JP2015193815A - Aqueous dispersion of core/shell type base agent particle and one-pack thermosetting resin emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a core/shell type base agent particle providing a one-pack thermosetting resin emulsion good in long time storage stability and low temperature curability and excellent in water resistance of a coated film after curing.SOLUTION: There is provided an aqueous dispersion by dispersing a core/shell type base agent particle containing a thermosetting resin where a core contains an epoxy group-containing compound and a shell has a weight average molecular weight of 5,000 to 150,000. There is also provided a one-pack thermosetting resin emulsion containing the core/shell type base agent particle containing the thermosetting resin where the core contains an epoxy group-containing compound and the shell has a weight average molecular weight of 5,000 to 150,000, and a curing agent which is a compound having at least 2 amino groups which is capable of reacting with an epoxy group and/or an epoxy polymerization catalyst.

Description

  The present invention relates to an aqueous dispersion of core / shell type main agent particles. More specifically, the present invention relates to an aqueous dispersion of core / shell type main agent particles that provides a one-part thermosetting resin emulsion having good long-term storage stability and low-temperature curability and excellent coating film strength.

Conventionally, when a base material containing a compound containing a glycidyl ether group or an isocyanate group and an aqueous dispersion of a curing agent containing a compound having a primary and secondary amino group are mixed to form a paint, the glycidyl ether group and When the reaction between amino groups or isocyanate groups and amino groups proceeds even at room temperature and stored for a long period of time, there is a problem that the viscosity of the paint rises and it cannot be used.
Therefore, in order to improve them, a one-component heat-curable aqueous epoxy resin composition comprising an aqueous dispersion containing an epoxy compound and a latent curing agent of a fine powder dihydrazide compound hardly soluble in water (for example, Patent Document 1), epoxy resin, glycidyl ether group-containing novolak phenol resin, primary or secondary amine compound having a primary hydroxyl group, and phenol compound having a phenolic hydroxyl group are allowed to react with each other and the resin does not contain an amino group and an epoxy group Known are resin compositions for water-based paints containing, as a main component (for example, see Patent Document 2).

Japanese Patent Laid-Open No. 11-293092 Japanese Patent Laid-Open No. 06-122850

However, although the storage stability is improved to some extent in the technique of Patent Document 1, a high temperature of 200 ° C. or higher is necessary for complete curing. In the technique of Patent Document 2, the cured coating film is used. There is a problem that the water resistance is inferior, and it has been eagerly desired to solve these problems particularly in paint applications.
An object of the present invention is to provide an aqueous dispersion of core / shell type main agent particles that provides a one-part thermosetting resin emulsion having good long-term storage stability and low-temperature curability, and a cured coating film having excellent water resistance. Is to provide.
In the present invention, excellent storage stability means that when left at 40 ° C., the particle size change of the emulsion is small and the viscosity change is small, and that low temperature curability is excellent is 140 ° C. for 20 minutes. A baked coating film having excellent pencil hardness and adhesion, and being excellent in water resistance means that the swelling of the coating film is small when immersed in water, and each can be evaluated by the methods described below.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides core / shell type main agent particles in which the core contains the epoxy group-containing compound (A) and the shell contains the thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000 ( An aqueous dispersion (D0) obtained by dispersing D); a core containing an epoxy group-containing compound (A), and a shell containing a thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000 Core / shell type main agent particles (D), and a compound (E1) having at least two amino groups capable of reacting with an epoxy group and / or a curing agent (E) which is an epoxy polymerization catalyst (E2) It is a one-component thermosetting resin emulsion (X).

The aqueous dispersion (D0) of the core / shell type main agent particles (D) of the present invention has the following effects.
(1) The coverage of the epoxy group-containing compound (A) as a core is high, and excellent storage stability is imparted to the one-part thermosetting resin emulsion (X).
(2) The one-component thermosetting resin emulsion (X) is imparted with excellent curability, particularly low temperature curability.
(3) The coating film obtained by reacting and curing the emulsion (X) is excellent in adhesion to the substrate and coating film strength.
(4) A coating film obtained by reacting and curing the emulsion (X) is excellent in water resistance.

[Epoxy group-containing compound (A)]
The epoxy group-containing compound (A) in the present invention has at least two epoxy groups in the molecule, and includes an aromatic ring-containing polyepoxide (A1), an aliphatic polyepoxide (A2), an alicyclic ring-containing polyepoxide (A3), Heterocycle containing polyepoxide (A4) etc. are mentioned.

(A1) Aromatic ring-containing polyepoxides Divalent to 10-valent or higher polyglycidyl ethers of polyhydric phenols (A1-1), aromatic ring-containing polyglycidylamines (A1-2), other aromatic ring-containing polyepoxides (A1) -3) and mixtures thereof.

(A1-1) Polyglycidyl ether of polyhydric phenol (A1-1) The polyhydric phenol constituting (A1-1) is a divalent to 10-valent or higher carbon number (hereinafter sometimes abbreviated as C) 6 The number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on the GPC method under the conditions described later. ] 10,000 or less polyhydric phenols (bisphenol A, -F, -B, -AD and -S, halogenated bisphenol A, pyrogallol, phenol novolac, cresol novolac, etc.), and their polyglycidyl ethers Bisphenol A type polyglycidyl ether (polyglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol or more of epichlorohydrin), bisphenol F type polyglycidyl ether, bisphenol S type polyglycidyl ether, phenol novolac type poly Examples thereof include glycidyl ether and cresol novolac type polyglycidyl ether.
Examples of other divalent to 10-valent or higher polyglycidyl ethers include polyglycidyl ethers of polyphenols obtained by the condensation reaction of phenol and glioxal, glutaraldehyde or formaldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone. Examples thereof include polyglycidyl ether.

(A1-2) Aromatic ring-containing polyglycidylamine The aromatic ring-containing amine constituting (A1-2) is, for example, a C6-30 aromatic ring-containing monovalent to tetravalent or higher aromatic ring-containing polyamine (aniline). 1,3- and / or 1,4-phenylenediamine), and the polyglycidylamine includes diglycidylamine [N, N-diglycidylaniline, etc.], tetraglycidyl or higher polyglycidyl. And amines [1,3- and / or 1,4-phenylenetetraglycidylamine, 2,4- and / or 2,6-tolylenetetraglycidylamine, etc.].

(A1-3) Other aromatic ring-containing polyepoxide TDI or MDI and diglycidyl urethane compound obtained by addition reaction of glycidol, glycidyl group-containing polyurethane (pre) polymer obtained by reacting TDI or MDI with glycidol and polyol, Examples include diglycidyl ethers of bisphenol A alkylene oxide (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO)] adduct.

(A2) Aliphatic polyepoxide 2-8 valent, polyglycidyl ether of aliphatic polyhydric alcohol (A2-1), polyglycidyl ester of aliphatic polycarboxylic acid (A2-2) and aliphatic polyglycidylamine (A2- 3) and mixtures thereof.

(A2-1) Polyglycidyl ether of aliphatic polyhydric alcohol As polyhydric alcohol constituting (A2-1), polyhydric alcohols of C2 or more and Mn 1,000 or less [ethylene glycol, propylene glycol, polyethylene glycol, polypropylene Glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as EG, PG, PEG, PPG, TMP, GR, PE, SO, etc.), etc., and as their polyglycidyl ether, diglycidyl ether [EG diglycidyl ether, PG diglycidyl ether, PEG (Mn 100 to 1,000) diglycidyl ether, PPG (Mn 100 to 1,500) diglycidyl ether, etc.], triglycidyl ether [TMP trigly Sidyl ether, GR triglycidyl ether, etc.], polyglycidyl ethers having a valence of 4 or more [PE tetraglycidyl ether, SO polyglycidyl ether, SO polyglycidyl ether, diPE polyglycidyl ether, poly (degree of polymerization 2-20) GR polyglycidyl Ether etc.] etc. are mentioned.

(A2-2) Polyglycidyl ester of aliphatic polycarboxylic acid As the aliphatic polycarboxylic acid constituting (A2-2), a divalent to hexavalent C4-24 aliphatic polycarboxylic acid [succinic acid, adipic acid , (Meth) acrylic acid, etc.], and polyglycidyl esters thereof include diglycidyl esters [diglycidyl succinate, diglycidyl adipate, etc.], tetraglycidyl esters [tetraglycidyl butanetetracarboxylate, etc.], unsaturated carboxylic acids Acid glycidyl ester [(meth) acrylic acid glycidyl ester and the like]. Examples of the polyglycidyl ester of the aliphatic polycarboxylic acid include polymers and copolymers of glycidyl esters of unsaturated carboxylic acids such as (meth) acrylic acid glycidyl ester.
(A2-3) Aliphatic polyglycidylamine Polyglycidylamines of 2 to 6 and C2-24 aliphatic amines such as tetraglycidylamine of ethylenediamine are exemplified.

(A3) Alicyclic ring-containing polyepoxide 2 to 6-valent polyepoxide of C6-36 alicyclic ring-containing compound is exemplified, and alicyclic ring-containing unsaturated hydrocarbon polyepoxide is 2 to 6 per molecule in C6-24. Polyepoxides of hydrocarbons having the above double bonds [vinylcyclohexene dioxide, dicyclopentadiene dioxide, etc.], polyepoxides of alicyclic ethers and alicyclic esters [bis (2,3-epoxycyclopentyl) ether, EG bis Epoxy dicyclopentyl ale, etc.], and a nuclear hydrogenated product of the aromatic ring-containing polyepoxide.

(A4) Examples of the heterocyclic ring-containing polyepoxide (A4) include divalent to hexavalent C5-30, such as trisglycidylmelamine.

  Of these epoxy group-containing compounds (A), aromatic ring-containing polyepoxides (A1) and (A2) are more preferable from the viewpoints of storage stability and coating strength of the emulsion (X) described later. Polyglycidyl ether of phenol (A1-1), polyglycidyl ether of aliphatic polyhydric alcohol (A2-1), particularly preferred are bisphenol A, bisphenol F, bisphenol S, phenol novolac, cresol novolac type polyglycidyl ether is there.

  The Mn of the epoxy group-containing compound (A) is preferably 500 to 20,000, more preferably 700 to 10,000, and particularly preferably 900, from the viewpoint of the water resistance of the coating film and the storage stability of the emulsion (X). -7,000, most preferably 1,000-4,000.

Mn and Mw in the present invention are measured by the GPC method under the following conditions.
Apparatus: “Alliance” Nippon Waters Co., Ltd. Column: Guardcolumn Super H-L
TSKgel Super H4000
TSKgel Super H3000
TSKgel Super H2000
(The above columns are connected in series.)
Solvent: Tetrahydrofuran (THF)
Reference substance: Polystyrene sample solution: 0.25 wt% tetrahydrofuran (THF) solution Column temperature: 40 ° C.

The number of epoxy groups in (A) is preferably 2 to 30 from the viewpoint of the coating strength of the coating film obtained by curing the one-component thermosetting resin emulsion (X) described below and the storage stability of (X). More preferably, it is 4-10.
The epoxy equivalent of (A) (unit: g / eq; only numerical values are shown below) is the viewpoint of the storage stability of the emulsion (X) described later and the coating strength of the coating film obtained by curing (X). To preferably 100 to 10,000, and more preferably 200 to 2,000.

  The softening point of (A) is preferably 20 to 170 ° C., more preferably 50 to 160 ° C., particularly preferably 60 to 150 ° C., from the viewpoint of storage stability and low-temperature curability of the emulsion (X) described later. It is. In the present invention, the softening point is measured in accordance with the ring and ball method (JIS K7234, “4.1 Ring and Ball Method” of “Test Method for Softening Point of Epoxy Resin”).

[Thermoplastic resin (B)]
The thermoplastic resin (B) in the present invention has a weight average molecular weight (sometimes abbreviated as Mw) of 5,000 to 150,000, preferably 8,000 to 100,000. The composition is not particularly limited as long as it is a resin capable of forming a resin.
When the Mw is less than 5,000, the storage stability of the one-component thermosetting resin emulsion (X) described later is deteriorated, and when the Mw is more than 150,000, the low temperature curability of (X) is deteriorated. Mw can be measured by the GPC method described later.
The softening point of (B) is preferably 30 to 170 ° C., more preferably 40 to 155 ° C., and particularly preferably 50 to 130 ° C. from the viewpoint of storage stability and low-temperature curability of (X). In the present invention, the softening point is measured in accordance with the ring and ball method (JIS K7234, “4.1 Ring and Ball Method” of “Test Method for Softening Point of Epoxy Resin”).

  Examples of (B) include vinyl resin (B1), polyester resin (B2), polyurethane resin (B3), polyurea resin (B4), polycarbonate resin (B5), and mixtures thereof.

(B1) Vinyl resin A vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (a1) to (a10).

(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, α-olefins other than those mentioned above; alkadienes such as butadiene and isoprene.
(A1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene and the like; terpenes such as pinene and limonene.
(A1-3) Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes, such as α-methylstyrene, vinyltoluene, ethylstyrene, and the like; and vinylnaphthalene.

(A2) Carboxyl group-containing vinyl monomer and salt thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-C24) ester, for example, (meth) acrylic acid, (meth) acrylic acid monoalkyl ester, ( Anhydrous) carboxyl group-containing vinyl monomers such as maleic acid, itaconic acid and cinnamic acid.

(A3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylate or (Meth) acrylamide, for example, sulfopropyl (meth) acrylate, 2- (meth) acrylamide-2-methylpropanesulfonic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random, block It is also possible to use mono (meth) acrylate sulfate ester [poly (n = 5-15) oxypropylene monomethacrylate sulfate ester, etc.], polyoxyethylene polycyclic phenyl ether sulfate ester, and the following general formulas (3-1) to ( 3-3) Sulfate Ether or sulfonic acid group-containing monomer; and the like salts thereof.

O- (AO) _n SO ₃ H
｜
_{CH 2 = CHCH 2 -OCH 2 CHCH} 2 O-Ar-R (3-1)

CH = CH-CH ₃
｜
R—Ar—O— (AO) _n SO ₃ H (3-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3-3)

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(A4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2-acryloyloxyethyl Phosphonic acid and the like.

  Examples of the salts (a2) to (a4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary salts. An ammonium salt is mentioned.

(A5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate and the like.

(A6) Nitrogen-containing vinyl monomer:
Examples of (a6) include (a6-1) to (a6-5).

(A6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, 4-vinylpyridine, and salts thereof;
(A6-2) Amide group-containing vinyl monomer: (meth) acrylamide, N-methyl (meth) acrylamide and the like;
(A6-3) Nitrile group-containing vinyl monomer: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc .;
(A6-4) Quaternary ammonium cation group-containing vinyl monomers: quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylamide (methyl chloride, dimethyl sulfate, benzyl) Quaternized with a quaternizing agent such as chloride or dimethyl carbonate);
(A6-5) Nitro group-containing vinyl monomer: nitrostyrene and the like.

(A7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(A8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(A9) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone:
(A9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, alkyl (meth) acrylates having 1 to 50 carbon atoms (methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.), etc .;
(A9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, etc. (a9-3) Vinyl ketone, such as vinyl methyl ketone, vinyl phenyl ketone;
Vinyl sulfones, such as divinyl sulfide, p-vinyl diphenyl sulfide, and the like.

(A10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

  Examples of the vinyl monomer copolymer include polymers obtained by (co) polymerizing any of the above-mentioned (a1) to (a10) monomers alone or in an arbitrary ratio. Copolymer, styrene- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester polymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene- (anhydrous) maleic acid (salt) copolymer Examples thereof include a polymer and a styrene- (meth) acrylic acid (salt) copolymer.

(B2) Polyester resin Examples of the polyester resin include a polycondensate of a polyol and a polycarboxylic acid or its acid anhydride or its lower alkyl ester. The polyol is a diol (b1) and a trivalent or higher polyol (b2), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (c1) and a trivalent or higher polycarboxylic acid (c2). And acid anhydrides or lower alkyl esters thereof.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/1, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]]. ˜1 / 1, particularly preferably 1.3 / 1 to 1.02 / 1.

As the diol (b1), alkylene glycol (ethylene glycol, neopentyl glycol, etc.);
Alkylene ether glycol (diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc.);
Alicyclic diols (such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A);
Bisphenol (bisphenol A, bisphenol F, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, etc.) adduct of the above alicyclic diol;
Alkylene oxide (ethylene oxide, propylene oxide, etc.) adduct of the above bisphenol;
In addition, polylactone diol (poly ε-caprolactone diol and the like), polybutadiene diol and the like can be mentioned.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenol, and particularly preferred are alkylene oxide adducts of bisphenol and combined use thereof with alkylene glycols having 2 to 12 carbon atoms. It is.

Examples of the trivalent or higher polyol (b2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.);
Trisphenol (such as trisphenol PA);
Novolac resins (phenol novolac, cresol novolac, etc.);
An alkylene oxide adduct of the above trisphenol;
Examples thereof include alkylene oxide adducts of the novolak resin.
Acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers]
Of these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and alkylene oxide adducts of novolac resins, and particularly preferred are alkylene oxide adducts of novolac resins.

Dicarboxylic acid (c1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, etc.); alkenylene dicarboxylic acid (maleic acid, etc.); branched alkylene dicarboxylic acid having 8 or more carbon atoms (dimer acid, alkenyl succinic acid (dodecenyl succinic acid, etc.)) Alkyl succinic acid (decyl succinic acid etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid etc.) and the like.
The dimer acid is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, and includes those obtained by hydrogenation to reduce the degree of unsaturation. As the dimer acid, for example, the commercially available Haridimer series (manufactured by Harima Kasei Co., Ltd.), Prepol series (manufactured by Croda Japan), and Empor series (manufactured by BASF Japan) can be used.

Examples of the trivalent or higher polycarboxylic acid (c2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
As the dicarboxylic acid (c1) or the trivalent or higher polycarboxylic acid (c2), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, etc.) described above may be used.

(B3) Polyurethane resin The polyurethane resin includes polyisocyanate (d), water, polyol [the diol (b1) and a trivalent or higher valent polyol (b2)], the dicarboxylic acid (c1), and a trivalent or higher polycarboxylic acid. (C2), polyamine (E1), polythiol (e) and the like} and the like.

  As polyisocyanate (d), C6-C20 aromatic polyisocyanate (d1), C2-C18 aliphatic polyisocyanate (d2), carbon number (excluding carbon in NCO group, the same applies hereinafter) 4-15 alicyclic polyisocyanate (d3), araliphatic polyisocyanate (d4) having 8-15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette) Group, uretdione group, uretoimine group, isocyanurate group, modified product containing oxazolidone group) (d5) and a mixture of two or more thereof.

The aromatic polyisocyanate (d1) is, for example, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI).
The aliphatic polyisocyanate (d2) is, for example, hexamethylene diisocyanate (HDI).
Examples of the alicyclic polyisocyanate (d3) include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), and methylcyclohexylene diisocyanate (hydrogenated TDI).
Examples of the araliphatic polyisocyanate (d4) include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified polyisocyanate (d5) include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, (d1), (d2), and (d3) are preferable, and TDI, MDI, HDI, hydrogenated MDI, and IPDI are particularly preferable.

  Examples of polythiol (e) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

(B4) Polyurea resin Examples of the polyurea resin include polyaddition products of polyisocyanate (d), water, and polyamine (E1).

  Of these thermoplastic resins (B), the vinyl resin (B1), the polyester resin (B2), the polyurethane (B3) resin, and those resins are preferable from the viewpoint that an aqueous dispersion (D0) described later is easily obtained. In combination, more preferred is (B1), particularly preferred is a styrene polymer, styrene- (maleic anhydride) (salt) copolymer, styrene- (meth) acrylic acid (salt) copolymer, (meth) acrylic. An acid ester polymer is a (meth) acrylic acid- (meth) acrylic acid ester copolymer.

[Surfactant (C)]
The surfactant (C) in the present invention is not particularly limited, and examples thereof include the following (C1) to (C4) and a mixture of two or more thereof.

(C1) Nonionic surfactant For example, an alkylene oxide addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant are mentioned.

Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, lauryl alcohol ethylene oxide adducts, stearyl alcohol ethylene oxide adducts, etc.); polyoxyalkylene higher fatty acid esters (for example, stearyl) Acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.);
Polyoxyalkylene polyhydric alcohol higher fatty acid esters (for example, lauric acid diester of polyethylene glycol, stearic acid diester of polyethylene glycol, etc.);
Polyoxyalkylene alkylphenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, bisphenol A ethylene oxide adduct, cumylphenol ethylene oxide adduct, styrenated cumylphenol ethylene oxide adduct Polyoxyalkylene alkylamino ether and (for example, laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamide (for example, ethylene oxide addition of hydroxyethyl lauric acid amide) Products, ethylene oxide adducts of hydroxypropyl oleic acid amide, etc.).

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, sorbitan monostearate, and sucrose monostearate.
Examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan monolaurate ethylene oxide adduct, and the like.
Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, and methyl glycoside.
Examples of the polyhydric alcohol alkyl ether alkylene oxide adduct include sorbitan monostearyl ether ethylene oxide adduct, methylglycoside ethylene oxide propylene oxide random adduct, and the like.

(C2) Cationic surfactant Examples include quaternary ammonium salt type and amine salt type.

  The quaternary ammonium salt type is obtained by reacting a tertiary amine with a quaternizing agent (alkylating agents such as methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate, ethylene oxide, etc.). For example, lauryl trimethyl Ammonium chloride, didecyldimethylammonium chloride, stearamide ethyl diethylmethylammonium methosulfate and the like can be mentioned.

The amine salt type can be obtained by neutralizing a primary to tertiary amine with an inorganic acid (hydrochloric acid, sulfuric acid, hydroiodic acid, etc.) or an organic acid (acetic acid, alkylphosphoric acid, etc.).
For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine and stearylamine); higher fatty acids of lower amines (such as stearic acid and oleic acid) Examples include salt.
Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines.
Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, etc.), aliphatic amine ethylene oxide (2 mol or more) adducts, alicyclic amines (N-methylpyrrolidine). , N-methylpiperidine, etc.), inorganic acid salts or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, etc.); triethanolamine monostearate, stearamide ethyl diethyl methyl ethanol Examples include inorganic acid salts or organic acid salts of tertiary amines such as amines.

(C3) Anionic surfactants Examples include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

  Examples of the carboxylic acid or a salt thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or a salt thereof. Specifically, saponified lauric acid, stearic acid, oleic acid, coconut oil, palm kernel oil, and the like. And a mixture of higher fatty acids obtained. Examples of the salt include salts of sodium, ammonium, alkanolamine and the like.

Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfate esters salts (1 to 10 moles of ethylene oxide of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (sulfurized lower alcohol esters of unsaturated fatty acids) And sulphated olefins (sulphated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt.
Specific examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester, stearyl alcohol sulfate ester, sulfate ester salt of alcohol synthesized using a Ziegler catalyst (for example, ALFOL 1214 manufactured by CONDEA), oxo method Sulfuric acid ester salts of synthesized alcohols (for example, Dovanol 23, 25, 45: manufactured by Mitsubishi Oil Chemical Co., Ltd., tridecanol: manufactured by Kyowa Hakko); specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mole adduct sulfuric acid Ester salts: Specific examples of sulfated oils include sodium oxide, castor oil, beef tallow and other sulfated sodium, ammonium, and alkanolamine salts. Specific examples of sulfated fatty acid esters include butyl oleate and butyl ricinoleate. Natri Ummum, ammonium, alkanolamine salts; Specific examples of sulfated olefins include teepol (manufactured by Shell).

Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms. It is done.
Specific examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt; aliphatic alcohol ethylene oxide 1-10 mol adduct carboxymethylated salt Specific examples include lauryl alcohol ethylene oxide 4 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide 5 mol adduct carboxymethylated sodium salt, and the like.

Examples of the sulfonate include alkylbenzene sulfonate, alkyl naphthalene sulfonate, sulfosuccinic acid diester type, α-olefin sulfonate, Igepon T type, and sulfonates of other aromatic ring-containing compounds.
Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include di-2 sulfosuccinic acid di-2 -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include higher alcohol phosphoric acid ester salts and higher alcohol ethylene oxide adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphate ester salts include lauryl alcohol phosphate monoester disodium salt; specific examples of higher alcohol ethylene oxide adduct phosphate ester salts include oleyl alcohol ethylene oxide 5-mole adduct phosphate monoester A disodium salt is mentioned.

(C4) Amphoteric surfactants Examples include carboxylate type amphoteric surfactants, sulfate ester type amphoteric surfactants, sulfonic acid type amphoteric surfactants, phosphate ester type amphoteric surfactants, and carboxylic acids Examples of the salt-type amphoteric surfactants include amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.

[R—NH— (CH ₂ ) _n —COO] _m M

[Wherein R is a monovalent hydrocarbon group; n is usually 1 or 2; m is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium cation, an amine cation, an alkanolamine cation. Etc. ]
Specific examples include alkylaminopropionic acid type amphoteric surfactants (such as sodium stearylaminopropionate); alkylaminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine), amide betaine (coconut oil fatty acid amidopropyl betaine etc.), alkyldihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.), etc. are mentioned.
Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroylglycine and dioctyldiaminoethylglycine hydrochloride; and sulfobetaine-type amphoteric surfactants such as pentadecylsulfotaurine.

Among the above (C), from the viewpoint of the aqueous dispersion (D0) described later, the coating film strength and the stability of the emulsion (X), (C1) and (C2) are preferable, and (C1) is more preferable. Particularly preferred are poly (20-80) oxyalkylene higher fatty acid esters and poly (20-80) oxyalkylene alkylphenyl ethers.
The number average molecular weight (Mn) of (C) is preferably from Mn 300 to 20,000, more preferably from the viewpoint of the emulsifiability of (A) and the coating strength of a cured product obtained by curing (X). Mn is 500 to 15,000, particularly preferably 1,000 to 10,000.

[Organic solvent (f)]
The organic solvent (f) used in the present invention is a thermoplastic resin (B) which is a shell component when preparing an aqueous dispersion (D0) of core / shell type main agent particles (D) of an epoxy group-containing compound (A). ) Is used for the purpose of dissolving. Moreover, it is used also for the purpose of melt | dissolving (A) as needed.

The organic solvent (f) can be used as long as it is incompatible with water. Here, the organic solvent incompatible with water has a water / octanol distribution coefficient (logPow) of 0 to 4.0, preferably 0.1 to 3.5, and more preferably 0.2 to 2. 0.
The octanol / water partition coefficient (logPow) can be determined by a flask shaking method described in JIS Z7260-107 (2000). The coefficient is expressed as a common logarithm of the concentration of each target substance when the target substance is in an equilibrium state in a system where the octanol phase and the aqueous phase are in contact with each other. It will be. It shows that hydrophobicity is so large that this coefficient is large.

  Furthermore, the organic solvent preferably has a boiling point lower than that of water, and more preferably, from the viewpoint of ease of solvent removal performed when preparing the aqueous dispersion (D0) of the core / shell type main agent particles (D). Has a boiling point of 90 ° C. or lower, particularly preferably a boiling point of 80 ° C. or lower.

  Specific examples of the organic solvent (f) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane and cyclohexane; methyl chloride, Halogen solvents such as methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene; esters or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, ethyl cellosolve acetate; diethyl ether Ether solvents such as tetrahydrofuran, dioxane, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone n- butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, alcohol solvents such as benzyl alcohol, and a mixed solvent of two or more thereof.

  The organic solvent (f) to be used varies depending on the composition of the thermoplastic resin (B). For example, when (B) is a vinyl resin, polyester resin or polyurethane resin, (f) is ethyl acetate, methyl ethyl ketone, tetrahydrofuran. , Chloroform and the like are preferable.

  The blending amount of the organic solvent (f) with respect to the thermoplastic resin (B) is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and particularly preferably 5 to 20% by weight as the concentration of (B) in the solution. %.

[Aqueous dispersion (D0) of core / shell type main agent particles (D)]
In the aqueous dispersion (D0) of the core / shell type main agent particles (D) of the present invention, the core contains the epoxy group-containing compound (A), and the shell has a weight average molecular weight of 5,000 to 150,000. Core / shell type main agent particles (D) containing the thermoplastic resin (B) are dispersed in an aqueous medium.
The core / shell type main agent particles (D) in the present invention are preferably composed of a core and a shell, and are preferably spherical.
That is, (D) is preferably “◎” in the TEM observation described later, in which case the inner circle is the core and the outer side is the shell.

Specific examples of the method for producing (D0) include the following methods [1] to [3]. In the present invention, the aqueous dispersion means that particles are dispersed in an aqueous medium to be described later, and includes emulsions.
[1] An aqueous dispersion containing an epoxy group-containing compound (A) and a surfactant (C) is gradually added to an organic solvent (f) solution of the thermoplastic resin (B) with stirring, and phase inversion emulsification is performed. To do. Next, the organic solvent (f) is distilled off by reducing the pressure while heating as necessary to obtain an aqueous dispersion (D0) of core / shell type main agent particles (D).
[2] After compatibilizing the epoxy group-containing compound (A), the thermoplastic resin (B) and the organic solvent (f), water is added and mixed by stirring to phase inversion emulsification. Here, the surfactant (C) may be added to the organic solvent (f), water, or both (f) and water. Preferable is a method of adding (C) to water.
Next, the organic solvent (f) is distilled off by heating under reduced pressure as necessary to obtain an aqueous dispersion (D0) of core / shell type main agent particles (D) of the epoxy group-containing compound (A). .
[3] An oil phase solution in which the epoxy group-containing compound (A), the thermoplastic resin (B), and the organic solvent (f) are compatibilized is prepared. A necessary amount of water is put into another container, and the oil phase solution prepared in the container is added at once, and then stirred and mixed to obtain a dispersion. Here, the surfactant (C) may be added to the organic solvent (f), water, or both (f) and water. Preferable is a method of adding (C) to water.
Next, the organic solvent (f) is distilled off by heating under reduced pressure as necessary to obtain an aqueous dispersion (D0) of core / shell type main agent particles (D) of the epoxy group-containing compound (A). .
In any of the methods [1] to [3], the organic solvent (f) may remain as long as the effects of the present invention are not impaired, but the organic solvent (f) is used from the viewpoint of storage stability. It is preferable to distill off. Based on the weight of (D0), the weight of (f) is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less.
Of the above [1] to [3], the methods [1] and [2] are preferable from the viewpoint of industrial and storage stability, and the method [1] is more preferable.

Examples of the aqueous medium in the present invention include water and hydrophilic organic solvents other than (f) [C1-3 lower alcohol (such as methanol, ethanol and isopropanol), C3 ketone (acetone), C2-6 glycol (ethylene Glycol, propylene glycol, diethylene glycol, triethylene glycol and the like) and monoalkyl (C1-2) ethers thereof, dimethylformamide and the like].
These may be used alone or in combination of two or more. Of the aqueous medium, water and a mixture of water and a hydrophilic organic solvent are preferable from the viewpoint of safety and storage stability, and water and a mixture of water and a hydrophilic solvent are more preferable ( Water is 50% by weight or more, preferably water is 90% by weight or more), and particularly preferred is water.

The content of (B) based on the weight of (A) in the aqueous dispersion (D0) of the present invention is preferably from 5 to 100%, more preferably from the viewpoint of the coating ratio of the core described later and the coating strength. Is 10 to 80%, particularly preferably 15 to 60%.
Further, the content of (C) based on the weight of (A) is preferably 2 to 30%, more preferably 5 to 25%, from the viewpoint of storage stability and coating strength of the emulsion (X) described later. Especially preferably, it is 8 to 20%.
The solid content concentration of (D0) is preferably 10 to 80%, more preferably 20 to 70%, and particularly preferably 40 to 55% from the viewpoint of storage stability and coating strength of the emulsion (X) described later. is there. The solid content concentration shown here is a value obtained by dividing the weight of (D0) obtained by heating and drying at 130 ° C. for 135 minutes by the weight before heating and drying.

The core coverage (%) of the aqueous dispersion (D0) of the core / shell type main agent particles (D) in the present invention is evaluated by the following two methods [1] and [2]. The core coverage is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more, from the viewpoint of the storage stability of (D0) and low-temperature curability.
[1] Core coverage by epoxy value (%)
In the prepared aqueous dispersion of core / shell type main agent particles, the ratio of the core covered by the shell is calculated based on the formula (1) from the epoxy value measured by the following two methods.

Core coverage (%) =
([Epoxy value by measurement method 2]-[Epoxy value by measurement method 1]) × 100
/ [Epoxy value by measurement method 2] Formula (1)

(1-1) Measurement of epoxy value [Measurement method 1]
The epoxy value of the prepared aqueous dispersion of core / shell type main agent particles was measured based on the method described in JIS K7236 except that the measurement solvent was changed from toluene to water. In the case where the core / shell type main agent particles are aqueous dispersions, a sample to be dehydrated by drying under reduced pressure (2 kPa) for 5 hours at 50 ° C. was used as a measurement sample.
(1-2) Measurement of epoxy value [Measurement method 2]
The epoxy value of the prepared aqueous dispersion of core / shell type main agent particles was measured by the method described in JIS K7236 except that the measurement solvent was changed from toluene to N, N′-dimethylformamide. In addition, when the core / shell type main agent particles were an aqueous dispersion, the dehydrated one was used as a measurement sample in the same manner as (1-1).

[2] Core coverage by TEM (%)
In the prepared aqueous dispersion of core / shell type main agent particles, the ratio of the core covered by the shell is adjusted by the method shown below, and observed with a transmission electron microscope (TEM). A total of 100 core / shell-type main agent particles were observed at random, and divided into particles with an exposed core and particles with no exposed core, and the ratio of the number of particles with no exposed core (%) Is calculated.
(1) First, core / shell type main agent particles are embedded in an acrylic resin and dyed with ruthenium tetroxide.
(2) Next, in a state where the dyed sample is cooled to −80 ° C. with an ultramicrotome, the sample is cut out to have a thickness of 80 nm, and TEM observation is performed on the cross section of the core / shell type main agent particles. Examples of the TEM to be used include “thermal FE-SEM JSM7000F” manufactured by JEOL and “cold FE-TEM” manufactured by Hitachi.

[Curing agent (E) which is compound (E1) having at least two amino groups capable of reacting with epoxy group and / or epoxy polymerization catalyst (E2)]
Examples of the curing agent (E) in the present invention include a compound (E1) having at least two amino groups capable of reacting with an epoxy group, an epoxy polymerization catalyst (E2), and a mixture thereof.

The number of functional groups in the compound (E1) having at least two amino groups capable of reacting with an epoxy group is the coating strength of a cured product obtained by curing the one-component thermosetting emulsion (X) described later and (X). From the viewpoint of storage stability, the number is preferably 2 to 15, more preferably 3 to 8.
The number average molecular weight (Mn) of the (E1) is preferably 50 to 20,000, more preferably from the viewpoint of the coating strength of the coating obtained by curing the (X) described later and the emulsifying dispersibility of (E). Is 70-5,000.
In the present invention, Mn and weight average molecular weight (Mw) can be measured by the GPC method.
Moreover, the active hydrogen equivalent of (E1) (molecular weight per active hydrogen, unit: g / eq. Only numerical values are shown below) is obtained by curing the storage stability of (X) and (X). From the viewpoint of the coating strength of the coating film, it is preferably 25 to 5,000, more preferably 50 to 2,500.

  Examples of the compound (E1) having at least two amino groups capable of reacting with an epoxy group include the following (E11) to (E15) and mixtures of two or more thereof.

(E11) Polyamine Aliphatic poly (2-7 valent) amine (E11-1), alicyclic ring-containing poly (2-3 valent) amine (E11-2), heterocyclic ring-containing poly (2-3 valent) amine (E11) -3), aromatic ring-containing polyamines and mixtures thereof.
(E11-1) Aliphatic poly (2-7 valent) amines C2 or more and Mn500 or less, for example, C2-10 alkylene diamine (ethylene diamine, propylene diamine, etc.), polyalkylene (C2-10) poly (trivalent ˜ Hexavalent or higher) amines (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.) and their alkyl (C1-4) or hydroxyalkyl (C2-4) substituents, for example dialkyl (C1-3) amino Propylamine, trimethylhexamethylenediamine, aminoethylethanolamine;

(E11-2) Alicyclic ring-containing poly (2 to 3 valent) amines having C4-15, such as 1,3-diaminocyclohexane, isophoronediamine;

(E11-3) Heterocycle-containing poly (2 to 3 valent) amines of C4-15, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine;

(E11-4) Aromatic ring-containing polyamines C8-15, such as xylylenediamine, tetrachloro-p-xylylenediamine, diaminodiphenylmethane.

(E12) Polyamidoamine Mn of 200 to 20,000, amine value of 1 to 50 mgKOH / g, acid value of 0 to 40 mgKOH / g;
In addition, an amine value is represented by the milligram number of potassium hydroxide used as a molar equivalent with the base component in 1g of resin. On the other hand, the acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. Both are measured by the method described in JIS K2501.

  (E12) is obtained, for example, by a condensation reaction between the above (E11) and dicarboxylic acid (c) in excess (1.1 to 2 equivalents per equivalent of carboxyl group). Examples of the dicarboxylic acid (c) constituting (E12) include the aforementioned (c1) and a mixture of two or more thereof.

(E13) Epoxy-added polyamines having Mn of 400 to 20,000, for example, 1 equivalent of epoxy group-containing compound (A) and 1.1 to 2 equivalents or more of the reaction product (1 mol of bisphenol A type polyglycidyl ether) And an addition reaction product of 2 mol of xylylenediamine, an addition reaction product of 1 mol of cresol novolac-type polyglycidyl ether and 3 mol of ethylenediamine);

(E14) Polyether polyamines having a Mn of 500 to 20,000, for example, hydrogenated products of cyanoethylated products of polyether polyols (polytetramethylene glycol, etc.);

(E15) Urethane-modified polyamines having a Mn of 500 to 20,000, for example, a reaction product of polyisocyanate (d) described later and (a) (alkylene diamine, polyalkylene polyamine, etc.);

  Examples of the epoxy polymerization catalyst (E2) include known ones such as trimethylamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, 1,8-diazabicyclo [5.4.0] -7-undecene. (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) or 1,4-diazabicyclo [2.2.2] octane (DABCO), imidazole, 2-methylimidazole, 1- Benzylimidazole, 2-ethyl-4-methylimidazole, boron trifluoride monoethylamine complex, boron trifluoride diethyl ether complex; and mixtures of two or more thereof.

  Among the above (E), from the viewpoint of the coating strength of a cured product obtained by curing the one-component thermosetting resin emulsion (X) and the storage stability of (X), (E11) and (E12) are preferable. , (E13), (E16), (E2), more preferably (E11), (E12), N, N-dimethylethanolamine, 1,8-diazabicyclo [5.4.0] -7-undecene ( DBU), particularly preferred is (E11), N, N-dimethylethanolamine.

[One-part thermosetting resin emulsion (X)]
The one-component thermosetting resin emulsion (X) of the present invention comprises, in an aqueous medium, the core / shell type main agent particles (D) and the compound (E1) having at least two amino groups capable of reacting with epoxy groups and And / or a curing agent (E) which is an epoxy polymerization catalyst (E2).
In addition, the one-component thermosetting resin emulsion (X) preferably contains the aqueous dispersion (D0) of (D) and (E) from the viewpoint of industrial and low-temperature curability.

As a specific production method of the (X), for example, the core / shell type main agent particles (D) and / or the aqueous dispersion (D0) of the (D) prepared by the above-described method, and an epoxy group are reacted. A curing agent (E) which is a compound (E1) having at least two amino groups and / or an epoxy polymerization catalyst (E2), an aqueous dispersion (E0) of the (E) and / or an aqueous solution of the (E) The method of mixing with a medium solution (E00) is mentioned. Of these (D) and (D0), (D0) is preferred from the industrial viewpoint.
Of the (E), the aqueous dispersion (E0) and the aqueous medium solution (E00), (E0) and (E00) are more preferable from the viewpoints of storage stability and low-temperature curability of (X) (E0). ).

Examples of the method for producing the aqueous dispersion (E0) of (E) and the aqueous medium solution (E00) of (E) include the methods [1] to [3].
[1] If necessary, an organic solvent (f) is added to the compound (E1) having at least two amino groups capable of reacting with an epoxy group and / or the curing agent (E) which is an epoxy polymerization catalyst (E2), and further the interface While adding the activator (C), the aqueous medium is gradually added dropwise, etc. while stirring, and phase inversion emulsified. Next, by reducing the pressure while heating as necessary, the organic solvent is distilled off, and the compound (E1) and / or epoxy polymerization catalyst (E2) having at least two amino groups that can react with the epoxy group. A method of obtaining an aqueous dispersion (E0) of a certain curing agent (E).
[2] If necessary, a surfactant (C) is added to the curing agent (E) which is a compound (E1) and / or an epoxy polymerization catalyst (E2) having at least two amino groups capable of reacting with an epoxy group to which an organic solvent is added. And a compound (E1) having at least two amino groups capable of reacting with an epoxy group by adding an aqueous medium solution or an aqueous medium of A method of obtaining an aqueous dispersion (E0) of a curing agent (E) that is an epoxy polymerization catalyst (E2).
[3] Under stirring, an aqueous medium is added to the compound (E1) having at least two amino groups capable of reacting with an epoxy group and / or the curing agent (E) which is an epoxy polymerization catalyst (E2) to dissolve the epoxy. A method for obtaining an aqueous medium solution (E00) of a curing agent (E) which is a compound (E1) having at least two amino groups capable of reacting with a group and / or an epoxy polymerization catalyst (E2).

In any of the methods [1] to [3], the organic solvent may remain as long as the effects of the present invention are not impaired, but it is preferable to distill off the organic solvent from the viewpoint of storage stability. .
Of the above [1] to [3], the methods [1] and [2] are preferred from the viewpoint of industrial and (X) storage stability, and the method [1] is more preferred.

The equivalent ratio [(A) / (E1)] of (A) and (E1) constituting the one-component thermosetting resin emulsion (X) of the present invention is a cured product obtained by curing (X). From the viewpoint of coating strength and storage stability of (X), it is preferably 30/70 to 90/10, more preferably 40/60 to 70/30.
The equivalent ratio [(A) / (E1)] can be calculated from the epoxy equivalent of (A) and the active hydrogen equivalent of (E1) (unit: g / eq. Only numerical values are shown below).
The weight ratio [(A) / (E2)] of (A) and (E2) constituting the one-component thermosetting resin emulsion (X) is the adhesion of a cured product obtained by curing (X). From the viewpoint of strength and storage stability of (X), it is preferably 80/20 to 99.9 / 0.1, more preferably 95/5 to 99.5 / 0.5.

  The total weight of (D) and (E) based on the weight of the one-component thermosetting resin emulsion (X) of the present invention is preferably 20 to 80% from the viewpoint of storage stability and paintability of (X). More preferably, it is 30 to 70%. In addition, the total weight of (D) and (E) based on the weight of (X) can be appropriately adjusted by adding or distilling an aqueous medium as necessary.

The viscosity (mPa · s) of (X) at 25 ° C. is preferably 1,000 to 100,000, and more preferably 2,000 to 5,000, from the viewpoint of sagging prevention and handling properties.
In addition, the median particle diameter (unit: μm, only numerical values are shown below) of the particles (D) and (E) in (X) is preferably from the viewpoint of the viscosity and storage stability of (X). It is 0.01-50, More preferably, it is 0.1-20. The median particle diameter in the examples is a value measured using a laser diffraction / scattering type particle size distribution measuring apparatus [trade name “LA-700”, manufactured by Horiba, Ltd.] applying light scattering theory. (Unit: μm).
Further, the median particle diameters of the aqueous dispersion (D0) (D) and the aqueous dispersion (E0) (E) were also measured in the same manner.

[Additive (F)]
In the one-component thermosetting resin emulsion (X) of the present invention, a filler, an antiseptic, a heat stabilizer, a weather stabilizer, a colorant, a thickener, and a leveling are necessary as long as the effects of the present invention are not impaired. 1 type, or 2 or more types of additives (F) chosen from the group which consists of an agent, an antifoamer, a viscoelasticity modifier, and a dynamic surface tension regulator can be contained.
The (F) can be added at any stage of the production process (X).
The total content of the additive (F) is usually 30% or less, preferably 0.1 to 20%, more preferably based on the total weight of the one-component thermosetting resin emulsion (X) after the addition of the additive. 0.2 to 10%.

Examples of the filler (F1) include sodium carbonate and silica.
The content of (F1) is usually 10% or less, preferably 0.1 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the preservative (F2) include methyl paraben and ethyl paraben.
The content of (F2) is usually 10% or less, preferably 0.1 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the heat resistance stabilizer (F3) include tris (2,4-di-t-butylphenyl) phosphate, dioctadecyl-3,3′-thiodipropionate, and the like.
The content of (F3) is usually 10% or less, preferably 0.1 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the weather stabilizer (F4) include ultraviolet absorbers such as salicylic acid compounds (such as phenyl salicylate), benzophenones (such as 2,4-dihydroxybenzophenone), and benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl). ) Benzotriazole, etc.], cyanoacrylate compounds (2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, etc.); light stabilizers such as hindered amines [octylated diphenylamine, isooctyl-3- (3,5-di-) tert-butyl-4-hydroxyphenol) propionate, etc.].
The content of (F4) is usually 10% or less, preferably 0.5 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Colorants (F5) include pigments and dyes. Among the pigments, inorganic pigments include titanium oxide, carbon black and the like; organic pigments include azo pigments (azo lakes, monoazos, etc.) and polycyclic pigments (benzimidazolones, phthalocyanines, etc.).
Examples of the dye include nigrosine and aniline.
The content of (F5) is usually 30% or less, preferably 1 to 10%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the thickener (F6) include montmorillonite and colloidal alumina.
The content of (F6) is usually 10% or less, preferably 0.1 to 5%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

As a leveling agent (F7), Mn is preferably 100 to 1,000, polyolefin resin [polyethylene, polypropylene, etc.], olefin- (meth) acrylic acid copolymer [ethylene- (meth) acrylic acid copolymer, etc. ], Polyvinylpyrrolidone, etc. are mentioned.
The content of (F7) is usually 6% or less, preferably 0.5 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the antifoaming agent (F8) include mineral oil defoaming agents and silicone oil defoaming agents.
The content of (F8) is usually 6% or less, preferably 0.5 to 3%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

As the viscoelasticity modifier (F9), a high molecular type (Mn 10,000-500,000, for example, polycarboxylic acid, polysulfonic acid, polyether-modified carboxylic acid, polyether), association type (Mn 10,000-500). 1,000, for example, urethane-modified polyether).
The content of (F9) is usually 10% or less, preferably 0.1 to 5%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

Examples of the dynamic surface tension adjusting agent (F10) include acetylene glycol and fluorine-containing compound silicone-containing compounds. The dynamic surface tension adjusting agent has a function of reducing the surface tension.
The content of (F10) is usually 20% or less, preferably 0.1 to 10%, based on the total weight of the one-component thermosetting resin emulsion (X) after addition of the additive.

[Coating film, article to be coated]
The coating film of the present invention is formed by curing the one-component thermosetting resin emulsion (X). The (X) can be applied using a spray coating machine, which is a conventional water paint coating equipment or solvent paint coating equipment, and does not require new equipment.
As a coating method, the wet film thickness (film thickness immediately after coating) is preferably 10 to 200 μm, more preferably 20 to 100 μm, from the viewpoint of coating effect and industry, with respect to the object to be coated (X). The method of spray-coating so that

The coated object is preferably 100 to 180 ° C., more preferably 120 to 160 ° C. from the viewpoint of coating film curability and industrial, and preferably from 60 to 60 minutes from the same viewpoint. More preferably, the coating film can be formed with a curing time of 8 to 30 minutes, particularly preferably 10 to 20 minutes.
The film thickness of the coating film after curing is preferably 10 to 150 μm, more preferably 15 to 50 μm, from the viewpoint of coating effect and industrial viewpoint.
The article to be coated, which is obtained by curing the object to be coated, is excellent in adhesion to the substrate, the strength of the coating film, and the water resistance of the coating film. Therefore, Emulsion (X) is suitable for various applications, especially paints and adhesives. ing.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

The composition, symbols, etc. of the raw materials used in the examples and comparative examples are as follows.
(1) Epoxy group-containing compound (A)
(A-1): Cresol novolac type polyglycidyl ether
[Product name “EOCN-104S”, Nippon Kayaku Co., Ltd.,
Mn 2,000, epoxy equivalent 200]
(A-2): Bisphenol A type polyglycidyl ether
[Product name “JER828”, manufactured by Mitsubishi Chemical Corporation, Mn340,
Epoxy equivalent 475]
(A-3): Bisphenol F type polyglycidyl ether
[Product name "JER4010P", manufactured by Mitsubishi Chemical Corporation,
Mn 8,800, epoxy equivalent 4,400]
(A-4): Ethylene glycol diglycidyl ether
[Product name "Denacol EX-810", manufactured by Nagase ChemteX Corporation,
Mn202, epoxy equivalent 113]
(A-5): Pentaerythritol polyglycidyl ether
[Product name "Denacol EX-411", manufactured by Nagase ChemteX Corporation,
Mn 1,200, epoxy equivalent 230]
(A-6): Hydrogenated bisphenol A diglycidyl ether
[Product name "Denacol EX-252", manufactured by Nagase ChemteX Corporation,
Mn352, epoxy equivalent 213

(2) Thermoplastic resin (B)
(B-1): Polystyrene [trade name “Dick Styrene CR-2500”,
Dainippon Ink, Mw 145,000]
(B-2): Styrene-maleic anhydride copolymer
[Product name “XIRAN SZ15170”, manufactured by POLYSCOPE,
Mw 150,000]
(B-3): Methyl methacrylate-styrene-butyl acrylate copolymer
[Product name "Acripet IRL-409"
Mitsubishi Rayon Co., Ltd., Mw 80,000]
(B-4): Polycarbonate resin [trade name “Panlite L-1250Y”,
Teijin Chemicals Ltd., Mw 40,000]

(3) Vinyl monomer (a)
(A-1): Styrene (a-2): Maleic anhydride (a-3): Methyl methacrylate (a-4): Butadiene

(4) Dicarboxylic acid (c)
(C-1): terephthalic acid (c-2): dimer acid [trade name “EMPOL 1061”,
BASF Japan Co., Ltd.]
(C-3): Adipic acid

(5) Surfactant (C)
(C-1): Styrenated phenol EO 17 mol adduct
[Product name "Sunspearl ST-36", manufactured by Sanyo Chemical Industries, Ltd.]
(C-2): Bisphenol AEO 18 mol adduct
[Product name "New Pole BPE-180", manufactured by Sanyo Chemical Industries, Ltd.]
(C0-3): 28% aqueous solution of stearyltrimethylammonium chloride (C-3)
[Product name "Econol TMS-28", manufactured by Sanyo Chemical Industries, Ltd.]
(C-4): Sodium lauryl sulfate (C0-5): 36% aqueous solution of coconut oil fatty acid amidopropyl betaine (C-5)
[Product name "Rebon 2000", manufactured by Sanyo Chemical Industries, Ltd.]
(6) Organic solvent (f)
(F-1): Ethyl acetate (logPow 0.73)
(F-2): methyl ethyl ketone (hereinafter referred to as MEK) (logPow 0.29)
(F-3): Toluene (logPow 2.73)
(7) Polyisocyanate (d)
(D-1): Isophorone diisocyanate

(8) Curing agent (E) which is compound (E1) and / or epoxy polymerization catalyst (E2) having at least two amino groups capable of reacting with epoxy groups
(E1-1): Triethylenetetramine (E1-2): Pentaethylenehexamine (E1-3): m-xylylenediamine (E1-4): Ethylenediamine (E2-1): 1,8-diazabicyclo [5. 4.0] -7-Undecene (DBU)
(E2-2): N, N-dimethylethanolamine (E2-3): 2-ethyl-4-methylimidazole (E2-4): Boron trifluoride monoethylamine complex

[Production of thermoplastic resin (B)]
Production Example 1
The reaction vessel was charged with 700 parts of (f-1) and heated up until the solvent was refluxed. In a separate container, a monomer solution in which 300 parts of (a-1), 32 parts of (a-2) and 140 parts of (f-1) are compatibilized, and 5 parts of dodecyl mercaptan and 2,2′-azobis (2 , 4-dimethylvaleronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.] 5 parts and (f-1) 80 parts of compatibilized initiator solution 1 are respectively prepared. The monomer solution and the initiator solution were added dropwise to the reaction vessel over 3 hours. After completion of the dropwise addition, the mixture was reacted for 3 hours under reflux conditions. Thereafter, an initiator solution 2 in which 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 25 parts of (f-1) are compatibilized is added dropwise, and after completion of the addition, 3 hours under reflux conditions. Reacted. Thereafter, the solvent was removed to obtain a thermoplastic resin (B-5) (Mw 60,000).

Production Example 2
In Production Example 1, (a-1) 300 parts and (a-2) 32 parts were replaced with (a-3) 300 parts, and Dodecyl Mercaptan 5 parts was replaced with 10 parts. Thus, a thermoplastic resin (B-6) (Mw 30,000) was obtained.

Production Example 3
In Production Example 1, (a-1) 300 parts and (a-2) 32 parts are replaced with (a-1) 275 parts, (a-3) 8 parts, and (a-4) 20 parts, and dodecyl mercaptan 5 A thermoplastic resin (B-7) (Mw 10,000) was obtained in the same manner as in Production Example 1, except that the part was changed to 20 parts.

Production Example 4
In a reaction vessel, 200 parts of (c-1), 92 parts of 1,3-propylene glycol, and 0.3 part of dibutyltin oxide were charged, pressurized to 0.3 MPa with nitrogen gas, and then heated to 220 ° C. The reaction was performed at the same temperature for 6 hours, the pressure in the reaction vessel was reduced from 0.3 MPa to 2 kPa, and the reaction was further continued for 1 hour. After returning the pressure to normal pressure, the product was cooled and taken out at 180 ° C. to obtain a thermoplastic resin (B-8) (Mw 18,000).

Production Example 5
In a reaction vessel, 330 parts of polytetramethylene glycol [trade name “PTMG3000”, manufactured by Mitsubishi Chemical Corporation, Mn3,000] and 9 parts of diethylene glycol, 57 parts of (d-1) and 600 parts of N, N′-dimethylformamide were added. While charging and stirring, the temperature was raised to 120 ° C., and the reaction was carried out at the same temperature for 5 hours. After confirming that the isocyanate group content in the system was not detected even when the content was measured, the reaction was stopped. Further, the solvent was removed to obtain a thermoplastic resin (B-9) (Mw 15,000).

Comparative production example 1
In Production Example 1, (a-1) 300 parts and (a-2) 32 parts were replaced with (a-1) 300 parts, except that dodecyl mercaptan was not added. A plastic resin (ratio B-1) (Mw 200,000) was obtained.

Comparative production example 2
In Production Example 1, a thermoplastic resin (ratio B-2) (Mw 3,000) was obtained in the same manner as in Production Example 1 except that 5 parts of dodecyl mercaptan was replaced with 20 parts.

[Production of Surfactant (C)]
Production Example 6
A reaction vessel was charged with 25.5 parts of 4-α-cumylphenol and 2.3 parts of Lewis acid catalyst “Galeon Earth” [manufactured by Mizusawa Chemical Co., Ltd.], and the system was replaced with nitrogen gas while stirring at 90 ° C. The temperature was raised to. At the same temperature, 89.5 parts of styrene was added dropwise over 3 hours, and the reaction was further performed at the same temperature for 5 hours (Friedel-Crafts reaction). After cooling the product to 30 ° C., the catalyst was filtered off to obtain 100 parts of 4-α-cumylphenol styrene 5 mol adduct.
Next, in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 100 parts of the resulting 4-α-cumylphenol styrene 5-mol adduct and 1 part of aluminum perchlorate nonahydrate were added. The mixture was purged with nitrogen, sealed, heated to 90 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 95 ° C., 152 parts of EO were added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 95 ° C. for 5 hours. Next, after cooling to 70 ° C., 15 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 70 ° C. for 1 hour and treated. C-6) was obtained.

Production Example 7
A reaction vessel was charged with 16.6 parts of (C-6) prepared in Production Example 6, 71.4 parts of PEG (Mn8,650) and 0.024 part of phosphoric acid, heated to 110 ° C., stirred and stirred. The inside was made uniform. After dehydration at the same temperature until the water content was 0.04%, 2.1 parts of HDI was added and reacted at 130 ° C. for 5 hours. Then, when it became 100 degreeC, 210 parts of water was thrown in in 10 minutes, and 30% aqueous solution (C0-7) of surfactant (C-7) was obtained.

[Aqueous dispersion (D0) of core / shell type main agent particles (D)]
Example 1
A container was charged with 39 parts of (A-1) and 39 parts of (f-1), and 5 parts of (C-6) was added thereto, followed by stirring at 30 ° C. for 30 minutes. Thereafter, 24 parts of water was added dropwise at the same temperature over 2 hours to effect phase inversion emulsification, and the solvent was removed at 50 ° C. under reduced pressure (30 kPa or less, the same shall apply hereinafter) for 2 hours to obtain an aqueous solution of (A-1). A dispersion (A0-1) was obtained.
112 parts of (f-1) was charged into another container, 6 parts of (B-1) was added, and the mixture was stirred at 30 ° C. for 2 hours. At the same temperature, 68 parts of the prepared aqueous dispersion (A0-1) of (A-1) was added dropwise over 2 hours and phase-inverted and emulsified at 50 ° C. under reduced pressure (30 kPa or less, the same applies hereinafter). The solvent was removed for 2 hours. Thereafter, 26 parts of water was added for the purpose of adjusting the solid content concentration, followed by stirring at 30 ° C. for 30 minutes to obtain an aqueous dispersion (D0-1) of core / shell type main agent particles (D-1). The solid content concentration of (D0-1) was 50%.

Examples 2-7, 9-10, 12-14, Comparative Examples 1-3
In Example 1, an aqueous dispersion of core / shell type main agent particles in the same manner as in Example 1 except that (A), (B), (C), (f) and water were used according to Table 1. Got.

Example 8
A container was charged with 43 parts of (A-1), 3 parts of (B-2), and 115 parts of (f-1), and stirred at 30 ° C. for 2 hours. Thereto, a surfactant aqueous solution in which 4 parts of (C-6) and 50 parts of water were compatibilized was added dropwise at 30 ° C. over 2 hours with stirring to effect phase inversion emulsification.
Next, the solvent was removed under reduced pressure for 2 hours to obtain an aqueous dispersion (D0-8) of core / shell type main agent particles (D-8).

Example 11
The container was charged with 39 parts of (A-1), 6 parts of (B-1), and 151 parts of (f-1), and stirred at 30 ° C. for 2 hours. Thereto, a surfactant aqueous solution in which 5 parts of (C-6) and 50 parts of water were compatibilized was added at once, and stirred at the same temperature for 1 hour to obtain a dispersion. Thereafter, the solvent was removed under reduced pressure for 2 hours to obtain an aqueous dispersion (D0-11) of core / shell type main agent particles (D-11).

The results of Examples 1 to 14 and Comparative Examples 1 to 3 are shown in Table 1.

[Production of curing agent (E)]
Production Example 8
The reaction vessel was charged with 124 parts of (E1-1) and 200 parts of (c-2), and the temperature was raised to 120 ° C. while nitrogen gas was passed at a flow rate of 1 L / min. After reacting at the same temperature for 3 hours, the temperature was further raised to 180 ° C. and reacted for 10 hours. Then, after the acid value of the content became 0 mgKOH / g, it was taken out to obtain a curing agent (E1-5) (Mn860, active hydrogen equivalent 88) which is a compound having at least two amino groups capable of reacting with an epoxy group. It was.

Production Example 9
In Production Example 8, (E1-1) 124 parts and (c-2) 200 parts were replaced with (E1-2) 368 parts and (c-3) 97 parts in the same manner as in Production Example 8, A curing agent (E1-6) (Mn610, active hydrogen equivalent 46), which is a compound having at least two amino groups capable of reacting with an epoxy group, was obtained.

Production Example 10
In a reaction vessel, 16.0 parts of (f-2) and 18.9 parts of (E1-3) were charged, 35.1 parts of (A-2) were added and mixed uniformly, and reacted at 50 ° C. for 2 hours. Thereafter, the solvent was removed under reduced pressure to obtain a curing agent (E1-7) (Mn1,560, active hydrogen equivalent 390), which is a compound having at least two amino groups capable of reacting with an epoxy group.

Production Example 11
In a reaction vessel, 400 parts of polytetramethylene glycol [trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation, Mn2,000] and 66 parts of (d-1) were charged, and the temperature was raised to 120 ° C. with stirring. For 5 hours. Thereafter, the mixture was cooled to room temperature, and 800 parts of (f-6) was charged and stirring was continued until the solution [prepolymer solution (1)] became uniform. In a separate container, a solution [amine solution (1)] containing 12 parts of (E-4) and 100 parts of (f-6) was mixed and stirred until the system became a uniform solution. Under stirring, at room temperature, the amine solution (1) was dropped into a reaction vessel containing the prepolymer solution (1) over 1 hour. The reaction was continued for 2 hours at room temperature. After confirming that the isocyanate group content in the system was not detected, the reaction was stopped. Further, the solvent was removed to obtain a curing agent (E1-8) (Mn 4,800, active hydrogen equivalent 1,197) which is a compound having at least two amino groups capable of reacting with an epoxy group.

[Production of aqueous dispersion (E0) and aqueous solution (E00) of curing agent (E)]
Production Example 12
A container was charged with 38 parts of (E1-5) and 50 parts of (f-1), and 12 parts of (C-6) was added thereto, followed by stirring at 30 ° C. for 30 minutes. Thereafter, 60 parts of water was added dropwise at the same temperature over 2 hours to effect phase inversion emulsification, and the solvent was removed at 50 ° C. under reduced pressure (30 kPa or less, the same shall apply hereinafter) for 2 hours to obtain an aqueous solution of (E1-5). A dispersion (E01-5) was obtained.

Production Examples 13-15, 19
In Production Example 12, an aqueous dispersion of a curing agent (E) was obtained in the same manner as in Production Example 12 except that (E1), (E2), (C), (f) and water were used according to Table 2. It was.

Production Example 16
A container was charged with 50 parts of (E1-1) and 50 parts of water and stirred at 30 ° C. for 30 minutes to obtain an aqueous solution (E001-1) of (E1-1).

Production Example 18
In Production Example 16, an aqueous solution (E002-1) of a curing agent (E2) was obtained in the same manner as in Production Example 16 except that water was used according to Table 2 (E2).

Production Example 17
A container was charged with 43 parts of (E1-7) and 50 parts of (f-1), and 17 parts of (C-7) was added thereto, followed by stirring at 30 ° C. for 30 minutes. Thereafter, 38 parts of water was added at the same temperature and mixed with stirring.
Next, the prepared mixed solution was stirred with a TK auto homomixer [manufactured by Primix Co., Ltd.] for 2 minutes at 10,000 rpm, and then transferred to a container equipped with a stirring device to remove the solvent (E1-7 ) Aqueous dispersion (E01-7β) was obtained.

  The results of Production Examples 12 to 19 are shown in Table 2.

[One-part thermosetting resin emulsion (X)]
Examples 15 to 37, Comparative Examples 4 to 6
Formulated and mixed according to Tables 3 and 4 (temperature 25 ° C., stirring time 30 minutes), one-component thermosetting resin emulsions (X-1) to (X-23), (ratio X-1) to (ratio X−) 3) was obtained. Each emulsion was evaluated for performance by the following test method. The results are shown in Tables 3 and 4.

<Test method>
(1) Median particle diameter of emulsion (X) particles The median particle diameter of emulsion particles is a laser diffraction / scattering type particle size distribution measuring device applying the light scattering theory [trade name “LA-700”, manufactured by Horiba, Ltd. ] (Unit: μm).
(2) Pencil hardness (evaluation of low-temperature curability and coating film strength)
The surface of a test steel sheet [0.5 mm × 80 mm × 150 mm cold-rolled steel sheet (SPCC-SD) specified in JIS G3141] is degreased with methanol, and the thickness of the coating film after baking is 30.
The emulsion was applied to ˜40 μm, a test piece was prepared by low-temperature baking (140 ° C., 20 minutes), and the pencil hardness was evaluated according to the pencil method of JIS K5600-5-4.
(3) Adhesion (Evaluation of low temperature curability)
Test pieces were prepared by the method of (2) above, and the adhesion was evaluated by the number of peeled squares in 100 squares according to the cross-cut method of JIS K5600-5-6.

(4) Water resistance of coating film A test piece was prepared by the method of (2) above, and the water resistance was evaluated by visual appearance in accordance with the immersion procedure of JIS K5600-6-2.
<Evaluation criteria>
◎: No swelling ○: Very little swelling △: Little swelling ×: Many swelling

(5) Storage Stability of Emulsion (X) The storage stability was evaluated according to the normal temperature storage stability operation of JIS K5600-2-7. That is, the median particle diameter and viscosity of the emulsion filled in 180 ml in a glass container having a capacity of 225 ml and an inner diameter of 5 cm and allowed to stand at 40 ° C. for 20 days were evaluated. Furthermore, about the emulsion left still at 40 degreeC for 20 days, pencil hardness and adhesiveness were measured in the way of said (2) and (3), and the storage stability was evaluated by comparing with the initial measured value.
(5-1) Median Particle Diameter The median particle diameter was measured by the measurement method of (1), and the degree of increase in median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: median particle size increase less than 5% ○: median particle size increase from 5% to less than 10% Δ: median particle size increase from 10% to less than 20% ×: median particle size increase from 20% or more (5 -2) Viscosity Viscosity at 25 ° C. was measured according to JIS K7117-1 using a BL type viscometer [model number “DVL-BII”, manufactured by Toki Sangyo Co., Ltd., rotation speed: 30 rpm, No. 3 spindle]. The degree of increase in viscosity before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in viscosity is less than 5% B: Increase in viscosity is 5% or more and less than 10% B: Increase in viscosity is 10% or more and less than 20% X: Increase in viscosity is 20% or more

(5-3) Change rate of pencil hardness (evaluation of storage stability)
About the emulsion which left still at 40 degreeC for 20 days, pencil hardness was measured like said (2). The degree of reduction in pencil hardness before and after standing for 20 days was evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: Pencil hardness is not reduced ○: Pencil hardness is reduced by one step Δ: Pencil hardness is reduced by two steps ×: Pencil hardness is reduced by three or more steps (5-4) Adhesion change rate (evaluation of storage stability)
The emulsion was allowed to stand at 40 ° C. for 20 days, and the adhesion was evaluated in the same manner as in the above (3).

From the results of Tables 3 and 4, the aqueous dispersion of the core / shell type main agent particles of the present invention is superior to the comparative one in one-part thermosetting resin emulsion, excellent storage stability and excellent curability, especially It can be seen that low temperature curability is imparted.
In addition, the one-component thermosetting resin emulsion of the present invention is superior in storage stability and low-temperature curability as compared with the comparative one, and the coating film formed by curing the emulsion is excellent in coating film strength, adhesion, and water resistance. It is clear that

  The aqueous dispersion of core / shell type main agent particles of the present invention has a high core coverage, and can impart excellent storage stability and excellent curability to a one-pack thermosetting resin emulsion. The one-component thermosetting resin emulsion of the present invention is excellent in storage stability and low-temperature curability, and the cured coating film is excellent in coating film strength and adhesion. It can be used widely and suitably as paints, adhesives, etc. for applications and adhesive applications, or coating applications and adhesive applications such as buildings and home appliances, and is extremely useful.

Claims (12)

  The core / shell type main agent particles (D) in which the core contains the epoxy group-containing compound (A) and the shell contains the thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000 are dispersed. An aqueous dispersion (D0).   The aqueous dispersion according to claim 1, wherein the content of (B) is 5 to 100% based on the weight of (A).   The aqueous dispersion according to claim 1 or 2, further comprising a surfactant (C).   Core / shell type main agent particles (D) having a core containing an epoxy group-containing compound (A) and a shell containing a thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000, and an epoxy group -Component thermosetting resin emulsion (X) comprising a curing agent (E) which is a compound (E1) having at least two amino groups capable of reacting with olefin and / or an epoxy polymerization catalyst (E2).   The equivalent ratio [(A) / (E1)] of (A) to (E1) is 30/70 to 90/10, and / or the weight ratio of (A) to (E2) [(A) / (E2 )] Is 80/20 to 99.9 / 0.1.   The emulsion according to claim 4 or 5, wherein the total weight of (D) and (E) is 20 to 80% based on the weight of (X).   The emulsion according to any one of claims 4 to 6, which is used for paint.   The coating film formed by hardening the emulsion (X) in any one of Claims 4-7.   An article to be coated, which is obtained by applying and curing the emulsion (X) according to any one of claims 4 to 7.   An aqueous dispersion (A0) of an organic solvent (f) solution of a thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000 and an epoxy group-containing compound (A) containing a surfactant (C) And an aqueous dispersion (D0) of core / shell type main agent particles (D) in which the core contains (A) and the shell contains (B).   Production including phase inversion emulsification of a solution containing an epoxy group-containing compound (A), a thermoplastic resin (B) having a weight average molecular weight of 5,000 to 150,000, and an organic solvent (f), and water. In the phase inversion emulsification, the core (shell) contains the surfactant (C) in the solution and / or water, the core contains the (A) and the shell contains the (B). The manufacturing method of the aqueous dispersion (D0) of type | mold main agent particle | grains (D).   The method according to claim 10 or 11, wherein the organic solvent (f) has a water / octanol partition coefficient (logPow) of 0 to 4.0.