BLACK INK COMPOSITION FOR INKJET PRINTING, AND METHOD FOR PRINTING ON HYDROPHOBIC FIBERS

Abstract

A black ink composition for inkjet printing that contains a water-soluble organic solvent, a resin emulsion, a dispersing agent, and at least four types of sublimation dyes. At least three of the sublimation dye types are C.I. disperse yellow, C.I. disperse red, and C.I. disperse blue, and at least one of the sublimation dye types has a maximum absorption wavelength in the wavelength band of 640 nm to less than 680 nm as measured from a visible spectral absorption of a solution obtained by dissolving the dye in acetone. An ink set for inkjet printing that includes the black ink composition for inkjet printing, and a method for printing on hydrophobic fibers that uses the composition and the ink set.

Claims

1. A black ink composition for inkjet textile printing, comprising a water-soluble organic solvent, a resin emulsion, a dispersant, and at least four sublimable dyes, wherein at least three of the sublimable dyes are selected from the group consisting of C.I. Disperse Yellow, C.I. Disperse Red, and C.I. Disperse Blue, and at least one of the sublimable dyes has a maximum absorption wavelength in a wavelength range of 640 nm or more and less than 680 nm in a visible spectroscopic absorption of a solution dissolved in acetone.

2. The black ink composition for inkjet textile printing according to claim 1, wherein the resin emulsion is a urethane resin emulsion.

3. The black ink composition for inkjet textile printing according to claim 1, wherein the dispersant is a styrene-(meth)acrylic copolymer or a formalin condensate of an aromatic sulfonic acid or a salt thereof.

4. The black ink composition for inkjet textile printing according to claim 1, wherein the sublimable dye includes C.I. Disperse Yellow 54, C.I. Disperse Red 60, and C.I. Disperse Blue 360.

5. The black ink composition for inkjet textile printing according to claim 1, wherein the sublimable dye having a maximum absorption wavelength in a wavelength range of 640 nm or more and less than 680 nm is a sublimable dye selected from the group consisting of C. I. Disperse Blue 359, C. I. Disperse Blue 60, and C. I. Disperse Blue 334.

6. The black ink composition for inkjet textile printing according to claim 1, wherein the resin emulsion is a polycarbonate-based urethane resin emulsion.

7. The black ink composition for inkjet textile printing according to claim 1, wherein the dispersant is a styrene-(meth)acrylic copolymer and the copolymer has a mass average molecular weight of 5,000 to 17,000 and an acid value of 100 to 250 mg KOH/g.

8. The black ink composition for inkjet textile printing according to claim 1, wherein the dispersant is selected from the group consisting of a formalin condensate of creosote oil sulfonic acid or a salt thereof and a formalin condensate of methylnaphthalene sulfonic acid or a salt thereof.

9. The black ink composition for inkjet textile printing according to claim 1, wherein the water-soluble organic solvent includes at least one selected from glycerin and diglycerin.

10. An ink set for inkjet textile printing, comprising the black ink composition for inkjet textile printing according to claim 1, a yellow ink composition for inkjet textile printing, a magenta ink composition for inkjet textile printing, and a cyan ink composition for inkjet textile printing.

11. A method for textile printing of a hydrophobic fiber, comprising: using, as an ink, the black ink composition for inkjet textile printing according to claim 1 and attaching a droplet of the ink to an intermediate recording medium using an inkjet printer to obtain a recorded image; and transferring the recorded image to the hydrophobic fiber by contacting the hydrophobic fiber with a surface to which the ink is attached in the intermediate recording medium, followed by heat treatment.

12. A dyed hydrophobic fiber obtained by the method for textile printing of a hydrophobic fiber according to claim 11.

13. A method for textile printing of a hydrophobic fiber, comprising: using, as an ink, each ink composition included in the ink set for inkjet textile printing according to claim 10 and attaching a droplet of the ink to an intermediate recording medium using an inkjet printer to obtain a recorded image; and transferring the recorded image to the hydrophobic fiber by contacting the hydrophobic fiber with a surface to which the ink is attached in the intermediate recording medium, followed by heat treatment.

14. A dyed hydrophobic fiber obtained by the method for textile printing of a hydrophobic fiber according to claim 13.

Description

EXAMPLES

[0087] In the following, the present invention is explained in more detail by way of the Examples; however, the present invention is not limited to these Examples. In the Examples, unless otherwise specified, “parts” indicates parts by mass and “%” indicates % by mass.

Preparation Example 1: Preparation of Emulsion Liquid

[0088] To a mixture of 48% lithium hydroxide (3.2 parts), ion-exchanged water (56.8 parts) and propylene glycol (20 parts), 20 parts of Joncryl 678 (manufactured by BASF Corporation) were added, and the mixture was heated to 90 to 120° C. and stirred for 5 hours to obtain an emulsion liquid of Joncryl 678.

Preparation Example 2: Preparation of Aqueous Dispersion 1

[0089] A mixture of Kayaset Yellow AG (30 parts) (C.I. Disperse Yellow 54, manufactured by Nippon Kayaku Co., Ltd.) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill including 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 1.

Preparation Example 3: Preparation of Aqueous Dispersion 2

[0090] A mixture of Kayaset Red B (30 parts) (C.I. Disperse Red 60, manufactured by Nippon Kayaku Co., Ltd.) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill including 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 2.

Preparation Example 4: Preparation of Aqueous Dispersion 3

[0091] A mixture of C.I. Disperse Blue 359 (30 parts) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill including 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 3.

Preparation Example 5: Preparation of Aqueous Dispersion 4

[0092] A mixture of C.I. Disperse Blue 360 (30 parts) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill including 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 4.

Preparation Example 6: Preparation of Aqueous Dispersion 5

[0093] A mixture of C.I. Disperse Brown 27 (30 parts) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill using 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 5.

Preparation Example 7: Preparation of Aqueous Dispersion 6

[0094] A mixture of C.I. Disperse Orange 25 (30 parts) as the sublimable dye, the emulsion liquid (60 parts) of Joncryl 678 obtained in Preparation Example 1, Proxel GXL (0.2 parts), Surfynol 104PG50 (0.4 parts), and ion-exchanged water (24 parts) was subjected to dispersing treatment while cooling for about 15 hours in a sand mill including 0.2 mm diameter glass beads. To the liquid obtained, ion-exchanged water (60 parts) and the emulsion liquid (30 parts) of Joncryl 678 obtained in Preparation Example 1 were added to adjust the dye content to 15%, followed by filtration using a glass fiber filter paper GC-50 (manufactured by Advantec Co., Ltd., pore size of the filter: 0.5 μm), to obtain aqueous dispersion 6.

Example 1

[0095] Aqueous dispersion 1 (16 parts) obtained in Preparation Example 2, aqueous dispersion 2 (26 parts) obtained in Preparation Example 3, aqueous dispersion 3 (7 parts) obtained in Preparation Example 4, and aqueous dispersion 4 (17 parts) obtained in Preparation Example 5 were mixed. To the mixture obtained, a mixed liquid of glycerin, Proxel GXL (manufactured by Lonza KK), UCOAT UX-320 (manufactured by Sanyo Chemical Co., Ltd.), Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), TEA-80 (manufactured by Junsei Chemical Industries, Ltd.), and ion-exchanged water was added and stirred so that the composition obtained has the composition of Table 1, followed by filtration through a filter having a pore diameter of 5 μm to obtain an aqueous black ink of Example 1.

Examples 2 to 3

[0096] Aqueous black inks of Examples 2 to 3 were obtained in the same manner as in Example 1, except that the amount of aqueous dispersion liquid 3 in Example 1 was changed as in Table 1.

Comparative Example 1

[0097] Aqueous dispersion 1 (3 parts) obtained in Preparation Example 2, aqueous dispersion 4 (14 parts) obtained in Preparation Example 5, and aqueous dispersion 5 (20 parts) obtained in Preparation Example 6 were mixed. To the mixture obtained, a mixed liquid of glycerin, Proxel GXL (manufactured by Zeneca Co., Ltd.), UCOAT UX-320 (manufactured by Sanyo Chemical Industry Co., Ltd.), Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), and ion-exchanged water was added and stirred so that the composition obtained has the composition described in Table 1, followed by filtration through a filter having a pore diameter of 5 μm to obtain an aqueous black ink of Comparative Example 1.

Comparative Examples 2 to 3

[0098] Aqueous black inks of Comparative Examples 2 to 3 were obtained in the same manner as in Comparative Example 1, except that, in Comparative Example 1, aqueous dispersion 6 obtained in Preparation Example 7 or aqueous dispersion 2 obtained in Preparation Example 3 was added as in Table 1, instead of aqueous dispersion 5.

Comparative Example 4

[0099] An aqueous black ink of Comparative Example 4 was obtained in the same manner as in Example 1, except that, in Example 1, UCOAT UX-320 was not used and the amount of aqueous dispersion 3 was changed as in Table 1.

TABLE-US-00001 TABLE 1 Aqueous black Example Comparative Example ink composition 1 2 3 1 2 3 4 Preparation Aqueous 16 16 16 3 3 16 16 Example 2 dispersion 1 Preparation Aqueous 26 26 26 26 26 Example 3 dispersion 2 Preparation Aqueous 7 5 3 9 Example 4 dispersion 3 Preparation Aqueous 17 17 17 14 17 17 17 Example 5 dispersion 4 Preparation Aqueous 20 Example 6 dispersion 5 Preparation Aqueous 17 Example 7 dispersion 6 Other Glycerin 15 15 15 15 15 15 15 Components Proxel 0.1 0.1 0.1 0.1 0.1 0.1 0.1 GXL UCOAT 7.5 7.5 7.5 7.5 7.5 7.5 UX-320 Surfynol 0.2 0.2 0.2 0.2 0.2 0.2 0.2 465 TEA-80 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion-exchanged Balance water Total 100 100 100 100 100 100 100

[Evaluation]

[0100] The respective inks prepared were filled into an inkjet printer (PX-504A, trade name of a product manufactured by EPSON Co., Ltd.), and respective intermediate recording media in each of which a single color solid image of 100% duty was printed were obtained using a low-coated paper having a basis weight of 45 g as an intermediate recording medium. Dyed products dyed by the sublimation transfer method were obtained by superimposing the ink attaching surface of each of the intermediate recording media obtained on polyester fabric (Teijin Tropical), and subjecting the resulting fabric to heat treatment using a desktop automatic flat pressing machine (AF-65TEN manufactured by Asahi Garment Machinery Co., Ltd.) under a condition of 200° C. for 60 seconds. The dyed products obtained were evaluated as follows.

(Evaluation of Dyeing Concentration)

[0101] Dyed parts of the respective dyed products obtained were subjected to colorimetry using a spectroscopic colorimeter “eXact (manufactured by X-Rite Inc.)”, and the dyeing concentration was measured. Colorimetry was carried out under the conditions of a D65 light source, a viewing angle of 2° and status I. The results are indicated in Table 2 below.

(Uniformity Evaluation of Sublimation Transfer)

[0102] Dyed products dyed by the sublimation transfer dyeing method were obtained by superimposing the ink attaching surface of each of the intermediate recording media on polyester fabric (Teijin Tropical), and subjecting the resulting fabric to heat treatment using a desktop automatic flat pressing machine (AF-65TEN manufactured by Asahi Garment Machinery Co., Ltd.) under a condition of 200° C. for 20 seconds. The difference in black color hue between the dyed products described above and the dyed products obtained under the condition of 200° C. for 60 seconds was visually observed and evaluated on the basis of the following evaluation criteria. The evaluation results are indicated in Table 2 below.

[0103] —Evaluation Criteria—

A: There is almost no variation in black hue between the transfer time of 60 seconds and 20 seconds, and sufficient dyeing concentration is achieved even at the transfer time of 20 seconds.
B: There is variation in black color hue between the transfer time of 60 seconds and 20 seconds, and in the case of 20 seconds of transfer time, dyeing concentration is low and sufficient concentration is not achieved.
C: Variation in black hue is large between the transfer time of 60 seconds and 20 seconds, and in the case of 20 seconds of transfer time, black hue is not achieved and the dyeing concentration is also low.

(Color Rendering Evaluation 1: Color Difference Between D65 Light Source and F2 Light Source)

[0104] Hue L*a*b* of dyed products obtained under the condition of 200° C. for 60 seconds described above was measured using spectroscopic colorimeter “eXact (manufactured by X-Rite Inc.)”. Colorimetry was performed using the conditions of a viewing angle of 2° and status I, and the respective values of L*a*b* at the D65 light source and F2 light source were obtained. From the values of L*a*b* obtained with respect to each light source, the color difference ΔE was obtained on the basis of the following equation (1). The results are indicated in Table 2 below.

ΔE=[(L*.sub.D65−L*.sub.F2).sup.2+(a*.sub.D65−a*.sub.F2).sup.2+(b*.sub.D65−b*.sub.F2).sup.2].sup.1/2  (1)

[0105] Further, the difference in the black color hue of the dyed products obtained between D65 light source and F2 light source was visually observed, and the difference was evaluated on the basis of the following evaluation criteria. The evaluation results are indicated in Table 2 below.

[0106] —Evaluation Criteria—

A: The difference in the black color hue between D65 light source and F2 light source is small and the difference is almost not perceived.
B: A slight difference in the black color hue between D65 light source and F2 light source is observed.
C: The difference in the black color hue between D65 light source and F2 light source is great, and it appears bluish under F2 light source.

(Color Rendering Evaluation 2: Color Difference Between D65 Light Source and a Light Source)

[0107] Hue L*a*b* of dyed products obtained under the condition of 200° C. for 60 seconds described above was measured using spectroscopic colorimeter “eXact (manufactured X-Rite Inc.)”. Colorimetry was performed using the conditions of a viewing angle of 2° and status I, and the respective values of L*a*b* at the D65 light source and A light source were obtained. From the values of L*a*b* obtained with respect to each light source, the color difference ΔE was obtained on the basis of the following equation (2). The results are indicated in Table 2 below.

ΔE=[(L*.sub.D65−L*.sub.A).sup.2+(a*.sub.D65−a*.sub.A).sup.2+(b*.sub.D65−b*.sub.A).sup.2].sup.1/2  (2)

[0108] Further, the difference in the black color hue of the dyed products obtained between D65 light source and A light source was visually observed, and the difference was evaluated on the basis of the following evaluation criteria. The evaluation results are indicated in Table 2 below.

[0109] —Evaluation Criteria—

A: The difference in the black color hue between D65 light source and A light source is small and the difference is almost not perceived.
B: A slight difference in the black color hue between D65 light source and A light source is observed.
C: The difference in the black color hue between D65 light source and A light source is great, and it appears reddish under A light source.

(Light Resistance Test)

[0110] The respective dyed products obtained under the condition of 200° C. for 60 seconds described above were left for 24 hours under the conditions of 100,000 Lux illuminance, humidity 60% RH, and temperature 24° C., using Low-temperature Xenon Weather Meter XL75, which is a trade name of a weather meter manufactured by Suga Test Instruments Co., Ltd. With regard to the respective dyed products after the test, a degree of change in color of an area irradiated by the xenon lamp was judged on the basis of JIS blue scale for change in color. The greater the judgement grade, the lower the degree of change in color, which means an excellent result. The test results are indicated in Table 2 below.

TABLE-US-00002 TABLE 2 Example Comparative Example 1 2 3 1 2 3 4 Evaluation of Density BK 1.52 1.51 1.51 1.47 1.48 1.50 1.44 dyeing concentration Uniformity Judgement A A A A C B A evaluation of by visual sublimation observation transfer Color Color 1.22 1.38 1.76 3.41 2.87 4.08 1.25 rendering difference evaluation 1 ΔE Judgement A A A C C C A by visual observation Color Color 1.22 1.51 2.07 3.42 2.44 3.81 1.28 rendering difference evaluation 2 ΔE Judgement A A B C B C A by visual observation Light Judgement Grades Grades Grades Grades Grades Grades Grades resistance grade 4 to 5 4 to 5 4 to 5 3 to 4 3 to 4 4 to 5 4 to 5 evaluation

[0111] As is clear from the results of Table 2, the aqueous black inks of Examples 1 to 3 had almost no influence on the color rendering property, had a high dyeing concentration, had black color of high quality, and were excellent in light resistance, compared to the aqueous black inks of Comparative Examples 1 to 4. From this result, it can be seen that the aqueous black inks of Examples 1 to 3 are extremely useful as an ink for various recording purposes, particularly as an ink for inkjet textile printing.