RESIN PARTICLES AND METHOD FOR PRODUCING SAME

Abstract

Provided are resin particles which have excellent thermal bondability, excellent low-temperature fixability, excellent heat resistant storage stability and high bonding strength, and which provide a coating film that has high gloss and excellent water resistance. The resin particles are composed of resin particles (X), each of which has a shell layer (S) containing a crystalline polyurethane resin (B) on the surface of a core layer (Q) containing a crystalline resin (A). The maximum peak temperature (Ta) of the heat of fusion of the crystalline resin (A) is 40 to 70 C. and the maximum peak temperature (Tu) of the heat of fusion of the crystalline polyurethane resin (B) is 50 to 90 C.

Claims

1-14. (canceled)

15. A method for producing a resin particle (X) resulting from attachment of a resin particle (E) to the surface of a resin particle (G) containing a crystalline resin (A), the resin particle (X) being obtained by following a step of dispersing a solution (D) prepared by dissolving the crystalline resin (A) in an organic solvent (C) in a dispersion medium (F) containing the resin particle (E) containing a crystalline polyurethane resin (B), thereby obtaining a dispersion (DF), and then removing the organic solvent (C) and the dispersion medium (F) from the dispersion (DF), wherein the resin particle (X) is structured to have a shell layer (S) containing the crystalline polyurethane resin (B) on the surface of a core layer (Q) containing the crystalline resin (A), the maximum peak temperature (Ta) of the heat of fusion of the crystalline resin (A) is 40 to 70 C., and the maximum peak temperature (Tu) of the heat of fusion of the crystalline polyurethane resin (B) is 50 to 90 C.

16. The method for producing a resin particle (X) according to claim 15, wherein the crystalline resin (A) is obtained from its precursor (A0).

17. The method for producing a resin particle (X) according to claim 16, wherein the precursor (A0) is a combination of a prepolymer () having a reactive group and a curing agent ().

18. The method for producing a resin particle (X) according to claim 15, wherein the volume average particle diameter of the resin particle (E) is 0.01 to 0.5 m.

19. The method for producing a resin particle (X) according to claim 15, wherein the resin particle (E) has one or more members selected from the group consisting of a carboxylic acid salt group, a sulfonic acid salt group, a sulfamic acid salt group, and a phosphoric acid salt group.

20. The method for producing a resin particle (X) according to claim 19, wherein the method comprises, after a step of dispersing the solution (D) in the dispersion medium (F) in which the resin particles (E) containing the crystalline polyurethane resin (B) are dispersed, a step of converting the group or groups of one or more members selected from the group consisting of a carboxylic acid salt group, a sulfonic acid salt group, a sulfamic acid salt group, and a phosphoric acid salt group possessed by the resin particle (E) into a group or groups of one or more members selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfamic acid group, and a phosphoric acid group, respectively.

21. The method for producing a resin particle (X) according to claim 15, wherein the dispersion medium (F) is a non-aqueous organic solvent (F2).

22. The method for producing a resin particle (X) according to claim 15, wherein the dispersion medium (F) is an aqueous medium (F3).

Description

EXAMPLES

[0243] The present invention is further described by examples below, but the invention is not limited thereto.

<Production Example 1> [Production of Crystalline Polyurethane Resin (B-1) Solution]

[0244] A reaction vessel equipped with a stirrer and a thermometer was charged with 74 parts by weight of a polyester diol NIPPOLAN 4073 [hydroxyl value=56, produced by Nippon Polyurethane Industry Co., Ltd.] composed of 1,6-hexanediol and adipic acid, 20 parts by weight of 1,9-nonanediol, 47 parts by weight of 2,2-dimethylolpropionic acid, 9 parts by weight of sodium 3-(2,3-dihydroxypropoxy)-1-propanesulfonate, 100 parts by weight of hexamethylene diisocyanate, 4 parts by weight of triethylamine and 250 parts by weight of acetone under introduction of nitrogen. Then, the temperature was raised to 50 C. and a urethanization reaction was carried out for 10 hours, thereby producing a solution of an isocyanate group-terminated urethane resin. Subsequently, 8 parts by weight of n-butylamine and 31 parts by weight of triethylamine were added and a reaction was carried out at 50 C. for 3 hours, affording an acetone solution of a crystalline polyurethane resin (B-1). The NCO content of (B-1) was 0% by weight.

<Production Example 2> [Production of Crystalline Polyurethane Resin (B-2) Solution]

[0245] A reaction vessel equipped with a stirrer and a thermometer was charged with 379.7 parts by weight of a polyester diol composed of ethylene glycol and sebacic acid (hydroxyl value=44), 26.9 parts by weight of 2,2-dimethylolpropionic acid, 2.4 parts by weight of N,N-bis(2-hydroxyethyl)sulfamic acid, 76 parts by weight of isophorone diisocyanate, and 500 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 90 C. and a urethanization reaction was carried out for 40 hours, thereby producing an acetone solution of a hydroxyl group-terminated crystalline urethane resin (B-2). The NCO content of (B-2) was 0% by weight.

<Production Example 3> [Production of Crystalline Polyurethane Resin (B-3) Solution]

[0246] A reaction vessel equipped with a stirrer and a thermometer was charged with 377.3 parts by weight of a polyester diol composed of 1,6-hexanediol and dodecanedicarboxylic acid (hydroxyl value=31), 30.3 parts by weight of 2,2-dimethylolpropionic acid, 2.4 parts by weight of bis(2-hydroxyethyl) phosphate, 95.0 parts by weight of isophorone diisocyanate, and 487.2 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 90 C. and a urethanization reaction was carried out for 40 hours, thereby producing an acetone solution of a hydroxyl group-terminated crystalline urethane resin (B-3). The NCO content of (B-3) was 0% by weight.

<Production Example 4> [Production of Crystalline Polyurethane Resin (B-4) Solution]

[0247] A reaction vessel equipped with a stirrer and a thermometer was charged with 447 parts by weight of a polyester diol composed of 1,12-dodecanediol, fumaric acid and terephthalic acid (hydroxyl value=51), 6.3 parts by weight of 2,2-dimethylolpropionic acid, 2.5 parts by weight of sodium 3-(2,3-dihydroxypropoxy)-1-propanesulfonate, 44 parts by weight of hexamethylene diisocyanate, and 500 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 90 C. and a urethanization reaction was carried out for 40 hours, thereby producing an acetone solution of a hydroxyl group-terminated crystalline urethane resin (B-4). The NCO content of (B-4) was 0% by weight.

<Production Example 5> [Production of Prepolymer Solution for Crystalline Polyurethane Resin (B-5)]

[0248] A reaction vessel equipped with a stirrer and a thermometer was charged with 99 parts by weight of a polyester diol SANESTER 4620 [hydroxyl value=56, produced by Sanyo Chemical Industries, Ltd.] composed of 1,4-butanediol and adipic acid, 50 parts by weight of a polyester diol SANESTER 4610 [hydroxyl value=112, produced by Sanyo Chemical Industries, Ltd.] composed of 1,4-butanediol and adipic acid, 50 parts by weight of 2,2-dimethylolpropionic acid, 17 parts by weight of N,N-bis (2-hydroxyethyl) sulfamic acid, 67 parts by weight of diphenylmethane diisocyanate, 3 parts by weight of triethylamine, and 250 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 50 C. and a urethanization reaction was carried out for 10 hours, thereby producing an acetone solution of a prepolymer (B0-5) to a crystalline urethane resin (B-5). The NCO content of (B0-5) was 1.7% by weight.

<Production Example 6> [Production of Crystalline Polyurethane Resin (B-6) Solution]

[0249] A reaction vessel equipped with a stirrer and a thermometer was charged with 111 parts by weight of nonamethylenediol, 21 parts by weight of 2,2-dimethylolpropionic acid, 1 part by weight of sodium 3-(2,3-dihydroxypropoxy)-1-propanesulfonate, 117 parts by weight of hexamethylene diisocyanate, 15 parts by weight of triethylamine, and 250 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 50 C. and a urethanization reaction was carried out for 15 hours, thereby producing a solution of a hydroxyl group-terminated crystalline urethane resin. The NCO content at the completion of the urethanization reaction was 0% by weight.

<Production Example 7> [Production of Crystalline Polyurethane Resin (B-7) Solution]

[0250] A reaction vessel equipped with a stirrer and a thermometer was charged with 379.7 parts by weight of a polyester diol composed of ethylene glycol and sebacic acid (hydroxyl value=44), 26.9 parts by weight of 2,2-dimethylolpropionic acid, 2.4 parts by weight of N,N-bis(2-hydroxyethyl)sulfamic acid, 76 parts by weight of isophorone diisocyanate, and 500 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 90 C. and a urethanization reaction was carried out for 40 hours, thereby producing an acetone solution of a hydroxyl group-terminated crystalline urethane resin (B-7). The NCO content of (B-7) was 0% by weight.

<Production Example 8> [Production of Crystalline Polyurethane Resin (B-8) Solution]

[0251] A reaction vessel equipped with a stirrer and a thermometer was charged with 379.7 parts by weight of a polyester diol composed of ethylene glycol and sebacic acid (hydroxyl value=44), 26.9 parts by weight of 2,2-dimethylolpropionic acid, 2.4 parts by weight of N,N-bis(2-hydroxyethyl)sulfamic acid, 76 parts by weight of isophorone diisocyanate, and 500 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 90 C. and a urethanization reaction was carried out for 40 hours, thereby producing an acetone solution of a hydroxyl group-terminated crystalline urethane resin (B-8). The NCO content of (B-8) was 0% by weight.

<Production Example 9> [Production of Aqueous Dispersion Liquid (W-1) of Particulates (E-1)]

[0252] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-1) obtained in Production Example 1 that was controlled to 40 C. was charged under stirring to emulsify (B-1) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-1) of particulates (E-1) made of (B-1).

<Production Example 10> [Production of Aqueous Dispersion Liquid (W-2) of Particulates (E-2)]

[0253] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-2) obtained in Production Example 2 that was controlled to 40 C. was charged under stirring to emulsify (B-2) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-2) of particulates (E-2) made of (B-2).

<Production Example 11> [Production of Aqueous Dispersion Liquid (W-3) of Particulates (E-3)]

[0254] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-3) obtained in Production Example 3 that was controlled to 40 C. was charged under stirring to emulsify (B-3) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-3) of particulates (E-3) made of (B-3).

<Production Example 12> [Production of Aqueous Dispersion Liquid (W-4) of Particulates (E-4)]

[0255] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-4) obtained in Production Example 4 that was controlled to 40 C. was charged under stirring to emulsify (B-4) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-4) of particulates (E-4) made of (B-4).

<Production Example 13> [Production of Aqueous Dispersion Liquid (W-5) of Particulates (E-5)]

[0256] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-5) obtained in Production Example 5 that was controlled to 40 C. was charged under stirring to emulsify (B-5) in water, and moreover 4.5 parts by weight of n-butylamine, 9.5 parts by weight of hexamethylenediamine, and 10 parts by weight of triethylamine were added and allowed to react for 5 hours with stirring, and then acetone was evaporated, affording an aqueous dispersion liquid (W-5) of particulates (E-5) made of a resin resulting from amine extension of (B-5).

<Production Example 14> [Production of Aqueous Dispersion Liquid (W-6) of Particulates (E-6)]

[0257] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-6) obtained in Production Example 6 that was controlled to 40 C. was charged under stirring to emulsify (B-6) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-6) of particulates (E-6) made of (B-6).

<Production Example 15> [Production of Aqueous Dispersion Liquid (W-7) of Particulates (E-7)]

[0258] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 18 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate ELEMINOL MON-7 [produced by Sanyo Chemical Industries, Ltd.] and 1800 parts by weight of water, and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-7) obtained in Production Example 7 that was controlled to 40 C. was charged under stirring to emulsify (B-7) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-7) of particulates (E-7) made of (B-7).

<Production Example 16> [Production of Decane Dispersion Liquid (W-8) of Particulates (E-8)]

[0259] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of decane and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-8) obtained in Production Example 8 that was controlled to 40 C. was charged under stirring to emulsify (B-8) in water and then acetone was evaporated, affording a decane dispersion liquid (W-8) of particulates (E-8) made of (B-8).

<Comparative Production Example 1> [Production of Comparative Polyurethane Resin (B-1) Solution]

[0260] A reaction vessel equipped with a stirrer and a thermometer was charged with 197.5 parts by weight of a polyester diol composed of 1,2-propylene glycol and isophthalic acid (hydroxyl value=56), 10 parts by weight of 2,2-dimethylolpropionic acid, 2.5 parts by weight of sodium 3-(2,3-dihydroxypropoxy)-1-propanesulfonate, 40 parts by weight of isophorone diisocyanate, 8 parts by weight of triethylamine, and 250 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 50 C. and a urethanization reaction was carried out for 15 hours, thereby producing an acetone solution of a hydroxyl group-terminated urethane resin (B-1). The NCO content of (B-1) was 0% by weight.

<Comparative Production Example 2> [Production of Comparative Polyurethane Resin (B-2) Solution]

[0261] A reaction vessel equipped with a stirrer and a thermometer was charged with 92 parts by weight of polyethylene glycol PEG-400 [hydroxyl value=278, produced by Sanyo Chemical Industries, Ltd.], 38 parts by weight of 2,2-dimethylolpropionic acid, 3 parts by weight of sodium 3-(2,3-dihydroxypropoxy)-1-propanesulfonate, 122 parts by weight of isophorone diisocyanate, 3 parts by weight of triethylamine, and 250 parts by weight of acetone under introduction of nitrogen. Then, heat was added to 50 C. and a urethanization reaction was carried out for 15 hours, and subsequently 29 parts by weight of triethylamine was added and mixed, thereby producing an acetone solution of a urethane resin (B-2). The NCO content of (B-2) was 0% by weight.

<Comparative Production Example 3> [Production of Aqueous Dispersion Liquid (W-1) of Particulates (E-1)]

[0262] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-1) obtained in Comparative Production Example 1 that was controlled to 40 C. was charged under stirring to emulsify (B-1) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-1) of particulates (E-1) made of (B-1). The volume average particle diameter of (E-1) in (W-1) was measured with ELS-800 and it was 0.30 m.

<Comparative Production Example 4> [Production of Aqueous Dispersion Liquid (W-2) of Particulates (E-2)]

[0263] A reaction vessel equipped with a stirrer, a thermometer, and a desolvating apparatus was charged with 1800 parts by weight of water and then the temperature was raised up to 40 C. Subsequently, 836 parts by weight of the acetone solution of (B-2) obtained in Comparative Production Example 2 that was controlled to 40 C. was charged under stirring to emulsify (B-2) in water and then acetone was evaporated, affording an aqueous dispersion liquid (W-2) of particulates (E-2) made of (B-2). The volume average particle diameter of (E-2) in (W-2) was measured with ELS-800 and it was 0.30 m.

[0264] As to the crystalline polyurethane resins (B-1) to (B-8) obtained in Production Examples 1 to 8, the polyurethane resins (B-1) and (B-2) obtained in Comparative Production Examples 1 to 2, the dispersion liquids (E-1) to (E-8) obtained in Production Examples 9 to 16, and the aqueous dispersion liquids (W-1) and (W-2) obtained in Comparative Production Examples 3 to 4, physical property values are given in Table 1. The volume average particle diameter of the particulates in an aqueous dispersion liquid was measured with ELS-800 even if this is not explicitly stated in the text.

TABLE-US-00001 TABLE 1 (B), (B) (B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-7) (B-8) (B-1) (B-2) Tu ( C.) 53 67 79 85 70 75 67 67 36 (B: urethane) 25 7.6 7.4 5 2 32.9 7.6 7.6 8.5 25.9 (% by weight) (B: urea) 2.2 0.4 1.3 0.5 3 0 0.4 0.4 0 0 (% by weight) (B: Mw) 10,000 24,000 64,000 30,000 100,000 10,000 24,000 24,000 40,000 20,000 Values of 19 6 19 5 27 25 6 6 12 22 [Condition 2] Acid value 79 23 25 5 180 35 23 23 10 50 (gKOH/g) Presence or absence Present Present Present Present Present Absent Present Present Present Present of carboxylic acid (salt) group Presence or absence Present Absent Absent Absent Absent Absent Absent Absent Present Present of sulfonic acid (salt) group Presence or absence Absent Present Absent Absent Present Absent Present Present Absent Absent of sulfamic acid (salt) group Presence or absence Absent Absent Present Absent Absent Present Absent Absent Absent Absent of phosphoric acid (salt) group (E), (E) (E-1) (E-2) (E-3) (E-4) (E-5) (E-6) (E-7) (E-8) (E-1) (E-2) Presence or absence Present Present Present Present Present Absent Present Present Present Present of carboxylate Presence or absence Present Absent Absent Absent Absent Absent Absent Absent Present Present of sulfonate Presence or absence Absent Present Absent Absent Present Absent Present Present Absent Absent of sulfamate Presence or absence Absent Absent Present Absent Absent Present Absent Absent Absent Absent of phosphate Volume average 0.05 0.15 0.30 0.30 0.05 0.30 0.20 0.20 0.30 0.30 particle diameter (m) (W), (W) (W-1) (W-2) (W-3) (W-4) (W-5) (W-6) (W-7) (W-8) (W-1) (W-2) Presence or absence Absent Absent Absent Absent Absent Absent Present Absent Absent Absent of activator

<Production Example 17> [Synthesis of Crystalline Polyester Resin (A1-1)]

[0265] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 683 parts by weight of sebacic acid, 436 parts by weight of 1,6-hexanediol, and 0.1 parts by weight of dibutyltin oxide under introduction of nitrogen, and after replacing the atmosphere in the system with nitrogen by vacuum operation, the temperature was raised to 180 C. and stirring was continued at this temperature for 6 hours. Then, the temperature was gradually raised to 230 C. under reduced pressure (0.007 to 0.026 MPa) while the stirring was continued, and then the temperature was further maintained for 2 hours. On arrival at a viscous state, the reaction was stopped by cooling to 150 C., thereby affording a crystalline polyester resin (A1-1).

<Production Example 18> [Synthesis of Crystalline Polyester Resin (A1-2)]

[0266] A crystalline polyester resin (A1-2) was obtained in the same manner as in Production Example 13 except that 683 parts by weight of sebacic acid was changed to a mixture of 703 parts by weight of sebacic acid and 56 parts by weight of adipic acid, and 436 parts by weight of 1,6-hexanediol was changed to 379 parts by weight of 1,4-butanediol.

<Production Example 19> [Synthesis of Crystalline Polyester Resin (A1-3)]

[0267] A crystalline polyester resin (A1-3) was obtained in the same manner as in Production Example 13 except that 683 parts by weight of sebacic acid was changed to 713 parts by weight of adipic acid, and 436 parts by weight of 1,6-hexanediol was changed to 462 parts by weight of 1,4-butanediol.

<Production Example 20> [Synthesis of Crystalline Polyester Resin (A1-4)]

[0268] A crystalline polyester resin (A1-4) was obtained in the same manner as in Production Example 13 except that the number of parts of sebacic acid was changed from 683 parts by weight to 848 parts by weight, and 436 parts by weight of 1,6-hexanediol was changed to a mixture of 226 parts by weight of ethylene glycol and 75 parts by weight of 1,4-butanediol.

<Production Example 21> [Synthesis of Crystalline Polyester Resin (A1-5)]

[0269] A crystalline polyester resin (A1-5) was obtained in the same manner as in Production Example 13 except that 683 parts by weight of sebacic acid was changed to 627 parts by weight of isophthalic acid, and the number of parts of 1,6-hexanediol was changed from 436 parts by weight to 508 parts by weight.

<Production Example 22> [Synthesis of Crystalline Polyester Resin (A1-6)]

[0270] A crystalline polyester resin (A1-6) was obtained in the same manner as in Production Example 13 except that the number of parts of sebacic acid was changed from 683 parts by weight to 787 parts by weight, and 436 parts by weight of 1,6-hexanediol was changed to 382 parts by weight of ethylene glycol.

<Production Example 23> [Production of Crystalline Polyurethane Resin (A2-1)]

[0271] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 216.0 parts by weight of the crystalline polyester (A1-2), 64.0 parts by weight of diphenylmethane diisocyanate, 20.0 parts by weight of 1,2-propylene glycol, and 300.0 parts by weight of tetrahydrofuran (THF) under introduction of nitrogen. Subsequently, the temperature was raised to 50 C., and a urethanization reaction was carried out for 15 hours at this temperature, thereby affording a THF solution of a hydroxyl group-terminated crystalline polyurethane resin (A2-1), and then THF was evaporated, affording the crystalline resin (A2-1). The NCO content of (A2-1) was 0% by weight.

<Production Example 24> [Production of Crystalline Polyurethane Resin (A2-2)]

[0272] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 150.0 parts by weight of the crystalline polyester (A1-3), 60.0 parts by weight of hexamethylene diisocyanate, 90.0 parts by weight of cyclohexane dimethanol, and 300.0 parts by weight of THF under introduction of nitrogen. Subsequently, the temperature was raised to 50 C., and a urethanization reaction was carried out for 15 hours at this temperature, thereby affording a THF solution of a hydroxyl group-terminated crystalline polyurethane resin (A2-2), and then THF was evaporated, affording the crystalline resin (A2-2). The NCO content of (A2-2) was 0% by weight.

<Production Example 25> [Production of Crystalline Polyurethane Resin (A2-3)]

[0273] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 285.0 parts by weight of the crystalline polyester (A1-4), 15.0 parts by weight of isophorone diisocyanate, and 300.0 parts by weight of THF under introduction of nitrogen. Subsequently, the temperature was raised to 50 C., and a urethanization reaction was carried out for 15 hours at this temperature, thereby affording a THF solution of a hydroxyl group-terminated crystalline polyurethane resin (A2-3), and then THF was evaporated, affording the crystalline resin (A2-3). The NCO content of (A2-3) was 0% by weight.

<Production Example 26> [Production of Crystalline Polyurethane Resin (A2-4)]

[0274] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 240.0 parts by weight of the crystalline polyester (A1-5), 33.0 parts by weight of diphenylmethane diisocyanate, 27.0 parts by weight of a bisphenol APO (2 mol) adduct, and 300.0 parts by weight of THF under introduction of nitrogen. Subsequently, the temperature was raised to 50 C., and a urethanization reaction was carried out for 15 hours at this temperature, thereby affording a THF solution of a hydroxyl group-terminated crystalline polyurethane resin (A2-4), and then THF was evaporated, affording the crystalline resin (A2-4). The NCO content of (A2-4) was 0% by weight.

<Production Example 27> [Production of Crystalline Polyurethane Resin (A2-5)]

[0275] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 240.0 parts by weight of the crystalline polyester (A1-6), 47.0 parts by weight of xylylene diisocyanate, 27.0 parts by weight of 1,2-propylene glycol, and 300.0 parts by weight of THF under introduction of nitrogen. Subsequently, the temperature was raised to 50 C., and a urethanization reaction was carried out for 15 hours at this temperature, thereby affording a THF solution of a hydroxyl group-terminated crystalline polyurethane resin (A2-5), and then THF was evaporated, affording the crystalline resin (A2-5). The NCO content of (A2-5) was 0% by weight.

<Production Example 28> [Synthesis of Precursor (A0-1)]

[0276] A reaction vessel equipped with a stirrer, a heating and cooling device, a cooling tube, and a thermometer was charged with 452 parts by weight of (A1-1) and 500 parts by weight of ethyl acetate. The resulting mixture was heated to 60 C. and stirred for 2 hours at this temperature to dissolve (A1-1), and then water was added so that the water content in the solution might become 0.06% by weight. After confirming the dissolution of (A1-1), 48 parts by weight of tolylene diisocyanate was added, and the resulting mixture was heated to 80 C. and was allowed to react for 1 hour at this temperature, thereby affording an ethyl acetate solution of an isocyanate group-terminated precursor (A0-1). (A0-1) had an Mw of 14,000, a maximum peak temperature of heat of fusion of 60 C., and an isocyanate content of 1.0% by weight.

<Comparative Production Example 5> [Production of Polyester Resin (A1-1)]

[0277] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen-inlet tube, and a decompression device was charged with 67 parts by weight of a bisphenol APO (2 mol) adduct, 700 parts by weight of a bisphenol APO (3 mol) adduct, 260 parts by weight of terephthalic acid, and 1 part by weight of dibutyltin oxide as a condensation catalyst. The resulting mixture was heated to 230 C. under atmospheric pressure and was allowed to react for 5 hours at this temperature. The resultant was further allowed to react for 2 hours under a reduced pressure of 0.013 MPa to 0.020 MPa. Subsequently, the resultant was cooled down to 180 C. and 24 parts by weight of trimellitic anhydride was added thereto. The resultant was allowed to react for 2 hours under atmospheric pressure in a sealed environment and was then cooled to room temperature, thereby affording a polyester resin (A1-1).

[0278] As to the crystalline resins (A1-1), (A2-1) to (A2-5) and (A1-1) obtained in Production Examples 17, 23 to 27 and Comparative Production Example 5, physical property values are given in Table 2.

TABLE-US-00002 TABLE 2 (A), (A) (A1-1) (A2-1) (A2-2) (A2-3) (A2-4) (A2-5) (A1-1) Ta ( C.) 70 60 45 63 50 65 Total endotherm (J/g) 150 60 40 80 40 120 Content of (a) (% by weight) 100 72 50 95 80 80 0 Mw 12,000 30,000 50,000 30,000 18,000 10,000 7,000 Presence or absence of ester group Present Present Present Present Present Present Present Presence or absence of urethane group Absent Present Present Present Present Present Absent Presence or absence of urea group Absent Present Present Present Present Present Absent

<Production Example 29> (Production of Colorant Dispersion Liquid)

[0279] A reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer, a cooling tube, and a nitrogen-inlet tube was charged with 557 parts by weight (17.5 parts by mol) of propylene glycol, 569 parts by weight (7.0 parts by mol) of dimethyl terephthalate, 184 parts by weight (3.0 parts by mol) of adipic acid, and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst, and these were caused to react with one another at 180 C. under a nitrogen gas flow for 8 hours while generated methanol being distilled off. Subsequently, a reaction was performed for 4 hours under a nitrogen gas flow while the temperature was gradually raised to 230 C. and generated propylene glycol and water were distilled off, and further the reaction was performed under a reduced pressure of 0.007 to 0.026 MPa for one hour. The recovered propylene glycol was 175 parts by weight (5.5 parts by mol). Subsequently, after cooling to 180 C., 121 parts by weight (1.5 parts by mol) of trimellitic anhydride was added, and after being allowed to react in a hermetically sealed condition under normal pressure for 2 hours, this was further caused to react at 220 C. under normal pressure until the softening point reached 180 C., affording a polyester resin (Mn=8,500).

[0280] A beaker was charged with 20 parts by weight of copper phthalocyanine blue, 4 parts by weight of a colorant dispersant SOLSPERSE 28000 [produced by Avecia], 20 parts by weight of the polyester resin obtained, and 56 parts by weight of ethyl acetate, which were then uniformly dispersed by stirring, and subsequently copper phthalocyanine blue was microdispersed with a bead mill, affording a colorant dispersion liquid. The volume average particle diameter of the colorant dispersion liquid measured with LA-920 was 0.2 m.

<Production Example 30> (Production of Modified Wax)

[0281] A pressure-resistant reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer, and a dropping cylinder was charged with 454 parts by weight of xylene and 150 parts by weight of a low molecular weight polyethylene SANWAX LEL-400 [softening point: 128 C., produced by Sanyo Chemical Industries, Ltd.]. After replacement with nitrogen, the temperature was raised to 170 C. under stirring and then a mixed solution of 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-tert-butyl peroxyhexahydroterephthalate, and 119 parts by weight of xylene was dropped for 3 hours at that temperature, and then the resultant was held at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa, affording a modified wax. The graft chain of the modified wax had an SP value of 10.35 (cal/cm.sup.3).sup.1/2, an Mn of 1,900, an Mw of 5,200, and a Tg of 56.9 C.

<Production Example 31> [Production of Releasing Agent Dispersion Liquid]

[0282] A reaction vessel equipped with a stirrer, a heating and cooling device, a cooling tube, and a thermometer was charged with 10 parts by weight of paraffin wax HNP-9 [the maximum peak temperature of heat of fusion: 73 C., manufactured by NIPPON SEIRO CO., LTD.], 1 part by weight of the modified wax obtained in Production Example 30, and 33 parts by weight of ethyl acetate, which were then heated to 78 C. with stirring, stirred at this temperature for 30 minutes, and then cooled down to 30 C. for 1 hour, thereby crystallizing and depositing paraffin wax into the shape of particulates, which were further subjected to wet pulverization by means of ULTRA VISCOMILL (manufactured by AIMEX CO., Ltd.), affording a releasing agent dispersion liquid. The volume average particle diameter was 0.25 m.

<Production Example 32> [Production of Resin Solution (D-1)]

[0283] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A1-1), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A1-1), affording a resin solution (D-1).

<Production Example 33> [Production of Resin Solution (D-2)]

[0284] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A2-1), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A2-1), affording a resin solution (D-2).

<Production Example 34> [Production of Resin Solution (D-3)]

[0285] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A2-2), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A2-2), affording a resin solution (D-3).

<Production Example 35> [Production of Resin Solution (D-4)]

[0286] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A2-3), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A2-3), affording a resin solution (D-4).

<Production Example 36> [Production of Resin Solution (D-5)]

[0287] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A2-4), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A2-4), affording a resin solution (D-5).

<Production Example 37> [Production of Resin Solution (D-6)]

[0288] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the crystalline resin (A1-1), and 153 parts by weight of tetrahydrofuran, which were then stirred to homogeneously dissolve (A1-1), affording a resin solution (D-6).

<Production Example 38> [Production of Resin Solution (D-7)]

[0289] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 50 parts by weight of the crystalline resin (A1-1), 50 parts by weight of the crystalline resin (A2-4), and 153 parts by weight of methyl ethyl ketone, which were then stirred to homogeneously dissolve (A1-1) and (A2-4), affording a resin solution (D-7).

<Production Example 39> [Production of Resin Solution (D-8)]

[0290] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 50 parts by weight of the crystalline resin (A2-1), 50 parts by weight of the crystalline resin (A2-5), and 153 parts by weight of acetone, which were then stirred to homogeneously dissolve (A2-1) and (A2-5), affording a resin solution (D-8).

<Production Example 40> [Production of Resin Solution (D-9)]

[0291] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 80 parts by weight of the crystalline resin (A2-1), 40 parts by weight of the precursor (A0-1), and 133 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A2-1) and (A0-1), affording a resin solution (D-9).

<Comparative Production Example 6> [Production of Resin Solution (D-1)]

[0292] A reaction vessel equipped with a stirrer and a thermometer was charged with 30 parts by weight of the colorant dispersion liquid, 140 parts by weight of the releasing agent dispersion liquid, 100 parts by weight of the polyester resin (A1-1), and 153 parts by weight of ethyl acetate, which were then stirred to homogeneously dissolve (A1-1), affording a resin solution (D-1).

[0293] The compositions of the resin solutions (D-1) to (D-9) and (D-1) obtained in Production Examples 32 to 40 and Comparative Production Example 6, respectively, are presented in Table 3.

TABLE-US-00003 TABLE 3 Solution (D-1) (D-2) (D-3) (D-4) (D-5) (D-6) (D-7) (D-8) (D-9) (D-1) Colorant dispersion liquid 30 30 30 30 30 30 30 30 30 30 Releasing agent dispersion liquid 140 140 140 140 140 140 140 140 140 140 Crystalline (A1-1) 100 100 50 resin (A) (A2-1) 100 50 80 (A2-2) 100 (A2-3) 100 (A2-4) 100 50 (A2-5) 50 (A'1-1) 100 Precursor (A0) (A0-1) 40 Organic Ethyl acetate 153 153 153 153 153 133 153 solvent (C) Acetone 153 Methyl ethyl 153 ketone Tetrahydrofuran 153

Example 1

[0294] A beaker was charged with 170.2 parts by weight of ion exchange water (F3), 0.3 parts by weight of (W-3), 1 part by weight of sodium carboxymethylcellulose, 36 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate ELEMINOL MON-7 [produced by Sanyo Chemical Industries, Ltd.], and 15.3 parts by weight of ethyl acetate, which were then stirred to dissolve uniformly. Subsequently, the temperature was raised to 50 C. and 75 parts by weight of the resin solution (D-1) was charged at that temperature under stirring with a TK autohomomixer at 10,000 rpm and was stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was evaporated at 50 C. until the concentration became 0.5% by weight or less, affording an aqueous resin dispersion of resin particles (X-1) in which a shell layer (S) made of (B) was deposited on the surface of a core layer (Q) composed of (A). Subsequently, the aqueous resin dispersion was subjected to washing, filtering, and drying at 40 C. for 18 hours to control the volatile content to 0.5% by weight or lower, affording resin particles (X-1).

Example 2

[0295] Resin particles (X-2) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-2) and 0.3 parts by weight of (W-3) was changed to 2.1 parts by weight of (W-2).

Example 3

[0296] Resin particles (X-3) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-3) and 0.3 parts by weight of (W-3) was changed to 7.2 parts by weight of (W-2).

Example 4

[0297] Resin particles (X-4) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-4) and 0.3 parts by weight of (W-3) was changed to 34.5 parts by weight of (W-2).

Example 5

[0298] Resin particles (X-5) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-5) and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-1).

Example 6

[0299] Resin particles (X-6) were obtained in the same manner as in Example 1 except that 15.3 parts by weight of ethyl acetate was changed to 15.3 parts by weight of tetrahydrofuran, 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-6), and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-6).

Example 7

[0300] Resin particles (X-7) were obtained in the same manner as in Example 1 except that 15.3 parts by weight of ethyl acetate was changed to 15.3 parts by weight of methyl ethyl ketone, 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-7), and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-5).

Example 8

[0301] Resin particles (X-8) were obtained in the same manner as in Example 1 except that 15.3 parts by weight of ethyl acetate was changed to 15.3 parts by weight of acetone, 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-8), and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-4).

Example 9

[0302] A beaker was charged with 170.2 parts by weight of ion exchange water (F3), 2.1 parts by weight of (W-2), 1 part by weight of sodium carboxymethylcellulose, 36 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate ELEMINOL MON-7 [produced by Sanyo Chemical Industries, Ltd.], and 15.3 parts by weight of ethyl acetate, which were then stirred to dissolve uniformly. Subsequently, the temperature was raised to 50 C. and 75 parts by weight of the resin solution (D-9) was charged at that temperature under stirring with a TK autohomomixer at 10,000 rpm and was stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was evaporated at 50 C. until the concentration became 0.5% by weight or less, affording an aqueous resin dispersion of resin particles (X-9) in which a shell layer (S) made of (B) was deposited on the surface of a core layer (Q) composed of (A). Subsequently, the aqueous resin dispersion of (X-1) was subjected to acid washing with a 0.1 mol/L aqueous hydrochloric acid solution until the pH thereof became 2.1, filtering, and drying at 40 C. for 18 hours to control the volatile content to 0.5% by weight or lower, affording resin particles (X-9).

Example 10

[0303] Resin particles (X-10) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-9) and 0.3 parts by weight of (W-3) was changed to 2.1 parts by weight of (W-7).

Example 11

[0304] A beaker was charged with 108 parts by weight of decane and 2.1 parts by weight of (W-8), and the resultant was stirred to homogeneously dissolve. Subsequently, the temperature was raised to 50 C. and 75 parts by weight of the resin solution (D-9) was charged at that temperature under stirring with a TK autohomomixer at 10,000 rpm and was stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was evaporated at 50 C. until the concentration became 0.5% by weight or less, affording a dispersion of resin particles (X-11) in which a shell layer (S) made of (B) was deposited on the surface of a core layer (Q) composed of (A). Subsequently, the dispersion was subjected to washing, filtering, and drying at 40 C. for 18 hours to control the volatile content to 0.5% by weight or lower, affording resin particles (X-11).

Comparative Example 1

[0305] Resin particles (X-1) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-1) and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-2).

Comparative Example 2

[0306] Resin particles (X-2) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of (D-1) and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-1).

Comparative Example 3

[0307] Resin particles (X-3) were obtained in the same manner as in Example 1 except that 75 parts by weight of the resin solution (D-1) was changed to 75 parts by weight of the resin solution (D-2) and 0.3 parts by weight of (W-3) was changed to 4.2 parts by weight of (W-2).

[0308] The composition ratios (% by weight) of (Q), (Q), (S), (S) of each of the resin particles (X-1) to (X-11) and (X-1) to (X-3) are presented in Table 4. Resin particles (X-1) to (X-11) and (X-1) to (X-3) were subjected to measurement of a volume average particle diameter and particle size distribution and were subjected to evaluation of heat resistant storage stability, low-temperature fixability, heat adhesion, adhesion strength, glossiness of a coating film, and water resistance of a coating film. The results are presented in Tables 4 and 5.

[1] Volume Average Particle Diameter, Particle Size Distribution

[0309] The resin particles (X-1) to (X-11) and (X-1) to (X-3) were each dispersed in water and subjected to measurement of a volume average particle diameter and particle size distribution by means of a Coulter Counter Multisizer III (manufactured by Beckman Coulter, Inc.).

[2] Heat Resistant Storage Stability

[0310] The resin particles (X-1) to (X-11) and (X-1) to (X-3) were each left to stand in an atmosphere of 40 C. for one day, and then the degree of blocking was visually judged. The heat resistant storage stability was evaluated on the basis of the following criteria.

[Evaluation Criteria]

[0311] : No blocking occurred.
X: Blocking occurred.

[3] Low-Temperature Fixability

[0312] To each of the resin particles (X-1) to (X-11) and (X-1) to (X-3), 1.0% by weight of Aerosil R972 [produced by Nippon Aerosil Co., Ltd.] is added and fully mixed to become uniform. Thereafter, the resulting powder is placed on paper uniformly in an amount of 0.6 mg/cm.sup.2 (in the method for placing the powder on paper, a printer with its heat fixing device having been removed is used; any other method may be used as long as it can uniformly place the powder in the aforementioned weight density). The temperature at which cold offset occurred was measured when the paper was passed through pressure rollers under the condition represented by a fixing speed (heat roller rim speed) of 213 mm/sec and a fixing pressure (the pressure of the pressure roller) of 10 kg/cm.sup.2. A lower temperature at which cold offset occurred means that low-temperature fixability is better.

[4] Heat Adhesion

[0313] Resin particles (X-1) to (X-11) and (X-1) to (X-3) were electrostatically applied to a zinc phosphate-treated steel standard plate [produced by Nippon Testpanel Co., Ltd] to achieve a film thickness of 40 to 60 m with a commercially available corona charge spray gun, baked at 100 C. for 20 minutes, and then subjected to a shear adhesion test in accordance with the method specified in JIS K6830. The heat adhesion was evaluated on the basis of the criteria shown below.

[Evaluation Criteria]

[0314] : Aggregation fracture
x: Interface fracture

[5] Adhesion Strength

[0315] Using an image fixed at 160 C. selected from among the samples for the above-described evaluation of the low-temperature fixability, a pencil hardness test was performed in accordance with the method specified in JIS K5600-5-4, and the adhesion strength or bonding strength was evaluated on the basis of the following criteria.

[Evaluation Criteria] : HB or harder

: 4B to B

[0316] A: 5B or softer

[6] Gloss of Coating Film

[0317] The gloss of an image fixed at 160 C. selected from among the samples for the above-described evaluation of the low-temperature fixability was visually judged, and the gloss of a coating film was evaluated on the basis of the following criteria.

[Evaluation Criteria]

[0318] : Sufficient gloss is possessed.
: Gloss is possessed.
X: Gloss is insufficient.

[7] Water Resistance of Coating Film

[0319] An image fixed at 160 C. selected from among the samples used for the evaluation of low-temperature fixability was cut into a size of 4 cm4 cm and then immersed for one hour in a red ink PILOT INK/RED [manufactured by PILOT CORPORATION] diluted 100 fold with water, and thereafter the distance of ink penetration from the edge was measured, and its maximum value (mm) was determined as a measure of water resistance. A smaller value thereof means better water resistance.

TABLE-US-00004 TABLE 4 Example Example Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 10 11 Resin particle (X-1) (X-2) (X-3) (X-4) (X-5) (X-6) (X-7) (X-8) (X-9) (X-10) (X-11) Solution (D) (D-1) (D-2) (D-3) (D-4) (D-5) (D-6) (D-7) (D-8) (D-9) (D-9) (D-9) Weight ratio of 99.8 98.5 95 80 97 97 97 97 98.5 98.5 98.5 core layer (Q) Crystalline (B-3) (B-2) (B-2) (B-2) (B-1) (B-6) (B-5) (B-4) (B-2) (B-7) (B-8) polyurethane resin (B) Weight ratio 0.2 1.5 5 20 3 3 3 3 1.5 1.5 1.5 of shell layer (S) Tu ( C.) 79 67 67 67 53 75 70 85 67 67 67 Ta ( C.) 70 60 45 63 50 70 60 62.5 60 60 60 Tu Ta ( C.) 9 7 22 4 3 5 10 23 7 7 7 Volume average 20 5.0 6.0 4.0 6.0 6.0 5.5 5.4 5.4 5.7 6.0 particle diameter (m) Particle size 1.20 1.15 1.11 1.16 1.13 1.15 1.12 1.17 1.17 1.19 1.20 distribution Step of X X X X X X X X X X converting acid Heat resistant storage stability Low- 110 100 90 100 95 105 105 110 110 110 110 temperature fixability ( C.) Heat adhesion Adhesion strength Gloss of coating film Water resistance 1 1 1 1 1 1 1 1 1 1 1 of coating film (mm)

TABLE-US-00005 TABLE 5 Comparative Comparative Comparative Example 1 Example 2 Example 3 Resin particle (X 1) (X 2) (X 3) Solution (D) (D 1) (D 1) .sup.(D 2) Weight ratio of core layer (Q) 97 97 97 Crystalline polyurethane .sup.(B 2) (B 1) (B 2) resin (B) Weight ratio of shell layer (S) 3 3 3 Tu ( C.) 67 36 Ta ( C.) 60 Tu Ta ( C.) 24 Volume average particle 5.5 6.0 11.0 diameter (m) Particle size distribution 1.20 1.20 1.54 Step of converting acid x x x Heat resistant storage x x stability Low-temperature fixability 130 130 140 ( C.) Heat adhesion x x x Adhesion strength Gloss of coating film x x Water resistance of coating 2 3 2 film (mm)

INDUSTRIAL APPLICABILITY

[0320] The resin particle (X) of the present invention is excellent in heat adhesion, low-temperature fixability, and heat resistant storage stability and high in adhesion strength, and a coating film obtained from the resin particle is high in glossiness and the coating film is excellent in water resistance. Therefore, the resin particle is useful as a base particle of an electrophotographic toner, an additive for paint, an additive for cosmetics, an additive for paper coating, a resin for slush molding, powder paint, a spacer for electronic parts production, a standard particle for an electronic measuring device, a particle for electronic paper, a carrier for medical diagnosis, a particle for electroviscosity, and resin particles for other molding applications.