so that the whole becomes uniform, and spread at 25 ° C. for 24 hours. After standing, it was dried at 105 ° C. for 3 hours using a circulation dryer, and then dried under reduced pressure at 105 ° C. and a pressure of 1.3 kPa for 1 hour to obtain a dry film.

[Measurement of gel fraction]
A sample obtained by cutting out the dry film obtained above so as to be about 0.035 to 0.045 g was placed in 20 ml of DMF and immersed at 23 ° C. for 24 hours. After the immersion, the DMF containing the sample was filtered using a tetrafluoroethylene resin (PTFE) filter (trade name: TORAST Disc GLCTD-PTFE2522, manufactured by Shimadzu GLC Co., Ltd.). Further, the 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 immersion in DMF" was measured. The gel fraction was determined by substituting "weight of film before DMF immersion", "weight of filter", and "total weight of filter and residue after immersion in DMF" into the following formula (1).
Gel fraction (%) = ("total weight of filter and residue after DMF immersion"-"weight of filter") / "weight of film before DMF immersion") x 100 ... (1)

[Storage 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]
The dry film obtained above was made into a dumbbell-shaped No. 3 test piece in accordance with JIS K6251, and the tensile speed was 500 mm / min using an autograph ["AGS-500D" manufactured by Shimadzu Corporation]. 100% stress, breaking strength and breaking elongation were measured in. In the composite resin aqueous dispersion obtained in Comparative Example 4, the elongation at break was less than 100%, so 100% stress could not be measured.

[Ethanol swelling rate]
The dry 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 soaked film was taken out, the ethanol adhering to the film surface was wiped off with a filter paper, and the "weight of the film after soaking in ethanol" 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 ethanol swelling rate 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" x 100 ... (4)

[König hardness]
The dry film obtained above was measured with a Pendrum hardness tester [{Pendulum Hardness Tester}] manufactured by BYK gardener Co., Ltd. using a König pendulum in accordance with ASTM D 4366. The measurement result shows that the larger the value, the higher the hardness.

[180 degree bending test]
The dry film obtained above was bent 180 degrees and tested 10 times, and the presence or absence of cracks was visually confirmed. Those without cracks were marked with ◯, and those with cracks were marked with x.

<Evaluation of painted matter>
[Haze]
The composite resin aqueous dispersion is applied on a polyethylene terephthalate film (Lumirror L-38T60 [manufactured by Toray Industries, Inc.]) with a bar coater so that the film thickness after drying is 25 μm, and heated at 105 ° C. for 60 minutes for coating. I made a thing. In accordance with JIS-K7136, the haze of the coating material was measured using a total light transmittance measuring device [trade name "haze-garddual" manufactured by BYK gardener Co., Ltd.].

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

From the results in 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 rate is 113. It can be seen that it is excellent in storage stability when it is made into paint or ink as low as% or less. In addition, the result of the bending test is also excellent, and it can be seen that the flexibility and flexibility are excellent. Further, it can be seen that the breaking strength is as high as 31 MPa or more, the König hardness is as high as 15 times or more, and the hardness and mechanical strength are excellent. Further, it can be seen that the haze is as small as 1.1% or less, the glossiness is as large as 78 or more, and the transparency and glossiness are excellent.

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 also have storage stability, hardness, flexibility, mechanical strength, water resistance, and water resistance. Paints, coating agents (rust-preventive coating agents, waterproof coating agents, water-repellent coating agents, antifouling coating agents, etc.), adhesives, fiber processing agents (pigment printing) because of their excellent performance such as solventiness, transparency and glossiness. It can be widely used in binders for papers, binders for non-woven fabrics, binders for reinforcing fibers, binders for antibacterial agents and raw materials for artificial leather / synthetic leather, etc.), paper treatment agents, inks, etc., especially water-based paints and water-based rust preventive coatings. It can be suitably used as a composite resin aqueous dispersion for agents, aqueous fiber processing agents and aqueous adhesives.

Claims (13)

A composite resin aqueous dispersion containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particles, wherein the polyurethane resin (U) is an active hydrogen component (A) and an organic isocyanate component. It is a reaction product of (B) and the chain extender (E), and 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. However, the film obtained by drying the composite resin aqueous dispersion satisfies all of the following (1) to (3):
(1) The gel fraction with respect to N, N-dimethylformamide is 35 to 100%;
(2) The elongation at break is 200 to 1,000%;
(3) The storage elastic modulus E'at 25 ° C. is 100 to 3,000 MPa. The composite resin aqueous according to claim 1, 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 8-valent 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 form of hexamethylene diisocyanate and / or an isocyanurate form of isophorone diisocyanate. The compound according to any one of claims 1 to 3, wherein the trifunctional or higher functional compound in the chain extender (E) is a polyalkylene polyamine having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms in the alkylene group. The composite resin aqueous dispersion according to the above. Any of claims 1 to 4, wherein the weight ratio [(U): (V)] of the polyurethane resin (U) and the vinyl resin (V) in the aqueous dispersion of the composite resin is 30:70 to 70:30. The composite resin aqueous dispersion according to item 1. Among the monomers constituting the vinyl resin (V), a simple monomer 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). Claim that the total [(M2) + (M12')] of the functional vinyl-based monomers (M12') is 4% by weight or less based on the total weight of the monomers constituting the vinyl-based resin (V). The composite resin aqueous dispersion according to any one of 1 to 5. A method for producing an aqueous dispersion of a composite resin containing composite resin particles containing a polyurethane resin (U) and a vinyl resin (V) in the same particles, which comprises the following steps (1) to (6) and is active. A method for producing an aqueous dispersion of a composite resin, 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): The active hydrogen component (A) and the organic isocyanate component (B) are reacted in the presence of a monofunctional vinyl monomer (M11) having no hydroxyl group, amino group, imino group or thiol group. A step of producing a urethane prepolymer (P) having an isocyanate group at the terminal;
Step (2): A monofunctional vinyl-based monomer that is an arbitrary step carried out between the step (1) and the following step (3) and has neither a hydroxyl group, an amino group, an imino group, or a thiol group. Step of adding (M11);
Step (3): The solution of the urethane prepolymer (P) obtained in the step (1) or, when the step (2) is carried out, the solution of the urethane prepolymer (P) obtained in the step (2) is aqueous. Step of dispersing in a medium to obtain an aqueous dispersion (α);
Step (4): A step of extending the urethane prepolymer (P) in the aqueous dispersion (α) with the chain extender (E);
Step (5): An arbitrary 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 carried out. .. 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 8-valent alcohol having 5 to 20 carbon atoms, and / or a saccharide. The production method according to claim 7 or 8, wherein the trifunctional or higher functional compound in the organic isocyanate component (B) is an isocyanurate form of hexamethylene diisocyanate and / or an isocyanurate form of isophorone diisocyanate. The compound according to any one of claims 7 to 9, wherein the trifunctional or higher functional compound in the chain extender (E) is a polyalkylene polyamine having 2 to 6 carbon atoms and 3 to 7 nitrogen atoms in the alkylene group. The manufacturing method described. The total weight of the active hydrogen component (A) and the organic isocyanate component (B) at the start of the step (1) and the weight of the monofunctional vinyl monomer (M11) having neither a hydroxyl group, an amino group, an imino group or a 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. Any of claims 7 to 12, wherein the weight ratio [(U): (V)] of the polyurethane resin (U) to the vinyl resin (V) in the aqueous dispersion of the composite resin is 30:70 to 70:30. The manufacturing method according to item 1.