JP2014129444A - Resin particles and process for producing resin particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin particles excellent in low-temperature fixability and durability against mechanical stress, and a process for producing the resin particles.SOLUTION: A core-shell shaped resin particles (C) comprises a core layer (P) and a shell layer (Q), wherein (P) contains a crystalline resin (A), (Q) contains an amorphous resin (B), and HLB of (B) is 4.7 or more. A method for producing the resin particles (C) comprises obtaining resin particles (C1) by a step of dispersing a solution (D) of the crystalline resin (A) in and the amorphous resin (B) having an HLB of 4.7 or more in an organic solvent in an aqueous medium (E), and thereafter obtaining resin particles (C) from (C1) by removing the organic solvent from (E), wherein the resin particles (C) are core-shell type resin particles composed of a core layer (P) and a shell layer (Q), wherein (P) contains the crystalline resin (A), (Q) contains the amorphous resin (B), and (C1) satisfies the following conditions. [Conditions] 1<Dv/Dn≤1.4[Dv:(C1) volume average particle diameter (μm) of (C1), Dn: number average particle diameter (μm) of (C1).

Description

  The present invention relates to resin particles and a method for producing resin particles.

Conventionally, resin particles that are used in powder coatings and the like are desired to be melted with low energy and fixed to a substrate. Therefore, there is a strong demand for resin particles having excellent low-temperature fixability that can be fixed at a lower temperature.
As a means for obtaining resin particles having excellent low-temperature fixability, a method of lowering the melt viscosity of resin particles has been known for a long time, and a method of using a crystalline resin as a binder resin to lower the melt viscosity of resin particles. Are known. However, when a crystalline resin and a modified product thereof are used alone as a binder resin, the strength as resin particles is insufficient, and aggregates are easily generated when mixed with other components (Patent Documents 1 and 2).
Therefore, as a means for solving this problem, a method of improving durability by reducing the addition amount of the crystalline resin and increasing the addition amount of the amorphous resin is disclosed (Patent Document 3). However, such a method has insufficient low-temperature fixability.

JP 2007-147927 A JP 2004 197051 A JP 2010-230917 A

  The object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide resin particles excellent in low-temperature fixability and durability against mechanical stress, and a method for producing the resin particles.

The inventors of the present invention have reached the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a core-shell type resin particle (C) composed of a core layer (P) and a shell layer (Q), wherein (P) contains a crystalline resin (A), Resin particles (C) in which Q) contains an amorphous resin (B), and the HLB in (B) is 4.7 or more; the resin (A) having crystallinity and HLB in which HLB is 4.7 or more After obtaining resin particles (C1) by dispersing the solution (D) obtained by dissolving the crystalline resin (B) in an organic solvent in the aqueous medium (E), the organic solvent is removed from (E). And (C1) to obtain resin particles (C), wherein the resin particles (C) are composed of a core layer (P) and a shell layer (Q). (P) contains a crystalline resin (A), (Q) contains an amorphous resin (B), (C1 There is a manufacturing method of the following conditions are satisfied resin particles (C).
[conditions]
1 <Dv / Dn ≦ 1.4
[Dv: Volume average particle diameter (μm) of (C1), Dn: Number average particle diameter (μm) of (C1)]

  The resin particles of the present invention are excellent in low-temperature fixability and durability against mechanical stress.

  The resin particles (C) of the present invention are core-shell type resin particles composed of a core layer (P) and a shell layer (Q), and (P) contains a crystalline resin (A). , (Q) contains the amorphous resin (B), and the HLB of (B) is 4.7 or more.

The crystalline resin (A) in the present invention has a ratio (Tm / Ta) of the softening point of the resin (hereinafter abbreviated as Tm) to the maximum peak temperature of heat of fusion (hereinafter abbreviated as Ta) of 0.8 to 0.8. 1.55, which means a resin having a clear endothermic peak rather than a stepwise endothermic change in DSC. Tm and Ta can be measured by the following method.
<Tm measurement method>
Using a Koka flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample is heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger. Is drawn from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger lowering amount (flow value)” and “temperature” is drawn, corresponding to 1/2 of the maximum value of the plunger lowering amount. The temperature is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as Tm.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Denshi Kogyo Co., Ltd.]}.
(A) used for the measurement of Ta is melted at 130 ° C. as a pretreatment, and then the temperature is lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./min. The temperature is lowered at a rate of ° C / min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min and the endothermic change is measured, and a graph of “endothermic amount” and “temperature” is drawn. A temperature indicating the maximum value of the endothermic peak at ° C. is Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, after the above (A) was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, the temperature was increased at a temperature increase rate of 20 ° C./min to measure the endothermic change and draw a similar graph. The temperature corresponding to the maximum peak of heat quantity is defined as the maximum peak temperature (Ta) of heat of fusion.
Ta ′ of the crystalline resin (A) is preferably 40 to 80 ° C., more preferably 45 to 78 ° C., from the viewpoint of low-temperature fixability.
From the viewpoint of low-temperature fixability, the endothermic peak start temperature (endothermic start temperature) in the DSC of the crystalline resin (A) is preferably 30 to 70 ° C, more preferably 32 to 65 ° C.

  The Tm of the crystalline resin (A) is preferably 50 to 150 ° C., more preferably 60 to 120 ° C., from the viewpoint of low-temperature fixability.

Ta of the crystalline resin (A) is preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and most preferably 55 to 87 ° C. from the viewpoint of heat-resistant storage stability.

  (Tm / Ta) of the crystalline resin (A) is 0.8 to 1.55, preferably 0.85 to 1.2, and more preferably 0.9 to 1.15.

The melting start temperature (X) of the crystalline resin (A) is within the temperature range of (Ta ± 30) ° C., preferably within the temperature range of (Ta ± 20) ° C., more preferably (Ta ± 15) ° C. Is within the temperature range.
Specifically, (X) is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.
The melting start temperature (X) of (A) can be measured by the following method.
<Melting start temperature>
Using a Koka-type flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, 1 g of (A) was heated at a rate of temperature increase of 6 ° C./min. A load was applied and extruded from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger descent amount (flow value)” and “temperature” was drawn. The piston was slightly raised due to thermal expansion of the sample. Thereafter, the temperature at the point where the piston clearly starts to descend again is read from the graph, and this value is defined as (X) in (A).

Examples of the crystalline resin (A) in the present invention include a crystalline polyester resin (A1), a crystalline polyurethane resin (A2), a crystalline vinyl resin (A3), and a crystalline polyether resin (A4).
As (A), (A1) to (A4) may be used alone or in combination of two or more.

  As crystalline polyester resin (A1), what has diol (1) and dicarboxylic acid (2) as a structural unit is mentioned.

Examples of the diol (1) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol). , Decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.); number average molecular weight (hereinafter abbreviated as Mn) = 106 to 10,000 alkylene ether glycol ( For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diol having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedi) (Tanol and hydrogenated bisphenol A, etc.); alkylene oxide (hereinafter abbreviated as AO) adduct (addition mole number 2 to 100) of Mn = 100 to 10,000 (for example, 1,4-cyclohexanedi) Ethylene oxide of methanol (hereinafter abbreviated as EO) 10 mol adduct, etc.]; Bisphenols having 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) or polyphenols having 12 to 24 carbon atoms (for example, catechol, hydroquinone) ASO [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 2 to 100) (for example, bisphenol A · EO 2 to 4 mole addition) And bisphenol A · PO 2-4 mol Weight average molecular weight (hereinafter abbreviated as Mw) = 100-5,000 polylactone diol (for example, poly-ε-caprolactone diol, etc.); Mw = 1,000-20,000 polybutadiene diol, etc. Can be mentioned.
Of these, an AO adduct of alkylene glycol and bisphenols is preferred, and an AO adduct of bisphenols and a mixture of an AO adduct of bisphenols and alkylene glycol are more preferred.

Examples of the dicarboxylic acid (2) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); alkene dicarboxylic acids having 4 to 32 carbon atoms. (Eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (eg phthalic acid, isophthalic acid, etc.) , Terephthalic acid and naphthalenedicarboxylic acid) And the like.
Of these, preferred are alkene dicarboxylic acids and aromatic dicarboxylic acids, and more preferred are aromatic dicarboxylic acids.

  (A1) is preferably one having a total carbon number of 10 or more as structural units of the diol (1) and the dicarboxylic acid (2), more preferably from the viewpoint of the durability of the resin particles (C) to mechanical stress. Is preferably 12 or more, and more preferably 14 or more. From the viewpoint of low-temperature fixability when (C) is used as a base particle of an electrophotographic toner, the total carbon number is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Moreover, as dicarboxylic acid (2), the C6-C30 aromatic dicarboxylic acid may be included if needed.

  As the crystalline polyurethane resin (A2), the diol (1) and / or the diamine (3), the diisocyanate (4) as a structural unit (A2-1), and the crystalline polyester resin (A1) And the diol (1) and / or the diamine (3) and the diisocyanate (4) as structural units (A2-2).

Examples of the diamine (3) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines (6 to 20 carbon atoms).
Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine) and polyalkylenes (having 2 to 6 carbon atoms) [diethylene triamine, imino. Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.].
Cycloaliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  Aromatic diamines (having 6 to 20 carbon atoms) include unsubstituted aromatic diamines and alkyl groups (alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n- or isopropyl and butyl groups). Group diamine and the like.

  Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, bis (3 , 4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine and mixtures thereof.

  The aromatic diamine having an alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) includes 2,4- or 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl -2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl -2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl -2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6 -Dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4, '-Diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-diisopropyl- 3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5 5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4 ′ -Diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and mixtures thereof Can be mentioned.

  As the diisocyanate (4), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

  Aromatic diisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate (XDI), α , Α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) ) Or a mixture thereof and a mixture thereof.

Examples of the aliphatic diisocyanate include a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.
Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.
Cycloaliphatic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

  Of the diisocyanates (4), aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are preferred, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferred. .

  The crystalline vinyl resin (A3) is a polymer obtained by homopolymerizing or copolymerizing a monomer having a polymerizable double bond. Examples of the monomer having a polymerizable double bond include the following (5) to (14).

(5) Hydrocarbon having a polymerizable double bond:
(5-1) Aliphatic hydrocarbon having a polymerizable double bond:
(5-1-1) Chain hydrocarbon having a polymerizable double bond:
Alkenes having 2 to 30 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene and octadecene); alkadienes having 4 to 30 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene) 1,6-hexadiene and 1,7-octadiene).
(5-1-2) Cyclic hydrocarbon having a polymerizable double bond:
Mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, and ethylidenebicycloheptene) and mono- or dicycloalkadiene having 5 to 30 carbon atoms [for example, (di) cyclopentadiene and the like].
(5-2) Aromatic hydrocarbon having a polymerizable double bond:
Styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substitution of styrene (for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl naphthalene.

(6) Monomers having a carboxyl group and a polymerizable double bond and their salts:
C3-C15 unsaturated monocarboxylic acid {For example, (meth) acrylic acid ["(meth) acryl" means acryl or methacryl. ], Crotonic acid, isocrotonic acid, cinnamic acid and the like}; C3-C30 unsaturated dicarboxylic acid (anhydride) [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. And monoalkyl (C1-10) esters of unsaturated dicarboxylic acids having 3 to 10 carbon atoms (eg maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracone) Acid monodecyl ester, etc.).
Examples of the salt constituting the monomer salt having a carboxyl group and a polymerizable double bond include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), and ammonium. Examples thereof include salts, amine salts, and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.
Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(7) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxy) Ethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [eg 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) acrylic Do-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid, etc.); poly [n (degree of polymerization, the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.). Oxyalkylene may be used alone or in combination. The addition type may be random addition or block addition.) Sulfate ester of mono (meth) acrylate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Esters etc.]; Compounds represented by the general formulas (1) to (3); and salts thereof.
In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (6) a carboxyl group and a polymerizable double bond is mentioned.

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



CH = CH-CH ₃
｜
R ³ —Ar—O— (R ¹ O) _n SO ₃ H (2)

CH ₂ COOR ⁴
｜
HOSO ₂ CHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3)

In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, and R ¹ O may be used alone or in combination of two or more, and when two or more are used in combination, the bonding form may be random or block. R ² and R ³ are each independently an alkyl group having 1 to 15 carbon atoms; m and n are each independently a number of 1 to 50; Ar is a benzene ring; R ⁴ is substituted with a fluorine atom; Or an alkyl group having 1 to 15 carbon atoms.

(8) Monomer having phosphono group and polymerizable double bond and salt thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as a salt, what was illustrated as a salt which comprises the monomer which has (6) carboxyl group and a polymerizable double bond is mentioned.

(9) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(10) Nitrogen-containing monomer having a polymerizable double bond:
(10-1) Monomer having amino group and polymerizable double bond:
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, and salts thereof.
(10-2) Monomer having a quaternary ammonium base and a polymerizable double bond:
Those obtained by quaternizing the above-mentioned monomer having an amino group and a polymerizable double bond with a quaternizing agent (C1-C12 alkyl chloride, dialkyl sulfuric acid, dialkyl carbonate, benzyl chloride, etc.) Specifically, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethylmethylmorpholinoammonium chloride , (Meth) acryloylaminoethyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylan Chloride, trimethyl-vinylphenyl chloride and vinyl imidazolium trichloride and the like.
(10-3) Monomer having amide group and polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(10-4) A monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(10-5) Monomers having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

(11) A monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

(12) A monomer having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(13) An ester having a polymerizable double bond, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
(13-1) C4-16 ester having a polymerizable double bond:
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -Α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) a Relate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono), such as allyloxybutane and tetrametaallyloxyethane) Acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) Acrylates, 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 and polyethylene glycol di (meth) acrylate, etc.].
(13-2) C3-C16 ether having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(13-3) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(13-4) C2-C16 sulfur-containing compound having a polymerizable double bond:
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

Examples of the crystalline polyether resin (A4) include crystalline polyoxyalkylene polyols.
It does not specifically limit as a manufacturing method of crystalline polyoxyalkylene polyol, It can manufacture by a well-known method.
For example, a method in which a chiral alkylene oxide is subjected to ring-opening polymerization using a catalyst used in usual polymerization of polyoxyalkylene polyols (Journal of the American Chemical Society, 1956, Vol. 78, No. 18, p. 4787). -4792) and ring-opening polymerization of an inexpensive racemic alkylene oxide using a sterically bulky complex having a special chemical structure as a catalyst.
As a method using a special complex, a method in which a compound obtained by contacting a lanthanoid complex and organoaluminum is used as a catalyst (described in JP-A-11-12353), or bimetal-μ-oxoalkoxide and a hydroxyl compound are reacted in advance. And the like (described in JP 2001-521957 A).
In addition, as a method for obtaining a polyoxyalkylene polyol having very high isotacticity, a method using a salen complex as a catalyst (Journal of the American Chemical Society, 2005, Vol. 127, No. 33, p. 11566-11567) Description) and the like.

For example, using a chiral alkylene oxide, as an initiator during the ring-opening polymerization,
When glyco or water is used, a polyoxyalkylene glycol having a hydroxyl group at the terminal and an isotacticity of 50% or more is obtained. The polyoxyalkylene glycol having an isotacticity of 50% or more may be modified such that its terminal is, for example, a carboxyl group. If the isotacticity is 50% or more, the polyoxyalkylene polyol usually has crystallinity.
Examples of the glycol include the diols described above, and examples of the carboxylic acid used for carboxy modification include the dicarboxylic acids described above.

The raw materials used for the production of the crystalline polyoxyalkylene polyol include PO, 1-chlorooxetane, 2-chlorooxetane, 1,2-dichlorooxetane, epichlorohydrin, epibromohydrin, BO, methyl glycidyl ether, 1 , 2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide, cyclohexene oxide, 1,2-hexylene oxide, 3-methyl-1,2-pentylene oxide, 2 , 3-hexylene oxide, 4-methyl-2,3-pentylene oxide, allyl glycidyl ether, 1,2-heptylene oxide, styrene oxide, phenyl glycidyl ether, and the like.
These raw materials may be used alone or in combination of two or more.
Of these, PO, BO, styrene oxide, and cyclohexene oxide are preferable.

  Of the crystalline resins (A), the crystalline polyester resin (A1) and the crystalline polyurethane resin (A2) are preferable, (A2) is more preferable, (A2-2) is particularly preferable, and most preferable. Of (A2-2) has a urethane group in the molecule.

The Mn of the crystalline resin (A) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000.
Mn and Mw of the resin in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection apparatus: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100,
18,100,37,900,96,400,190,000,355,000,
1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The solubility parameter (hereinafter abbreviated as SP value) of the crystalline resin (A) is preferably 7 to 18 (cal / cm ³ ) ^1/2 from the viewpoint of durability against mechanical stress, preferably ^{8~14 (cal / cm 3) 1/2} , particularly preferably ^{9~14 (cal / cm 3) 1/2} .
In addition, SP value in this invention is the method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

  The glass transition temperature (hereinafter abbreviated as Tg) of the crystalline resin (A) is preferably 40 to 80 ° C., more preferably 43 to 75 ° C., from the viewpoint of durability against mechanical stress. In addition, Tg can be measured by the method (DSC) prescribed | regulated to ASTM D3418-82 using "DSC20, SSC / 580" [made by Seiko Electronic Industry Co., Ltd.].

In the method for producing the resin particles (C) of the present invention described later, as the crystalline resin (A), those obtained from the precursor (A0) may be used.
The precursor (A0) is not particularly limited as long as it can be converted into the resin (A) by a chemical reaction, and (A) is a crystalline polyester resin (A1) or a crystalline polyurethane resin (A2). , (A0) includes a combination of a prepolymer (α) having a reactive group and a curing agent (β).
When (A) is a crystalline vinyl resin (A3), examples of (A0) include the monomers (5) to (14).
Among (A0), preferred from the viewpoint of productivity is a combination of a prepolymer (α) having a reactive group and a curing agent (β).

  When a combination of a prepolymer (α) having a reactive group and a curing agent (β) is used as the precursor (A0), the “reactive group” possessed by (α) is a reaction with the curing agent (β). A possible group. In this case, as a method for forming the precursor (A0) by reacting the precursor (A0), (α) and (β) are dispersed in a dispersion medium (W) described later, and (α) and (( and a method of forming (A) by reacting β).

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1] A combination in which the reactive group of (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and (β) is an active hydrogen group-containing compound (β1).
[2] A combination in which the reactive group of (α) is an active hydrogen-containing group (α2), and (β) is a compound (β2) that can react with the active hydrogen-containing group.
In the combination [1], as the functional group (α1) capable of reacting with the active hydrogen compound, an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and An acid halide group (α1e) and the like can be mentioned. Of these, (α1a), (α1b) and (α1c) are preferred, and (α1a) and (α1b) are more preferred.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes (acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.); lactams (γ-butyrolactam, ε-caprolactam and γ-valerolactam) C1-20 aliphatic alcohols (ethanol, methanol, octanol, etc.); phenols (phenol, m-cresol, xylenol, nonylphenol, etc.); active methylene compounds (acetylacetone, ethyl malonate, and ethyl acetoacetate) Etc.); basic nitrogen-containing compounds (N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.); and mixtures of two or more thereof And the like.
Of these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

Examples of the structural unit of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy) and (αz) are preferred, and (αx) and (αz) are more preferred.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide.
Examples of polyester (αx) include polycondensates of diol (1) and dicarboxylic acid (2), polylactones (ring-opening polymerization products of ε-caprolactone), and the like.
Examples of the epoxy resin (αy) include addition condensates of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include a polyaddition product of diol (1) and diisocyanate (4) and a polyaddition product of polyester (αx) and diisocyanate (4).

As a method of incorporating reactive groups into polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent at the terminal by using one of two or more constituents in excess.
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of two or more structural components How to react.
Etc.
In the method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, and An isocyanate group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is preferably such that the ratio of the polyol component and the polycarboxylic acid component is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.
In the method [2], an isocyanate group-containing prepolymer can be obtained by reacting the preprimer obtained in the method [1] with a polyisocyanate, and a blocked polyisocyanate can be reacted to react with a blocked isocyanate group. A prepolymer is obtained, an epoxy group-containing prepolymer is obtained by reacting a polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting a polyacid anhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2. 5/1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2 on average. .5. By setting it in the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, at 100 ° C. Setting it to 200 Pa · s or less is preferable in that resin particles (C) having a narrow particle size distribution can be obtained.

Examples of the active hydrogen group-containing compound (β1) include diamine (β1a), diol (β1b), dimercaptan (β1c) and water which may be blocked with a detachable compound. Among these, (β1a), (β1b) and water are preferable, (β1a) and water are more preferable, and blocked polyamines and water are particularly preferable.
Examples of (β1a) include the same as the diamine (3). Preferred as (β1a) is 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.

  Examples of the case where (β1a) is a polyamine blocked with a detachable compound include ketimine compounds obtained from the polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And aldimine compounds, enamine compounds and oxazolidine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde and the like).

Examples of the diol (β1b) include those similar to the diol (1), and preferred ranges thereof are also the same.
Examples of dimercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (β1) at a certain ratio, (A) can be adjusted to a predetermined molecular weight.
As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) And monophenols (such as butyl mercaptan and lauryl mercaptan); monoisocyanates (such as lauryl isocyanate and phenyl isocyanate); and monoepoxides (such as butyl glycidyl ether).

The active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2] includes an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Among these, (α2a), (α2b) and (α2e) are preferable, and (α2b) is more preferable.
Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include diisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyacid anhydride (β2d), and polyacid halide (β2e). . Of these, (β2a) and (β2b) are preferred, and (β2a) is more preferred.

  Examples of the diisocyanate (β2a) include those similar to the diisocyanate (4), and preferred ones are also the same.

Examples of the diepoxide (β2b) include aromatic diepoxy compounds and aliphatic diepoxy compounds.
Examples of aromatic diepoxy 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 ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-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, phenol or Glycidyl ether of cresol novolak resin, glycidyl ether of limonenephenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde And a polyglycidyl ether body of polyphenol obtained by a condensation reaction of resorcin and acetone.
Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine.
Further, as the aromatic polyepoxy compound, p-aminophenol triglycidyl ether, tolylene diisocyanate or a diglycidyl urethane compound obtained by the addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting the two reactants with a polyol. And glycidyl group-containing polyurethane (pre) polymer and bisphenol A AO adduct diglycidyl ether.

  Examples of the aliphatic polyepoxy compound include a chain aliphatic polyepoxy compound and a cyclic aliphatic polyepoxy compound.

Examples of chain aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, 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 Examples include 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. It is done.
Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
Examples of the aliphatic polyepoxy compound include a copolymer of diglycidyl ether and glycidyl (meth) acrylate.

Examples of the cycloaliphatic polyepoxy compounds include trisglycidyl melamine, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4 -Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6 -Methylcyclohexylmethyl) butylamine and dimer acid diglycidyl ester.
Moreover, as a cycloaliphatic polyepoxy compound, the hydrogenated thing of the said aromatic polyepoxide compound is also mentioned.

  Examples of the dicarboxylic acid (β2c) include those similar to the dicarboxylic acid (2), and preferred ones are also the same.

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

  When (A) is a crystalline vinyl resin (A3) and the monomers (5) to (14) are used as (A0), as a method of reacting (A0) to (A), For example, a method in which an oil phase containing an oil-soluble initiator and a monomer is dispersed and suspended in an organic solvent described later, and a radical polymerization reaction is performed by heating, and the like can be mentioned.

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

Oil-soluble peroxide polymerization initiator (I):
Acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, cumene peroxide, and the like.

Oil-soluble azo polymerization initiator (II):
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobis (2-methylpropionate) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like.

Non-aqueous redox polymerization initiator (III):
Oil-soluble peroxides such as hydroperoxides, dialkyl peroxides and diacyl peroxides, and oil-soluble reducing agents such as tertiary amines, naphthenates, mercaptans, organometallic compounds (such as triethylaluminum, triethylboron and diethylzinc) And in combination.

The crystalline resin (A) preferably satisfies the following condition 1 in the viscoelasticity measurement of (A) from the viewpoint of low-temperature fixability.
[Condition 1] 1 × 10 ² ≦ G ′ (Ta + 20) ≦ 9 × 10 ⁴ [Pa]
{G ′ (Ta + 20): Storage modulus of (A) at (Ta + 20) ° C. [Pa]}
The crystalline resin (A) satisfying [Condition 1] can be obtained by adjusting the ratio of the crystalline component in (A), adjusting the weight average molecular weight, or the like. For example, when the ratio of the crystalline part (b) and the ratio of the crystalline component described later are increased, the value of G ′ (Ta + 20) decreases. Further, the value of G ′ (Ta + 20) is decreased by decreasing the weight average molecular weight of (A).

The crystalline resin (A) preferably satisfies the following [Condition 2] and satisfies [Condition 2-1] with respect to the loss elastic modulus G ″ and the melting start temperature (X) in the viscoelasticity measurement of (A). More preferably, [Condition 2-2] is satisfied.
[Condition 2] 2.0 <| logG "(X + 20) -logG" (X) |
{G ″ (X): Loss elastic modulus [Pa] of (A) at X ° C., G ″ (X + 20): Loss elastic modulus [Pa] of (A) at (X + 20) ° C.}
When the melting start temperature (X) of the crystalline resin (A) is within the above range and [Condition 2] is satisfied, the low viscosity speed of (A) is increased, and the low temperature side and high temperature side of the fixing temperature region are increased. Can obtain the same image quality. In addition, the process from the start of melting to the fixable viscosity is accelerated, which is advantageous for obtaining excellent low-temperature fixability. [Condition 2] is an index of the sharp melt property of (A), which indicates how fast it can be fixed with less heat, and was obtained experimentally.
The crystalline resin (A) satisfying the range of the melting start temperature (X) and [Condition 2] can be obtained by adjusting the ratio of the crystalline component in the constituent components of (A). For example, when the ratio of the crystalline component is increased, the temperature difference between (Ta) and (X) is decreased.

The storage elastic modulus G ′ and loss elastic modulus G ″ of the crystalline resin (A) can be measured using a dynamic viscoelasticity measuring device “RDS-2” (Rheometric Scientific) under a frequency of 1 Hz. it can.
Viscoelasticity measurement of (A) is carried out by setting (A) on the jig of the measuring device, raising the temperature to (Ta + 30) ° C. of (A) and bringing it into close contact with the jig, and then changing from (Ta + 30) ° C. to (Ta− 30) Decrease in temperature at a rate of 0.5 ° C./min to 30 ° C., leave at (Ta-30) ° C. for 1 hour, then decrease to (Ta-10) ° C. at a rate of 0.5 ° C./min. (Ta-10) The sample is allowed to stand at 1 ° C. for 1 hour, and after sufficiently allowing crystallization to proceed, measurement is performed using this. The measurement temperature range is 30 ° C. to 200 ° C., and by measuring the binder melt viscoelasticity between these temperatures, it can be obtained as temperature-G ′ and temperature-G ″ curves.

The amorphous resin (B) in the present invention is the same as the crystalline polyester resin (A1), crystalline polyurethane resin (A2) and crystalline vinyl resin (A3) exemplified as the crystalline resin (A). A resin having a composition in which the ratio of Tm to Ta (Tm / Ta) is greater than 1.55.
Among the amorphous resins (B), those selected from the group consisting of amino groups, quaternary ammonium bases, sulfonic acid (salt) groups, and phosphoric acid (salt) groups are preferable from the viewpoint of durability against mechanical stress. A resin having one or more groups. Note that sulfonic acid (salt) means sulfonic acid or sulfonate, and phosphoric acid (salt) means phosphoric acid or phosphate.
As a specific example of the preferred amorphous resin (B), (B) having an amino group is exemplified by “(10-1) polymerization with amino group exemplified as a monomer constituting the crystalline vinyl resin (A3)”. Resin having a monomer having an ionic double bond ”as a constituent monomer.
As (B) having a quaternary ammonium base, “(10-2) a monomer having a quaternary ammonium base and a polymerizable double bond” exemplified as a monomer constituting the crystalline vinyl resin (A3). As a constituent monomer, a resin may be used.
Examples of (B) having a sulfonic acid (salt) group include “(7) monomers having a polymerizable double bond and a sulfo group and a monomer having a crystalline vinyl resin (A3)”. A resin having “salt” as a constituent monomer may be mentioned.
As (B) having a phosphoric acid (salt) group, “(8) monomers having a phosphono group and a polymerizable double bond and salts thereof exemplified as monomers constituting the crystalline vinyl resin (A3)” ”As a constituent monomer.

The amorphous resin (B) in the present invention has an HLB of 4.7 or more, and is preferably 5.0 to 10.0, more preferably 7.0 to 9 from the viewpoint of durability against mechanical stress. .0. HLB is a value calculated by the following equation from the ratio of the nonpolar value (I) and the organic value (O) in the organic conceptual diagram.
HLB = [inorganic value (I) / organic value (O)] × 10
Specifically, it can be calculated using the nonpolar value (I) and the organic value (O) described in “Systematic Organic Qualitative Analysis Mixture” written by Satoshi Fujita, Kazama Shobo, published in 1974.

  Mn of the amorphous resin (B) is preferably 500 to 15,000, and more preferably 700 to 10,000.

  The Tg of the amorphous resin (B) is preferably 40 to 85 ° C, more preferably 43 to 75 ° C, from the viewpoint of durability against mechanical stress.

The SP value of the amorphous resin (B) is preferably 9 to 14 (cal / cm ³ ) ^1/2 , more preferably 10 to 13.5 (cal / cm ³ ) ^1/2 , and particularly preferably. Is 11 to 13 (cal / cm ³ ) ^1/2 .

The crystalline resin (A) in the present invention is exemplified by the crystalline polyester resin (A1), the crystalline polyurethane resin (A2), the crystalline vinyl resin (A3) and the crystalline polyether resin exemplified as the above (A). A4) and a resin composed only of a crystalline part (a) selected from the composite resin may be used, or an amorphous substance composed of one or more crystalline parts (a) and an amorphous resin (B). Although it may be a block resin having one or more active parts (b), it is preferably a block resin composed of (a) and (b) from the viewpoint of low-temperature fixability.
The crystalline part (a) is preferably a crystalline polyester resin (A1), a crystalline polyurethane resin (A2), or a crystalline polyether resin (A4).
The amorphous part (b) is preferably an amorphous polyester resin or an amorphous polyurethane resin.

When the crystalline resin (A) is a block resin composed of a crystalline part (a) and an amorphous part (b), (a) and (b) consider the reactivity of each terminal functional group Then, the use or non-use of the binder is selected, and when the binder is used, the binder type suitable for the terminal functional group is selected, (a) and (b) are bonded, and the block resin and can do.
When the binder is not used, the reaction between the terminal functional group of (A) that forms (a) and the terminal functional group of (B) that forms (b) proceeds while heating and reducing pressure as necessary. In particular, in the case of a reaction between an acid and an alcohol or a reaction between an acid and an amine, if the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high, the reaction proceeds smoothly. The reaction temperature is preferably 180 ° C to 230 ° C.
When binders are used, various binders can be used. Examples of the binder include the diol (1), dicarboxylic acid (2), diamine (3), diisocyanate (4), and polyepoxide.

Examples of the method for combining (a) and (b) include dehydration reaction and addition reaction of (a) and (b).
Examples of the dehydration reaction include a reaction in which both (a) and (b) have a hydroxyl group and these are bonded with a binder [for example, dicarboxylic acid (2)]. The dehydration reaction can be carried out at a reaction temperature of 180 to 230 ° C. without solvent.
As an addition reaction, both (a) and (b) have a hydroxyl group and these are bonded with a binder [for example, diisocyanate (4)], or one of (a) and (b) has a hydroxyl group. In the case where the other is a resin having an isocyanate group, a reaction for bonding them without using a binder can be mentioned. The addition reaction can be carried out at a reaction temperature of 80 ° C. to 150 ° C. by dissolving them in a solvent that can dissolve both (a) and (b) and adding a binder if necessary.

  When the crystalline resin (A) is a block resin composed of (a) and (b), the content of (a) in (A) is preferably 50 to 99% by weight, Preferably it is 55 to 98% by weight, particularly preferably 60 to 95% by weight, most preferably 62 to 80% by weight. When the content of (a) is in the above range, the crystallinity of (A) is not impaired, and the low-temperature fixability, storage stability, and gloss of the toner are favorable.

  The weight ratio of the crystalline resin (A) and the amorphous resin (B) constituting the resin particles (C) is preferably 30/70 to 99/1 from the viewpoint of durability against mechanical stress. More preferably, it is 40 / 60-90 / 10.

  The absolute value of the difference in SP value between the crystalline resin (A) and the amorphous resin (B) constituting the resin particles (C) is preferably 1.2 or more from the viewpoint of durability against mechanical stress. More preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.5.

The volume average particle diameter of the resin particles (C) is preferably 0.0005 to 30 μm, more preferably 0.01 to 20 μm, and particularly preferably 0.02 to 10 μm.
In addition, the volume average particle diameter of (C) can be measured by the same method as the measurement of the median diameter of the release agent (B).

  The resin particles (C) preferably have an average circularity of 0.94 to 1.0, more preferably 0.95 to 1.0, particularly preferably 0, from the viewpoints of fluidity and melt leveling. 96-1.0. The average circularity in (C) is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. The closer the numerical value is to 1.0, the closer to a true sphere. means. The average circularity of (C) can be measured using a flow type particle image analyzer “FPIA-2000” [manufactured by Sysmex Corporation].

The method for producing the resin particles (C) of the present invention includes a solution (D) obtained by dissolving a crystalline resin (A) and an amorphous resin (B) having an HLB of 4.7 or more in an organic solvent. After obtaining resin particles (C1) by the step of dispersing in (E), the organic solvent is removed from (E) to obtain resin particles (C) from (C1).
The crystalline resin (A) and the amorphous resin (B) in the method for producing the resin particles (C) of the present invention are the same as those described above.

Organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic hydrocarbon solvents (n-hexane, n-heptane, n-decane, mineral spirits, cyclohexane, etc.); halogen solvents (chlorinated) Methyl, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc.); ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, methoxybutyl acetate) , Methyl cellosolve acetate, ethyl cellosolve acetate, methyl pyruvate and ethyl pyruvate); ether solvents (diethyl ether, tetrahydrofuran, dioxane, dioxolane, ethyl cellosolve, butyl cellosolve, ethylene glycol) Coal monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.); ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.); alcohol solvents (methanol, ethanol, etc.) , N-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol and trifluoroethanol); amide solvents (dimethylformamide and Dimethylacetamide, etc.); sulfoxide solvent (dimethylsulfoxide, etc.); heterocyclic compound solvent (N-methylpyrrolidone, etc.) These mixed solvent of two or more thereof. Moreover, the mixed solvent of these organic solvents, alcohol solvent, or water can also be used.
Of these, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone and tetrahydrofuran are preferred.

The solution (D) is obtained by dissolving the crystalline resin (A) and the amorphous resin (B) in an organic solvent.
The solution (D) can further contain additives (coloring agent, charge control agent, antioxidant, anti-blocking agent, heat stabilizer, fluidizing agent, etc.).

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitonianiline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o It mentioned tetrazole brown B and oil pink OP, etc., and these may be mixed alone or two or more.
The content of the colorant is preferably 0.5 to 15% by weight based on the weight of (A).

As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.
The content of the charge control agent is preferably 0 to 5% by weight based on the weight of (A).

As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, and barium carbonate.
The content of the fluidizing agent is preferably 0 to 10% by weight based on the weight of (A).

As an aqueous medium (E), if it is the liquid which has water as an essential component, it can be used without a restriction | limiting, The aqueous solution etc. which made the water contain surfactant are mentioned.
As the surfactant, a known surfactant (for example, a surfactant described in JP-A No. 2004-124059) can be used.

By the step of dispersing the crystalline resin (A) and the amorphous resin (B) having an HLB of 4.7 or more dissolved in an organic solvent in the aqueous medium (E), resin particles ( C1) is obtained.
(C1) satisfies the following conditions.
[conditions]
1 <Dv / Dn ≦ 1.4
[Dv: Volume average particle diameter (μm) of (C1), Dn: Number average particle diameter (μm) of (C1)]
Further, from the viewpoint of durability against mechanical stress, the following condition 1 is preferably satisfied, and the following condition 2 is more preferably satisfied.
[Condition 1]
1.05 <Dv / Dn ≦ 1.3
[Condition 2]
1.08 <Dv / Dn ≦ 1.25
Dv and Dn in (C1) are a laser particle size distribution measuring device “LA-920” [manufactured by Horiba, Ltd.] and “Multisizer III” [manufactured by Beckman Coulter, Inc.], and a laser Doppler method as an optical system. “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), “LB-550” (manufactured by Shimadzu Corporation) using a light scattering method, and the like.

There is no restriction | limiting in particular as a method to disperse | distribute solution (D) in aqueous medium (E), For example, the method of disperse | distributing (D) in (E) using a disperser is mentioned.
The disperser is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a batch emulsifier {“homogenizer” (manufactured by IKA), “polytron” (manufactured by Kinematica) and “ TK Auto Homo Mixer "[made by Tokushu Kika Kogyo Co., Ltd.], etc.}, Continuous Emulsifier {" Ebara Milder "[Made by Ebara Corporation]," TK Filmix "," TK Pipeline Homo Mixer " [Made by Koki Kogyo Kogyo Co., Ltd.], “Colloid Mill” [Made by Shinko Pantech Co., Ltd.], “Slasher”, “Trigonal Wet Fine Crusher” [Made by Suntec Co., Ltd.], “Capitol” (Eurotech) Etc.), “Fine Flow Mill” [manufactured by Taiheiyo Kiko Co., Ltd.], etc.), high-pressure emulsifier {“Microfluidizer” [manufactured by Mizuho Industry Co., Ltd.], “Nanomizer” [SGS Njiniaring Co., Ltd.] and "APV Gaurin" (manufactured by Gaurin Co., Ltd.)}, membrane emulsifier {"membrane emulsifier" [manufactured by Chilling Industries Co., Ltd.]}, vibration emulsifier {"Vibro mixer" Etc.}, an ultrasonic emulsifier {“ultrasonic homogenizer” (manufactured by Branson), etc.}, and the like.

After obtaining the resin particles (C1), the organic solvent is removed from the aqueous medium (E) to obtain resin particles (C) from (C1).
(C1) is a resin particle in a state where the crystalline resin (A) and the amorphous resin (B) are mixed. In the step of removing the organic solvent from (E), (C1) When B) is oriented around (A), a core layer (P) containing (A) and a shell layer (Q) containing (B) are formed, and core-shell type resin particles (C ) Is possible.
(E) There is no restriction | limiting in particular as a method of removing an organic solvent from inside, The method of removing by reduced pressure is mentioned.

In the method for producing resin particles (C) of the present invention, the resin particles (C) are separated from (E) by passing through the step of removing the aqueous medium (E) after the step of removing the organic solvent. Can do.
Although it does not specifically limit as a method of removing (E), For example, the method of removing by reduced pressure and the method of performing solid-liquid separation using filtration and / or a centrifuge, and drying are mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these.

<Production Example 1> [Synthesis of crystalline part (a-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 683.8 parts by weight of sebacic acid, 436.9 parts by weight of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction was performed for 4 hours while distilling off the water generated under a nitrogen stream, and further the reaction was performed while distilling off the water under a reduced pressure of 0.007 to 0.026 MPa. I took it out. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a crystalline part (a-1). The melting point of (a-1) was 67 ° C., Mw was 12,000, and the hydroxyl value was 30.

<Production Example 2> [Synthesis of crystalline part (a-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe, a thermometer, and a nitrogen introduction pipe, 884.0 parts by weight of dodecanedioic acid, 741.2 parts by weight of ethylene glycol, and titanium dihydroxybis (triethanol as a condensation catalyst) Aminate) 1 part by weight was added, heated to 180 ° C., reacted for 10 hours while distilling off the water generated in the nitrogen stream at the same temperature, and then gradually heated to 220 ° C. under a nitrogen stream. The reaction is carried out for 4 hours while distilling off the water and ethylene glycol produced in the above, and further the reaction is carried out while distilling off the water and ethylene glycol under a reduced pressure of 0.007 to 0.026 MPa, when the Mw becomes 12,000. I took it out. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a crystalline part (a-2). The melting point of (a-2) was 85 ° C., Mw was 12,000, and the hydroxyl value was 30.

<Production Example 3> [Synthesis of Crystalline Part (a-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 756.6 parts by weight of sebacic acid, 377.1 parts by weight of 1,4-butanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolamitate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water generated under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off water and 1,4-butanediol generated under a nitrogen stream, and further while distilling off water and 1,4-butanediol under a reduced pressure of 0.007 to 0.026 MPa. It was taken out when Mw reached 9,000. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a crystalline part (a-3). The melting point of (a-4) was 61 ° C., Mw was 9,000, and the hydroxyl value was 41.

<Production Example 4> [Synthesis of Crystalline Resin (A-1)]
139 parts by weight of tolylene diisocyanate and 250 parts by weight of methyl ethyl ketone are charged into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer so that the water content in this solution becomes 0.06% by weight. Water was added. To this solution, 111 parts by weight of cyclohexanedimethanol was added and reacted at 80 ° C. for 12 hours to obtain an amorphous part (a′-1) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 362 parts by weight of (a-1) and 362 parts by weight of methyl ethyl ketone are charged, the temperature is raised to 60 ° C., and the temperature is maintained for 2 hours. After stirring and dissolving, water was added so that the water content in the solution was 0.06% by weight. After confirming dissolution, 276 parts by weight of (a′-1) was added, and the temperature was raised to 80 ° C. and reacted for 3 hours to obtain a methyl ethyl ketone solution of crystalline resin (A-1). Subsequently, (A-1) was obtained by removing methyl ethyl ketone. Table 1 shows the physical properties of (A-1).

<Production Example 5> [Synthesis of Crystalline Resin (A-2)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 140 parts by weight of hexamethylene diisocyanate and 250 parts by weight of methyl ethyl ketone are added so that the water content in this solution becomes 0.06% by weight. Water was added. To this solution, 110 parts by weight of cyclohexanedimethanol was added and reacted at 80 ° C. for 12 hours to obtain an amorphous part (a′-2) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 410 parts by weight of (a-2) and 410 parts by weight of methyl ethyl ketone are charged, the temperature is raised to 60 ° C., and the temperature is maintained for 2 hours. After stirring and dissolving, water was added so that the water content in the solution was 0.06% by weight. After confirming dissolution, 180 parts by weight of (a′-2) was added, the temperature was raised to 80 ° C., and the reaction was performed at the same temperature for 5 hours to obtain a methyl ethyl ketone solution of crystalline resin (A-2). Subsequently, (A-2) was obtained by removing methyl ethyl ketone. Table 1 shows the physical properties of (A-2).

<Production Example 6> [Synthesis of Crystalline Resin (A-3)]
(A-3) 468 parts by weight and 500 parts by weight of methyl ethyl ketone are charged into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, heated to 60 ° C., and stirred at the same temperature for 2 hours. After dissolution, water was added so that the water content in the solution was 0.06% by weight. After confirming dissolution, 32 parts by weight of isophorone diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 8 hours to obtain a methyl ethyl ketone solution of crystalline resin (A-3). Subsequently, methyl ethyl ketone was removed to obtain (A-3). Table 1 shows the physical properties of (A-3).

<Production Example 7> (Production of colorant dispersion)
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 557 parts by weight of propylene glycol (17.5 moles), 569 parts by weight of dimethyl terephthalate (7.0 moles) Then, 184 parts by weight (3.0 parts by mole) of adipic acid and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, and the reaction was performed at 180 ° C. for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight (5.5 mole parts). Next, the mixture is cooled to 180 ° C., 121 parts by weight (1.5 mol parts) of trimellitic anhydride is added, and after 2 hours of reaction under normal pressure sealing, the reaction is continued at 220 ° C. and normal pressure until the softening point is 180 ° C. A polyester resin (Mn = 8,500) was obtained.
Into a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solsper's 28000” [manufactured by Avicia Co., Ltd.], 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate were added and stirred uniformly. After the dispersion, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm.

<Production Example 8> (Production of modified wax)
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sunwax LEL-400” [softening point: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 parts by weight were added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring. At the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate, and xylene 119 A part by weight of the mixed solution was added dropwise over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The modified wax had a graft chain SP value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1,900, Mw of 5,200, and Tg of 56.9 ° C.

<Production Example 9> [Production of release agent dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 1 part by weight of the modified wax obtained in 8 and 33 parts by weight of ethyl acetate were added, the temperature was raised to 78 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then cooled to 30 ° C. over 1 hour to obtain paraffin wax. Crystallization was performed in the form of fine particles, and further wet pulverized with Ultraviscomil (manufactured by IMEX) to obtain a release agent dispersion. The volume average particle size of the release agent was 0.25 μm.

<Production Example 10> (Production of fine particle dispersion)
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 690.0 parts by weight of water, sodium salt of ethylene oxide methacrylate adduct sulfate “ELEMINOL RS-30” [Sanyo Kasei Industrial Co., Ltd.] 9.0 parts by weight, 90.0 parts by weight of styrene, 90.0 parts by weight of methacrylic acid, 110.0 parts by weight of butyl acrylate and 1.0 part by weight of ammonium persulfate were charged at 350 rpm. When stirring for 15 minutes, a white emulsion was obtained. Next, the temperature was raised to 75 ° C., and the reaction was carried out at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). [Fine particle dispersion 1] was obtained. The volume average particle diameter of the particles dispersed in the fine particle dispersion 1 was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.), and 0.1 μm. Met. A part of [Fine Particle Dispersion 1] was taken out and Tg and Mw were measured. As a result, Tg was 65 ° C. and Mw was 150,000.

<Production Example 11> (Production of Amorphous Resin (B-1))
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe, and a nitrogen introduction pipe, 550 parts by weight of bisphenol A / PO2 mole adduct (1.6 mole parts), 212 parts of terephthalic acid (1.3 moles) Part), 11 parts by weight (0.04 mole part) of dimethyl isophthalate-5-sodium sulfonate, and 3 parts by weight of tetrabutoxy titanate, and 8 Reacted for hours. Next, the reaction was carried out under a reduced pressure of 0.007 to 0.026 MPa, and when the acid value reached 2, it was cooled to 180 ° C., and 26 parts by weight (0.13 mol part) of trimellitic anhydride was added and sealed at normal pressure. After the reaction for 2 hours, it was taken out to obtain an amorphous resin (B-1). Tg of (B-1) was 65 ° C., Mn was 2,100, and Mw was 6,500. Table 2 shows the physical properties of (B-1).

<Production Example 12> (Production of Amorphous Resin (B-2))
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe,
Bisphenol A / PO2 mole adduct 38 parts by weight (0.1 mole part), 1,2-propylene glycol 442 parts by weight (5.8 mole part), terephthalic acid 483 parts by weight (2.9 mole part), isophthalic acid Sodium dimethyl-5-5 sulfonate 46 parts by weight (0.16 mole part), 61 parts by weight of adipic acid (0.21 mole part) and 3 parts by weight of tetrabutoxy titanate were added and produced at 180 ° C. under a nitrogen stream. The reaction was carried out for 8 hours while distilling off the water. Next, the mixture was heated to 230 ° C., reacted under reduced pressure of 0.007 to 0.026 MPa, cooled to 180 ° C. when the molecular weight reached the target, and 34 parts by weight (0.18 mol part) of trimellitic anhydride was added. In addition, it was taken out after reaction for 2 hours under sealed at normal pressure to obtain an amorphous resin (B-2). Tg of (B-2) was 63 ° C., Mn was 4,100, and Mw was 11,100. Table 2 shows the physical properties of (B-2).

<Production Example 13> (Production of Amorphous Resin (B-3))
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe,
465 parts by weight of ethylene glycol (7.5 parts by mole), 311 parts by weight of terephthalic acid (1.9 parts by weight), 311 parts by weight of isophthalic acid (1.9 parts by weight), 47 parts by weight of dimethyl-5-sodium sulfonate Parts (0.16 mol part) and 3 parts by weight of tetrabutoxy titanate were added and reacted for 8 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, the mixture was heated to 230 ° C., reacted under reduced pressure of 0.007 to 0.026 MPa, cooled to 180 ° C. when the molecular weight reached the target, and 34 parts by weight (0.18 mol part) of trimellitic anhydride was added. In addition, it was taken out after reaction for 2 hours under normal pressure sealing to obtain an amorphous resin (B-3). Tg of (B-3) was 49 ° C., Mn was 4,700, and Mw was 12,400. Table 2 shows the physical properties of (B-3).

<Comparative Production Example 1> (Production of Amorphous Resin (B-4))
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe,
551 parts by weight of bisphenol A / PO 2 mole adduct (1.6 parts by mole), 219 parts by weight of terephthalic acid (1.3 parts by weight), and 3 parts by weight of tetrabutoxy titanate were added and produced at 230 ° C. under a nitrogen stream. The reaction was carried out for 8 hours while distilling off the water. Then 0.
The reaction was carried out under a reduced pressure of 007 to 0.026 MPa. When the acid value reached 2, the mixture was cooled to 180 ° C., added with 26 parts by weight (0.13 mol) of trimellitic anhydride, and sealed under normal pressure for 2 hours. It took out after reaction and obtained amorphous resin (B-4). Tg of (B-4) was 74 ° C., Mn was 2,700, and Mw was 7,000. Table 2 shows the physical properties of (B-4).

<Production Examples 14 to 18> [Production of solutions (D-1) to (D-6)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, each material was charged at the ratio shown in Table 2, and stirred at 40 ° C. for 24 hours to obtain solutions (D-1) to (D-6). It was.

<Production Example 19> [Production of aqueous medium (E-1)]
In a reaction vessel equipped with a stirrer, 97 parts by weight of ion-exchanged water, 11 parts by weight of [fine particle dispersion 1], 1 part by weight of sodium carboxymethylcellulose, and “eleminol MON-7” [48.5 weights of sodium dodecyldiphenyldisulfonate] % Aqueous solution and 10 parts by weight [manufactured by Sanyo Chemical Industries, Ltd.] were added and stirred at 25 ° C. for 2 hours to obtain an aqueous medium (E-1).

<Production Example 20> [Production of aqueous medium (E-2)]
In a reaction vessel equipped with a stirrer, 108 parts by weight of ion-exchanged water, 1 part by weight of sodium carboxymethyl cellulose, and “eleminol MON-7” [48.5% by weight aqueous solution of sodium dodecyldiphenyldisulfonate, [Sanyo Chemical Industries, Ltd.] Product] 10 parts by weight were added and stirred at 25 ° C. for 2 hours to obtain an aqueous medium (E-2).

<Example 1>
In a beaker, 160 parts by weight of the aqueous medium (E-1) was added, and the temperature was adjusted in a warm bath so that the solution temperature was 50 ° C. 150 parts by weight of the solution (D-1) was put in a sealable container, and the temperature was similarly adjusted in a warm bath to 50 ° C. It is confirmed that (E-1) and (D-1) are 50 ° C., 140 parts by weight of (D-1) is added to 160 parts by weight of (E-1), and TK-auto homomixer [Primics ( The product was stirred at 10,000 rpm for 2 minutes and then transferred to a container equipped with a stirrer, a heating / cooling device, a thermometer, and a cooling pipe. The temperature of the dispersion is adjusted to 50 ° C., the solvent is removed by decompression, the organic solvent content is confirmed to be 0.1% by weight or less, and the resulting dispersion (DE-1) is filtered off. And drying at 40 ° C. for 18 hours to obtain resin particles (C-1). Table 4 shows the physical properties of the obtained (C-1).

<Example 2>
Resin particles (C-2) were obtained in the same manner as in Example 1 except that (D-1) was changed to (D-2). Table 4 shows the physical properties of the obtained (C-2).

<Example 3>
Resin particles (C-3) were obtained in the same manner as in Example 1 except that (D-1) was changed to (D-3). Table 4 shows the physical properties of the obtained (C-3).

<Example 4>
Resin particles (C-4) were obtained in the same manner as in Example 1 except that (D-1) was changed to (D-4). Table 4 shows the physical properties of the obtained (C-4).

<Example 5>
Except having changed (E-1) into (E-2), it carried out similarly to Example 1 and obtained resin particle (X-5). Table 4 shows the physical properties of the obtained (X-5).

<Example 6>
Resin particles (C-6) were obtained in the same manner as in Example 1 except that (E-1) was changed to (E-2) and (D-1) was changed to (D-2). Table 4 shows the physical properties of the obtained (C-6).

<Comparative Example 1>
Except having changed (D-1) into (D-5), it carried out similarly to Example 1 and obtained the resin particle for a comparison (R-1). Table 4 shows the physical properties of the obtained (R-1).

<Comparative example 2>
Except having changed (D-1) into (D-6), it carried out similarly to Example 1 and obtained the resin particle for a comparison (R-2). Table 4 shows the physical properties of the obtained (R-2).

<Comparative Example 3>
Comparative resin particles (R-3) were obtained in the same manner as in Example 1 except that (E-1) was changed to (E-2) and (D-1) was changed to (D-5). Table 4 shows the physical properties of the obtained (R-3).

  For the resin particles (C-1) to (C-6) and (R-1) to (R-3) obtained in Examples 1 to 6 and Comparative Examples 1 to 3, low-temperature fixability was obtained by the following method. The durability against mechanical stress and the formation state of the shell were evaluated. The results are shown in Table 4.

<Low temperature fixability>
Resin particles (C-1) to (C-6) and (R-1) to (R-3) are referred to as “Aerosil R9”.
72 ”[manufactured by Nippon Aerosil Co., Ltd.] was added in an amount of 1.0% by weight and mixed well to make uniform, and then this powder was uniformly placed on the paper surface so as to be 0.6 mg / cm ² . At this time, as a method of placing the powder 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 uniformly placed at the above-mentioned weight density). The MFT (minimum fixing temperature) was measured when this paper was passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 5 kg / cm ² . A lower MFT means better low temperature fixability.

<Durability against mechanical stress>
1 g of resin particles (C-1) to (C-6) and (R-1) to (R-3) are placed in a 20 ml sample bottle and placed in a vibrator “Mixer Mill MM-400” (manufactured by Retsch). The temperature was adjusted for 30 minutes in a drier set at 50 ° C. Thereafter, vibration was applied at 15 Hz for 5 hours, the sample was observed with an optical microscope, the degree of aggregation was judged visually, and the durability was evaluated according to the following criteria.
[Evaluation criteria]
○: Aggregates are not observed Δ: Aggregates of 10 to 30 μm are observed.
X: Aggregates of 30 μm or more are observed.

<Shell formation state>
The resin particles (C-1) to (C-6) and (R-1) to (R-3) are embedded in an epoxy resin, and a sample sliced at 50 to 80 nm using a microtome is used as a transmission electron. Observed with a microscope (TEM) and evaluated according to the following criteria [Evaluation criteria]
X: Shell is not observed.
Δ: The shell is not uniformly covered.
○: A uniform shell is formed.

Since the resin particles (C) obtained by the production method of the present invention are excellent in low-temperature fixability and durability against mechanical stress, the base particles of electrophotographic toner, paint additives, cosmetic additives, paper coating Useful as industrial additives, slush molding resins, powder coatings, electronic component manufacturing spacers, electronic measuring instrument standard particles, electronic paper particles, medical diagnostic carriers, electrorheological particles, and other molding resin particles is there.

Claims (10)

  Core-shell type resin particles (C) composed of a core layer (P) and a shell layer (Q), wherein (P) contains a crystalline resin (A) and (Q) is amorphous Particles (C) containing a functional resin (B) and having an HLB of (B) of 4.7 or more.   The resin particle (C) according to claim 1, wherein an absolute value of a difference in solubility parameter between (A) and (B) is 1.2 or more.   3. The resin according to claim 1, wherein (B) is a resin having one or more groups selected from the group consisting of amino groups, quaternary ammonium bases, sulfonic acid (salt) groups, and phosphoric acid (salt) groups. Resin particles (C).   The resin particles (C) according to any one of claims 1 to 3, wherein the weight ratio of (A) to (B) is 30/70 to 99/1.   (A) is resin which has a urethane group, The resin particle (C) in any one of Claims 1-4.   The temperature which shows the maximum value of the endothermic peak of (A) is 40-80 degreeC, The resin particle (C) in any one of Claims 1-5.   The resin particle (C) according to any one of claims 1 to 6, wherein the endothermic start temperature of (A) is 30 to 70 ° C.   The glass transition point of (B) is 40-85 degreeC, The resin particle (C) in any one of Claims 1-7. The ratio (softening point / Ta) between the softening point of (A) and the temperature (Ta) showing the maximum value of the endothermic peak is 0.8 to 1.55, and the melting start temperature (X) is (Ta ± 30) ° C. Within the temperature range and satisfying the following conditions 1 and 2, (A) is a resin composed of a crystalline part (a) and an amorphous part (b), and the crystalline part (a) The crystalline polyester resin, the crystalline polyurethane resin, or the crystalline polyether resin, and the amorphous part (b) is an amorphous polyester resin or an amorphous polyurethane resin. The resin particle (C) described.
[Condition 1] 1 × 10 ² ≦ G ′ (Ta + 20) ≦ 9 × 10 ⁴ [Pa]
[Condition 2] | logG ″ (X + 20) −logG ″ (X) |> 2.0
{G ′ (Ta + 20): (A) storage elastic modulus [Pa] at (Ta + 20) ° C., G ″ (X): (A) loss elastic modulus [Pa] at X ° C., G ″ (X + 20): ( X + 20) Loss elastic modulus [Pa]} of (A) at ° C By the step of dispersing the crystalline resin (A) and the amorphous resin (B) having an HLB of 4.7 or more dissolved in an organic solvent in the aqueous medium (E), resin particles ( After obtaining C1), the organic solvent is removed from (E) to obtain resin particles (C) from (C1). C) is a core-shell type resin particle composed of a core layer (P) and a shell layer (Q), (P) contains a crystalline resin (A), and (Q) is amorphous. A method for producing resin particles (C) containing a functional resin (B), wherein (C1) satisfies the following conditions.
[conditions]
1 <Dv / Dn ≦ 1.4
[Dv: Volume average particle diameter (μm) of (C1), Dn: Number average particle diameter (μm) of (C1)]