Colored resin particle dispersion and inkjet ink

Abstract

A colored resin particle dispersion and an ink are provided which exhibit excellent abrasion resistance of the printed items and excellent storage stability of the dispersion. Specifically provided is a colored resin particle dispersion comprising colored resin particles containing a colorant and a solid resin, a basic dispersant, and a non-aqueous solvent, wherein the solid resin is a resin having alkoxy groups and/or a polysilsesquioxane. The resin having alkoxy groups preferably has methoxy groups and/or ethoxy groups. Further, the resin having alkoxy groups preferably contains at least one of a polyamide resin having methoxymethyl groups, a methoxypolysilsesquioxane and an ethoxypolysilsesquioxane.

Claims

1. A colored resin particle dispersion comprising colored resin particles containing a colorant and a solid resin, a basic dispersant, and a non-aqueous solvent, wherein the solid resin is a resin having alkoxy groups and/or a polysilsesquioxane, and the resin having alkoxy groups is a polyamide resin having alkoxymethyl groups and/or a polysilsesquioxane having alkoxy groups.

2. The colored resin particle dispersion according to claim 1, wherein the solid resin is a polyamide resin having alkoxymethyl groups and/or a polysilsesquioxane having alkoxy groups.

3. The colored resin particle dispersion according to claim 1, wherein the solid resin is a polysilsesquioxane.

4. The colored resin particle dispersion according to claim 1, wherein the resin having alkoxy groups has methoxy groups and/or ethoxy groups.

5. The colored resin particle dispersion according to claim 1, wherein the resin having alkoxy groups has methoxy groups.

6. The colored resin particle dispersion according to claim 1, wherein the resin having alkoxy groups has ethoxy groups.

7. The colored resin particle dispersion according to claim 1, wherein the solid resin comprises at least one of a polyamide resin having methoxymethyl groups, a methoxypolysilsesquioxane and an ethoxypolysilsesquioxane.

8. The colored resin particle dispersion according to claim 1, wherein the solid resin comprises a polyamide resin having methoxymethyl groups.

9. The colored resin particle dispersion according to claim 1, wherein the solid resin comprises a methoxypolysilsesquioxane.

10. The colored resin particle dispersion according to claim 1, wherein the solid resin comprises an ethoxypolysilsesquioxane.

11. The colored resin particle dispersion according to claim 1, wherein the colored resin particles further comprise a liquid organic compound having an acidic group.

12. The colored resin particle dispersion according to claim 11, wherein the liquid organic compound having an acidic group comprises a liquid organic compound having a phosphoric acid group.

13. The colored resin particle dispersion according to claim 1, wherein the colored resin particles further comprise at least one compound selected from the group consisting of liquid polyesters, liquid polyethers, and liquid (meth)acrylic polymers.

14. The colored resin particle dispersion according to claim 1, wherein the colored resin particles further comprise a liquid polyester.

15. The colored resin particle dispersion according to claim 1, wherein the colored resin particles further comprise a liquid polyether.

16. The colored resin particle dispersion according to claim 1, wherein the colored resin particles further comprise a liquid (meth)acrylic polymer.

17. An inkjet ink comprising the colored resin particle dispersion according to claim 1.

18. A colored resin particle dispersion comprising colored resin particles containing a colorant and a solid resin, a basic dispersant, and a non-aqueous solvent, wherein the solid resin is a resin having alkoxy groups and/or a polysilsesquioxane, and the colored resin particles further comprise a liquid organic compound having an acidic group.

19. The colored resin particle dispersion according to claim 18, wherein the liquid organic compound having an acidic group comprises a liquid organic compound having a phosphoric acid group.

Description

EXAMPLES

(1) The present invention is described below in further detail using a series of examples, but the present invention is in no way limited by these examples. Unless specifically state otherwise, “%” refers to “mass %”.

(2) <Ink Preparation>

(3) Formulations of oil-in-oil emulsions for a series of examples and comparative examples prior to removal of the solvent B are shown in Table 2 to Table 4. In each table, when a dispersant includes a volatile component, the total amount of the dispersant is shown, and the non-volatile fraction amount is also shown in parentheses (this also applies in Tables 5 to 7 below).

(4) The continuous phase was prepared by mixing the solvent A and the basic dispersant in the blend amounts shown in each table. Subsequently, the dispersed phase was prepared by mixing the dye, the solid resin and the acidic compound with the solvent B in the blend amounts shown in each table.

(5) With the continuous phase in a state of continuous stirring with a magnetic stirrer under ice cooling, a 10 minute irradiation with an ultrasonic homogenizer (Ultrasonic Processor VC-750, manufactured by Sonics & Materials, Inc.) was conducted while the premixed dispersed phase was added dropwise to the continuous phase, thus obtaining an oil-in-oil (O/O) emulsion.

(6) The solvent B within the dispersed phase was removed from the obtained emulsion under reduced pressure using an evaporator, thus obtaining a colored resin particle dispersion. The rate of removal of the solvent B was essentially 100 mass %. This colored resin particle dispersion was used as an ink with no further modification.

(7) Inks of the examples and comparative examples were also prepared in the same manner as described above, with the following exceptions.

(8) In Examples 5 and 14, the acidic compound was not added to the dispersed phase.

(9) In Examples 8 and 17, the acidic compound was not added to the dispersed phase, but a polyester polyol was added.

(10) In Comparative Examples 1 to 6, the acidic compound was not added to the dispersed phase. Moreover, in Comparative Examples 5 and 6, an alkoxy group-containing liquid compound and a polyester polyol respectively were added to the dispersed phase.

(11) Formulations of the inks of the examples and comparative examples following removal of the solvent B are shown in Table 5 to Table 7. The amount of the non-volatile fraction was determined from the combined total of the amount of each of the non-volatile components (the basic dispersant, the dye, the resin component and the acidic compound) relative to the total mass of the ink, and this amount of the non-volatile fraction is also shown in each table.

(12) TABLE-US-00002 TABLE 2 Formulations of oil-in-oil emulsions of Examples (prior to solvent B removal) Example Units: mass % 1 2 3 4 5 6 7 8 9 Continuous Solvent A “Isopar M” 57.0 57.0 57.0 57.0 57.0 57.0 57.0 57.0 54.0 phase Basic dispersant “S17000” 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (non-volatile fraction 100%) Basic dispersant “S11200” 6.0 (non-volatile fraction 50%) (3.0) Dispersed Solvent B “Methanol” 28.0 28.0 28.0 28.0 28.0 24.0 30.0 28.0 27.0 phase Black metal complex dye 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Yellow metal complex dye Carbon black 3.0 Acidic compound “BYK111” 4.0 4.0 4.0 4.0 4.0 4.0 5.0 (non-volatile fraction 95.0%) (3.8) (3.8) (3.8) (3.8) (3.8) (3.8) Polyester polyol 4.0 Solid PSQ “SR13” 4.0 2.0 4.0 5.0 resin PSQ “SR23” 2.0 PSQ “SR33” 4.0 8.0 8.0 2.0 Polyvinyl alcohol 2.0 Polyvinyl acetal resin 2.0 Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

(13) TABLE-US-00003 TABLE 3 Formulations of oil-in-oil emulsions of Examples (prior to solvent B removal) Example Units: mass % 10 11 12 13 14 15 16 17 Continuous Solvent A “Isopar M” 57.0 57.0 57.0 57.0 57.0 57.0 57.0 57.0 phase Basic dispersant “S17000” 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (non-volatile fraction 100%) Dispersed Solvent B “Methanol” 28.0 28.0 28.0 28.0 28.0 24.0 30.0 24.0 phase Black metal complex dye 4.0 4.0 4.0 4.0 4.0 4.0 Yellow metal complex dye 4.0 4.0 Acidic compound “BYK111” 4.0 4.0 4.0 4.0 4.0 4.0 (non-volatile fraction 95.0%) (3.8) (3.8) (3.8) (3.8) (3.8) (3.8) Polyester polyol 4.0 Solid Methoxymethylated 4.0 4.0 8.0 4.0 resin nylon “FR101” Methoxymethylated 4.0 4.0 8.0 2.0 nylon “FR301” Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

(14) TABLE-US-00004 TABLE 4 Formulations of oil-in-oil emulsions of Comparative Examples (prior to solvent B removal) Comparative Example Units: mass % 1 2 3 4 5 6 Continuous Solvent A “Isopar M” 57.0 57.0 57.0 57.0 57.0 57.0 phase Basic dispersant “S17000” 3.0 3.0 3.0 3.0 3.0 3.0 (non-volatile fraction 100%) Dispersed Solvent B “Methanol” 32.0 32.0 32.0 28.0 32.0 28.0 phase Black metal complex dye 4.0 4.0 4.0 4.0 Yellow metal complex dye 4.0 4.0 Polyester polyol 4.0 Solid Polyvinyl alcohol 4.0 4.0 8.0 2.0 4.0 resin Polyvinylpyrrolidone 4.0 Alkoxy group-containing liquid 2.0 compound (KR500) Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0

(15) The components shown in each of the tables are described below.

(16) (Continuous Phase)

(17) Solvent A “Isopar M”: an isoparaffin-based hydrocarbon-based solvent, manufactured by TonenGeneral Sekiyu K.K.

(18) Basic dispersant “S17000”: Solsperse 17000 manufactured by Lubrizol Japan Ltd., base value 2 mgKOH/g, non-volatile fraction 100%.

(19) Basic dispersant “S11200”: Solsperse 11200 manufactured by Lubrizol Japan Ltd., base value 37 mgKOH/g, non-volatile fraction 50%.

(20) (Dispersed Phase)

(21) Solvent B “Methanol”: an alcohol-based solvent having a carbon number of 1, manufactured by Wako Pure Chemical Industries, Ltd.

(22) Black metal complex dye: “Valifast Black 3810” manufactured by Orient Chemical Industries Co., Ltd.

(23) Yellow metal complex dye: “Valifast Yellow 1101” manufactured by Orient Chemical Industries Co., Ltd.

(24) Carbon black: a black pigment “PBk7”, Pigment Black 7, manufactured by Cabot Specialty Chemicals, Inc.

(25) Acidic compound 1 “BYK111”: a liquid organic compound having two phosphate ester groups (a phosphate ester compound having phosphoric acid groups at both terminals of a copolymer), “DISPERBYK-111” manufactured by BYK-Chemie Japan K.K., acid value 129 mgKOH/g, non-volatile fraction 95.0%.

(26) Polyester polyol: a liquid, “Adeka Polyether CM294” (Mw) 2,900, manufactured by Adeka Corporation.

(27) (Solid Resin)

(28) PSQ “SR13”: a polymethylsilsesquioxane (functional groups: methyl groups, terminal groups: silanol groups, ethoxysilane groups (ethoxy groups)), (Mw) 6,000, manufactured by Konishi Chemical Ind. Co., Ltd.

(29) PSQ “SR23”: a polyphenylsilsesquioxane (functional groups: phenyl groups, terminal groups: silanol groups, ethoxysilane groups (ethoxy groups)), (Mw) 1,000, manufactured by Konishi Chemical Ind. Co., Ltd.

(30) PSQ “SR33”: a polymethyl/phenylsilsesquioxane (functional groups: methyl groups and phenyl groups, terminal groups: silanol groups, ethoxysilane groups (ethoxy groups)), (Mw) 1,000, manufactured by Konishi Chemical Ind. Co., Ltd.

(31) Polyvinyl alcohol: degree of saponification 2.7 mol %, (Mw) 15,000, acetate groups 97.3 mol %, “JMR-8L” manufactured by Japan VAM & Poval Co., Ltd.

(32) Polyvinyl acetal resin: “S-LEC BL-10”, a polyvinyl butyral resin, (Mw) 15,000, manufactured by Sekisui Chemical Co., Ltd.

(33) Alkylphenol resin: “Tamanol 7509”, manufactured by Arakawa Chemical Industries, Ltd.

(34) Methoxymethylated nylon “FR101”: methoxymethylation rate 30%, (Mw) 20,000, manufactured by Namariichi Co., Ltd.

(35) Methoxymethylated nylon “FR301”: methoxymethylation rate 20%, (Mw) 17,000, manufactured by Namariichi Co., Ltd.

(36) Polyvinylpyrrolidone: “PVP K-30”, (Mw) 40,000, manufactured by Wako Pure Chemical Industries, Ltd.

(37) Alkoxy group-containing liquid organic compound “KR500”: an alkoxy oligomer having methoxy groups (methyl-based silicone alkoxy oligomer), amount of alkoxy groups 28 mass %, (Mw) 1,000, manufactured by Shin-Etsu Chemical Co., Ltd.

(38) The above Mw values indicate the weight-average molecular weight.

(39) Among the above resins, the PSQ “SR13”, PSQ “SR23”, PSQ “SR33”, polyvinyl alcohol, polyvinyl acetal resin, alkylphenol resin, methoxymethylated nylon “FR101”, methoxymethylated nylon “FR301” and polyvinylpyrrolidone are all solid at 23° C.

(40) The polyester polyol and the alkoxy group-containing liquid organic compound “KR500” are liquid at 23° C.

(41) The solubility of the methanol of the solvent B in the hydrocarbon-based solvent (Isopar M) of the solvent A at 23° C. is 0.4 g/100 g. Further the boiling point of methanol is 64.7° C., and the 50% distillation point of Isopar M is 234° C.

(42) The Solsperse 17000 and 11200 used as the basic dispersants were dissolved in the solvent A in accordance with the continuous phase blend proportions shown in Table 2 to Table 4, whereas the solubility of each of these components in the solvent B at 23° C. was less than 3 g/100 g.

(43) The resins were dissolved in the solvent B in accordance with the dispersed phase blend proportions shown in Table 2 to Table 4, whereas the solubility of the resins in the solvent A at 23° C. was less than 3 g/100 g, and the solubility in water at 23° C. was less than 3 g/100 g.

(44) The acidic compound was dissolved in the solvent B in accordance with the dispersed phase blend proportions shown in Table 2 to Table 4, whereas the solubility of the acidic compound in the solvent A at 23° C. was less than 3 g/100 g.

(45) The alkoxy group-containing liquid organic compound and the polyester polyol were dissolved in the solvent B in accordance with the dispersed phase blend proportions shown in Table 2 to Table 4, whereas the solubility of each of these components in the solvent A at 23° C. was less than 3 g/100 g.

(46) The solubility parameter (HSP value) of each component is detailed below. The units are MPa/cm.sup.3. Further, the dispersion parameter δd, the polar parameter δp, and the hydrogen bonding parameter δh are also shown below.

(47) Solvent A “Isopar M”: 16 (δd=16, δp=0, δh=0).

(48) Solvent B “Methanol”: 29.6 (δd=15.1, δp=12.3, δh=22.3).

(49) The various solid resins: within a range from 22 to 27 (δd=12 to 20, δp=5 to 12, δh=10 to 20).

(50) The acidic compound: within a range from 22 to 27 (δd=12 to 20, δp=5 to 12, δh=10 to 20).

(51) The oxidation-reduction potential (ORP value) of each component is listed below. The units are mV.

(52) Solsperse 17000: the ORP value when dissolved in dodecane at 5.0 mass % was lower than the ORP value when dissolved at 0.5 mass %, and the ORP value when dissolved in dodecane at 5.0 mass % was 325.

(53) Solsperse 11200: the ORP value when dissolved in dodecane at 5.0 mass % was lower than the ORP value when dissolved at 0.5 mass %, and the ORP value when dissolved in dodecane at 5.0 mass % was −85.

(54) DISPERBYK-111: the ORP value when dissolved in methanol at 5.0 mass % was higher than the ORP value when dissolved at 0.5 mass %, and the ORP value when dissolved in methanol at 5.0 mass % was 350.

(55) TABLE-US-00005 TABLE 5 Ink formulations of Examples (after solvent B removal) and evaluation results Example Units: mass % 1 2 3 4 5 6 7 8 9 Continuous Solvent A “Isopar M” 79.2 79.2 79.2 79.2 79.2 75.0 81.4 79.2 74.0 phase Basic dispersant “S17000” 4.2 4.2 4.2 4.2 4.2 3.9 4.3 4.2 (non-volatile fraction 100%) Basic dispersant “S11200” 8.2 (non-volatile fraction 50%) (4.1) Dispersed Solvent B “Methanol” 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 phase Black metal complex dye 5.6 5.6 5.6 5.6 5.6 5.3 5.7 5.6 Yellow metal complex dye Carbon black 4.1 Acidic compound “BYK111” 5.6 5.6 5.6 5.6 5.3 5.7 6.9 (non-volatile fraction 95.0%) (5.3) (5.3) (5.3) (5.3) (5.0) (5.4) (6.5) Polyester polyol 5.6 Solid PSQ “SR13” 5.6 2.8 5.6 6.9 resin PSQ “SR23” 2.8 PSQ “SR33” 5.6 11.1 10.5 2.9 Polyvinyl alcohol 2.8 Polyvinyl acetal resin 2.8 Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Amount of non-volatile fraction (mass %) 20.7 20.7 20.7 20.7 20.9 24.7 18.3 21.0 21.9 Evaluations Particle size [nm] 140 150 130 140 230 200 150 150 200 Rub fastness after short time A A A A B A B B A Rub fastness after standing A A A A A A A A A for 1 day Storage stability at 70° C. A A A A B A A B A (precipitation) Oil resistance after standing A A A A A A A A A for 1 day Water resistance after standing A A A A A A A A A for 1 day

(56) TABLE-US-00006 TABLE 6 Ink formulations of Examples (after solvent B removal) and evaluation results Example Units: mass % 10 11 12 13 14 15 16 17 Continuous Solvent A “Isopar M” 79.2 79.2 79.2 79.2 79.2 75.0 81.4 79.2 phase Basic dispersant “S17000” 4.2 4.2 4.2 4.2 4.2 3.9 4.3 42 (non-volatile fraction 100%) Dispersed Solvent B “Methanol” 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 phase Black metal complex dye 5.6 5.6 5.6 5.3 5.7 5.6 Yellow metal complex dye 5.6 5.6 Acidic compound “BYK111” 5.6 5.6 5.6 5.6 5.3 5.7 (non-volatile fraction 95.0%) (5.3) (5.3) (5.3) (5.3) (5.0) (5.4) Polyester polyol 5.6 Solid Methoxymethylated 5.6 5.6 11.1 5.6 resin nylon “FR101” Methoxymethylated 5.6 5.6 10.5 2.9 nylon “FR301” Polyester polyol 5.6 Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Amount of non-volatile fraction (mass %) 20.7 20.7 20.7 20.7 20.9 24.7 18.3 21.0 Evaluations Particle size [nm] 160 200 150 190 240 190 160 160 Rub fastness after short time A A A A B A B B Rub fastness after standing A A A A A A A A for 1 day Storage stability at 70° C. A A A A B A A B (precipitation) Oil resistance after standing A A A A A A A A for 1 day Water resistance after standing A A A A A A A A for 1 day

(57) TABLE-US-00007 TABLE 7 Ink formulations of Comparative Examples (after solvent B removal) and evaluation results Comparative Example Units: mass % 1 2 3 4 5 6 Continuous Solvent A “Isopar M” 83.8 83.8 83.8 79.2 83.8 79.2 phase Basic dispersant “S17000” 4.4 4.4 4.4 4.2 4.4 4.2 (non-volatile fraction 100%) Dispersed Solvent B “Methanol” 0.0 0.0 0.0 0.0 0.0 0.0 phase Black metal complex dye 5.9 5.9 5.6 5.6 Yellow metal complex dye 5.9 5.9 Polyester polyol 5.6 Solid Polyvinyl alcohol 5.9 5.9 11.1 2.9 5.6 resin Polyvinylpyrrolidone 5.9 Alkoxy group-containing liquid 2.9 compound (KR500) Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 Amount of non-volatile fraction (mass %) 16.2 16.2 16.2 20.9 16.6 21.0 Evaluations Particle size [nm] 200 150 250 >1000 300 >1000 Rub fastness after short time C C C C C C Rub fastness after standing A B A C B C for 1 day Storage stability at 70° C. C B C C C C (precipitation) Oil resistance after standing C C C C C C for 1 day Water resistance after standing A C A A A A for 1 day
<Evaluations>

(58) Using each of the inks described above, each of the following evaluations was performed. The results are shown in the above tables.

(59) (Rub Fastness)

(60) Each of the inks described above was mounted in a line-type inkjet printer “Orphis-X9050” (manufactured by Riso Kagaku Corporation), and a printed item was obtained by printing a solid image onto a high-quality coated paper “Aurora Coated Paper” (manufactured by Nippon Paper Industries Co., Ltd.). The printing was performed at a resolution of 300×300 dpi, under discharge conditions including an ink volume per dot of 42 pl. The “Orphis X9050” is a system that uses a line-type inkjet head, wherein the paper is transported in a sub-scanning direction perpendicular to the main scanning direction (the direction along which the nozzles are aligned) while printing is conducted.

(61) Following standing for 10 seconds (short time) or 24 hours (1 day) after printing, the solid image portion of the printed item was rubbed strongly 5 times with a finger. The state of the printed item was then inspected visually, and the rub fastness was evaluated against the following criteria.

(62) A: almost no separation of the image could be detected.

(63) B: minor separation of the image was confirmed, but not problematic in actual use.

(64) C: marked separation of the image occurred, at a level problematic for actual use.

(65) (Storage Stability)

(66) A 7 g sample of the ink was placed in a glass bottle (capacity 10 ml), the lid of the bottle was sealed, and the bottle was then stored in a thermostatic chamber at 70° C. After storage for 2 weeks, the ink was inspected for the presence or absence of precipitation, and the storage stability was evaluated against the following criteria.

(67) A: no precipitation.

(68) B: a small amount of fluid precipitate.

(69) C: non-fluid precipitate.

(70) (Oil Resistance after Standing for 1 Day)

(71) A printed item was obtained in the same manner as that described above for the rub fastness evaluation. Following standing for 24 hours (1 day) after printing, 0.5 ml of a salad oil was applied to the solid image portion of the printed item and left to stand for 300 seconds. After this standing period, the oil was wiped away with a Bemcot wipe (manufactured by Asahi Kasei Corporation), and the degree of separation of the printed image was evaluated visually. The evaluation criteria are as described below.

(72) A: no color loss from the image, and only very minor soiling around the image periphery.

(73) B: slight color loss from the image is noticeable, and some soiling around the image periphery, but of a level not problematic in actual use.

(74) C: significant color loss from the image, and severe soiling around the image periphery, at a level problematic for actual use.

(75) (Water Resistance after Standing for 1 Day)

(76) A printed item was obtained in the same manner as that described above for the rub fastness evaluation. Following standing for 24 hours (1 day) after printing, 0.5 ml of water was dripped onto the solid image portion of the printed item, the level of bleeding was observed visually, and the water resistance was evaluated against the following criteria.

(77) A: no bleeding of the printed image portion.

(78) B: minor bleeding of the printed image portion, but not problematic in actual use.

(79) C: bleeding of the printed image portion, at a level problematic for actual use.

(80) (Average Particle Size of Colored Resin Particles)

(81) For each of the inks described above, the volume-based average particle size of the colored resin particles dispersed in the ink was measured using a dynamic light scattering particle size distribution analyzer “LB-500” (manufactured by Horiba, Ltd.).

(82) As is evident from the tables shown above, the ink of each example exhibited favorable results for all the evaluations, and furthermore, the average particle size of the colored resin particles also fell within an appropriate range.

(83) In Examples 1 to 9, a polysilsesquioxane having ethoxy groups was used, and favorable results were obtained in each case.

(84) In Examples 3 and 4, a polysilsesquioxane having ethoxy groups was used together with another resin, and favorable results were obtained that were similar to those of Examples 1 and 2 which used only the polysilsesquioxane with ethoxy groups.

(85) In Example 5, the acidic compound was not included, but satisfactory results were still obtained. In Example 6, which used a similar blend to Example 5 but also included the acidic compound, more favorable results were obtained. Further, by including the acidic compound, the particle size of the colored resin particles was able to be kept small.

(86) In Examples 2 and 6, the blend amount of the polysilsesquioxane having alkoxy groups was larger than that used in Example 7, and the rub fastness after standing for a short time was able to be further enhanced.

(87) In Example 8, the acidic compound was not included, and the amount of the polysilsesquioxane was less than that used in Example 5, but the polyester polyol acted as a plasticizer, and therefore satisfactory results were able to be obtained.

(88) In Examples 10 to 17, a methoxymethylated nylon was used, and favorable results were obtained in each case.

(89) In Examples 10 to 13, combinations of methoxymethylated nylons having different methoxymethylation rates and different dyes were used, but favorable results were obtained in each case.

(90) Example 14 did not include the acidic compound, but satisfactory results were still obtained. In Example 10, which used a similar blend to Example 14 but also included the acidic compound, more favorable results were obtained. Further, by including the acidic compound, the particle size of the colored resin particles was able to be kept small.

(91) In Examples 12 and 15, the blend amount of the methoxymethylated nylon was larger than that used in Example 16, and the rub fastness after standing for a short time was able to be further enhanced.

(92) In Example 17, the acidic compound was not included, but the polyester polyol acted as a plasticizer, and therefore satisfactory results were able to be obtained.

(93) In each of the comparative examples, neither a solid resin having alkoxy groups nor a polysilsesquioxane was included, and satisfactory results could not be obtained.

(94) In Comparative Examples 1 and 3, although different dyes were used, a PVA was used as the resin, and the rub fastness after standing for a short time, the 70° C. storage stability and the oil resistance after standing for 1 day all deteriorated.

(95) In Comparative Example 4, although the amount of PVA relative to the dye was large, satisfactory results could not be obtained.

(96) In Comparative Example 2, a polyvinylpyrrolidone was used as the resin, and the rub fastness after standing for a short time and the oil resistance after standing for 1 day both deteriorated. Further, the water resistance was also inferior.

(97) In Comparative Example 5, a combination of a PVA and an alkoxy group-containing liquid compound was used, but compared with the examples which used the solid resin having alkoxy groups, satisfactory results could not be obtained.

(98) In Comparative Example 6, a PVA and the polyester polyol which acted as a plasticizer were included, but satisfactory results could not be obtained.

(99) It is to be noted that, besides those already mentioned above, many modifications and variations of the above embodiments may be made without departing from the novel and advantageous features of the present invention. Accordingly, all such modifications and variations are intended to be included within the scope of the appended claims.