CN116133865A

CN116133865A - Aqueous inkjet ink and method for printing fiber structure by inkjet method

Info

Publication number: CN116133865A
Application number: CN202180060799.1A
Authority: CN
Inventors: 丹下晃介
Original assignee: Gifu Shellac Manufacturing Co Ltd
Current assignee: Gifu Shellac Manufacturing Co Ltd
Priority date: 2020-07-15
Filing date: 2021-07-08
Publication date: 2023-05-16
Also published as: WO2022014454A1; JPWO2022014454A1

Abstract

The present invention provides an aqueous inkjet ink suitable for inkjet printing of a structure made of cotton or synthetic fibers. The present invention also provides a method for printing a fiber structure by an inkjet method, which is excellent in Optical Density (OD) after printing, permeation inhibition, and color development. The aqueous inkjet ink (1) of the present invention contains at least a pigment, a dispersant, a solvent and water; (2) The dispersant is a cationic dispersant having an amine value of 10mgKOH/g or more and an amine value higher than an acid value; (3) The pigment content is 0.01 mass% or more and 30 mass% or less; (4) A value of 5 to 200 inclusive of dispersant content/pigment content x 100; (5) An ink for printing a structure made of cotton or synthetic fibers.

Description

Aqueous inkjet ink and method for printing fiber structure by inkjet method

Technical Field

The present invention relates to an aqueous inkjet ink for cotton or synthetic fiber structures. The present invention also relates to a method for anionizing a fiber structure and printing the fiber structure by an inkjet method.

Background

Examples of image recording methods for forming an image on a recording medium such as paper include an electrophotographic method, a sublimation method, a thermal transfer method, and an inkjet method. Among these, the inkjet printing apparatus is inexpensive, and plate making is not required for printing. In addition, since the ink composition is discharged only in a necessary image portion to directly form an image on a recording medium, the ink composition can be used efficiently, and the running cost is low particularly in the case of small-volume production.

Dye inks and pigment inks exist as inkjet inks. When pigment ink is used, the color tone and sharpness are generally inferior to those of dye ink, but the light resistance and water resistance of the pigment itself are excellent. In addition, there is an advantage that the inkjet dyeing using pigment ink does not require complicated post-treatment of the fabric, compared with the case of using dye ink. Accordingly, an inkjet printing method using pigment ink has been attracting attention as a printing method for fiber structures such as clothing.

As an inkjet printing method using pigment ink, there is known: a method for dyeing a fabric containing a nonionic water-soluble polymer, a nonionic surfactant or an amphoteric surfactant, and at least one of a water-soluble metal salt and a cationic compound (patent document 1); a method of dyeing a fabric treated with a cationic resin and a metal ion of 2 or 3 valences with a pigment ink (patent document 2); a method of dyeing a fabric to which a hydrophobic low molecular compound and a cationic resin are applied with a pigment ink and performing a heat treatment to form a film (patent document 3). The purpose of these methods is to improve sharpness, water resistance, abrasion resistance, etc. of the printed image.

Patent document 4 discloses an aqueous pigment dispersion having a low viscosity and excellent storage stability, and an aqueous inkjet ink having excellent hiding properties, each of which contains titanium oxide as a pigment. The aqueous pigment dispersion of patent document 4 uses titanium oxide whose surface is treated with an organic compound (any one of a polyol, an alkanolamine or a derivative thereof, an organosilicon compound, a higher fatty acid or a metal salt thereof, and an organometallic compound).

Patent document 5 discloses a nonaqueous white ink for an active energy ray-curable inkjet including titanium oxide, a pigment dispersant, and a polymerizable compound. In patent document 5, titanium oxide surface-treated with silica is preferably used as titanium oxide.

Prior art literature:

patent literature:

patent document 1: japanese patent laid-open No. 7-119047;

patent document 2: japanese patent laid-open No. 2000-226781;

patent document 3: japanese patent application laid-open No. 2001-140174;

patent document 4: japanese patent No. 5998747;

patent document 5: international publication No. 2014/175440.

Disclosure of Invention

Problems to be solved by the invention:

however, when a structure (fiber structure) made of fibers such as a T-shirt, a fabric, or a flag is printed by an inkjet method using an aqueous inkjet ink, there is a problem that the OD (optical density) is inferior to that in the case of printing on printing paper even if the same aqueous inkjet ink is used, and particularly when a structure made of synthetic fibers such as polyester is a printing object, the problem is remarkable.

In addition, although titanium oxide is generally used as a white pigment in a white aqueous inkjet ink, even if titanium oxide surface-treated with an organic compound is used, it is difficult to ensure stability and dispersibility in the case of an aqueous ink. In addition, when printing on a fiber structure, there are cases where it is difficult to sufficiently mask the color of the fiber.

The present invention provides an aqueous inkjet ink suitable for inkjet printing of a structure made of cotton or synthetic fibers. The present invention also provides a method for printing a fiber structure by an inkjet method, which is excellent in OD after printing, permeation inhibition, and color development.

Means for solving the problems:

the present inventors have continuously studied a color or black aqueous inkjet ink suitable for use in printing a fiber structure, particularly a structure made of polyester fibers, by an inkjet method, and as a result, have found that a printed matter having an excellent OD value after printing the anionized structure can be obtained by combining a pigment and a dispersant having a cationic functional group in a specific ratio, and have completed the present invention.

Further, the present inventors have conducted studies on a white aqueous inkjet ink containing titanium oxide as a white pigment to solve the above-mentioned problems, and as a result, have found that the stability and dispersibility of the white pigment can be improved by combining the surface-treated titanium oxide as the white pigment with a cationic dispersant having a specific amine value and acid value in a specific ratio. Further, the present inventors have found that a printed matter excellent in hiding (color development) after printing on a fiber structure can be obtained by using such a white aqueous inkjet ink, and completed the present invention.

In particular, the invention relates to an aqueous inkjet ink which at least contains pigment, dispersant, solvent and water,

the dispersant is a cationic dispersant having an amine value of 10mgKOH/g or more and an amine value higher than an acid value,

the pigment content is 0.01 to 30 mass%,

the value of the dispersant content/the pigment content x 100 is 5 to 200,

is an ink for printing a structure made of cotton or synthetic fibers.

The aqueous inkjet ink of the present invention can improve the dispersibility of the pigment and the OD after printing by combining the pigment and the dispersant having a cationic functional group. In addition, penetration of printing can be suppressed.

Preferably, the dispersant is a cationic dispersant having an amine value of 60mgKOH/g or more and 150mgKOH/g or less and an acid value of 0 mgKOH/g. The term "acid value of 0mgKOH/g" as used herein means that the acid value=0 mgKOH/g is included, and that the measurement limit in a usual acid value measurement method is not higher than that.

Preferably, the synthetic fibers are polyester fibers.

Preferably, the polyester fiber is an anionized polyester.

Preferably, for a color or Black Pigment, the Pigment is any of Pigment Yellow 155, pigment Red 122, pigment Blue 15:3, or Pigment Black 7.

Preferably, for white pigments, the pigment is titanium oxide surface treated with alumina, silica, polyols and/or polysiloxanes.

In a white aqueous inkjet ink containing titanium oxide as a white pigment, the stability and dispersibility of titanium oxide particles cannot be improved by using only the surface-treated titanium oxide disclosed in patent document 4 or 5. In addition, depending on the kind of the dispersant used together, there are cases where the color development (hiding) is insufficient when printing the fiber structure. However, a white aqueous inkjet ink containing a specific surface-treated titanium oxide and a specific cationic dispersant in a specific ratio is excellent in color development (hiding property) even when a fiber structure is printed, and in addition, the stability and dispersion of titanium oxide particles in the white aqueous inkjet ink should be excellent.

Preferably, in the case of an aqueous inkjet ink containing a white pigment, the (dispersant concentration (mass%)/titanium oxide concentration (mass%)) x amine value (mgKOH/g) =2.50 to 8.50 in the aqueous inkjet ink.

In addition, the invention relates to a method,

is a method for printing a fiber structure made of synthetic fibers by an inkjet method,

The method comprises the following steps:

a step A of anionizing the fiber structure with an anionizing agent; and

a step B of printing the fiber structure by an inkjet method using an aqueous inkjet ink containing at least a pigment, a dispersant, a solvent, and water,

the pigment content is 0.01 to 30 mass%,

the dispersant content/pigment content x 100 has a value of 5 to 200.

In addition, the invention relates to a method,

is a method for printing a fiber structure made of cotton material by an inkjet method,

the method comprises the following steps:

a step B of printing the fiber structure by an inkjet method using an aqueous inkjet ink,

the aqueous inkjet ink contains at least pigment, dispersant, solvent and water,

the pigment content is 0.01 to 30 mass%, and the dispersant content/pigment content x 100 value is 5 to 200.

The invention has the following effects:

according to the present invention, in particular, when an anionized structure made of synthetic fibers is subjected to inkjet printing with color or black, the OD after printing can be improved and permeation can be prevented.

In addition, according to the present invention, in a white aqueous inkjet ink containing surface-treated titanium oxide particles as a white pigment, the stability and dispersibility of the pigment particles can be improved. According to the present invention, particularly when an anionized structure made of synthetic fibers is subjected to inkjet printing with white, the color development after printing can be improved.

Detailed Description

Embodiments of the present invention are described below.

[ pigment ]

The color or black pigment that can be used in the present invention is not particularly limited, for example, carbon black, titanium black, C.I. No. PY-1, PY-3, PY-12, PY-13, PY-14, PY-17, PY-24, PY-34, PY-55, PY-62, PY-74, PY-79, PY-81, PY-83, PY-87, PY-93, PY-94, PY-97, PY-108, PY-109, PY-110, PY-120, PY-128, PY-129, PY-130, PY-133, PY-136, PY-138, PY-139, PY-147, PY-150, PY-151, PY-152, PY-154, PY-155, PY-156, PY-165, PY-167, PY-168 PY-169, PY-170, PY-173, PY-175, PY-180, PY-183, PY-184, PY-185, PY-191, PY-193, PR-2, PR-5, PR-8, PR-9, PR-15, PR-17, PR-22, PR-23, PR-48:1, PR-48:2, PR-48:3, PR-48:4, PR-53:1, PR-57:1, PR-58:4, PR-63:2, PR-104, PR-112, PR-122, PR-144, PR-146, PR-149, PR-150, PR-151, PR-166, PR-168, PR-170, PR-171, PR-176, PR-177, PR-185, PR-220, PR-222, PR-237, PR-238, PR-239, PR-240, PR-254, PR-264, PB-15:1, PB-15:3, PB-15:4, PB-15:6, PB-16, PB-60, PV-1, PV-19, PV-23, PV-29, PV-32, PV-37, PG-7, PG-36, PO-13, PO-16, PO-34, PO-36, PO-38, PO-43, PO-61, PO-62, PO-64, PO-71, PO-73, etc., but are not limited thereto. These pigments may be used alone or in combination of two or more.

The average particle diameter of the color or black pigment (average particle diameter of primary particles) in the aqueous inkjet ink of the present invention is preferably 10 to 250nm from the viewpoints of the sedimentation property of the color or black pigment particles and the optical density of the printed matter. If the average particle diameter is less than 10nm, it is difficult to ensure dispersion stability of the ink. On the other hand, if the particle diameter exceeds 250nm, sedimentation of pigment particles is liable to occur.

The average particle diameter as used herein refers to the average value of the major diameter and minor diameter (average value of the number of measured particles of 1 particle (nm) +minor diameter (nm)/2) when 100 or more pigment particles are observed by a transmission electron microscope. The average particle diameter of the surface-treated titanium oxide to be described later is also the same.

The white pigment which can be used in the present invention is titanium oxide surface-treated with alumina, silica, polyol and/or polysiloxane.

As the titanium oxide, either anatase type or rutile type can be used, but rutile type having higher coverage of printed matter is preferable. Titanium oxide prepared by a known preparation method such as a chlorine method or a sulfuric acid method can be used, but titanium oxide prepared by a chlorine method having a high whiteness is preferable.

Untreated titanium oxide has numerous hydroxyl groups on its surface, which are responsible for the hydrophilicity of titanium oxide. The hydroxyl groups are removed from the surface of the titanium oxide by reacting the hydroxyl groups with a polyol or polysiloxane which is an organic compound, and covered with the polyol or polysiloxane, thereby hydrophobizing the titanium oxide.

In patent document 4, the organic compound for performing the surface treatment of titanium oxide is not particularly limited as long as it can hydrophobize titanium oxide, and examples thereof include a polyol, an alkanolamine or a derivative thereof, an organosilicon compound, a higher fatty acid or a metal salt thereof, an organometallic compound, and the like.

Patent document 4 discloses a surface treatment of titanium oxide with an inorganic compound in order to improve weather resistance and dispersion stability, in addition to a surface treatment with an organic compound. Examples of the inorganic compound include compounds of silicon, aluminum, zirconium, tin, antimony, and titanium.

On the other hand, the surface-treated titanium oxide used in the present invention is a titanium oxide surface-treated with three components of (1) alumina, (2) silica, and (3) a polyol and/or polysiloxane of an organic compound.

The average particle diameter of the surface-treated titanium oxide (average particle diameter of the primary particles) in the aqueous inkjet ink of the present invention is preferably 100 to 400nm from the viewpoints of the sedimentation property of the surface-treated titanium oxide particles and the coverage of the printed matter. If the average particle diameter is less than 100nm, sedimentation of titanium oxide is less likely to occur, but the coverage is lowered, and the practicality as a white inkjet ink is lowered. On the other hand, if it exceeds 400nm, the coverage is sufficient but sedimentation is easily caused. The average particle diameter of the surface-treated titanium oxide is more preferably 150 to 350nm, still more preferably 200 to 300nm.

[ dispersant ]

The dispersant used in the present invention is a cationic dispersant having an amine value of 10mgKOH/g or more and an amine value higher than an acid value. The dispersant is preferably "an amine value of 10mgKOH/g or more and an acid value of 0", more preferably "an amine value of 60mgKOH/g or more and 150mgKOH/g or less and an acid value of 0mgKOH/g". The dispersant may be used alone or in combination of 1 or more than 2.

The amine number herein means the amine number per 1g of dispersant solid, and means the equivalent (unit: mgKOH/g) of potassium hydroxide as determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution. The acid value is an acid value per 1g of the dispersant solid, and can be determined by a potentiometric titration method according to JIS K0070 (1992) (unit: mgKOH/g).

Cationic dispersants having an amine value of 10mgKOH/g or more and an amine value higher than the acid value are commercially available in many forms, examples of which include DISPRBYK-182, 183, 184, 185, 191, 2013, 2050, 2070, 2055, BYKBET-9151, 9152, 9171 (produced by BYK JAPAN Co., ltd.), EFKAPX-4330, 4350, 4701, 4703, 4733, 4753, 4780 (produced by BASF Co., ltd.), TEGO Dispers 650 (produced by Evonik Co., ltd.), and the like. These dispersants may be used alone or in combination of 2 or more.

In the present invention, the value of (dispersant concentration (mass%)/titanium oxide concentration (mass%)) x amine value (mgKOH/g) in the white aqueous inkjet ink is preferably 2.50 to 8.50, more preferably 3.20 to 8.20, still more preferably 3.20 to 7.00. Here, "dispersant concentration (mass%)" refers to the concentration of solids as dispersants contained in the aqueous inkjet ink. The "titanium oxide concentration (mass%) means the concentration of titanium oxide after surface treatment contained in the aqueous inkjet ink.

The solvent which can be used in the present invention is not particularly limited, and for example, monohydric alcohols such as methanol, ethanol, and isopropanol can be used; a polyol; ketones or ketoalcohols such as acetone and diacetone alcohol; cyclic ethers such as tetrahydrofuran and dioxane.

The aqueous inkjet ink of the present invention may further contain additives such as a pH adjuster, a surfactant, a chelating agent, a rust inhibitor, an antioxidant, an ultraviolet absorber, a preservative, an antifungal agent, and an antifoaming agent, as required. The content (concentration) of these additives may be adjusted within a range that can exert their functions.

The pH adjuster that can be used in the present invention is not particularly limited, and examples thereof include hydroxides of alkali metals such as sodium oxide, potassium hydroxide, and lithium hydroxide; tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, and diethylethanolamine; ammonia, hydrochloric acid, acetic acid, formic acid, etc.

The surfactant that can be used in the present invention is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorosurfactants, and silicone surfactants.

The aqueous inkjet ink of the present invention can be obtained by preparing a pigment dispersion (pigment dispersion), adding a solvent, an additive, and the like thereto, and mixing. The pigment dispersion liquid can be obtained by mixing a pigment, a dispersion or the like and performing dispersion treatment with a sand mill (bead mill), a roll mill, a ball mill, a paint stirrer, an ultrasonic dispersion machine, a high-pressure emulsifying machine or the like.

The aqueous inkjet ink of the present invention can be obtained by preparing a pigment dispersion (pigment dispersion), adding a solvent, an additive, and the like thereto, and mixing them. Pigment dispersions can be prepared by mixing pigments, dispersions and the like and performing dispersion treatment with a sand mill (bead mill), a roll mill, a ball mill, a paint stirrer, an ultrasonic disperser, a high-pressure emulsifying machine and the like.

As an example, a case of performing dispersion treatment with a sand mill will be described. First, beads of pigment, dispersant and dispersion medium are charged into a sand mill. As the beads, glass beads, zirconia beads, etc. having a particle diameter of 0.01 to 1mm can be used. The amount of the beads to be used is preferably 2 to 6 weight per 1 weight of the ink. Thereafter, the sand mill was operated to perform dispersion treatment. The dispersion treatment is preferably carried out at about 1000 to 2000rpm for 1 to 20 hours. After the dispersion treatment, beads and the like are removed by filtration, and a pigment dispersion liquid is obtained.

The pigment concentration (mass%) in the aqueous inkjet ink of the present invention is preferably 0.01 mass% to 30 mass%, more preferably 0.01 mass% to 20 mass%, and still more preferably 1 mass% to 15 mass% for any of the color, black or white pigments. Within this range, sufficient color development (hiding power) can be obtained, and the ink tends to be excellent in storage stability.

The pH of the aqueous inkjet ink is preferably 3 to 11, more preferably 4 to 10, and in this range, the ink is excellent in storage stability and can also suppress damage to the ejection device or the fiber structure.

Preparation of aqueous inkjet ink 1: color or black >, of

Example 1/cyan ink

15.0 parts by weight of CYANINE BLUE KRO (PB-15:3, manufactured by Shanyang pigment Co., ltd.) as a cyan pigment, 11.5 parts by weight of dispersant C (DISPERBYK-185 (BYK JAPAN Co., ltd./amine value=17 mgKOH/g, active ingredient 52%), 73.5 parts by weight of deionized water, 400 parts by weight of zirconia beads having a diameter of 0.5mm were charged into a sand mill, and subjected to a dispersion treatment at 1,500rpm for 3 hours, after which the zirconia beads were removed to obtain a pigment dispersion, and the particle diameters of the pigment and dispersant were adjusted to about 100 to 110 nm.

In this pigment dispersion, as shown in table 1, BYK-348 (polyether modified siloxane manufactured by BYK JAPAN corporation) as a surfactant, formic acid or triethanolamine as a pH adjuster, 1, 2-hexanediol as a solvent, glycerin, and deionized water were mixed to prepare a cyan ink of pH 9. In addition, the aqueous inkjet inks of examples 1 to 11 and comparative examples 1 to 10 were prepared to a total of 100.0 parts by weight.

TABLE 1

Example 2/magenta ink

A magenta ink was prepared in the same manner as in example 1, except that FASTOGEN SUPER MAGENTARG (PR-122, manufactured by DIC Co.) was used as the magenta pigment.

Example 3/yellow ink

A Yellow ink was prepared in the same manner as in example 1, except that Inkjet Yellow 4GC (PY-155, a product of Clariant corporation) was used as the Yellow pigment.

Example 4/Black ink

A black ink was prepared in the same manner as in example 1, except that NIPex 160IQ (carbon black produced by Orion Engineered Carbons company) was used as a black pigment.

Example 5/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 6.0 parts by weight of dispersant D (EFKA PX4701 (manufactured by BASF corporation, amine value=40 mgKOH/g, active ingredient 100%) was used as the dispersant, and 79.0 parts by weight of deionized water was used.

Example 6/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 6.0 parts by weight of dispersant E (BYKJET-9151 (BYK JAPAN company product/amine value=18 mgKOH/g, acid value=8 mgKOH/g, active ingredient 100%) was used as the dispersant, and deionized water was 79.0 parts by weight.

Example 7/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 6.0 parts by weight of dispersant I (BYKJET-9152 (BYK JAPAN company product/amine value=19 mgKOH/g, acid value=6 mgKOH/g, active ingredient 100%) was used as the dispersant, and 79.0 parts by weight of deionized water was used.

Example 8/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 8.7 parts by weight of dispersant C and 76.3 parts by weight of deionized water were used.

Example 9/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 17.3 parts by weight of dispersant C and 67.7 parts by weight of deionized water were used.

Example 10/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 37.5 parts by weight of dispersant A (amine value: 67mgKOH/g, solid content: 20%) described below was used as the dispersant, and 47.5 parts by weight of deionized water was used.

Example 11/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 37.5 parts by weight of dispersant B (amine value: 135mgKOH/g, solid content: 20%) described below was used as the dispersant, and 47.5 parts by weight of deionized water was used.

[ method for producing dispersant A ]

A resin was prepared having a monomer composition ratio of benzyl methacrylate/dimethylaminoethyl methacrylate=80/20 (mass ratio) and an amine value of 67 mgKOH/g. Formic acid and deionized water were added to the resin to dissolve, and the solids were adjusted to 20% to obtain dispersant a.

[ method for producing dispersant B ]

A resin was prepared having a monomer composition ratio of benzyl methacrylate/dimethylaminoethyl methacrylate=60/40 (mass ratio) and an amine value of 135 mgKOH/g. Formic acid and deionized solution were added to the resin, and the solids were adjusted to 20% to obtain dispersant B.

Comparative example 1/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that dispersant F (DISPERBYK-190 (BYK JAPAN company/acid value=10 mgKOH/g, active ingredient 40%) was set to 15.0 parts by weight and deionized water was set to 70.0 parts by weight as a dispersant.

Comparative example 2/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that dispersant J (Joncryl 63J (BASF company/acid value=213 mgKOH/g, active ingredient 30%) was set to 20.0 parts by weight and deionized water was set to 65.0 parts by weight as a dispersant.

Comparative example 3/magenta ink

A magenta ink was produced in the same manner as in example 2, except that 15.0 parts by weight of dispersant F and 70.0 parts by weight of deionized water were used as the dispersant.

Comparative example 4/magenta ink

A magenta ink was produced in the same manner as in example 2, except that 20.0 parts by weight of dispersant J and 65.0 parts by weight of deionized water were used as the dispersant.

Comparative example 5/yellow ink

A yellow ink was prepared in the same manner as in example 3, except that 15.0 parts by weight of dispersant F and 70.0 parts by weight of deionized water were used as the dispersant.

Comparative example 6/yellow ink

A yellow ink was prepared in the same manner as in example 3, except that 20.0 parts by weight of dispersant J and 65.0 parts by weight of deionized water were used as the dispersant.

Comparative example 7/Black ink

A black ink was prepared in the same manner as in example 4, except that 15.0 parts by weight of dispersant F and 70.0 parts by weight of deionized water were used as the dispersant.

Comparative example 8/Black ink

A black ink was prepared in the same manner as in example 4, except that 20.0 parts by weight of dispersant J and 65.0 parts by weight of deionized water were used as the dispersant.

Comparative example 9/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 7.5 parts by weight of dispersant G (DISPERBYK-180 (BYK JAPAN Co., ltd., amine value: 94mgKOH/G, acid value: 94mgKOH/G, active ingredient 100%) was used as the dispersant, and 77.5 parts by weight of deionized water was used.

Comparative example 10/cyan ink

A cyan ink was prepared in the same manner as in example 1, except that 7.5 parts by weight of dispersant H (DISPERBYK-191 (BYK JAPAN Co., ltd., amine value: 20mgKOH/g, acid value: 30mgKOH/g, active ingredient 100%) was used as the dispersant, and 77.5 parts by weight of deionized water was used.

Fiber structure

As the fiber structure of the sample for printing, the following three samples were used:

cotton structure: 100% pure cotton fabric (mercerized broad cotton cloth produced by dyeing company);

polyester structure (untreated polyester structure): polyester 100% cotton (Amina, east asia);

structure of anionized polyester (anionized polyester structure): and a structure obtained by treating the same structure as the polyester structure with an anionizing agent.

< anionizing method/Process A >)

A cationic polymerization agent (cationic polymer/mountain cationic dye Co., ltd., cationizing agent CT F1101) was attached to the polyester structure as a 6g/L preparation by 1DIP/1NIP, and then dried at 130℃for 3 minutes. Then, an anionic polymerization agent was allowed to adhere to 1DIP/1NIP as a 60g/L preparation, and then dried at 130℃for 3 minutes, thereby obtaining an anionized polyester structure.

Here, the term "anionizing treatment" in the present invention means that an anionic polymerization agent is attached to a structure made of synthetic fibers. The anionic polymerizer may be selected from anionic polyester resins, anionic surfactants, polyester emulsions, and the like, with polyester emulsions being preferred. Examples of the polyester resin that can be used for the polyester emulsion include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, which are emulsified with an activator.

In addition, it is preferable that the cationization treatment is performed with a cationic polymerization agent before such treatment. Here, as the cationic polymerization agent, a known polymer (polymer or prepolymer) containing a tertiary amino group, a quaternary ammonium group, or both of them in the molecule can be used, and a cationic compound generally used as a cationizing agent can be used.

The tertiary amino group-containing polymer may be exemplified by the following polymers. Namely, (a) polymers of alkylaminoalkyl (meth) acrylamides, for example, polymers of dimethyl or diethylaminoethyl (meth) acrylamide, dimethyl or diethylaminopropyl (meth) acrylamide, and the like; (b) Polymers of dialkylaminoalkyl (meth) acrylates, for example, polymers of dimethyl (meth) acrylate or diethylaminoethyl (meth) acrylate, dimethyl (meth) acrylate or diethylaminopropyl (meth) acrylate, and the like; (c) an acrylamide styrene copolymer; (d) a tertiary amino group-containing urethane polymer, etc.

The quaternary ammonium group-containing polymer may be exemplified by the following polymers. Namely, (e) polymers of (meth) acryloyloxy alkyl trialkylammonium salts, for example, polymers of 2- (meth) acryloyloxy ethyl trimethyl ammonium chloride, 3- (meth) acryloyloxy-2-hydroxypropyl trimethyl ammonium chloride, and the like; (f) Polymers of (meth) acrylamide alkyl trialkylammonium salts, for example, polymers of (3- (meth) acrylamide propyl trimethylammonium chloride), 3- (meth) acrylamido-2-hydroxypropyl trimethylammonium chloride, and the like; (g) Polymers of 2- (meth) acryloyloxyalkyl benzyl ammonium salts, for example, polymers of 2- (meth) acryloyloxyethyl benzyl ammonium chloride or 2- (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride, copolymers of monomers of acryloyloxyethyl benzyl ammonium chloride or 2- (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride with acrylamide, dimethylaminoethyl acrylate, or the like; (h) Copolymers of acrylamidopropyldimethylbenzyl chloride with N, N-dimethylacrylamide, N-methyl-N-benzylallylamine salt with N-methyl-N-hydroxyethylaminopropyl acrylamide, and the like; (i) Other polymers such as dimethyl or diethyl diallyl ammonium chloride, beta-vinyloxy ethyl trialkyl ammonium salt, vinylbenzyl ammonium salt, and the like.

Further, as the cationic compound, (j) a compound containing a quaternary ammonium group, for example, hexamethylenebis (3-chloro-2-hydroxypropyl-dimethyl ammonium chloride), trimethylenebis (3-chloro-2-hydroxypropyl-dimethyl ammonium chloride), hexamethylenebis (2, 3-epoxypropyl-dimethyl ammonium chloride), trimethylenebis (2, 3-epoxypropyl-dimethyl ammonium chloride), 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 2, 3-epoxypropyl-trimethyl ammonium chloride, or the like can be used, and among these, polydialkylamino (meth) acrylate, polydimethyldiallyl ammonium chloride, a tertiary amino group-containing urethane polymer or the like is preferable.

The anionizing treatment in the present invention is not limited to the treatment described in step a described later.

Printing of fiber Structure/Process B

With three types of fiber structures as printing targets, solid images were formed by printing with an inkjet printer having a resolution of 600dpi using the prepared aqueous inkjet ink.

< OD value measurement method >)

The optical density of the resulting solid image surface was measured by a reflectometer GretagMacbeth RD-19 (SAKATA INX CORPORATION).

< penetration >

With respect to the obtained solid image, the distance at which the ink oozes out most was measured with a ruler.

The results of OD value, OD evaluation, and permeation evaluation of the cyan, magenta, yellow, and black aqueous inkjet inks are shown in tables 2 to 5, respectively. Here, in tables 2 to 5, OD values of 1.15 or more were evaluated as "verygood", 1.10 or more were evaluated as "good", 1.05 or more and less than 1.10 were evaluated as "delta", less than 1.05 were evaluated as "×", and OD values of 1.00 or more were evaluated as "good", less than 1.00 were evaluated as "delta" for magenta. For the permeation evaluation, the ink oozing distance was evaluated as "O" for 4 colors, as "delta" for 1mm or more and less than 2mm, and as "X" for 2mm or more. The evaluation is also the same as in tables 6 to 8 described below.

TABLE 2

TABLE 3

TABLE 4

TABLE 5

For the cotton structures, all colors were OD evaluation and permeation evaluation of the inks (examples 1 to 4) using dispersant C were "o". On the other hand, when dispersant F (comparative examples 1, 3, 5, 7) or dispersant J (comparative examples 2, 4, 6, 8) was used as dispersant, OD evaluation or permeation evaluation was "x", and it was judged that the practicability was lacking.

For the untreated polyester structure, all colors and virtually all dispersants were OD rated or permeation rated as "x", and were judged to be lacking in practicality. However, in the structure of the anionized polyester (represented by the treated polyester in tables 2 to 5) obtained by anionizing the same structure, all the colors were evaluated as "o" in terms of OD and permeation of the inks (examples 1 to 4) using the dispersant C.

The OD values, OD evaluations, and permeation evaluations of the cyan aqueous inkjet of examples 5 to 7 are shown in table 6. Examples 5 to 7, in which dispersant D, dispersant E and dispersant I were used as dispersants for the pigment dispersion, gave the same results as in example 1.

TABLE 6

The OD values, OD evaluations, and permeation evaluations of the cyan aqueous inkjet of example 1, example 8, and example 9 are shown in table 7. When the value of the dispersant content (D)/pigment content (P). Times.100 is in the range of 30 to 60, the OD evaluation and penetration evaluation of the cotton or the anionized polyester can be determined as "O".

TABLE 7

The OD values, OD evaluations, and permeation evaluations of the cyan aqueous inkjet of examples 10 to 11 and comparative examples 9 and 10 are shown in table 8. Examples 10 to 11, in which the dispersant a and the dispersant B were used as the dispersant for the pigment dispersion, were evaluated as "excellent" OD, evaluated as "o" penetration, and most excellent in examples.

TABLE 8

In this way, it was confirmed that the aqueous inkjet ink of the present invention containing a pigment and a specific cationic dispersant is suitable for printing a fiber structure composed of cotton or anionized polyester fiber, as compared with an aqueous inkjet ink containing the same pigment and other dispersants.

As can be seen from tables 2 to 8, in the case of an aqueous inkjet ink containing a pigment of color or black, the dispersant is preferably "a cationic dispersant having an amine value of 10mgKOH/g or more and an amine value higher than the acid value", more preferably "a cationic dispersant having an amine value of 60mgKOH/g or more and 150mgKOH/g or less and an acid value of 0 mgKOH/g" as in the case of the dispersant A and the dispersant B.

Preparation of aqueous inkjet ink 2: white >

Example 12

40.0 parts by weight of TIPAQUE PF-728 (manufactured by Shimadzu corporation, alumina/silica/polysiloxane treatment), 20.0 parts by weight of dispersant A, 40.0 parts by weight of deionized water, 400 parts by weight of zirconia beads having a diameter of 0.5mm as a dispersant were charged into a sand mill, and the dispersion treatment was performed at 1,500rpm for 2 hours. Thereafter, the zirconia beads were removed to obtain a titania dispersion.

The titanium oxide dispersion, BYK-348 (polyether modified siloxane manufactured by BYK JAPAN corporation) as a surfactant, 1, 2-hexanediol as a solvent, glycerin, and deionized water were mixed in the amounts shown in table 9 to prepare a white ink of example 12. The total amount of the aqueous inkjet inks of examples 12 to 25 and comparative examples 11 to 27 was adjusted to 100.0 parts by weight.

TABLE 9

Titanium oxide dispersion	25.0 parts by weight
		1, 2-hexanediol	1.0 part by weight
Glycerol	13.0 parts by weight
		BYK-348	0.3 part by weight
Deionized water	Remainder of the
		Totalizing	100.0 parts by weight

。

Example 13

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 10.0 parts by weight of dispersant B was used as the dispersant, and 50.0 parts by weight of deionized water was used. Thereafter, the white ink of example 13 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 14

A titanium oxide dispersion was obtained in the same manner as in example 1, except that 15.3 parts by weight of dispersant C (DISPERBYK-185, manufactured by BYK JAPAN Co., ltd., amine value of 17mgKOH/g, solid content of 52%) was used as the dispersant, and 44.7 parts by weight of deionized water was used. Thereafter, the white ink of example 3 was prepared in the same manner as in example 1, except for the blending amount shown in table 9.

Example 15

A titanium oxide dispersion was obtained in the same manner as in example 1, except that 6.0 parts by weight of dispersant D was used as the dispersant, and 54.0 parts by weight of deionized water was used. Thereafter, the white ink of example 15 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 16

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 6.0 parts by weight of dispersant E was used as the dispersant, and 54.0 parts by weight of deionized water was used. Thereafter, the white ink of example 16 was prepared in the same manner as in example 1, except for the blending amount shown in table 9.

Example 17

A titanium oxide dispersion was obtained in the same manner as in example 12, except that TIPAQUE PF-740 (alumina/zirconia/silica/polysiloxane treated) was changed to 40.0 parts by weight. Thereafter, the white ink of example 17 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 18

A titanium oxide dispersion was obtained in the same manner as in example 15, except that TIPAQUE PF-740 was changed to 40.0 parts by weight. Thereafter, the white ink of example 18 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 19

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 40.0 parts by weight of TIPAQUE CR-63 (alumina/silica/polyol/polysiloxane treatment, manufactured by Shimadzu corporation) was used as the titanium oxide. Thereafter, the white ink of example 19 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 20

A titanium oxide dispersion was obtained in the same manner as in example 15, except that 40.0 parts by weight of TIPAQUE CR-63 was used as the titanium oxide. Thereafter, the white ink of example 20 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 21

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 40.0 parts by weight of TIPAQUE PF-671 (alumina/silica/polyol treated, manufactured by Shimadzu corporation) was used as titanium oxide. Thereafter, the white ink of example 21 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 22

A titanium oxide dispersion was obtained in the same manner as in example 15, except that 40.0 parts by weight of TIPAQUE PF-671 was used as titanium oxide. Thereafter, the white ink of example 22 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 23

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 10.0 parts by weight of dispersant A and 50.0 parts by weight of deionized water were used. Thereafter, the white ink of example 23 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 24

A titanium oxide dispersion was obtained in the same manner as in example 13, except that the amount of the dispersant B was 6.0 parts by weight and the amount of deionized water was 54.0 parts by weight. Thereafter, the white ink of example 13 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Example 25

A titanium oxide dispersion was obtained in the same manner as in example 15, except that the dispersant D was 8.0 parts by weight and deionized water was 52.0 parts by weight. Thereafter, the white ink of example 25 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Comparative example 11

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 40.0 parts by weight of TIPAQUE PF-726 (manufactured by Shiniter Co., ltd., alumina/silica treatment) was used as titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 11 was prepared in the same manner as in example 12.

Comparative example 12

A titanium oxide dispersion was obtained in the same manner as in example 13, except that 40.0 parts by weight of TIPAQUE PF-726 was used as titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 12 was prepared in the same manner as in example 12.

Comparative example 13

A titanium oxide dispersion was obtained in the same manner as in example 14, except that 40.0 parts by weight of TIPAQUE PF-726 was used as titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 13 was prepared in the same manner as in example 12.

Comparative example 14

A titanium oxide dispersion was obtained in the same manner as in example 15, except that TIPAQUE PF-726 was changed to 40.0 parts by weight. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 14 was prepared in the same manner as in example 12.

Comparative example 15

A titanium oxide dispersion was obtained in the same manner as in example 16, except that 40.0 parts by weight of TIPAQUE PF-726 was used as titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 15 was prepared in the same manner as in example 12.

Comparative example 16

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 40.0 parts by weight of TIPAQUE CR-50 (alumina treatment, manufactured by Shimadzu corporation) was used as titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 16 was prepared in the same manner as in example 12.

Comparative example 17

A titanium oxide dispersion was obtained in the same manner as in example 15, except that 40.0 parts by weight of TIPAQUE CR-50 was used as the titanium oxide. Then, the ink of comparative example 17 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Comparative example 18

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 40.0 parts by weight of TIPAQUE CR-50-2 (alumina/polyol treatment, manufactured by Shimadzu corporation) was used as titanium oxide. Thereafter, a white ink of comparative example 18 was prepared in the same manner as in example 12, except for the blending amount shown in table 9.

Comparative example 19

A titanium oxide dispersion was obtained in the same manner as in example 15, except that 40.0 parts by weight of TIPAQUE CR-50-2 was used as the titanium oxide. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 19 was prepared in the same manner as in example 12.

Comparative example 20

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 10.0 parts by weight of dispersant F was used as the dispersant, and 50.0 parts by weight of deionized water was used. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 20 was prepared in the same manner as in example 12.

Comparative example 21

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 3.2 parts by weight of dispersant G was used as the dispersant, and 56.8 parts by weight of deionized water was used. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 21 was prepared in the same manner as in example 12.

Comparative example 22

A titanium oxide dispersion was obtained in the same manner as in example 12, except that 6.0 parts by weight of dispersant H was used as the dispersant, and 54.0 parts by weight of deionized water was used. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 22 was prepared in the same manner as in example 12.

Comparative example 23

A titanium oxide dispersion was obtained in the same manner as in example 12, except that the amount of the dispersant A was 6.0 parts by weight and the amount of deionized water was 54.0 parts by weight. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 23 was prepared in the same manner as in example 12.

Comparative example 24

A titanium oxide dispersion was obtained in the same manner as in example 1, except that the dispersant a was 30.0 parts by weight and deionized water was 30.0 parts by weight. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 14 was prepared in the same manner as in example 1.

Comparative example 25

A titanium oxide dispersion was obtained in the same manner as in example 13, except that 16.0 parts by weight of dispersant B and 44.0 parts by weight of deionized water were used. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 25 was prepared in the same manner as in example 12.

Comparative example 26

A titanium oxide dispersion was obtained in the same manner as in example 15, except that the dispersant D was changed to 2.0 parts by weight and deionized water was changed to 58.0 parts by weight. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 26 was prepared in the same manner as in example 12.

Comparative example 27

A titanium oxide dispersion was obtained in the same manner as in example 15, except that 10.0 parts by weight of dispersant D and 50.0 parts by weight of deionized water were used. Thereafter, as the blending amount shown in table 9, a white ink of comparative example 27 was prepared in the same manner as in example 12.

< stability test >

10g of the white inks of examples 12 to 25 and comparative examples 10 to 27 were placed in a closed container and allowed to stand in a constant temperature apparatus at 60℃for 1 week. After cooling to room temperature, the average particle diameter (average particle diameter of titanium oxide particles as a pigment) and viscosity of the white ink were measured with a light scattering photometer and an E-type viscometer. The average particle diameter (average particle diameter of titanium oxide particles as a pigment) and viscosity were also measured before the start of the stability test. The average particle diameter or viscosity before the start of the stability test was (a), and the average particle diameter or viscosity after the stability test was (B), and the increase rate of the measured value was calculated by the following calculation formula:

increase rate (%) = (B-ase:Sub>A)/a×100.

Then, the calculated increase rate was evaluated for stability of each white ink based on the following evaluation criteria. Further, "Δ" or more is a level of practicality:

o: the rate of increase of both the average particle size and the viscosity is less than 10%;

delta: the rate of increase in either the average particle diameter or viscosity is 10% or more;

x: the increase rate of both the average particle diameter and the viscosity is 10% or more.

< Settlement test >)

10g of the white inks of examples 12 to 25 and comparative examples 10 to 27 were put into a glass container and allowed to stand in a thermostatic device at 25℃for 3 days. Thereafter, the sedimentation properties of each white ink were evaluated based on the following evaluation criteria. In addition, "≡o" is a level of practicality:

O: no sediment was confirmed in the lower part of the glass vessel;

x: sediment was confirmed in the lower part of the glass container.

< anionizing method/Process A >)

The anionized polyester structure was obtained by the step a of the preparation 1 of the aqueous inkjet ink.

Printing of fiber Structure/Process B

For the white inks of examples 12 to 25 and comparative examples 10 to 27, solid printing was performed on the following substrates using a printer having a resolution of 600 dpi:

substrate 1: black cotton (h.444, kurabo corporation);

substrate 2: the black polyester fabric after the anionizing treatment.

< hiding test >

For substrate 1 and substrate 2, the OD values of the resulting image surfaces were measured by a reflectance densitometer (GretagMacbeth RD-19, SAKATA INX CORPORATION), and the hiding power was calculated based on the following calculation formula: hiding power (%) = (OD of 1-print/OD of black cotton before printing) ×100.

Thereafter, the hiding power of each white ink was evaluated based on the following evaluation criteria. Further, "Δ" or more is a level of practicality:

and (3) the following materials: the covering capacity is more than 70%;

o: the covering power is more than 50% and less than 70%;

delta: covering power is more than 30% and less than 50%;

X: the hiding power was less than 30%.

Table 10 shows the contents of the white pigment, the dispersant, and the deionized water in the (1) pigment dispersion liquid of the white inks of examples 11 to 25; (2) Values of (dispersant concentration (mass%)/titanium oxide concentration (mass%)) ×amine value (mgKOH/g); (3) Stability test, sedimentation test, and hiding test. Table 11 shows the contents of (1) white pigment, dispersant, and deionized water of the white inks of comparative examples 10 to 27; (2) Values of (dispersant concentration (mass%)/titanium oxide concentration (mass%)) ×amine values; (3) Stability test, sedimentation test, and hiding test.

TABLE 10

/>

TABLE 11

According to table 10, all evaluation items of the white inks of examples 12 to 25 were "practical". All evaluation items except example 16 were "o" or more. Further, examples 12, 13, 17, 19, 21, 23, and 24 were excellent in stability and sedimentation property as "good", and in covering power as "good". On the other hand, according to table 11, any of the white inks of comparative examples 10 to 27 was judged to be not practical as having an evaluation item "x".

Here, in the case of the white ink of example 12, the dispersant in the titanium oxide dispersion of 25.0 parts by weight was 20.0× (25/100) parts by weight, and the solid content of the dispersant was 20.0× (25/100) ×0.2 parts by weight. The titanium oxide in the titanium oxide dispersion of 25.0 parts by weight was 40.0× (25/100) parts by weight. Since the total amount of the white ink is 100 parts by weight, the (dispersant concentration (mass%)/titanium oxide concentration (mass%)) x amine value (mgKOH/g) in the white ink (aqueous inkjet ink) was calculated to be 20.0× (25/100) ×0.2 (%)/40.0× (25/100) (%) x 67=6.70. The same procedure was carried out for the white ink of the other examples and comparative examples, in which the concentration of the dispersant (mass%)/concentration of titanium oxide (mass%). Times.amine value (mgKOH/g) was calculated.

From tables 10 and 11, it can be confirmed that the white ink excellent in stability, sedimentation property and hiding power had the following conditions: (i) As white pigment, titanium oxide surface-treated with alumina, silica, polyol and/or polysiloxane is used; (ii) The cationic dispersant has an amine value of 10mgKOH/g or more, an amine value > acid value, and (iii) (dispersant concentration (mass%)/titanium oxide concentration (mass%). Times.amine value (mgKOH/g) values of 2.50 to 8.50. It is considered that the value of (dispersant concentration (mass%)/titanium oxide concentration (mass%)) x amine value (mgKOH/g) is preferably 3.20 to 8.20, more preferably 3.20 to 7.00. It is considered that the cationic dispersant is preferably 60mgKOH/g or more and 150mgKOH/g or less in value and 0mgKOH/g in acid value.

As described above, it was confirmed that the aqueous inkjet ink of the present invention containing a pigment and a specific cationic dispersant is suitable for printing a fiber structure composed of cotton or anionized polyester fiber, as compared with the aqueous inkjet ink containing the same pigment and other dispersants. In addition, when the aqueous inkjet ink of the present invention is an aqueous ink containing surface-treated titanium oxide as a white pigment, the stability and dispersibility of pigment particles are excellent. In addition, when the fiber structure is used, the color of the fiber can be fully covered.

Industrial applicability:

the aqueous inkjet ink and the method of printing a fiber structure by the inkjet method of the present invention are useful in the field of printing.

Claims

1. An aqueous ink-jet ink which comprises a substrate,

is an aqueous inkjet ink containing at least pigment, dispersant, solvent and water,

the pigment content is 0.01 to 30 mass%,

the value of the dispersant content/the pigment content x 100 is 5 to 200,

is an ink for printing a structure made of cotton or synthetic fibers.

2. The aqueous inkjet ink according to claim 1 wherein,

the dispersant is a cationic dispersant having an amine value of 60mgKOH/g or more and 150mgKOH/g or less and an acid value of 0 mgKOH/g.

3. The aqueous inkjet ink according to claim 1 or 2 wherein,

the synthetic fiber is polyester fiber.

4. The aqueous inkjet ink according to claim 3 wherein,

the polyester fiber is anionized polyester.

5. The aqueous inkjet ink according to any one of claims 1 to 4 wherein,

The Pigment is any one of Pigment Yellow 155, pigment Red 122, pigment Blue 15:3 and Pigment Black 7.

6. The aqueous inkjet ink according to any one of claims 1 to 4 wherein,

the pigment is titanium oxide surface-treated with alumina, silica, polyol and/or polysiloxane.

7. The aqueous inkjet ink according to claim 6 wherein,

in the aqueous inkjet ink, the (dispersant concentration (mass%)/titanium oxide concentration (mass%)) x amine value (mgKOH/g) =2.50 to 8.50.

8. A method of manufacturing a semiconductor device, the method comprising,

the method comprises the following steps:

a step A of anionizing the fiber structure with an anionizing agent, and

a step B of printing the fiber structure by an inkjet method using an aqueous inkjet ink after the step A,

the pigment content is 0.01 to 30 mass%,

The dispersant content/pigment content x 100 has a value of 5 to 200.

9. A method of manufacturing a semiconductor device, the method comprising,

the method comprises a step (B) of printing a fiber structure by an inkjet method using an aqueous inkjet ink,

the pigment content is 0.01 to 30 mass%,

the dispersant content/pigment content x 100 has a value of 5 to 200.

10. The method according to claim 8 or 9, wherein,

11. The method according to claim 8 or 10, wherein,

the synthetic fiber is polyester fiber.

12. The method according to claim 8, 10 or 11, characterized in that,

the anionizing agent is a polyester emulsion.

13. The method according to any one of claims 8 to 12, wherein,

The Pigment is any one of Pigment Yellow 155, pigment Red 122, pigment Blue 15:3 or Pigment Black 7.

14. The method according to any one of claims 8 to 12, wherein,

15. The aqueous inkjet ink according to claim 14 wherein,