White inkjet ink composition for textile printing

Abstract

An object is to achieve both good washing fastness and texture by combining a urethane resin of high fracture elongation with a small quantity of crosslinking agent. As a means for achieving the object, a white inkjet ink composition for textile printing is provided that contains a white pigment, a water-dispersible urethane resin having reactivity to cationic compounds, a crosslinking agent, a water-soluble organic solvent, and water; wherein the crosslinking agent is contained by 0.02 to 0.15 parts by mass relative to 1 part by mass of the water-dispersible urethane resin, and as the water-soluble organic solvent, a glycol ether that dissolves by 1 to 60 g in 100 g of water is contained.

Claims

1. A white inkjet ink composition for textile printing, containing a white pigment, a water-dispersible urethane resin having reactivity to cationic compounds, at least one type of crosslinking agent selected from a group consisting of blocked isocyanate compounds and carbodiimide compounds, a water-soluble organic solvent, and water; wherein the crosslinking agent is contained by 0.02 to 0.15 parts by mass relative to 1 part by mass of the water-dispersible urethane resin, and as the water-soluble organic solvent, tripropylene glycol-n-butyl ether is contained.

Description

EXAMPLES

(1) Preparation of White Inkjet Ink Compositions for Textile Printing

(2) The present invention is explained in greater detail below using examples; however, the present invention is not limited to these examples. It should be noted that, unless otherwise specified, “%” means “percent by mass,” while “part(s)” means “part(s) by mass.”

(3) The materials used in the Examples and Comparative Examples below are as follows.

(4) TABLE-US-00001 TABLE 1 Product name Solid Fracture Tensile (Manufactured Reactivity content (% elongation strength by) to cations by weight) (%) (MPa) Water- NeoRez Yes 40 600 19.6 dispersible R-967 urethane (DSM, Co., resin (1) Ltd.) Water- TAKELAC Yes 30 560 60 dispersible WS-5000 urethane (Mitsui resin (2) Chemicals, Co., Ltd.) Water- Impranil Yes 40 1100 50 dispersible DLH urethane (Sumika resin (3) Covestro Urethane, Co., Ltd.) Water- Superflex No 45 1100 18 dispersible 500M urethane (DKS Co. resin (4) Ltd.) Water- Baybond No 40 1200 40 dispersible PU407 urethane (Sumika resin (5) Covestro Urethane, Co., Ltd.)

(5) TABLE-US-00002 TABLE 2 Product name Solid (Manufactured content (% by) Structure by weight) Crosslinking Bayhydur BL2867 Blocked 38 agent (1) (Sumika Covestro isocyanate Urethane, Co., Ltd.) compound Crosslinking CARBODILITE SV-02 Carbodiimide 40 agent (2) (Nisshinbo Chemical, Co., compound Ltd.) Crosslinking EPOCROS WS-700 (Nippon Oxazoline 25 agent (3) Shokubai, Co., Ltd.) group- containing polymer

(6) TABLE-US-00003 TABLE 3 Quantity dissolved in 100 g Glycol ether of water TPnB Tripropylene glycol-n-butyl ether 3 DPnB Dipropylene glycol-n-butyl ether 19 DMM Dipropylene glycol dimethyl ether 53 BDB Diethylene glycol dibutyl ether 0.3 TPM Tripropylene glycol methyl ether >100

(7) (Preparation of Aqueous Resin Varnish)

(8) Twenty-five parts by mass of the below-mentioned anionic group-containing resin were dissolved in a mixed liquid of 4.9 parts by mass of potassium hydroxide and 70.1 parts by mass of water, to obtain an aqueous resin varnish of 25 percent by mass in solid content of anionic group-containing resin.

(9) Anionic group-containing resin: Acrylic acid/lauryl acrylate/styrene copolymer (weight-average molecular weight 30000, acid value 185 mg KOH/g)

(10) (Preparation of Pigment Dispersion Liquid)

(11) To 36 parts by mass of the aforementioned aqueous resin varnish, 19 parts by mass of water were added and the ingredients were mixed, to prepare a resin varnish for pigment dispersion. To this resin varnish for pigment dispersion, 45 parts by mass of CR-90 (titanium oxide, manufactured by Ishihara Sangyo Kaisha, Co., Ltd.) were added further as a pigment and the ingredients were mixed under agitation, after which the mixture was kneaded using a wet circulation mill, to prepare a pigment dispersion liquid.

(12) (Preparation of White Inkjet Ink Compositions for Textile Printing)

(13) To the aforementioned pigment dispersion liquid, water-dispersible urethane resins, crosslinking agents, water, water-soluble organic solvents (glycerin, 2-pyrrolidone, glycol ethers), and surface-active agents (Olfine E1010, Surfynol 440) were added to prepare white inkjet ink compositions for textile printing.

(14) (Preparation of Pretreatment Solution for Inkjet Textile Printing)

(15) Ten parts by mass of a calcium nitrate tetrahydrate, 6.0 parts by mass of a nonionic styrene-acrylic self-crosslinkable resin emulsion with a glass transition temperature of −30° C. (product name: Mowinyl 966A, manufactured by Japan Coating Resin, Co., Ltd., solid content 45%), and 0.3 parts by mass of ACETYLENOL E100 (HLB 13.5, ethylene oxide adduct of acetylene glycol, manufactured by Kawaken Fine Chemicals, Co., Ltd.) were added to 83.7 parts by mass of water, and the mixture was agitated to obtain a pretreatment solution for inkjet textile printing.

(16) (Methods for Pretreatment and Production of Printed Matter)

(17) A black fabric made of 100% cotton was impregnated with 10 g of the aforementioned treatment solution per A4 size area, and then dried by heating.

(18) The obtained pretreated black fabric was printed by solid printing in a manner overlapping four times with each of the white inkjet ink compositions for textile printing in Examples 1 to 9 and Comparative Examples 1 to 8 using an evaluation printer equipped with a head manufactured by SPECTRA.

(19) Thereafter, a heat-press machine was used to heat the printed area at 170° C. for 1 minute, thereby fixing the white inkjet ink composition for textile printing on the fabric and thus obtaining each of the printed fabrics in Examples 1 to 9 and Comparative Examples 1 to 8.

(20) (Evaluation Methods)

(21) (Image Density)

(22) The luminance (L*) of each printed fabric was measured using a spectrophotometer (SpectroEye, manufactured by X-Rite).

(23) ⊙: L*=80 or higher

(24) ◯: L*=70 or higher, but lower than 80

(25) Δ: L*=50 or higher, but lower than 70

(26) x: L*=Lower than 50

(27) (Coating Film Resistance)

(28) Each printed fabric was stretched five times (stretched to its limit each time), and then visually evaluated for cracking and peeling of the coating film.

(29) ⊙: The coating film does not crack or peel.

(30) ◯: The coating film does not peel, but cracks slightly.

(31) Δ: The coating film does not peel, but cracks.

(32) x: The coating film cracks and peels.

(33) (Texture)

(34) Each printed fabric was evaluated by touch. ⊙: The printed fabric creases easily, preserving softness close to that of the original 100% cotton black fabric. ◯: The printed fabric creases easily, but a little more roughness is felt compared to the original black fabric. Δ: The printed fabric feels rough. x: The printed fabric is so stiff that it does not crease freely.

(35) (Washing Fastness)

(36) The luminance (L*) of each printed fabric was measured using a spectrophotometer (SpectroEye, manufactured by X-Rite) before and after the fabric was washed five times normally (washing conditions: wash in a standard mode.fwdarw.spin.fwdarw.dry) with a home washing machine, and the rate of change from the initial value before washing was evaluated. ⊙: The image density remains equal to or higher than 90% of the initial value after washing. ◯: The image density remains equal to or higher than 80%, but is lower than 90%, of the initial value after washing. Δ: The image density remains equal to or higher than 70%, but is lower than 80%, of the initial value after washing. x: The image density is lower than 70% of the initial value after washing.

(37) TABLE-US-00004 TABLE 4 Examples 1 2 3 4 5 6 7 8 9 Pigment dispersion liquid 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 Water-dispersible urethane 30.0 30.0 30.0 30.0 30.0 30.0 30.0 resin (1) Water-dispersible urethane 40.0 resin (2) Water-dispersible urethane 30.0 resin (3) Water-dispersible urethane resin (4) Water-dispersible urethane resin (5) Crosslinking agent (1) 1.0 1.0 1.0 3.2 4.1 1.0 1.0 Crosslinking agent (2) 0.9 Crosslinking agent (3) 1.4 Olfine E1010 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Surfynol 440 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Glycerin 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 2-pyrrolidone 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 TPnB 1.0 1.0 1.0 1.0 1.0 1.0 1.0 DPnB 1.0 DMM 1.0 BDB TPM Water 20.3 20.3 20.3 18.1 17.2 20.4 19.9 10.3 20.3 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Crosslinking agent 0.03 0.03 0.03 0.10 0.13 0.03 0.03 0.03 0.03 quantity relative to resin (ratio by mass) Evaluation results Image density ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Coating film resistance ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Texture ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚ ⊚ ⊚ Washing fastness ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Comparative Examples 1 2 3 4 5 6 7 8 Pigment dispersion liquid 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 Water-dispersible urethane 30.0 30.0 30.0 30.0 30.0 30.0 resin (1) Water-dispersible urethane resin (2) Water-dispersible urethane resin (3) Water-dispersible urethane 27.0 resin (4) Water-dispersible urethane 30.0 resin (5) Crosslinking agent (1) 1.0 1.0 1.0 1.0 1.0 0.3 6.3 Crosslinking agent (2) Crosslinking agent (3) Olfine E1010 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Surfynol 440 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Glycerin 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 2-pyrrolidone 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 TPnB 1.0 1.0 1.0 1.0 1.0 DPnB DMM BDB 1.0 TPM 1.0 Water 21.3 20.3 20.3 23.3 20.3 21.3 21.0 15.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Crosslinking agent 0.03 0.03 0.03 0.03 0.03 0.00 0.01 0.20 quantity relative to resin (ratio by mass) Evaluation results Image density ⊚ ⊚ ⊚ X Δ ⊚ ⊚ ⊚ Coating film resistance Δ Δ Δ X X Δ Δ ◯ Texture ⊚ ⊚ ⊚ Δ Δ ⊚ ⊚ Δ Washing fastness Δ Δ Δ X X Δ Δ ◯

(38) The Examples conforming to the present invention resulted in particularly high image density, sufficient washing fastness, as well as good coating film resistance and texture.

(39) By contrast, Comparative Example 1 containing no glycol ether that dissolves by 1 to 60 g in 100 g of water, and Comparative Examples 2 and 3 blended only with an organic solvent that does not dissolve by 1 to 60 g, resulted in poor coating film resistance and washing fastness.

(40) Furthermore, Comparative Examples 4 and 5 using a water-dispersible urethane resin having no reactivity to cationic compounds, turned out poor in all of image density, coating film resistance, texture, and washing fastness.

(41) Also, Comparative Example 6 not blended with any crosslinking agent resulted in poor coating film resistance and washing fastness. Additionally, Comparative Example 7 using less crosslinking agent resulted in poor coating film resistance and washing fastness, while Comparative Example 8 using too much crosslinking agent led to texture deterioration.