Non-white textile printing inkjet ink composition, ink set, and recording method

Abstract

To provide a non-white textile printing inkjet ink composition which has favorable color developability, washing fastness and rubbing fastness that are hardly influenced by the water absorbency of a fabric, which can inhibit bleeding (bleeding between colors) from occurring, and which can be stably continuously printed during textile printing by using an inkjet method.SOLUTION: A non-white textile printing inkjet ink composition according to the present invention contains a pigment, resin particles, an acetylene-based surfactant having an HLB value from 6 to 10 inclusive, and water. The content of the acetylene-based surfactant is from 0.5 mass% to 2.0 mass% inclusive based on the total amount of the ink composition. The ink composition is used for a fabric having water absorbency evaluated by a method described below of 1 or more. In the method, a test fabric cut into 2 cm square is placed on a water surface in a glass bottle which has a volume of 50 mL and in which 30 mL of pure water is introduced such that the height from a bottom to the water surface is 4 cm, where a surface of the fabric is set to be parallel to the water surface, and the time (in seconds) elapsed from the fabric being mounted until a portion of the fabric reaching the bottom of the glass bottle is regarded as water absorbency.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a non-white textile printing inkjet ink composition, an ink set, and a recording method. [Background technology]

[0002] Inkjet recording methods have been attempted to be applied not only to recording images on media such as paper but also to textile printing on fabrics, and various ink compositions and recording methods for inkjet textile printing have been studied. For example, Patent Document 1 describes a method for textile printing on fabrics, in which a treatment liquid composition is applied to the fabric, a white inkjet ink composition is applied, and then a non-white inkjet ink composition is applied on top of the white inkjet ink composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-186702 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when printing on fabrics, the water absorbency of the fabrics varies depending on the fabric, which can lead to poor color development, bleeding (intercolor bleeding), and poor washing fastness. Furthermore, when continuous printing is performed using inkjet printing, print voids and irregularities occur, resulting in a problem of low stability of continuous printing. In the case of light-colored fabrics, the treatment liquid composition is not applied to the fabric in advance, but rather a non-white ink, i.e., a colored ink, is applied directly to the fabric for printing, and therefore such problems arise more significantly. [Means for solving the problem]

[0005] The present invention provides an ink composition for non-white textile printing, which comprises a pigment, resin particles, an acetylene surfactant having an HLB value of 6 or more and 10 or less, and water, wherein the content of the acetylene surfactant is 0.5% by mass or more and 2.0% by mass or less relative to the total amount of the ink composition, and the ink composition is used on a fabric having a water absorbency of 1 or more as evaluated by the following method. (method) A test fabric cut into a 2 cm square was placed on the water surface of a 50 mL glass bottle containing 30 mL of pure water and 4 cm high from the bottom to the water surface, with the fabric surface parallel to the water surface. The time from when the fabric was placed until a part of the fabric reached the bottom of the glass bottle was taken as the water absorbency (seconds). [Brief explanation of the drawings]

[0006] [Figure 1] 3 is a flowchart illustrating an example of a textile printing recording method according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0007] Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0008] 1. Non-white textile printing inkjet ink composition The non-white textile printing inkjet ink composition of this embodiment (hereinafter also referred to as "ink composition" or "non-white textile printing ink") contains a pigment, resin particles, an acetylene surfactant having an HLB value of 6 or more and 10 or less, and water, wherein the content of the acetylene surfactant is 0.5% by mass or more and 2.0% by mass or less with respect to the total amount of the ink composition, and the ink composition is used for fabrics having a water absorbency of 1 or more as evaluated by the following method. (method) A test fabric cut into a 2 cm square was placed on the water surface of a 50 mL glass bottle containing 30 mL of pure water and 4 cm high from the bottom to the water surface, with the fabric surface parallel to the water surface. The time from when the fabric was placed until a part of the fabric reached the bottom of the glass bottle was taken as the water absorbency (seconds).

[0009] According to this embodiment, it is possible to obtain a non-white textile printing inkjet ink composition that is less dependent on the water absorbency of the fabric, has good color development and washing fastness, can suppress bleeding (intercolor bleeding), and allows stable continuous printing in textile printing by the inkjet method.In addition, according to this embodiment, the ink composition also has good rub fastness. Although the reason why such excellent effects are obtained by this embodiment is not clear, the inventors presume as follows. That is, fabrics, particularly cotton fabrics, typically include those with low water absorbency and those with high water absorbency. In fabrics with low water absorbency, the ink composition has high permeability, which tends to cause inter-color bleeding, resulting in poor color development and a tendency for blurring. Furthermore, in fabrics with high water absorbency, the ink composition has low permeability, which tends to cause the ink composition to remain near the surface of the fabric, resulting in poor wash fastness and abrasion fastness. Taking into account the water absorbency of such fabrics, a method of incorporating a silicone-based or fluorine-based surfactant into the ink composition has been considered. However, these surfactants have too low a surface tension with respect to the fabric, and therefore ink compositions containing such surfactants tend to have poor ejection stability. Therefore, it is difficult to perform stable continuous printing in textile printing using the inkjet method. On the other hand, the non-white textile printing inkjet ink composition of this embodiment contains a pigment, resin particles, water, and a specific amount of an acetylene-based surfactant having an HLB value of 6 to 10. With this specific ink composition, the ink composition penetrates into the fabric favorably, regardless of the water absorption of the fabric. Therefore, it is believed that bleeding between colors is unlikely to occur, and the ink composition is unlikely to remain near the surface of the fabric, thereby achieving good color development, washing fastness, and abrasion fastness. Furthermore, by including the specific amount of the acetylene-based surfactant in the ink composition, the ink composition has favorable surface tension with respect to the fabric and good ejection stability. Therefore, it is believed that stable continuous printing is possible in textile printing by the inkjet method. However, the reasons for this are not limited to these.

[0010] Next, each component contained in the ink composition will be described, and the fabric will be described later.

[0011] 1.1.Pigments The ink composition of this embodiment contains a non-white pigment (hereinafter also referred to as a "non-white pigment"). In this specification, the non-white pigment refers to a pigment other than white. Preferred examples of such non-white pigments include cyan, yellow, magenta, and black color pigments. Herein, in the present specification, the term "white" when referring to a white pigment or a white inkjet ink composition (hereinafter also referred to as "white ink") described later means that the recorded matter is, for example, a white ink having a color similar to that of L in CIELAB. * The color where L is 100 * is between 60 and 100, and a * and b * is referred to as a color in which the deviation is within ±10. Note that CIELAB can be measured using, for example, a fluorescence spectrodensitometer (FD-7 (trade name), Konica Minolta, Inc.).

[0012] The non-white pigment has excellent storage stability such as light resistance, weather resistance, and gas resistance, and from this viewpoint, it is preferable that the non-white pigment is an organic pigment.

[0013] Specific examples of pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, and carbon black. The above pigments can be used alone or in combination of two or more. Furthermore, a luster pigment can be used as a non-white pigment.

[0014] Specific examples of pigments include the following:

[0015] Examples of black pigments include No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, and Raven 700 (all manufactured by Carbon Columbia), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, and Monarch 1400 (manufactured by CABOT JAPAN). KK), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, and Special Black 4 (all manufactured by Degussa).

[0016] In this embodiment, as a non-white pigment, a black self-dispersing pigment that has been surface-treated by oxidation treatment with hypohalous acid and / or a hypohalite, oxidation treatment with ozone, or oxidation treatment with persulfuric acid and / or a persulfate is preferred in terms of high color development. Commercially available products can also be used as the self-dispersing pigment for the black ink composition, and a preferred example is Microjet CW1 (manufactured by Orient Chemical Industries Co., Ltd.).

[0017] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, and 180.

[0018] Examples of magenta pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48(Ca), 48(Mn), 57(Ca), 57:1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, and 245, and CI Pigment Violet. Examples include 19, 23, 32, 33, 36, 38, 43, and 50.

[0019] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and CI Vat Blue 4 and 60.

[0020] Examples of pigments other than magenta, cyan, and yellow include CI Pigment Green 7, 10, CI Pigment Brown 3, 5, 25, 26, and CI Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, and 63.

[0021] Examples of pearl pigments include pigments having pearlescent or interference luster, such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride.

[0022] Examples of metallic pigments include particles of simple metals such as aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and copper, or alloys thereof.

[0023] The non-white pigment is preferably one that can be stably dispersed or dissolved in a dispersion medium, and may be dispersed using a dispersant as needed. Examples of such dispersants include resin dispersants, which are selected from those that can improve the dispersion stability of the non-white pigment in the ink composition. Furthermore, the non-white pigment may be used as a self-dispersing pigment by modifying the surface of the pigment particles by oxidizing or sulfonating the pigment surface with, for example, ozone, hypochlorous acid, fuming sulfuric acid, or the like.

[0024] Examples of the resin dispersant include (meth)acrylic resins and salts thereof, such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid copolymer, and vinylnaphthalene-(meth)acrylic acid copolymer; styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, and styrene-α-methylstyrene-(meth)acrylic acid copolymer. Examples of suitable water-soluble resins include styrene-based resins such as acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, and styrene-maleic anhydride copolymers, as well as their salts; polymeric compounds (resins) containing urethane bonds formed by the reaction of isocyanate groups and hydroxyl groups, which may be linear and / or branched and may have a crosslinked structure; urethane-based resins and their salts; polyvinyl alcohols; vinyl naphthalene-maleic acid copolymers and their salts; vinyl acetate-maleic acid ester copolymers and their salts; and vinyl acetate-crotonic acid copolymers and their salts. Among these, preferred are copolymers of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and polymers composed of a monomer having both a hydrophobic and a hydrophilic functional group. The copolymers may be random copolymers, block copolymers, alternating copolymers, or graft copolymers.

[0025] Commercially available styrene resin dispersants include, for example, X-200, X-1, X-205, X-220, and X-228 (manufactured by Seiko PMC Co., Ltd.), Nopcosperse (registered trademark) 6100 and 6110 (manufactured by San Nopco Ltd.), Joncryl (registered trademark) 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK (registered trademark) -190 (manufactured by BYK Japan KK), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0026] Commercially available acrylic resin dispersants include, for example, DISPERBYK-187, BYK-190, BYK-191, BYK-194N, and BYK-199 (manufactured by BYK Japan K.K.), and Aron (registered trademark) A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0027] Commercially available urethane resin dispersants include, for example, DISPERBYK-182, BYK-183, BYK-184, and BYK-185 (manufactured by BYK Japan K.K.), TEGO (registered trademark) Disperse 710 (manufactured by Evonic Tego Chemi), and Borchi (registered trademark) Gen 1350 (manufactured by OMG Borschers).

[0028] Although commercially available products are listed above, the dispersants may also be obtained by synthesis using conventional methods.

[0029] The dispersant may be used alone or in combination of two or more. The total content of the dispersant in the ink composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 1 to 20 parts by mass, and even more preferably 1.5 to 15 parts by mass, per 100 parts by mass of the non-white pigment. By having the dispersant content be 0.1 parts by mass or more per 100 parts by mass of the non-white pigment, the dispersion stability of the non-white pigment can be further improved. Furthermore, by having the dispersant content be 30 parts by mass or less per 100 parts by mass of the non-white pigment, the viscosity of the resulting dispersion can be further reduced.

[0030] The weight-average molecular weight of the dispersant is more preferably 500 or more. By using such a resin dispersant as a dispersant, odor can be reduced and the dispersion stability of the non-white pigment can be further improved. When a dispersant is used, the non-white pigment that serves as the base particles may or may not be surface-treated. In this specification, the weight-average molecular weight refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0031] From the viewpoint of achieving a good balance between color development and ejection stability, the content of the non-white pigment relative to the total amount of the ink composition is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, even more preferably 1% by mass to 10% by mass, and even more preferably 2% by mass to 7% by mass.

[0032] 1.2.Resin particles The ink composition of this embodiment contains resin particles. Resin particles can further improve the adhesion of images formed by the ink composition deposited on a recording medium. Examples of resin particles include urethane-based resins, acrylic-based resins (including styrene-acrylic-based resins), fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate-based resins, and the like. Among these, urethane-based resins, acrylic-based resins, polyolefin-based resins, and polyester-based resins are preferred. These resin particles are often handled in emulsion form, but may also be supplied in powder form. Furthermore, the resin particles can be used alone or in combination of two or more types.

[0033] Urethane resin is a general term for resins containing urethane bonds. Examples of urethane resins include polyether urethane resins containing ether bonds in the main chain in addition to urethane bonds, polyester urethane resins containing ester bonds in the main chain, and polycarbonate urethane resins containing carbonate bonds in the main chain. Furthermore, commercially available urethane resins may be used, such as Superflex (registered trademark) 460, 460s, 840, and E-4000 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Rezamin (registered trademark) D-1060, D-2020, D-4080, D-4200, D-6300, and D-6455 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), Takelac (registered trademark) WS-6021 and W-512-A-6 (manufactured by Mitsui Chemicals, Inc.), Sancure (registered trademark) 2710 (manufactured by Lubrizol), and Permarin (registered trademark) UA-150 (manufactured by Sanyo Chemical Industries, Ltd.).

[0034] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or a (meth)acrylic acid ester as one component. Examples of acrylic resins include resins obtained from acrylic monomers and copolymers of acrylic monomers with other monomers. More specifically, examples include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Examples of vinyl monomers include styrene.

[0035] Examples of acrylic monomers that can be used include acrylamide and acrylonitrile. Commercially available resin emulsions using acrylic resins as raw materials may also be used, such as FK-854 (manufactured by Chuo Rika Kogyo Co., Ltd.), Movinyl (registered trademark) 952B and 718A (manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.), and Nipol (registered trademark) LX852 and LX874 (manufactured by Zeon Corporation).

[0036] In this specification, the acrylic resin may be a styrene-acrylic resin, which will be described later. In addition, in this specification, the term "(meth)acrylic" means at least one of acrylic and methacrylic.

[0037] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic monomers, and examples include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer. As the styrene-acrylic resin, commercially available products may be used, such as JONCRYL (registered trademark) 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, and 7610 (manufactured by BASF), Mowinyl (registered trademark) 966A and 975N (manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan (registered trademark) 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0038] The polyolefin resin has an olefin such as ethylene, propylene, or butylene in its structural skeleton, and any known polyolefin resin can be appropriately selected and used. As the olefin resin, commercially available products can be used, such as Arrowbase (registered trademark) CB-1200 and CD-1200 (manufactured by Unitika Ltd.).

[0039] Although commercially available products are listed above, the resin particles may also be obtained by synthesis using conventional methods.

[0040] The content of the resin particles, as solid content, relative to the total amount of the ink composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and even more preferably 2% by mass or more and 10% by mass or less.

[0041] 1.3. Acetylenic surfactants with an HLB value of 6 or more and 10 or less The ink composition of this embodiment contains an acetylene surfactant having an HLB value of 6 or more and 10 or less. The content of the acetylene surfactant is 0.5% by mass or more and 2.0% by mass or less with respect to the total amount of the ink composition.

[0042] In this specification, the HLB (Hydrophile-Lipophile Balance) value is a value proposed by Davis et al. to evaluate the hydrophilicity of a compound, and is a numerical value determined by the Davis method defined in, for example, JT Davis and EK Rideal, "Interface Phenomena," 2nd ed., Academic Press, New York, 1963, and is calculated by the following formula (i): HLB value = 7 + Σ[1] - Σ[2] (i) (In formula (i), [1] represents the number of hydrophilic groups, and [2] represents the number of hydrophobic groups.)

[0043] The HLB value is preferably from 6 to 9, since this allows for an ink composition to be obtained that is less dependent on the water absorbency of the fabric, has better color development and washing fastness, has better rub fastness, and can further suppress bleeding (intercolor bleeding).Furthermore, the HLB value is more preferably from 7 to 8, since this allows for an ink composition to be obtained that has better washing fastness, better rub fastness, can further suppress bleeding (intercolor bleeding), and has better color development for low water absorbency fabrics.

[0044] The acetylene-based surfactant may be used alone or in combination of two or more types, so long as it has an HLB value of 6 or more and 10 or less. In this embodiment, for example, an acetylene-based surfactant having an HLB value of more than 10 and an acetylene-based surfactant having an HLB value of less than 6 may be used in combination so that the ink composition contains an acetylene-based surfactant having an HLB value of 6 or more and 10 or less. Furthermore, surfactants other than the acetylene-based surfactant may be contained as long as the effects of the present invention are achieved.

[0045] The acetylene-based surfactant is preferably an acetylene glycol-based surfactant, since this allows for an ink composition that is not dependent on the water absorbency of the fabric and allows for more stable continuous printing in inkjet printing. More preferred acetylene glycol-based surfactants are acetylene glycols having an HLB value of 6 or more and 10 or less and represented by the following formula (1), and ethylene oxide adducts of acetylene glycols having an HLB value of 6 or more and 10 or less and represented by the following formula (2). More preferred acetylene glycol-based surfactants include ethylene oxide adducts of acetylene glycols having an HLB value of 6 or more and 10 or less and represented by the following formula (2).

[0046] [ka]

[0047] In formula (1), R 1 and R 2 R each independently represents an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may have a linear or branched structure. Specific examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. 1 and R 2 may be the same or different.

[0048] [ka]

[0049] In equation (2), R 3 and R 4R each independently represents an alkyl group having 1 to 5 carbon atoms, m and n each represent an integer of 0 to 25, and m+n is 1 to 40. The alkyl group having 1 to 5 carbon atoms may have a linear or branched structure. Specific examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. 3 and R 4 may be the same or different. Furthermore, m and n represent the number of moles of ethylene oxide added, and m+n must be 1 or more and 40 or less, preferably 10 or more and 30 or less, and more preferably 15 or more and 25 or less. When m+n is 40 or less, the surface tension on the fabric can be prevented from increasing, resulting in better discharge stability and enabling more stable continuous printing in textile printing by the inkjet method.

[0050] Examples of acetylene glycols represented by formula (1) include 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 5,8-dimethyl-6-dodecyne-5,8-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 4,7-dimethyl-5-decyne-4,7-diol, 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, and 2,5-dimethyl-3-hexyne-2,5-diol.

[0051] Examples of the ethylene oxide adduct of acetylene glycol represented by formula (2) include ethylene oxide adducts of the compounds listed as specific examples of acetylene glycol represented by formula (1).

[0052] The acetylene surfactant may be a commercially available product, such as Surfynol (registered trademark) 440 (HLB value: 8), Surfynol SE (HLB value: 6), Surfynol SE-F (HLB value: 6), Surfynol 61 (HLB value: 6), Surfynol 2502 (HLB value: 8), and Surfynol TG (HLB value: 9) (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.); Olfin (registered trademark) PD-002W (HLB value: 10), Olfin E1004 (HLB value: 7 to 9) (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.); and Acetylenol (registered trademark) E40 (HLB value: 10) (trade name, manufactured by Kawaken Fine Chemicals Co., Ltd.). These may be used alone or in combination of two or more.

[0053] The content of the acetylene surfactant is preferably 0.7% by mass or more and 1.5% by mass or less relative to the total amount of the ink composition, since this results in an ink composition that is less dependent on the water absorbency of the fabric, has better color development and washing fastness, and has excellent friction fastness, and can further suppress bleeding (intercolor bleeding).

[0054] 1.4.Water The ink composition of this embodiment contains water. The ink composition is a water-based ink. A water-based ink is a composition that contains water as one of its main solvent components. The use of a water-based ink can reduce the environmental impact and, for example, enable recording with less odor.

[0055] Water is a component that evaporates and dissipates upon drying. It is preferable that the water be pure water or ultrapure water, such as ion-exchanged water, ultrafiltered water, reverse osmosis water, or distilled water, from which ionic impurities have been removed as much as possible. Furthermore, using water that has been sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferable, as this can prevent the growth of mold and bacteria when the ink is stored for a long period of time.

[0056] The water content is preferably 45% by mass or more, more preferably 50% by mass or more and 98% by mass or less, and even more preferably 55% by mass or more and 95% by mass or less, based on the total amount of the ink composition.

[0057] 1.5.Other Ingredients The ink composition of this embodiment may contain, in addition to the non-white pigment, resin particles, acetylene-based surfactant having an HLB value of 6 or more and 10 or less, and water, components such as an organic solvent, surfactants other than acetylene-based surfactants having an HLB value of 6 or more and 10 or less, wax, additives, preservatives / anti-fungal agents, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and anti-mold agents, as long as the effects of the present invention are achieved.

[0058] (organic solvent) The ink composition may contain an organic solvent. The organic solvent is preferably water-soluble. Functions of the organic solvent include, for example, improving the wettability of the ink composition to a recording medium and increasing the moisture retention of the ink composition. The organic solvent also functions as a penetrant.

[0059] Examples of organic solvents include esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, and polyhydric alcohols. Examples of nitrogen-containing solvents include cyclic amides and non-cyclic amides. Examples of non-cyclic amides include alkoxyalkylamides.

[0060] On the other hand, it is particularly preferable that the organic solvent does not contain 2-pyrrolidone, diethylene glycol, or ethylene glycol, because this allows for the suitable production of recorded matter that meets the standards of GOTS (Global Organic Textile Standard) certification and Oeko-Tex certification. From the same viewpoint, it is preferable that the content of these organic solvents is 0.05% by mass or less in total, with the lower limit being 0% by mass being particularly preferable.

[0061] Examples of esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; ethylene glycol diacetate; Examples of glycol diesters include glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, and dipropylene glycol acetate propionate.

[0062] The alkylene glycol ethers may be monoethers or diethers of alkylene glycol, and alkyl ethers are preferred. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like. and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0063] Furthermore, among the alkylene glycols, diethers tend to dissolve or swell resin particles in the ink more easily than monoethers, and are therefore more preferred in terms of improving the abrasion resistance of the formed image.

[0064] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-nonalactone, and ε-decanolactone, as well as compounds in which the hydrogen atom of the methylene group adjacent to the carbonyl group is substituted with an alkyl group having 1 to 4 carbon atoms.

[0065] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, and 3-n-propoxy. -N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N-diethylpropionamide, 3-iso-propoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, and the like.

[0066] Examples of cyclic amides include lactams, and more specifically, pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0067] Examples of polyhydric alcohols include 1,2-alkanediols (e.g., alkanediols such as ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and 1,2-octanediol), polyhydric alcohols (polyols) other than 1,2-alkanediols (e.g., diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-propanediol, and 1,3-butanediol (also known as 1,3-butylene glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, trimethylolpropane, glycerin, etc.

[0068] Polyhydric alcohols can be divided into alkanediols and polyols. Alkanediols are diols of alkanes having 5 or more carbon atoms. The number of carbon atoms in the alkanes is preferably 5 or more and 15 or less, more preferably 6 or more and 10 or less, and even more preferably 6 or more and 8 or less. The polyhydric alcohol is preferably 1,2-alkanediol.

[0069] The polyols are polyols of alkanes having 4 or less carbon atoms, or intermolecular condensation products of hydroxyl groups of polyols of alkanes having 4 or less carbon atoms. The number of carbon atoms of the alkane is preferably 2 or more and 3 or less. The number of hydroxyl groups in the polyol molecule is 2 or more and preferably 5 or less, and more preferably 3 or less. When the polyol is an intermolecular condensation product, the number of intermolecular condensation groups is 2 or more and preferably 4 or less, and more preferably 3 or less. The polyhydric alcohols can be used alone or in combination of two or more.

[0070] Alkanediols and polyols can mainly function as penetrating solvents and / or moisturizers. Alkanediols tend to have strong penetrating solvent properties, while polyols tend to have strong moisturizing properties. An example of an organic solvent with strong moisturizing properties is glycerin.

[0071] When the ink composition contains an organic solvent, the organic solvent may be used alone or in combination of two or more kinds.

[0072] The content of the organic solvent is, for example, 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 45% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, relative to the total amount of the ink composition.

[0073] (Surfactants other than acetylene surfactants with an HLB value of 6 to 10) As long as the ink composition exhibits the effects of the present invention, it may contain a surfactant other than an acetylene-based surfactant having an HLB value of 6 or more and 10 or less. Examples of such surfactants include silicone-based surfactants and fluorine-based surfactants.

[0074] (wax) The ink composition may contain a wax. Examples of components that make up the wax include plant and animal waxes such as carnauba wax, candelilla wax, beeswax, rice wax, and lanolin; petroleum waxes such as paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, and petrolatum; mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, and stearic acid amide; and natural and synthetic wax emulsions and blended waxes such as α-olefin-maleic anhydride copolymers. These can be used alone or in combination of two or more.

[0075] (additives) The ink composition may contain additives such as ureas, amines, and sugars. Examples of ureas include urea, ethyleneurea, tetramethylurea, thiourea, 1,3-dimethyl-2-imidazolidinone, and the like, and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N,N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, and the like).

[0076] Examples of amines include diethanolamine, triethanolamine, and triisopropanolamine. Ureas and amines may also function as pH adjusters.

[0077] Examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0078] (others) The ink composition may further contain components such as preservatives, antifungals, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and antifungal agents, as required.

[0079] 1.6. Physical properties and preparation of ink composition The viscosity of the ink composition at 20°C is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less.

[0080] From the viewpoint of ensuring appropriate wetting and spreading properties on a recording medium, the upper limit of the surface tension of the ink composition at 25°C is preferably 40 mN / m or less, more preferably 38 mN / m or less, even more preferably 35 mN / m or less, even more preferably 32 mN / m or less, and particularly preferably 30 mN / m or less. From the same viewpoint, the lower limit of the surface tension is preferably 15 mN / m or more, more preferably 20 mN / m or more, even more preferably 25 mN / m or more, and even more preferably 27 mN / m or more. In this specification, the surface tension can be measured using a surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) as the surface tension when a platinum plate is wetted with the composition at room temperature and normal pressure. For specific measurement methods, see the Examples. If the surface tension of the ink composition is within the above range, the ejection stability and initial filling property in ink jet recording can be improved.

[0081] 1.7. Method for producing ink composition The ink composition can be prepared by mixing a non-white pigment, resin particles, an acetylene surfactant with an HLB value of 6 to 10, water, and other components as needed in any order, and then removing impurities and foreign matter by filtration as needed. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, stirring, and mixing them. Filtration methods include, for example, centrifugal filtration and filter filtration.

[0082] 2. White inkjet ink composition The white inkjet ink composition (hereinafter also referred to as "white ink") of this embodiment contains a white pigment, resin particles, a silicone surfactant with an HLB value of 10 or more and 14 or less, and water.

[0083] 2.1.White pigment The white ink of this embodiment contains a white pigment. Examples of white pigments include metal oxides, barium sulfate, calcium carbonate, and other metal compounds. Examples of metal oxides include titanium dioxide, zinc oxide, silica, alumina, and magnesium oxide. Furthermore, the white pigment may be a particle having a hollow structure, and known particles having a hollow structure may be used.

[0084] Among these, a typical example of a white pigment is titanium dioxide, and examples thereof include Typepaque CR-50-2, CR-57, CR-58-2, CR-60-2, CR-60-3, CR-Super-70, CR-90-2, CR-95, CR953, PC-3, PF-690, PF-691, PF-699, PF-711, PF-728, PF-736, PF-737, PF-739, PF-740, PF-742, R-980, and UT-771 (all manufactured by Ishihara Sangyo Kaisha, Ltd.), and CI Pigment White 6.

[0085] When titanium dioxide is selected as the white pigment, the color development of the white image can be further improved. The white pigment may be used alone or in combination of two or more kinds.

[0086] The content of the white pigment, in terms of solid content, relative to the total amount of the white ink, is preferably 0.5% by mass to 20.0% by mass, more preferably 1.0% by mass to 20.0% by mass, even more preferably 3.0% by mass to 15.0% by mass, and still more preferably 7.0% by mass to 13.0% by mass. If the content of the white pigment is within the above range, an image with more sufficient visibility can be obtained.

[0087] It is preferable that the white pigment can be stably dispersed in the dispersion medium, and for this purpose, a dispersant may be used for dispersion. Examples of the dispersant include the same dispersants as those used for the non-white coloring materials in the non-white textile printing inks.

[0088] 2.2.Resin particles The white ink of this embodiment contains resin particles. Examples of the resin particles include the same resin particles as those contained in the non-white textile printing ink.

[0089] The content of the resin particles is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and even more preferably 2% by mass or more and 10% by mass or less, in terms of solid content, relative to the total amount of the white ink.

[0090] 2.3. Silicone surfactants with an HLB value of 10 or more and 14 or less The white ink of this embodiment contains a silicone surfactant with an HLB value of 10 or more and 14 or less.

[0091] In order to obtain better color development, washing fastness, and rubbing fastness, the HLB value is preferably 10 or more and 13 or less, and more preferably 11 or more and 12 or less.

[0092] The silicone surfactants may be used alone or in combination of two or more types, so long as they have an HLB value of 10 or more and 14 or less. In this embodiment, for example, a silicone surfactant with an HLB value of more than 14 and a silicone surfactant with an HLB value of less than 10 may be used in combination so that the white ink contains a silicone surfactant with an HLB value of 10 or more and 14 or less. Furthermore, the white ink may contain surfactants other than silicone surfactants, as long as the effects of the present invention are achieved.

[0093] Examples of silicone surfactants include side-chain modified polydimethylsiloxanes, both-end modified polydimethylsiloxanes, one-end modified polydimethylsiloxanes, and both-end modified polydimethylsiloxanes of side chains, all of which have an HLB value of 10 or more and 14 or less. Such silicone surfactants may be commercially available products, such as those available from BYK Japan K.K., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd. Examples include BYK-348 (HLB value: 11) manufactured by BYK Japan K.K., and KF-6004 (HLB value: 9) manufactured by Shin-Etsu Chemical Co., Ltd.

[0094] In order to achieve even better color development, washing fastness, and abrasion fastness, the content of the silicone surfactant is preferably from 0.1% to 2.0% by mass, more preferably from 0.4% to 1.5% by mass, and even more preferably from 0.5% to 1.0% by mass, relative to the total amount of the white ink.

[0095] 2.4.Water The white ink of this embodiment contains water. As for the water, reference may be made to the water contained in the non-white textile printing ink.

[0096] The water content is preferably 45% by mass or more, more preferably 50% by mass or more and 98% by mass or less, and even more preferably 55% by mass or more and 95% by mass or less, relative to the total amount of the white ink.

[0097] 2.5.Other Ingredients The white ink of this embodiment may contain, in addition to the white pigment, resin particles, silicone surfactant with an HLB value of 10 to 14, and water, ingredients such as an organic solvent, surfactants other than silicone surfactants with an HLB value of 10 to 14, wax, additives, preservatives / fungicides, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and antifungal agents, as long as the effects of the present invention are achieved. For details of these ingredients, refer to the ingredients contained in the non-white textile printing ink described above.

[0098] 2.6.Physical properties of white ink The viscosity of the white ink at 20°C is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less.

[0099] From the viewpoint of ensuring appropriate wetting and spreading properties on a recording medium, the upper limit of the surface tension of the white ink at 25° C. is preferably 40 mN / m or less, more preferably 38 mN / m or less, even more preferably 35 mN / m or less, even more preferably 32 mN / m or less, and particularly preferably 30 mN / m or less. From the same viewpoint, the lower limit of the surface tension is preferably 15 mN / m or more, more preferably 20 mN / m or more, even more preferably 25 mN / m or more, and even more preferably 27 mN / m or more. If the surface tension of the white ink falls within the above range, the ejection stability and initial filling property in inkjet recording can be improved.

[0100] 2.7. White ink manufacturing method As a method for producing the white ink, the above-mentioned method for producing the non-white textile printing ink may be referred to.

[0101] 3. Ink set The ink set includes the non-white textile printing ink described above and the white ink described above.

[0102] The ink set of this embodiment can be used on the fabric described below. In this embodiment, the treatment liquid composition is first applied to the fabric described below to obtain a fabric to which the treatment liquid composition is applied. The fabric to which the treatment liquid composition is applied is then printed with a white ink, and the printed surface is then printed with a non-white printing ink, thereby easily obtaining a recorded material having good color development, washing fastness, and abrasion fastness. Furthermore, in textile printing by the inkjet method, stable continuous printing can be performed. The treatment liquid composition will be described later.

[0103] The white ink according to this embodiment contains a silicone-based surfactant with an HLB value of 10 or more and 14 or less. The non-white textile printing ink according to this embodiment contains a specific amount of an acetylene-based surfactant with an HLB value of 6 or more and 10 or less. This allows a base layer of white ink to be suitably formed on a fabric to which the treatment liquid composition has been applied, and a color layer of non-white ink to be suitably formed on the base layer. As a result, penetration of the ink into the fabric can be suppressed, and the color layer can be retained on the base layer on the fabric surface. This reduces the influence of the color of the fabric itself, allowing for the production of a printed product with good color development, washing fastness, and abrasion fastness. Furthermore, stable continuous printing is possible in textile printing using the inkjet method.

[0104] 3.1. Treatment liquid composition The treatment liquid composition contains a cationic compound, resin particles, a surfactant, and water.

[0105] 3.1.1. Cationic Compounds The treatment liquid composition contains a cationic compound. A cationic compound is a compound that releases or contains cations. Cationic compounds have the effect of aggregating components such as pigments and resin particles. The degree of aggregation of pigments and resin particles caused by a cationic compound varies depending on the type of cationic compound, pigment, and resin particles, and can be adjusted. Such aggregation can, for example, enhance color development, improve the fixability of resin particles, and / or increase the viscosity of the ink.

[0106] Examples of cationic compounds include metal salts and cationic organic compounds. Examples of cationic organic compounds that can be used include cationic polymers and cationic surfactants. Preferred metal salts are polyvalent metal salts, and preferred cationic organic compounds are cationic polymers. Furthermore, organic acids may be used because they release protons.

[0107] The metal salt is preferably a polyvalent metal salt, but metal salts other than polyvalent metal salts can also be used. Among these cationic compounds, it is preferable to use at least one metal salt, as it easily induces cation responsiveness in pigments and resin particles. The cationic compounds can be used alone or in combination of two or more.

[0108] Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Examples of divalent or higher metal ions include calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron ions. Among the metal ions that compose these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferred because they have excellent coagulation properties for ink components.

[0109] The anions constituting polyvalent metal salts are inorganic or organic ions. That is, polyvalent metal salts are composed of inorganic or organic ions and divalent or higher metal ions. Examples of inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of organic ions include organic acid ions, more specifically carboxylate ions.

[0110] Specific examples of the polyvalent metal salt include calcium carbonate, such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, and aluminum acetate. These polyvalent metal salts may be used alone or in combination. Among these, magnesium sulfate, calcium nitrate, and / or calcium chloride are preferred, as they can ensure sufficient solubility in water and reduce residues from the treatment liquid composition, with calcium nitrate being more preferred. These metal salts may contain water of hydration in their raw material form.

[0111] Examples of metal salts other than polyvalent metal salts include monovalent metal salts such as sodium salts and potassium salts, and more specifically, sodium sulfate and potassium sulfate.

[0112] Suitable examples of organic acids include poly(meth)acrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. One organic acid may be used alone, or two or more organic acids may be used in combination. Metal salts of organic acids are included in the above-mentioned metal salts.

[0113] Suitable inorganic acids include, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and salts thereof. The inorganic acids may be used alone or in combination of two or more. Salts of inorganic acids that are metal salts are included in the above-mentioned metal salts.

[0114] Examples of cationic polymers include cationic urethane resins, cationic olefin resins, and cationic amine resins. The cationic polymers are preferably water-soluble.

[0115] As the cationic urethane-based resin, commercially available products can be used, such as Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, and CP-7610 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 600, 610, 620, 630, 640, and 650 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Urethane Emulsion WBR-2120C and WBR-2122C (trade names, manufactured by Taisei Fine Chemical Co., Ltd.).

[0116] The cationic olefin resin has an olefin such as ethylene or propylene in its structural skeleton, and known resins can be appropriately selected and used. The cationic olefin resin may also be in the form of an emulsion dispersed in a solvent containing water or an organic solvent. Commercially available cationic olefin resins can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0117] The cationic amine-based resin may be any resin having an amino group in its structure, and known resins may be appropriately selected and used. Examples include polyamine-based resins, polyamide-based resins, and polyallylamine-based resins. Polyamine-based resins are resins having amino groups in their main skeletons. Polyamide-based resins are resins having amide groups in their main skeletons. Polyallylamine-based resins are resins having a structure derived from allyl groups in their main skeletons.

[0118] Examples of cationic polyamine resins include Unisense KHE103L (hexamethylenediamine / epichlorohydrin resin, 1% aqueous solution having a pH of approximately 5.0, a viscosity of 20 mPa·s or more and 50 mPa·s or less, and a solids concentration of 50% by mass) and Unisense KHE104L (dimethylamine / epichlorohydrin resin, 1% aqueous solution having a pH of approximately 7.0, a viscosity of 1 mPa·s or more and 10 mPa·s or less, and a solids concentration of 20% by mass) manufactured by Senka Corporation. Specific examples of commercially available cationic polyamine resins include FL-14 (manufactured by SNF Co., Ltd.), Arafix 100, 251S, 255, and 255LOX (manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, and 6885; WS-4010, 4011, 4020, 4024, 4027, and 4030 (manufactured by Seiko PMC Co., Ltd.), and Papiogen P-105 (manufactured by Senka Co., Ltd.). , Sumirez Resin 650 (30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Co., Ltd.), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Synthetic Co., Ltd.), Jetfix 36N, 38A, 5052 (manufactured by Satoda Chemical Co., Ltd.).

[0119] Examples of polyallylamine resins include polyallylamine hydrochloride, polyallylamine amidosulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amidosulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-acrylamide copolymer, and the like.

[0120] These cationic compounds may be used alone or in combination of two or more. Furthermore, if at least one of polyvalent metal salts, organic acids, and cationic polymers is selected from these cationic compounds, the aggregation action of dispersed particles is improved, and therefore images with better color development can be formed.

[0121] The content of the cationic compound is preferably 0.1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and even more preferably 2% by mass or more and 10% by mass or less, relative to the total amount of the treatment liquid composition.

[0122] 3.1.2.Resin particles The treatment liquid composition contains resin particles. As the resin particles, for example, a resin emulsion can be used. Examples of resins used for the resin particles include urethane resins, addition polymerization resins, fluororesins, and natural resins. Examples of addition polymerization resins include homopolymers or copolymers of (meth)acrylic acid, (meth)acrylic acid esters, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, silicone, rosin, terpene, epoxy, polyester, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylimidazole, and vinylidene chloride.

[0123] Commercially available resin emulsions include, for example, Vinyblan (registered trademark) 150, 603, 745, and 1245L (manufactured by Nissin Chemical Industry Co., Ltd.), Danfix (registered trademark) MM11 (manufactured by Nissin Chemical Industry Co., Ltd.), Senka Antiflick (registered trademark) CX-2 (manufactured by Senka Co., Ltd.), Mowinyl (registered trademark) 966A (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Microgel (registered trademark) E-100. 2, E-5002 (manufactured by Nippon Paint Co., Ltd.), Boncoat (registered trademark) 4001, 5454 (manufactured by DIC Corporation), SAE1014 (manufactured by Zeon Corporation), Saivinol (registered trademark) SK-200 (manufactured by Saiden Chemical Co., Ltd.), Joncryl (registered trademark) 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 85 2, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (manufactured by BASF), NK Binder R-5HN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Sancure 2710 (manufactured by The Lubrizol Group, Inc.), Parmarin (registered trademark) UA-150 (manufactured by Sanyo Chemical Industries, Ltd.), Examples of such a surfactant include Superflex (registered trademark) 460, 470, 610, and 700 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), NeoRez (registered trademark) R-9660, R-9637, and R-940 (manufactured by Kusumoto Chemicals Co., Ltd.), Adeka Bontiter (registered trademark) HUX-380 and 290K (manufactured by ADEKA Corporation), and Takelac (registered trademark) W-605, W-635, and WS-6021 (manufactured by Mitsui Chemicals, Inc.).

[0124] The content of the resin particles is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, and even more preferably 0.1% by mass to 3% by mass, relative to the total amount of the treatment liquid composition.

[0125] Surfactants The treatment liquid composition contains a surfactant. Examples of surfactants include acetylene glycol surfactants, silicone surfactants, and fluorine surfactants.

[0126] Examples of acetylene glycol surfactants include Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (manufactured by Nissin Chemical Industry Co., Ltd.), and Olfine (registered trademark) Examples of suitable acrylic acid esters include acrylic acid esters B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, and AE-3 (trademarks manufactured by Nissin Chemical Industry Co., Ltd.), and Acetylenol (registered trademark) E00, E00P, E40, and E100 (trademarks manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0127] Examples of silicone surfactants include polysiloxane compounds such as polyether-modified organosiloxane. Commercially available polyether-modified organosiloxanes include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (manufactured by BYK Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0128] Examples of fluorine-based surfactants include fluorine-modified polymers, such as BYK-340 (manufactured by BYK Japan KK).

[0129] The content of the surfactant is preferably 0.01% by mass or more and 10.0% by mass or less, more preferably 0.05% by mass or more and 5.0% by mass or less, and even more preferably 0.07% by mass or more and 1.0% by mass or less, relative to the total amount of the treatment liquid composition.

[0130] 3.1.4.Water The treatment liquid composition contains water. As for the water, reference may be made to the water contained in the non-white textile printing ink.

[0131] The water content is preferably 45% by mass or more, more preferably 50% by mass or more and 98% by mass or less, and even more preferably 55% by mass or more and 95% by mass or less, based on the total amount of the treatment liquid composition.

[0132] 3.1.5. Other ingredients The treatment liquid composition may contain various additives such as a solubilizing agent, a viscosity adjusting agent, a pH adjusting agent, an antioxidant, a preservative, a mildew inhibitor, a corrosion inhibitor, and a chelating agent. The additives may be used alone or in combination of two or more.

[0133] The content of each additive is, for example, 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the treatment liquid composition.

[0134] 3.1.6. Method for preparing processing liquid composition The treatment liquid composition can be prepared by mixing the components in any order and, if necessary, filtering the mixture to remove impurities and foreign matter. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. Examples of filtration methods include centrifugal filtration and filter filtration.

[0135] 4.Fabric The fabric according to this embodiment has a water absorbency evaluated by the following method of at least 1. For specific evaluation methods, see the examples. (method) A test fabric cut into a 2 cm square was placed on the water surface of a 50 mL glass bottle containing 30 mL of pure water and 4 cm high from the bottom to the water surface, with the fabric surface parallel to the water surface. The time from when the fabric was placed until a part of the fabric reached the bottom of the glass bottle was taken as the water absorbency (seconds).

[0136] The water absorbency of the fabric is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more, since this provides better color development and washing fastness, better friction fastness, and further suppresses bleeding (intercolor bleeding).

[0137] In the case of light-colored fabrics, a non-white ink, i.e., a colored ink, is directly applied to the fabric for printing without applying a treatment liquid composition to the fabric in advance. The ink composition according to this embodiment does not depend on the water absorbency of the fabric, has good color development and washing fastness, has excellent friction fastness, can suppress bleeding (intercolor bleeding), and enables stable continuous printing in inkjet printing. Therefore, it is more preferably used for light-colored fabrics to which no treatment liquid composition has been applied. In this specification, light-colored fabrics refer to fabrics having a color temperature of 1000 to 12000°C in the CIELAB standard. * The dark colored fabric is a fabric having a value of 75 or more in CIELAB. * This indicates a fabric having a tensile strength of less than 75.

[0138] Furthermore, the ink composition according to this embodiment can be suitably used for printing on fabrics to which no treatment liquid composition has been previously applied, and can produce recorded matter having good color development and washing fastness, excellent friction fastness, and excellent suppression of bleeding (intercolor bleeding). Furthermore, stable continuous printing is possible on such fabrics when printing by the inkjet method. In this specification, fabrics to which no treatment liquid composition has been applied refer to fabrics that do not contain a cationic compound. Specifically, when the amount of cationic compound attached to the fabric is 0.02 g / cm or less, the ink composition can be used for printing on such fabrics. 2 The lower limit of the amount of adhesion is 0.00 g / cm 2 is.

[0139] The fabric may be any fabric as long as it has a water absorbency of 1 or higher as evaluated by the above method, and typically includes fibers. Examples of such fibers include natural fibers such as cotton, linen, wool, and silk, which have a water absorbency of 1 or higher; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, which have a water absorbency of 1 or higher; and biodegradable fibers such as polylactic acid, which have a water absorbency of 1 or higher. The fibers may also be blends of these fibers. Cotton is preferred as the fiber in the fabric because it has good color development and washing fastness, excellent friction fastness, can suppress bleeding (intercolor bleeding), and allows stable continuous printing in textile printing by the inkjet method.

[0140] Examples of the form of fabric include woven fabrics, knitted fabrics, nonwoven fabrics, fabrics, and clothing and other accessories. Examples of clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, furniture such as curtains, sheets, bedspreads, and wallpaper; and fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to size, and finished products.

[0141] The basis weight of the fabric is preferably, for example, 1.0 oz or more and 10.0 oz or less. If the basis weight of the fabric is in this range, better recording can be performed.

[0142] The fabric may be pre-colored with a dye, as long as it has a water absorbency of 1 or more. Examples of dyes that pre-color the fabric include water-soluble dyes such as acid dyes and basic dyes; disperse dyes used in combination with dispersants; reactive dyes; and solvent dyes. When cotton fabric is used as the fabric, it is preferable to use a disperse dye or reactive dye suitable for dyeing cotton, and a disperse dye is more preferable.

[0143] 5. Inkjet recording method The inkjet recording method according to this embodiment is carried out using an ink composition. Specifically, the inkjet recording method includes a step of ejecting an ink composition from an inkjet head by an inkjet method and depositing the ink composition on a fabric having a water absorption index of 1 or higher. By employing the inkjet method, even dyed portions with fine patterns can be easily and reliably formed. Furthermore, the inkjet method can be applied to various fabrics, allowing for good printing. Such a textile printing method using the inkjet recording method can produce good printing with little color difference between the front and back sides, even on thick fabrics. Furthermore, by recording on a fabric using the ink composition, a printed matter having good color development, washing fastness, and excellent abrasion fastness can be easily obtained. Furthermore, textile printing using the inkjet method allows for stable continuous printing.

[0144] In the step of applying the ink composition to the fabric, the maximum amount of the ink composition applied to the fabric is 50 mg / cm 2 More than 200mg / cm 2 Preferably, it is 80 mg / cm or less. 2 More than 150mg / cm 2 When the maximum adhesion amount is within the above range, the color development is better. In addition, the washing fastness and friction fastness are also excellent, and aggregation unevenness tends to be less noticeable.

[0145] 5.1. Inkjet recording device The inkjet recording device used in the textile printing method is not particularly limited as long as it has at least an ink container that contains an ink composition and a recording head connected to the ink container, and is capable of ejecting the ink composition from the recording head to form an image on a fabric. Furthermore, either a serial type or a line type inkjet recording device can be used. These types of inkjet recording devices are equipped with a recording head, and while changing the relative positional relationship between the fabric and the recording head, droplets of the ink composition are ejected intermittently and in a predetermined volume from the nozzle holes of the recording head at predetermined timing. This allows the ink composition to adhere to the fabric, forming a predetermined transfer image.

[0146] In general, in a serial inkjet recording device, the transport direction of the fabric, which is the recording medium, intersects with the direction of the reciprocating motion of the recording head, and the relative positional relationship between the fabric and the recording head is changed by combining the reciprocating motion of the recording head and the transport motion of the fabric. In this case, the recording head generally has a plurality of nozzle holes, and a row of the nozzle holes, i.e., a nozzle row, is formed along the transport direction of the fabric. The recording head may also have a plurality of nozzle rows formed depending on the type and number of ink compositions.

[0147] Generally, in a line-type inkjet recording device, the recording head does not reciprocate, but changes the relative positional relationship between the recording medium, fabric, and the recording head by transporting the fabric. Even in this case, the recording head generally has a plurality of nozzle holes arranged therein, and a nozzle row is formed in a direction intersecting the transport direction of the fabric.

[0148] 5.2.Other processes In the recording method, it is preferable to heat the fabric to which the ink composition is attached, as necessary, thereby obtaining a recorded matter having better color development, washing fastness, and excellent abrasion fastness.

[0149] Examples of the heating method include a heat press method, a normal pressure steam method, a high pressure steam method, and a Thermofix method. Examples of the heat source for heating include hot air, infrared rays, and microwaves.

[0150] During heating, the surface temperature of the heated fabric is preferably 60°C or higher and 180°C or lower. Having a surface temperature within this range reduces damage to the inkjet head and fabric, and also makes it easier for the ink to wet and spread evenly across the fabric and penetrate more easily. The surface temperature can be measured, for example, using a non-contact thermometer (product name "IT2-80", manufactured by Keyence Corporation).

[0151] The heating time is preferably, for example, from 5 seconds to 5 minutes. By keeping the heating time within this range, it becomes possible to sufficiently heat the fabric while reducing damage to the inkjet head and the fabric.

[0152] 5.3. Recording method using ink set In this embodiment, for example, it is preferable to use an ink set for recording on dark-colored fabrics. Such a recording method preferably includes a white ink application step in which white ink is ejected and applied to the fabric, and a non-white textile printing ink application step in which non-white textile printing ink is applied to the area where the white ink has been applied. Furthermore, it is more preferable to perform the non-white textile printing ink application step without performing a drying step after the white ink application step. More preferably, as shown in FIG. 1 , the recording method includes a treatment liquid composition application step, a heating step, a white ink application step, a non-white textile printing ink application step, and a post-heating step. A recording method having such steps can produce a recorded product with good color development, washing fastness, and abrasion fastness. Furthermore, stable continuous printing is possible.

[0153] 5.3.1. White ink application process The white ink application step may be performed in any manner as long as the white ink is applied while the recording head is scanning the fabric, thereby enabling efficient printing of a wide variety of images in small quantities using a small device.

[0154] 5.3.2. Non-white textile ink application process The non-white textile ink application step may be performed in any manner as long as the non-white textile ink is applied while the recording head is scanned over the fabric, thereby enabling efficient printing of a wide variety of small quantities using a small device.

[0155] In the non-white textile ink application step, a non-white textile ink is applied to the area where the white ink has been applied. That is, in the non-white textile ink application step, a non-white textile ink is applied in an overlapping manner to the area where the white ink has been applied. This further improves the color development of the non-white image by concealing the background with the white image. Furthermore, when the fabric is colored, the visibility of the formed image can be improved. Furthermore, in this embodiment, a non-white textile ink containing a specific amount of an acetylene-based surfactant with an HLB value of 6 to 10 is applied to the area where the white ink containing a silicone-based surfactant with an HLB value of 10 to 14 has been applied, thereby obtaining a printed matter with good color development, washing fastness, and abrasion fastness. Furthermore, textile printing using the inkjet method enables stable continuous printing.

[0156] In the non-white textile ink application process, the non-white textile ink may be ejected from a recording head to which the nozzles that ejected the white ink belong and applied to the fabric, or may be ejected from a recording head separate from the recording head to which the nozzles that ejected the white ink belong.

[0157] This step is preferably carried out in the same inkjet recording device as the white ink deposition step, in which case the non-white textile ink is adjusted to be ejected from nozzles different from the nozzles of the recording head that eject the white ink.

[0158] After the white ink application step, it is preferable to perform the non-white textile printing ink application step without performing a drying step. "Without performing a drying step" means that no active heating, air blowing, decompression, or other operations are performed. More specifically, after the white ink application step, the non-white textile printing ink application step is performed without placing the non-white textile printing ink in an environment at a temperature of 35°C or higher, preferably 30°C or higher, and more preferably 25°C or higher. In the recording method, by using an ink set, an image with excellent color development, washing fastness, and rubbing fastness can be formed even if the non-white textile printing ink application step is started without performing a drying step after the white ink application step is completed. Furthermore, the ink composition enables stable continuous printing in textile printing by the inkjet method, thereby enabling images with excellent color development, washing fastness, and rubbing fastness to be formed on fabrics at even higher speeds.

[0159] 5.3.3. Time intervals between each step In the recording method, it is preferable to start the non-white textile ink application step within 1 minute after the white ink application step is completed. By using an ink set, the recording method can form an image with good color development, washing fastness, and rubbing fastness even if the non-white textile ink application step is started a short time interval after the white ink application step is completed. Furthermore, the ink composition enables stable continuous printing in textile printing by the inkjet method, so that an image with good color development, washing fastness, and rubbing fastness can be formed on the fabric at even higher speed.

[0160] The time between the completion of the white ink application step and the start of the non-white textile printing ink application step is preferably within 50 seconds, more preferably within 40 seconds, and even more preferably within 30 seconds. According to the recording method, even in such a short time interval, an image with good color development, washing fastness, and abrasion fastness can be formed.

[0161] 5.3.4. Configuration of Inkjet Printing Apparatus In the recording method, the non-white textile printing ink applying step can be started after a short time interval following completion of the white ink applying step, and such a time interval may be realized by appropriately setting the arrangement of the recording head of the inkjet recording device used, the scanning speed, the fabric conveying speed, etc.

[0162] For example, if the distance between the downstream end of the nozzle of the recording head that ejects the white ink in the fabric transport direction and the upstream end of the nozzle of the recording head that ejects the non-white textile printing ink in the fabric transport direction is set to 200 mm and the scanning speed of the recording head, the number of printing passes, etc. are adjusted so that the fabric feed speed is 20 mm / s, the time from the completion of the white ink application step to the start of the non-white textile printing ink application step can be set to 20 seconds.

[0163] 5.3.5. Other processes The recording method may further include a step of applying one or more of another white inkjet ink composition and another non-white textile printing inkjet ink composition to the recording medium, as needed. In this case, the order and number of these steps are not limited and can be performed appropriately as needed. Furthermore, the inkjet recording method may include a treatment liquid composition application step, a step of heating the recording medium (post-heating step), etc.

[0164] 5.3.5.1. Treatment composition application step The recording method may include a treatment liquid composition applying step of applying the treatment liquid composition to the fabric. The treatment liquid composition applying step is a step of applying the treatment liquid composition to the fabric before the white ink applying step. Note that the treatment liquid composition may be described above.

[0165] The amount of the treatment liquid composition applied to the fabric is, for example, 0.02 g / cm 2 More than 0.5g / cm 2 It is preferable that the value is 0.02 g / cm or less. 2 More than 0.3g / cm 2By setting the amount of the treatment liquid composition to be applied within the above range, the treatment liquid composition can be applied more uniformly to the fabric, aggregation unevenness of the image on the printed textile can be further suppressed, and color development can be improved.

[0166] Examples of methods for applying the treatment liquid composition to a fabric include a dip coating method in which the fabric is immersed in the treatment liquid composition, a roller coating method in which the treatment liquid composition is applied using a mangle roller, a roll coater, or the like, a spray coating method in which the treatment liquid composition is sprayed using a spray device, or an inkjet coating method in which the treatment liquid composition is sprayed by an inkjet method. Of these coating methods, the treatment liquid composition may be applied to the fabric using one method alone, or two or more methods may be combined to apply the treatment liquid composition to the fabric.

[0167] This step may be carried out by coating, immersion, or the like, and may be carried out in the same inkjet recording device as the white ink application step. In this case, the recording head is set so that the treatment liquid composition is ejected from a nozzle different from the nozzles from which the white ink and non-white textile printing ink are ejected.

[0168] In this step, it is preferable to heat and dry the fabric to which the treatment liquid composition has been applied, if necessary. As the drying method, the above-mentioned heating step may be referred to.

[0169] 5.3.5.2. Post-heating process The recording method may further include a post-heating step of heating the fabric after the non-white textile printing ink application step. The post-heating step is also called a secondary heating step. The post-heating step can be carried out, for example, using an appropriate heating means. A heated press or the like may also be used. This allows the resulting image to be dried and more sufficiently fixed, thereby making it possible, for example, to make the recorded matter usable sooner. [Example]

[0170] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. Unless otherwise specified, "parts" below refer to parts by mass.

[0171] 1. Non-white textile printing inkjet ink composition and white inkjet ink composition 1.1. Preparation of Ink Composition (Examples 1 to 4, Comparative Examples 1 to 6, and Reference Examples 1 to 3) The components were placed in a container and mixed and stirred for two hours using a magnetic stirrer to obtain the non-white textile printing inkjet ink composition shown in Table 1 and the white inkjet ink composition shown in Table 2. The components were then thoroughly mixed by dispersion treatment using a bead mill filled with zirconia beads having a diameter of 0.3 mm. After stirring for one hour, the mixture was filtered using a 5.0 μm PTFE membrane filter to obtain the inks according to the Examples, Comparative Examples, and Reference Examples. The values ​​in Tables 1 and 2 indicate % by mass. Ion-exchanged water was used, and added so that the mass of each ink was 100% by mass.

[0172] The components shown in Tables 1 and 2 are as follows: [Pigments] Carbon black dispersion Microjet CW1 (trade name, specific gravity: 1.8 g / mL to 1.9 g / mL) (manufactured by Orient Chemical Industries Co., Ltd.) was used as the pigment, and an anionic resin dispersant was used as the pigment dispersant. Specifically, a styrene-acrylic resin synthesized using 55% by weight of styrene, 20% by weight of acrylic acid, and 30% by weight of methyl methacrylate was used. Three parts by weight of pigment was mixed with 1 part by weight of dispersant and 10 parts by weight of ion-exchanged water. The resulting mixture was premixed and then dispersed using a bead mill disperser (manufactured by Kotobuki Industries Co., Ltd., UAM-015) with 0.03 mm diameter zirconia beads at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes. Coarse particles were separated by centrifugation using a centrifuge (manufactured by Kuboyama Shoji Co., Ltd., Model-3600) to obtain a carbon black dispersion.

[0173] Titanium oxide dispersion A titanium oxide dispersion was obtained in the same manner as for the carbon black dispersion, except that CI Pigment White 6 (specific gravity: 4.2 g / mL) was used as the pigment instead of Microjet CW1 (trade name).

[0174] [Resin dispersion] Takelac® WS-6021 (trade name, manufactured by Mitsui Chemicals, Inc.), urethane resin particles

[0175] [Moisturizing agent (organic solvent)] Glycerin

[0176] [Organic solvent] Triethylene glycol Triethylene glycol monobutyl ether Propylene glycol

[0177] [Surfactant] BYK (registered trademark)-348 (trade name, manufactured by BYK Japan Co., Ltd.), HLB value: 11, polyether-modified organosiloxane surfactant Surfynol (registered trademark) 104 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), HLB value: 4, acetylene glycol surfactant (2,4,7,9-tetramethyl-5-decyne-4,7-diol) Surfynol (registered trademark) SE (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), HLB value: 6, acetylene glycol surfactant (containing 2,4,7,9-tetramethyl-5-decyne-4,7-diol and an ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol) Surfynol (registered trademark) 440 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), HLB value: 8, acetylene glycol surfactant (ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol) Surfynol (registered trademark) 485 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), HLB value: 13, acetylene glycol surfactant (ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, number of moles of ethylene oxide added: 30) F-444 (trade name, manufactured by DIC Corporation), HLB value: 8.5, fluorine-based surfactant

[0178] [Table 1]

[0179] [Table 2]

[0180] 2. Preparation of printed items 2.1.Fabric The following four types of commercially available T-shirt fabric were prepared as fabrics. 1 white cotton T-shirt (Printstar 085CVT, manufactured by Tom's Co., Ltd.) White cotton T-shirt 2 (Fruit of the loom Heavy HP cotton, manufactured by TMS Co., Ltd.) 1 black cotton T-shirt (Printstar 085CVT, manufactured by Tom's Co., Ltd.) Black cotton T-shirt 2 (Fruit of the loom Heavy HP cotton, manufactured by TMS Co., Ltd.)

[0181] 2.2. Evaluation of water absorbency of fabrics The water absorbency (unit: seconds) of the fabrics of the white cotton T-shirts 1 and 2 and the black cotton T-shirts 1 and 2 was evaluated according to the following evaluation method. The evaluation results are shown in Table 3. (Water absorption evaluation) First, white cotton T-shirts 1 and 2 and black cotton T-shirts 1 and 2 were each cut into 2 cm pieces (2 cm x 2 cm) to prepare test fabrics. Next, 30 mL of pure water was placed in a 50 mL glass bottle (screw cap bottle, manufactured by Maruel Co., Ltd.) with a height of 4 cm from the bottom to the water surface. The test fabric cut into 2 cm pieces was placed on the water surface so that the surface of the fabric was parallel to the water surface. The time (seconds) from when the test fabric was placed until it reached the bottom of the glass bottle was defined as the water absorbency. The time until the fabric reached the bottom was defined as the time from when the fabric was placed until a part of the fabric reached the bottom of the glass bottle. A shorter time until the fabric reached the bottom indicates a more water-absorbent fabric.

[0182] [Table 3]

[0183] 2.3.Textile printing 1 2.3.1. Textile printing 1 (no adhesion of treatment liquid composition to fabric) (Examples 1 to 4 and Comparative Examples 1 to 6) Images were printed on white cotton T-shirts 1 and 2 using the non-white textile printing inks obtained in Examples 1 to 4 and Comparative Examples 1 to 6 by an inkjet method using an inkjet printer (modified SC-F2000, manufactured by Seiko Epson Corporation). The ink deposition rate was 30 ng / dot, and the number of nozzles used was 360 nozzles / row x 1 row. The printed pattern (image) had a resolution of 1440 x 720 dpi, the printing area was A4 size, and a solid pattern was printed with a duty of 10% to 100%, and the number of prints was one. The evaluation was conducted in an environment with a temperature of 25.0°C and a relative humidity of 40.0% until the ink application was completed. In other words, the temperature near the fabric surface was approximately the same as the ambient temperature until the ink application was completed. Specifically, it was 28.0°C or lower. The printed images were dried in a heat press dryer (AF-54TEN (trade name), manufactured by Asahi Fiber Co., Ltd., lower iron dimensions 500 mm × 400 mm) under conditions of 170°C, 60 seconds, and 4.5 kN to obtain the printed materials in Examples 1 to 4 and Comparative Examples 1 to 6, respectively.

[0184] 2.3.2. Textile Printing 2 (with adhesion of treatment liquid composition to the printed textile) (Reference examples 1~3) To each of black cotton T-shirts 1 and 2, 20 g of the following treatment liquid composition was applied by inkjet printing using an inkjet printer (a modified SC-F2000, manufactured by Seiko Epson Corporation). The treatment liquid composition was applied to an area of ​​A4 size. The T-shirts were then dried in a heat press dryer (AF-54TEN (trade name), manufactured by Asahi Fiber Co., Ltd., lower iron dimensions: 500 mm × 400 mm) under conditions of 170°C, 45 seconds, and 4.5 kN, to obtain black cotton T-shirts with the treatment liquid composition adhered thereto. [Treatment liquid composition] Polyvalent metal salt: calcium nitrate tetrahydrate, 5% by mass, manufactured by Kanto Chemical Industry Co., Ltd. Resin dispersion: Vinyblan (registered trademark) 1245L (product name, solid content 40%), 1% by mass (as solid content), manufactured by Japan Coating Resins Co., Ltd., acrylic copolymer aqueous emulsion Surfactant: Olfine (registered trademark) E1010 (trade name, HLB value: 13 to 14), 0.1% by mass, manufactured by Nissin Chemical Industry Co., Ltd., acetylene-based surfactant Solvent: ion-exchanged water, residue

[0185] Each of the white inks obtained in Reference Examples 1 to 3 was applied to a black cotton T-shirt 1 or 2 with the treatment liquid composition adhered thereto. The ink deposition amount was 30 ng / dot, and the number of nozzles used was 360 nozzles / row x 4 rows. The printed pattern (image) had a resolution of 1440 x 1440 dpi, the printing range was A4 size, and the duty was a solid pattern of 10% to 100%, and printing was performed twice. After printing the image, the printed image was dried in a heat press dryer (AF-54TEN (trade name), manufactured by Asahi Fiber Co., Ltd., lower iron dimensions 500 mm x 400 mm) under conditions of 170°C, 60 seconds, and 4.5 kN to obtain the printed materials in Reference Examples 1 to 3, respectively.

[0186] 2.3.3. Textile Printing 3 (with adhesion of treatment liquid composition to the printed textile) (Examples 5 to 6, Comparative Examples 7 to 9, and Reference Examples 4 to 5) Each of the white inks obtained in Reference Examples 1 to 3 was applied as a lower layer to a black cotton T-shirt 1 to which the treatment liquid composition had been applied, as shown in Table 4. Next, each of the non-white textile printing inks obtained in Examples 1 and 2 and Comparative Examples 1, 5, and 6 was applied as an upper layer to the area to which the white ink had been applied (lower layer), as shown in Table 4. The time from the completion of application of the white ink to the start of application of the non-white textile printing ink was within 15 seconds in all cases. The amount of white ink ejected was 30 ng / dot, and the number of nozzles used was 360 nozzles / row x 4 rows. The print pattern (image) had a resolution of 1440 x 1440 dpi, the print area was A4 size, the duty was 10% to 100%, and the solid pattern was printed twice. The amount of non-white printing ink was 30 ng / dot, and the number of nozzles used was 360 nozzles / row x 1 row. The printing pattern (image) had a resolution of 1440 x 720 dpi, the printing range was A4 size, the duty was 10% to 100%, and the pattern was a solid pattern, and the number of printings was one. The evaluation was carried out in an environment with a temperature of 25.0°C and a relative humidity of 40.0% from the start of application of the white ink to the completion of application of the non-white textile printing ink, and no heat drying was performed between the completion of application of the white ink and the start of application of the non-white textile printing ink. That is, the temperature near the fabric surface was approximately the same as the environmental temperature from the start of application of the white ink to the completion of application of the non-white textile printing ink. Specifically, it was 28.0°C or lower.

[0187] After printing the image, the printed image was dried in a heat press dryer (AF-54TEN (trade name), manufactured by Asahi Fiber Co., Ltd., lower iron dimensions 500 mm × 400 mm) under conditions of 170°C, 60 seconds, and 4.5 kN to obtain the printed materials in Examples 5 to 6, Comparative Examples 7 to 9, and Reference Examples 4 to 5, respectively.

[0188] [Table 4]

[0189] 3. Evaluation Method 3.1.Ink surface tension 20 g of each of the non-white textile printing inks obtained in Examples 1 to 4 or Comparative Examples 1 to 6, or the white inks obtained in Reference Examples 1 to 3, was placed in a glass Petri dish, and a platinum plate was placed in vertical contact with the ink. The ink surface tension (mN / m) was measured at room temperature and normal pressure by the Wilhelmy method using a surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Tables 5 and 6.

[0190] 3.2. Discharge reliability A white cotton T-shirt 1 or a black cotton T-shirt 1 with the treatment liquid composition applied thereto was continuously printed for 1 minute using an inkjet printer (a modified SC-F2000, manufactured by Seiko Epson Corporation) with the non-white textile printing inks obtained in Examples 1 to 4, Comparative Examples 1 to 6, or the white inks obtained in Reference Examples 1 to 3 circulating. The amount of ink applied per dot was 30 ng / dot for both the white and non-white textile printing inks. Until ink application was complete, evaluation was performed in an environment with a temperature of 25.0°C and a relative humidity of 40.0%. The temperature near the fabric surface remained approximately the same as the ambient temperature until ink application was complete. Specifically, it was 28.0°C or lower. After printing, the number of nozzles that had experienced abnormal ejection was confirmed. This test was performed three times, and the average value of the three results was used to evaluate the ejection reliability according to the following criteria 1 or 2. The results are shown in Tables 5 and 6. (Criterion 1) A: After continuous ejection, no print defects or irregularities were observed. B: After continuous ejection, there are print defects and irregularities in one or more but two or fewer nozzles. C: After continuous ejection, there are print defects and irregularities in 3 to 5 nozzles. D: After continuous ejection, there are print omissions and irregularities in six or more nozzles. (Criterion 2) A: After continuous ejection, no print defects or irregularities were observed. B: After continuous ejection, there are print defects and irregularities in one or more but two or fewer nozzles. C: After continuous ejection, there are print defects and irregularities in 3 to 4 nozzles. D: After continuous ejection, there are print omissions and irregularities in five or more nozzles.

[0191] 3.3. Washing fastness Using a general household laundry detergent (fluorescent brightener-free), the printed textiles obtained in Examples 1 to 4 and Comparative Examples 1 to 6 in the above-mentioned Textile Printing 1, the printed textiles obtained in the above-mentioned Textile Printing 2 in Reference Examples 1 to 3, and the printed textiles obtained in the above-mentioned Textile Printing 3 in Examples 5 to 6, Comparative Examples 7 to 9, and Reference Examples 4 to 5 were washed in a household washing machine (ZABOON (trade name), manufactured by Toshiba Corporation). The washing was carried out twice each in the standard mode. After that, for each part with a duty of 10% or more and 100% or less, the color difference ΔE expressed by the CIE DE2000 color difference formula before and after washing was measured. 00 Calculate the maximum value of ΔE 00 The obtained ΔE 00 The washing fastness was evaluated using Max according to the following criteria. The results are shown in Tables 5 to 7. (standard) S:ΔE 00 Max is less than 2.0. A:ΔE 00 Max is greater than or equal to 2.0 and less than 4.0. B:ΔE 00 Max is greater than or equal to 4.0 and less than 6.0. C:ΔE 00 Max is greater than or equal to 6.0 and less than 8.0. D:ΔE 00 Max is 8.0 or higher.

[0192] 3.4.Color development The printed textiles of Examples 1 to 4 and Comparative Examples 1 to 6 obtained in the above-mentioned Textile Printing 1, the printed textiles of Reference Examples 1 to 3 obtained in the above-mentioned Textile Printing 2, and the printed textiles of Examples 5 to 6, Comparative Examples 7 to 9, and Reference Examples 4 to 5 obtained in the above-mentioned Textile Printing 3 were each measured for L * a* b * and O.D. Black The obtained values ​​were used to evaluate color development according to the following criteria 1 or 2. The results are shown in Tables 5 to 7. (Criterion 1) S:OD Black The value is 1.31 or greater. A:OD Black The value is greater than or equal to 1.21 and less than 1.31. B:OD Black The value is greater than or equal to 1.11 and less than 1.21. C:OD Black The value is greater than or equal to 1.01 and less than 1.11. D:OD Black The value is less than 1.01. (Criterion 2) S:L * The value is 96 or greater. A:L * The value is greater than or equal to 93 and less than 96. B:L * The value is greater than or equal to 91 and less than 93. C:L * The value is greater than or equal to 88 and less than 91. D:L * The value is less than 88.

[0193] 3.5.Image Quality (Blurring) White cotton T-shirts 1 and 2, and black cotton T-shirts 1 and 2 coated with the treatment liquid composition, were printed with the non-white textile printing inks obtained in Examples 1 to 4 or Comparative Examples 1 to 6, or the white inks obtained in Reference Examples 1 to 3, by an inkjet method using an inkjet printer (modified SC-F2000, manufactured by Seiko Epson Corporation). The line width patterns were formed by printing vertical lines, horizontal lines (lines perpendicular to the vertical direction), left diagonal lines (lines diagonally at 45° to the left from the vertical direction), and right diagonal lines (lines diagonally at 45° to the right from the vertical direction), each with a line width of 0.5 mm or 1.0 mm. The ink deposition amount was 30 ng / dot. Evaluations were conducted in an environment with a temperature of 25.0°C and a relative humidity of 40.0% until ink application was complete. The temperature near the fabric surface remained approximately the same as the ambient temperature until ink application was complete. Specifically, it was below 28.0°C. After printing the line width pattern, the printed line width pattern was dried in a heat press dryer (AF-54TEN (trade name), manufactured by Asahi Fiber Co., Ltd., lower iron dimensions 500 mm × 400 mm) under conditions of 170 °C, 60 seconds, and 4.5 kN to obtain each printed product. The resulting printed textile was observed under an optical microscope for the extent of bleeding at the boundaries of the vertical, horizontal, and diagonal lines, and the maximum extent of bleeding was measured. The image quality was evaluated according to the following criteria. The results are shown in Tables 5 and 6. (standard) A: The bleeding range at the color boundary is less than 0.6 mm. B: The bleeding range at the color boundary is 0.6 mm or more and less than 1.1 mm. C: The bleeding range at the color boundary is 1.1 mm or more.

[0194] 3.6.Abrasion resistance For each of the printed textiles obtained in the above-mentioned Printing 3 in Examples 5 and 6, Comparative Examples 7 to 9, and Reference Examples 4 and 5, rub fastness was evaluated according to the dry or wet rub test specified in JIS L 0849, "Testing method for color fastness to rubbing," using the following dry rub criteria 1 or wet rub criteria 2. The tests were carried out using the crock meter method. The evaluation was carried out by visually determining the staining grade in accordance with JIS L 0801, Clause 10 (Determination of color fastness), which is cited in JIS L 0849. The results are shown in Table 7. (Dry friction standard) S: Abrasion resistance is between grade 3-4 (intermediate grade) and grade 4. A: The abrasion resistance is between grade 2-3 (intermediate grade) and grade 3. B: Abrasion resistance is between grade 1-2 (intermediate grade) and grade 2. C: The abrasion resistance is grade 1 or lower. (Wet friction standard) S: Abrasion resistance is between grade 3-4 (intermediate grade) and grade 4. A: The abrasion resistance is between grade 2-3 (intermediate grade) and grade 3. B: Abrasion resistance is between grade 1-2 (intermediate grade) and grade 2. C: The abrasion resistance is grade 1 or lower.

[0195] [Table 5]

[0196] [Table 6]

[0197] [Table 7]

[0198] As shown in Table 1, it was found that the ink composition of this embodiment can produce recorded matter that has good color development, washing fastness, and friction fastness, and that can suppress bleeding (intercolor bleeding), regardless of the water absorbency of the fabric. It was also found that the ink composition of this embodiment can be used for stable continuous printing in textile printing by the inkjet method.

[0199] Furthermore, a comparison between Examples 1 and 2 revealed that by using an ink composition containing an acetylene-based surfactant with an HLB value of 7 or more and 8 or less, it is possible to obtain a printed matter having better washing fastness and friction fastness, further suppressing bleeding (intercolor bleeding), and further improving color development on low-water-absorbent fabrics.

[0200] Furthermore, by comparing Examples 2 with Examples 3 and 4, it was found that by using an ink composition containing an acetylene surfactant with an HLB value of 7 or more and 8 or less, and in which the content of the acetylene surfactant is 0.7% by mass or more and 1.5% by mass or less relative to the total amount of the ink composition, it is possible to obtain a printed matter that is independent of the water absorbency of the fabric, has even better color development, washing fastness, and friction fastness, and can further suppress bleeding (intercolor bleeding).

[0201] As shown in Table 3, it was found that the ink set of this embodiment can produce printed matter with good color development, washing fastness, and abrasion fastness.

[0202] Furthermore, a comparison between Examples 5 and 6 revealed that by printing an ink composition containing an acetylene-based surfactant with an HLB value of 7 or more and 8 or less on a white ink containing a silicone-based surfactant with an HLB value of 10 or more and 14 or less, a printed matter having better wash fastness and abrasion fastness, as well as better color development on low-water-absorbent fabrics, can be obtained.

Claims

1. a white ink applying step of applying a white inkjet ink composition to a fabric by an inkjet method; a non-white textile printing ink applying step of applying the non-white textile printing inkjet ink composition by an inkjet method, the white inkjet ink composition comprises a white pigment, resin particles, a silicone surfactant having an HLB value of 10 or more and 14 or less, and water; the non-white textile printing inkjet ink composition comprises a pigment, resin particles, an acetylene-based surfactant having an HLB value of 6 or more and 10 or less, and water; the content of the acetylene surfactant is 0.5% by mass or more and 2.0% by mass or less relative to the total amount of the non-white textile printing inkjet ink composition, The water absorbency of the fabric evaluated by the following method is 1 or more: An inkjet recording method using the non-white textile inkjet ink composition. (method) A test fabric cut into a 2 cm square was placed on the water surface of a 50 mL glass bottle containing 30 mL of pure water and having a height of 4 cm from the bottom to the water surface, with the surface of the fabric parallel to the water surface. The time from when the fabric was placed until a part of the fabric reached the bottom of the glass bottle was taken as the water absorbency (seconds).

2. The inkjet recording method according to claim 1 , wherein the fabric is light-colored.

3. The inkjet recording method according to claim 1 or 2, wherein the fabric does not contain a cationic compound.

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