JP2017057374A - Core/shell type main agent particle and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a core/shell type main agent particle providing a thermosetting resin composition good in storage stability for a long time and low temperature curability and excellent in physical properties of a cured article.SOLUTION: There are provided a core/shell type main agent particle wherein a core contains an epoxy group-containing compound and a shell contains a thermoplastic resin having drain initiation temperature measured by a flow tester of 70 to 180°C, and a thermosetting resin composition having the core/shell type main agent particle, a compound having at least 2 functional groups which may react with an epoxy group and/or a curing agent which is an epoxy polymerization catalyst.SELECTED DRAWING: None

Description

  The present invention relates to core / shell type main agent particles. More specifically, the present invention relates to core / shell type main agent particles containing an epoxy group-containing compound in the core and a thermoplastic resin in the shell, and a thermosetting resin composition containing the same.

  Conventionally, compounds containing an epoxy group have been used in a wide variety of applications such as adhesives, paints and coating agents. Moreover, the compound containing an epoxy group is usually used in combination with various curing agents and curing accelerators and is often thermally cured. These general-purpose thermosetting resin compositions contain a compound containing an epoxy group, a curing agent, and, if necessary, a curing accelerator, but depending on the manner in which they are mixed, there are two types, one-pack type and two-pack type. It is divided roughly into.

In the one-pack type, a latent curing agent that does not react at room temperature is stored in a state mixed with an epoxy group-containing compound, and when used, for example, the curing agent is activated by heating to a high temperature to react. Make it progress.
On the other hand, in the two-pack type, the epoxy group-containing compound and the curing agent, which have been stored separately, are mixed immediately before use to advance the reaction. Although it is a thermosetting resin composition containing an epoxy group-containing compound that is used in this way, the one-pack type requires energy at a high temperature of 180 ° C. or higher in order to activate the latent curing agent. The cost is very high, and in the case of the two-pack type, the working time after mixing is short, and when it is used in a large amount, it is necessary to blend many times in small amounts, so that the work efficiency is poor.
An epoxy resin having a softening point of 90 to 120 ° C., which is a solid at room temperature, for the purpose of lowering the curing temperature of a one-component adhesive with good work efficiency, for the purpose of lowering the curing temperature. There is known a method of using a reaction product of polyamine with polyamine (see, for example, Patent Document 1).

JP 2004-99886 A

However, with the technique of Patent Document 1, although the low-temperature curability has been improved to some extent, the storage stability and the adhesion to the substrate have not been sufficient.
An object of the present invention is to provide a core / shell type main agent particle that provides a thermosetting resin composition having good long-term storage stability and low-temperature curability and excellent physical properties (such as adhesive strength) of a cured product. There is.
In the present invention, excellent storage stability means that the viscosity change is small in the case of a one-component thermosetting resin composition when left at 40 ° C., in the case of a powder thermosetting resin composition. Means excellent blocking properties.
Moreover, being excellent in low-temperature curability means that the physical properties (tensile strength, adhesion, adhesiveness, etc.) of the cured product after baking at 100 ° C. for 20 minutes are excellent, and each is evaluated by the methods described below. can do.

  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 a core / shell type in which the core contains the epoxy group-containing compound (A) and the shell contains the thermoplastic resin (B) having an outflow start temperature measured by a flow tester of 70 to 180 ° C. Main agent particles (D); Core / shell type main agent particles (D), and a curing agent (E) which is a compound (E1) and / or an epoxy polymerization catalyst (E2) having at least two functional groups capable of reacting with an epoxy group Is a thermosetting resin composition (X).

The core / shell type main agent particles (D) of the present invention have the following effects.
(1) The coverage of the epoxy group-containing compound (A) as a core is high, and the storage stability of the thermosetting resin composition (X) is extremely good.
(2) The aqueous one-component thermosetting resin composition (X1) containing the curing agent (E) which is the specific epoxy polymerization catalyst (E2) is excellent in temperature dispersion stability.
(3) The thermosetting resin composition (X) is imparted with excellent curability, particularly low temperature curability.
(4) The cured product (coating film) obtained by curing the thermosetting resin composition (X) is excellent in adhesiveness to the substrate and further excellent in water resistance.
(5) The hardened | cured material which this thermosetting resin composition (X) hardened | cured is excellent in adhesiveness (adhesion strength) with a base material.

<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), And heterocyclic ring-containing polyepoxide (A4).

(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) may be abbreviated as C in the following. ] 6 or more and 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) 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), from the viewpoint of storage stability of a thermosetting resin composition (X) described later and physical properties of a cured product obtained by curing (X), (A1) is preferable. (A2) More preferred are polyglycidyl ethers of polyhydric phenols (A1-1), polyglycidyl ethers of aliphatic polyhydric alcohols (A2-1), and particularly preferred are bisphenol A, bisphenol F, bisphenol S, and phenol. Novolak and cresol novolac type polyglycidyl ether.

  Mn of the epoxy group-containing compound (A) is preferably 500 to 20,000 from the viewpoint of the physical properties of the cured product obtained by curing (X) and the storage stability of the thermosetting resin composition (X), Preferably it is 700-10,000, Especially preferably, it is 900-7,000, Most preferably, it is 1,000-4,000.

Mn and Mw (weight average molecular weight) in the present invention are measured by the GPC method under the following conditions.
Apparatus: “Alliance” manufactured by Nippon Waters Co., Ltd. Column: Guardcolumn super HL
TSKgel Super H4000
TSKgel Super H3000
TSKgel Super H2000
(The above columns are connected in series.)
Solvent: Tetrahydrofuran (THF)
Reference material: 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, more preferably 4 from the viewpoint of the physical properties of the cured product obtained by curing the thermosetting resin composition (X) described below and the storage stability of (X). -10.
The epoxy equivalent of (A) (unit: g / eq. Only numerical values are shown below) is the storage stability of the thermosetting resin composition (X) described later and the physical properties of the cured product obtained by curing (X). From the viewpoint, it is preferably 100 to 10,000, and more preferably 200 to 2,000.

  The softening point of (A) is preferably 0 to 170 ° C, more preferably 10 to 140 ° C, particularly preferably from the viewpoint of storage stability and low-temperature curability of the thermosetting resin composition (X) described later. Is 20-130 ° C. 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)>
As a thermoplastic resin (B) in this invention, outflow start temperature is 70-180 degreeC, Preferably it is 75-150 degreeC, More preferably, it is 80-120 degreeC.
When the outflow start temperature is less than 70 ° C, the storage stability of the thermosetting resin composition (X) described later is inferior. On the other hand, when the outflow start temperature exceeds 180 ° C, the low temperature curability of (X) is inferior.
In the present invention, the outflow start temperature of the thermoplastic resin (B) is measured using a flow tester under <flow tester measurement conditions> described later.

<Measurement conditions for flow tester>
Measuring apparatus: “Elevated flow tester CFT500 type” manufactured by Shimadzu Corporation Measurement start temperature: 50 ° C., preheating time: 5 minutes, heating rate: 5.0 ° C./min
Die diameter: 0.50 mm, Die length: 1.0 mm
Cylinder pressure: 0.4903 MPa
In addition, the outflow start temperature of (B) in the below-mentioned Example followed the above.

Further, the water absorption (%) of the thermoplastic resin (B) measured according to ASTM D570 is the physical properties of the cured product obtained by curing the thermosetting resin composition (X) described later and the storage stability of (X). From this viewpoint, it is preferably 0.01 to 2.0%, more preferably 0.015 to 1.5%, and particularly preferably 0.02 to 1.0%.
The water absorption rate of the thermoplastic resin (B) is measured from the change in weight of the test piece before and after immersing a test piece having a length of 60 mm, a width of 60 mm, and a thickness of 1 mm in water at 23 ° C. for 24 hours in accordance with ASTM D570. .
In addition, the water absorption rate of (B) in the below-mentioned Example followed the above.

The weight average molecular weight (sometimes abbreviated as Mw) of (B) is preferably from 5,000 to 150,000, more preferably from 8,000, from the viewpoint of storage stability and low-temperature curability of (X). 120,000, particularly preferably 10,000 to 100,000.
Mw can be measured by the GPC method described later.

  Examples of the thermoplastic resin (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, etc .;
(A9-4) Vinyl sulfone, 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 to 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.
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), polyamines (e), polythiols (f) and the like} and the like, and those having no isocyanate group are preferred.

  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 polyisocyanate such as urethane modified TDI, isocyanurate (HDI isocyanurate, IPDI isocyanurate, etc.) And mixtures of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].
Of these, preferred are (d1), (d2), (d3) and (d5), and particularly preferred are isocyanurates of TDI, MDI, HDI, hydrogenated MDI, IPDI and HDI.

  Examples of the polyamine (e) include the following (e1) to (e4) and a mixture of two or more thereof.

(E1) Aliphatic poly (2-7 valent) amines C2 or more and Mn500 or less, such as C2-10 alkylene diamines (ethylenediamine, propylenediamine, etc.), polyalkylene (C2-10) poly (trivalent-6 valent) Or more) amines [diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.], and their alkyl (C1-4) or hydroxyalkyl (C2-4) substituents such as dialkyl (C1-3) aminopropylamine , Trimethylhexamethylenediamine, aminoethylethanolamine;

(E2) Alicyclic ring-containing poly (2 to 3 valent) amines having C4-15, such as 1,3-diaminocyclohexane, isophoronediamine;

(E3) Heterocycle-containing poly (2 to 3 valent) amines of C4-15, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine;

(E4) Aromatic ring-containing polyamines C8-15, such as xylylenediamine, tetrachloro-p-xylylenediamine, diaminodiphenylmethane.

  Examples of polythiol (f) 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) with water and polyamine (e).

  Among these thermoplastic resins (B), a vinyl resin (B1), a polyester resin (B2), a polyurethane (B3) resin, and the like are preferable from the viewpoint that core / shell type main agent particles (D) described later are easily obtained. And a combination thereof, more preferably (B1), particularly preferably a styrene polymer, a styrene- (anhydride) maleic acid (salt) copolymer, a styrene- (meth) acrylic acid (salt) copolymer, ( They are a (meth) acrylic acid ester polymer and a (meth) acrylic acid- (meth) acrylic acid ester copolymer.

<Surfactant (C)>
Examples of the surfactant (C) in the present invention 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), (C1) and (C2) are more preferable from the viewpoint of the physical properties of the cured product obtained by curing the thermosetting resin composition (X) described later and the storage stability of (X). Are (C1), particularly preferred are poly (20-80) oxyalkylene higher fatty acid esters and poly (20-80) oxyalkylene alkylphenyl ethers.
In addition, the number average molecular weight (Mn) of (C) is preferably from 300 to 20,000, more preferably from 500 to 20,000, from the viewpoint of the storage stability of (X) and the physical properties of the cured product obtained by curing (X). 15,000, particularly preferably 1,000 to 10,000.

<Organic solvent (g)>
The organic solvent (g) used in the present invention is used for the purpose of dissolving the thermoplastic resin (B) as a shell component when preparing the core / shell type main agent particles (D) of the epoxy group-containing compound (A). Is done. Moreover, it is used also for the purpose of melt | dissolving (A) as needed.

The organic solvent (g) can be used as long as it is an organic solvent incompatible with water. Here, the organic solvent incompatible with water is one having a water / octanol partition coefficient (logPow) value of 0 to 4.0, preferably 0.1 to 3.5, more preferably 0.2. ~ 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.

  The boiling point of the organic solvent (g) is preferably from 20 to 100 ° C., more preferably from 25 to 90 ° C., from the viewpoints of handling properties and ease of solvent removal when preparing the core / shell type main agent particles (D). Especially preferably, it is 30-80 degreeC.

  Specific examples of the organic solvent (g) 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 (g) used varies depending on the composition of the thermoplastic resin (B). For example, when a vinyl resin, a polyester resin or a polyurethane resin is used as (B), (g) is ethyl acetate, methyl ethyl ketone, tetrahydrofuran. , Chloroform and the like are preferable.
The blending amount of the organic solvent (g) with respect to the thermoplastic resin (B) is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, particularly preferably 5 to 20% by weight as the concentration of (B) in the solution. %.

<Core / Shell Type Main Particle (D)>
The core / shell type main agent particles (D) of the present invention have a core containing the epoxy group-containing compound (A) and a shell containing the thermoplastic resin (B). That is, the core / shell type main agent particles (D) are suitable as the thermosetting resin main agent particles when used in the thermosetting resin composition described below.
The core / shell type main agent particles (D) 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 production method (D) include the following methods [1] to [4]. In the present invention, the aqueous dispersion means a dispersion in which particles are dispersed in an aqueous medium described later.

[1] An aqueous dispersion (A0) containing an epoxy group-containing compound (A) and a surfactant (C) is gradually added to an organic solvent (g) solution of the thermoplastic resin (B) with stirring. Phase inversion emulsification. Next, the organic solvent (g) 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). If necessary, the aqueous medium can be further distilled off to obtain (D).

[2] After compatibilizing the epoxy group-containing compound (A), the thermoplastic resin (B) and the organic solvent (g), an aqueous medium is gradually added, and the mixture is stirred and mixed for phase inversion emulsification. Here, the surfactant (C) may be added to the organic solvent (g), to the aqueous medium, or to both (g) and water. Preferable is a method of adding (C) to water.
Next, the organic solvent (g) 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) of the epoxy group-containing compound (A). . If necessary, the aqueous medium can be further distilled off to obtain (D).

[3] An aqueous medium containing the surfactant (C) is gradually added to the organic solvent (g) solution of the thermoplastic resin (B) with stirring to perform phase inversion emulsification. Then, the organic solvent (g) solution of the epoxy group-containing compound (A) prepared in another container is gradually added with stirring. After adding the total amount, the organic solvent (g) is distilled off by reducing the pressure while heating, if necessary, to obtain an aqueous dispersion (D0) of core / shell type main agent particles (D). In addition, (D) can be obtained by distilling water further as needed.

[4] An oil phase solution in which the epoxy group-containing compound (A), the thermoplastic resin (B), and the organic solvent (g) are compatibilized is prepared. A required amount of an aqueous medium is put in 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 (g), to the aqueous medium, or to both (g) and the aqueous medium. Preferable is a method of adding (C) to water.
Next, the organic solvent (g) 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) of the epoxy group-containing compound (A). . If necessary, the aqueous medium can be further distilled off to obtain (D).

In any of the methods [1] to [4], the organic solvent (g) may remain as long as the effects of the present invention are not impaired, but the organic solvent (g) is used from the viewpoint of storage stability. It is preferable to distill off.
Of the above [1] to [4], the methods [1] to [3] are preferable from the viewpoint of industrial and storage stability, and the methods [1] and [3] are more preferable.

Examples of the aqueous medium in the present invention include hydrophilic organic solvents other than water and (g) [C1-3 lower alcohol (methanol, ethanol, isopropanol, etc.), 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 core / shell type main agent particles (D) of the present invention is determined by curing the core coverage described below and the thermosetting resin composition (X). From the viewpoint of physical properties of the material, it is preferably 10 to 150% by weight, more preferably 15 to 100% by weight, and particularly preferably 20 to 80% by weight.

Further, the content of (C) based on the weight of (A) is preferably 2 from the viewpoint of the storage stability of the thermosetting resin composition (X) described later and the physical properties of the cured product obtained by curing (X). -50% by weight, more preferably 5-45% by weight, particularly preferably 8-30% by weight.
The total weight of (g) and the aqueous medium is preferably 5% by weight or less based on the total weight of (A) and (B) from the viewpoint of industrial and storage stability of (X). More preferably, it is 3 weight% or less, Most preferably, it is 1 weight% or less.

  In the present invention, the median particle diameter (unit: μm; only numerical values are shown below) of the core / shell type main agent particles (D) is preferably 0.01 to from the viewpoint of the viscosity and storage stability of (X). 50, more preferably 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).

The core coverage (%) of the core / shell type main agent particles (D) of the present invention is evaluated by the following two methods [1] and [2]. The core coverage in the examples described later was in accordance with this method.
The coverage of the core is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more, from the viewpoint of storage stability and low-temperature curability of (X).
[1] Core coverage by epoxy value (%)
In the produced core / shell type main agent particles, the ratio of the core covered with 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 produced 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 produced 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] Evaluation of core coverage by TEM (%)
In the produced 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.

Moreover, in the said manufacturing method of the core / shell type main ingredient particle | grains (D) of this invention, the following [1]-[3] are mentioned as conditions with which (D) is more preferable more easily.
[1] Preferable (A), (B), (C), (g), an aqueous medium, especially preferable (C), (g), an aqueous medium is used.
[2] A preferred amount of (A), (B), (C), (g), aqueous medium is used.
[3] The aqueous dispersion (D0) tends to be obtained more easily by increasing the amount of each of (C), (g) and the aqueous medium, especially by increasing the amount of (C).

<Aqueous dispersion (D0) of core / shell type main agent particles (D)>
The aqueous dispersion (D0) of the core / shell type main agent particles (D) of the present invention is one in which the core / shell type main agent particles (D) are dispersed in an aqueous medium. In the present invention, the aqueous dispersion refers to those in which particles are dispersed in the aqueous medium, and includes emulsions.
The content of (D) based on the weight of the aqueous dispersion (D0) of the core / shell type main agent particles (D) in the present invention is the handling of (D0) and storage of the thermosetting resin composition (X) described later. From the viewpoint of stability, it is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and particularly preferably 15 to 50% by weight.

  Further, the content of (g) based on the weight of (D0) in the aqueous dispersion (D0) of the core / shell type main agent particles (D) is 15% by weight or less, and a thermosetting resin composition (X described later) ) Is preferably 5% by weight or less, more preferably 3% by weight or less, particularly preferably 0.5% by weight or less, and most preferably 0.1% by weight or less.

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.

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

The compound (E1) having at least two functional groups capable of reacting with an epoxy group is a functional group capable of undergoing an addition reaction with an epoxy group, such as an amino group, a carboxyl group, an acid anhydride, a thiol group, or a hydroxyl group. The compound which has 2 or more in the inside is mentioned, It will not specifically limit if it is a compound which has 2 or more of at least 1 type of functional group among the said functional groups.
The number of functional groups in (E1) is preferably 2 to 15, more preferably from the viewpoint of the physical properties of the cured product obtained by curing the thermosetting resin composition (X) described below and the storage stability of (X). 3-8

  Examples of the compound (E1) having at least two functional groups capable of reacting with an epoxy group include the following (E11) to (E14) and a mixture of two or more thereof.

(E11) Amino group-containing compound For example, the above-mentioned polyamine (e), dicyandiamide, organic acid dihydrazide, imidazole, polyamidoamine, epoxy addition amine, polyether polyamine, and urethane-modified polyamine can be mentioned.

Examples of the polyamide amine include those having a Mn of 200 to 20,000, an amine value of 1 to 50 mgKOH / g, and an 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.
The polyamidoamine can be obtained, for example, by a condensation reaction between an excess (1.1 to 2 equivalents per equivalent of carboxyl group) of the above (e) and a dicarboxylic acid (c) described later. Examples of the dicarboxylic acid (c) constituting the polyamidoamine include the aforementioned dicarboxylic acid (c1) and a mixture of two or more thereof.

  Examples of the epoxy-added polyamine include those having Mn of 400 to 20,000, for example, 1 equivalent of the aforementioned epoxy group-containing compound (A) and 1.1 to 2 equivalents or more of the reaction product (bisphenol A type polyglycidyl ether). 1 mol and xylylenediamine 2 mol addition reaction product, cresol novolac type polyglycidyl ether 1 mol and ethylenediamine 3 mol addition reaction product, etc.).

  Examples of the polyether polyamine include those having a Mn of 500 to 20,000, for example, hydrogenated products of cyanoethylated products of polyether polyols (polytetramethylene glycol and the like).

  Examples of the urethane-modified polyamine include those having a Mn of 500 to 20,000, such as a reaction product of the aforementioned polyisocyanate (d) and the aforementioned (e) (alkylene diamine, polyalkylene polyamine, etc.).

(E12) Thiol group-containing compound For example, the above-mentioned polythiol (f), a known polymercaptan curing agent (for example, pentaerythritol tetrakis (3-mercaptopropionate) [trade name “Adeka Hardener EH317”, manufactured by Adeka Corporation) ], Pentaerythritol tetrakis (3-mercaptobutyrate), [trade name “Karenz MT PEI”, manufactured by Showa Denko KK], 1,4-bis (3-mercaptobutyryloxy) butane, [trade name “Karenz MT BDI ", manufactured by Showa Denko KK], 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion, [trade name “Karenz MT NRI”, manufactured by Showa Denko KK], polyether polythiol, [trade name “jER Cure Q X11 ", manufactured by Mitsubishi Chemical Corporation]) and the like.

(E13) Carboxyl group-containing compound For example, the aforementioned dicarboxylic acid (c1), trivalent or higher polycarboxylic acid (c2), acid anhydride of (c1) or (c2), dodecenyl succinic anhydride, carboxyl group-terminated polyester, etc. Is mentioned.

(E14) Hydroxyl-containing compound For example, the above-mentioned diol (b1), trivalent or higher valent polyol (b2), hydroxyl-terminated polyester and the like can be mentioned.

  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) and its salt, 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) and its salt, 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.

  Of the above (E), from the viewpoint of low temperature curability and storage stability of the thermosetting resin composition (X), (E11), (E12), N, N-dimethylethanolamine, 1,8 -Diazabicyclo [5.4.0] -7-undecene (DBU) and its salt, 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) and its salt, aqueous one-component thermosetting described below From the viewpoint of the temperature dispersibility of the conductive resin composition (X1), DBU and a salt thereof, DBN and a salt thereof are more preferable, and a DBU salt and a DBN salt are particularly preferable. Examples of the salt include salts of DBU or DBN with formic acid, acetic acid, octylic acid, orthophthalic acid, toluenesulfonic acid, phenol, phenol novolac, or tetraphenylboric acid.

[Thermosetting resin composition (X)]
The thermosetting resin composition (X) of the present invention comprises the core / shell type main agent particles (D) and the curing agent (E) which is the (E1) and / or (E2).
The thermosetting resin composition (X) includes an aqueous one-component thermosetting resin composition (X1), a non-aqueous one-component thermosetting resin composition (X2), and a powder thermosetting resin composition (X3). Is included.

The (X1) is one in which the core / shell type main agent particles (D) are dispersed in an aqueous medium and is liquid at 25 ° C.
In (X1), the compound (E1) having at least two functional groups capable of reacting with an epoxy group and / or the curing agent (E) which is an epoxy polymerization catalyst (E2) may be dispersed in an aqueous medium. Either may be dissolved. The (X1) contains substantially no organic solvent (g) (in the composition, 5% by weight or less, preferably 2% by weight or less).
Further, the total weight of (D) and (E) based on the weight of (X1) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight from the viewpoint of dispersion stability and handling properties. %.

Said (X2) is a compound (E1) having at least two functional groups capable of reacting with an epoxy group and / or a curing agent (E) which is an epoxy polymerization catalyst (E2), or a functional group capable of reacting with an epoxy group. Core / shell type main agent particles (D) are dispersed in a solution (E00) of a curing agent (E) which is a compound (E1) having at least two groups and / or an epoxy polymerization catalyst (E2). Yes, it is liquid at 25 ° C.
The (X2) is substantially free of an aqueous medium (in the composition, 5% by weight or less, preferably 2% by weight or less), and if necessary, the organic solvent as long as the effect of the present invention is not impaired. (G) may be contained. In this case, the content of the organic solvent (g) in the composition is preferably 15% by weight or less, more preferably 10% by weight or less.
The total weight of (D) and (E) based on the weight of (X2) is preferably 80% by weight or more from the viewpoint of storage stability and handling properties of (X2), From the viewpoint of storage stability and handling properties, it is more preferably 88 to 99.5% by weight.

(X3) is a compound (E1) having at least two functional groups capable of reacting with core / shell type main agent particles (D) and epoxy groups and / or a curing agent (E) which is an epoxy polymerization catalyst (E2); It is a powder at 25 ° C.
The (X3) includes the following (X31), (X32) and mixtures thereof.
(X31): Curing agent (E) which is a compound (E1) and / or an epoxy polymerization catalyst (E2) having at least two functional groups capable of reacting with core / shell type main agent particles (D) and the epoxy group of the powder Mixture with.
(X32): A composition comprising (D) and a compound (E1) having at least two functional groups capable of reacting with an epoxy group and / or a curing agent (E) which is an epoxy polymerization catalyst (E2). Powder.
Of the above (X3), (X31) is preferred from the industrial viewpoint.
(X3) is substantially free of an aqueous medium and an organic solvent (g) (in the composition, the total of the aqueous medium and the organic solvent (g) is 5% by weight or less, preferably 2% by weight or less) Is.
Further, the total weight of (D) and (E) based on the weight of (X3) is preferably 95% by weight or more, more preferably 98% by weight or more.

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 method described above and a curing agent (E ), The aqueous dispersion (E0) of (E) and / or the solution (E00) of (E), and then, if necessary, water and the solvent are distilled off.
Among the (D) and the aqueous dispersion (D0), from the viewpoint of the storage stability of (X) and the ease of production of (X), (D1) is preferred for (X1) and (X2). In (D) and (X3), it is (D).
Among the (E), the aqueous dispersion (E0) and the solution (E00), from the viewpoint of storage stability of (X) and ease of production of (X), (X1) is preferably (E), (E0) and (X2) are (E), (E00) and (X3) are (E).
In the case of the above (X3), the core / shell type main agent particles (D), the compound (E1) having at least two functional groups capable of reacting with the epoxy group of the powder, and / or the epoxy polymerization catalyst (E2) It is good also as a powder thermosetting resin composition by mixing a certain hardening | curing agent (E) uniformly.
In the present invention, the aqueous dispersion refers to a dispersion of particles (A), (D) or (E) in an aqueous medium.

Examples of the method for producing the aqueous dispersion (E0) of (E) and the solution (E00) of (E) include the methods [1] to [3].
[1] The organic solvent (g) is added to the curing agent (E) as necessary, and the surfactant (C) is further added, and while stirring, an aqueous medium is gradually added dropwise or the like to perform phase inversion emulsification. .
Next, a method of obtaining an aqueous dispersion (E0) of the curing agent (E) by distilling off the organic solvent by reducing the pressure while heating as necessary.
[2] If necessary, add an aqueous medium solution or aqueous medium of the surfactant (C) to (E) to which an organic solvent is added, and disperse with an ordinary disperser, and distill off the organic solvent as necessary. To obtain an aqueous dispersion (E0) of (E).
[3] A method in which an aqueous medium and / or an organic solvent is added to (E) and dissolved under stirring to obtain a solution (E00) of (E). Examples of the organic solvent include the organic solvent (g) and an aqueous medium other than water.
Of these solutions (E00), an aqueous medium is preferable from the viewpoint of industrial and storage stability of (X).

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

The equivalent ratio [(A) / (E1)] of (A) and (E1) constituting the thermosetting resin composition (X) of the present invention is the physical properties of the cured product obtained by curing (X) and ( From the viewpoint of storage stability of X), it is preferably 30/70 to 90/10, more preferably 40/60 to 70/30.
In addition, equivalent ratio [(A) / (E1)] is the epoxy equivalent of (A), the active hydrogen equivalent of (E1), the thiol equivalent (unit: g / eq. Only numerical values are shown below), carboxyl It can be calculated from the group equivalent (unit: g / eq. Only numerical values are shown below) and the hydroxyl equivalent (unit: g / eq. Only numerical values are shown below).
Moreover, the weight ratio [(A) / (E2)] of (A) and (E2) constituting the thermosetting resin composition (X) is the physical property of the cured product obtained by curing (X) and (X ) Is preferably 80/20 to 99.9 / 0.1, more preferably 95/5 to 99.5 / 0.5.

The viscosity (mPa · s) at 25 ° C. of (X1) and (X2) is preferably 100 to 100,000, more preferably 500 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) in (X) is preferably 0.01 to from the viewpoint of the viscosity and storage stability of (X). 50, more preferably 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).
The median particle diameters of the aqueous dispersion (D0) of (D) and the aqueous dispersion (E0) of (E) were also measured in the same manner.
Furthermore, the median particle diameter of (X3) is preferably 1 to 150 μm, more preferably 10 to 130 μm, and particularly preferably 20 to 120 μm from the viewpoint of coating efficiency and coating film appearance.
The median particle diameter in Examples described later is a value measured using a particle size distribution measuring instrument using a laser diffraction scattering method [trade name “Microtrack MT3000II particle size analyzer”, manufactured by Nikkiso Co., Ltd.]. (Unit: μm).

[Additive (F)]
In the thermosetting resin composition (X) of the present invention, a filler, an antiseptic, a heat stabilizer, a weather stabilizer, a colorant, a thickener, and a leveling agent 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 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 0, based on the total weight of the thermosetting resin composition (X) after the addition of the additive. .2-10%.

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 thermosetting resin composition (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 thermosetting resin composition (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 thermosetting resin composition (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 thermosetting resin composition (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 thermosetting resin composition (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 thermosetting resin composition (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 thermosetting resin composition (X) after addition of the additive.

Examples of the antifoaming agent (F8) include mineral oil defoaming agents and silicone oil defoaming agents.
Content of (F8) is 6% or less normally based on the total weight of the thermosetting resin composition (X) after additive addition, Preferably it is 0.5 to 3%.

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 thermosetting resin composition (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 thermosetting resin composition (X) after addition of the additive.

[Adhesives, paints, molded products]
The thermosetting resin composition (X) of the present invention is excellent in storage stability, and further, the cured product obtained by curing (X) is excellent in strength. Therefore, the thermosetting resin composition (X) is useful for adhesives, paints, and molded products. .

When the thermosetting resin composition (X) of the present invention is used as an adhesive, the (X) is applied to an adherend. When used as an adhesive, an aqueous one-component thermosetting resin composition (X1) and a non-aqueous one-component thermosetting resin composition (X2) are preferable from the viewpoint of adhesive strength and coating efficiency.
The film thickness (film thickness immediately after coating) is preferably 20 μm to 3 mm, more preferably 50 μm to 1 mm from the viewpoints of adhesiveness and industry. Examples of the application method include coating by coating (for example, blade coater, roll coater, bar coater, gravure coater, etc.), dip coating, brush coating, spray coating, electrostatic powder coating, fluidized dip coating, and the like.

The applied adherend is preferably 80 to 180 ° C., more preferably 100 to 160 ° C. from the viewpoint of curability and industry, and preferably 100 to 160 ° C., and preferably 5 to 60 minutes from the same viewpoint. It can be cured and bonded with a curing time of preferably 8 to 30 minutes, particularly preferably 10 to 20 minutes.
Since an article to be bonded formed by curing an object to be bonded is excellent in adhesion to the substrate and strength of the cured product, (X) is suitable as an adhesive.

When the thermosetting resin composition (X) of the present invention is used as a paint, the (X) is applied to an object to be coated. In addition, when using as a coating material, an aqueous | water-based one-component thermosetting resin composition (X1) and a powder thermosetting resin composition (X3) are preferable from a viewpoint of a coating-film external appearance and coating efficiency.
As a coating method, when using the above (X1) or (X2) with respect to an object to be coated, the wet film thickness (film thickness immediately after coating) is preferably 10 to 10 from the viewpoint of coating effect and industrial. The method of spray-coating so that it may become 200 micrometers, More preferably, 20-100 micrometers is mentioned. When using the above (X3), there is a method of electrostatic powder coating or the like so that the film thickness (film thickness after curing) is 10 to 150 μm, more preferably 15 to 100 μm, and particularly preferably 20 to 50 μm. Can be mentioned.

The coated object is preferably from 80 to 180 ° C., more preferably from 100 to 160 ° C. from the viewpoint of coating film curability and industrial viewpoint, and from the same viewpoint, preferably from 5 to 60 minutes. 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 after curing is preferably 10 to 150 μm, more preferably 15 to 50 μm, and particularly preferably 20 to 50 μm from the viewpoint of coating effect and industrial viewpoint.
Since the article to be coated formed by curing the article to be coated is excellent in adhesion to the substrate and water resistance of the coating film, (X) is suitable as a coating material.

  The method for producing the thermosetting resin composition (X) of the present invention as a molded product includes injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, film molding (casting method). , Tenter method, inflation method, etc.), etc., and can be molded by any method depending on the purpose.

  Since the cured product obtained by curing the resin composition (X) of the present invention is excellent in resin strength, the thermosetting resin composition (X) is suitable for various uses, adhesives, paints, and molded products.

  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): Pentaerythritol polyglycidyl ether
[Product name "Denacol EX-411", manufactured by Nagase ChemteX Corporation,
Mn 1,200, epoxy equivalent 230]

(3) Vinyl monomer (a)
(A-1): Styrene (a-2): Methacrylic acid (a-3): Butyl acrylate (a-4): Methyl methacrylate

(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.]

(6) Organic solvent (g)
(G-1): ethyl acetate (logPow 0.73)
(G-2): Methyl ethyl ketone (hereinafter referred to as MEK) (logPow 0.29)
(G-3): Toluene (logPow 2.73)

(9) Curing agent (E) which is compound (E1) and / or epoxy polymerization catalyst (E2) having at least two functional groups capable of reacting with an epoxy group
(E1-1): Dimer acid polyamide polyamine
[Product name "Polymide L-45-3", manufactured by Sanyo Chemical Industries,
Amino group equivalent 180 g / eq]
(E1-2): Carboxyl group-containing polyester resin
[Product name "Fine Dick M-8842", manufactured by DIC Corporation,
Acid value 55 mgKOH / g]
(E2-1): 1,8-diazabicyclo [5.4.0] -7-undecene (DBU)
Octylate (E2-2): 1,5-diazabicyclo [4.3.0] -5-nonene (DBN)
Orthophthalic acid

<Manufacture of thermoplastic resin (B)>
Production Example 1
The reaction vessel was charged with 100 parts of xylene and heated with stirring until the solvent was refluxed. In a separate container, a monomer solution in which 492 parts of (a-1) and 8 parts of (a-2) are compatibilized, and di-t-butyl peroxide [trade name “Perbutyl D”, manufactured by NOF CORPORATION Initiator solution 1 in which 0.8 part and xylene 50 part are compatibilized is 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, the solvent was removed to obtain a thermoplastic resin (B-1) (outflow start temperature: 175 ° C., water absorption: 0.14%).

Production Example 2
After charging 100 parts of xylene into a reaction vessel capable of pressurization and replacing the inside of the reaction tank with nitrogen (gas phase oxygen concentration of 10 ppm or less), the inside of the reaction tank is pressurized to 0.15 MPaG with nitrogen. Thereafter, the temperature was raised while stirring until the solvent was refluxed. In a separate container, a monomer solution in which 420 parts of (a-1), 8 parts of (a-2) and 72 parts of (a-3) are compatibilized, and di-t-butyl peroxide [trade name “Perbutyl D” Manufactured by NOF Corporation] Initiator solution 1 in which 1.5 parts and 50 parts of xylene are compatibilized is 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 reaction was allowed to proceed for 3 hours under a reflux condition of 0.30 MPaG in the tank. Thereafter, the solvent was removed to obtain a thermoplastic resin (B-2) (outflow start temperature: 71 ° C., water absorption rate: 0.15%).

Production Example 3
In Production Example 2, (a-1) 420 parts, (a-2) 8 parts, and (a-3) 72 parts, (a-1) 448 parts, (a-2) 7 parts, and (a-3) ) Thermoplastic resin (B-3) (outflow start temperature of 97 ° C.) in the same manner as in Production Example 2 except that 1.5 parts of di-t-butyl peroxide was replaced with 0.8 parts instead of 45 parts. , Water absorption 0.13%).

Production Example 4
In Production Example 2, 420 parts of (a-1), 8 parts of (a-2) and 72 parts of (a-3) were replaced with 500 parts of (a-1), and di-t-butyl peroxide 1.5 A thermoplastic resin (B-4) (outflow start temperature 105 ° C., water absorption 0.02%) was obtained in the same manner as in Production Example 2, except that the part was changed to 0.8 part.

Production Example 5
In Production Example 2, (a-1) 420 parts, (a-2) 8 parts, and (a-3) 72 parts, (a-2) 60 parts, (a-3) 45 parts, and (a-4) ) Thermoplastic resin (B-5) (outflow start temperature: 101 ° C.) in the same manner as in Production Example 2, except that 1.5 parts of di-t-butyl peroxide was replaced with 0.8 parts instead of 295 parts. Water absorption 1.50%).

Comparative production example 1
In Production Example 2, (a-1) 420 parts, (a-2) 8 parts, and (a-3) 72 parts, (a-1) 240 parts, (a-2) 50 parts, and (a-3). ) A thermoplastic resin (ratio B-1) (outflow start temperature 30 ° C., water absorption 0.80%) was obtained in the same manner as in Production Example 2 except that the amount was changed to 210 parts.

Comparative production example 2
In Production Example 1, the same procedure as in Production Example 1 except that 0.8 part of di-t-butyl peroxide was replaced with 0.4 part. Water absorption 0.14%).

<Manufacture of core / shell type main agent particles (D)>
Example 1
A container was charged with 33 parts of (A-1) and 33 parts of (g-1), 9 parts of (C-1) was added thereto, and the mixture was stirred 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 applies hereinafter) for 2 hours to obtain an aqueous solution of (A-1). A dispersion (A0-1) was obtained.
In a separate container, 145 parts of (g-1) was charged, 8 parts of (B-1) was added, and the mixture was stirred at 30 ° C. for 2 hours. At the same temperature, 65 parts of the aqueous dispersion (A0-1) prepared (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, 27 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). This operation was performed a total of 4 times to obtain 400 parts of an aqueous dispersion (D0-1) of (D-1).
Next, half of the obtained aqueous dispersion (D0-1) was dehydrated at 50 ° C. under reduced pressure to obtain 100 parts of core / shell type main agent particles (D-1).

<Examples 2-7, Comparative Examples 1-2>
In Example 1, core / shell type main agent particles (D) and (A), (B), (C), (g) and core / shell type main agent particles (D) and The aqueous dispersion (D0) was obtained.

<Example 8>
A container was charged with 27 parts of (A-1), 14 parts of (B-3), and 239 parts of (g-1), and stirred at 30 ° C. for 2 hours. Thereto, a surfactant aqueous solution in which 9 parts of (C-1) and 50 parts of water were compatibilized was added dropwise at 30 ° C. over 2 hours with stirring to effect phase inversion emulsification. Thereafter, the solvent was removed under reduced pressure for 2 hours to obtain 100 parts of an aqueous dispersion (D0-8) of core / shell type main agent particles (D-8). This operation was performed a total of 4 times to obtain 400 parts of an aqueous dispersion (D0-8) of (D-8).
Next, half of the obtained aqueous dispersion (D0-8) was dehydrated at 50 ° C. under reduced pressure to obtain 100 parts of core / shell type main agent particles (D-8).

<Example 9>
A container was charged with 14 parts of (B-3), 42 parts of (g-1) and 9 parts of (C-1) and stirred at 30 ° C. for 1 hour. Thereafter, 50 parts of water was added dropwise at 30 ° C. with stirring over 2 hours to effect phase inversion emulsification to obtain an aqueous dispersion (B-3).
In a separate container, 27 parts of (A-1) and 12 parts of (g-1) were charged and stirred at 30 ° C. for 2 hours. The (g-1) solution of (A-1) was added dropwise to the prepared aqueous dispersion (B-3) over 2 hours with stirring. After the completion of dropping, stirring was continued for 30 minutes, and then the solvent was removed at 50 ° C. under reduced pressure for 2 hours to obtain 100 parts of an aqueous dispersion (D0-9) of core / shell type main agent particles (D-9). . This operation was performed 4 times in total to obtain 400 parts of an aqueous dispersion (D0-9) of (D-9).
Next, half of the obtained aqueous dispersion (D0-9) was dehydrated at 50 ° C. under reduced pressure to obtain 100 parts of core / shell type main agent particles (D-9).
The median particle diameter of the obtained (D) was μm, the core coverage of (D) obtained from the isocyanate group content was 100%, and the coverage obtained from TEM observation was 100%.

<Example 10>
A beaker was charged with 27 parts of (A-1), 14 parts of (B-3) and 239 parts of (g-1), and a precision emulsification disperser (product name “CLEARMIX CLM-0.8S”, M Technique Co., Ltd.) And stirred at 20,000 rpm for 5 minutes at 30 ° C. Thereto, a surfactant aqueous solution in which 9 parts of (C-1) and 50 parts of water were compatibilized was added all at once, and stirred for 10 minutes at the same temperature and at the same rotation speed to obtain a dispersion. Thereafter, the entire amount was transferred to another container, and the solvent was removed under reduced pressure for 2 hours to obtain 100 parts of an aqueous dispersion (D0-10) of core / shell type main agent particles (D-10).
This operation was performed 4 times in total to obtain 400 parts of an aqueous dispersion (D0-10) of (D-10).
Next, half of the obtained aqueous dispersion (D0-10) was dehydrated at 50 ° C. under reduced pressure to obtain 100 parts of core / shell type main agent particles (D-10).

  Table 1 shows the results of Examples 1 to 10 and Comparative Examples 1 and 2.

<Production of aqueous dispersion (E0) of curing agent which is a compound having at least two functional groups capable of reacting with epoxy group>
<Production Example 6>
A reaction vessel was charged with 400 parts of (E1-1) and 100 parts of (C-1), heated to 50 ° C., and stirred for 30 minutes. Thereafter, 500 parts of water was added dropwise at the same temperature over 2 hours to perform phase inversion emulsification to obtain an aqueous dispersion (E01-1) of (E1-1).

<Thermosetting resin composition (X)>
[Aqueous one-component thermosetting resin composition]
<Examples 11 to 21, Comparative Examples 3 to 4>
In a reaction vessel capable of stirring, blended and mixed according to Table 2 (temperature 25 ° C., stirring time 30 minutes), aqueous one-component thermosetting resin compositions (X-1) to (X-11), (ratio X -1) to (ratio X-2). Each water-based thermosetting resin composition was evaluated for performance according to the following test methods (1), (4), and (5). The results are shown in Table 2.

[Non-aqueous one-component thermosetting resin composition]
<Examples 22 to 32, Comparative Examples 5 to 6>
Formulated and mixed according to Table 3 (temperature 25 ° C., stirring time 30 minutes), non-aqueous one-component thermosetting resin compositions (X-12) to (X-22), (ratio X-3) to (ratio X) -4) was obtained. Each non-aqueous one-component thermosetting resin composition was evaluated for performance according to the following test methods (2) to (4). The results are shown in Table 3.

[Powder thermosetting resin composition]
<Examples 33 to 43, Comparative Examples 7 to 8>
Blended and mixed according to Table 4 (temperature 25 ° C., stirring time 30 minutes), powder thermosetting resin compositions (X-23) to (X-33), (ratio X-5) to (ratio X-6) ) Each powder thermosetting resin composition was evaluated for performance according to the following test methods (1) to (4). The results are shown in Table 4.

<Test method>
(1) Coating film evaluation (low-temperature curability, physical properties of cured product)
(1-1) Adhesiveness of coating film The surface of the test steel sheet [0.5 mm × 80 mm × 150 mm cold rolled steel sheet (SPCC-SD) specified in JIS G3141] was degreased with methanol, The thermosetting resin composition is applied so that the thickness becomes 30 to 40 μm, and a test piece is prepared by low-temperature baking (100 ° C., 20 minutes), and the cross-cut method of JIS K-5600-5-6 is applied. In accordance with this, the adhesion was evaluated by the number of peeled cells in 100 cells.
(1-2) Water resistance of coating film A test piece was prepared by the method of (1-1) above, and the water resistance was evaluated by visual appearance based on the immersion procedure of JIS K5600-6-2.
<Evaluation criteria>
◎: No swelling ○: Very little swelling △: Little swelling ×: Many swelling

(2) Tensile shear bond strength (unit: MPa) (Evaluation of low temperature curability and bond strength)
The surface of the 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 0.1 mm. A resin composition is applied, a test piece is prepared by low-temperature baking (100 ° C., 20 minutes), and the adherend is a test steel plate [0.5 mm as defined in JIS G3141] according to the tensile shear bond strength measurement method of JIS K6850. × 80 mm × 150 mm cold-rolled steel sheet (SPCC-SD)] was evaluated.

(3) Peel strength (N / 25mm) (Evaluation of low temperature curability and adhesiveness)
(1) After degreasing the surface of the test steel sheet with methanol, the resin composition is applied so that the thickness of the coating film after baking is 0.1 mm, and the test piece is subjected to low-temperature baking (100 ° C., 20 minutes). Was prepared, and the adhesion strength when the adherends were test strips was evaluated by the peel strength measurement method of JIS K6854-2.

(4) Storage stability of thermosetting resin composition (X) Storage stability was evaluated based on the storage stability operation of JIS K6833-1. That is, 150 ml was filled in a glass container having a capacity of 300 ml and allowed to stand at 40 ° C. for 30 days.
About the aqueous one-pack thermosetting resin composition, what was left still at 40 degreeC for 30 days was evaluated according to the following (4-1), (4-2), and said (1).
About the non-aqueous one-component thermosetting resin composition, the thing after still standing at 40 degreeC for 30 days was evaluated according to the following (4-2) and (4-3).
About the powder thermosetting resin composition, the thing after standing at 40 degreeC for 30 days was evaluated according to the following (4-3), (4-4), and said (1).

(4-1) Median particle diameter The median particle diameter before and after the test was measured, and the degree of increase in the 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

(4-2) Viscosity Using a BL-type viscometer [model number “DVL-BII”, manufactured by Toki Sangyo Co., Ltd., 12 rpm, number 3 spindle], the viscosity at 25 ° C. is measured according to JIS K7117-1. did. 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

(4-3) Tensile Shear Adhesive Strength Measure the adhesive strength when the adherend is between test strips by the method of measuring the tensile shear adhesive strength of JIS K6850 in (2) above, and tensile shear before and after the test. The degree of decrease in adhesive strength was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Decrease in tensile shear bond strength is less than 10% B: Decrease in tensile shear bond strength is 10% or more and less than 20% Δ: Decrease in tensile shear bond strength is 20% or more and less than 50% X: Tensile shear bond Over 50% strength reduction

(4-4) Blocking property The powder thermosetting resin composition was allowed to stand at 40 ° C. for 30 days, and then the state of the powder thermosetting resin composition was observed to evaluate the degree of blocking.
<Evaluation criteria>
◎: No change in the state of the powder thermosetting resin composition ○: There is a lump of the thermosetting resin composition slightly, but it returns to the original powder by hand △: Lump of the thermosetting resin composition And does not return to the original powder by hand ×: There is a large lump of the thermosetting resin composition and does not return to the original powder by hand

(5) Temperature dispersion stability (5-1) High temperature dispersion stability Each aqueous thermosetting resin composition (X1) 12g was put into a 20 mL screw tube, and left still at high temperature (70 degreeC) for 48 hours. The median particle diameter was measured before and after the test, and the degree of increase in the median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in median particle diameter is less than 10% B: Increase in median particle diameter is 10% or more and less than 20% B: Increase in median particle diameter is 20% or more and less than 50% X: Increase in median particle diameter is 50% or more (5 -2) Low-temperature dispersion stability Each aqueous thermosetting composition (X2) 12g was put into a 20 mL screw rod, and left still at low temperature (10 degreeC) for 48 hours. The median particle diameter was measured before and after the test, and the degree of increase in the median particle diameter before and after the test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Increase in median particle diameter is less than 10% B: Increase in median particle diameter is 10% or more and less than 20% B: Increase in median particle diameter is 20% or more and less than 50% X: Increase in median particle diameter is 50% or more

From the results of Tables 1 to 4, the core / shell type main agent particles of the present invention have a high core coverage, and have superior storage stability and excellent curability compared to the comparative one. In particular, it can be seen that low temperature curability is imparted.
In addition, it is clear that the thermosetting resin composition of the present invention is superior in storage stability and low-temperature curability as compared with the comparative one, and that the cured product obtained by curing the resin composition is excellent in physical properties.

The core / shell type main agent particles of the present invention have a high core coverage, and can impart excellent storage stability and excellent curability to the thermosetting resin composition.
Furthermore, the thermosetting resin composition of the present invention is excellent in storage stability and low-temperature curability, and the cured product obtained by curing the resin composition is excellent in adhesive strength and adhesiveness. It can be used widely and suitably as an adhesive, paint, etc. for bonding applications and coating applications of structural materials such as ships, or bonding applications and coating applications such as buildings and home appliances.

Claims (10)

  Core / shell type main agent particles (D) containing a thermoplastic resin (B) whose core contains an epoxy group-containing compound (A) and whose shell has an outflow start temperature measured by a flow tester of 70 to 180 ° C.   The core / shell type main agent particle according to claim 1, wherein the thermoplastic resin (B) has a water absorption of 0.01 to 2.0% as measured in accordance with ASTM D570.   The core / shell type main agent particles according to claim 1 or 2, wherein the content of the thermoplastic resin (B) is 10 to 150% by weight based on the weight of the (A).   The core / shell type main agent particle according to any one of claims 1 to 3, further comprising a surfactant (C).   An aqueous dispersion (D0) in which the core / shell type main agent particles (D) according to any one of claims 1 to 4 are dispersed in an aqueous medium.   Curing which is the core / shell type main agent particle (D) according to any one of claims 1 to 4, and the compound (E1) and / or the epoxy polymerization catalyst (E2) having at least two functional groups capable of reacting with an epoxy group Thermosetting resin composition (X) containing an agent (E).   It is one selected from the group consisting of an aqueous one-component thermosetting resin composition (X1), a non-aqueous one-component thermosetting resin composition (X2), and a powder thermosetting resin composition (X3). 6. The thermosetting resin composition according to 6.   The equivalent ratio [(A) / (E1)] of the compound (A) to the compound (E1) is 30/70 to 90/10, and / or the compound (A) and the epoxy polymerization catalyst (E2) The thermosetting resin composition according to claim 6 or 7, wherein the weight ratio [(A) / (E2)] is 80/20 to 99.9 / 0.1.   The thermosetting resin composition according to any one of claims 6 to 8, wherein the thermosetting resin composition is one selected from the group consisting of a paint, an adhesive, and a molded product.   Hardened | cured material which the thermosetting resin composition (X) in any one of Claims 6-9 hardened | cured.