JP2008056915A - Resin particle and resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resin particles excellent in melting properties and blocking resistance at high temperatures and high humidities and uniform in size. <P>SOLUTION: An aqueous dispersion(X1) of the resin particles(C1) is provided, which is obtained by mixing an aqueous dispersion(W) of resin particles(A) consisting of a resin(a) and a resin(b) or its organic solvent solution together to disperse the resin(b) or its organic solvent solution in the aqueous dispersion(W) and form resin particles(B) consisting of the resin(b) in the aqueous dispersion of the resin particles(A), wherein the resin particles(C1) is such that the resin particles(A) adhere to the surface of the resin particles(B). In the aqueous dispersion(X1), the resin(b) consists of a polyester resin(b1) formed in the presence of at least one titanium-containing catalyst(e) represented by the general formula(I):Ti(-X)<SB>m</SB>(-OR)<SB>n</SB>and/or a resin(b2) including the resin(b1) as the constitutive unit. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin dispersion and resin particles. More specifically, the present invention relates to resin particles and aqueous dispersions thereof useful for various applications such as powder coating materials, electrophotographic toners, and electrostatic recording toners.

As resin particles having a uniform particle size and excellent electrical characteristics, thermal characteristics, chemical stability, and the like, resin particles obtained using polymer fine particles as a dispersion stabilizer are known (see Patent Document 1). ).
JP 2002-284881 A

However, in order to improve the melting characteristics of the resin particles (melting at a lower temperature), it is necessary to lower the molecular weight and the glass transition temperature (hereinafter abbreviated as Tg). Has the problem of poor blocking resistance.
The present invention has been made in view of the above circumstances in the prior art. That is, it aims at providing the resin particle which is excellent in a melt characteristic and blocking resistance, and whose particle size is uniform.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention includes the following [I] to [III].
[I] An aqueous dispersion (W) of resin particles (A) made of resin (a) and resin (b) or an organic solvent solution thereof are mixed, and (b) or an organic solvent solution thereof is added to (W). Is obtained by forming the resin particles (B) comprising (b) in the aqueous dispersion of (A), and the resin particles (C1) obtained by adhering (A) to the surface of (B) A polyester resin (b1) formed by the presence of at least one titanium-containing catalyst (e) represented by the following general formula (I): An aqueous resin dispersion comprising a resin (b2) containing / b (1) as a structural unit.
Ti (-X) m (-OR) n (I)
[Wherein, R represents H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. X is a residue obtained by removing one carboxyl group H from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, other carboxyl groups are polycondensed in the molecule with an OR group in the same molecule. A structure may be formed, or a structure containing 2 to 5 Ti atoms may be formed by polycondensation between an OR group of another molecule and the molecule. m = 1 to 3 and n = 1 to 3, and the sum of m and n is 4. ]
[II] In the aqueous resin dispersion (X1), the resin particles (A) attached to the resin particles (B) are dissolved in an organic solvent and / or melted, whereby (B) An aqueous resin dispersion (X2) comprising resin particles (C2) obtained by forming a shell layer (P) in which (A) is formed on the surface of a core layer (Q) composed of
[III] Resin particles obtained by removing an aqueous medium from the aqueous resin dispersion of [I] or [II].

The resin dispersion of the present invention and the resin particles obtained therefrom have the following effects.
1. Excellent melting characteristics and blocking resistance, and uniform particle size.
2. Even if a tin compound having environmental problems is not used as a catalyst, it has good resin performance.
3. Excellent charging characteristics and powder flowability.
4). Excellent particle surface smoothness (especially when having a shell layer formed into a film).
5. Since the resin particles can be obtained by dispersion in water, they can be produced at low cost.
6). The mechanical properties of the heat-melted coating film are also good.

Hereinafter, the present invention will be described in detail.
The titanium-containing catalyst (e) used in the present invention is a compound represented by the formula (I), and two or more compounds having the structure of the formula (I) may be used in combination.
In the general formula (I), R is H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. Carbon number of a hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-4.
Specific examples of the hydrocarbon group having 1 to 24 carbon atoms include an aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing an ether bond and / or a hydroxyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, β-ethoxyethyl group, β-hydroxyethyl group, etc.), aromatic hydrocarbon group, and ether bond and / or fragrance containing hydroxyl group Hydrocarbon group [phenyl group; hydroxyphenyl group; alkylene oxide having 2 to 4 carbon atoms such as bisphenol A, bisphenol F and bisphenol AD (hereinafter abbreviated as AO unless otherwise specified) [ethylene oxide (hereinafter abbreviated as EO) ), Propylene oxide (hereinafter abbreviated as PO), and butylene oxide (hereinafter BO) Abbreviated) and the like] adducts (such as residues obtained by removing one of the OH from the additional number of moles of 1 to 3)] and the like.
Of these R, a hydrocarbon group having 1 to 6 carbon atoms is preferable, and an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-hexyl group are particularly preferable. N-propyl group, isopropyl group, and n-butyl group.

X is a residue obtained by removing H of one carboxyl group from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, another carboxyl group is the same as that bonded to a Ti atom to form a residue. OR group in the molecule {hydroxyl group bonded directly to Ti atom (when R is H), alkoxy group (when R is hydrocarbon group), or R is a hydrocarbon group containing 1 to 2 hydroxyl groups The hydroxyl group may be polycondensed within the molecule to form a ring structure, and may be polycondensed between an OR group (similar to the above) of another molecule of the titanium-containing catalyst (a) between the molecules, and a plurality of Ti atoms A repeating structure containing may be formed.
The aromatic carboxylic acid preferably has 7 to 50 carbon atoms, and includes benzoic acids (benzoic acid, parahydroxybenzoic acid, paramethylbenzoic acid, etc.), aromatic monocarboxylic acids such as naphthalene monocarboxylic acid; phthalic acids ( Terephthalic acid, isophthalic acid, orthophthalic acid and the like), naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid, and the like.
In the case of an aromatic polycarboxylic acid, a repeating structure containing a plurality of Ti atoms may be formed by the plurality of carboxyl groups as described above. In this case, the number of Ti atoms in one molecule is 2 to 5 It is. When the number of Ti atoms in one molecule is 6 or more, the catalytic activity is lowered, which is not preferable.
Preferred as X are residues of phthalic acids (terephthalic acid, isophthalic acid, orthophthalic acid, etc.), and residues of benzoic acids (benzoic acid, parahydroxybenzoic acid, paramethylbenzoic acid, etc.), and particularly preferred are Residues of terephthalic acid, isophthalic acid, and orthophthalic acid.

In formula (I), m = 1 to 3 and n = 1 to 3, and the sum of m and n, that is, the valence number of Ti atoms is 4. Preferably, m = 1 to 2 and n = 2 to 3. When m exceeds 3, the catalytic activity decreases, and when n exceeds 3, the hydrolysis resistance decreases, both of which are unfavorable for polyester production. When m is 1 or 2, the catalyst activity is particularly high and preferable. When the valence number of Ti atom is other than 4, it is not preferable even if the structure is similar to that of formula (I), the catalytic activity is inferior or a side reaction occurs.

  Specific examples of the compound represented by the general formula (I) include titanium triisopropoxybenzene carboxylate, titanium tributoxybenzene carboxylate, titanium triisopropoxyterephthalate, titanium tributoxyterephthalate, titanium triisopropoxyisophthalate, titanium. Triisopropoxyphthalate, titanium diisopropoxydibenzenecarboxylate, titanium dibutoxydibenzenecarboxylate, titanium diisopropoxy diterephthalate, titanium dibutoxy diterephthalate, titanium diisopropoxy diisophthalate, titanium diisopropoxy diphthalate, Titanium dihydroxydibenzenecarboxylate, titanium dihydroxy diterephthalate, titanium dihydroxy diisophthalate, titanium dihydro Shijifutareto, titanium-isopropoxy tri terephthalate, and the like These intramolecular or intermolecular polycondensates thereof.

  The titanium-containing catalyst (e) used in the present invention preferably has a solubility in water at 30 ° C. of [5 g / 100 ml] or less, and [2 g / 100 ml] or less, from the viewpoint of catalytic activity during polyester polymerization. Is more preferable, and [1 g / 100 ml] or less is particularly preferable. When the solubility is [5 g / 100 ml] or less, the catalyst is hardly subjected to hydrolysis during the polymerization reaction, which is preferable from the viewpoint of sustainability of the catalyst activity.

  These titanium-containing catalysts (e) can be obtained, for example, by reacting a commercially available titanium tetraalkoxide and an aromatic carboxylic acid in ethyl acetate at 70 to 90 ° C.

As the polycondensation polyester resin constituting the polyester resin (b1) used in the present invention, the polyepoxide (f) and the like are further reacted with the polyester resins (bX) and (bX) which are polycondensates of polyol and polycarboxylic acid. Modified polyester resin (bY) obtained in this way. (BX), (bY) and the like may be used alone or in combination of two or more.
Examples of the polyol include a diol (g) and a trivalent or higher polyol (h), and examples of the polycarboxylic acid include a dicarboxylic acid (i) and a trivalent or higher polycarboxylic acid (j). You may use together.
Examples of the polyester resins (bX) and (bY) include the following, and these can also be used in combination.
(BX1): Linear polyester resin using (g) and (i) (bX2): Non-linear polyester resin using (h) and / or (j) together with (g) and (i) ( bY1): Modified polyester resin obtained by reacting (bX2) with (f)

As the diol (g), those having a hydroxyl value of 180 to 1900 (mg KOH / g, the same shall apply hereinafter) are preferable. Specifically, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol , Neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.); alicyclic diol (Such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A); C 2-4 alkylene oxide [ethylene oxide (hereinafter referred to as EO); ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] addition products (number of added moles 1-30); bisphenols (such as bisphenol A, bisphenol F and bisphenol S) Examples include adducts having 2 to 4 carbon atoms (such as EO, PO and BO) (addition moles of 2 to 30).
Of these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof. Particularly preferred are alkylene oxide adducts of bisphenols, alkylene glycols having 2 to 4 carbon atoms. And a combination of two or more of these, most preferred is alkylene glycol having 2 to 4 carbon atoms.
In the above and below, the hydroxyl value and the acid value are measured by the methods specified in JIS K 0070.

As the diol (g), a diol (g1) having another functional group may be used in addition to the diol having no functional group other than the hydroxyl group. Examples of (g1) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid and 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

The trivalent or higher (3 to 8 or higher) polyol (h) is preferably a hydroxyl value of 150 to 1900. Specifically, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms having 3 to 8 or more carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, triethylolethane, trimethylolpropane, pentane). Erythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof such as sucrose and methyl glucoside; ) Adducts (addition mole number 1-30); Trisphenols (trisphenol PA, etc.) C2-C4 alkylene oxide (EO, PO, BO etc.) addition products (addition mole number 2-30); Novolac Resin (phenol novolac and cresol novola Click like: average polymerization degree of 3 to 60 alkylene oxide (EO 2-4 carbon atoms), PO, BO, etc.) adducts (added mole number 2 to 30) are exemplified.
Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and alkylene oxide adducts of novolac resins (addition mole number: 2 to 30), and particularly preferred are alkylene oxide adducts of novolak resins. It is.

  As the dicarboxylic acid (i), those having an acid value of 180 to 1250 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); carbon Branched alkylene dicarboxylic acid having a number of 8 or more [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.) ); Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. As (i), acid anhydrides or lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  The trivalent or higher (3 to 6 or higher) polycarboxylic acid (j) is preferably one having an acid value of 150 to 1250. Specifically, aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, gel permeation chromatography) (By GPC): 450-10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.), and the like. . Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the trivalent or higher polycarboxylic acid (j), acid anhydrides or lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Further, together with (g), (h), (i) and (j), an aliphatic or aromatic hydroxycarboxylic acid (k) having 4 to 20 carbon atoms and a lactone (l) having 6 to 12 carbon atoms are copolymerized. You can also
Examples of the hydroxycarboxylic acid (k) include hydroxystearic acid and hydrogenated castor oil fatty acid. Examples of the lactone (l) include caprolactone.

Examples of the polyepoxide (f) include polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac ( Average polymerization degree 3 to 60) glycidyl tetrates, etc.]; Among these, polyglycidyl ether is preferable, and ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are more preferable.
The number of epoxy groups per molecule of (f) is preferably 2 to 8, more preferably 2 to 6, particularly preferably 2 to 4.
The epoxy equivalent of (f) is preferably 50 to 500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is further preferably 300, particularly preferably 200. When the number of epoxy groups and the epoxy equivalent are within the above ranges, both developability and fixability are good. It is more preferable if the above-mentioned ranges of the number of epoxy groups per molecule and the epoxy equivalent are satisfied at the same time.

  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. The types of polyol and polycarboxylic acid to be used are selected in consideration of molecular weight adjustment so that the glass transition point of the resin particles finally adjusted is 45 to 85 ° C.

  In the present invention, the ratio of the component having a molecular weight of 1500 or less in the resin (b) is preferably 1.8% or less, more preferably 1.3% or less, and particularly preferably 1.1% or less. When the ratio of the component having a molecular weight of 1500 or less is 1.8% or less, the storage stability becomes better. Above and below,% means% by weight unless otherwise stated.

In the above and the following, the peak top molecular weight (Mp), Mn, weight average molecular weight (Mw), and the ratio of components having a molecular weight of 1500 or less of the resin (excluding polyurethane resin) in the present invention are the GPC for the THF-soluble component. And measured under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement 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)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). Furthermore, the abundance ratio of low molecular weight substances is evaluated by the ratio of the peak areas when the molecular weight is 1500.
In addition, Mp, Mn, Mw of polyurethane resin, and the ratio of the component of molecular weight 1500 or less are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α
TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Injection volume: 100 μl
Flow rate: 1 ml / min 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)

The acid value of the polyester resin (b1) is preferably 0.1 to 60, more preferably 0.2 to 50, particularly 0.5 to 40. When the acid value is in the range of 0.1 to 60, the chargeability is good.
The hydroxyl value of the polyester resin (b1) is preferably 1 to 70, more preferably 3 to 60, particularly 5 to 55. When the acid value is in the range of 1 to 70, the environmental stability is good.
The Tg of the polyester resin (b1) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, particularly 55 to 75 ° C. When the Tg is in the range of 40 ° C. to 90 ° C., the heat resistant storage stability and the low temperature fixability are good.
In the above and below, the Tg of the polyester resin (b1) is measured by a method (DSC method) defined in ASTM D3418-82 using DSC20, SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.

In the present invention, the polyester resin (b1) can be produced in the same manner as an ordinary polyester production method. For example, the reaction temperature is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, and particularly preferably 170 to 240 ° C in the presence of a titanium-containing catalyst (e) in an inert gas (nitrogen gas or the like) atmosphere. It can be performed by reacting. 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, 1 to 50 mmHg) in order to improve the reaction rate at the end of the reaction.
The addition amount of (e) is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6%, particularly preferably 0.0002 to 0.6%, based on the weight of the polymer obtained from the viewpoint of polymerization activity and the like. Preferably it is 0.0015 to 0.55%.
In addition, other esterification catalysts can be used in combination as long as the catalytic effect of (e) is not impaired. Examples of other esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts other than (e) [eg, titanium alkoxide, potassium titanyl oxalate, titanium terephthalate, and titanium dihydroxybis ( Triethanolaminate) and its intramolecular polycondensate], zirconium-containing catalyst (eg zirconyl acetate), germanium-containing catalyst, alkali (earth) metal catalyst (eg alkali metal or alkaline earth metal carboxylate: lithium acetate Sodium acetate, potassium acetate, calcium acetate, sodium benzoate, and potassium benzoate), zinc acetate, and the like. The addition amount of these other catalysts is preferably 0 to 0.6% with respect to the obtained polymer. By making it within 0.6%, the coloration of the polyester resin is reduced, which is preferable for use in color toners. The content of (e) in all the added catalysts is preferably 50 to 100%.

  Examples of the method for producing the linear polyester resin (bX1) include a diol in the presence of 0.0001 to 0.8% of the catalyst (e) and, if necessary, another catalyst based on the weight of the obtained polymer. The method of obtaining (bX1) by heating (g) and dicarboxylic acid (i) to 180 to 260 degreeC and carrying out dehydration condensation on a normal pressure and / or pressure reduction condition is mentioned.

  As a method for producing the non-linear polyester resin (bX2), for example, 0.0001 to 0.8% of the catalyst (e) with respect to the weight of the obtained polymer, and if necessary, in the presence of another catalyst, Diol (g), dicarboxylic acid (i), and trihydric or higher polyol (h) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions. The method of reacting polycarboxylic acid (j) and obtaining (bX2) is mentioned. (J) can also be reacted simultaneously with (g), (i) and (h).

Examples of the method for producing the modified polyester resin (bY1) include a method of obtaining (bY1) by adding a polyepoxide (f) to the polyester resin (bX2) and performing a molecular extension reaction of the polyester at 180 ° C. to 260 ° C. .
The acid value of (bX2) to be reacted with (f) is preferably 1 to 60, more preferably 5 to 50. When the acid value is 1 or more, (f) remains unreacted and does not adversely affect the performance of the resin, and when it is 60 or less, the thermal stability of the resin is good.
In addition, the amount of (f) used to obtain (bY1) is preferably 0.01 to 10%, more preferably 0.1%, relative to (bX2), from the viewpoints of low-temperature fixability and hot offset resistance. 05 to 5%.

When two or more polyester resins are used in combination, and when at least one polyester resin and another resin are mixed, powder mixing or melt mixing may be performed.
The temperature at the time of melt mixing is preferably 80 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 120 to 160 ° C.
If the mixing temperature is too low, sufficient mixing cannot be achieved, which may result in non-uniformity. When two or more kinds of polyester resins are mixed, if the mixing temperature is too high, averaging due to the transesterification reaction or the like occurs, so that necessary resin physical properties may not be maintained.

The mixing time in the case of melt mixing is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes, and particularly preferably 30 seconds to 5 minutes. When two or more kinds of polyester resins are mixed, if the mixing time is too long, averaging due to the transesterification reaction or the like occurs, so that necessary resin physical properties may not be maintained.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll. Of these, extruders and continuous kneaders are preferred.
In the case of powder mixing, it can be mixed with normal mixing conditions and mixing equipment.
As mixing conditions in the case of powder mixing, the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The mixing time is preferably 3 minutes or more, more preferably 5 to 60 minutes. Examples of the mixing apparatus include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferable.

  The resin (b2) containing the polyester resin (b1) as a structural unit is not particularly limited as long as it contains (b1) as a structural unit. For example, in the case of a polyurethane resin, the resin (a In the polyurethane resin described in the section), it can be obtained by using (b1) as at least a part of the active hydrogen group-containing compound (D). The content of (b1) in (D) is preferably 60% or more, more preferably 80% or more, and particularly preferably 100%.

In addition to (b1) and (b2), (b) can contain other resins if necessary.
Examples of other resins include polyester resins, vinyl resins, epoxy resins and polyurethane resins formed in the presence of a catalyst other than (e). About the specific example, the thing similar to (a) mentioned later can be used.
The Mw of other resins is preferably 1,000 to 2,000,000.
The content of the other resin in the resin (b) is preferably 0 to 40%, more preferably 0 to 30%, and particularly preferably 0 to 20%. Further, the content of the resin other than polyester in (b) is preferably 30% or less, more preferably 20% or less, particularly preferably 10% or less, and most preferably 0% from the viewpoint of resin physical properties.

The Mn, Mw, melting point, Tg, and sp value of the resin (b) may be appropriately adjusted within a preferable range depending on the application.
The sp value of the resin (b) is preferably such that the difference in sp value from the resin (a) is within the above range, preferably 7 to 18, more preferably 8 to 14, and particularly preferably 9 to 14. is there.
For example, when the resin particles (C1) or (C2) [hereinafter (C1) or (C2) may be referred to as (C)], the resin particles (B) are used as a slush molding resin or powder coating, Mn in (b) is preferably 2,000 to 500,000, more preferably 4,000 to 200,000.
The melting point of (b) (measured by DSC, hereinafter the melting point is a measured value by DSC), preferably 0 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C. The Tg of (b) is preferably −60 ° C. to 100 ° C., more preferably −30 ° C. to 60 ° C.
When used as a spacer for manufacturing electronic parts such as liquid crystal displays and standard particles for electronic measuring instruments, the Mn of (b) is preferably 20,000 to 10,000,000, more preferably 40,000 to 2,000,000. The melting point of (b) is preferably 40 ° C to 300 ° C, more preferably 70 ° C to 250 ° C. The Tg of (b) is preferably −0 ° C. to 250 ° C., more preferably 50 ° C. to 200 ° C.
When used as a toner used for electrophotography, electrostatic recording, electrostatic printing, etc., the Mn of (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. The sp value of (b) is preferably 8-16, more preferably 9-14. From the viewpoint of achieving both meltability and image fixability, 50 to 90% (particularly 60 to 80%) of (b) is preferably a linear polyester having a tetrahydrofuran soluble Mw of 2000 to 12000. The Mw of the linear polyester is more preferably 4000-11000, particularly preferably 7000-10000. When the Mw of the linear polyester is within this range, the balance between the meltability and the image adhesion is particularly good.

  In the present invention, the resin (a) may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Examples of (a) include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. It is done. As (a), two or more of the above resins may be used in combination. Among these, polyurethane resins, vinyl resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and their metal salts:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-C24) ester, such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropanesulfonic acid, 2- ( T) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-C18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, Propylene, butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and Sulfate ester or sulfonic acid group-containing monomers represented by general formulas (1-1) to (1-3); and salts thereof.

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

CH = CH-CH ₃
｜
R-Ar-O- (AO) nSO 3 H (1-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (1-3)

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

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

Examples of the salts (2) to (4) include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K.
Preferred are alkali metal salts and amine salts, and more preferred are sodium salts and salts of tertiary monoamines having 3 to 20 carbon atoms.

(5) 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, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) 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 (6-2) amide Containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic acid Amides, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, Cyanostyrene, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide Diethylaminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomers: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomers:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as 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-ethoxy acrylate, alkyl (meth) acrylate 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, heptadec (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (Two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, Tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide (ethylene oxide) Is hereinafter abbreviated as EO) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: 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.] etc. (9-2) vinyl (thio) Ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketone , For example vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  In the present invention, when a vinyl resin containing a structural unit of an organic acid metal salt (m) is used as (a), this resin is, for example, as the monomer (2) to (4) as at least a part of the monomer. Among them, it can be obtained by using one or more metal salts selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr. The amount of these organic acid metal salt monomers (m) used in all monomers used for polymerization is preferably 5 to 60%. The lower limit is more preferably 10%, and the upper limit is more preferably 50%.

  As the copolymer of vinyl monomers, any of the monomers (1) to (10) described above is a binary or higher number, and the carboxyl group content in the resin particles (A) is preferably 0.00. Examples include polymers copolymerized at an arbitrary ratio so as to be 1 to 10%. For example, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic. Acid copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- Examples thereof include divinylbenzene copolymers, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymers, and salts of these copolymers.

  Since the resin (a) needs to form the resin particles (A) in the aqueous dispersion, it may not be completely dissolved in water at least under the conditions for forming the aqueous resin dispersion (X1). is necessary. Therefore, when the vinyl resin is a copolymer, the ratio between the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10% or more. It is preferable that it is 30% or more. When the ratio of the hydrophobic monomer is 10% or less, the vinyl resin becomes water-soluble, and the particle size uniformity of (C1) or (C2) is impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. As the polyol, the above-mentioned diol (g) [including (g1)] and the trivalent or higher polyol (h) are used as the polycarboxylic acid or its acid anhydride or its lower alkyl ester. Examples thereof include polycarboxylic acids (j) having higher valences and acid anhydrides or lower alkyl esters thereof.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1 / 1.2, more preferably 1.5 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1 to 1 / 1.1, particularly preferably 1.3 / 1 to 1 / 1.05.

In the present invention, when a polyester resin containing a structural unit of an organic acid metal salt (m) is used as (a), this resin is, for example, a polyester having a residue of COOH (acid value is preferably 1 to 100, More preferably, 5-50) is synthesized, and at least one part of the COOH group is converted to a salt of at least one metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr. can get.
As a method for forming a metal salt, for example, it is obtained by reacting a polyester having a COOH group with a hydroxide of the corresponding metal.

As the polyurethane resin, polyisocyanate (11) and active hydrogen-containing compound (D) {water, polyol [diol (g) [including diol (g1) having a functional group other than hydroxyl group], and 3 to 8 valences or Further polyol (h)], polycarboxylic acid [dicarboxylic acid (i), and polycarboxylic acid (j) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, A ring-opening polymer of a lactone having 6 to 12 carbon atoms, a polyaddition of polyamine (12), polythiol (13), and combinations thereof}, and a terminal isocyanate formed by reacting (11) with an active hydrogen-containing compound A primary prepolymer and an equivalent of primary and / or secondary monoamines (1 ) And obtained by reacting, and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10%.

  As polyisocyanate (11), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (except for carbon in NCO group) Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and minor amounts (eg 5-20%] )) With a trifunctional or higher polyamine]: Polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p -Isocyanatophenylsulfonyl isocyanate Etc., and the like.
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 And aliphatic polyisocyanates.
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- and / or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Use in combination with an isocyanate-containing 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 polyamine (12) include aliphatic polyamines (C2 to C18): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hex Methylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aroma such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Polyamines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 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, etc .; [2] aromatic polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), for example 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethylto Range amine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′- Tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-di Minodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl- 4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substitution electrons Aromatic polyamines having an attractive group (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2- Chlor-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-di Lol-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) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-) 3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylene (4-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [1] A part or all of —NH _{2 in} the aromatic polyamine of [3] is replaced by —NH—R ′ (where R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4, 4 '-Di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamines: dicarboxylic acids (such as dimer acids) and excess polyamines (more than 2 moles per mole of acid) Polyether polyamines such as low molecular weight polyamide polyamines obtained by condensation with (the above alkylene diamines, polyalkylene polyamines, etc.) Hydrides of cyanoethylation products of Le polyols (polyalkylene glycol and the like).

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).

In the present invention, when a polyurethane resin containing the structural unit of the organic acid metal salt (m) is used as (a), this resin is, for example, a diol (g), (g1) and / or a trivalent or higher polyol. As at least a part of (h), a diol having at least one group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and the above metal base of these acids and / or a trivalent or higher polyol is used. Can be obtained. When using a diol and / or polyol having a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group, after forming the polyurethane resin, for example, by further reacting these acid groups with the corresponding metal hydroxide. A polyurethane resin containing the structural unit of the organic acid metal salt (m) is obtained.
Diols or polyols having a carboxylic acid (salt) group include dialkyrol alkanoic acids (salts) [of C6-24, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2, 2-dimethylol heptanoic acid, 2,2-dimethylol octanoic acid, and the metal salts of these acids, etc.].
Examples of the diol or polyol having a sulfonic acid (salt) group include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, and the above metal salts of these acids. Is mentioned.
Examples of the diol or polyol having a phosphoric acid (salt) group include bis (2-hydroxyethyl) phosphate and the metal salt thereof.
The amount of the diol having an organic acid metal (salt) group or a trivalent or higher polyol is preferably 10 to 90 mol% based on the total amount of (g), (g1) and (h). The lower limit is more preferably 20 mol%, and the upper limit is more preferably 60 mol%.

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (14), polyepoxide (14) and active hydrogen group-containing compound (D) {water, polyol [the diol (g), (g1) and trivalent or higher valent polyol (h) )], Dicarboxylic acid (i), trivalent or higher polycarboxylic acid (j), polyamine (12), polythiol (13) and the like}, or polyepoxide (14) and dicarboxylic acid (i) or 3 Examples thereof include a cured product of an acid anhydride of polycarboxylic acid (j) having a value equal to or higher than that of polyvalent acid.

  The polyepoxide (14) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. 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 (14). The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (14) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

  Examples of the polyepoxide (14) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols 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, and 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 di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, 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, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol 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 ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. 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, polypropylene glycol Diglycidyl 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 Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid 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. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

In the present invention, from the viewpoint of charging characteristics, the unit of the organic acid metal salt (m) of the metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr as the structural unit of the resin (a) is used. It is preferable to contain and / or to contain the said organic acid metal salt (m) in the resin particle (A). As the organic acid constituting the organic acid metal salt (m), carboxylic acid is preferable. Among metals, Zn and Fe are preferable, and Zn is more preferable.
Among these, it is preferable that the organic acid metal salt (m) is contained in (A) from the viewpoint of easy adjustment.

Among the organic acid metal salts (m), specific examples of the carboxylic acid metal salts include (alkyl substituted) benzoic acid, (alkyl substituted) salicylic acid, aromatic acids having 7 to 35 carbon atoms such as naphthenic acid, and stearyl. Preferred are higher fatty acids having 12 to 35 carbon atoms such as acids, and those exemplified as metal salts of carboxyl group-containing vinyl monomers constituting the resin (a). Specific examples of the sulfonic acid metal salt include those exemplified as the metal salt of the alkylbenzene sulfonic acid having 7 to 30 carbon atoms and the sulfone group-containing vinyl monomer constituting (a). What was illustrated as a metal salt of the phosphoric acid group containing vinyl monomer which comprises (a) as a phosphoric acid metal salt is preferable. Among these, oil-soluble metal salts are more preferable in order to exhibit the charging effect of the resin particles (C). From the viewpoint of composition, carboxylic acid metal salts are more preferable, and Zn salts and Fe salts of carboxylic acids are particularly preferable.
As a method of containing the organic acid metal salt (m) in (A), if the resin (a) is not reactive with the precursor of the resin (a), it may be added before the preparation of (a). It is preferable to mix with (a) after preparation.
Although there is no restriction | limiting in particular in the usage rate of the structural unit of these organic acid metal salt (m), and organic acid metal salt (m), These total amount with respect to the resin particle (C) obtained is 0.01 to 10%. It is preferable that The lower limit is more preferably 0.05%, and the upper limit is more preferably 1%.

In the present invention, an aqueous dispersion (X1) of resin particles (C1) having a uniform particle size is obtained in order to obtain an aqueous dispersion (W) of fine spherical resin particles (A), excellent in heat-resistant storage stability and charging characteristics. ), The resin (a) preferably contains a sulfonate anion group (—SO ₃ ⁻ ). The total content of sulfonic acid anion groups (—SO ₃ ⁻ ) is preferably 0.001 to 10% based on the weight of (a). The lower limit is more preferably 0.002%, and the upper limit is more preferably 5%, particularly preferably 2%, and most preferably 1%. Further, a sulfonic acid anion group to form the resin (-SO ₃ ^-) preferred carbon number of the monomer containing 3 to 50, more preferably 3 to 30, particularly preferably from 4 to 15.
When the sulfonate anion group (—SO ₃ ⁻ ) group content is not less than the lower limit of the above range and the carbon number of the monomer containing the sulfonate anion group (—SO ₃ ⁻ ) forming the resin is not more than the upper limit of the above range. The resin (a) is easily dispersed in an aqueous medium, and an aqueous dispersion (W) of fine spherical resin particles (A) can be easily obtained. Further, the blocking resistance and charging characteristics of the obtained resin particles (C1) or (C2) are improved.

In the present invention, in order to obtain an aqueous dispersion (W) of fine spherical resin particles (A), the resin (a) preferably contains a carboxyl group. At least a part of the carboxyl group may be neutralized with a base. The base neutralization rate of the carboxyl group is preferably 20 to 100 equivalent%, and more preferably 40 to 100 equivalent%.
The content of the carboxyl group [the content converted to a carboxyl group (—COOH group when neutralized with a base)] is preferably 0.1 to 10% based on the weight of (a). The lower limit is more preferably 0.5%, particularly preferably 1%, most preferably 3%, and the upper limit is more preferably 9.5%, particularly preferably 9%, most preferably 8%.
When the base neutralization rate and the carboxyl group content are at least the lower limit of the above range, the resin (a) is easily dispersed in the aqueous medium, and the aqueous dispersion (W) of fine spherical resin particles (A) is obtained. Can be easily obtained. Further, the charging characteristics of the obtained resin particles (C) are improved.

Examples of the base that forms the neutralized salt include ammonia, monoamine having 1 to 30 carbon atoms, polyamine (21), quaternary ammonium, alkali metal (sodium, potassium, etc.), and alkaline earth metal (calcium salt). , Magnesium salts, etc.).
Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), and tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine). , Lauryl dimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, monoamines and polyamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are 3 having 3 to 20 carbon atoms. Grade monoamine.
Moreover, the preferable carbon number of the monomer containing the carboxyl group or its salt which forms a vinyl-type resin and a polyester resin is 3-30, More preferably, it is 3-15, Most preferably, it is 3-8.

In the present invention, when the sp value difference (Δsp) between the resin (a) and the resin (b) is K, and the natural logarithm of the weight average molecular weight (Mw) of the resin (a) is ln (Mw) is H. , (A) and (b) are selected so that the point (K, H) is included in the inside including the side of the quadrilateral ABCD including the following four points A, B, C, D shown in FIG. Is preferred.
A (0.3, ln3000), B (1.5, ln1000),
C (1.3, ln200000), D (0.1, ln200000)
The point (K, H) is more preferably included in the inside including the side of the quadrangle A′B′C′D ′ composed of the following four points A ′, B ′, C ′, and D ′. It is particularly preferable that it is included in the inside including the side of a quadrangle A ″ B ″ C ″ D ″ composed of four points A ″, B ″, C ″, D ″.
A ′ (0.3, ln3200), B ′ (1.45, ln1500),
C ′ (1.3, ln100,000), D ′ (0.15, ln100,000)

A ″ (0.3, ln3400), B ″ (1.4, ln2000),
C ″ (1.3, ln50000), D ″ (0.2, ln50000)

  When the point (K, H) is below the straight line AB, the resin particles (A) are likely to dissolve in an organic solvent or the like during granulation, and granulation may not be successful. Further, when the point (K, H) is above the straight line CD, the resin particles (A) do not swell at all in an organic solvent or the like, and the resin particles (C1) are not sufficiently smooth because they are difficult to melt. This may lead to a decrease in powder fluidity. Further, when the point (K, H) is to the left of the straight line AD, since the sp value difference between the resin (a) and the resin (b) is small, the resin particles (A) are dissolved in the resin (b) solution. Granulation may not be successful. Further, when the point (K, H) is to the right of the straight line BC, the difference in sp value between the resin (a) and the resin (b) is large, and the resin particles (A) do not swell at all in an organic solvent or the like and the smoothness of the particles. If the point (K, H) is located on the right side, that is, if the sp value difference between the resin (a) and the resin (b) is further widened, the resin (a) And the adsorption force of the resin (b) may be reduced, making granulation difficult.

  In the present invention, the sp value of the resin particle (A) with respect to the resin particle (B) (the calculation method of the sp value is based on Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154), Moreover, the particle | grain surface of the resin particle (C1) can be smoothed by controlling the molecular weight of the resin particle (A).

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) in water or an organic solvent used at the time of dispersion, the molecular weight, sp value, crystallinity, and cross-linking molecular weight of the resin (a). Etc. are preferably adjusted as appropriate.

  The Mn of the resin (a) is preferably from 1 to 5 million, more preferably from 2 to 5 million, particularly preferably from 500 to 500,000, and the sp value is preferably from 7 to 18, more preferably from 8 to 14. It is. The melting point (measured by DSC) of the resin (a) is preferably 50 ° C. or higher, more preferably 80 to 200 ° C. When it is desired to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (C), a crosslinked structure may be introduced into the resin (a). Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. When the crosslinked structure is introduced into the resin (a), the molecular weight between crosslinking points is preferably 50 or more, more preferably 500 or more, and particularly preferably 1000 or more.

The glass transition temperature (Tg) of the resin (a) is preferably 20 ° C. to 250 ° C. from the viewpoints of particle size uniformity, powder flowability, heat resistance during storage, and stress resistance of the resin particles (C). More preferably, it is 30 degreeC-230 degreeC, More preferably, it is 40 degreeC-200 degreeC, Most preferably, it is 50 degreeC-120 degreeC. If the Tg is lower than the temperature at which the aqueous resin dispersion (X1) is prepared, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of particle size is reduced.
The Tg of the resin particles (A) comprising (a) and (m) if necessary is preferably 20 to 200 ° C., more preferably 30 to 120 ° C., particularly preferably 40 to 80 ° C. for the same reason. is there.
In addition, Tg in this invention is a value calculated | required from the said DSC measurement or a flow tester measurement (when it cannot measure by DSC).

For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 10.0 mm

  Also, point A (the temperature at which the sample begins to deform under compression load) in the flowchart shown in FIG. 2 is the glass transition temperature (Tg), and point B (the internal void disappears and the appearance is maintained with a non-uniform stress distribution. The temperature at the uniform single transparent body or phase becomes the softening start temperature (Ts), point C (the piston slightly rises due to the thermal expansion of the sample, and then the piston clearly starts to fall again) The temperature at the point) is the outflow start temperature (Tfb), and the temperature at the point D (the point where the difference between the outflow end point Smax and the minimum value Smin is 1/2 (X) and X and Smin are added) Temperature (T1 / 2).

  The softening start temperature (Ts) of the resin (a) is preferably 40 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C., from the viewpoint of heat resistance during storage, stress resistance, and fixing properties to the paper surface. Particularly preferably, it is 60 ° C to 220 ° C, most preferably 70 ° C to 160 ° C, and the outflow temperature (T1 / 2) is preferably 60 ° C to 300 ° C, more preferably 65 ° C to 280 ° C, and particularly preferably 70 ° C. C. to 250.degree. C., most preferably 80.degree. C. to 185.degree. When used as a toner or the like, if the softening start temperature (Ts) and the outflow temperature (T1 / 2) are high, it may cause deterioration factors such as low-temperature fixability and high glossiness. In addition, the softening start temperature and outflow temperature in this invention are the values calculated | required from the said flow tester measurement.

  The temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2) of the resin (a) is preferably 0 ° C to 130 ° C, more preferably 0 ° C to 125 ° C, and particularly preferably 0 ° C to 120 ° C. Most preferably, it is 0 ° C to 105 ° C. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

  Moreover, the preferable temperature difference of the glass transition temperature (Tg) and softening start temperature (Ts) of resin (a) is 0 degreeC-100 degreeC, More preferably, it is 0 degreeC-70 degreeC, More preferably, it is 0 degreeC-50 degreeC. Especially preferably, it is 0 degreeC-35 degreeC. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

  The glass transition temperature (Tg), softening start temperature (Ts) and outflow temperature (T1 / 2) of the resin (a) change the molecular weight of (a) and / or the monomer composition constituting (a). Therefore, it can be adjusted easily. As a method for adjusting the molecular weight of (a) (the higher the molecular weight, these temperatures are higher), a known method may be used. For example, when polymerization is performed by a sequential reaction such as a polyurethane resin or a polyester resin. In the case of polymerizing by a chain reaction such as vinyl resin, adjustment of the polymerization initiator amount and chain transfer agent amount, reaction temperature, and reaction concentration can be mentioned. In order to adjust the temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2) to a preferable range, the combination of the molecular weight of (a) and the monomer composition constituting (a) is appropriately selected. do it.

  In the aqueous dispersion (W) of the resin particles (A), an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) may be contained in the organic solvent (u) described later in addition to water. At this time, the organic solvent to be contained is one that does not cause aggregation of the resin particles (A), one that does not dissolve the resin particles (A), and one that does not interfere with granulation of the resin particles (C1). Any kind and any content may be used, but it is preferable to use 40% or less of the total amount with water and not to remain in the resin particles (C) after drying.

Although the method to make resin (a) the aqueous dispersion of resin particle (A) is not specifically limited, the following [1]-[8] are mentioned.
[1] In the case of polyaddition or condensation resins such as polyester resins and polyurethane resins, a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant if necessary. And then heating it or adding a curing agent to cure the precursor and produce an aqueous dispersion of resin particles (A).
[2] In the case of a polyaddition or condensation resin such as a polyester resin and a polyurethane resin, in a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof (preferably a liquid, which may be liquefied by heating) A method for producing an aqueous dispersion of resin particles (A) by dissolving a suitable emulsifier in the mixture, then adding water to effect phase inversion emulsification, and adding a curing agent to cure the precursor.
[3] In the case of a vinyl resin, an aqueous dispersion of resin particles (A) is directly formed by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. How to manufacture.
[4] Resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same shall apply hereinafter) The resin particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of a suitable dispersant.
[5] A method of obtaining resin particles by spraying a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent in a mist, and then dispersing the resin particles in water in the presence of an appropriate dispersant.
[6] The resin particles are precipitated by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent, or by cooling a resin solution previously heated and dissolved in an organic solvent. A method of obtaining resin particles by removing the solvent, and then dispersing the resin particles in water in the presence of a suitable dispersant.
[7] A method in which a resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the organic solvent is removed by heating or decompression.
[8] A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, and then water is added to perform phase inversion emulsification.

  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.

  Examples of the surfactant (s) include an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), and a nonionic surfactant (s-4). Is mentioned. The surfactant (s) may be a combination of two or more surfactants. Specific examples of (s) include those described below and JP-A-2002-284881.

  As the anionic surfactant (s-1), carboxylic acid or a salt thereof, a sulfate ester salt, a salt of carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.

As the carboxylic acid or a salt thereof, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms or a salt thereof can be used. For example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, olein Examples thereof include a mixture of acids, linoleic acid and ricinoleic acid, and higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like.
Examples of the salt include salts such as sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, and alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).

Examples of sulfate salts include higher alcohol sulfate salts (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters (EO or PO 1 to 10 moles of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated fats and oils having a carbon number of 12 to 50 or neutralized by neutralization), sulfated fatty acid esters (unsaturated fatty acids (carbon number) 6-40) lower alcohols (one obtained by sulfating and neutralizing esters of 1 to 8 carbon atoms) and sulfated olefins (one obtained by sulfating and neutralizing olefins having 12 to 18 carbon atoms) can be used.
Examples of the salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

  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, trade name: ALFOL). 1214: manufactured by CONDEA) and alcohol synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: Tridecanol) : Manufactured by Kyowa Hakko, trade names: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.) and the like.

Examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt and octyl alcohol EO 3 mol adduct sulfate ester salt.
Examples of sulfated oils include sulfate salts such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, and sheep fat.
Examples of sulfated fatty acid esters include sulfate salts such as butyl oleate and butyl ricinoleate.
Examples of the sulfated olefin include trade name: TEPOL (manufactured by Shell).

  Examples of the carboxymethylated salt include carboxymethylated salts of aliphatic alcohols having 8 to 16 carbon atoms and EO or carboxymethylated salts of 1 to 10 mol adducts of aliphatic alcohols having 8 to 16 carbon atoms. Can be used.

  Examples of the salt of a carboxymethylated product of an aliphatic alcohol include octyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol carboxymethylated sodium salt, and the like. It is done.

  Examples of carboxymethylated salts of EO 1 to 10 mol adducts of aliphatic alcohols include, for example, octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated sodium salt, and tridecanol EO5 mol addition. Carboxymethylated sodium salt and the like.

As sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates, sulfonates of Igepon T-type and other aromatic ring-containing compounds can be used.
Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate.

Examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate.
Examples of the sulfosuccinic acid diester salt include sulfosuccinic acid di-2-ethylhexyl ester sodium salt.
Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether and styrenated phenol sulfonate.

As the phosphate ester salt, a higher alcohol phosphate ester salt, a higher alcohol EO adduct phosphate ester salt and the like can be used.
Examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt.
Examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
Examples of the quaternary ammonium salt type surfactant include tertiary amines having 3 to 40 carbon atoms and quaternizing agents (for example, alkylating agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, and EO). For example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, poly Examples thereof include oxyethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate.

As amine salt type surfactants, primary to tertiary amines are inorganic acids (eg hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid). , Gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid, etc.).
Examples of the primary amine salt-type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Alternatively, organic acid salts and higher fatty acid (carbon number 8 to 40, stearic acid, oleic acid, etc.) salts of lower amines (having 2 to 6 carbon atoms) can be used.

Examples of the secondary amine salt type surfactant include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms.
Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (for example, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adduct of aliphatic amine (2 to 40 carbon atoms), alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0) -7-undecene), nitrogen-containing heterocyclic aromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methylimidazole) And 4,4'-dipyridyl) and inorganic acid salts or organic acid salts and triethanolamine monostearate, stearamide ethyl diethyl Such as tertiary mineral or organic acid salts of amines such as chill ethanolamine.

  Examples of the amphoteric surfactant (s-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be used.

  As the carboxylate type amphoteric surfactant, an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant, an imidazoline type amphoteric surfactant and the like are used. 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 a compound represented by the general formula (2).

_{[R-NH- (CH 2)} n-COO] mM (2)
[Wherein R is a monovalent hydrocarbon group; n is 1 or 2; m is 1 or 2; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium cation, an amine cation, an alkanolamine cation, etc. It is. ]

  Examples of the double-sided active agent represented by the general formula (2) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (eg, sodium stearylaminopropionate, sodium laurylaminopropionate); alkyl ( Examples thereof include C4-C24) aminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

  The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule, for example, alkyl (having 6 to 40 carbon atoms) dimethyl betaine. (Stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), C6-C40 amide betaines (coconut oil fatty acid amidopropyl betaine, etc.), alkyls (C6-C40) dihydroxyalkyls (C6-C40) Examples include betaine (such as lauryl dihydroxyethyl betaine).

  The imidazoline type amphoteric surfactant is an amphoteric surfactant having a cation part having an imidazoline ring and a carboxylic acid type anion part. For example, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoli Examples include nitrobetaine.

  Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaines such as pentadecyl sulfotaurine Examples include amphoteric surfactants, sulfonate amphoteric surfactants, and phosphate ester type amphoteric surfactants.

As the nonionic surfactant (s-4), an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant can be used.
The AO addition type nonionic surfactant is a compound having 8 to 40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms, alkylamine having 8 to 40 carbon atoms, or the like. AO is added to an esterified product obtained by adding a higher fatty acid or the like to a polyalkylene glycol obtained by adding AO to glycol or by reacting a higher fatty acid with a polyhydric alcohol. Or by adding AO to a higher fatty acid amide.

Examples of AO include EO, PO, and BO.
Of these, preferred 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% of the AO is preferably EO.

  As the AO addition type nonionic surfactant, for example, oxyalkylene alkyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number 8 to 40) (for example, octyl alcohol EO 20 mol adduct, lauryl alcohol EO 20 mol) Adducts, stearyl alcohol EO 10 mol adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (alkylene having 2 to 24 carbon atoms, higher fatty acid having 8 carbon atoms) -40) (for example, stearyl acid EO 10 mol adduct, lauric acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (alkylene having 2 to 24 carbon atoms, polyhydric alcohol having 3 to 3 carbon atoms) 40, carbon number of higher fatty acids -40) (for example, lauric acid diester of polyethylene glycol (polymerization degree 20), oleic acid diester of polyethylene glycol (polymerization degree 20), etc.); polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon) 8 to 40) (for example, nonylphenol EO 4 mol adduct, nonylphenol EO 8 mol PO 20 mol block adduct, octylphenol EO 10 mol adduct, bisphenol A · EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxyalkylene Alkylamino ethers (alkylene having 2 to 24 carbon atoms, alkyl having 8 to 40 carbon atoms) and (for example, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct, etc.); polyoxy Lucylene alkanolamide (C2-C24 of alkylene, C8-C24 of amide (acyl moiety)) (for example, EO 10 mol adduct of hydroxyethyl lauric acid amide, EO 20 mol adduct of hydroxypropyl oleic acid amide, etc.) Is mentioned.

  As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct and the like can be used. The polyhydric alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

  Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, and sucrose monostearate. Can be mentioned.

  Examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO 10 mol adduct, ethylene glycol monostearate EO 20 mol adduct, trimethylolpropane monostearate EO 20 mol PO 10 mol random adduct, sorbitan monolaurate. EO 10 mol adduct, sorbitan distearate EO 20 mol adduct, sorbitan dilaurate EO 12 mol PO 24 mol random adduct and the like.

  Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

  Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO 10 mol adduct and stearyl glycoside EO 20 mol PO 20 mol random adduct. Can be mentioned.

  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, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (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) used in the present invention may be added to an aqueous medium as needed during emulsification and dispersion, or may be added to the dispersion to be emulsified [in the oil phase containing the resin (b)].
Specific examples of the organic solvent (u) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane. Solvents: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ester or ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; Examples include amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these.

The plasticizer (v) may be added to the aqueous medium as needed during the emulsification dispersion, or may be added to the emulsified dispersion [in the oil phase containing the resin (b)].
As a plasticizer (v), it is not limited at all, The following are illustrated.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) used in the present invention is usually smaller than the particle size of the formed resin particles (B). From the viewpoint of particle size uniformity, the particle size ratio [volume of the resin particles (A) The value of [average particle diameter] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the obtained particle size distribution of (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 size of (A) is generally preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 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 ( In the case of obtaining C), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm of particles (C) are preferably 0.05 to 30 μm, particularly preferably. 0.1 to 20 μm.
The volume average particle size is determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using the laser Doppler method as an optical system, and the like. Can be measured. If there is a difference in the measured particle size between the measuring devices, the measured value of ELS-800 is adopted.
In addition, since the said particle size ratio is easy to be obtained, 0.1-300 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. More preferably, it is 0.5-250 micrometers, Most preferably, it is 1-200 micrometers.

  In the method for producing the aqueous resin dispersion and the resin particles (C) of the present invention, the aqueous resin dispersion (X1) includes an aqueous dispersion (W) of resin particles (A) made of the resin (a), a resin ( b) or an organic solvent solution thereof, and (b) or the organic solvent solution is dispersed in (W), and the resin particles (B) comprising (b) in the aqueous dispersion of (A) Can be obtained as an aqueous dispersion of resin particles (C1) having a structure in which (A) is adhered to the surface of (B).

  In the above production method, when the resin (b) or an organic solvent solution thereof is dispersed in the aqueous dispersion (W) to form the resin particles (B) comprising (b), the resin particles (B ) Adsorb the resin particles (A) on the surface to prevent the resin particles (C1) from being united with each other, and (C1) is less likely to be split under high shear conditions. Thereby, the particle diameter of (C1) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, the resin particles (A) have such a strength that they cannot be broken by shearing at the temperature at which they are dispersed, are not easily dissolved or swelled in water, and are dissolved in (b) or an organic solvent solution thereof. It is listed as a desirable characteristic that

In the case of dispersing the resin (b) or the organic solvent solution thereof, a dispersing device can be used.
The dispersion apparatus used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifier such as Special Machine Industries Co., Ltd., Ebara Milder (Ebara Manufacturing Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (Special Machine Industries Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), fine flow mill (Pacific Kiko Co., Ltd.), microfluidizer (Mizuho Kogyo Co., Ltd.) ), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), etc., membrane emulsifier (manufactured by Chilling Industries) Membrane emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of homogenizing the particle diameter.

When the resin (b) is dispersed in the aqueous dispersion (W) of the resin particles (A), the resin (b) is preferably a liquid. When the resin (b) is solid at room temperature, it may be dispersed in a liquid state at a high temperature equal to or higher than the melting point, or the organic solvent solution (b) may be used.
The viscosity of the resin (b) or the organic solvent solution thereof is preferably 10 to 50,000 mPa · s (measured with a B-type viscometer), more preferably 100 to 10,000 mPa · s, from the viewpoint of particle size uniformity. s.
The temperature at the time of dispersion is preferably 0 to 150 ° C. (under pressure), more preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to carry out emulsification dispersion by lowering the viscosity to the above preferred range by increasing the temperature.
The solvent used for the organic solvent solution of the resin (b) is not particularly limited as long as it can dissolve the resin (b) at room temperature or under heating, and specifically, the same solvent as the organic solvent (u) may be used. Illustrated. The preferred one varies depending on the type of the resin (b), but the sp value difference from (b) is preferably 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 amount of the aqueous dispersion (W) used with respect to 100 parts 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 dispersed state of (b) is good, and if it is 2,000 parts by weight or less, it is economical.

In the present invention, resins (a) and (b) in which the above points (K, H) are included in a specific range, or resins having physical properties such as (Ts) and (Tg) in the preferred ranges ( When using a), particularly when using the organic solvent solution (particularly the following preferred solvent) of (b), the organic solvent is preferably 10 to 50% (particularly 20 to 40%) in the aqueous resin dispersion (X1). The resin particles (A) are dissolved in an organic solvent to form a film by simply removing the solvent at 40 ° C. or lower, preferably 1% or lower (particularly 0.5% or lower), and on the surface of (B). In many cases, an aqueous resin dispersion (X2) of resin particles (C2) formed with the coating (A) is obtained. However, even when the coating film of (A) is not formed or when the coating film is formed from at least a part of (A), the smoothness of the coating film on the surface of the resin particles (C) is further improved. Therefore, when the following operation is performed, a coating having a smooth surface (shell layer (P)) formed from (A) on at least a part of the surface of the core layer (Q) composed of (B), preferably the entire surface. It is preferable from the point that the aqueous resin dispersion (X2) of the resin particles (C2) having the above is obtained and the storage stability of (C2) obtained therefrom is excellent.
Examples of the method include a method in which (A) attached to (B) is dissolved in an organic solvent, and a method in which the aqueous resin dispersion (X1) is heated to melt (A) to form a film. These methods may be used in combination.

The solvent used when the resin particles (A) are dissolved in an organic solvent to form a film may be added to (X1) when forming the film. When the organic solvent solution of b) is used without removing the solvent immediately after the formation of the resin particles (B), the solvent is contained in (B). It is easy and it is preferable that the resin does not aggregate.
As an organic solvent, a thing with high affinity with (b) is preferable, and the thing similar to the said organic solvent (u) is mentioned as a specific example. Preferred among (u) are tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate from the viewpoint of film formation, and more preferably ethyl acetate.
The solvent concentration in the aqueous resin dispersion when (A) is dissolved in the organic solvent is preferably 3 to 60%, more preferably 10 to 45%, and particularly preferably 15 to 30%. The dissolution is performed by stirring the aqueous resin dispersion, for example, for 1 to 10 hours, and the temperature during dissolution is preferably 15 to 45 ° C, more preferably 15 to 30 ° C.

When (A) is melted to form a film on the surface of (B), the solid content [content of components other than water and organic solvent] in the aqueous resin dispersion (X1) is preferably 1 to 50%, More preferably, it is adjusted to 5-30%. Further, the solvent content at this time is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.5% or less. When the solid content in (X1) is high or the solvent content exceeds 2%, aggregates may be generated when the temperature of (X1) is raised to 60 ° C. or higher. The heating conditions at the time of melting are not particularly limited as long as (A) is melted. For example, the stirring is preferably 40 to 100 ° C, more preferably 60 to 90 ° C, and particularly preferably 60 to 80 ° C. A method of heating at a temperature of preferably 1 to 300 minutes can be mentioned.
It is to be noted that, as a film-forming treatment method, the aqueous dispersion (X1) of the resin particles (C1) having a solvent content of 2% or less is subjected to heat treatment, and (A) is melted on the core (Q) to obtain a more surface. The preferable heat treatment temperature when obtaining the smooth resin particles (C2) is not less than the Tg of (P) and a temperature range of not more than 80 ° C. The surface smoothness of the resin particles (C2) obtained when the heat treatment temperature is lower than the Tg of (P) hardly changes. Moreover, when heat-processing at the temperature exceeding 80 degreeC, a shell (P) may peel from a core.
Among these (A) film-forming methods, preferred methods are a method of melting (A) and a combination of a method of dissolving (A) and a method of melting (A).

  Resin particles (C1) or (C2) are prepared by mixing an aqueous dispersion (W) of resin particles (A) made of resin (a) with an organic solvent solution of resin (b) or (b). ) In which the organic solvent solution (b) or (b) is dispersed and the resin particles (A) are attached to the surface of the resin particles (B) made of the resin (b). Aqueous dispersion of resin particles (C2) having a structure having the shell layer (P) formed from (A) on the surface of the core layer (Q) composed of the aqueous dispersion (X1) and / or (B) After forming the body (X2), the aqueous resin dispersion (X1) or (X2) [hereinafter, “(X1) or (X2)” may be referred to as (X). It is obtained by removing the aqueous medium from

As a method of removing the aqueous medium,
[1] A method of drying an aqueous resin dispersion under reduced pressure or normal pressure [2] A method of solid-liquid separation with a centrifuge, a spacula filter, a filter press, etc., and drying the resulting powder [3] Aqueous resin dispersion Method of freezing and drying the body (so-called freeze-drying)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed 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.

The resin particles (C1) are substantially composed of relatively small resin particles (A) and relatively large resin particles (B), and (A) is attached to the surface of (B). To do. The resin particles (C2) were dissolved and / or melted after (A) was attached to (B), and (A) was coated on the surface of the core layer (Q) composed of (B). A shell layer (P) is formed.
When it is desired to further increase the adhesion of both particles, when dispersed in an aqueous medium, (A) and (B) have positive and negative charges, or (A) and (B) have the same charge. In the case of having a surfactant (s) or a water-soluble polymer (t), one having a charge opposite to (A) and (B) is used, or the resin (a) and the resin (b) It is effective to make the difference in sp value as small as possible within the above range (for example, 2 or less).
is there.

Moreover, when manufacturing the aqueous resin dispersion and resin particle (C) of this invention, the adsorptive power with respect to the resin particle (B) of the resin particle (A) can be controlled by the following methods.
[1] When the aqueous dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) have positive and negative charges, an adsorption force is generated. In this case, the resin particles (A) As the charge of each resin particle (B) is increased, the adsorptive power is increased and the coverage of the resin particles (A) to the resin particles (B) is 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 is It tends to go down. In this case, generally, the use of the activator (s) and / or the water-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] increases the coverage.
[3] When the aqueous dispersion (X1) is produced, the resin (a) has a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is 1). The coverage is increased as the pH of the aqueous medium is lower. Conversely, the higher the pH, the smaller the coverage.
[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 ammonium base (in general, In the case where the molecular weight per basic functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the higher the coverage. Conversely, the coverage decreases as the pH is lowered.
[5] When the Δsp value of the resin particles (A) and the resin particles (B) is decreased, the coverage is increased.

  The resin particles (C) are composed of 0.01 to 60% (A) and 40 to 99.99% (B) from the viewpoints of particle size uniformity and storage stability of the resin particles (C). More preferably 0.1 to 50% (A) and 50 to 99.9% (B), particularly preferably 1 to 45% (A) and 55 to 99% (B). .

From the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C1), 5% or more of the surface of the resin particles (B), preferably 30% or more, more preferably 50% or more, It is particularly preferable that 80% or more is covered with the resin particles (A). The surface coverage of (C1) can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [area of the portion covered with the resin particles (A) / area of the portion covered with the resin particles (A) + area of the portion where the resin particles (B) are exposed] × 100

The surface coverage determined by the following formula in the resin particles (C2) may be any rate, but from the viewpoint of particle size uniformity, powder flowability, storage stability, etc., the core layer (Q) 70% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more of the surface of the film is covered with the shell layer (P). 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 (%) = [area of the portion covered by (P) / area of the portion covered by (P) + area of the exposed portion of (Q)] × 100

From the viewpoint of particle size uniformity, the variation coefficient of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1 to 15%.
From the viewpoint of particle size uniformity, the value of [volume average particle size / number average particle size] (Dv / Dn) of the resin particles (C) is preferably 1.0 to 1.4. More preferably, it is -1.2.
The volume average particle size of (C) varies depending on the application, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

The shape of the resin particles (C2) of the present invention can be controlled by the following method.
By controlling the sp value difference between the resin particles (A) and the resin particles (B) and the molecular weight of the resin particles (A), the particle shape and particle surface properties can be controlled. If the difference in sp value is small, irregularly-shaped and smooth surface particles can be easily obtained, and if the difference in sp value is large, spherical particles having a rough surface are likely to be obtained. Moreover, when the molecular weight of (A) is large, particles having a rough surface are easily obtained, and when the molecular weight is small, particles having a smooth surface are easily obtained. However, if the difference in sp value between (A) and (B) is too small or too large, granulation becomes difficult. If the molecular weight of the resin particles (A) is too small, granulation becomes difficult. From this, the sp value difference between (A) and (B) is preferably 0.01 to 5.0, more preferably 0.1 to 3.0, and still more preferably 0.2 to 2.0. Moreover, Mw of a preferable resin particle (A) is 1,000 to 1,000,000, More preferably, it is 1000 to 500,000, More preferably, it is 2000 to 200,000, Most preferably, it is 3000 to 100,000.

The resin particles (C) of the present invention include the particle diameters of the resin particles (A) and the resin particles (B), the coverage of the surface of the resin particles (B) by the resin particles (A), or the core by the shell layer (P). By changing the coverage of the layer (Q) surface, desired irregularities can be imparted to the particle surface. When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area of the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen).
Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (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, it is preferable that the particles (A) and the particles (B) are also spherical. (C) preferably has an average circularity of 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) to a dispersion concentration of 3,000 to 10,000 / μL. To measure the shape and distribution of the resin particles.

In the method for producing the aqueous resin dispersion and the resin particles (C) of the present invention, the resin particles (C) include a particle diameter ratio of the resin particles (A) to the resin particles (B), and an aqueous resin dispersion (X1). The coverage of the surface of the resin particles (B) by the resin particles (A) in the resin particles (A) on the resin particle (B) side on the resin particle (B) / aqueous medium interface in the aqueous resin dispersion (X1) By changing the depth embedded in the particle surface, the particle surface can be smoothed or desired irregularities can be imparted to the particle surface.
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 resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) 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 resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative), the covering rate Tends to decrease and decrease in depth. In this case, in general, 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 resin dispersion (X1) is produced, the resin (a) has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is When the pH of the aqueous medium is lower, the coverage and depth are increased. Conversely, the higher the pH, the smaller the coverage and depth.
[4] When the aqueous resin 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 ammonium base ( In general, the molecular weight per basic functional group is preferably 1,000 or less), and the higher the pH of the aqueous medium, 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.

In the resin particles (A) and / or (B) constituting the resin particles (C), additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, oxidation agents) Inhibitor, blocking inhibitor, heat stabilizer, flame retardant, etc.) may be mixed. As a method of adding an additive in (A) or (B), the aqueous resin dispersion (X1) may be mixed in an aqueous medium, but the resin (a) or the resin (b It is more preferable that the mixture is added and dispersed in an aqueous medium after mixing an additive) and an additive.
In the present invention, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium, and may be added after the particles are formed. For example, after forming particles containing no colorant, a colorant may be added by a known dyeing method, or the additive may be impregnated with the organic solvent (u) and / or the plasticizer (v). it can.
When the charge control agent consisting of the organic acid salt (m) is contained in the resin particles (A) as an additive, the charging characteristics are preferably improved.
Examples of (m) include those described above, and the amount used is also the same.

In the present invention, when the resin particles (B) contain, as the additive, the resin (b), the wax (c), and the modified wax (d) grafted with a vinyl polymer chain, the heat-resistant storage stability Is more preferable.
The content of (c) in (B) is preferably 20% or less, more preferably 1 to 15%. The content of (d) is preferably 10% or less, more preferably 0.5 to 8%. The total content of (c) and (d) is preferably 25% or less, more preferably 1 to 20%.

The wax (c) is dispersed in the resin (b) after being previously melt-kneaded in the absence of the organic solvent and / or heat-dissolved and mixed in the presence of the organic solvent (u).
Examples of the wax (c) include polyolefin wax, paraffin wax, carbonyl group-containing wax, and a mixture thereof. Among these, paraffin wax (c1) is particularly preferable. Examples of (c1) include petroleum waxes whose main component is a linear saturated hydrocarbon having a melting point of 50 to 90 ° C. and a carbon number of 20 to 36.
Further, from the viewpoint of releasability, Mn in (c) is preferably 400 to 5000, more preferably 1000 to 3000, and particularly 1500 to 2000. In the above and below, Mn of the wax is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is mixed with the modified wax (d) grafted with the vinyl polymer chain in a solvent-free melt-kneading process and / or heat-dissolved and mixed in the presence of the organic solvent (u), and then the resin (b). Preferably it is dispersed. By the coexistence of the modified wax (d) during the wax dispersion treatment by this method, the wax base portion of (d) is efficiently adsorbed on the surface or partly entangled in the wax matrix structure, The affinity between the surface of the wax (c) and the resin (b) is improved, and (c) can be more uniformly encapsulated in the resin particles (B), and the dispersion state can be easily controlled.

  The modified wax (d) is obtained by grafting a vinyl polymer chain onto the wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same. Examples of the vinyl monomer constituting the vinyl polymer chain of (d) include the same monomers as the monomers (1) to (10) constituting the vinyl resin. Among these, (1) is particularly preferred. , (2), and (6). The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. The Tg of (d) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, from the viewpoint of heat resistant storage stability of the resin particles (C).
Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the mechanical strength of the resin particles (C) is good.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in an organic solvent (for example, toluene or xylene), heating to 100 to 200 ° C., and then converting the vinyl monomer to a peroxide initiator (benzoyl peroxide, It is obtained by distilling together with ditertiary butyl peroxide, tertiary butyl peroxide benzoate, etc.) and polymerizing, and then distilling off the organic solvent.
The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total weight of the raw material (d).

As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used.
Examples of the oil-soluble peroxide polymerization initiator include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, and t-butyl peroxide. Oxybivalate, 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, t-butylperoxyisobuty , T-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t- Butyl peroxyacetate, t-butyl peroxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumylper Oxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5- Hydroperoxide and cumene peroxide.

  Examples of the water-soluble peroxide polymerization initiator include hydrogen peroxide, peracetic acid, ammonium persulfate, potassium persulfate, and sodium persulfate.

As a method of mixing the wax (c) and the modified wax (d), [1] a method of melt kneading at a temperature equal to or higher than the melting point of each, [2] (c) and (d) in the organic solvent (u) A method of dissolving or suspending, then precipitating in a liquid by cooling crystallization, solvent crystallization or the like, or precipitating in a gas by spray drying or the like, [3] (c) and (d) as an organic solvent (u) Examples of the method include a method of dissolving or suspending the material in the inside and then performing mechanical wet pulverization with a disperser. Among these, the method [2] is preferable.
As a method of dispersing the wax (c) and the modified wax (d) in (b), (c), (d), and (b) are made into an organic solvent solution or a dispersion, respectively, And the like.

  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” indicates parts by weight.

Production Example 1 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel in which a stir bar and a thermometer were set, 177 parts of polyester (number average molecular weight 1000) obtained from adipic acid and 1,4-butanediol (molar ratio 1: 1), 1,2-propylene glycol (hereinafter referred to as “1”) 7 parts, 72 parts of dimethylolpropionic acid, 4 parts of 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, and 500 parts of acetone are charged. To this solution, 246 parts of isophorone diisocyanate (IPDI) was added and reacted at 55 ° C. for 11 hours to obtain [Urethane Prepolymer 1]. 14 parts of di-tert-butylsalicylic acid Zn is added to this prepolymer, triethylamine is further added, and 100 equivalent% of carboxylic acid derived from dimethylolpropionic acid is neutralized with an amine to make a uniform solution. This solution is added to 1500 parts of water with stirring and emulsified. Further, 320 parts of water, 9 parts of ethylenediamine and 6 parts of n-butylamine were added, and an elongation reaction was performed at 50 ° C. for 4 hours to obtain an aqueous dispersion of urethane resin [fine particle dispersion W1]. The volume average particle diameter of [fine particle dispersion W1] measured by ELS-800 was 0.09 μm. A part of [Fine Particle Dispersion W1] was dried to isolate the resin component, the glass transition temperature was 62 ° C., the softening start temperature was 105 ° C., and the outflow temperature was 180 ° C. by flow tester measurement. It was.

Production Example 2 (Production of aqueous dispersion of resin particles (A))
A reaction vessel equipped with a stir bar and a thermometer was charged with 130 parts of isopropanol, and with stirring, a mixed solution of 80 parts of styrene, 85 parts of methacrylic acid, 120 parts of butyl acrylate, and 62 parts of benzoyl peroxide (containing 25% water). Was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ionic water under stirring to obtain an aqueous dispersion [fine particle dispersion W2]. The volume average particle diameters of [fine particle dispersion W2] measured by LA-920 and ELS-800 were both 0.09 μm. A portion of [fine particle dispersion W2] was dried to isolate the resin component. The resin component had a Tg of 72 ° C. by DSC measurement, a softening start temperature of 98 ° C., and an outflow temperature of 175 ° C.

Production Example 3 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 377 parts of propylene glycol, 350 parts of dimethyl terephthalate, 40 parts of adipic acid, and 0.3 part of tetrabutoxy titanate as a polycondensation catalyst were added. The reaction was carried out for 8 hours while distilling off the methanol produced under nitrogen flow at ℃. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and further under a reduced pressure of 5 to 20 mmHg. When s reached 85 ° C, it was taken out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain [Polyester b0]. Mw of [Polyester b0] was 3200. Next, 30 parts of acetone was added to 30 parts of this [polyester b0] and dissolved, and 2.5 parts of triethylamine was further added. By adding 90 parts of water to this well-stirred solution, an aqueous polyester resin dispersion [fine particle dispersion W3] was obtained. The volume average particle diameter of [fine particle dispersion W3] measured by ELS-800 was 0.05 μm. A part of [Fine Particle Dispersion W3] was dried to isolate the resin component, the glass transition temperature was 60 ° C., the softening start temperature was 90 ° C., and the outflow temperature was 155 ° C. by flow tester measurement. It was.

Production Example 4 (Production of aqueous dispersion of resin particles (A))
A reaction vessel equipped with a stir bar and thermometer was charged with 130 parts of isopropanol, and under stirring, 71 parts of methyl methacrylate, 143 parts of vinyl acetate, 73 parts of acrylic acid, and 25 parts of benzoyl peroxide (25% water-containing product) were mixed. The solution was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W4]. The volume average particle diameters of [fine particle dispersion W4] measured by LA-920 and ELS-800 were both 0.05 μm. A part of [fine particle dispersion W4] was dried to isolate the resin component. Tg by DSC measurement of the resin was 50 ° C., the softening start temperature was 60 ° C., and the outflow temperature was 120 ° C.

Production Example 5 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 130 parts of isopropanol was charged. Under stirring, 30 parts of butyl acrylate, 25 parts of styrene, 45 parts of methacrylic acid, sodium salt of alkylallylsulfosuccinic acid (Eleminol JS-2, Sanyo) A mixed solution of 8 parts by Kasei Kogyo) and 25 parts of benzoyl peroxide (25% water-containing product) was added dropwise over 120 minutes. 29 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W5]. The volume average particle diameters of [fine particle dispersion W5] measured by LA-920 and ELS-800 were both 0.05 μm. A portion of [fine particle dispersion W5] was dried to isolate the resin component. Tg by DSC measurement of the resin was 120 ° C., the softening start temperature was 160 ° C., and the outflow temperature was 250 ° C.

Production Example 6 [Synthesis of titanium-containing catalyst (e)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube capable of bubbling in the liquid, 126 parts of ethyl acetate and 200 parts of terephthalic acid are placed and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. Then, 1617 parts of titanium tetraisopropoxide was added dropwise to react at 60 ° C. for 4 hours to obtain a slurry-like reaction mixture. The reaction mixture was filtered off with filter paper and dried at 40 ° C./20 kPa · s to obtain a mixture (e1) of titanium triisopropoxyterephthalate and unreacted terephthalic acid (titanium triisopropoxyterephthalate concentration 65%). The solubility of (e1) in water was [0.6 g / 100 ml], and the solubility of titanium triisopropoxyterephthalate obtained by further purification in water was [0.9 g / 100 ml].

Production Example 7 [Synthesis of titanium-containing catalyst (e)]
520 parts of ethyl acetate and 340 parts of isophthalic acid are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe capable of bubbling in liquid, and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. Then, 284 parts of titanium tetraisopropoxide was added dropwise to react at 60 ° C. for 5 hours to obtain a reaction mixture as a slurry. The reaction mixture was filtered with a filter paper and dried at 40 ° C./20 kPa · s, so that a mixture of titanium diisopropoxy diisophthalate and unreacted isophthalic acid (e2) (concentration of titanium diisopropoxy diisophthalate 95%) Got.
The solubility of (e2) in water was [0.3 g / 100 ml], and the solubility of titanium diisopropoxydiisophthalate obtained by further purification in water was also [0.3 g / 100 ml].

Production Example 8 [Synthesis of titanium-containing catalyst (e)]
520 parts of ethyl acetate and 244 parts of benzoic acid are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube capable of bubbling in liquid, and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. Then, 284 parts of titanium tetraisopropoxide was added dropwise and reacted at 60 ° C. for 5 hours, and then 50 parts of ion exchange water was added and reacted for 30 minutes to obtain a slurry-like reaction mixture. The reaction mixture was filtered off with a filter paper and dried at 40 ° C./20 kPa · s to obtain titanium dihydroxydibenzenecarboxylate (e3). The solubility of (e3) in water was [0.1 g / 100 ml].

Production Example 9 [Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts and 2 parts of (e1) as a polycondensation catalyst were added and reacted for 10 hours at 220 ° C. while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (bX1-1) was obtained.
(BX1-1) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 11, Tg of 61 ° C., Mn of 7040, Mw of 17100, and Mp of 18900. The ratio of components having a molecular weight of 1500 or less was 1.0%.

Production Example 10 [Synthesis of Non-Linear Polyester Resin]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 350 parts of an EO2 molar adduct of bisphenol A, 326 parts of a PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and polycondensation 2 parts of (e1) was added as a catalyst and reacted at 230 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature To obtain a non-linear polyester resin (bX2-1).
(BX2-1) contained no THF-insoluble matter, and its acid value was 34, the hydroxyl value was 18, Tg was 68 ° C., Mn was 3820, and Mp was 11100. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 11 [Synthesis of linear polyester resin]
A linear polyester resin (bX1-2) was obtained by reacting in the same manner as in (bX1-1) of Production Example 9 except that the polycondensation catalyst was replaced with (e2), cooling to room temperature, and pulverizing.
(BX1-2) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 10, Tg of 60 ° C., Mn of 6690, Mw of 17250, and Mp of 2,080. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 12 [Synthesis of Non-Linear Polyester Resin]
A linear polyester resin (bX2-2) was obtained by reacting in the same manner as in (bX2-1) of Production Example 10 except that the polycondensation catalyst was replaced with (e2), cooling to room temperature, and pulverizing.
(BX2-2) contained no THF-insoluble matter, and had an acid value of 32, a hydroxyl value of 16, Tg of 69 ° C., Mn of 4220, and Mp of 11780. The ratio of components having a molecular weight of 1500 or less was 0.7%.

Production Example 13 [Synthesis of linear polyester resin]
A linear polyester resin (bX1-3) was obtained by reacting in the same manner as in (bX1-1) of Production Example 9 except that the polycondensation catalyst was replaced with (e3), cooling to room temperature, and pulverizing.
(BX1-3) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 10, Tg of 61 ° C., Mn of 6810, Mw of 17400, and Mp of 20170. The ratio of components having a molecular weight of 1500 or less was 1.1%.

Production Example 14 [Synthesis of Non-Linear Polyester Resin]
A linear polyester resin (bX2-3) was obtained by reacting in the same manner as in (bX2-1) of Production Example 10 except that the polycondensation catalyst was replaced with (e3), cooling to room temperature, and pulverizing.
(BX2-3) contained no THF-insoluble matter, and had an acid value of 31, a hydroxyl value of 14, Tg of 66 ° C., Mn of 4250, and Mp of 11,920. The ratio of components having a molecular weight of 1500 or less was 0.7%.

Production Example 15 [Synthesis of urethane-modified polyester resin (polyurethane resin)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts and 2 parts of (e1) as a polycondensation catalyst were added and reacted at 220 ° C. for 6 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and when the acid value became 12, it cooled to 80 degreeC, 1000 parts of ethyl acetate was put, and it stirred for 1 hour. Thereafter, 60 parts of isophorone diisocyanate was added and reacted for 2 hours, then cooled to room temperature and pulverized to obtain a solvent solution (resin solution i) of urethane-modified polyester resin (bZ-1).
(BZ-1) contained no THF-insoluble matter, and had an acid value of 5, a hydroxyl value of 9, Tg of 61 ° C., Mn of 8790, and Mp of 13200. The ratio of components having a molecular weight of 1500 or less was 0.9%.

Production Example 16 [Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts of propylene glycol, 716 parts of dimethyl terephthalate, 180 parts of adipic acid, and 3 parts of (e1) as a polycondensation catalyst were placed at 180 ° C. The reaction was carried out for 8 hours while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature up to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water generated under a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point becomes 150 ° C. It was taken out at the time. The recovered propylene glycol was 316 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a linear polyester resin (bX1-4). (BX1-4) contained no THF-insoluble matter, and had an acid value of 15, a hydroxyl value of 26, Tg of 61 ° C., Mn of 8800, Mw of 27600, and Mp of 32200. The ratio of components having a molecular weight of 1500 or less was 4.0%.

Production Example 17 [Synthesis of Non-Linear Polyester Resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 557 parts of propylene glycol, 569 parts of dimethyl terephthalate, 184 parts of adipic acid, and 2 parts of (e1) as a polycondensation catalyst were placed at 180 ° C. The reaction was carried out for 8 hours while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off propylene glycol and water produced under a nitrogen stream, and further, the reaction was performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 175 parts. Next, it is cooled to 180 ° C., 121 parts of trimellitic anhydride is added, and after reacting for 2 hours under normal pressure sealing, it is reacted at 220 ° C. and normal pressure, taken out when the softening point is 180 ° C. Then, it was pulverized and granulated to obtain a non-linear polyester resin (bX2-4). (BX2-4) contained no THF-insoluble matter, and had an acid value of 5, a hydroxyl value of 24, Tg of 66 ° C., Mn of 7200, and Mp of 41900. The ratio of components having a molecular weight of 1500 or less was 2.3%.

Production Example 18 [Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 420 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid and a polycondensation catalyst As (e1), 2 parts were added and reacted at 220 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 13, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (bX1-5) was obtained.
(BX1-5) contained no THF-insoluble matter, and had an acid value of 15, a hydroxyl value of 13, Tg of 55 ° C., Mn of 2830, Mw of 7100, and Mp of 6810. The ratio of components having a molecular weight of 1500 or less was 1.0%.

Production Example 19 [Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 700 parts of propylene glycol, 700 parts of dimethyl terephthalate, 90 parts of adipic acid, and 3 parts of (e1) as a polycondensation catalyst were placed at 180 ° C. The reaction was carried out for 8 hours while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point becomes 90 ° C. It was taken out at the time. The recovered propylene glycol was 316 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a linear polyester resin (bX1-6). (BX1-6) contained no THF-insoluble matter, and had an acid value of 17, a hydroxyl value of 23, Tg of 54 ° C., Mn of 3300, Mw of 9100, and Mp of 9400. The ratio of components having a molecular weight of 1500 or less was 3.8%.

Production Example 20 [Synthesis of linear polyester resin for comparison]
The reaction was conducted in the same manner as in (bX1-1) of Production Example 9 except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. Since the reaction was stopped in the middle due to catalyst deactivation and the problem that the produced water could not be distilled occurred, 2 parts of titanium tetraisopropoxide was added four times during the reaction, and a comparative linear polyester resin (CbX1) was added. -1) was obtained.
(CbX1-1) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 12, Tg of 59 ° C., Mn of 6180, Mw of 13700, and Mp of 18600. The ratio of components having a molecular weight of 1500 or less was 2.4%.

Production Example 21 [Synthesis of non-linear polyester resin for comparison]
The reaction was conducted in the same manner as in (bX2-1) of Production Example 10 except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide were added three times during the reaction to obtain a comparative non-linear polyester resin (CbX2-1).
(CbX2-1) did not contain THF-insoluble matter, and its acid value was 35, the hydroxyl value was 14, Tg was 67 ° C., Mn was 3520, and Mp was 11800. The ratio of components having a molecular weight of 1500 or less was 2.3%.

Production Example 22 [Synthesis of urethane-modified polyester resin (polyurethane resin) for comparison]
A solvent solution (resin solution ii) of a comparative urethane-modified polyester resin (CbZ-1) was obtained by reacting in the same manner as in (bZ-1) of Production Example 15 except that the polycondensation catalyst was replaced with titanium tetraisopropoxide.
(CbZ-1) contained no THF-insoluble matter, and had an acid value of 4, a hydroxyl value of 11, Tg of 61 ° C., Mn of 7800, and Mp of 13000. The ratio of components having a molecular weight of 1500 or less was 1.2%.

Production Example 23 [Synthesis of comparative linear polyester resin]
The reaction was conducted in the same manner as in Production Example 16 (bX1-4) except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide was added three times during the reaction to obtain a comparative non-linear polyester resin (CbX1-2).
(CbX1-2) contained no THF-insoluble matter, and had an acid value of 13, a hydroxyl value of 28, Tg of 61 ° C., Mn of 7830, Mw of 27400, and Mp of 33900. The ratio of components having a molecular weight of 1500 or less was 4.6%.

Production Example 24 [Synthesis of Comparative Linear Polyester Resin]
The reaction was conducted in the same manner as in Production Example 17 (bX2-4) except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide were added three times during the reaction to obtain a comparative non-linear polyester resin (CbX2-2).
(CbX2-2) contained no THF-insoluble matter, and had an acid value of 13, a hydroxyl value of 28, Tg of 61 ° C., Mn of 7800, and Mp of 33900. The ratio of components having a molecular weight of 1500 or less was 4.6%.

Production Example 25 (Production of Colorant Dispersion)
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.) and 76 parts of ethyl acetate were stirred and dispersed uniformly. Then, the copper phthalocyanine was finely dispersed by a bead mill. [Colorant dispersion 1] was obtained. The volume average particle diameter of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.3 μm.

Production Example 26 (Production of modified wax)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. Sun Wax LEL-400: softening point 128 ° C.) were added, and after nitrogen substitution, 170 parts were obtained. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax 1]. The sp value of the graft chain of [modified wax 1] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1872, Mw was 5194, and Tg was 56.9 ° C.

Production Example 27 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of paraffin wax (melting point: 73 ° C.), 1 part of [modified wax 1] and 33 parts of ethyl acetate are added, heated to 78 ° C. and sufficiently dissolved. After cooling to 30 ° C. over time, the wax was crystallized into fine particles and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 1].

Production Example 28 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of polyester resin (bX1-1), 60 parts of polyester resin (bX2-1) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 1]

Production Example 29 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of polyester resin (bX1-2), 60 parts of polyester resin (bX2-2) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 2]

Production Example 30 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of a polyester resin (bX1-3), 60 parts of a polyester resin (bX2-3) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 3]

Production Example 31 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of a polyester resin (bX1-1), 120 parts of a solvent solution [resin solution i] of urethane-modified polyester resin (bZ-1) and 40 parts of ethyl acetate are placed. The mixture was stirred and dispersed uniformly to obtain [Resin Solution 4].

Production Example 32 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 60 parts of a polyester resin (bX1-4), 40 parts of a polyester resin (bX2-4) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 5]

Production Example 33 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 60 parts of polyester resin (bX1-5), 40 parts of polyester resin (bX2-1) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 6] was obtained.

Production Example 34 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 80 parts of polyester resin (bX1-6), 20 parts of polyester resin (bX2-1) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 7] was obtained.

Production Example 35 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of polyester resin (CbX1-1), 60 parts of (CbX2-1) and 100 parts of ethyl acetate are stirred and uniformly dispersed. [Resin Solution 8] Got

Production Example 36 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of a polyester resin (CbX1-1), 120 parts of a solvent solution of a urethane-modified polyester resin (CbZ-1) [resin solution ii] and 40 parts of ethyl acetate are placed. The mixture was stirred and dispersed uniformly to obtain [Resin Solution 9].

Production Example 37 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 40 parts of a polyester resin (CbX1-2), 60 parts of a polyester resin (CbX2-2) and 100 parts of ethyl acetate are stirred and uniformly dispersed. 10]

Example 1
In a beaker, put 60 parts of [resin solution 1], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1], and stir at 8,000 rpm with a TK homomixer at 25 ° C. Was dissolved and dispersed in [resin solution 1A].
In a beaker, 92 parts of ion-exchanged water, 30.8 parts of [fine particle dispersion W1], 1 part of sodium carboxymethyl cellulose, and 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Then, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration became 0.5% or less, and the core layer composed of (B) ( An aqueous resin dispersion (XF1) of resin particles in which the shell layer (P) in which (A) was formed on the surface of Q) was formed was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain resin particles (F1) with a volatile content of 0.5% or less.

Example 2
(P) is formed on the surface of (Q) in the same manner as in Example 1, except that 20 parts of [fine particle dispersion W2] is used instead of 30.8 parts of [fine particle dispersion W1] of Example 1. An aqueous resin dispersion (XF2) of resin particles and resin particles (F2) were obtained.

Example 3
In the same manner as in Example 1 except that 27.2 parts of [Fine Particle Dispersion Liquid W3] is used instead of 30.8 parts of [Fine Particle Dispersion Liquid W1] in Example 1, (P) An aqueous resin dispersion (XF3) of resin particles formed with resin particles (F3) was obtained.

Example 4
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1 except that 60 parts of [Resin Solution 2] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF4) and resin particles (F4) were obtained.

Example 5
(P) is formed on the surface of (Q) in the same manner as in Example 4 except that 20 parts of [fine particle dispersion W2] is used instead of 30.8 parts of [fine particle dispersion W1] of Example 4. A resin resin aqueous dispersion (XF5) and resin particles (F5) were obtained.

Example 6
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1, except that 60 parts of [Resin Solution 3] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF6) and resin particles (F6) were obtained.

Example 7
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1, except that 60 parts of [Resin Solution 4] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF7) and resin particles (F7) were obtained.

Example 8
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1, except that 60 parts of [Resin Solution 5] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF8) and resin particles (F8) were obtained.

Example 9
(P) is formed on the surface of (Q) in the same manner as in Example 1 except that 15 parts of [fine particle dispersion W4] is used instead of 30.8 parts of [fine particle dispersion W1] of Example 1. An aqueous resin dispersion (XF9) of resin particles and resin particles (F9) were obtained.

Example 10
(P) is formed on the surface of (Q) in the same manner as in Example 1, except that 70 parts of [fine particle dispersion W5] is used instead of 30.8 parts of [fine particle dispersion W1] of Example 1. An aqueous resin dispersion (XF10) of resin particles and resin particles (F10) were obtained.

Example 11
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1 except that 60 parts of [Resin Solution 6] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF11) and resin particles (F11) were obtained.

Example 12
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1 except that 60 parts of [Resin Solution 7] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF12) and resin particles (F12) were obtained.

Comparative Example 1
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1, except that 60 parts of [Resin Solution 8] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF13) and resin particles (F13) were obtained.

Comparative Example 2
(P) is formed on the surface of (Q) in the same manner as in Comparative Example 1, except that 20 parts of [Fine Particle Dispersion Liquid W2] is used instead of 30.8 parts of [Fine Particle Dispersion Liquid W1] of Comparative Example 1. An aqueous resin dispersion (XF14) of resin particles and resin particles (F14) were obtained.

Comparative Example 3
(P) on the surface of (Q) in the same manner as in Comparative Example 1 except that 27.2 parts of [Fine Particle Dispersion Liquid W3] is used instead of 30.8 parts of [Fine Particle Dispersion Liquid W1] of Comparative Example 1. An aqueous resin dispersion (XF15) of resin particles formed with resin particles (F15) was obtained.

Comparative Example 4
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1 except that 60 parts of [Resin Solution 9] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF16) and resin particles (F16) were obtained.

Comparative Example 5
Resin particles in which (P) is formed on the surface of (Q) in the same manner as in Example 1 except that 60 parts of [Resin Solution 10] is used instead of 60 parts of [Resin Solution 1] in Example 1. Aqueous resin dispersion (XF17) and resin particles (F17) were obtained.

Example of measuring physical properties The resin particles (F1) to (F17) obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were dispersed in water, and the particle size distribution was measured with a Coulter counter. Further, the average circularity, charging characteristics, heat-resistant storage stability, and low-temperature fixability of the resin particles were measured. The results are shown in Table 1. In addition, (circle) means the inside of the square ABCD of Claim 4, and x means the exterior.

  The measuring method of charging characteristics, heat-resistant storage stability, meltability, and image adhesion is as follows. In addition, all the physical property measuring methods described in Table 1 are based on the above methods.

[Charging characteristics] (Charge amount)
In a 50 cc glass bottle with a stopper, 0.5 g of resin particles and 10 g of iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.) are precisely weighed, stoppered and placed in an atmosphere of 23 ° C. and 50% RH. Set in a turbula shaker mixer (manufactured by Willy a Baschofen) and stir for 2 minutes at 90 rpm. 0.2 g of the mixed powder after stirring is loaded into a blow-off powder charge measuring device (TB-203, manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel mesh is set, and the blow pressure is 10 KPa and the suction pressure is 5 KPa. Then, the charge amount of the residual iron powder is measured, and the charge amount of the resin particles is calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics.

[Heat resistant storage stability 1]
Resin particles were allowed to stand for 15 hours in a dryer controlled to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.
[Heat-resistant storage stability 2]
A 100 ml capacity plastic cup containing 2 g of resin particles was placed in a dryer controlled to 50 ° C. for 72 hours and evaluated according to the following criteria based on the degree of blocking.
A: When the plastic cup after the test is tilted to 45 degrees, the resin particles flow.
○: Resin particles do not flow even if the plastic cup after the test is tilted 45 degrees, but 4
Resin particles when gently stimulated by tapping the bottom of the cup while tilted at 5 degrees
Flows.
△: The above conditions of ◎ and ○ are not satisfied, but it is easy to apply force by gently picking it with your fingers.
scatter.
X: Blocking occurs and does not return to the state of the resin particles before the test even when force is applied.

[Melting property]
After adding 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well, the powder is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time As a method for placing the body on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). The temperature at which cold offset was generated when passing through a roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.

(Image adhesion)
After adding 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well, the powder is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time As a method for placing the body on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). A fixed image created by passing through a roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² is bent at a constant load (500 g weight). The image density was measured (using a reflection densitometer “RD-19” manufactured by Gretag Macbeth), and the temperature at which the image density (after folding) / image density (before folding) was 60% was defined as the image contact temperature.

  Since the resin dispersion and resin particles of the present invention have a uniform particle size and are excellent in charging characteristics, heat-resistant storage stability, etc., spacers for manufacturing electronic parts such as slush molding resins, powder paints, and liquid crystals, electronic measuring instruments This is extremely useful as a standard particle, a toner used for electrophotography, electrostatic recording, electrostatic printing, etc., various hot melt adhesives, and other resin particles used for molding materials.

It is a graph which shows the relationship between the sp value difference (K) of (a) and (b) in this invention, and the natural logarithm ln (Mw) (H) of the weight average molecular weight (Mw) of (a). It is a conceptual diagram which shows the flowchart in the flow tester measurement of a resin particle.

Claims (10)

The aqueous dispersion (W) of the resin particles (A) made of the resin (a) and the resin (b) or an organic solvent solution thereof are mixed, and (b) or the organic solvent solution is dispersed in (W). The aqueous resin particles (C1) obtained by forming the resin particles (B) comprising (b) in the aqueous dispersion of (A) and having (A) attached to the surface of (B) Dispersion (X1), wherein (b) is formed in the presence of at least one titanium-containing catalyst (e) represented by the following general formula (I) and / or polyester resin (b1) and / or ( An aqueous resin dispersion comprising a resin (b2) containing b1) as a structural unit.
Ti (-X) m (-OR) n (I)
[Wherein, R represents H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. X is a residue obtained by removing one carboxyl group H from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, other carboxyl groups are polycondensed in the molecule with an OR group in the same molecule. A structure may be formed, or a structure containing 2 to 5 Ti atoms may be formed by polycondensation between an OR group of another molecule and the molecule. m = 1 to 3 and n = 1 to 3, and the sum of m and n is 4. ] 2. (a) has a softening onset temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature and the outflow temperature of 0 to 130 ° C. The aqueous resin dispersion described. The aqueous resin dispersion according to claim 1 or 2, wherein (a) is at least one resin selected from a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl resin. When the difference in sp value (Δsp) between (a) and (b) is K, and the natural logarithm [ln (Mw)] of the weight average molecular weight in (a) is H, the points (K, H) are as follows: The aqueous resin dispersion according to any one of claims 1 to 3, wherein the aqueous resin dispersion is contained inside including a side of a quadrilateral ABCD including four points A, B, C and D.
A (0.3, ln3000), B (1.5, ln1000),
C (1.3, ln200000), D (0.1, ln200000) (A) a sulfonic acid anion group (-SO ₃ ^-) The aqueous resin dispersion according to any one of claims 1 to 4 containing 0.001 to 10% by weight, based on the weight of (a). The aqueous resin dispersion according to any one of claims 1 to 5, wherein (a) contains a constituent unit of the following organic acid metal salt (m) and / or (A) contains the following organic acid metal salt (m). .
Organic acid metal salt (m): One or more salts selected from carboxylates, sulfonates, and phosphates of metals selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr. In the aqueous resin dispersion (X1) according to any one of claims 1 to 6, the resin particles (A) attached to the resin particles (B) are dissolved and / or melted in an organic solvent. The aqueous resin dispersion (X2) comprising the resin particles (C2) obtained by forming the shell layer (P) in which (A) is formed on the surface of the core layer (Q) composed of (B) . The aqueous resin dispersion according to any one of claims 1 to 7, wherein 50 to 90% by weight of (b) is a linear polyester having a weight average molecular weight of 2000 to 12000 in a portion soluble in tetrahydrofuran. Resin particles obtained by removing an aqueous medium from the aqueous resin dispersion according to claim 1. Resin particles according to claim 9, for use in slush molding resins, powder paints, spacers for manufacturing electronic components, standard particles for electronic measuring devices, electrophotographic toners, electrostatic recording toners, electrostatic printing toners or hot melt adhesives. .