JP4874907B2 - Method for producing resin dispersion and resin particles - Google Patents

Description

  The present invention relates to a resin dispersion, a method for producing resin particles, and resin particles. More specifically, the present invention relates to resin particles useful for various applications, a method for producing an aqueous dispersion thereof, and resin particles.

When the resin (b) or the precursor (b0) of the resin (b) is dispersed in the aqueous dispersion of the resin particles (A) and the precursor (b0) is used, the precursor (b0) is reacted, Resin particles having a structure in which resin particles (A) are adhered to the surface of resin particles (B) by forming resin particles (B) made of resin (b) in an aqueous dispersion of particles (A). A method for obtaining an aqueous dispersion (X1) of (C), and resin particles (B) and resin particles (C) obtained by removing an aqueous medium from the aqueous dispersion (X1) are known (Patent Literature). 1).
JP 2002-284881 A

However, the above resin particles have low affinity for the adherend depending on the kind of the adherend when applied to an application in which the resin particles are thermally melted to adhere to the adherend (metal, paper, wood, etc.). Has the disadvantage of becoming. For this reason, for example, when resin particles are used as an additive for paint, the adhesion of the coating film to the adherend is low, and the coating film may be easily peeled off. Further, when used as toner base particles, the adhesion to paper is low, and offset may occur during low-temperature fixing.
Even when the present invention is applied to an application in which resin particles are thermally melted and adhered to an adherend (metal, paper, wood, etc.), the adhesiveness (adhesion) with the adherend is good, It is an object of the present invention to provide a resin dispersion containing resin particles having a uniform particle size and a method for stably producing resin particles.

The present inventors have found that by producing resin particles using a resin produced using a specific esterification catalyst, the adhesion (adhesion) with the adherend is improved, and the present invention has been achieved. did.
That is, the present invention is the following six inventions.
(I) An aqueous dispersion (W) of resin particles (A) made of resin (a) and a precursor (b0) of resin (b) or an oily liquid (OL) made of (b0) and an organic solvent (B0) or oily liquid (OL) is dispersed in (W), and (b0) is reacted in (W) to form resin particles (B) consisting of (b). A step of obtaining an aqueous dispersion (X1) of resin particles (C) having a structure in which (A) is attached to the surface of B),
Polyester resin (p1) formed by at least one of resin (a) and resin (b) in the presence of a titanium catalyst (t) represented by the following general formula (I) or (II), or (p1 A resin (p2) having a structural unit as a structural unit. A method for producing an aqueous dispersion (X1).
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
(II) In the aqueous dispersion (X1) obtained by the production method of (I) above,
Removing the adhering resin particles (A) from the resin particles (B) and then separating and removing (A) from the aqueous dispersion to obtain an aqueous dispersion (X2) of (B), or (A ) And, if necessary, separating and removing the dissolved product of (A) to obtain an aqueous dispersion (X2) of (B). A method for producing an aqueous dispersion (X2).
(III) A step of removing the aqueous solvent from the aqueous dispersion (X1) obtained by the production method (I) to obtain resin particles (C), or an aqueous dispersion obtained by the production method (II) A method for producing resin particles, comprising a step of removing the aqueous solvent from (X2) to obtain resin particles (B).
(IV) Resin particles obtained by the production method of (III) above.

(V) The resin particles (C) having a structure in which the resin particles (A) made of the resin (a) are attached to the surface of the resin particles (B) made of the resin (b),
[1] [Volume average particle diameter of (A) / Volume average particle diameter of (C)] is 0.001 to 0.3,
[2] The volume average particle diameter of (A) is 0.0005 to 30 μm, and the volume average particle diameter of (C) is 0.1 to 300 μm.
[3] 5% or more of the surface of (B) is covered with (A),
[4] The [volume average particle diameter / number average particle diameter] of (C) is 1.0 to 1.5,
[5] Polyester resin (p1) or (p1) in which at least one of (a) and (b) is formed in the presence of a titanium catalyst (t) represented by the following general formula (I) or (II) ) As a structural unit, and (a) and / or (b) is selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins other than (p1) as necessary. A resin particle comprising one or more resins.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
(VI) Polyester resin (p1) formed in the presence of a titanium catalyst (t) represented by the following general formula (I) or (II) or a resin (p2) having a polyester resin (p1) as a structural unit And, if necessary, resin particles (B) comprising a resin (b) containing one or more resins selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins other than (p1) ,
[1] The [volume average particle size / number average particle size] of (B) is 1.0 to 1.5,
[2] Resin particles having a volume average particle diameter of (B) of 0.1 to 300 μm.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]

The present invention has the following effects.
1. Even in the case where the resin particles are applied to an application in which the resin particles are melted by heat and adhered to an adherend (metal, paper, wood, etc.), the resin particles having high affinity for the adherend can be easily produced.
Therefore, for example, when the resin particles obtained by the production method of the present invention are used as an additive for paint, the adhesion of the coating film to the adherend is excellent. Similarly, when used as toner base particles, it has excellent adhesion to paper, and no offset occurs even at low temperature fixing.
2. A resin particle dispersion and resin particles having a uniform particle size can be stably produced.
3. Since the resin particles are obtained in the aqueous dispersion, the resin particles can be produced safely and at low cost.

The present invention is described in detail below.
In the present invention, at least one of the resin (a) contained in the resin particles (A) and the resin (b) contained in the resin particles (B) is represented by the general formula (I) or (II). A polyester resin (p1) formed in the presence of at least one titanium catalyst (t) or a resin (p2) having a polyester resin (p1) as a structural unit is contained. Two or more of the polyester resin (p1) and the resin (p2) may be used in combination, or the polyester resin (p1) and the resin (p2) may be used in combination. In addition, the polyester resin (p1) or the resin (p2) can obtain the effect of the present invention regardless of whether it is contained in the resin (a) or the resin (b), but it is contained in at least the resin (b). Is preferred.

A titanium catalyst (t) is a compound represented by the said general formula (I) or (II), and may use 2 or more types together.
In the general formulas (I) and (II), X represents a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or a polyoxygen having 2 to 12 carbon atoms. This is a residue obtained by removing hydrogen atoms in two hydroxyl groups from alkanolamine. The number of nitrogen atoms contained in X {total number of primary, secondary, and tertiary amino groups} is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).
When X is a residue obtained by removing hydrogen atoms in two hydroxyl groups from polyalkanolamine, the oxygen atoms of these two hydroxyl groups may be bonded to the same titanium atom to form a ring structure { In this case, m is an integer of 1 to 3, and the oxygen atoms of the two hydroxyl groups may be bonded to different titanium atoms to form a repeating structure. When forming a repeating structure, the number of repetitions is 2-5. In the case of 6 or more, since the catalytic activity is lowered, the oligomer component (low molecular weight component) is increased, which causes, for example, deterioration of toner blocking properties.
Preferred as X is a residue of monoalkanolamine (especially ethanolamine), dialkanolamine (especially diethanolamine), or trialkanolamine (especially triethanolamine), and particularly preferred is a residue of triethanolamine. is there.
R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, and Examples include β-ethoxyethyl group. Of these R, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms not containing an ether bond are preferable, and a hydrogen atom, an ethyl group, and an isopropyl group are more preferable.

In formula (I), m is an integer of 1-4, Preferably it is an integer of 2-4. n is an integer of 0 to 3, preferably an integer of 0 to 2. In addition, when not forming a ring structure, the sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably the same.

Specific examples of the titanium catalyst (t) represented by the general formula (I) in the present invention include titanium tetrakis (monoethanolamate), titanium monohydroxytris (triethanolamate), titanium dihydroxy. Bis (triethanolaminate), Titanium trihydroxytriethanolamate, Titanium dihydroxybis (diethanolamate), Titanium dihydroxybis (monoethanolamate), Titanium dihydroxybis (monopropanolamate), Titanium dihydroxybis (N- Methyldiethanolaminate), titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium and N, N, N ′, N′-tetrahydroxyethyl ester Reaction products of diamine, and polycondensates between these intramolecular or molecule.
Examples of intramolecular or intermolecular polycondensates include at least one compound represented by the following general formula (I-1), (I-2), or (I-3).

[In formula, Q < ¹ > and Q < ⁶ > are a hydrogen atom, a C1-C4 alkyl group, or a hydroxyalkyl group. Q ^{2 to} Q ⁵ and Q ^{7 to} Q ⁹ are alkylene groups having 1 to 6 carbon atoms. X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms. ]
Specific examples of those represented by the general formula (II) include titanyl bis (triethanolaminate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanylhydroxytriethanolamate, Examples include titanyl ethoxytriethanolamate, titanyl isopropoxytriethanolamate, and intramolecular or intermolecular polycondensates thereof.
Examples of intramolecular or intermolecular polycondensates include at least one compound represented by the following general formula (II-1) or (II-2).

[In formula, Q < ¹ > and Q < ⁶ > are a hydrogen atom, a C1-C4 alkyl group, or a hydroxyalkyl group. Q < ² > -Q < ⁵ > is a C1-C6 alkylene group. ]

  Among these titanium catalysts, preferred are titanium dihydroxybis (triethanolamate), titanium dihydroxybis (diethanolamate), titanium monohydroxytris (triethanolamate), titanium tetrakis (ethanolamate), and titanylhydroxy. Intramolecular or intermolecular polycondensates of triethanolaminate, titanyl bis (triethanolaminate), titanium dihydroxybis (triethanolamate) [(t1) and (t3) below], titanium monohydroxytris (triethanolamin) Nate) intramolecular polycondensate [following (t2)], and mixtures thereof, more preferably titanium dihydroxybis (triethanolaminate), titanium Hydroxy tris (triethanolaminate), in their molecular polycondensates [(t1) and (t2)], in particular (t1).

  These titanium catalysts (t) are prepared by reacting, for example, a commercially available titanium dialkoxybis (alcohol aminate) [such as DuPont Tyzor TE] at 70 to 90 ° C. in the presence of water. Can be obtained stably. The polycondensate can be obtained by further distilling off the condensed water at 100 ° C. under reduced pressure.

As the polyester resin (p1), a polycondensate of a polyol and a polycarboxylic acid, an acid anhydride thereof, or a lower alkyl (carbon group having 1 to 4 carbon atoms) can be used. As the polyol, diol (1), trivalent to octavalent polyol (2), and the like are used. As the polycarboxylic acid, its acid anhydride or lower alkyl ester, dicarboxylic acid (3), trivalent to hexavalent polycarboxylic acid (4), these acid anhydrides, lower alkyl esters and the like are used.
The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

Examples of the diol (1) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octane). Diol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.); weight average molecular weight {determined by gel permeation chromatography. Hereinafter, abbreviated as Mw. } 106-10000 alkylene ether glycol (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol); alicyclic diols having 6-24 carbon atoms (e.g., 1, 4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); alkylene oxides (AO) [ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), etc.) of the above alicyclic diols] 2-100) (for example, EO 10 mol adduct of 1,4-cyclohexanedimethanol, etc.); Bisphenol having 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol) Etc.) or AO adduct (addition mole number 2 to 100) of polyphenols having 6 to 24 carbon atoms (for example, catechol, hydroquinone and resorcin) (for example, bisphenol A · EO 2 to 4 mol adduct, bisphenol A · PO 2 − 4 mol adducts and the like); polylactone diols having Mw of 100 to 5000 (for example, poly ε-caprolactone diol and the like); polybutadiene diols having Mw of 1000 to 20000 and the like.
Of these, alkylene glycols (particularly 1,2-propylene glycol) and bisphenol AO adducts are preferred, bisphenol AO adducts, and mixtures thereof with alkylene glycols are more preferred.

Examples of the tri- to 8-valent polyol (2) include 3 to 8 valent aliphatic polyhydric alcohols having 3 to 8 carbon atoms (for example, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and sorbitol); AO adducts (2 to 100 addition moles) of novolak resins having a polymerization degree of 3 to 50 (for example, phenol novolak and cresol novolak) (phenol novolac PO 2 mol addition, phenol novolak EO 4 mol addition, etc.); carbon number 6 AO adducts of 2 to 30 polyphenols (eg, pyrogallol, phloroglucinol and 1,2,4-benzenetriol) (addition moles 2-100) (eg, pyrogallol EO 4 mol adduct); and degree of polymerization 20-2000 Acrylic polyol [hydroxyl Le (meth) acrylate and other vinyl monomers (e.g. styrene, (meth) acrylic acid, and the like (meth) copolymer of acrylic acid ester and the like.
Of these, AO adducts of aliphatic polyhydric alcohols and novolac resins are preferred, and AO adducts of novolak resins are more preferred.

Examples of the dicarboxylic acid (3) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); Alkenedicarboxylic acids (for example, maleic acid, fumaric acid, citraconic acid and mesaconic acid); branched alkenedicarboxylic acids having 8 to 40 carbon atoms [for example, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid) Branched alkanedicarboxylic acids having 12 to 40 carbon atoms [for example, alkyl succinic acids (decylsuccinic acid, dodecylsuccinic acid, octadecylsuccinic acid, etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (For example, phthalic acid, isophthalic acid, terephthalic acid And naphthalene dicarboxylic acid) and the like.
Of these, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.

Examples of the trivalent to hexavalent polycarboxylic acid (4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid).
Examples of the acid anhydride of the dicarboxylic acid (3) or the trivalent to hexavalent polycarboxylic acid (4) include trimellitic acid anhydride and pyromellitic acid anhydride. Examples of these lower alkyl esters include methyl esters, ethyl esters, and isopropyl esters.

The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the polyester resin (p1) or the resin (p2) having (p1) as a structural unit is preferably 1,000 to 500,000, Preferably it is 2,000-200,000.
The melting points (measured by DSC, hereinafter the same) of (p1) and (p2) are preferably 0 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C.
The glass transition temperature (Tg) of (p1) and (p2) (measured by DSC; the same applies hereinafter) is preferably −60 ° C. to 100 ° C., more preferably −30 ° C. to 60 ° C. .
The SP values of the polyester resin (p1) and the resin (p2) (the SP value is calculated by the method described in Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). , Preferably 7-18, more preferably 8-14.

The polyester resin (p1) can be produced in the same manner as a normal polyester production method except that the titanium catalyst (t) is used. For example, in an inert gas (nitrogen gas or the like) atmosphere, in the presence of a titanium catalyst (t), the reaction temperature is preferably 150 to 280 ° C., more preferably 160 to 250 ° C., and particularly preferably 170 to 240 ° C. Can be performed. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure (for example, 130 to 7000 Pa) in order to improve the reaction rate at the end of the reaction.
The addition amount of (t) is preferably 0.0001 to 0.8% by weight, more preferably 0.0002 to 0.6% by weight, based on the weight of the obtained polymer, from the viewpoint of polymerization activity and the like. Particularly preferably, it is 0.0015 to 0.55% by weight.
Moreover, another esterification catalyst can also be used together in the range which does not impair the catalytic effect of a titanium catalyst (t). Examples of other esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium catalysts other than titanium catalyst (t) (eg, titanium alkoxide, potassium titanyl oxalate, and titanium terephthalate), zirconium-containing Catalysts (eg zirconyl acetate), germanium-containing catalysts, alkali (earth) metal catalysts (eg alkali metal or alkaline earth metal carboxylates: lithium acetate, sodium acetate, potassium acetate, calcium acetate, sodium benzoate, and benzoic acid) And potassium acetate) and the like. The addition amount of these other esterification catalysts is preferably 0 to 0.6% by weight with respect to the obtained polymer. When the amount is within 0.6% by weight, the color of the polyester resin is further reduced, which is preferable for use as base particles for color toners. When using another esterification catalyst, the content of the titanium catalyst (t) is preferably 50 to 100% by weight based on the weight of the total catalyst.

As a resin (p2) having a polyester resin (p1) as a structural unit, a polyurethane resin obtained from (p1) and a polyisocyanate (15) described later, an epoxy resin obtained from (p1) and a polyepoxide (18) described later, Examples thereof include polyamide resins obtained from (p1) and polyamine (16) described later.
Of these (p2), preferred are polyurethane resins and epoxy resins, and more preferred are polyurethane resins.
When the resin (a) contains the polyester resin (p1) or the resin (p2) having the polyester resin (p1) as a structural unit, the resin (p2) having the polyester resin (p1) or the polyester resin (p1) as a structural unit A preferable example is a polyurethane resin having a polyester resin (p1) and / or a polyester resin (p1) as a structural unit from the viewpoint of good adhesion to various adherends.
Resin (a) is made of polyester resin other than polyurethane resin, epoxy resin, vinyl resin and polyester resin (p1) as necessary, in addition to polyester resin (p1) or resin (p2) having polyester resin (p1) as a structural unit. Any resin may be used as long as it may contain one or more resins selected from the group described above and can form the aqueous dispersion (W). Further, the resin (a) may contain a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, a melamine resin, a urea resin, an aniline resin, an ionomer resin, a polycarbonate resin and the like in addition to the above resins.

The polyester resin other than the vinyl resin, polyurethane resin, epoxy resin, and polyester resin (p1) will be described, but other resins can be used in the same manner as these resins.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. A known polymerization catalyst or the like can be used for the polymerization.
Examples of the vinyl monomer include the following (5) to (14).

(5) Vinyl hydrocarbon:
(5-1) Aliphatic vinyl hydrocarbon: Alkene having 2 to 12 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and α-olefin having 3 to 24 carbon atoms) C4-12 alkadienes (for example, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene).
(5-2) Alicyclic vinyl hydrocarbon: mono- or di-cycloalkene having 6 to 15 carbon atoms (such as cyclohexene, vinylcyclohexene and ethylidenebicycloheptene), mono- or di- having 5 to 12 carbon atoms Cycloalkadienes (eg, (di) cyclopentadiene, etc.); and terpenes (eg, pinene, limonene, indene, etc.) and the like.
(5-3) Aromatic vinyl hydrocarbon: styrene; hydrocarbon (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 24 carbon atoms) substituted styrene (for example, α-methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, and trivinylbenzene); and vinylnaphthalene and the like.

(6) Carboxyl group-containing vinyl monomers and their salts:
C3-C30 unsaturated monocarboxylic acid (for example, (meth) acrylic acid (representing acrylic acid and / or methacrylic acid, the same shall apply hereinafter), crotonic acid isocrotonic acid and cinnamic acid); C3-C30 Of unsaturated dicarboxylic acids (anhydrides) (e.g. (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid and mesaconic acid); and monoalkyls (carbons) of unsaturated dicarboxylic acids having 3 to 30 carbon atoms (Equation 1 to 24) esters (for example, maleic acid monomethyl ester, maleic acid monooctadecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester, itaconic acid glycol monoether and citraconic acid monoeicosyl ester) and the like.
Examples of the salt of the carboxyl group-containing vinyl monomer include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts. . The amine salt is not particularly limited as long as it is an amine compound. For example, a primary amine salt (ethylamine salt, butylamine salt, octylamine salt, etc.), secondary amine (diethylamine salt, dibutylamine salt, etc.), tertiary amine, etc. (Triethylamine salt, tributylamine salt, etc.). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, tributyllaurylammonium salt and the like.
Specific examples of the carboxyl group-containing vinyl monomer salt include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, lithium acrylate, acrylic acid Examples include cesium, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(7) Sulfo group-containing vinyl monomers and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfonic acid) C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxy) Ethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamides having 5 to 18 carbon atoms (for example, 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) ac (Luamido-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid); alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid); poly [n (degree of polymerization, the same shall apply hereinafter) = 2 to 30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene: single, random or block) mono (meth) acrylate sulfate ester [For example, poly (n = 5 to 15) oxyethylene monomethacrylate sulfate, poly (n = 5 to 15) oxypropylene monomethacrylate sulfate]; represented by the following general formulas (7-1) to (7-3) And compounds thereof; and salts thereof It is done.
In addition, as a salt, the salt etc. similar to the salt of (6) carboxyl group-containing vinyl monomer are used.

O (AO) nSO ₃ H
｜
_{CH 2 = CHCH 2 OCH 2 CHCH} 2 O-Ar-R (7-1)

CH ₂ = CHCH ₃
｜
R—Ar—O (AO) nSO ₃ H (7-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (7-3)
(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different. And 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.)

(8) Phosphono group-containing vinyl monomer and salts thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as a salt, the salt etc. similar to the salt of (6) carboxyl group-containing vinyl monomer are used.

(9) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(10) Nitrogen-containing vinyl monomer:
(10-1) Amino group-containing vinyl monomer:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof and the like.
(10-2) Amide group (carbamoyl group) -containing vinyl monomer:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like.
(10-3) A nitrile group (cyano group) -containing vinyl monomer having 3 to 10 carbon atoms:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(10-4) Vinyl monomer containing a group having a quaternary ammonium cation (quaternary ammonio group):
Trimethylammonioethyl (meth) acrylate chloride, methyldiethylammonioethyl (meth) acrylate bromide, trimethylammonioethyl (meth) acrylamide methosulfate, benzyldiethylammonioethyl (meth) acrylamide carbonate, dimethyldiallylammonium chloride, trimethylallyl Ammonium chloride and the like.
(10-5) Nitro group-containing vinyl monomer having 8 to 12 carbon atoms:
Nitrostyrene etc.

(11) Epoxy group-containing vinyl monomer having 6 to 18 carbon atoms:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(12) C2-C16 halogen atom-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(13) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone:
(13-1) a vinyl ester having 4 to 16 carbon atoms,
Vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl Benzoate, ethyl α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eikoshi (Meth) acrylates, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups) Is a straight chain, branched chain or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkane [dialyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraaryl. Loxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.], vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (number average molecular weight 300) mono (meth) acrylate, polypropylene glycol (number average molecular weight 500) monoacrylate, Methyl alcohol EO 10 mol adduct (meth) acrylate, lauryl alcohol EO3 0 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohol: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
(13-2) C3-16 vinyl (thio) ether,
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro 1,2 -Pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene.
(13-3) Vinyl ketone having 4 to 12 carbon atoms Vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone.
(13-4) Vinyl sulfone having 2 to 16 carbon atoms, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

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

  Among the vinyl resins, as a polymer obtained by copolymerizing vinyl monomers (copolymer of vinyl monomers), any of the above monomers (5) to (14) may be binary or more in any proportion. A polymer copolymerized with is used. Examples of such polymers include styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-acrylonitrile copolymers, styrene. -(Anhydrous) maleic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer and styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer Etc.

Since the resin (a) needs to be present as the resin particles (A) in the aqueous dispersion (W), at least the conditions (5 to 90 ° C.) for forming the aqueous dispersion (X1) are preferable. ), It is necessary that the resin (a) is not completely dissolved in water. Therefore, when the vinyl resin is a copolymer, the ratio of the hydrophobic monomer to the hydrophilic monomer constituting the vinyl resin is generally 10% by weight or more of the hydrophobic monomer, although it depends on the type of monomer selected. Is preferable, and it is more preferable that it is 30 weight% or more. If the ratio of the hydrophobic monomer is 10% by weight or less, the vinyl resin tends to be water-soluble, and the particle size uniformity of the resin particles (C) may be impaired.
Here, the hydrophilic monomer means a monomer that dissolves 100 g or more in 100 g of water at 25 ° C., and the hydrophobic monomer means another monomer (a monomer that does not dissolve 100 g or more in 100 g of water at 25 ° C.). It is the same for the resin in the above).

Examples of the polyurethane resin include polyisocyanate (15) and active hydrogen compound (D) {water, polyol [the diol (1) and 3-8 valent polyol (2)], the dicarboxylic acid (3), and the 3-6. And polyaddition products with polyvalent polycarboxylic acid (4), polyamine (16), polythiol (17), etc.}.
A known polymerization catalyst or the like can be used for the polyaddition.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Examples thereof include polyisocyanates of the formula, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- or 4, 4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; trifunctional or more of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)] A mixture of a polyamine and a polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl An isocyanate etc. are mentioned.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane-modified, carbodiimide-modified, allophanate-modified, urea-modified, burette-modified, uretdione-modified, uretoimine-modified, isocyanurate-modified, or oxazolidone-modified. Specific examples of the modified products include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and a mixture of two or more of these [for example, modified MDI and urethane-modified TDI (isocyanate-containing TDI). In combination with a prepolymer).
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines having 2 to 18 carbon atoms, alicyclic polyamines having 4 to 15 carbon atoms, heterocyclic polyamines having 4 to 15 carbon atoms, and aromatic polyamines having 6 to 20 carbon atoms. , Polyamide polyamines and polyether polyamines.
Aliphatic polyamine having 2 to 18 carbon atoms [1] Aliphatic polyamine having 2 to 6 carbon atoms Alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (carbon number of alkylene) 2-6) Polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.].
[2] Alkyl (alkyl having 1 to 4 carbon atoms) or hydroxyalkyl (alkyl having 2 to 4 carbon atoms) substituted dialkyl (alkyl having 1 to 3 carbon atoms) aminopropylamine, trimethylhexamethylenediamine, Aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine and the like.
[3] Alicyclic or heterocyclic-containing aliphatic polyamine 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like.
[4] C8-C15 aromatic ring-containing aliphatic amine xylylenediamine, tetrachloro-p-xylylenediamine, and the like.
C4-C15 alicyclic polyamine 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), and the like.
C4-C15 heterocyclic polyamine piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, and the like.

C6-C20 aromatic polyamine [1] Unsubstituted aromatic polyamine 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 "-triamine, naphthylenediamine and the like.
[2] Nuclear-substituted alkyl group [Aromatic polyamine having 1 to 4 carbon atoms (methyl, ethyl, n- and i-propyl, butyl, etc.)]
2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), Dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4- Diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl- 2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diamy Benzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl -1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3 , 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′- Tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodi Phenylmethane, 3,5-diisopropyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5 '-Tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.), and mixtures of various proportions of these isomers.
[3] Nuclear substituted electron withdrawing group {Aromatic polyamine having halogen (fluorine, chlorine, bromine, iodine, etc.) atom, alkoxy (methoxy, ethoxy etc.) group}
Methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5 -Dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline, 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo -Diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2 -Chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfi Bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′- Methylenebis (2-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, and the like.
[4] Aromatic polyamines having secondary amino groups [partial or all of —NH ₂ of the aromatic polyamines of the above [1] to [3] are —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl Or a lower alkyl group such as
4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.]
Polyamide polyamine:
Low molecular weight polyamide polyamines and the like obtained by condensation of dicarboxylic acids (such as dimer acids) with excess (more than 2 moles per mole of acid) polyamines (such as the above alkylene diamines, polyalkylene polyamines).
Polyether polyamine:
Hydrates of cyanoethylated polyether polyols (such as polyalkylene glycols).

  Examples of polythiol (17) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol and the like.

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (18), a polyaddition product of polyepoxide (18) and active hydrogen compound (D), or polyepoxide (18) and dicarboxylic acid (3) or 3 to 6 valences. And a cured product of the polycarboxylic acid (4) with an acid anhydride.

  The polyepoxide (18) is not particularly limited as long as it has two or more epoxy groups in the molecule. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). 65-1000 are preferable and, as for the epoxy equivalent (molecular weight per epoxy group) of polyepoxide (18), 90-500 are more preferable. Within this range, the water resistance, chemical resistance, and mechanical strength of the cured product are further improved. Note that it is difficult to synthesize a polyepoxide having an epoxy equivalent of less than 65.

Examples of polyepoxides (18) include aromatic polyepoxides, heterocyclic polyepoxides, alicyclic polyepoxides and aliphatic polyepoxides.
Examples of the aromatic polyepoxide include glycidyl ether of polyhydric phenol, polyhydric phenol glycidyl ester, glycidyl aromatic polyamine, and glycidylated product of aminophenol.
Polyglycol glycidyl ethers include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl Diglycidyl ether, tetramethylbiphenyl diglycidyl Ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, By condensation reaction of glycidyl ether of enol or cresol novolac resin, glycidyl ether of limonenephenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ether of polyphenol obtained and polyglycidyl ether of polyphenol obtained by condensation reaction of resorcin and acetone.

Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like.
Examples of the glycidylated product of aminophenol include triglycidyl ether of P-aminophenol.
For aromatic polyepoxy compounds, diglycidyl urethane compounds obtained by addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, glycidyl group-containing polyurethanes obtained by reacting tolylene diisocyanate or diphenylmethane diisocyanate, glycidol and polyol ( Also included are diglycidyl ethers of pre) polymers and AO adducts of bisphenol A.

Examples of the heterocyclic polyepoxide include trisglycidylmelamine.
Examples of the alicyclic polyepoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) Examples include butylamine, diglycidyl dimer acid ester and aromatic hydrogenated product of aromatic polyepoxide.
Aliphatic polyepoxides include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.

Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycol. Examples include glycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether. It is done.
Examples of polyglycidyl esters of polyvalent fatty acids include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
Aliphatic polyepoxides also include (co) polymers of diglycidyl ether and glycidyl (meth) acrylate.
Of these, preferred are aliphatic polyepoxides and aromatic polyepoxides. Two or more polyepoxides may be used in combination.

  Specific examples of the polyester resin other than the polyester resin (p1) include those obtained from the same raw materials as those exemplified as the polyester resin (p1) except that the titanium catalyst (t) is not used. The preferable ones are also the same.

  In the production method of the present invention, an aqueous dispersion (W) of resin particles (A) made of resin (a) and an oily liquid made of precursor (b0) or precursor (b0) of resin (b) and an organic solvent (OL) [The oily liquid (OL) may contain a resin (b) if necessary. ], The precursor (b0) or the oily liquid (OL) is dispersed in the aqueous dispersion (W), the precursor (b0) is reacted, and the resin particles (B) made of the resin (b) (B) ) Is adsorbed on the surface of the resin particles (B), the resin particles (B) or the resin particles (C) are unlikely to coalesce. For this reason, even under high shear conditions, the resin particles (C) are less likely to be split. Due to such a phenomenon, the particle diameter of the resin particles (C) is converged to a constant value, and as a result, resin particles having a uniform particle diameter are obtained. Therefore, the resin particles (A) have a strength that is not broken by shearing at the temperature at which the precursor (b0) and the like are dispersed, are not easily dissolved or swelled in water, b0) or an oily liquid (OL) is preferably difficult to dissolve or swell.

  The glass transition temperature (Tg) of the resin (a) is preferably 0 to 300 ° C. from the viewpoint of the uniformity of the particle size of the resin particles (C), powder fluidity, heat resistance during storage, and stress resistance. More preferably, it is 20-250 degreeC, More preferably, it is 50-200 degreeC. In addition, when Tg is lower than the temperature at which the aqueous dispersion (X1) is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of particle size is reduced.

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) in an aqueous solvent {solvent consisting of water and, if necessary, an organic solvent (U)}, the molecular weight and SP value of the resin (a). It is preferable to appropriately adjust the crystallinity, the molecular weight between cross-linking points, and the like.

  The Mn of the resin (a) is preferably 2 to 5 million, more preferably 2,000 to 500,000. Further, the SP value of the resin (a) is preferably 7 to 18, more preferably 8 to 14. The melting point (measured by DSC) of the resin (a) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. In addition, when it is desired to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (C), the resin (a) has a crosslinked structure using, for example, a trifunctional or higher monomer as a raw material. May be introduced. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. In the case of introducing a crosslinked structure into the resin (a), the molecular weight between crosslinking points is preferably 30 or more, and more preferably 50 or more. On the other hand, when the resin particles (A) adhering to the resin particles (B) are separated and removed to obtain an aqueous dispersion (X2) of the resin particles (B), it is preferable not to introduce a crosslinked structure into the resin (a). preferable.

Although the method to make resin (a) the aqueous dispersion (W) of resin particle (A) is not specifically limited, The following [1]-[8] are mentioned.
[1] In the case of a vinyl resin, an aqueous dispersion of resin particles (A) is directly produced by a polymerization reaction such as suspension polymerization, emulsion polymerization, seed polymerization or dispersion polymerization using a monomer as a starting material. Method.
[2] In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or an organic solvent (U) solution thereof is added with an aqueous solvent (water and A method of producing an aqueous dispersion of resin particles (A) by dispersing in a solvent comprising an organic solvent (U) if necessary, followed by heating or adding a curing agent to cure the precursor.
[3] In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it is preferably a precursor (monomer, oligomer, etc.) or an organic solvent (U) solution (liquid). It is also possible to dissolve a suitable emulsifier in the mixture, and then add water to emulsify the phase inversion, and then heat or add a curing agent to cure the precursor, thereby dispersing the aqueous dispersion of the resin particles (A). A method for producing a liquid.
[4] A finely-pulverized machine such as a mechanical rotary type or jet type resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) A resin dispersion of resin particles (A) is produced by obtaining resin particles by pulverization using an aqueous solution, followed by classification, and then dispersing in an aqueous solvent in the presence of a suitable dispersant.

[5] After obtaining resin particles by spraying a resin solution in which a resin prepared in advance by a polymerization reaction is dissolved in an organic solvent (U) in the form of a mist, the resin particles are placed in an aqueous solvent in the presence of an appropriate dispersant. To produce a resin dispersion of resin particles (A).
[6] Add a poor solvent to a resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent (U), or cool a resin solution previously dissolved in an organic solvent (U) to cool resin particles. Then, after removing the organic solvent (U) to obtain resin particles, the resin particles are dispersed in an aqueous solvent in the presence of a suitable dispersant to obtain a resin dispersion of the resin particles (A). How to manufacture.
[7] A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent (U) is dispersed in an aqueous solvent in the presence of a suitable dispersant, and the organic solvent (U) is removed by heating or decompression. A method of removing and producing a resin dispersion of resin particles (A).
[8] Disperse the resin particles (A) by dissolving an appropriate emulsifier in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent (U) and then adding an aqueous solvent to perform phase inversion emulsification. A method for producing a liquid.

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (S), water-soluble polymer (T) and the like can be used. Moreover, an organic solvent (U), a plasticizer (V), etc. can be used together as an auxiliary agent for emulsification or dispersion.

  As the surfactant (S), anionic surfactant (S-1), cationic surfactant (S-2), amphoteric surfactant (S-3), nonionic surfactant (S-4) and the like. Is mentioned. The surfactant (S) may be a combination of two or more surfactants.

  Examples of the anionic surfactant (S-1) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

  Examples of the carboxylic acid or salt thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid. And a mixture of higher fatty acids obtained by saponifying oleic acid, linoleic acid, ricinoleic acid and coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt include salts of sodium, potassium, 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), higher alkyl ether sulfate esters (EO 1 to 10 mol adducts of aliphatic alcohols having 8 to 18 carbon atoms). Sulfate salts), sulfated oils (natural unsaturated fats or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (lower alcohol esters of unsaturated fatty acids were neutralized by sulfation) And sulfated olefins (sulfurized 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 salt, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, alcohol synthesized using a Ziegler catalyst (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohol synthesized by the oxo method (for example, tridecanol: manufactured by Kyowa Hakko Kogyo Co., Ltd., Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Industries, Ltd., Dovanol 23, 25, 45, Diadol) 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation).
Specific examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt, octyl alcohol EO 3 mol adduct sulfate ester salt, and the like.
Specific examples of the sulfated oil include castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep oil salts (sodium salt, potassium salt, ammonium salt, alkanolamine salt) and the like.
Specific examples of the sulfated fatty acid ester include sulfate salts (sodium salt, potassium salt, ammonium salt, alkanolamine salt) such as butyl oleate and butyl ricinoleate.
Specific examples of the sulfated olefin include tee pole (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 EO 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms.
Specific examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, sec-tridecanol 23 carboxymethylated sodium salt, Examples include decanol carboxymethylated sodium salt.
Specific examples of salts of carboxymethylated products of EO 1 to 10 mol adducts of aliphatic alcohols include octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated sodium salt, sec-tridecanol 23EO3. Mole adduct carboxymethylated sodium salt, tridecanol EO 5 mol adduct carboxymethylated sodium salt and the like can be mentioned.

As the sulfonate, (d1) alkylbenzene sulfonate, (d2) alkylnaphthalene sulfonate, (d3) sulfosuccinic acid diester type, (d4) α-olefin sulfonate (Tapol), (d5) Igepon T type (D6) Other aromatic ring-containing compounds sulfonates.
Specific examples of alkyl benzene sulfonates include sodium dodecylbenzene sulfonate.
Specific examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate.
Specific examples of the sulfosuccinic acid diester type include sulfo-2-succinic acid di-2-ethylhexyl ester sodium salt.
Other sulfonates of aromatic ring-containing compounds include mono- or disulfonates of alkylated diphenyl ethers, styrenated phenol sulfonates, and the like.

  Examples of phosphoric acid ester salts include (e1) higher alcohol phosphoric acid ester salts and (e2) higher alcohol EO adduct phosphoric acid ester salts.

Specific examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt, lauryl alcohol phosphate diester sodium salt, and the like.
Specific examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

  Examples of the cationic surfactant (S-2) include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt types include lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethyl Ammonium chloride, stearamide ethyl diethyl methyl ammonium methosulfate, etc. are mentioned.

  As the amine salt type, the primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, succinic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) Obtained by neutralization. The primary amine salt type includes inorganic acid salts or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine); higher fatty acids (stearic acid, Oleic acid) and the like. The secondary amine salt type includes inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines. The tertiary amine salt type includes aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adducts of aliphatic amines, Alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.), nitrogen-containing heterocycles Examples include inorganic acid salts or organic acid salts of aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.).

  Examples of the amphoteric surfactant (S-3) include carboxylate-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. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include compounds represented by the following general formula.
_{[R-NH- (CH 2)} n-COO] mM
[Wherein R is a monovalent hydrocarbon group; n is 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. It is. ]
Specific examples of the amino acid type amphoteric surfactant include, for example, alkylaminopropionic acid type amphoteric surfactants (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); alkylaminoacetic acid type amphoteric surfactants (laurylaminoacetic acid) Glycine type amphoteric surfactant (sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride, etc.) and the like.

  Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cationic moiety and a carboxylic acid-type anionic moiety in the molecule. For example, alkyldimethylbetaine (stearyldimethylaminoacetic acid betaine, lauryl). Dimethylaminoacetic acid betaine), amide betaine (coconut oil fatty acid amidopropyl betaine etc.), alkyldihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.), etc. are mentioned.

  Examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of the nonionic surfactant (S-4) include an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant.

  AO addition type nonionic surfactants can be used by adding AO directly to higher alcohol, higher fatty acid or alkylamine, or adding higher fatty acid to polyalkylene glycol obtained by adding AO to glycol. It is obtained by reacting, adding AO to an esterified product obtained by reacting a polyhydric alcohol and a higher fatty acid, or adding AO to a higher fatty acid amide.

Preferred among AO are EO and random or block adducts of EO and PO.
The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% by weight of the AO is preferably EO.

  Specific examples of the AO addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol EO adduct, lauryl alcohol EO adduct, stearyl alcohol EO adduct, oleyl alcohol EO adduct, lauryl alcohol EO). PO block adducts, etc.); polyoxyalkylene higher fatty acid esters (eg, stearyl acid EO adduct, lauric acid EO adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid esters (eg, lauric acid of polyethylene glycol) Diester, oleic acid diester of polyethylene glycol, stearic acid diester of polyethylene glycol, etc.); polyoxyalkylene alkylphenyl ether (eg nonylphenol EO adduct, nonylphenol) O / PO block adduct, octylphenol EO adduct, bisphenol A / EO adduct, dinonylphenol EO adduct, styrenated phenol EO adduct, etc .; polyoxyalkylene alkylamino ether and (eg, laurylamine EO addition) Polyoxyalkylene alkyl alkanolamides (for example, EO adducts of hydroxyethyl lauric acid amide, EO adducts of hydroxypropyl oleic acid amide, EO adducts of dihydroxyethyl lauric acid amide, etc.) ).

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

Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned.
Specific examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO adduct, ethylene glycol monostearate EO adduct, trimethylolpropane monostearate EO / PO random adduct, sorbitan monolaurate EO addition Sorbitan monostearate EO adduct, sorbitan distearate EO adduct, sorbitan dilaurate EO / PO random adduct and the like.

Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like.
Specific examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO adduct, methyl glycoside EO / PO random adduct, lauryl glycoside EO adduct, stearyl glycoside EO / PO random adduct, and the like.

  Examples of the water-soluble polymer (T) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide partial neutralization of polyacrylic acid Sodium acrylate-acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide (Partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The organic solvent (U) may be added to the aqueous solvent as necessary when emulsifying and dispersing the resin (a), or in the dispersion to be emulsified [in the oily liquid (OL) containing the precursor (b0)]. ] May be added.
Specific examples of organic solvents (U) include aromatic hydrocarbon solvents {toluene, xylene, ethylbenzene, tetralin, etc.}; aliphatic or alicyclic hydrocarbon solvents {n-hexane, n-heptane, mineral spirit, cyclohexane, etc. }; Halogen solvent {methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc.}; ester or ester ether solvent {ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, etc .; ether solvents {diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.}; ketone solvents {acetone, methyl ethyl ketone , Methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.}; alcohol solvent {methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, etc.}; Amide solvents {dimethylformamide, dimethylacetamide, etc.}; sulfoxide solvents {dimethylsulfoxide, etc.}; heterocyclic compound solvents {N-methylpyrrolidone, etc.} and mixed solvents of two or more of these. The organic solvent (U) used in the aqueous solvent is preferably a solvent {acetone, methanol or the like} that is miscible with water at 25 ° C. at an arbitrary ratio.

The plasticizer (V) may be added to an aqueous solvent as necessary when emulsifying and dispersing the resin (a), or in the dispersion to be emulsified [in the precursor (b0) or oily liquid (OL)]. You may add to.
The plasticizer (V) is not limited in any way. (V1) Phthalic acid ester [dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, etc.]; (V2) Aliphatic dibasic acid ester [adipine] (V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.]; (V4) phosphoric acid ester [triethyl phosphate, Tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.]; (V5) fatty acid esters [butyl oleate, etc.]; (V6) and mixtures of two or more thereof.

  The particle size of the resin particles (A) is usually smaller than the particle size of the resin particles (B), and from the viewpoint of uniformity of the particle size of the obtained resin particles (C) or (B), the particle size ratio [ The value of volume average particle diameter of resin particles (A) / volume average particle diameter of resin particles (C)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, particularly preferably 0.005, and the upper limit is more preferably 0.25, particularly preferably 0.1. When the particle size ratio is larger than 0.3, the resin particles (A) are not efficiently adsorbed on the surface of the resin particles (B), and thus the particle size distribution of the obtained resin particles (C) tends to be wide.

The volume average particle size of the resin particles (A) can be appropriately adjusted within the above range of particle size ratios so as to be a particle size suitable for obtaining the resin particles (C) having a desired particle size.
The volume average particle diameter of the resin particles (A) is preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 μm, most preferably 2 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain resin particles (C) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles (C). When it is desired to obtain resin particles (C) of preferably 0.005 to 3 μm, particularly preferably 0.04 to 2 μm, most preferably 0.05 to 1 μm, 100 μm, preferably 0.05 to 30 μm. Particularly preferably, the thickness is 0.1 to 20 μm. The volume average particle diameter can be measured with a laser type particle size distribution measuring apparatus {for example, LA-920 (manufactured by Horiba, Ltd.)} or a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
In addition, since the said particle size ratio is easy to obtain, 0.1-300 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. The upper limit is more preferably 250 μm, particularly preferably 200 μm, most preferably 20 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm, and most preferably 4 μm.

The resin (b) preferably contains the polyester resin (p1) or the resin (p2) having the polyester resin (p1) as a structural unit. However, as described above, at least of the resin (a) and the resin (b) One is a polyester resin (p1) formed in the presence of the titanium catalyst (t) represented by the general formula (I) or (II) or a resin (p2) having a polyester resin (p1) as a structural unit When the resin (a) contains the polyester resin (p1) or the resin (p2) having the polyester resin (p1) as a structural unit, the resin (b) contains the polyester resin (p1) or the resin. (P2) may not be contained.
When the resin (b) contains the polyester resin (p1) as a structural unit, the precursor (b0) of the resin (b) contains the polyester resin (p1) as a structural unit.
When the resin (b) contains the polyester resin (p1) or the resin (p2) having the polyester resin (p1) as a structural unit, the resin (p2) having the polyester resin (p1) or the polyester resin (p1) as a structural unit Preferred is a polyurethane resin having a polyester resin (p1) as a structural unit.
The resin (b) is one or more selected from the group consisting of a polyurethane resin, an epoxy resin, a vinyl resin and a polyester resin other than the polyester resin (p1), if necessary, in addition to the polyester resin (p1) and the resin (p2). A resin may be contained. About the specific example, the thing similar to resin (a) can be used. The resin (b) may contain a resin {a dead polymer or the like described later) other than the resin obtained by reacting the precursor (b0) of the resin (b) if necessary.
Resins other than the polyester resin (p1) and the resin (p2) contained in the resin (b) can be appropriately selected depending on applications and purposes. Generally preferred are polyester resins other than polyurethane resins, epoxy resins, vinyl resins and polyester resins (p1), more preferably polyester resins other than vinyl resins, polyurethane resins and polyester resins (p1) and mixtures thereof.

The Mn, melting point, Tg, and SP value of the resin (b) may be appropriately adjusted within a preferable range depending on the use of the resin particle (C) or the resin particle (B). For example, when the resin particles (C) and the resin particles (B) are used as a slush molding resin and a powder coating, the Mn of the resin (b) is preferably 2,000 to 500,000, more preferably 4,000 to 200,000. The melting point of the resin (b) is preferably 0 to 200 ° C, more preferably 35 to 150 ° C. Tg of the resin (b) is preferably -60 to 100 ° C, more preferably -30 to 60 ° C. 7-18 are preferable and, as for SP value of resin (b), More preferably, it is 8-14.
When the resin particles (C) or resin particles (B) are used as spacers for manufacturing electronic components (liquid crystal displays, etc.) and standard particles for electronic measuring machines, the Mn of the resin (b) is preferably 20,000 to 10,000,000. More preferably, it is 40,000 to 2,000,000. 40-300 degreeC is preferable and, as for melting | fusing point of resin (b), More preferably, it is 70-250 degreeC. The Tg of the resin (b) is preferably −0 to 250 ° C., and more preferably 50 to 200 ° C. 8-18 are preferable and, as for SP value of resin (b), More preferably, it is 9-14.
When the resin particle (C) or the resin particle (B) is used as a toner base particle {a toner base particle used in electrophotography, electrostatic recording, electrostatic printing, etc.}, Mn of the resin (b) is 1 1,000 to 5,000,000 is preferable, and 2,000 to 500,000 is more preferable. 20-300 degreeC is preferable and, as for melting | fusing point of resin (b), More preferably, it is 80-250 degreeC. The Tg of the resin (b) is preferably 20 to 200 ° C, more preferably 40 to 100 ° C. The SP value of the resin (b) is preferably 8 to 16, and more preferably 9 to 14.

  In the production method of the present invention, an aqueous dispersion (W) of resin particles (A) made of resin (a), a precursor (b0) or precursor (b0) of resin (b) and an oily solvent made of an organic solvent. Liquid (OL) [The resin liquid (b) may be contained in the oily liquid (OL) if necessary. And the precursor (b0) or oily liquid (OL) is dispersed in the aqueous dispersion (W), and the precursor (b0) is further reacted to obtain an aqueous dispersion of the resin particles (A). An aqueous dispersion of resin particles (C) having a structure in which resin particles (A) are adhered to the surface of resin particles (B) by forming resin particles (B) made of resin (b) in the liquid. (X1) is obtained.

When dispersing the precursor (b0) of the resin (b) or the oily liquid (OL) composed of the precursor (b0) and an organic solvent in the aqueous dispersion (W), a dispersing device can be used.
The dispersion apparatus is not particularly limited as long as it is generally marketed as an emulsifier or a disperser. For example, a batch type emulsifier {homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK autohomo Mixer (made by Special Machine Industries Co., Ltd.)}, continuous emulsifier {Ebara Milder (made by Ebara Corporation), TK Fillmix, TK Pipeline Homo Mixer (made by Special Machine Industries Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Pulverizer (Suntech Co., Ltd.), Capitolon (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.)}, High Pressure Emulsifier {Microfluidics Dizer (manufactured by Mizuho Industry Co., Ltd.), Nanomizer (manufactured by SG Engineering Co., Ltd.), APV Urine (manufactured by Gaurin Co., Ltd.)}, membrane emulsifier {membrane emulsifier (manufactured by Chilling Industries Co., Ltd.)}, vibration emulsifier {vibro mixer (manufactured by Chilling Industries Co., Ltd.)}, ultrasonic emulsifier { Ultrasonic homogenizer (manufactured by Branson Co., Ltd.), etc.}. Among these, the batch type emulsifier, the continuous type emulsifier, the high pressure emulsifier, more preferably the APV Gaurin, the homogenizer, the TK auto homomixer, the Ebara milder, and the TK fill mix are preferable from the viewpoint of homogenizing the particle size. TK pipeline homomixer.

When the precursor (b0) of the resin (b) is dispersed in the aqueous dispersion (W) of the resin particles (A), the precursor (b0) is preferably a liquid. When the precursor (b0) is solid at room temperature, it may be dispersed at a temperature equal to or higher than the melting point of the precursor (b0).
The viscosity of the oily liquid (OL) composed of the precursor (b0) or the precursor (b0) of the resin (b) and an organic solvent is preferably 10 to 50,000 mPa · s (B-type) from the viewpoint of particle size uniformity. (Temperature measured and dispersed with a viscometer), more preferably 100 to 10,000 mPa · s.
The temperature during dispersion is preferably 0 to 150 ° C. (under pressure), more preferably 5 to 98 ° C. When the viscosity is high, it is preferable to carry out emulsification dispersion by raising the temperature and reducing the viscosity to the above preferred range.
The organic solvent used for the oily liquid (OL) is not particularly limited as long as it can dissolve the precursor (b0) at a temperature of 25 ° C. to dispersion, and specifically, the same as the organic solvent (U). Are illustrated. Although what is preferable changes with kinds of resin (b) obtained from a precursor (b0), it is suitable that SP value difference with resin (b) is 3 or less. Moreover, from the viewpoint of the particle size uniformity of the resin particles (C), a solvent that dissolves the resin (b) but hardly dissolves and swells the resin particles (A) made of the resin (a) is preferable.

  The precursor (b0) of the resin (b) is not particularly limited as long as it can become the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin, the precursor (b0) Includes the above-mentioned vinyl monomers (which may be used alone or in combination). When the resin (b) is a condensation resin (for example, a polyurethane resin, an epoxy resin, and a polyester resin), the precursor (b0) is composed of a prepolymer (α) having a reactive group and a curing agent (β). Combinations are illustrated.

When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to make the resin (b) includes, for example, an oil-soluble initiator, a vinyl monomer, and, if necessary, an organic solvent (U). A method of dispersing and suspending the resin particles (A) in the aqueous dispersion (W) in the presence of the water-soluble polymer (T) and performing a radical polymerization reaction by heating (so-called suspension polymerization method); vinyl monomer and, if necessary, An organic solvent (U) is emulsified in an aqueous dispersion (W) of resin particles (A) containing an emulsifier (similar to the surfactant (S)) and a water-soluble initiator, and radicals are formed by heating. Examples thereof include a method for performing a polymerization reaction (so-called emulsion polymerization method).
The polyester resin (p1) is constituted by reacting in advance with the polyester resin (p1) using a vinyl monomer having a functional group capable of reacting with the functional group (hydroxyl group, carboxyl group, etc.) of the polyester resin (p1). The vinyl resin which has as a unit can be obtained.

  Examples of the oil-soluble or water-soluble initiator include peroxide-based polymerization initiator (I) and azo-based polymerization initiator (II). Further, the redox polymerization initiator (III) may be formed by using a peroxide polymerization initiator (I) and a reducing agent in combination. Furthermore, you may use 2 or more types together from (I)-(III).

(I) Peroxide-based polymerization initiator (I-1) Oil-soluble peroxide-based polymerization initiator: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile Peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide Id, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5- Dibenzoylperoxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-dit-butylperoxide Oxyhexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide 2,5-dimethyl-2,5-dihydro peroxide, cumene peroxide and the like.
(I-2) Water-soluble peroxide polymerization initiator: hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate and the like.

(II) Azo polymerization initiator:
(II-1) Oil-soluble azo polymerization initiator: 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy-2 , 4-dimethylvaleronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobis (2-methylpropionate), 1,1′-azobis (1-acetoxy- 1-phenylethane), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like.
(II-2) Water-soluble azo polymerization initiator: azobisamidinopropane salt, azobiscyanovaleric acid (salt), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide ]etc.

(III) Redox polymerization initiator (III-1) Non-aqueous redox polymerization initiator: oil-soluble peroxide {hydroperoxide, dialkyl peroxide, diacyl peroxide, etc.} and oil-soluble reducing agent {tertiary amine , Naphthenates, mercaptans, organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.), etc.}.
(III-2) Water-based redox polymerization initiator: water-soluble peroxide {persulfate, hydrogen peroxide, hydroperoxide, etc.} and water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite) , Alcohol, polyamine, etc.).

As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). When the resin (b) has the polyester resin (p1) as a structural unit, the prepolymer (α) of the precursor (b0) preferably has the polyester resin (p1) as a structural unit.
In this case, as a method of forming the resin (b) by reacting the precursor (b0), a reactive group-containing prepolymer (α), a curing agent (β) and, if necessary, an organic solvent (U) are used as resin particles. The resin particles (B) made of the resin (b) are formed by dispersing in the aqueous dispersion (W) of (A) and reacting the reactive group-containing prepolymer (α) with the curing agent (β) by heating. A method in which a reactive group-containing prepolymer (α) or a solvent solution thereof is dispersed in an aqueous dispersion (W) of resin particles (A), and a water-soluble curing agent (β) is added thereto and reacted. A method of forming resin particles (B) comprising the resin (b); when the reactive group-containing prepolymer (α) is cured by reacting with water, the reactive group-containing prepolymer (α) or its By dispersing the solvent solution in the aqueous dispersion (W) of the resin particles (A) Examples thereof include a method of reacting with water to form resin particles (B) comprising the resin (b).

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1]: The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen compound (β1). combination.
[2]: The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) capable of reacting with an active hydrogen-containing group. combination.
Among these, the combination of [1] is more preferable from the viewpoint of the reaction rate in the aqueous solvent.
In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound is an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (1,3 -Oxo-2-oxapropylene group) (α1d) and acid halide group (halocarbonyl group) (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam, etc.] An aliphatic alcohol having 1 to 20 carbon atoms [ethanol, methanol, octanol, etc.]; phenol [phenol, m-cresol, xylenol, nonylphenol, etc.]; active methylene compound [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.]; base Nitrogenous compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine and the like]; and mixtures of two or more thereof. Of these, oxime is preferred, and methyl ethyl ketoxime is particularly preferred.

Examples of the structural unit of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Among these, (αx), (αy) and (αz) are preferable, and (αx) and (αz) are particularly preferable.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like.
Examples of the polyester (αx) include polyester resins (p1) and / or polyester resins other than the polyester resin (p1), polylactones (such as a ring-opening polymer of ε-caprolactone), and the like.
Examples of the epoxy resin (αy) include addition condensates of bisphenol (bisphenol A, bisphenol F, bisphenol S, etc.) and epichlorohydrin.
Examples of the polyurethane (αz) include a polyaddition product of the diol (1) and / or a tri- to octavalent polyol (2) and a polyisocyanate (15), a polyaddition product of a polyester (αx) and a polyisocyanate (15), and the like. Is mentioned.

The following two methods and the like can be mentioned as a method for incorporating a reactive group into polyester (αx), epoxy resin (αy), polyurethane (αz), and the like.
[1]: A method in which a functional group of a constituent component is left at the terminal by using one of two or more constituent components in excess.
[2]: The functional group of the constituent component is left at the terminal by using one of two or more constituent components in excess, and further contains a functional group and a reactive group capable of reacting with the remaining functional group. A method of reacting with a compound.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group (halocarbonyl group) -containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, and a hydroxyl group-containing A polyurethane prepolymer, an isocyanate group-containing polyurethane prepolymer, and the like are obtained.
The ratio of two or more components is, for example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the polyol component and the polycarboxylic acid component is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 2/1 to 1.01 / 1, more preferably 1.5 / 1 to 1.01 / 1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.
In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, and an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group (1,3-oxo-2-oxapropylene is obtained by reacting an acid anhydride having 4 or more carbonyl groups. Group) -containing prepolymer.
The amount of the compound containing a functional group and a reactive group is, for example, when an isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1.01 / 1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2. 5/1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. Setting it to 2,000 poise or less is preferable in that resin particles (C) having a sharp particle size distribution can be obtained.

Examples of the active hydrogen compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Of these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d) It is.
Examples of the polyamine (β1a) are the same as those of the polyamine (16). Of these, 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof are preferred.

  When the polyamine (β1a) is a polyamine blocked with a detachable compound, examples thereof include a ketimine obtained from the polyamine and a ketone having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), Examples thereof include aldimine, enamine, oxazolidine and the like obtained from aldehydes having 2 to 8 carbon atoms (formaldehyde, acetaldehyde).

Examples of the polyol (β1b) are the same as the diol (1) and the trivalent to octavalent polyol (2). Diol (1) alone or a mixture of diol (1) and a small amount of polyol (2) is preferred.
Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

If necessary, a reaction terminator (βs) can be used together with the active hydrogen compound (β1). By using a reaction terminator together with the active hydrogen compound (β1) at a certain ratio, the resin (b) can be adjusted to a predetermined molecular weight.
As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) And phenol; monomercaptan (such as butyl mercaptan and lauryl mercaptan); monoisocyanate (such as lauryl isocyanate and phenyl isocyanate); monoepoxide (such as butyl glycidyl ether) and the like.

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred. Examples of the organic group blocked with the compound from which the amino group can be removed include those similar to the case of (β1a).

  Examples of the compound (β2) capable of reacting with an active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyanhydride (β2d), and polyacid halide (β2e). It is done. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same.
Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (18), and preferred ones are also the same.

Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred.
Examples of the dicarboxylic acid (β2c-1) include the same dicarboxylic acid (3), and examples of the polycarboxylic acid include the same ones as the trivalent to hexavalent polycarboxylic acid (4), and preferable ones are also the same. .

Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride.
Examples of the polyacid halide (β2e) include the acid halide (acid chloride, acid bromide, acid iodide) of the above (β2c).
Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is handled as a divalent active hydrogen compound.

  The resin (b) obtained by reacting the precursor (b0) composed of the reactive group-containing prepolymer (α) and the curing agent (β) in an aqueous solvent is a resin particle (B) and a resin particle (C). It becomes a component. The Mw of the resin (b) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3,000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000. ~ 1 million.

In the aqueous dispersion (W), a polymer that does not react with the reactive group-containing prepolymer (α) and the curing agent (β) during the reaction of the reactive group-containing prepolymer (α) with the curing agent (β). [So-called dead polymer] can also be contained in the system. In this case, the resin (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) with a dead polymer.
As the dead polymer, a vinyl resin and a polyester resin are preferable, a polyester resin is more preferable, and a polyester resin (p1) is particularly preferable.
The content of the dead polymer (polymer other than the resin obtained by reacting the precursor (b0)) in the resin (b) is preferably 0 to 80% by weight, more preferably 5 to 70% by weight.

Other additives in the resin particles (A) and / or resin particles (B) (pigments, fillers, antistatic agents, colorants, mold release agents, charge control agents, ultraviolet absorbers, antioxidants, antiblocking agents) Mixing agents, heat stabilizers, flame retardants, etc.). As another method for adding the resin particles (A) or the resin particles (B), the aqueous dispersion (X1) may be mixed in the aqueous dispersion (W). More preferably, after the precursor (b0) of (a) or the resin (b) and the additive are mixed, the mixture is added and dispersed in the aqueous dispersion (W).
In the present invention, the additive does not necessarily need to be mixed when the particles are formed in the aqueous dispersion (W), and may be added after the particles are formed. For example, after forming resin particles not containing a colorant, a colorant is added by a known dyeing method, or the above additives are added to the resin particles together with an organic solvent (U) and / or a plasticizer (V). It can also be impregnated.

  The amount of the aqueous dispersion (W) used with respect to 100 parts by weight of the resin (b) is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersion state of the resin (b) is good. It is economical that it is 2,000 parts by weight or less.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity depending on the combination of the structure of the reactive group of the prepolymer (α) and the curing agent (β), preferably 10 minutes to 40 hours, more preferably 30. Min to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 50 to 120 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of reaction of an isocyanate and an active hydrogen compound.

The resin particles (C) can be obtained by removing the aqueous solvent from the aqueous dispersion (X1). Examples of the method for removing the aqueous solvent include the following methods.
[1] A method of drying the aqueous dispersion (X1) under reduced pressure or atmospheric pressure.
[2] A method in which the aqueous dispersion (X1) is subjected to solid-liquid separation using a centrifuge, a spatula filter, a filter press, or the like, and the obtained powder is dried.
[3] A method in which the aqueous dispersion (X1) is frozen and dried (so-called lyophilization).
In the method [1] or [2], the obtained powder can be dried using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer. Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

  When it is desired to increase the adhesion between the resin particles (A) and the resin particles (B), when the precursor (b0) or the oily liquid (OL) is dispersed in the aqueous dispersion (W), the resin particles (A) When the resin particles (B) have positive and negative charges, or when the resin particles (A) and the resin particles (B) have the same charge, the resin particles (A) and the resin particles (B) have opposite charges. It is effective to use a surfactant (S) or a water-soluble polymer (T), or to reduce the SP value difference between the resin (a) and the resin (b) to 2 or less.

  From the viewpoints of particle size uniformity, storage stability, etc. of the resin particles (C), the resin particles (C) are 0.1 to 50 (preferably 0.2 to 40) wt% of the resin particles (A) and 50 It is preferably composed of ˜99.9 (preferably 60 to 99.8)% by weight of resin particles (B).

From the viewpoints of particle size uniformity, powder fluidity, storage stability, and the like of the resin particles (C), 5 (preferably 30, more preferably 80)% or more of the surfaces of the resin particles (B) are resin particles (A ). The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = (SA) × 100 / (SA) + (SB)
(SA): Area of the portion covered with the resin particles (A) (SB): Area of the portion where the resin particles (B) are exposed

In view of the particle size uniformity, the [volume average particle size / number average particle size] of the resin particles (C) is preferably 1.0 to 1.5, more preferably 1.0 to 1.45, and particularly preferably 1. 0.05 to 1.2.
The volume average particle diameter of the resin particles (C) varies depending on the use, but is preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, most preferably 20 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm, and most preferably 4 μm.
The volume average particle diameter and the number average particle diameter can be simultaneously measured with a Coulter counter.

The resin particle (C) has a desired irregularity on the particle surface by changing the particle size of the resin particle (A) and the resin particle (B) and the coverage of the resin particle (B) surface by the resin particle (A). Can be granted.
When it is desired to improve the powder fluidity, the BET specific surface area of the resin particles (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area can be measured (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen) using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics).
Similarly, from the viewpoint of powder fluidity, the surface average centerline roughness Ra of the resin particles (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, the resin particles (A) and the resin particles (B) are also preferably spherical. The resin particles (C) preferably have a Wadell's practical sphericity of 0.85 to 1.00, more preferably 0.90 to 1.00. Wadell's practical sphericity is obtained from the ratio of the diameter of a circle having an area equal to the projected area of the particle to the diameter of a circle having the smallest area circumscribing the projected image of the particle. The projected image of the particles can be taken with, for example, a scanning electron microscope (SEM).

The aqueous dispersion (X2) of the resin particles (B) is obtained by removing the resin particles (A) from the resin particles (B) in the aqueous dispersion (X1), and then removing the resin particles (A) from the aqueous dispersion. ) Or the resin particles (A) are dissolved in the aqueous dispersion (X1) without dissolving the resin particles (B). You may isolate | separate and remove the melt | dissolution of a resin particle (A) as needed.
Furthermore, resin particles (B) are obtained by removing the aqueous solvent from the aqueous dispersion (X2). Examples of the method for removing the aqueous solvent include the same method as in the case of the resin particles (C).
Examples of the method for detaching the adhering resin particles (A) from the resin particles (B) in the aqueous dispersion (X1) include the following methods.
[1] A method of ultrasonically treating the aqueous dispersion (X1).
[2] A method in which the aqueous dispersion (X1) is diluted with a large amount of water or a water-soluble organic solvent {methanol, ethanol, acetone, or the like} and sheared by stirring.
[3] A method in which an acid, alkali, inorganic salt or the like is added to the aqueous dispersion (X1), and shearing is performed by stirring.
[4] A method in which the aqueous dispersion (X1) is heated and sheared by stirring.
[5] A method of distilling off the organic solvent when the aqueous dispersion (X1) contains an organic solvent.

Examples of the method for dissolving the resin particles (A) in the aqueous dispersion (X1) include the following methods.
[1] When the resin (a) is a resin having an acidic functional group such as a carboxyl group, a phosphono group, or a sulfo group (generally, the molecular weight per acidic functional group is preferably 1,000 or less) A method of adding a base {sodium hydroxide, potassium hydroxide, ammonia, DBU, etc.} or an aqueous solution thereof to the dispersion (X1).
[2] Resin (a) having a basic functional group such as a primary amino group, secondary amino group, tertiary amino group, or quaternary ammonio group (generally, the molecular weight per basic functional group is 1, 000 or less), a method of adding an acid {hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, etc.} or an aqueous solution thereof to the aqueous dispersion (X1).
[3] When the resin (a) is dissolved in a specific organic solvent (U) {generally, the difference in SP value between the resin (a) and the organic solvent (U) is preferably 2.5 or less} A method of adding a specific organic solvent (U) to the aqueous dispersion (X1).

Examples of the method for separating and removing the resin particles (A) or a dissolved product thereof from the aqueous dispersion include the following methods.
[1] A method in which only resin particles (B) are filtered by filtration using a filter paper, a filter cloth, a mesh or the like having a certain opening.
[2] A method in which only the resin particles (B) are sedimented by centrifugation, and the resin particles (A) contained in the supernatant or a lysate thereof are removed.

The particle size ratio of the resin particles (A) to the resin particles (B), and the coverage of the resin particles (B) surface by the resin particles (A) in the aqueous dispersion (X1), in the aqueous dispersion (X1) By changing the depth at which the resin particles (A) are embedded on the resin particle (B) side on the resin particle (B) / aqueous solvent interface, the surface of the resin particles (B) can be smoothed or Desired irregularities can be imparted.
The coverage of the surface of the resin particle (B) with the resin particle (A) and the depth at which the resin particle (A) is embedded on the resin particle (B) side can be controlled by the following method.
[1] When the aqueous dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) are made to have positive and negative charges, the coverage and depth are increased. In this case, the coverage and the depth increase as the electric charges of the resin particles (A) and the resin particles (B) are increased.
[2] When the aqueous dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative), the coverage ratio Tends to decrease and decrease in depth. In this case, generally, when the surfactant (S) and / or the water-soluble polymer (T) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased. Moreover, when using water-soluble polymer (T), depth becomes small, so that the molecular weight of water-soluble polymer (T) is large.
[3] When the aqueous dispersion (X1) is produced, the resin (a) has an acidic functional group such as a carboxyl group, a phosphono group, or a sulfo group (generally, the molecular weight per acidic functional group is 1,000). In the case of the following), the lower the pH of the aqueous solvent, the greater the coverage and depth. Conversely, the higher the pH, the smaller the coverage and depth.
[4] When the aqueous dispersion (X1) is produced, the resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonio group (generally, When the molecular weight per basic functional group is preferably 1,000 or less), the higher the pH of the aqueous solvent, the greater the coverage and depth. Conversely, the lower the pH, the smaller the coverage and depth.
[5] The coverage and depth increase as the SP value difference between the resin (a) and the resin (b) decreases.

  The volume average particle diameter of the resin particles (B) varies depending on the intended use, but is preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, most preferably 20 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm, and most preferably 4 μm. Further, in view of the particle size uniformity, the [volume average particle size / number average particle size] of the resin particles (B) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.45. Especially preferably, it is 1.05-1.15.

When it is desired to improve the powder fluidity, the BET specific surface area of the resin particles (B) is preferably 0.5 to 5.0 m ² / g, and the surface average center line roughness Ra is 0.01. It is preferable to set it to -0.8 micrometer.
The shape of the resin particles (B) is preferably spherical from the viewpoint of powder flowability, melt leveling properties, etc., and Wadell's practical sphericity is preferably 0.85 to 1.00, more preferably. 0.90 to 1.00.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” means parts by weight and “%” means% by weight.

The measurement conditions for resin physical properties in the examples are as follows.
1. Glass transition temperature (Tg)
The method defined in ASTM D3418-82 (DSC method).
Apparatus: Seiko Electronics Co., Ltd. DSC20, SSC / 5803.
2. Acid value and hydroxyl value Method defined in JIS K0070-1992.

3. Mn and Mw
Mn and Mw of resins other than polyurethane resin {including polyester resin} were measured for the soluble content of tetrahydrofuran (THF) using gel permeation chromatography (GPC) under the following conditions.
Device: HLC-8120 manufactured by Tosoh Corporation
Column: TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (Molecular weight 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000 4480000)
Moreover, Mn and Mw of the polyurethane resin were measured under the following conditions using GPC.
Equipment: Tosoh HLC-8220GPC
Column: Guardcolumn α
TSKgel α-M
Flow rate: 1 ml / min Sample solution: 0.125% dimethylformamide solution Solution injection volume: 100 μl
Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

4). Volume average particle size and particle size distribution The volume average particle size of the resin particles (A) was measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) {1% deionized water dispersion, 25 ° C}. .
The volume average particle size and particle size distribution {volume average particle size / number average particle size} of the resin particles (B) and the resin particles (C) were measured with a coal counter {Multisizer III, manufactured by Coulter, Inc.} {0.5 % Ion-exchanged water dispersion, 25 ° C.}.

<Production Example 1>
[Synthesis of Titanium Catalyst (t)]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube capable of bubbling in liquid, 1617 parts of titanium diisopropoxybis (triethanolaminate) and 126 parts of ion-exchanged water are bubbled in liquid with nitrogen. Then, the temperature was gradually raised to 90 ° C., and reaction (hydrolysis) was performed at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolaminate). Furthermore, an intramolecular polycondensate (t1) was obtained by reaction (dehydration condensation) at 100 ° C. for 2 hours under reduced pressure of 400 Pa.
Other titanium catalysts (t) used in the present invention can also be obtained by the same synthesis method.

<Production Example 2>
[Synthesis of Amine Cured Epoxy Resin Aqueous Dispersion [Resin Particle (A-1) Dispersion]]
In a reaction vessel equipped with a stirrer and a thermometer, 48 parts of a styrenated phenol EO adduct (Eleminol HB-12, manufactured by Sanyo Chemical Industries) and bisphenol A diglycidyl ether (Epicoat 828, manufactured by Yuka Shell) 232 The portion was charged and dissolved uniformly at 40 ° C. Subsequently, water was dripped at 40 degreeC under stirring in reaction container. When 30 parts of water was added, the inside of the reaction vessel was emulsified milky white. Further, 225 parts of water was added dropwise to obtain an emulsion. After heating this emulsion and heating up to 70 degreeC, the mixed solution of 20 parts of ethylenediamine and 446 parts of water was dripped over 2 hours, maintaining the emulsion at 70 degreeC. After dropping, the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an amine-cured epoxy resin aqueous dispersion [resin particle (A-1) dispersion].
The volume average particle diameter of [resin particle (A-1) dispersion] was 0.85 μm. In addition, a part of the resin particle (A-1) dispersion is centrifuged, and the process of adding 10 times weight water to the resin particle (A-1) and centrifuging is repeated twice, followed by drying. {40 ° C. × 12 hours} to isolate {resin particles (A-1)}. The Tg (measured by DSC) of the resin particles (A-1) was 118 ° C.

<Production Example 3>
[Synthesis of aqueous dispersion of vinyl resin [dispersion of resin particles (A-2)]]
In a reaction vessel equipped with a stir bar and a thermometer, 682 parts of water, 11 parts of sodium salt of methacrylic acid EO adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid Then, 1 part of ammonium persulfate was charged and stirred at 25 ° C. and 400 rpm for 15 minutes, whereby a white emulsion was obtained. The emulsion was heated to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a sodium salt copolymer of styrene-methacrylic acid-methacrylic acid EO adduct sulfate) [resin particles ( A-2) Dispersion] was obtained.
The volume average particle diameter of [resin particle (A-2) dispersion] was 0.10 μm. Moreover, a part of [resin particle (A-2) dispersion] was dried to isolate the resin particle (A-2). The Tg of the resin particles (A-2) was 148 ° C.

<Production Example 4>
[Synthesis of [Resin Particle (A-3) Dispersion] Consisting of Mixture of Water Elongation Reaction Product of [Urethane Prepolymer 1] and [Polyester Resin p1-2]]
In a reaction vessel equipped with a stirrer and a dehydrator, 681 parts of bisphenol A · EO 2 mol adduct, 81 parts of bisphenol A · PO 2 mol adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, 2 parts of titanium dihydroxybis (triethanolaminate) obtained in Production Example 1 was added as a condensation catalyst, and dehydration reaction was performed at 230 ° C. for 5 hours under atmospheric pressure, followed by dehydration reaction for 5 hours under reduced pressure of 400 Pa. And [Polyester resin p1-1] was obtained. [Polyester resin p1-1] had a Tg of 54 ° C., an Mn of 2200, an Mw of 9500, an acid value of 0.8, and a hydroxyl value of 53.

  407 parts of the above-mentioned [Polyester resin p1-1], 54 parts of IPDI, and 485 parts of ethyl acetate are put into an autoclave and reacted for 8 hours in a sealed state to have polyester resin (p1-1) as a structural unit. A solution of [urethane prepolymer 1] having an isocyanate group at the molecular end was obtained. The NCO content of the [urethane prepolymer 1] solution was 0.8%.

On the other hand, 570 parts of bisphenol A · EO 2 molar adduct, 217 parts of terephthalic acid, and 2 parts of titanium dihydroxybis (triethanolaminate) obtained in Production Example 1 as a polycondensation catalyst were added at 230 ° C. under atmospheric pressure. Polycondensation was performed for 8 hours to obtain [Polyester resin p1-2] having Mn 2400, hydroxyl value 51 and acid value 5.
400 parts of [urethane prepolymer 1] and 800 parts of [polyester resin p1-2] were dissolved and mixed in 2,000 parts of ethyl acetate to obtain [resin solution 1]. A portion of [Resin Solution 1] was dried under reduced pressure {1300 Pa, 40 ° C., 8 hours} to isolate the resin component. The resin content Tg was 55 ° C.

In a beaker, 500 parts of water and 4 parts of nonylphenol EO 14 mol adduct (Nonipol 200, manufactured by Sanyo Chemical Industries, Ltd.) were placed and dissolved uniformly. While stirring at 18,000 rpm with a TK homomixer, [Resin Solution 1] was added and stirred for 15 minutes. Then, this mixed solution was transferred to a reaction vessel equipped with a stirrer and a thermometer, heated to distill off ethyl acetate, further heated to 98 ° C., reacted for 5 hours, and water of [urethane prepolymer 1]. [Resin particle (A-3) dispersion] composed of a mixture of the elongation reaction product and [polyester resin p1-2] was obtained.
The volume average particle diameter of [resin particle (A-3) dispersion] was 0.21 μm. In addition, after a part of [resin particle (A-3) dispersion] is centrifuged, 10 times weight of water is added to the resin particle (A-3) and centrifuged twice. And dried {40 ° C. × 12 hours} to isolate resin particles (A-3). Tg of (A-3) was 74 ° C.

<Production Example 5>
[Synthesis of [Polyester Resin p1-3]]
In Production Example 1 as a polycondensation catalyst in a reaction vessel equipped with a stirrer and a dehydrator, 218 parts of bisphenol A · EO 2 mol adduct, 537 parts of bisphenol A · PO 3 mol adduct, 213 parts of terephthalic acid, 47 parts of adipic acid 2 parts of the obtained titanium dihydroxybis (triethanolaminate) was added and subjected to dehydration reaction at 230 ° C. for 5 hours under atmospheric pressure, and then for 5 hours under reduced pressure of 400 Pa. The mixture was further cooled to 180 ° C., 43 parts of trimellitic anhydride was added, and the reaction was performed under atmospheric pressure for 2 hours to obtain [Polyester resin p1-3]. [Polyester resin p1-3] was Tg44 ° C., Mn2700, Mw6500, and acid value 25.

<Production Example 6>
[Synthesis of [Polyurethane Prepolymer 2 Having Polyester Resin (p1-4) as Structural Unit]]
In a pressure-resistant reaction vessel equipped with a stirrer and a dehydrator, 396 parts of 1,2-propylene glycol, 317 parts of terephthalic acid, 67 parts of adipic acid, 9 parts of trimellitic anhydride, titanium obtained in Production Example 1 as a polycondensation catalyst After adding 0.25 part of dihydroxybis (triethanolaminate) and performing dehydration reaction under pressure {0.3 MPa} at 230 ° C. for 6 hours, the pressure was gradually returned to atmospheric pressure and excessive water and condensed water were added. Propylene glycol was distilled off. When the system became atmospheric pressure, 0.25 part of titanium dihydroxybis (triethanolaminate) was added, and dehydration and dealcoholization reaction were carried out under reduced pressure of 400 Pa for 6 hours to obtain [Polyester Resin p1-4]. . [Polyester resin p1-4] was Tg42 ° C., Mn5200, Mw21200, and acid value 0.8.
422 parts of the above [Polyester resin p1-4], 61 parts of IPDI, and 517 parts of ethyl acetate are put into an autoclave and reacted for 8 hours at 100 ° C. in a sealed state to have a polyester resin (p1-4) as a structural unit. And the solution of [urethane prepolymer 2] which has an isocyanate group in the molecular terminal was obtained. The NCO content of the [urethane prepolymer 2] solution was 0.8%.

<Production Example 7>
[Synthesis of [Polyurethane Prepolymer 3 Having Polyester Resin (p1-5) as Structural Unit]]
[Polyester resin p1-5] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was replaced with titanium dihydroxybis (diethanolaminate). [Polyester resin p1-5] was Tg42 ° C., Mn5150, Mw21500, and acid value 1.2.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-5], it is reacted in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-5) as a structural unit. A solution of [urethane prepolymer 3] having an isocyanate group at the molecular end was obtained. The NCO content of the [urethane prepolymer 3] solution was 0.7%.

<Production Example 8>
[Synthesis of [Polyurethane Prepolymer 4 Having Polyester Resin (p1-6) as Structural Unit]]
[Polyester resin p1-6] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was replaced with titanium tetrakis (ethanolamate). [Polyester resin p1-6] was Tg43 ° C., Mn5280, Mw22100, and acid value 0.5.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-6], it is reacted in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-6) as a structural unit. And the solution of [urethane prepolymer 4] which has an isocyanate group in the molecular terminal was obtained. The NCO content of the [urethane prepolymer 4] solution was 0.7%.

<Production Example 9>
[Synthesis of [Polyurethane Prepolymer 5 Having Polyester Resin (p1-7) as Structural Unit]]
[Polyester resin p1-7] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was replaced with titanyl bis (triethanolaminate). [Polyester resin p1-7] was Tg42 ° C., Mn5130, Mw21600, and acid value 0.7.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-7], the reaction is carried out in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-7) as a structural unit. A solution of [urethane prepolymer 5] having an isocyanate group at the molecular end was obtained. The NCO content of the [urethane prepolymer 5] solution was 0.9%.

<Production Example 10>
[Synthesis of [Polyurethane Prepolymer 6 Having Polyester Resin (p1-8) as Structural Unit]]
[Polyester resin p1-8] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was replaced with titanylhydroxy (triethanolaminate). [Polyester resin p1-8] was Tg43 ° C, Mn5240, Mw22200, and acid value 1.1.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-8], it is reacted in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-8) as a structural unit. And the solution of [urethane prepolymer 6] which has an isocyanate group in the molecular terminal was obtained. The NCO content of the [urethane prepolymer 6] solution was 0.9%.

<Production Example 11>
[Synthesis of [Polyurethane Prepolymer 7 Having Polyester Resin (p1-9) as Structural Unit]]
[Polyester resin p1-9] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was changed to (t1). [Polyester resin p1-9] had Tg of 42 ° C, Mn5170, Mw21300, and acid value of 0.9.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-9], it is reacted in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-9) as a structural unit. A solution of [urethane prepolymer 7] having an isocyanate group at the molecular end was obtained. The NCO content of the [urethane prepolymer 7] solution was 0.7%.

<Production Example 12>
[Synthesis of [Polyurethane Prepolymer 8 Having Polyester Resin (p1-10) as Structural Unit]]
[Polyester resin p1-10] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was changed to (t2). [Polyester resin p1-10] was Tg42 ° C, Mn5200, Mw22400, and acid value 1.1.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-10], the reaction is carried out in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-10) as a structural unit. And the solution of [urethane prepolymer 8] which has an isocyanate group in the molecular terminal was obtained. The NCO content of the [urethane prepolymer 8] solution was 0.8%.

<Production Example 13>
[Synthesis of Urethane Prepolymer 9 Having Polyester Resin (p1-11) as a Structural Unit]
[Polyester resin p1-11] was obtained by reacting in the same manner as [Polyester resin p1-4] in Production Example 6 except that the polycondensation catalyst was changed to (t3). [Polyester resin p1-11] was Tg43 ° C, Mn5260, Mw22800, and acid value 0.5.
Further, except that [polyester resin p1-4] is replaced with [polyester resin p1-11], the reaction is carried out in the same manner as [urethane prepolymer 2] in Production Example 6 to have polyester resin (p1-11) as a structural unit And the solution of [urethane prepolymer 9] which has an isocyanate group in the molecular terminal was obtained. The NCO content of the [urethane prepolymer 9] solution was 0.7%.

<Production Example 14>
[Synthesis of [Vinyl resin solution]]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 160 parts of ethyl acetate was charged and heated to 75 ° C., and then 40 parts of styrene, 120 parts of butyl methacrylate, 60 parts of acrylic acid, 60 parts of ethyl acetate. And 0.3 part of azobisisobutyronitrile was added dropwise over 4 hours, and 0.5 part of azobisisobutyronitrile was added, followed by aging at 75 ° C. for 8 hours to obtain Mn4200, hydroxyl value. A [resin solution 2] [copolymer concentration of 50%] containing [styrene-acrylic copolymer] having an acid value of 0 and 210 was obtained.

<Production Example 15>
[Synthesis of [Curing Agent 1]]
Into a reaction vessel equipped with a stirrer, a desolventizer, and a thermometer, 50 parts of isophoronediamine and 300 parts of methyl ethyl ketone were added and reacted at 50 ° C. for 5 hours. Got. The total amine value of [Curing Agent 1] was 415.

<Production Example 16>
[Creation of [Aqueous Dispersion Liquid W1] Containing [Resin Particle (A-1) Dispersion]]
A reaction vessel equipped with a stir bar and a thermometer was charged with 787 parts of polycaprolactone diol (Mn2000) and 800 parts of polyether diol (Mn4,000, EO unit content 50%, PO unit content 50%, block), 120 Dehydration was performed under reduced pressure at 1300 Pa. The water content after dehydration was 0.05% {the water content was measured by the Karl Fischer method. }. Subsequently, 55.5 parts of HDI, 65.5 parts of hydrogenated MDI, and 0.6 part of dibutyltin dilaurate were added and reacted at 80 ° C. for 5 hours to obtain [Water-soluble polymer T1]. Next, 100 parts of [resin particle (A-1) dispersion], 1 part of [water-soluble polymer T1] and 107 parts of water were mixed and stirred to obtain a milky white liquid [aqueous dispersion W1].

<Production Example 17>
[Creation of [Aqueous Dispersion W2] Containing [Resin Particles (A-2) Dispersion]]
784 parts of water, 136 parts of [resin particle (A-2) dispersion], 2 parts of carboxymethyl cellulose (“CMC Daicel 1170”, manufactured by Daicel Chemical Industries, Ltd.), and sodium dodecyl diphenyl ether disulfonate {phenyl dodecyl phenyl ether disulfone 80 parts of a 48.5% aqueous solution of sodium acid} (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries, Ltd.) was mixed and stirred to obtain a milky white liquid [aqueous dispersion W2].

<Production Example 18>
[Creation of [Aqueous Dispersion Liquid W3] Containing [Resin Particle (A-3) Dispersion]]
634 parts of water, 286 parts of [resin particle (A-3) dispersion], 2 parts of carboxymethyl cellulose (“CMC Daicel 1170”, manufactured by Daicel Chemical Industries, Ltd.), and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate ( 154 parts of “Eleminol MON-7” (manufactured by Sanyo Chemical Industries, Ltd.) were mixed and stirred to obtain a milky white liquid [aqueous dispersion W3].

<Production Example 19>
[Synthesis of [Polyester Resin 1]
In a reaction vessel equipped with a stirrer and a dehydrator, 218 parts of bisphenol A · EO 2 mol adduct, 537 parts of bisphenol A · PO 3 mol adduct, 213 parts of terephthalic acid, 47 parts of adipic acid, dibutyltin oxide 1 as a polycondensation catalyst After dehydrating at 230 ° C. for 5 hours under atmospheric pressure, the dehydrating reaction was performed under reduced pressure at 230 ° C./400 Pa for 5 hours. The mixture was further cooled to 180 ° C., 43 parts of trimellitic anhydride was added, and the reaction was performed under atmospheric pressure for 2 hours to obtain [Polyester Resin 1]. [Polyester resin 1] had a Tg of 45 ° C., a Mn of 2740, a Mw of 6550, and an acid value of 24.

<Production Example 20>
[Synthesis of [urethane prepolymer 10]
In a reaction vessel equipped with a stirrer and a dehydrator, 681 parts of bisphenol A · EO 2 mol adduct, 81 parts of bisphenol A · PO 2 mol adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, 1 part of dibutyltin oxide was added as a condensation catalyst, and after 5 hours of dehydration reaction at 230 ° C. under atmospheric pressure, 5 hours of dehydration reaction was performed under reduced pressure of 230 ° C./400 Pa to obtain [Polyester Resin 2]. It was. [Polyester resin 2] had a Tg of 55 ° C., Mn 2260, Mw 9470, an acid value of 0.6, and a hydroxyl value of 54.
407 parts of [Polyester resin 2], 54 parts of IPDI, and 485 parts of ethyl acetate are put into an autoclave and reacted in a sealed state at 100 ° C. for 5 hours to prepare a solution of [urethane prepolymer 10] having an isocyanate group at the molecular end. Obtained. The NCO content of the [urethane prepolymer 10] solution was 1.0%.

<Production Example 21>
[Synthesis of [Polyester Resin 3]
[Polyester resin 3] was obtained by reacting in the same manner as [Polyester resin 1] in Production Example 19 except that the polycondensation catalyst was replaced with 2 parts of titanium tetraisopropoxide. [Polyester resin 3] had a Tg of 42 ° C., Mn5100, Mw21000, and an acid value of 1.2.

<Production Example 22>
[Synthesis of [Urethane Prepolymer 11]]
[Polyester resin 4] was obtained by reacting in the same manner as [Polyester resin 2] in Production Example 20 except that the polycondensation catalyst was replaced with 2 parts of titanium tetraisopropoxide. [Polyester resin 4] had a Tg of 41 ° C., Mn5130, Mw21100, and an acid value of 1.4.
Except for replacing [Polyester resin 2] with [Polyester resin 4], the reaction was carried out in the same manner as [Urethane prepolymer 10] in Production Example 20 to obtain a solution of [Urethane prepolymer 11] having an isocyanate group at the molecular end. The NCO content of the [urethane prepolymer 11] solution was 0.9%.

<Example 1>
177 parts of [Polyester resin p1-3], 181 parts of ethyl acetate, 39.2 parts of [urethane prepolymer 1] solution, and 0.9 part of [curing agent 1] are put into a beaker to dissolve and mix them uniformly. [Resin solution 3] was obtained. In [Resin Solution 3], 600 parts of [Aqueous Dispersion W1] was added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. Further, the solvent was removed with a film evaporator under the conditions of a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 240 minutes to obtain an aqueous dispersion (X1-1). Centrifugation of 100 parts of the aqueous dispersion (X1-1), further adding 60 parts of water, centrifugation and solid-liquid separation were repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (C1 ) Furthermore, 20 parts of MEK oxime blocked HDI was added to 100 parts of resin particles (C1), and stirred for 30 minutes with a Henschel mixer to obtain a coating composition (CP1).

<Example 2>
In the above <Example 1>, the aqueous dispersion (X1-2), the resin particles (C2), and the coating composition were prepared in the same manner except that the [aqueous dispersion W2] was used instead of the [aqueous dispersion W1]. A product (CP2) was obtained.

<Example 3>
In the above <Example 1>, the aqueous dispersion (X1-3), the resin particles (C3), and the coating composition were prepared in the same manner except that the [aqueous dispersion W3] was used instead of the [aqueous dispersion W1]. A product (CP3) was obtained.

<Example 4>
In the above <Example 1>, instead of 177 parts of [polyester resin p1-3] and 181 parts of ethyl acetate, 358 parts of [resin solution 2] containing [styrene-acrylic copolymer] prepared in Production Example 14; An aqueous dispersion (X1-4), resin particles (C4) and a coating composition (CP4) were obtained by the same method except that [aqueous dispersion W2] was used instead of [aqueous dispersion W1].

<Example 5>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 2] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1] By the method, an aqueous dispersion (X1-5), resin particles (C5) and a coating composition (CP5) were obtained.

<Example 6>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 3] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-6), resin particles (C6) and a coating composition (CP6) were obtained.

<Example 7>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 4] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-7), resin particles (C7), and a coating composition (CP7) were obtained.

<Example 8>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 1] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-8), resin particles (C8), and a coating composition (CP8) were obtained.

<Example 9>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 1] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-9), resin particles (C9) and a coating composition (CP9) were obtained.

<Example 10>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 1] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-10), resin particles (C10) and a coating composition (CP10) were obtained.

<Example 11>
In the above-mentioned <Example 1>, the same thing except using the [urethane prepolymer 8] solution instead of the [urethane prepolymer 1] solution and the [aqueous dispersion W2] instead of the [aqueous dispersion W1] By the method, an aqueous dispersion (X1-11), resin particles (C11) and a coating composition (CP11) were obtained.

<Example 12>
In the above-mentioned <Example 1>, the same thing except using the solution of [urethane prepolymer 9] instead of the solution of [urethane prepolymer 1] and [aqueous dispersion W2] instead of [aqueous dispersion W1]. By the method, an aqueous dispersion (X1-12), resin particles (C12) and a coating composition (CP12) were obtained.

<Example 13>
100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of the aqueous dispersion (X1-2) obtained in <Example 2> above, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used. The resin particles (A-2) adhering to the surface of the resin particles (C2) were dissolved by adjusting the temperature to 0 ° C. and mixing for 10 minutes at a rotational speed of 12,000 rpm. Next, the supernatant was removed by centrifugation, and the process of adding 100 parts of water and centrifuging was repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (B2). Further, 20 parts of MEK oxime blocked HDI was added to 100 parts of resin particles (B2), and stirred for 30 minutes with a Henschel mixer to obtain a coating composition (BP2).

<Example 14>
In the same manner as in <Example 13> above, except that the aqueous dispersion (X1-4) obtained in <Example 4> is used instead of the aqueous dispersion (X1-2), the resin particles (B4) and A coating composition (BP4) was obtained.

<Example 15>
Resin particles (B5) and a resin particle (B5) were prepared in the same manner as in <Example 13> except that the aqueous dispersion (X1-5) obtained in <Example 5> was used instead of the aqueous dispersion (X1-2). A coating composition (BP5) was obtained.

<Comparative Example 1>
[Polyester resin 1] 177 parts, ethyl acetate 181 parts, [urethane prepolymer 10] solution 39.2 parts, and [curing agent 1] 0.9 part in a beaker to dissolve and mix and homogenize [resin Solution 4] was obtained. In this [resin solution 4], 600 parts of [Aqueous dispersion W1] is added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used, and the dispersion operation is performed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm. Furthermore, the solvent was removed by a film evaporator under the conditions of a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 240 minutes to obtain a comparative aqueous dispersion (HX1-1). Centrifugation of 100 parts of aqueous dispersion (HX1-1), further adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, followed by drying at 35 ° C. for 1 hour for comparison resin particles (HC1) was obtained. Further, 20 parts of MEK oxime blocked HDI was added to 100 parts of resin particles (HC1), and stirred for 30 minutes with a Henschel mixer to obtain a comparative coating composition (HCP1).

<Comparative example 2>
In the above <Comparative Example 1>, a comparative aqueous dispersion (HX1-2), resin particles (HC2), and a comparative aqueous dispersion (HX1-2) were used in the same manner except that [aqueous dispersion W2] was used instead of [aqueous dispersion W1]. A coating composition (HCP2) was obtained.

<Comparative Example 3>
The same method as in <Comparative Example 1> except that [Polyester resin 3] is used instead of [Polyester resin 1], and [Urethane prepolymer 11] solution is used instead of [Urethane prepolymer 10] solution. As a result, a comparative aqueous dispersion (HX1-3), resin particles (HC3) and a coating composition (HCP3) were obtained.

<Comparative example 4>
In the above <Comparative Example 1>, in the same manner except that [Polyester resin 1] is 177 parts, and [Resin solution 2] containing 358 parts of [Styrene-acrylic copolymer] instead of 181 parts of ethyl acetate, A comparative aqueous dispersion (HX1-4), resin particles (HC4) and coating composition (HCP4) were obtained.

<Comparative Example 5>
In the above <Example 13>, the comparative resin particles (HB2) and the coating composition (with the same method) except that the comparative aqueous dispersion (HX1-2) was used instead of the aqueous dispersion (X1-2). HBP2) was obtained.

<Physical Property Measurement Example 1>
Resin particles (C1) to (C12) obtained in Examples 1 to 15, resin particles (B2), (B4) and (B5), and comparative resin particles (HC1) to (HC1) to (H) obtained in Comparative Examples 1 to 5 For HC4) and (HB2), volume average particle size and particle size distribution (volume average particle size / number average particle size), surface coverage, BET specific surface area, surface average centerline roughness, and circularity (Wadell's practical spherical shape) Degree).
Furthermore, in order to check the heat resistant storage stability of each resin particle, it was stored for 7 days in an atmosphere of 40 ° C., and the presence or absence of fusion was confirmed. The method for confirming the fusion was to spread 50 g of each stored resin particle and shake it for 15 minutes with a standard sieve of 150 μm, measure the amount of resin particles remaining on the sieve, and determined based on the ratio based on the following criteria: .
◎: Aggregate less than 0.2% ○: Aggregate 0.2% to less than 1.0% Δ: Aggregate 1.0% to less than 2.0% ×: Aggregate 2.0% or more

  Furthermore, the coating compositions (CP1) to (CP12), (BP2), (BP4), (BP5), (HCP1) to (HCP4) and (HBP2) prepared above were replaced with zinc phosphate manufactured by Nippon Test Panel Co., Ltd. Using a commercially available corona charging spray gun on the treated steel plate, electrostatic coating is performed so that the film pressure is 40 to 60 μm, baking is performed at 180 ° C. for 20 minutes, and then shearing is performed according to the method specified in JIS K6830-1996. An adhesion test was conducted and the results are shown in Tables 1 and 2. Evaluation criteria for adhesiveness (adhesion) are as follows.

◯: Complete cohesive failure △: Trace destruction causing partial interface failure ×: Complete interface failure Similar to the evaluation of adhesion, the coating composition was electrostatically coated and baked, and then heated to 40 ° C. in warm water. Soaked for days. Next, a shear adhesion test (water-resistant adhesion) was performed according to the method specified in JIS K6830-1996. The evaluation criteria were the same as in the case of the adhesiveness (adhesion).
The evaluation results are shown in Tables 1 and 2.

  Even when the aqueous dispersion and resin particles obtained by the production method of the present invention are applied to an application in which the resin particles are thermally melted and adhered to an adherend (metal, paper, wood, etc.), The resin dispersion and the resin particles obtained by the production method of the present invention are used for slush molding resins, powder coatings, electronic components (liquid crystals). Etc.) Useful for manufacturing spacers, standard particles for electronic measuring devices, base particles for electrophotographic toners, base particles for electrostatic recording toners, base particles for electrostatic printing toners, various hot melt adhesives, other molding materials, etc. It is extremely useful as resin particles.

Claims (11)

An aqueous dispersion (W) of resin particles (A) made of resin (a) and a precursor (b) of resin (b)
0) or (b0) and an oily liquid (OL) comprising an organic solvent, and (W)
b0) or an oily liquid (OL) is dispersed, and (b0) is reacted in (W) to form resin particles (B) comprising (b), whereby (A) is formed on the surface of (B). A step of obtaining an aqueous dispersion (X1) of resin particles (C) having an attached structure, wherein at least one of the resin (a) and the resin (b) is represented by the following general formula (I) or (II): A polyester resin (p1) formed in the presence of a titanium catalyst (t), or a resin (p2) having (p1) as a structural unit, and a method for producing an aqueous dispersion (X1) .
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ] The production method according to claim 1, wherein X in the formula is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono-, di- or trialkanolamine. The production method according to claim 1 or 2, wherein m or p in the formula is 2 or more and all Xs are the same group. The method for producing an aqueous dispersion according to any one of claims 1 to 3, wherein the titanium catalyst (t) is a titanium catalyst represented by any one of the following general formulas (I-1) to (I-3).

[In formula, Q < ¹ > and Q < ⁶ > are a hydrogen atom, a C1-C4 alkyl group, or a hydroxyalkyl group. Q ^{2 to} Q ⁵ and Q ^{7 to} Q ⁹ are alkylene groups having 1 to 6 carbon atoms.
X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms. ] Resin (a) and / or (b) other than resin (p2) having polyester resin (p1) and (p1) as structural units, polyurethane resin, epoxy resin, vinyl resin, and polyester resin other than (p1) The manufacturing method in any one of Claims 1-4 containing 1 or more types of resin chosen from the group which consists of. The production method according to any one of claims 1 to 5, wherein the precursor (b0) comprises a prepolymer (α) having a structural unit and a reactive group of the polyester resin (p1) and a curing agent (β). In the aqueous dispersion (X1) obtained by the production method according to claim 1,
After removing the adhering resin particles (A) from the resin particles (B), the aqueous dispersion (A)
(B) to obtain an aqueous dispersion (X2) of (B), or (A) is dissolved, and if necessary, the dissolved product of (A) is separated and removed to obtain an aqueous dispersion (X2) of (B) The manufacturing method of the aqueous dispersion (X2) including the process of obtaining. The production method according to claim 7, wherein [B average particle size / number average particle size] of (B) is 1.0 to 1.5. A step of removing the aqueous solvent from the aqueous dispersion (X1) obtained by the production method according to any one of claims 1 to 6 to obtain resin particles (C), or obtained by the production method according to claim 7 or 8. The manufacturing method of the resin particle including the process of removing an aqueous solvent from the obtained aqueous dispersion (X2), and obtaining the resin particle (B). Resin particles (A) made of resin (a) are resin particles (C) having a structure formed by adhering to the surface of resin particles (B) made of resin (b),
[1] [Volume average particle diameter of (A) / Volume average particle diameter of (C)] is 0.001 to 0.3,
[2] The volume average particle diameter of (A) is 0.0005 to 30 μm, and the volume average particle diameter of (C) is 0.1 to 300 μm.
[3] 5% or more of the surface of (B) is covered with (A),
[4] The [volume average particle diameter / number average particle diameter] of (C) is 1.0 to 1.5,
[5] Polyester resin (p1) or (p1) in which at least one of (a) and (b) is formed in the presence of a titanium catalyst (t) represented by the following general formula (I) or (II) ) As a structural unit, and (a) and / or (b) is selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins other than (p1) as necessary. A resin particle comprising one or more resins.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ] A polyester resin (p1) formed in the presence of a titanium catalyst (t) represented by the following general formula (I) or (II) or a resin (p2) having a polyester resin (p1) as a structural unit If necessary, resin particles (B) comprising a resin (b) containing one or more resins selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins other than (p1),
[1] The [volume average particle size / number average particle size] of (B) is 1.0 to 1.5,
[2] The volume average particle diameter 0.1~300μm der of (B) is, resin particles practical sphericity of Wadell is characterized 0.90 to 1.00 der Rukoto.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing a hydrogen atom in one hydroxyl group from a mono- or poly-alkanolamine having 2 to 12 carbon atoms, or two hydroxyl groups from a polyalkanolamine having 2 to 12 carbon atoms. In which the oxygen atoms of the two hydroxyl groups may be bonded to the same titanium atom to form a ring structure, and the oxygen atoms of the two hydroxyl groups are different. It may be bonded to an atom to form a repeating structure {repetition number 2 to 5}. R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4 (when a ring structure is formed, an integer of 1 to 3), and n is an integer of 0 to 3. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]