WHITE INKJET INK FOR TEXTILE PRINTING, INK SET, AND METHOD FOR PRODUCING PRINTED TEXTILE ITEM

Abstract

Provided is a white inkjet ink for textile printing including: a white inorganic pigment, resin particles A, resin particles B, and water, in which a film elongation of the resin particles A is at least 1000%, the resin particles B are ionic resin particles with an average particle size of not more than 150 nm, and an average particle size of the resin particles A is twice or more than the average particle size of the resin particles B. An ink set and a method for producing a printed textile item are also provided.

Claims

1. A white inkjet ink for textile printing comprising: a white inorganic pigment; resin particles A; resin particles B; and water, wherein a film elongation of the resin particles A is at least 1000%, the resin particles B are ionic resin particles with an average particle size of not more than 150 nm, and an average particle size of the resin particles A is twice or more than the average particle size of the resin particles B.

2. The white inkjet ink for textile printing according to claim 1, wherein the film elongation of the resin particles A is at least 1500%.

3. The white inkjet ink for textile printing according to claim 1, wherein a charge density of the resin particles B is at least 60 μeq/g.

4. The white inkjet ink for textile printing according to claim 1, wherein the average particle size of the resin particles A is four times or more than the average particle size of the resin particles B.

5. The white inkjet ink for textile printing according to claim 1, wherein a mass ratio of a total amount of the resin particles A and the resin particles B relative to the white inorganic pigment, “(the resin particles A+the resin particles B)/the white inorganic pigment”, is at least 1.

6. The white inkjet ink for textile printing according to claim 1, wherein a mass ratio of the resin particles A relative to the resin particles B “the resin particles A/the resin particle B” is at least 2.5.

7. An ink set comprising: the white inkjet ink for textile printing according to claim 1; and a pretreatment liquid containing a polyvalent metal salt, water, and a water-soluble organic solvent.

8. The ink set according to claim 7, further comprising: a non-white inkjet ink for textile printing.

9. The ink set according to claim 7, wherein the film elongation of the resin particles A is at least 1500%.

10. The ink set according to claim 7, wherein a charge density of the resin particles B is at least 60 μeq/g.

11. The ink set according to claim 7, wherein the average particle size of the resin particles A is four times or more than the average particle size of the resin particles B.

12. The ink set according to claim 7, wherein a mass ratio of a total amount of the resin particles A and the resin particles B relative to the white inorganic pigment “(the resin particles A+the resin particles B)/the white inorganic pigment” is at least 1.

13. The ink set according to claim 7, wherein a mass ratio of the resin particles A relative to the resin particles B “the resin particles A/the resin particle B” is at least 2.5.

14. A method for producing a printed textile item comprising: applying a pretreatment liquid containing a polyvalent metal salt, water, and a water-soluble organic solvent to a fabric; and applying the white inkjet ink for textile printing according to claim 1, using an inkjet method and a wet-on-wet method, to the fabric to which the pretreatment liquid has been applied.

15. The method for producing a printed textile item according to claim 14, further comprising: applying a non-white inkjet ink for textile printing to the fabric to which the white inkjet ink for textile printing has been applied.

16. The method for producing a printed textile item according to claim 14, wherein the film elongation of the resin particles A is at least 1500%.

17. The ink method for producing a printed textile item according to claim 14, wherein a charge density of the resin particles B is at least 60 μeq/g.

18. The method for producing a printed textile item according to claim 14, wherein the average particle size of the resin particles A is four times or more than the average particle size of the resin particles B.

19. The method for producing a printed textile item according to claim 14, wherein a mass ratio of a total amount of the resin particles A and the resin particles B relative to the white inorganic pigment, “(the resin particles A+the resin particles B)/the white inorganic pigment”, is at least 1.

20. The method for producing a printed textile item according to claim 14, wherein a mass ratio of the resin particles A relative to the resin particles B “the resin particles A/the resin particle B” is at least 2.5.

Description

EXAMPLES

[0197] Embodiments of the present invention will be described below in further detail by using examples. The present invention is not limited to the examples below.

[0198] In the following descriptions, except for the film elongation, “%” represents “% by mass” unless specifically stated otherwise. With respect to the materials in the form of a solution, dispersion, or the like, the amounts shown in each table indicate the total amounts of the materials (in the form of a solution, dispersion, or the like), and the proportions of pigment fractions, resin fractions, active components, and the like are also shown.

1. Production of Pretreatment Liquid

[0199] Table 1 shows the formulation of the pretreatment liquid. The raw materials were mixed at the blending ratio shown in Table 1, and the obtained mixture was filtered by using a cellulose acetate membrane filter having a pore size of 3 μm. Accordingly, pretreatment liquid UC1 was obtained.

[0200] Details of the raw materials shown in Table 1 are as follows.

(Polyvalent Metal Salt)

[0201] Calcium nitrate tetrahydrate: manufactured by FUJIFILM Wako Pure Chemical Corporation, active components (as an anhydrous salt) 69% by mass

(Surfactant)

[0202] OLFINE E1010: acetylene glycol-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd.

(Water-Soluble Organic Solvent)

[0203] Diethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Corporation

TABLE-US-00001 TABLE 1 Formulation of pretreatment liquid Pretreatment Units: % by mass liquid UC1 Polyvalent metal salt Calcium nitrate tetrahydrate 29.0 (active component 69%) Surfactant OLFINE E1010 0.5 Water-soluble organic Diethylene glycol 29.0 solvent Water Ion-exchanged water 41.5 Total (% by mass) 100.0

2. Production of Inkjet Inks for Textile Printing

(1) Production of White Pigment Dispersion

[0204] First, 250 g of titanium oxide “R62N” (manufactured by Sakai Chemical Industry Co., Ltd.) as a white inorganic pigment and 10 g (active component: 2.5 g) of “DEMOL EP” (manufactured by Kao Corporation) as a pigment dispersant were mixed with 740 g of ion-exchanged water, and a beads mill (DYNO-MILL KDL model A, manufactured by Shinmaru Enterprises Corporation) containing 0.5 mmø zirconia beads at a fill ratio of 80% was used to disperse the mixture under conditions including a retention time of 2 minutes, thus obtaining a white pigment dispersion (pigment fraction: 25% by mass).

(2) Production of White Inks

[0205] Tables 2 to 4 show the formulations of white inks W1 to W15. The raw materials were mixed at the blending ratios shown in the tables, and the obtained mixtures were filtered by using a cellulose acetate membrane filter having a pore size of 3 μm. Accordingly, the white inks W1 to W15 were obtained.

[0206] Details of the raw materials of the white inks W1 to W15 shown in Tables 2 to 4 are as follows.

(Pigment Dispersion)

[0207] White pigment dispersion: obtained using the method described above, pigment fraction: 25% by mass

(Resin Particles A)

[0208] Dispersion A1: “Impranil DLP-R”, water dispersion of polyurethane resin particles, manufactured by Sumika Covestro Urethane Co., Ltd., resin fraction: 50% by mass

[0209] Dispersion A2: “SUPERFLEX E2000”, water dispersion of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 50% by mass

[0210] Dispersion A3:“SUPERFLEX 740”, water dispersion of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 40% by mass

[0211] Dispersion C1: “SUPERFLEX 470”, water dispersion of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 38% by mass

(Resin Particles B)

[0212] Dispersion B 1: “SUPERFLEX 420”, water dispersion of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 32% by mass, ionic

[0213] Dispersion B2: “DAOTAN TW6460” water dispersion of polyurethane resin particles, manufactured by Daicel Allnex Ltd., resin fraction: 35% by mass, ionic

[0214] Dispersion B3: “SUPERFLEX 150HS”, water dispersion of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 30% by mass, ionic

[0215] Dispersion B4: “Elitel KT9204”, water dispersion of polyester resin particles, manufactured by UNITIKA LTD., resin fraction: 30% by mass, ionic

[0216] Dispersion C2: “Aquacer 515”, water dispersion of polyolefin resin particles, manufactured by BYK-Chemie Japan K.K., resin fraction: 35% by mass, nonionic

(Surfactant)

[0217] OLFINE E1010: acetylene glycol-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd.

(Water-Soluble Organic Solvents)

[0218] Glycerol: manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0219] Diethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Corporation.

3. Measurement of Film Elongations of Resin Particles

[0220] Tables 2 to 4 show the film elongations of resin particles of each of the resin particle dispersions used for white inks W1 to W15 except for dispersion C2. The film elongations of the resin particles shown in the tables are the values obtained by means of the following procedure.

[0221] First, each of the water dispersions of the resin particles was applied to a polytetrafluoroethylene sheet in an amount sufficient to achieve a dried film thickness of 500 μm. Then, the applied resin dispersion was dried at 23° C. for 15 hours, and then dried at 80° C. for 6 hours, and at 120° C. for 20 minutes. Thereafter, the resulting film was detached from the sheet to complete production of a resin film. The obtained resin film was cut into columns 2 cm wide and 4 cm long, thus obtaining a resin film test piece. Using a Tensilon Universal Tester RTC-1225A (manufactured by ORIENTEC CO., LTD.), at a measurement temperature of 20° C. and a measurement speed of 200 mm/min, the obtained resin film test piece was stretched, and the length of the stretched resin film test piece when the resin film test piece breaks was measured. The value of the ratio of this stretched length relative to the original length expressed as a percentage was deemed the film elongation.

[0222] 4. Measurement of average particle size of resin particles

[0223] Tables 2 to 4 show average particle sizes of each of the resin particles used for the white inks W1 to W15. A dynamic light scattering type of particle size distribution measuring apparatus “nanoparticle analyzer nano Partica SZ-100” (manufactured by HORIBA, Ltd.) was used to measure the average particle size. The average particle sizes of the resin particles shown in the tables are volume-based median diameters which are obtained by diluting each of the water dispersions of the resin particles with purified water such that the particle concentration becomes 0.5% by mass, and the measurement was performed at a temperature of 25° C. under the following conditions: dispersion medium refractive index: 1.333, sample refractive index: 1.600, and calculation conditions: polydisperse and narrow setting.

5. Measurement of charge density of resin particles

[0224] Tables 2 to 4 show charge densities of each of the water dispersions of the resin particles used for white inks W1 to W15. The charge densities of each of the water dispersions of the resin particles shown in the tables are values obtained by means of a streaming potential method based on the following procedure. A colloid particle charge meter (manufactured by AFG Analytic GmbH, Model CAS) was used to measure the charge densities. The water dispersion of the resin particles to be measured was diluted 100 times with ion-exchanged water, the dilute liquid was titrated by using 0.0025N poly(diallyldimethylammonium chloride) solution (manufactured by FUJIFILM Wako Pure Chemical Corporation), and the reaction end point where the streaming potential of the sample reaches 0 V was measured. The total amount of charge of the sample (diluted water dispersion of resin particles) was obtained from the amount of the 0.0025N poly(diallyldimethylammonium chloride) solution used in reaching this reaction end point. A value obtained by dividing the total amount of charge of the sample (diluted water dispersion of resin particles) by the solid fraction amount of the resin particles contained in the sample is the charge density of the resin particles (μeq/g)

6. Production of Printed Textile Items

[0225] The printed textile items of Examples 1 to 10 and Comparative Examples 1 to 5 were produced by means of the following procedure using the pretreatment liquid and white ink produced as above.

[0226] Tables 2 to 4 show the white inks used for producing the printed textile items of Examples 1 to 10 and Comparative Examples 1 to 5.

[0227] A black cotton T-shirt (product name: Printstar) manufactured by Toms Co., Ltd. was used as a substrate. The pretreatment liquid UC1 was applied to a 10 cm×20 cm portion of the surface of the black cotton T-shirt by means of an inkjet method. The application amount of the pretreatment liquid was about 50 g/m.sup.2. After the pretreatment liquid was applied, the white ink was applied, by means of an inkjet method without providing a drying step, to the portion to which the pretreatment liquid has been applied. The application amount of the white ink was about 180 g/m.sup.2. An “MMP-8130” manufactured by Mastermind Inc., was used as a printing device for both the application of the pretreatment liquid and the application of the white ink. Thereafter, heat drying was performed at 160° C. for 2 minutes using a heat press machine manufactured by Fusion Co. Accordingly, printed textile items were obtained.

7. Evaluation of printed textile items

[0228] The concealment properties due to white images of the printed textile items of Examples 1 to 10 and Comparative Examples 1 to 5 were determined based on the following criteria. Tables 2 to 4 show the evaluation results. [0229] A: The white image has high whiteness and also has good uniformity [0230] B: Although the white image has slightly lower whiteness, the white image has good uniformity [0231] C: The white image has high or slightly low whiteness and slight irregularities are observed in the white image [0232] D: The white image has low whiteness and/or many irregularities are observed in the white image

TABLE-US-00002 TABLE 2 (Units: % by mass) Charge Examples density Average 1 2 3 4 5 Film of resin particle White White White White White elongation particles size Resin Pigment ink ink ink ink ink Raw material (%) (μeq/g) (nm) (%) (%) W1 W2 W3 W4 W5 White pigment 25 40.0 35.0 30.0 50.0 40.0 dispersion Resin Dispersion 1600 46 426 50 25.0 30.0 35.0 20.0 20.0 particles A1 A Dispersion 1350 1 588 50 A2 Dispersion 1300 69 170 40 A3 Dispersion 640 36 108 38 C1 Resin Dispersion 290 101 73 32 9.4 11.3 13.1 5.0 17.2 particles B1 B Dispersion 680 57 70 35 B2 Dispersion 480 85 83 30 B3 Dispersion <100 20 108 30 B4 Dispersion 81 74 35 C2 OLFINE E1010 0.5 0.5 0.5 0.5 0.5 Glycerol 5.0 5.0 5.0 5.0 5.0 Diethylene glycol 15.0 15.0 15.0 15.0 15.0 Ion-exchanged water 5.1 3.3 1.4 4.5 2.3 Total (% by mass) 100.0 100.0 100.0 100.0 100.0 Amount of white inorganic pigment (% by mass) 10.0 8.8 7.5 12.5 10.0 Amount of resin particles A (% by mass) 12.5 15.0 17.5 10.0 10.0 Amount of resin particles B (% by mass) 3.0 3.6 4.2 1.6 5.5 Average particle size of resin particles A/ 5.8 5.8 5.8 5.8 5.8 average particle size of resin particles B Mass ratio “(resin particles A + resin particles B)/ 1.6 2.1 2.9 0.9 1.6 white inorganic pigment” Mass ratio “resin particles A/resin particles B” 4.2 4.2 4.2 6.3 1.8 Concealment properties A A A C C

TABLE-US-00003 TABLE 3 (Units: % by mass) Charge Examples density Average 6 7 8 9 10 Film of resin particle White White White White White elongation particles size Resin Pigment ink ink ink ink ink Raw material (%) (μeq/g) (nm) (%) (%) W6 W7 W8 W9 W10 White pigment 25 40.0 40.0 40.0 32.0 40.0 dispersion Resin Dispersion 1600 46 426 50 25.0 25.0 25.0 particles A1 A Dispersion 1350 1 588 50 25.0 A2 Dispersion 1300 69 170 40 31.3 A3 Dispersion 640 36 108 38 C1 Resin Dispersion 290 101 73 32 9.4 9.4 particles B1 B Dispersion 680 57 70 35 8.6 B2 Dispersion 480 85 83 30 10.0 B3 Dispersion <100 20 108 30 10.0 B4 Dispersion 81 74 35 C2 OLFINE E1010 0.5 0.5 0.5 0.5 0.5 Glycerol 5.0 5.0 5.0 5.0 5.0 Diethylene glycol 15.0 15.0 15.0 15.0 15.0 Ion-exchanged water 5.9 4.5 4.5 6.9 5.1 Total (% by mass) 100.0 100.0 100.0 100.0 100.0 Amount of white inorganic pigment (% by mass) 10.0 10.0 10.0 8.0 10.0 Amount of resin particles A (% by mass) 12.5 12.5 12.5 12.5 12.5 Amount of resin particles B (% by mass) 3.0 3.0 3.0 3.0 3.0 Average particle size of resin particles A/ 6.1 5.1 3.9 2.3 8.1 average particle size of resin particles B Mass ratio “(resin particles A + resin particles B)/ 1.6 1.6 1.6 1.9 1.6 white inorganic pigment” Mass ratio “resin particles A/resin particles B” 3.8 4.2 4.2 4.2 4.2 Concealment properties B A B C C

TABLE-US-00004 (Units: % by mass) Charge Comparative examples density Average 1 2 3 4 5 Film of resin particle White White White White White elongation particles size Resin Pigment ink ink ink ink ink Raw material (%) (μeq/g) (nm) (%) (%) W11 W12 W13 W14 W15 White pigment 25 40.0 40.0 40.0 40.0 32.0 dispersion Resin Dispersion 1600 46 426 50 25.0 31.0 particles A1 A Dispersion 1350 1 588 50 A2 Dispersion 1300 69 170 40 31.3 A3 Dispersion 640 36 108 38 32.9 C1 Resin Dispersion 290 101 73 32 9.4 48.4 particles B1 B Dispersion 680 57 70 35 B2 Dispersion 480 85 83 30 B3 Dispersion <100 20 108 30 10.0 B4 Dispersion 81 74 35 8.6 C2 OLFINE E1010 0.5 0.5 0.5 0.5 0.5 Glycerol 5.0 5.0 5.0 5.0 5.0 Diethylene glycol 15.0 15.0 12.2 6.1 15.0 Ion-exchanged water 5.9 8.5 0 0 6.2 Total (% by mass) 100.0 100.0 100.0 100.0 100.0 Amount of white inorganic pigment (% by mass) 10.0 10.0 10.0 10.0 8.0 Amount of resin particles A (% by mass) 12.5 15.5 0.0 0.0 12.5 Amount of resin particles B (% by mass) 0.0 0.0 3.0 15.5 3.0 Average particle size of resin particles A/ — — — — 1.6 average particle size of resin particles B Mass ratio “(resin particles A + resin particles B)/ 1.3 1.6 0.3 1.55 1.9 white inorganic pigment” Mass ratio “resin particles A/resin particles B” — — — — 4.2 Concealment properties D D D D D

[0233] The white images of the printed textile items in Examples 1 to 10 had excellent whiteness and uniformity and exhibited excellent concealment properties.

[0234] Meanwhile, none of the white images of the printed textile items in Comparative Examples 1 to 5 exhibited sufficient concealment properties. In the printed textile items of Comparative Examples 1 and 2 in which the white ink without the resin particles B is used, the whiteness of the white images was low. In the printed textile items of Comparative Examples 3 and 4 in which the white ink without the resin particles A is used, the uniformity of the white images was poor. In the printed textile item of Comparative Example 5 using the white ink in which the average particle size of the resin particles A was less than twice the average particle size of the resin particles B, the whiteness of the white image was low, and sufficient concealment properties could not be obtained.

8. Production of Non-White Ink

[0235] Table 5 shows the formulations of non-white inks K1, C1, M1, and Y1. The raw materials were mixed at the blending ratios shown in Table 5, and the obtained mixtures were filtered by using a cellulose acetate membrane filter having a pore size of 3 μm. Accordingly, the non-white inks K1, C1, M1, and Y1 were obtained.

[0236] Details of the raw materials of the non-white inks K1, C1, M1, and Y1 shown in Table 5 are as follows.

(Pigment Dispersion)

[0237] CAB-O-JET 300: self-dispersing pigment dispersion (black), manufactured by Cabot Japan K.K., pigment fraction: 15% by mass

[0238] CAB-O-JET 250C: self-dispersing pigment dispersion (cyan), manufactured by Cabot Japan K.K., pigment fraction: 10% by mass

[0239] CAB-O-JET 260M: self-dispersing pigment dispersion (magenta), manufactured by Cabot Japan K.K., pigment fraction: 10% by mass

[0240] CAB-O-JET 270: self-dispersing pigment dispersion (yellow), manufactured by Cabot Japan K.K., pigment fraction: 10% by mass

(Resin Particles)

[0241] SUPERFLEX 470: water dispersions of polyurethane resin particles, manufactured by DKS Co., Ltd., resin fraction: 38% by mass

(Surfactant)

[0242] OLFINE E1010: acetylene glycol-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd.

(Water-Soluble Organic Solvent)

[0243] Diethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Corporation.

TABLE-US-00005 TABLE 5 Non-white inks (Units: % by mass) K1 C1 M1 Y1 Pigment CAB-O-JET 300 Pigment 33.3 15% dispersion CAB-O-JET 250C Pigment 50.0 10% CAB-O-JET 260M Pigment 50.0 10% CAB-O-JET 270 Pigment 50.0 10% Resin SUPERFLEX 470 Resin 26.3 26.3 26.3 26.3 particles 38% Surfactant OLFINE E1010 1.0 1.0 1.0 1.0 Water- Diethylene glycol 20.0 20.0 20.0 20.0 soluble organic solvent Water Ion-exchanged water 19.4 2.7 2.7 2.7 Total (% by mass) 100.0 100.0 100.0 100.0

9. Production of Color Printed Textile Item

[0244] The printed textile item was produced by means of the following procedure using the pretreatment liquid UC1, the white ink W2, and the non-white inks K1, C1, M1, and Y1 which were produced as above. A black cotton T-shirt (product name: Printstar) manufactured by Toms Co., Ltd. was used as a substrate, and the pretreatment liquid UC1 was applied to a 10 cm×20 cm portion of the surface of the black cotton T-shirt by means of an inkjet method. The application amount of the pretreatment liquid was about 100 g/m.sup.2. After the pretreatment liquid was applied, the white ink W2 was applied, by means of an inkjet method without providing a drying step, to the portion to which the pretreatment liquid has been applied. The application amount of the white ink was about 180 g/m.sup.2. After the white ink was applied, 2 cm ×2 cm monochromatic solid images of the non-white inks K1, C1, M1, and Y1 were printed on the white image individually without providing a drying step. The application amount of each of the non-white inks was 20 g/m2. For the application of all of the pretreatment liquid, white ink, and non-white inks, an “MMP-8130” manufactured by Mastermind Co., Ltd. was used as a printing device. Then, heat drying was performed at 160° C. for 2 minutes by using a heat press machine manufactured by Fusion Co. Accordingly, a color printed textile item was obtained.

10. Evaluation of Color Printed Textile Item

[0245] The color printed textile item in which the monochromatic solid images of the non-white inks K1, C1, M1, and Y1 were formed on the white image obtained as described above was evaluated visually. The color printed textile item was favorable both in terms of color development properties and bleeding.

[0246] 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.