CN116888322A - Pretreatment composition, printing component and printing and dyeing method - Google Patents

Abstract

The present invention relates to an aqueous ink composition for forming a wet precoat layer for containing an image formed on a fabric by an inkjet method, which satisfies the following [1 ]]To [4 ]]All conditions require: [1]The aqueous ink composition comprises water, pigment, resin emulsion, water-soluble organic solvent and surfactant; [2]For forming the pretreatment composition coating per unit areaThe amount is more than 0.035g/cm ² And less than 0.070g/cm ² Is a wet precoat layer of (a); [3]The pretreatment composition comprises water, more than 1.4 mass% and less than 10.0 mass% of a cationic polymer relative to the total mass of the pretreatment composition, and more than 0.1 mass% and less than 2.7 mass% of a crosslinking agent relative to the total mass of the pretreatment composition; [4]The cationic polymer comprises at least any one selected from the group consisting of allylamine structural units, diallylamine structural units, and epihalohydrin structural units.

Description

Pretreatment compositions, printing components and printing and dyeing methods

Technical field

The present invention relates to a pretreatment composition for inkjet printing and dyeing, an inkjet printing and dyeing method, a printing assembly (also called a "printing set") containing the pretreatment composition, and printed matter printed using the printing assembly.

Background technique

In the past, hand-painting and screen printing were the mainstream methods of fiber printing and dyeing. However, fiber printing and dyeing (inkjet printing) methods using inkjet printers are increasing recently.

As for the inkjet printing and dyeing method, it is more suitable for printing materials with a small quantity and a large variety than analog printing methods such as screen printing or gravure printing. It is expected to expand the scope of application of fabrics through the inkjet printing and dyeing method. With the expansion of such application scope, in clothing printing or home textile printing, various fabrics (such as cotton, polyester, nylon or blends containing two or more fibers, etc.) or various texture types (such as knitted fabrics) can be used , sheet cloth, broadcloth, Oxford cloth, striped cloth, net, etc.), it is necessary to further improve the concentration and fastness (such as color fastness to rubbing, color fastness to washing, light fastness, etc.).

Examples of colorants used in inkjet printing include water-soluble dyes. This dye has vivid hues and a wide color gamut that can be reproduced. On the other hand, water-soluble dyes have disadvantages such as low light resistance, complicated processes such as fixation and water washing after adhering the dye to fibers, and complicated treatment of dye waste liquid generated by water washing. Therefore, in order to replace water-soluble dyes, the application of water-insoluble colorants has attracted attention.

In inkjet printing using water-insoluble colorants, "bleeding" on the fibers becomes a problem. Regarding this problem, a solution for pretreatment of fibers was proposed. For example, the following Patent Documents 1 and 2 propose such a treatment liquid.

On the other hand, if one side of polyester fiber (a mesh texture used in sportswear, etc.) or a fiber with a thin base material or a fiber with a thick weave is printed and dyed, the colorant may penetrate into the fiber. The "bleed-through" phenomenon (the phenomenon of penetrating to the back side) on the side that is not printed on the opposite side becomes one of the big problems in reducing the density.

In addition, in order to prevent this print-through phenomenon, some people have proposed pre-treating the fiber. However, if an excessively high concentration of pretreatment liquid (hereinafter also referred to as a pretreatment composition) or a large amount of pretreatment liquid is applied (attached) to the fiber in order to prevent offset, the part where the pretreatment liquid is applied will There is also a problem that "traces" of the pretreatment liquid remain on the fibers. The so-called "traces" can be observed as a whitish-looking state in fibers with dark colors such as black, for example. On the other hand, for example, light-colored fibers such as aqua (light blue) can be observed to appear in a darker state as if they are wetted with water. If such traces remain, the appearance of the printed matter will significantly deteriorate. Therefore, the value of the printed matter as a commodity is reduced or even disappears, so there is a strong demand for a pretreatment liquid that prevents print show-through and leaves no "trace".

In addition, if a color ink other than white is directly printed on a dark fiber containing black, the color of the color ink may not be visually recognized. Therefore, when printing and dyeing dark-colored fibers with colored inks, a white base is usually provided, and the base is printed with colored inks. If the whiteness of the base is low, the color development of images printed with color inks will be reduced. For this reason, a base with high whiteness and hiding properties is preferred. However, it is known that the whiteness and hiding properties are reduced depending on the type of pretreatment liquid.

In addition, when using white ink to lay a base on dark fibers, the above-mentioned "print-through" phenomenon may occur depending on the type of fiber (fabric texture), which is a major problem that reduces whiteness and hiding properties. one.

In addition to print-through, unevenness is sometimes observed on the white base due to fiber fluffing in the pre-treated parts. Due to this uneven phenomenon, the quality of the printed matter is also greatly reduced.

Therefore, there is a strong desire for pretreatment compositions that can solve these problems, as well as printing and dyeing methods, printing components having pretreatment compositions and ink compositions.

In addition, when printing and dyeing light-colored fibers containing white with yellow, cyan, magenta, red, blue, purple, orange and black inks, in many cases a white base is not provided and these colored inks are directly attached on the fiber. Even in this case, it is strongly desired to have a pretreatment composition, a printing and dyeing method, a pretreatment composition, and a color ink (ink composition) that can obtain a color image with high color rendering properties (color development properties). components.

existing technical documents

patent documents

Patent Document 1: Japanese Patent Application Publication No. 07-119047

Patent Document 2: Japanese Patent Application Publication No. 2000-226781

Contents of the invention

Invent the technical problem you want to solve

The technical problem to be solved by the present invention is to provide a pretreatment composition, a printing component with a pretreatment composition and an ink composition (and a printing component with color ink), and an inkjet printing and dyeing method. Based on the pretreatment combination The object is less likely to produce the above-mentioned marks, print-through and fluffing phenomena. When using color inks containing white, images with high whiteness and high hiding properties can be obtained.

Means used to solve problems

The present inventors conducted in-depth research and found that the above technical problems can be solved by a pretreatment composition containing a cationic polymer with specific structural units and a cross-linking agent. In addition, by using a pre-treatment composition containing a cationic polymer and a cross-linking agent, An inkjet printing method using a predetermined process of treating a composition and an aqueous ink composition can solve the above technical problems, and the present invention has been completed.

That is, the present invention relates to the following technical solutions 1) to 39).

1) item

A pretreatment composition used to form a wet precoat layer that contains an aqueous ink composition for forming images on fabrics by inkjet; wherein,

The pretreatment composition meets all of the following requirements [1] to [4]:

[1] The aqueous ink composition contains water, pigment, resin emulsion, water-soluble organic solvent, and surfactant;

[2] Used to form a moist pre-coating layer with a coating amount of the pre-treatment composition per unit area greater than 0.035 g/cm ² and less than 0.070 g/cm ² ;

[3] The pretreatment composition contains water, a cationic polymer greater than 1.4% by mass and less than 10.5% by mass relative to the total mass of the pretreatment composition, and 0.1% by mass relative to the total mass of the pretreatment composition. Mass% or more and less than 2.7 mass% of cross-linking agent;

[4] The cationic polymer contains at least one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and epihalohydrin structural units.

2) item

The pretreatment composition according to item 1) above, wherein the cross-linking agent is selected from the group consisting of a compound containing a blocked isocyanate group, a compound containing a carbodiimide group, and a compound containing an oxazoline group. More than one cationic cross-linking agent in the group.

3) item

The pretreatment composition according to item 2) above, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher.

4) item

The pretreatment composition according to any one of items 1) to 3) above, wherein the surface tension at 25°C is 35 mN/m to 60 mN/m.

5) item

A printing component comprising an aqueous ink composition and the pretreatment composition described in any one of items 1) to 4), the aqueous ink composition including water, pigment, resin emulsion, water-soluble Organic solvents, surfactants.

6) item

An inkjet printing and dyeing method, which includes:

The pretreatment process of applying the pretreatment composition described in any one of the above items 1) to 4) on the fabric to form a wet precoat layer; and

A recording process of applying an aqueous ink composition containing water, pigment, resin emulsion, water-soluble organic solvent, and surfactant to at least a part of the area where the wet precoat layer is formed by an inkjet method, and forming an image area. .

7) Item

The inkjet printing and dyeing method according to the above item 6), wherein after the pretreatment process, the remaining amount of the pretreatment composition applied on the fabric is relative to the amount of the pretreatment composition applied in the pretreatment process. The recording step is performed in a state where the total amount is 20% by mass or more.

8) item

A printed matter in which the aqueous ink composition is printed on a fabric coated with the pretreatment composition according to any one of items 1) to 4) above.

9) item

A printing component, which has a pretreatment composition and an aqueous white ink composition. The pretreatment composition includes water, a cationic polymer, and a cross-linking agent. The aqueous white ink composition includes water, a white ink composition, and a water-based white ink composition. Pigments, polyurethane resins, water-soluble organic solvents; among them,

The content of the cationic polymer in the pretreatment composition is greater than 1.4 mass% and less than 10.5 mass% relative to the total mass of the pretreatment composition, and the content of the cross-linking agent relative to the total mass of the pretreatment composition is 0.1 mass% or more and less than 2.7 mass%.

10) items

The printing component according to item 9) above, wherein the cationic polymer is selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and epihalohydrin structural units. A polymer of at least one structural unit.

11) items

The printing component according to item 9) or 10) above, wherein the cross-linking agent is selected from the group consisting of compounds containing blocked isocyanate groups, compounds containing carbodiimide groups, and compounds containing oxazoline groups. More than one cationic cross-linking agent in the group.

12) items

The printing component according to item 11) above, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher.

13) items

The printing component according to any one of the above items 9) to 12), wherein the surface tension of the pretreatment composition at 25°C is 35mN/m˜60mN/m.

14) items

The printing component according to any one of items 9) to 13) above, wherein the polyurethane resin contains at least any one selected from the group consisting of polyether polyurethane resin and polycarbonate polyurethane resin.

15) items

The printing component according to any one of the above items 9) to 14), wherein the glass transition temperature of the polyurethane resin is 0° C. or lower.

16) items

The printing component according to any one of the above items 9) to 15), wherein the aqueous white ink composition further contains a base.

17) items

The printing component according to any one of the above items 9) to 16) further includes an aqueous ink composition containing water, a pigment, and a polymer dispersant.

18) items

The printing component according to the above item 17), wherein the polymer dispersant contains at least one selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1). Two polymers that make up the monomers;

Monomer A: a monomer in which R in the above formula (1) is a hydrogen atom;

Monomer B: a monomer in which R in the above formula (1) is a C1-C4 alkyl group;

Monomer C: a monomer in which R in the above formula (1) is an aryl group or an aryl C1-C4 alkyl group.

19) items

The printing component according to item 17) or 18) above, wherein the aqueous ink composition further contains at least any one selected from the group consisting of polyurethane resin, styrene-butadiene resin and acrylic resin. .

20) items

An inkjet printing and dyeing method, which includes:

The pretreatment process of applying the pretreatment composition contained in the printing component according to any one of the above items 9) to 19) on the fabric to form a wet precoat layer;

Without drying the fabric after the pretreatment process, the printing component described in any one of the above items 9) to 19) is sprayed by inkjet to a part or all of the wet precoat area. The process of forming an image by containing an aqueous white ink composition.

21) items

An inkjet printing and dyeing method, which includes:

The pretreatment process of applying the pretreatment composition contained in the printing component according to any one of the above items 9) to 19) on the fabric to form a wet precoat layer;

Without drying the fabric after the pretreatment process, the printing component described in any one of the above items 9) to 19) is ejected by inkjet to a part or all of the wet precoat layer. A process containing an aqueous white ink composition to form an image:

The aqueous material contained in the printing unit according to any one of the above items 17) to 19) is ejected by an inkjet method to a part or all of the area where the image is formed by ejecting the aqueous white ink composition. The process of forming an image using an ink composition.

22) items

The inkjet printing and dyeing method as described in item 20) or 21) above, wherein the fabric is polyester or a blend containing polyester.

23) items

The inkjet printing method according to the above item 22) includes a step of drying the fabric on which the image is formed at 130° C. or lower after the step of applying the aqueous ink composition.

24) items

The inkjet printing and dyeing method as described in the above item 20) or 21), wherein the fabric is cotton or a blend containing cotton.

25) items

The inkjet printing method according to the above item 24), further comprising a pressurizing step of applying pressure to the area where the wet precoat layer is formed after the pretreatment step.

26) items

An inkjet printing and dyeing method, which is an inkjet printing and dyeing method that uses a pretreatment composition containing water, a cationic polymer, a cross-linking agent, and at least one aqueous ink composition to form an image on cloth; wherein,

The method includes: a pretreatment process of coating the pretreatment composition on the fabric to form a wet precoat layer; and

without drying the fabric after the pretreatment step, applying the at least one aqueous ink composition to the wet precoat area, and

The coating amount per unit area of the pretreatment composition in the fabric is greater than 0.035g/cm ² and less than 0.070g/cm ² , and the content of the cationic polymer in the pretreatment composition is relative to the pretreatment amount. The total mass of the treatment composition is greater than 1.4 mass% and less than 10.5 mass%, the content of the cross-linking agent is 0.1 mass% or more and less than 2.7 mass% relative to the total mass of the pretreatment composition, and the aqueous ink composition contains Water, pigments, resin emulsions, water-soluble organic solvents and surfactants.

27) items

The inkjet printing method according to the above item 26), wherein the resin emulsion contains at least one selected from the group consisting of polyurethane resin, styrene-butadiene resin and acrylic resin.

28) items

The inkjet printing method according to the above item 26) or 27), wherein the aqueous ink composition further contains a polymer dispersant.

29) items

The inkjet printing method according to the above item 28), wherein the polymer dispersant is selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1) A polymer of at least two constituent monomers;

Monomer A: a monomer in which R in the above formula (1) is a hydrogen atom;

Monomer B: a monomer in which R in the above formula (1) is a C1-C4 alkyl group;

Monomer C: a monomer in which R in the above formula (1) is an aryl group or an aryl C1-C4 alkyl group.

30) items

The inkjet printing method according to any one of the above items 26) to 29), wherein the pigment is a white pigment.

31) items

The inkjet printing method according to any one of the above items 27) to 30), wherein the polyurethane resin includes at least any one selected from the group consisting of polyether polyurethane resin and polycarbonate polyurethane resin. kind.

32) items

The inkjet printing method according to any one of the above items 26) to 31), wherein the cationic polymer is selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and cyclic A polymer of at least any structural unit in the group consisting of oxyhalohydrin structural units.

33) items

The inkjet printing method according to any one of the above items 26) to 32), wherein the cross-linking agent includes a compound selected from the group consisting of a blocked isocyanate group-containing compound, a carbodiimide group-containing compound, and an oxonium-containing compound. One or more cationic cross-linking agents in the group consisting of oxazoline-based compounds.

34) items

The inkjet printing method as described in 33) above, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or above.

35) items

The inkjet printing method according to any one of the above items 26) to 34), wherein the surface tension of the pretreatment composition at 25°C is 35mN/m˜60mN/m.

36) items

The inkjet printing method according to any one of the above items 26) to 35), wherein the fabric is polyester or a polyester-containing blend.

37) items

The inkjet printing method as described in 36) above, including the step of drying the fabric on which the image is formed at 130° C. or lower after the step of applying the aqueous ink composition.

38) items

The inkjet printing and dyeing method according to any one of the above items 26) to 35), wherein the fabric is cotton or a blend containing cotton.

39) items

The inkjet printing method according to any one of items 26) to 38) above, further comprising a pressurizing process of applying pressure to the area where the wet precoat layer is formed after the pretreatment process.

Invention effect

Based on the present invention, it is possible to provide a pretreatment composition, a printing component having a pretreatment composition and an ink composition (and thus a printing component having color ink), and an inkjet printing and dyeing method. Based on the pretreatment composition, it is not easy to produce the above-mentioned When using color inks containing white to prevent traces, printouts and fluffing, images with high color rendering (high color development) can be obtained.

In addition, the present invention can provide an inkjet printing method that is less likely to produce the above-mentioned marks, show-through, and fluffing, and can obtain images with high color rendering properties when using color inks containing white.

Detailed ways

Hereinafter, the best embodiments for implementing the present invention will be described in detail, but the present invention is not limited to these. In addition, unless otherwise specified, the numerical values of "%" and "part" in this specification including examples and the like are described on a mass basis.

The pretreatment composition of this embodiment contains water, a cationic polymer, and a cross-linking agent.

In addition, the printing component of this embodiment has the above-mentioned pretreatment composition and an aqueous ink composition, and the aqueous ink composition contains water and a pigment.

Moreover, the pretreatment composition of a preferred embodiment of the present invention is used to form a wet precoat layer that contains an aqueous ink composition for forming an image on a fabric by an inkjet method; wherein,

The pretreatment composition meets all of the following requirements [1] to [4]:

[1] The aqueous ink composition contains water, pigment, resin emulsion, water-soluble organic solvent, and surfactant;

[2] Used to form a moist pre-coating layer with a coating amount of the pre-treatment composition per unit area greater than 0.035 g/cm ² and less than 0.070 g/cm ² ;

[3] The pretreatment composition contains water, a cationic polymer greater than 1.4% by mass and less than 10.5% by mass relative to the total mass of the pretreatment composition, and 0.1% by mass relative to the total mass of the pretreatment composition. Mass% or more and less than 2.7 mass% of cross-linking agent;

[4] The cationic polymer contains at least one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units, and epihalohydrin structural units.

In addition, a printing component according to a preferred embodiment of the present invention has a pretreatment composition and an aqueous white ink composition. The pretreatment composition includes water, a cationic polymer, and a cross-linking agent. The aqueous white ink composition The ink composition contains water, white pigment, polyurethane resin, and water-soluble organic solvent.

Conventionally, in the method of using a pretreatment liquid to agglomerate the resin in the ink composition, the color development can be improved because the aggregation of the resin in the ink composition and the penetration of the pigment into the fabric fibers can be suppressed. However, since the resin Early aggregation occurs before contact with the recording medium, so the adhesiveness (adhesion) decreases. On the other hand, the printing module of this embodiment includes a pretreatment composition containing a cationic polymer and a cross-linking agent, so that the adhesion can be improved while maintaining high color rendering properties.

In addition, in order to speed up printing and dyeing, if the ink composition is adhered to the fabric without drying after applying the pretreatment liquid, the above-mentioned decrease in adhesion will become more significant. However, in this embodiment The printing unit can also improve the adhesion even when achieving such high speed.

Furthermore, in order to not only retain the texture of the fabric but also achieve fixation (fixation) of the ink composition during printing and dyeing, even when the surface of the fabric to which the ink composition is attached is heated without applying pressure, it is different from applying pressure. The above-mentioned decrease in adhesion will also become more significant compared with the case of the printing module of this embodiment. However, the printing module of this embodiment can also improve the adhesion even when this printing and dyeing method is used.

<Pretreatment composition>

The above-mentioned pretreatment composition contains water, a cationic polymer greater than 1.4 mass% and less than 10.5 mass% relative to the total mass of the pretreatment composition, and 0.1 mass% or more relative to the total mass of the pretreatment composition. Less than 2.7% by mass of cross-linking agent;

[water]

The above pretreatment composition contains water. The water is not particularly limited, and pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water can be used. The water content is not particularly limited and can be appropriately determined as needed. In order to adjust the solid component weight content (solid weight content) of the pretreatment composition to an appropriate range, it is preferably relative to the total mass of the pretreatment composition (100 mass). %) contains 70 to 99 mass%, more preferably 80 to 98 mass%.

[Cationic polymer]

The above-mentioned pretreatment composition is characterized by containing more than 1.4 mass% and less than 10.0 mass% of cationic polymer relative to the total mass of the pretreatment composition. The cationic polymer includes at least any one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and epihalohydrin structural units, and more preferably includes an allylamine structure. At least any one of the group consisting of units and epihalohydrin structural units. The above-mentioned cationic polymers are all strong electrolytes, have good dissolution stability in the pretreatment composition, and have excellent ability to reduce the dispersion of pigments in the ink.

As the above-mentioned cationic polymer containing an allylamine structural unit, known cationic polymers can be appropriately selected and used. Examples thereof include polyallylamine hydrochloride, polyallylamine amide sulfate, and 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 amide sulfate, polymethyldiallylamine acetate Salt, polydiallyldimethylammonium chloride, diallylamine acetate · sulfur dioxide copolymer, diallyl methyl ammonium ethyl sulfate · sulfur dioxide copolymer, methyldiallylamine salt acid salt·sulfur dioxide copolymer, diallyldimethylammonium chloride·sulfur dioxide copolymer, diallyldimethylammonium chloride·acrylamide copolymer, etc. As the cationic polymer containing an allylamine structural unit, commercially available products can be used. Specific examples thereof include PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA- HCL-10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA- D11-HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS- H-5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (the above are trade names, manufactured by NITTOBOMEDICAL CO.,LTD.) ), Hymo Neo-600, Himoloc Q-101, Q-311, Q-501, Himax SC-505, SC-505 (the above are trade names, manufactured by HYMO CORPORATION), etc.

As the above-mentioned cationic polymer containing a diallylamine structural unit, known cationic polymers can be appropriately selected and used. Specific examples thereof include: PAS-21CL, PAS-21, PAS-M-1L, and PAS-M. -1. PAS-M-1A, PAS-92, PAS-92A (manufactured by Nittobo Pharmaceutical Co., Ltd.); UNISENCE KCA 100L, KCA 101L (manufactured by SENKA Co., Ltd.).

As the cationic polymer containing the above-mentioned diallylammonium structural unit, a known cationic polymer can be appropriately selected and used. Specific examples thereof include diallyldimethylammonium or diallylmethylethyl. Ammonium hydrochloride or ethyl sulfate salt, etc. The above-mentioned cationic polymer containing a diallylammonium structural unit is preferred because it exhibits particularly excellent cohesion properties and can obtain printed matter with less mixed color bleeding and color unevenness (color unevenness) and excellent color development on the substrate. As the above-mentioned cationic polymer containing a diallylammonium structural unit, commercially available products can be used. Specific examples thereof include: PAS-H-1L, PAS-H-5L, PAS-H-10L, PAS -24. PAS-J-81L, PAS-J-81, PAS-J-41 (manufactured by Nittobo Pharmaceutical Co., Ltd.); UNISENCE FPA100L, FPA101L, FPA102L, FPA1000L, FPA1001L, FPA1002L, FCA1000L, FCA1001L, FCA5000L (SENKA company system). In addition, an example of a commercial product of a cationic polymer compound containing both a diallylamine structural unit and a diallylammonium structural unit is PAS-880 (manufactured by Nittobo Pharmaceutical Co., Ltd.).

As the above-mentioned cationic polymer containing an epihalohydrin structural unit, a known cationic polymer can be appropriately selected and used. Specific examples thereof include epihalohydrin-modified polyamine compounds, epihalohydrin-modified polyamine compounds, and epihalohydrin-modified polyamine compounds. Amide compounds, epihalohydrin-modified polyamide polyamine compounds, epihalohydrin-amine copolymers, etc. In addition, from the viewpoint of availability, etc., it is preferable to select epichlorohydrin or methylepichlorohydrin as the epihalohydrin. Printed materials using the cationic polymer containing the epihalohydrin structural unit are excellent in water resistance. From this point of view, it is preferable to select a cationic polymer containing the epihalohydrin structural unit. As the cationic polymer containing an epihalohydrin structural unit, commercially available products can be used. Specific examples thereof include: FL-14 (manufactured by SNF Corporation), ARAFIX100, 251S, 255, and 255LOX (Arakawa Chemical Industry Co., Ltd.) ), DK-6810, 6804, 6850, 6854, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Starlight PMC Co., Ltd.), UNISENCE KHE100L, PAPYOGEN P-105 (manufactured by SENKA Co., Ltd.), Sumirez650 (30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Industry Co., Ltd.), Catiomaster PD-7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Gosei Co., Ltd.), JETFIX36N, 38A, 5052 (manufactured by Satoda Chemical Co., Ltd.).

As the above-mentioned cationic polymer, a cationic polymer synthesized by a known synthesis method may be used, or a commercially available product may be used.

The content of the above-mentioned cationic polymer is greater than 1.4 mass% and less than 10.5 mass% relative to the total mass of the pretreatment composition, preferably 1.7 to 8.0 mass%, more preferably 2.0 to 7.0 mass%, particularly preferably 2.5 to 6.0 mass% . By adding more than 1.4% by mass, effective aggregation ability can be obtained, and there is a tendency that printout and whiteness become good. In addition, when the addition amount is less than 10.5% by mass, storage stability and trace reduction tend to be excellent.

The viscosity of the 10% by mass aqueous solution of the above-mentioned cationic polymer at 25° C. is preferably 1.0 to 5.0 mPa·s, more preferably 1.0 to 2.5 mPa·s, still more preferably 1.0 to 2.0 mPa·s, and extremely preferably 1.0 to 1.5 mPa·s. By selecting a cationic polymer having a viscosity of 10% by mass aqueous solution of 1.0 to 5.0 mPa·s, the fluidity of the pretreatment composition and the color development during printing tend to be improved.

Taking into consideration the miscibility with other components contained in the pretreatment composition, the water resistance, color fastness to washing, adhesion, etc. of the pretreated fabric, the weight average molecular weight of the above-mentioned cationic polymer is usually 300 to 40,000. , preferably 500 to 18,000, more preferably 750 to 15,000, even more preferably 1,000 to 10,000. If the weight average molecular weight is 300 or more, effective aggregation ability can be obtained, and there is a tendency that the offset and whiteness will be improved. When the weight average molecular weight is 40,000 or less, it can be used as an aqueous solution and tends to have excellent storage stability. In addition, by setting the weight average molecular weight to 40,000 or less, the occurrence of unevenness in the white base and the decrease in whiteness tend to be suppressed, and further, the decrease in offset tends to decrease.

The weight average molecular weight of the above-mentioned cationic polymer can be measured by gel permeation chromatography (GPC) in standard polystyrene conversion.

[Cross-linking agent]

The above-mentioned pretreatment composition is characterized by containing 0.1 mass % or more and less than 2.7 mass % of a cross-linking agent with respect to the total mass of the above-mentioned pretreatment composition. The cross-linking agent preferably contains one or more cationic cross-linking agents selected from the group consisting of, for example, a blocked isocyanate group-containing compound, a carbodiimide group-containing compound, and an oxazoline group-containing compound. More preferably, it contains at least a blocked isocyanate group-containing compound and a carbodiimide group-containing compound.

In addition, in the present invention, the “blocked isocyanate group-containing compound” means a compound obtained by blocking the isocyanate group in a polyisocyanate compound with a blocking agent.

The above-mentioned blocked isocyanate group-containing compound means a compound obtained by blocking the isocyanate group in a polyisocyanate compound with a blocking agent. By blocking the highly reactive isocyanate group and stabilizing the isocyanate group, the storage stability of the aqueous composition can be improved and a strong ink coating can be formed after the cross-linking reaction. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound include aliphatic isocyanates, alicyclic isocyanates, aromatic aliphatic isocyanates, aromatic isocyanates, and modifications thereof. sexual body. Examples of modified forms of polyisocyanate compounds include polymers such as isocyanurate compounds, biuret compounds, and adducts with polyols such as trimethylolpropane and pentaerythritol.

As the aliphatic isocyanate, for example, a diisocyanate having a linear or branched aliphatic hydrocarbon group between two isocyanate groups is preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 3 or more, and is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less. Specific examples include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate. Isocyanate, dodecyl methylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, etc. Examples of the alicyclic isocyanate include hydrogenated xylylene diisocyanate (H6XDI), 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), and isophor Ketone diisocyanate (IPDI), 2,5- or 2,6-norbornane diisocyanate, etc. Examples of the aromatic aliphatic isocyanate include m-xylylene diisocyanate, tere-xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and the like. Examples of the aromatic isocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'- or 2,4 '-Diphenylmethane diisocyanate (MDI), m-isocyanatobenzenesulfonyl isocyanate or p-isocyanatobenzenesulfonyl isocyanate, biphenyl 4,4'-diisocyanate, 3,3'-dimethyl Biphenyl-4,4'-diisocyanate, 1,5-naphthalene diisocyanate, 2,6-dimethylbenzene-1,4-diisocyanate, etc.

Examples of the blocking agent include amines such as 3,5-dimethylpyrazole (DMP), 1,2,4-triazole, and diisopropylamine, phenols such as phenol and cresol, and methyl ethyl ketoxime. Compounds with active hydrogen such as oximes, lactams such as ε-caprolactam, and active methylene compounds such as diethyl malonate and ethyl acetoacetate. Among these, 3,5-dimethylpyrazole (DMP) and methyl ethyl ketoxime are preferred, and 3,5-dimethylpyrazole (DMP) is more preferred.

From the viewpoint of improving storage stability, scratch resistance, and adhesion, the dissociation temperature of the blocked isocyanate group-containing compound is preferably 120°C or higher, and more preferably 125°C or higher. When the temperature is 120° C. or higher, the storage stability of the pretreatment composition tends to become good. In addition, from the viewpoint of suppressing damage such as deformation of the recording medium, the dissociation temperature is preferably 200°C or lower, and more preferably 180°C or lower. In particular, when the fabric is made of polyester or a blend containing polyester, in order to prevent dye migration (hereinafter also simply referred to as color migration), it is necessary to perform a drying process after printing at a drying temperature of 130°C or lower, so this dissociation The temperature is preferably 130°C or lower.

Examples of commercially available products of the blocked isocyanate group-containing compound include: Trixeneblocked isocyanates Aqua BI120, Aqua BI200, Aqua Aqua BI220, Aqua BI522, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (The above are trade names, manufactured by Baxenden Co., Ltd.), DM-6400, MEIKANATE DM-3031CONC, MEIKANATE DM-35HC, MEIKANATE TP-10, MEIKANATE ST, MEIKANATE PRO, NBP-873D (the above are trade names, Meisei Chemical Industry Co., Ltd. (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), ELASTRON BN-69, BN-77, BN-27, BN-11 (the above are trade names, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), TAKENATE WB-700, WB-770, WB-920 (the above are trade names) Name, Mitsui Chemicals Polyurethane Co., Ltd.); DURANATE MF-K60B, SBN-70D, MF-B60B, MF-B90B, 17B-60P, TPA-B80B, TPA-B80E, E402-B80B (the above are trade names, Asahi Kasei Co., Ltd. Co., Ltd.), Fixer N (the above are produced by Matsui Pigment Chemical Laboratory Co., Ltd.), etc.

From the viewpoint of storage stability, scratch resistance, solvent resistance, and adhesion of the pretreatment composition, the carbodiimide group-containing compound preferably contains two or more carbodiimide groups in one molecule. Polycarbodiimide compounds. As the carbodiimide group-containing compound, for example, it is preferable to seal the terminal isocyanate group of the condensation reaction product obtained by a decarboxylation condensation reaction in the presence of a carbodiimide catalyst of diisocyanates with a hydrophilic group. compound of.

Examples of diisocyanates used in the decarboxylation condensation reaction include hexamethylene diisocyanate (HDI), decamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. Aliphatic diisocyanates; 4,4-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,5- or 2,6-norbornane diisocyanate, hydrogenated xylylene diisocyanate Alicyclic diisocyanates such as isocyanate (H6XDI), hydrogenated toluene diisocyanate, 2,4-bis-(8-octyl isocyanate)-1,3-dioctylcyclobutane (OCDI); isocyanate Isocyanates or aromatic aliphatic diisocyanates such as p-xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI); 2,4,6-triisopropylphenyl diisocyanate (TIDI), Aromatic diisocyanates such as 4,4- or 2',4-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), etc.

The compound obtained by sealing the terminal isocyanate group of the condensation reaction product with a hydrophilic group is a compound having a functional group capable of reacting with the isocyanate group. Examples thereof include polyethylene glycol monomethyl ether, Polypropylene glycol monomethyl ether, etc. Among these, polyethylene glycol monomethyl ether is preferred from the viewpoint of the compatibility of the carbodiimide group-containing compound in the pretreatment composition and the storage stability of the pretreatment composition. By adjusting the number of added moles of ethylene oxide in this polyethylene glycol monomethyl ether, the form of the obtained carbodiimide group-containing polymer can be blended with an aqueous composition as an emulsion or aqueous solution.

The above-mentioned carbodiimide group-containing compound is preferably blended into the pretreatment composition as an aqueous solution or emulsion from the viewpoint of storage stability, scratch resistance, solvent resistance, and substrate adhesion of the pretreatment composition. The case where it is formed; from the viewpoint of the storage stability of the pretreatment composition, it is preferable to mix it into the pretreatment composition as an aqueous solution.

Examples of commercially available products of the carbodiimide group-containing compound include Carbodilite E-02, Carbodilite E-03A, Carbodilite E-05, Carbodilite V-02, Carbodilite V-02-L2, and Carbodilite V-04. (The above are trade names, manufactured by Nisshinbo Chemical Inc.) and the like. Among these, from the viewpoint of storage stability of the pretreatment composition, Carbodilite E-02 and Carbodilite V-04 are preferred.

The above-mentioned oxazoline group-containing compound is preferably blended into the pretreatment composition as an aqueous solution or emulsion from the viewpoint of storage stability, scratch resistance, solvent resistance, and adhesion of the pretreatment composition. In this case, a polyoxazoline compound having two or more oxazoline groups in one molecule is preferred.

Examples of commercially available products of the oxazoline group-containing compound include "EPOCROS WS series" such as "EPOCROS WS-300", "EPOCROS WS-500", and "EPOCROS WS-700" (the above are Nippon Shokubai Co., Ltd. (Nippon Shokubai Co., Ltd., water-soluble type); EPOCROS K-2010E, EPOCROS K-2020E and other "EPOCROS K series" (trade name, Nippon Shokubai Co., Ltd., emulsion type), etc. Among them, from the viewpoint of storage stability of the pretreatment composition, EPOCROS WS-300, EPOCROS WS-500, and EPOCROS WS-700 are preferred.

The content of the cross-linking agent is 0.1 mass % or more and less than 2.7 mass % relative to the total mass of the pretreatment composition, preferably 0.2 to 2.0 mass %, more preferably 0.4 to 1.5 mass %, even more preferably 0.6 to 1.0 mass %. . If it is 0.1 mass % or more, effective adhesion will tend to be obtained. In addition, when the content is 2.7% by mass or less, storage stability tends to be excellent and trace reduction tends to be excellent.

[Other ingredients]

In addition to the above-mentioned components, the above-mentioned pretreatment composition may also contain resin emulsion, water-soluble organic solvent, surface tension regulator, antifungal agent, preservative, pH regulator, chelating agent, rust inhibitor, and water-soluble ultraviolet absorber. , antioxidants, pastes and other regulators.

--Resin emulsion--

Examples of the resin emulsion include (meth)acrylic resin, (meth)acrylic resin copolymer, styrene-maleic anhydride copolymer resin, epoxy resin, polyurethane resin, polyether resin, and polyamide resin. , unsaturated polyester resin, phenolic resin, silicone resin, fluorine resin, polyvinyl resin (vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), vinyl acetate-(meth)acrylic acid copolymer resin, vinyl acetate - Emulsions made of ethylene copolymer resins, alkyd resins, polyester resins, amino resins (melamine resin [Melamine resin], urea resin, melamine formaldehyde resin [Melamine formaldehyde resin], etc.), etc. Resin emulsions may contain two or more resins. In addition, two or more resins can also form a core/shell structure. One type of resin emulsion may be used alone or two or more types of resin emulsions may be used in combination. Among the resin emulsions, it is preferable to use a resin that forms a clear coating film, and from the viewpoint of the storage stability, scratch resistance, and adhesion of the pretreatment composition, an acrylic resin emulsion and a polyurethane resin emulsion are preferable.

The emulsions of the above-mentioned (meth)acrylic resins and (meth)acrylic resin copolymers are available as commercial products, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. For example, Nippon Synthetic Chemical Industry Co., Ltd.'s Mowinyl 966A, 6963, 6960 (all trade names, acrylic resin emulsion), 6969D, RA-033A4 (all trade names, styrene/acrylic resin emulsion), BASF's JONCRYL 7100 , PDX-7370, PDX-7341 (all are trade names, styrene/acrylic resin emulsion), VONCOAT EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion) of DIC Co., Ltd., etc.

The above-mentioned polyurethane resin emulsion is available as a commercial product, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. Examples of commercially available polyurethane resin emulsions include: PERMARIN UA-150, 200, 310, 368, 3945, UCOAT UX-320, 340 (the above are manufactured by Sanyo Chemical Co., Ltd.), Hidran WLS-201, 210 , HW-312B latex (the above are manufactured by DIC Co., Ltd.), SUPERFLEX 150, 170, 470 (the above are manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), etc. Among them, examples of polycarbonate polyurethane resins include PERMARIN UA-310, 3945, UCOAT UX-320, HYDRAN WLS-210, 213, 250, and the like. Examples of polyether polyurethane resins include PERMARIN UA-150 and 200, UCOAT UX-340, HYDRAN WLS-201, 202, and 230.

When the polyurethane resin in the above-mentioned polyurethane resin emulsion has an acidic group such as a carboxyl group, a sulfo group, or a hydroxyl group, the acidic group may also be alkaline-salted. For example, a polyurethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and a basic compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group can be alkali-salted. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and hydrogen of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. Oxides etc. A basic compound may be used individually by 1 type, or may use 2 or more types together.

--Water-soluble organic solvent--

Examples of the water-soluble organic solvent include glycol solvents, polyols, polyol alkyl ethers, and the like. Examples of glycol solvents include glycerol, polyglycerol (#310, #750, #800), diglycerin, triglycerin, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerin, nonaglycerol, and decaglycerol. , eleven glycerol, twelve glycerol, thirteen glycerol, fourteen glycerol, etc. Examples of polyols include C2-C6 polyols having 2 to 3 alcoholic hydroxyl groups, di- or tri-C2-C3 alkylene glycols, and polyC2-C3 having 4 or more repeating units and a molecular weight of about 20,000 or less. Alkylene glycol (preferably liquid polyalkylene glycol), etc. Specific examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1 ,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol Alcohol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol, etc. Examples of polyol alkyl ethers include alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether, and the like. Specific examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and triethylene glycol. Monoisobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, etc. In addition, triethylene glycol monobutyl ether and the like can be cited.

For convenience, the water-soluble organic solvent may also contain a compound that dissolves in water and functions as a wetting agent. Examples of such compounds include urea, ethylene urea, sugars, and the like. One type of water-soluble organic solvent may be used alone or two or more types may be used in combination.

As the water-soluble organic solvent, it is preferably selected from the group consisting of glycerin, diethylene glycol, triethylene glycol, propylene glycol, 1,2-hexanediol, 1,6-hexanediol, 1,5-pentanediol, and diethylene glycol mono. At least one of butyl ethers.

The content of the water-soluble organic solvent is usually 0.5 to 20 mass%, preferably 1 to 15 mass%, and more preferably 2 to 10 mass% relative to the total mass of the pretreatment composition. By making the content within the above range, the whiteness and offset of the base tend to become good, and the pretreatment composition has excellent storage stability.

--Surface tension regulator--

The type of the surface tension adjuster is not particularly limited, but for example, surfactants selected from acetylene glycol and polyalkylene glycol are preferred. By containing a surfactant, it is possible to suppress an increase in the viscosity of the pretreatment composition, aggregation of components, etc., thereby improving the storage stability.

Among them, a pretreatment composition containing at least polyalkylene glycol as a surfactant tends to further improve the whiteness and print-through of the substrate.

As the acetylenic diol surfactant, for example, one selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl- 5-decyn-4,7-diol, 2,4-dimethyl-5-decyn-4-ol, and 2,4-dimethyl-5-decyn-4-ol or their alkylenes The surfactant in the oxygen adduct (alkylene oxide adduct, also called alkylene oxide adduct) is more preferably a surfactant selected from the above-mentioned alkylene oxide adduct. Examples of the alkyleneoxide (also called alkylene oxide) include C2-C4 linear, branched, and cyclic alkylene oxides. Among these, linear or branched alkylene oxides are preferred. Examples of surfactants selected from the alkylene oxide adducts include Surfynol series (420, 440, 465, 61, etc.) and Olfine series (E1004, E1010, EXP-4001) manufactured by Nissin Chemical Industry Co., Ltd. wait).

The polyalkylene glycol surfactant is preferably selected from the group consisting of polyoxyalkylene alkyl ethers (for example, polyoxyethylene alkyl ethers), fatty acid ethylene oxide adducts, and higher alkylamine epoxy Ethane adduct and surfactant in polyoxy C2-C4 alkylene glycols. Among these, polyoxy C2-C4 alkylene glycol is preferred.

Examples of the polyoxyalkylene alkyl ether include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene isodecyl ether, and polyoxyalkylene lauryl ether. Ether etc. Examples of commercially available products include NOIGEN XL-40, 50, 60, 70, 80, 100, 140, 160, NOIGEN TDS-30, 50, 70, 80, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. 90, 100, 120, etc.

Examples of fatty acid ethylene oxide adducts include stearic acid ethylene oxide adducts, polyethylene glycol laurate, and the like. Examples of commercially available products include EMANON 1112, 3199V, 3299V, 3299VR, and 3201M-V manufactured by Kao Corporation.

Examples of commercially available products of higher alkylamine ethylene oxide adducts include AMIET 102, 105, 105A, 302, and 320 manufactured by Kao Corporation.

Examples of commercially available polyoxy C2-C4 alkylene glycols include EMULGEN PP-290 (polyethylene glycol/polypropylene glycol 160/30 copolymer) manufactured by Kao Corporation, Sanyo NEWPOL manufactured by Chemical Industry Co., Ltd. PE-61, PE-62, PE-64, PE-68, PE-71, PE-74, PE-75, PE-78, PE-108 (polyoxyethylene polyoxypropylene seal terminal polymer), EPAN 410, 420, 450, 485, 680, 710, 720, 740, 750, 785, U-103, U-105, U-108 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. (weight average of polypropylene glycol Polyoxyethylene (polyoxypropylene glycol) with a molecular weight of about 950 to 4000 and a polyoxyethylene content of about 5 to 95%. As the polyoxy C2-C4 alkylene glycol, polyoxy C2-C3 alkylene glycol is preferred, and polyoxyethylene polyoxypropylene glycol is more preferred. In addition, among the total number of oxy C2-C4 alkylene groups in the polyoxy C2-C4 alkylene glycol, the number of oxy C2 alkylene groups is usually less than 50%, preferably 15 to 45%, and more preferably 20~40%. For example, when the sum of the number of bonds (number of bonds) of the oxygen C2 alkylene group, the oxygen C3 alkylene group and the oxygen C4 alkylene group is 10, it means that the number of bonds of the oxygen alkylene group is less than 5. In addition, the number of bonds of the oxy C2-C4 alkylene group is an average value. In addition, in polyoxyalkylene glycol, when the polyoxy C3-C4 alkylene group is the hydrophobic group and the polyoxy C2 alkylene group is the hydrophilic group, the weight average molecular weight of the hydrophobic group is usually 2250 to 4000. Preferably it is 2750-3600. Examples of those that satisfy both the oxygen C2 alkylene group content and the hydrophobic group weight average molecular weight include Epan U-103. By containing such a surfactant as a pretreatment composition containing a cationic polymer, storage stability can be improved.

The content of the surfactant is usually 0.05 to 5%, preferably 0.05 to 3%, more preferably 0.05 to 1%, and even more preferably 0.1 to 0.5% relative to the total mass of the pretreatment composition. By setting the content to such a content, the printed fiber tends to be excellent in color fastness to washing and rub resistance. In addition, the pretreatment composition also tends to have excellent storage stability.

--Anti-mildew agent--

Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, and 1,2-benzisothiazoline. -3-ketone and its salts, etc.

--preservative--

Examples of the above-mentioned antiseptic include organic sulfur, organic nitrogen and sulfur, organic halogen, halogenated allyl sulfone, iodinated propargyl (ester), N-halogenated alkyl sulfide, nitrile, and pyridine. Classes, 8-oxyquinolines, benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropanes, organotins, phenols, quaternary ammonium salts, triazines , thiazides, anilide, adamantane, dithiocarbamate, bromoindanone, benzyl bromide acetate, inorganic salts and other compounds. Specific examples of organohalogen compounds include sodium pentachlorophenolate and the like. Specific examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide (sometimes referred to as "sodium 2-pyridine-1-oxide salt"). Specific examples of isothiazoline compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl Base-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one Calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Specific examples of other preservatives (preservatives and antifungal agents) include sodium acetic anhydride, sodium sorbate, sodium benzoate, PROXEL ^RTM GXL (S) and PROXEL ^RTM XL-2 (S) manufactured by LONZA Corporation, etc. .

--pH adjuster--

As the pH adjuster, any substance can be used as long as it does not adversely affect the prepared pretreatment composition and can control the pH of the ink within the range of, for example, 3.0 to 9.0. Examples of the pH adjuster include alkali metal hydroxides, alkaline earth metal hydroxides, aliphatic amine compounds, alcohol amine compounds, and the like. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. Among these, hydroxides of alkaline earth metals are preferred, and lithium hydroxide and sodium hydroxide are more preferred. Examples of the aliphatic amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine and triethylamine, with ammonia or triethylamine being preferred. Examples of the alcoholamine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, and N-methyl Diethanolamine is preferably a tertiary amine, and more preferably triethanolamine.

Other specific examples include alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; and phosphates such as disodium phosphate. wait.

--Chelating reagent--

Specific examples of the chelating agent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentacetate, and uracil diacetic acid. Sodium etc.

--Rust inhibitor--

Specific examples of the rust inhibitor include bisulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrate, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrate, and the like.

--Water-soluble UV absorber--

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

--Antioxidants--

As the antioxidant, for example, various organic and metal complex antioxidants (also referred to as “anti-fading agents”) can be used. Specific examples of the organic antioxidants include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxy Anilines, heterocyclics, etc.

--paste--

Examples of the paste include starches such as corn and wheat, cellulose compounds such as carboxymethylcellulose and hydroxymethylcellulose, sodium alginate, gum arabic, carob gum, tragacanth gum, and guar gum. and polysaccharides such as tamarind seeds, proteins such as gelatin and casein, natural water-soluble polymers such as tannins and lignin, and synthetic water-soluble polymers containing polyvinyl alcohol, polyethylene oxide, acrylic acid, and maleic anhydride. Sexual polymer compounds, etc. The content of the paste is usually about 0 to 20% relative to the total mass of the pretreatment composition.

[Surface tension of pretreatment composition]

The surface tension of the above-mentioned pretreatment composition at 25°C is preferably 35 to 60 mN/m, more preferably 36 to 58 mN/m, and still more preferably 35 to 60 mN/m, from the viewpoint of being able to exhibit sufficient wettability to various fabrics. 37 to 56 mN/m, particularly preferably 38 to 54 mN/m.

From the viewpoint of preventing bleeding of the printed matter, the surface tension of the pretreatment composition at 25° C. is preferably set to be equal to or higher than the surface tension of the aqueous ink composition described below. By making the surface tension of the pretreatment composition larger than the surface tension of the aqueous ink composition, the amount of surfactant oriented on the surface of the precoat layer formed by applying the pretreatment composition to the fabric can be reduced, and the pretreatment composition can be pre-treated. The surface energy of the coating layer is not excessively reduced, so the wettability of the ink composition for subsequent printing becomes appropriate, and no bleeding (no bleeding), high dot (pixel) circularity, and high image quality can be obtained. Prints.

The surface tension of the pretreatment composition can be measured by the platinum plate method in a 25° C. environment using a surface tensiometer (CBVPZ manufactured by Kyowa Interface Science Co., Ltd.), for example.

[Viscosity of pretreatment composition]

The viscosity of the above-mentioned pretreatment composition at 25° C. is preferably 0.5 to 4.0 mPa·s, more preferably 0.7 to 3.5 mPa·s, and particularly preferably 0.8 to 3.0 mPa·s. As long as the pretreatment composition satisfies the above viscosity range, the pretreatment composition can be applied uniformly regardless of the method of applying the pretreatment composition or the type of fabric, and uneven dot shapes or uneven images can be suppressed. quality. Furthermore, excellent printed matter can be obtained from the viewpoint of wettability to fabric and suppression of unevenness during drying.

The viscosity of the pretreatment composition can be measured using, for example, an E-type viscometer (TVE25L type viscometer manufactured by Toki Sangyo Co., Ltd.).

[pH of pretreatment composition]

The pH of the above-mentioned pretreatment composition at 25°C is preferably 3.0 to 10.0, more preferably 3.5 to 8.0, and particularly preferably 4.0 to 6.0. If the pretreatment composition is in the above-mentioned pH range, embrittlement of the fabric can be prevented, and printed matter with less mixed color bleeding and color unevenness (color unevenness) and excellent color development can be obtained.

The pH of the above-mentioned pretreatment composition can be measured using a well-known method such as a desktop pH meter F-72 manufactured by Horiba Seisakusho Co., Ltd. and using a standard ToupH electrode or a sleeve ToupH electrode.

[Preparation method of pretreatment composition]

Examples of a method for preparing the pretreatment composition of the present embodiment include further adding water, a cationic polymer, a cross-linking agent, and, if necessary, a regulator such as those listed above, followed by stirring and mixing as needed. And the method of filtering. However, the preparation method of the pretreatment composition of the present invention is not limited to the above method.

<Aqueous ink composition>

The aqueous ink composition of this embodiment contains water and a pigment.

Furthermore, the aqueous ink composition according to a preferred embodiment of the present invention preferably contains water, a pigment, a resin emulsion, a water-soluble organic solvent, a surfactant, and further preferably contains a polymer dispersant. In addition, in this specification, the aqueous ink composition may be simply called an ink composition or ink.

In addition, the aqueous ink composition according to another preferred embodiment of the present invention is an aqueous white ink composition, which contains water, a white pigment, a polyurethane resin, a water-soluble organic solvent, and preferably further contains a base. In addition, in this specification, the aqueous white ink composition may be simply called a white ink composition or white ink. The aqueous white ink composition will be described in detail later.

In addition, the aqueous ink composition according to another preferred embodiment of the present invention contains water, a pigment, and a polymer dispersant, and preferably also contains a polyurethane resin, a styrene-butadiene resin, a (meth)acrylic resin, and (meth)acrylic resin. At least any one of the group consisting of meth)acrylic resin copolymers may also contain a water-soluble organic solvent and a surfactant; the aqueous ink composition is preferably used in combination with the above-mentioned aqueous white ink composition.

[water]

As the water contained in the aqueous ink composition, for example, the water exemplified for the pretreatment composition can be used. The content of water is not particularly limited and can be appropriately determined as needed; however, in order to adjust the viscosity of the aqueous ink composition to an appropriate range, the content relative to the total mass (100% by mass) of the aqueous ink composition may be It is 20 to 80% by mass. In addition, it is not limited, but for example, it is preferably 40 to 80 mass%, more preferably 45 to 75 mass%, and still more preferably 50 to 70 mass%.

[pigment]

There are no particular restrictions on the above-mentioned pigments, and known pigments can be used. As pigments, inorganic pigments, organic pigments, extender pigments, etc. are known.

Examples of the inorganic pigment include carbon black, metal oxides, hydroxides, sulfides, ferrocyanides, metal chlorides, and the like. Among these, carbon black is preferred as the black pigment.

There are many types of carbon black, such as thermal black and acetylene black obtained by thermal decomposition, oil furnace black, gas furnace black, lamp black, gas black and channel black obtained by incomplete combustion method. Carbon black; etc.

Among the above, preferred carbon blacks are acetylene black, oil furnace black, gas furnace black, lamp black, channel black, and the like.

Specific examples of carbon black include Raven 760ULTRA, Raven 780ULTRA, Raven790ULTRA, Raven 1060ULTRA, Raven 1080ULTRA, Raven 1170, Raven 1190ULTRA II, Raven1200, Raven 1250, Raven 1255, Raven 1500, Raven 2000, Raven 250 0ULTRA、 Raven 3500, Raven 5000ULTRA II, Raven 5250, Raven 5750, Raven 7000 (the above are made by Columbia Carbon Company), Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch1000, Monarch 1100, Monarch 1300, Monarch 1400, Regal 1330R, Regal1400R, Regal 1660R, Mogul L (the above are made by Cabot), Color Black FW1, Color Black FW2, Color Black FW2 V, Color BlackFW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, PrintexU, Printex V, Printex 140U, Printex 140V, Special Black 4, Special Black 4A, Special Black 5, Special Black6 (the above are made by Degussa), MA7, MA8, MA100, MA600, MCF-88, No.25, No .33, No.40, No.47, No.52, No.900, No.2300 (the above are made by Mitsubishi Chemical Corporation); etc.

In addition, as the white pigment, it is preferable to use metal oxides. Examples of metal oxides include zinc oxide, titanium oxide, zirconium oxide, and the like, with titanium oxide being preferred. Examples of types of titanium oxide include rutile type, anatase type, and the like. Titanium oxide may be used directly as a powder, or may be surface-treated with silica, alumina, zirconium oxide, zinc oxide, or an organic substance having a hydroxyl group. Among them, titanium oxide obtained by surface treatment is preferably selected.

Specific examples of titanium oxide include DUAWHITE TCR-52, TITONE R-32, TITONER-7E, TITONE R-21, TITONE R-62N, and TITONE R-42 (the above are manufactured by Sakai Chemical Industry Co., Ltd., TIPAQUE CR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (the above are made by Ishihara Sangyo Co., Ltd.), TITANIX JA-600A, TITANIX JR-605 (The above are made by TAYCA Co., Ltd.), ST-455, ST-455WB, ST-457SA, ST-457EC (the above are made by Titanium Kogyo, Ltd.), etc.

In addition, since the aqueous white ink composition described below contains a white pigment, the aqueous ink composition used in combination with the aqueous white ink composition preferably contains a pigment other than the white pigment.

Examples of the organic pigment include azo pigments having at least one azo group in the molecule, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, and perylene pigments. , pyrenone pigments, thioindigo pigments, anthraquinone pigments and quinophthalone pigments.

Specific examples of organic pigments include: C.I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97 , 98, 108, 114, 128, 129, 138, 139, 150, 151, 154, 155, 180, 185, 193, 199, 202 and other yellow pigments, C.I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, 254, 255, 257, 260, 264, 272 and other red ones Pigments, C.I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 25, 60, 66, 80 and other blue pigments, C.I. Pigment Violet 19, 23, 29, 37, 38, 50 and other purple pigments, C.I. Pigment Orange 13, 16, 36, 34, 43, 68, 69, 71, 73 and other orange to brown pigments, C.I. Pigment Green 7 , 36, 54 and other green pigments, C.I. pigment black 1 and other black pigments; etc.

Examples of the extender pigment include silica, calcium carbonate, talc, clay, barium sulfate, white carbon, and the like. These extender pigments can be used alone, but are often used in combination with inorganic or organic pigments.

As the above-mentioned pigment, a single pigment is usually used. However, two or more pigments may be used together as necessary. Examples of combinations include organic pigments and extender pigments, organic pigments and inorganic pigments, and the like. In addition to the organic pigment and the inorganic pigment, in order to improve the fluidity, an extender pigment may be used in combination. Furthermore, in order to adjust the hue of a dyed product, two or more pigments selected from inorganic pigments and organic pigments may be used together. The color tone adjustment mentioned here is performed for the purpose of obtaining dyed products with different shades and expanding the color gamut of dyeing. For this purpose, a plurality of organic pigments can be used together to adjust the color to a desired hue.

The pigment content is preferably 1.5 to 15.0 mass%, more preferably 2.0 to 14.0 mass%, and even more preferably 2.5 to 13.0 mass% relative to the total mass of the ink composition (100 mass%).

[Resin emulsion]

Examples of the resin emulsion contained in the aqueous ink composition include styrene-butadiene resin, (meth)acrylic resin, (meth)acrylic resin copolymer, and styrene-maleic anhydride copolymer. Resin, epoxy resin, polyurethane resin, polyether resin, polyamide resin, unsaturated polyester resin, phenolic resin, silicone resin, fluorine resin, polyvinyl resin (vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), Vinyl acetate-(meth)acrylic acid copolymer resin, vinyl acetate-ethylene copolymer resin, alkyd resin, polyester resin, amino resin (melamine resin [メラニン resin], urea resin, melamine formaldehyde resin [メラニンホルムアルデヒド resin ], etc.), etc. Resin emulsions may contain two or more resins. In addition, two or more resins can also form a core/shell structure. One type of resin emulsion may be used alone or two or more types of resin emulsions may be used in combination. Among the resin emulsions, from the viewpoint of ink performance, styrene-butadiene resin emulsions, (meth)acrylic resin emulsions, (meth)acrylic resin copolymer emulsions, and polyurethane resin emulsions are preferred.

For example, many styrene-butadiene resin emulsions are sold in the form of latex (emulsion) and can be easily purchased. Specific examples thereof include: Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, Nipol 2507H, and Nipol LX303A (the above are manufactured by Nippon ZEON Co., Ltd.), and the grades (grades) include 0695, 0696, 0561, and 0589. , 0602, 2108, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z latex (the above are made by JSR Co., Ltd.), etc. Most of them are liquids obtained by emulsifying resin to a solid content of 30 to 60%. As the styrene-butadiene resin, any of the above-mentioned latexes can be used, and among them, carboxyl-modified styrene-butadiene resin is preferably used. Examples of such resins include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, 0695, 0696, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, and 0850Z, and 0695, 0533, and 0568 are preferred. , 0597C, 0850Z, and more preferably JSR0568 (manufactured by JSR Corporation). As the styrene-butadiene resin, a single resin may be used or two or three resins may be used in combination.

The content of the styrene-butadiene resin emulsion is preferably 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the ink composition.

The above-mentioned (meth)acrylic resin emulsion and (meth)acrylic resin copolymer emulsion are available as commercial products, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. For example, Mowinyl 966A, 6963, 6960 (all trade names, acrylic resin emulsion), 6969D, RA-033A4 (all trade names, styrene/acrylic resin emulsion) of Nippon Synthetic Chemical Industry Co., Ltd., and BASF's JONCRYL 7100, PDX-7370, PDX-7341 (all are trade names, styrene/acrylic resin emulsion), DIC Co., Ltd.'s VONCOAT EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion), etc.

The content of the (meth)acrylic resin emulsion and the (meth)acrylic resin copolymer emulsion is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3, relative to the total mass of the ink composition. ~17% by mass.

The polyurethane resin emulsion is not particularly limited, and known polyurethane resin emulsions can be used.

Examples include emulsions of polyurethane resins such as polyether polyurethane resins, polycarbonate polyurethane resins, and polyester polyurethane resins, and emulsions of polyether polyurethane resins and polycarbonate polyurethane resins are preferred.

The above-mentioned polyurethane resin emulsion is available as a commercial product, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. Examples of commercially available polyurethane resin emulsions include: PERMARIN UA-150, 200, 310, 368, 3945, UCOAT UX-320, 340 (the above are manufactured by Sanyo Chemical Co., Ltd.), Hidran WLS-201, 202 , 210, 213, 221, 230, 250, HW-312B latex (the above are manufactured by DIC Co., Ltd.), SUPERFLEX 150, 170, 470 (the above are manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), etc. Among them, examples of polycarbonate polyurethane resins include PERMARIN UA-310, 3945, UCOAT UX-320, HYDRAN WLS-210, 213, 250, and the like. Examples of polyether polyurethane resins include PERMARIN UA-150 and 200, UCOAT UX-340, HYDRAN WLS-201, 202, and 230. As the polyurethane resin, a single polyurethane resin may be used, or two or three types may be used in combination.

When the polyurethane resin in the above-mentioned polyurethane resin emulsion has an acidic group such as a carboxyl group, a sulfo group, or a hydroxyl group, the acidic group may also be alkaline-salted. For example, a polyurethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and a basic compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group can be alkali-salted. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and hydrogen of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. Oxides etc. A basic compound may be used individually by 1 type, or may use 2 or more types together.

The glass transition temperature of the polyurethane resin is preferably -90°C to 0°C, more preferably -85°C to -20°C, still more preferably -85°C to -30°C. When the glass transition temperature exceeds 0° C., the printed matter becomes hard to the touch, which is not preferable. When the glass transition temperature is lower than -90°C, the adhesion (adhesion) of the coating film of the printed matter is enhanced and stickiness is easily generated, and the color fastness to washing is also poor. Therefore, the glass transition temperature is preferably -90°C or higher. The glass transition temperature can be measured, for example, by differential scanning calorimetry (DSC).

The above-mentioned polyurethane resin preferably has a freezing point of -8°C or lower. The so-called freezing point below -8°C means that it freezes or solidifies below -8°C, which means that so-called denaturation such as gelation does not occur and will return to the emulsion state when returning to normal temperature. If a polyurethane resin with a freezing point of -8°C or less is used, a white ink composition excellent in low-temperature storage stability can be obtained. The freezing point is more preferably -11°C or lower. In addition, the above freezing point can be measured, for example, by adding 30 cc of polyurethane resin emulsion to a 50 cc plastic bottle, leaving it to stand in a constant temperature bath at a predetermined temperature for 20 hours, and then confirming whether there is freezing.

The content of the polyurethane resin emulsion is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the ink composition.

[Water-soluble organic solvent]

In one embodiment, the aqueous ink composition contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include C1-C4 monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; ethylene glycol, 1,2-or 1,3-propanediol, 1,2-or 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1, C2-C6 glycols such as 6-hexanediol, C3-C6 triols such as glycerol, hexane-1,2,6-triol, and trimethylolpropane, and carboxylic acids such as N,N-dimethylacetamide Amides, heterocyclic ureas such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyridin-2-one, Acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one and other ketones or ketone alcohols, 2-dimethoxyethane, tetrahydrofuran, dioxane and other linear or cyclic ethers, diethylene glycol , triethylene glycol, dipropylene glycol, thiodiglycol and other two or three C2-C3 alkylene glycols or thiodiglycol, tetraethylene glycol, polyethylene glycol (preferably molecular weight 400, 800, 1540, etc. (compounds of 2000 or less), polypropylene glycol and other polyC2-C3 alkylene glycols (preferably liquid) with a repeating unit of 4 or more and a molecular weight of about 20000 or less, polyglycerols such as diglycerol, triglycerol and polyglycerol. Ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglyceride C1-C4 alkyl ethers of polyols such as alcohol monobutyl ether, cyclic esters or carbonates such as γ-butyrolactone and ethylene carbonate, dimethyl sulfoxide, acetic acid, etc.

Among them, preferred are C2-C6 diols (among them 1,2-propanediol), C3-C6 triols (among them glycerol), polyglycerol ethers (among them diglycerin) and C1-C4 alkyl ethers of polyols (among them butyl carbitol).

These water-soluble organic solvents may be used alone or in combination. Among these, polyglycerol ethers (preferably glycerol and/or diglycerol) are preferably contained.

The content of the water-soluble organic solvent is preferably 10 to 50 mass%, more preferably 14 to 45 mass%, and even more preferably 16 to 35 mass% relative to the total mass of the ink composition (100 mass%). By setting the content of the water-soluble organic solvent within the above range, there is an excellent tendency to reduce discharge defects.

[Surfactant]

Examples of the surfactant contained in the ink composition include known surfactants such as anionic, cationic, nonionic, amphoteric, silicone, and fluorine surfactants. Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl Taurine, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkyl Phenol phosphate ester, alkyl phosphate ester, alkyl aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, etc. Specific examples of commercially available products include HITENOL LA-10, LA-12, LA-16, NEO-HITENOL ECL-30S, ECL-45, etc., all manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. Examples of cationic surfactants include 2-vinylpyridine derivatives, poly4-vinylpyridine derivatives, and the like. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene. Ethers such as lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbose Esters such as alcohol anhydride monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5- Acetylene diols such as decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. (alcohols), such as Surfynol 104, 105, 82, 465, Olfine STG, etc. manufactured by Nissin Chemical Industry Co., Ltd., polyglycol ethers (for example, Tergitol 15-S-7 manufactured by SIGMA-ALDRICH, etc.), etc. Examples of amphoteric surfactants include lauryldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and coconut oil fatty acid amidopropyldimethyl Betaine aminoacetate, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. Examples of silicone surfactants include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane), BYK-345, and BYK-348 (polyether-modified polydimethylsiloxane), all manufactured by BYK Chemical Co., Ltd. Oxane) etc. Examples of fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ethylene oxide adducts. Polyoxyalkylene ether polymer compounds (polyoxyalkylene ether polymers) having a perfluoroalkyl ether group in the chain, etc. Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, and FS-31 (manufactured by DuPont), PF-151N, PF-154N (manufactured by OMNOVA Co., Ltd.), etc.

[Polymer dispersant]

In one embodiment, the aqueous ink composition preferably contains a polymer dispersant.

As a method of stabilizing a pigment dispersion in an aqueous medium, a method in which a dispersant such as a resin is used to stabilize the pigment dispersion through entropy, ionic repulsion, steric repulsion, etc. is generally used. Here, the dispersant is considered to have a hydrophilic part and a hydrophobic part. The hydrophobic part is adsorbed on the surface of the pigment and has the property of being dispersed in an aqueous medium through the hydrophilic part. In addition, depending on the adsorption state of the pigment surface, the pigment can also be dissolved in the aqueous medium. The above-mentioned polymer dispersant can be used as a dispersant having such properties.

The polymer dispersant is a polymer containing at least two structural monomers selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1). Preferably, at least one monomer is selected from monomer A, monomer B and monomer C respectively.

Monomer A: a monomer in which R in formula (1) is a hydrogen atom;

Monomer B: a monomer in which R in formula (1) is a C1-C4 alkyl group;

Monomer C: a monomer in which R in the formula (1) is an aryl group or an aryl C1-C4 alkyl group. It is preferable that R is an aryl group, and more preferable is a monomer in which R is a benzyl group.

In addition, the polymer dispersant may be any of random copolymers, alternating copolymers, block copolymers, and graft copolymers of these monomers.

The mass average molecular weight of the above-mentioned polymer dispersant is usually 10,000 to 60,000, preferably 10,000 to 40,000, and more preferably 10,000 to 30,000. When the weight average molecular weight is within these ranges, the stability of the pigment dispersion is good.

The acid value of the above-mentioned polymer dispersant is measured in mgKOH/g, which is usually 50 to 300, preferably 90 to 200, and more preferably 100 to 150. If the acid value is too small, the solubility of the polymer dispersant in water or an aqueous medium may decrease, and if it is too large, the color development property may decrease.

Examples of the polymer dispersant include HIROS random polymers), etc.

In addition, the polymer dispersant may be used after neutralizing the acid value as necessary. When neutralized with the theoretical equivalent of the acid value of the polymer dispersant, the degree of neutralization is 100%. The neutralization degree of the polymer dispersant in the ink composition is usually 50 to 200%, preferably 80 to 150%, and more preferably about 100 to 120%.

Examples of the neutralizing agent used for neutralizing the polymer dispersant include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as ammonia, aliphatic amine compounds, and alkanolamine compounds. and other organic bases, etc.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.

Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and the like.

Among the inorganic bases, alkali metal hydroxides and ammonia are preferred, and lithium hydroxide, sodium hydroxide, and ammonia are preferred among them.

Examples of the alkanolamine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, N-methyldiethanolamine, and the like. Mono-, di- or tri-C1-C3 alkanolamine compounds. Among these, tertiary amines are preferred, and triethanolamine is particularly preferred.

Examples of aliphatic amine compounds include mono-, di- or tri-C1-C3 amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, and trimethylamine. Among these, triethylamine is preferred.

These neutralizers may be used alone or in combination of two or more.

[Monomer A]

Monomer A is a monomer in which R in the above formula (1) is a hydrogen atom, that is, methacrylic acid.

[Single B]

Monomer B is a monomer in which R in the above formula (1) is a C1-C4 alkyl group. Examples of the monomer B include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.

[Monomer C]

Monomer C is a monomer in which R in the above formula (1) is an aryl group or an aryl C1-C4 alkyl group.

As the above-mentioned aryl group, a C6-C10 aryl group is preferred, and a phenyl group or a naphthyl group is particularly preferred.

Examples of the aryl C1-C4 alkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl and other alkyl groups whose alkyl moiety is linear or branched, with linear phenyl groups being preferred. C1-C4 alkyl; the alkyl part such as naphthylmethyl, naphthylethyl, naphthylpropyl, naphthylbutyl, etc. is linear or branched, preferably linear naphthyl C1-C4 alkyl, etc. Among them, phenyl C1-C4 alkyl group is preferred. Specific examples of the monomer C include phenyl methacrylate, benzyl methacrylate, and phenethyl methacrylate.

The content of the polymer dispersant is usually 0.1 to 15.0 mass%, preferably 0.1 to 9.0 mass%, and more preferably 0.2 to 6.0 mass% relative to the total mass of the ink composition (100 mass%).

[resin]

In one embodiment, the aqueous ink composition preferably further contains at least one selected from the group consisting of polyurethane resin, styrene-butadiene resin, (meth)acrylic resin, and (meth)acrylic resin copolymer.

In particular, it is preferable that the aqueous ink composition containing water, a pigment, and a polymer dispersant further contains a polyurethane resin, a styrene-butadiene resin, a (meth)acrylic resin, and a (meth)acrylic resin copolymer. At least any kind.

The above-mentioned resin may be used individually by 1 type, or may use 2 or more types together. Among the above resins, polyurethane resin and styrene-butadiene resin are preferred from the viewpoint of ink performance.

Examples of the polyurethane resin used in the aqueous ink composition include the same polyurethane resins as those listed in the white ink composition. As the polyurethane resin, a single polyurethane resin may be used, or two or three types may be used in combination.

When the polyurethane resin in the polyurethane resin has an acidic group such as a carboxyl group, a sulfo group, or a hydroxyl group, the acidic group may also be alkaline-salted. For example, a polyurethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and a basic compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group can be alkali-salted. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and hydrogen of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. Oxides etc. A basic compound may be used individually by 1 type, or may use 2 or more types together.

The content of the polyurethane resin is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the ink composition.

The above-mentioned styrene-butadiene resin is generally sold in the form of latex (emulsion) and can be easily purchased. Specific examples thereof include: Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, Nipol 2507H, and Nipol LX303A (the above are manufactured by Nippon ZEON Co., Ltd.), and the grades (grades) include 0695, 0696, 0561, and 0589. , 0602, 2108, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z latex (the above are made by JSR Co., Ltd.), etc. Most of them are liquids obtained by emulsifying resin to a solid content of 30 to 60%. As the styrene-butadiene resin, any of the above-mentioned latexes can be used, and among them, carboxyl-modified styrene-butadiene resin is preferably used. Examples of such resins include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, 0695, 0696, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, and 0850Z, and 0695, 0533, and 0568 are preferred. , 0597C, 0850Z, and more preferably JSR0568 (manufactured by JSR Corporation). As the styrene-butadiene resin, a single resin may be used or two or three resins may be used in combination.

The content of the styrene-butadiene resin is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the ink composition.

The above-mentioned (meth)acrylic resin and (meth)acrylic resin copolymer are available as commercial products, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. For example, Mowinyl 966A, 6963, 6960 (all trade names, acrylic resin emulsion), 6969D, RA-033A4 (all trade names, styrene/acrylic resin emulsion) of Nippon Synthetic Chemical Industry Co., Ltd., JONCRYL of BASF Company 7100, PDX-7370, PDX-7341 (all are trade names, styrene/acrylic resin emulsion), VONCOAT EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion) of DIC Co., Ltd., etc.

The content of the (meth)acrylic resin and (meth)acrylic resin copolymer is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the ink composition. quality%.

[additive]

The above-mentioned ink composition may further contain additives.

Examples of the additives include antiseptics, chelating agents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, pigment solubilizers, anti-fading agents, antioxidants, and the like.

--preservative--

Examples of the preservatives in the above additives include organic sulfur, organic nitrogen and sulfur, organic halogens, halogenated allyl sulfones, iodopropynes, N-halogenated alkyl sulfides, nitriles, and pyridines. 8-oxyquinolines, benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropanes, organotins, phenols, quaternary ammonium salts, triazines, thiazines Compounds such as azines, acyanilides, adamantane, dithiocarbamates, bromoindanones, benzyl bromoacetates, inorganic salts, etc. Specific examples of the organohalogen compounds include sodium pentachlorophenolate; specific examples of the pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide (sometimes referred to as "2- Pyrithione-1-oxide sodium salt"); Specific examples of isothiazoline compounds include 1,2-benzisothiazolin-3-one and 2-n-octyl-4-isothiazoline -3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2- Methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Specific examples of other antiseptic and antifungal agents include sodium acetic anhydride, sodium sorbate, sodium benzoate, Arc Chemical Company, trade name PROXEL ^RTM GXL (S) or PROXEL ^RTM XL-2 (S), and the like.

--Chelating reagent--

Specific examples of the chelating agent in the above additives include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentacetate, and uracil. Sodium diacetate, etc.

--Rust inhibitor--

Examples of the rust inhibitor among the above additives include bisulfite, sodium thiosulfate, ammonium thiocholate, diisopropyl ammonium nitrate, pentaerythritol tetranitrate, or dicyclohexyl ammonium nitrate.

--Water-soluble UV absorber--

Examples of the water-soluble ultraviolet absorber among the additives include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

--Water-soluble polymer compounds--

Examples of the water-soluble polymer compound in the additive include polyvinyl alcohol, cellulose derivatives, polyamine or polyimine.

--Viscosity regulator--

Examples of the viscosity modifier in the above-mentioned additives include the water-soluble organic solvents or water-soluble polymer compounds mentioned in the item (content) of the above-mentioned aqueous ink composition. Examples of the water-soluble polymer compounds include, for example, polymer Vinyl alcohol, cellulose derivatives, polyamine, polyimine, etc.

--Pigment dissolving agent--

Examples of the pigment dissolving agent among the above additives include urea, ε-caprolactam, and ethylene carbonate.

--Anti-fading agent--

The anti-fading agent among the above additives is used to improve image preservation. As the anti-fading agent, for example, various organic and metal complex anti-fading agents can be used. Examples of organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, and heterocyclic compounds. wait. Examples of metal complex compounds include nickel complex compounds, zinc complex compounds, and the like.

--Antioxidants--

As the antioxidant among the above-mentioned additives, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxy Anilines, heterocyclics, etc.

[Surface tension of aqueous ink composition]

In one embodiment, the surface tension of the aqueous ink composition at 25°C is preferably 20 to 48 mN/m, and more preferably 25 to 25 mN/m, from the viewpoint of being able to exhibit sufficient wettability to various fabrics. 46 mN/m, more preferably 30 to 44 mN/m, particularly preferably 32 to 42 mN/m.

In addition, the surface tension at 25° C. of a preferred aqueous ink composition to be combined with an aqueous white ink composition described below is preferably: 20 to 48 mN/m, more preferably 25 to 44 mN/m, still more preferably 30 to 42 mN/m, particularly preferably 32 to 40 mN/m.

The surface tension of the aqueous ink composition can be measured by the platinum plate method in a 25° C. environment using a surface tensiometer (CBVPZ manufactured by Kyowa Interface Science Co., Ltd.), for example.

[Viscosity of aqueous ink composition]

The viscosity of the aqueous ink composition at 25°C is preferably 2 to 20 mPa·s, and more preferably 3 to 18 mPa·s. If the aqueous ink composition satisfies the above viscosity range, the ejection responsiveness tends to be good in high-speed printing.

[pH of aqueous ink composition]

The pH of the aqueous ink composition is preferably pH 5.0 to 11.0, and more preferably pH 7.0 to 10.0 in order to improve storage stability.

[Preparation method of aqueous ink composition]

The preparation method of the aqueous ink composition is not particularly limited. For example, an aqueous dispersion (pigment dispersion) containing the above components is prepared and additives such as a water-soluble organic solvent are further added as necessary.

Examples of methods for preparing the aqueous dispersion include using a sand mill (bead mill), roller mill, ball mill, coating oscillator, ultrasonic disperser, microjet disperser, etc. together with pigments and dispersants (such as the above-mentioned high A method of dispersing (molecular dispersant, resin, etc.) together with water or an aqueous solvent, among which a sand mill (bead mill) is preferred. As for the preparation of a pigment dispersion using a sand mill (bead mill), it is preferable to use beads with small diameters (about 0.01 to 1 mm in diameter) and perform treatment under conditions that improve dispersion efficiency by increasing the filling rate of beads, for example. By dispersing under such conditions, the particle size of the pigment can be reduced and a dispersion liquid with good dispersibility can be obtained. In addition, after preparing the dispersion, it is preferable to remove components with large particle sizes by filtration and/or centrifugation. In addition, when violent foaming occurs during the preparation of the dispersion, in order to suppress the foaming, a very small amount of antifoaming agents such as silicones (also called silicones or silicones) and acetylene glycols may be added. . However, since some defoaming agents inhibit the dispersion or micronization of the pigment, it is preferable to appropriately select and use a defoaming agent that does not have such adverse effects.

The dispersant may be adsorbed on a part of the pigment surface, or may be in a state covering the entire pigment surface (called microencapsulated pigment, etc.). The latter is preferred. In addition, as mentioned above, a polymer dispersant is preferably used as a pigment dispersant.

When the entire surface of the pigment is covered with a dispersant (which may also be the case in microencapsulation of the pigment), any known microencapsulation method can be used. The methods are roughly divided into two types: physical and mechanical methods and chemical methods. As the latter chemical method, surface precipitation method, kneading method, interfacial polymerization method (also called surface polymerization method), etc. have been proposed. Among them, surface precipitation methods include acid precipitation method and phase inversion emulsification method. When performing microencapsulation, any method can be used without particular limitation, but among them, the surface precipitation method is preferred, and the phase inversion emulsification method is particularly preferred.

Examples of the phase inversion emulsification method include mixing a solution of a hydrophobic organic solvent in which a dispersant is dissolved and a liquid containing a neutralizer and water to form an emulsion (emulsion or microemulsion), and then adding a pigment and mixing. A method of obtaining an aqueous pigment dispersion by removing the solvent after dispersion. The average particle size of the pigment in the pigment dispersion prepared as described above is usually 200 nm or less, preferably 50 to 150 nm, and more preferably 60 to 120 nm. By setting the average particle diameter within this range, dispersion stability and discharge stability are excellent, and the dyeing concentration becomes high. In addition, the average particle diameter can be measured using the laser scattering method.

The above-mentioned aqueous ink composition can be subjected to ultrafiltration (microfiltration) using a membrane filter or the like. In particular, when used as an ink for inkjet printing, ultrafiltration is preferably performed in order to prevent nozzle clogging. The pore size of the filter used for ultrafiltration is usually 0.1 to 1 μm, preferably 0.1 to 0.8 μm.

In addition, when the above-mentioned polymer dispersant is used as the dispersant, the content of the polymer dispersant can be expressed using a numerical value called "the atomic ratio", and the atomic ratio can be determined by the following formula.

Dispersion ratio=parts of dispersant/parts of pigment

In this embodiment, the atomic ratio is usually 0.1 to 1.0, preferably 0.1 to 0.6, and more preferably 0.2 to 0.4. When the atomic ratio is within this range, a pigment dispersion with excellent stability and a good dyed product can be obtained.

<Aqueous white ink composition>

The above-mentioned aqueous white ink composition contains water, white pigment, polyurethane resin, and water-soluble organic solvent. In addition, in this specification, the aqueous white ink composition may be simply called a white ink composition or white ink.

[water]

As the water contained in the white ink composition, for example, the water exemplified for the pretreatment composition can be used. The content of water is not particularly limited and can be appropriately determined as needed. However, in order to adjust the viscosity of the white ink composition to an appropriate range, it may contain 20 to 100% by mass relative to the total mass of the ink composition. 80% by mass. In addition, it is not limited, but for example, it is preferably 40 to 80 mass%, more preferably 45 to 75 mass%, and still more preferably 50 to 70 mass%.

[white pigment]

As the white pigment, metal oxides are preferably used. Examples of metal oxides include zinc oxide, titanium oxide, zirconium oxide, and the like, with titanium oxide being preferred. Examples of types of titanium oxide include rutile type, anatase type, and the like. Titanium oxide may be used directly as a powder, or may be surface-treated with silica, alumina, zirconium oxide, zinc oxide, or an organic substance having a hydroxyl group. Among them, titanium oxide obtained by surface treatment is preferably selected.

Specific examples of titanium oxide include DUAWHITE TCR-52, TITONE R-32, TITONER-7E, TITONE R-21, TITONE R-62N, and TITONE R-42 (the above are manufactured by Sakai Chemical Industry Co., Ltd.) , TIPAQUECR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (the above are made by Ishihara Sangyo Co., Ltd.), TITANIX JA-600A, TITANIX JR-605 (The above are made by TAYCA Co., Ltd.), ST-455, ST-455WB, ST-457SA, ST-457EC (the above are made by Titan Kogyo, Ltd.), etc.

The content of the white pigment is preferably 3.0 to 16.0 mass%, more preferably 4.0 to 15.0 mass%, and even more preferably 5.0 to 14.0 mass% relative to the total mass of the white ink composition (100 mass%).

The polyurethane resin is not particularly limited, and known polyurethane resins can be used.

Specific examples of the polyurethane resin include polyurethane resins such as polyether polyurethane resin, polycarbonate polyurethane resin, and polyester polyurethane resin, and polyether polyurethane resins and polycarbonate polyurethane resins are preferred.

The above-mentioned polyurethane resin is available as a commercial product, and most of them are emulsions with a solid content concentration of 30 to 60% by mass. Commercially available polyurethane resins include, for example, PERMARIN UA-150, 200, 310, 368, 3945, UCOAT UX-320, and 340 (the above are manufactured by Sanyo Chemical Co., Ltd.), Hidran WLS-201, 202, 210, 213, 221, 230, 250, HW-312B latex (the above are manufactured by DIC Co., Ltd.), SUPERFLEX 150, 170, 470 (the above are manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), etc. Among them, examples of polycarbonate polyurethane resins include PERMARINUA-310, 3945, UCOAT UX-320, HYDRAN WLS-210, 213, 250, and the like. Examples of polyether polyurethane resins include PERMARIN UA-150 and 200, UCOAT UX-340, HYDRAN WLS-201, 202, and 230. As the polyurethane resin, a single polyurethane resin may be used, or two or three types may be used in combination.

The glass transition temperature of the polyurethane resin is preferably -90°C to 0°C, more preferably -85°C to -20°C, still more preferably -85°C to -30°C. When the glass transition temperature exceeds 0° C., the printed matter becomes hard to the touch, which is not preferable. When the glass transition temperature is lower than -90°C, the adhesion (adhesion) of the coating film of the printed matter is enhanced and stickiness is easily generated, and the color fastness to washing is also poor. Therefore, the glass transition temperature is preferably -90°C or higher. The glass transition temperature can be measured, for example, by differential scanning calorimetry (DSC).

The above-mentioned polyurethane resin preferably has a freezing point of -8°C or lower. The so-called freezing point below -8°C means that it freezes or solidifies below -8°C, which means that so-called denaturation such as gelation does not occur and will return to the emulsion state when returning to normal temperature. If a polyurethane resin with a freezing point of -8°C or less is used, a white ink composition excellent in low-temperature storage stability can be obtained. The freezing point is more preferably -11°C or lower. In addition, the above freezing point can be measured, for example, by adding 30 cc of polyurethane resin emulsion to a 50 cc plastic bottle, leaving it to stand in a constant temperature bath at a predetermined temperature for 20 hours, and then confirming whether there is freezing.

The content of the polyurethane resin is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 17 mass% relative to the total mass of the white ink composition.

[Water-soluble organic solvent]

The above-mentioned white ink composition contains a water-soluble organic solvent. Examples of water-soluble organic solvents include C1-C4 monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; ethylene glycol, 1 ,2-or 1,3-propanediol, 1,2-or 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6 -C2-C6 glycols such as hexanediol; C3-C6 triols such as glycerol, hexane-1,2,6-triol, and trimethylolpropane; carboxylic acid amides such as N,N-dimethylacetamide ; Heterocyclic ureas such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyridin-2-one; acetone , methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one and other ketones or keto-alcohols; 2-dimethoxyethane, tetrahydrofuran, dioxane and other linear or cyclic ethers; diethylene glycol, Two or three C2-C3 alkylene glycols or thiodiglycols such as triethylene glycol, dipropylene glycol, and thiodiglycol; tetraethylene glycol and polyethylene glycol (preferred molecular weights are 400, 800, 1540, etc. (compounds of less than 2000), polypropylene glycol, etc., polyC2-C3 alkylene glycols (preferably liquid) with a repeating unit of 4 or more and a molecular weight of about 20000 or less; polyglycerols such as diglycerol, triglycerol, polyglycerol, etc. Ether; Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglycerol C1-C4 alkyl ethers of polyols such as alcohol monobutyl ether; cyclic esters or carbonates such as γ-butyrolactone, ethylene carbonate, dimethyl sulfoxide, acetic acid; etc.

Among them, preferred are C2-C6 diols (among them 1,2-propanediol), C3-C6 triols (among them glycerol), polyglycerol ethers (among them diglycerin) and C1-C4 alkyl ethers of polyols (among them butyl carbitol).

These water-soluble organic solvents may be used alone or in combination. Among these, polyglycerol ethers (preferably glycerol and/or diglycerol) are preferably contained.

The content of the water-soluble organic solvent is preferably 10 to 50 mass%, more preferably 14 to 45 mass%, and even more preferably 16 to 35 mass% relative to the total mass of the white ink composition (100 mass%). . By setting the content of the water-soluble organic solvent within the above range, there is an excellent tendency to reduce discharge defects.

[base]

The white ink composition preferably further contains a base. The base is not particularly limited, and examples thereof include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as ammonia, and organic bases such as aliphatic amine compounds and alkanolamine compounds.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Examples of the alkaline earth metal hydroxide include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and the like. Among the above-mentioned inorganic bases, alkali metal hydroxides and ammonia are preferred, among which lithium hydroxide, potassium hydroxide, sodium hydroxide and ammonia are preferred, and sodium hydroxide is extremely preferred.

Examples of the aliphatic amine compound include mono-, di- or tri-C1-C3 amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, and trimethylamine. Among these, triethylamine is preferred.

Examples of the alkanolamine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, N-methyldiethanolamine, and the like. Mono-, di- or tri-C1-C3 alkanolamine compounds. Among these, tertiary amines are preferred, and diethanolamine and triethanolamine are further preferred.

When sodium hydroxide is included as the alkali in the white ink composition, a white ink composition excellent in whiteness and hiding rate can be obtained.

As the above-mentioned base, one type may be used or two or more types may be used in combination. When two or more types are used in combination, the mixing ratio of each base can be arbitrarily set according to the purpose.

[additive]

The above-mentioned white ink composition may further contain additives.

Examples of the additives include preservatives, chelating agents, rust inhibitors, surfactants, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, pigment solubilizers, anti-fading agents, antioxidants, and the like.

--preservative--

Examples of the above-mentioned antiseptic include organic sulfur, organic nitrogen and sulfur, organic halogen, halogenated allyl sulfone, iodinated propargyl (ester), N-halogenated alkyl sulfide, nitrile, and pyridine. Classes, 8-oxyquinolines, benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropanes, organotins, phenols, quaternary ammonium salts, triazines , thiazides, anilide, adamantane, dithiocarbamate, bromoindanone, benzyl bromide acetate, inorganic salts and other compounds. Specific examples of the organohalogen compounds include sodium pentachlorophenolate; specific examples of the pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide (sometimes referred to as "2- Pyrithione-1-oxide sodium salt"); Specific examples of isothiazoline compounds include 1,2-benzisothiazolin-3-one and 2-n-octyl-4-isothiazoline -3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2- Methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Specific examples of other antiseptic and antifungal agents include sodium acetic anhydride, sodium sorbate, sodium benzoate, Arc Chemical Company, trade name PROXEL ^RTM GXL (S) or PROXEL ^RTM XL-2 (S), and the like.

--Surfactant--

Examples of the surfactant include known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and silicone surfactants.

Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl Taurine, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkyl Phenol phosphate ester, alkyl phosphate ester, alkyl aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, etc. Specific examples of commercially available products include HITENOL LA-10, LA-12, LA-16, NEO-HITENOL ECL-30S, ECL-45, etc., all manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.

Examples of cationic surfactants include 2-vinylpyridine derivatives, poly4-vinylpyridine derivatives, and the like.

Examples of amphoteric surfactants include lauryldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and coconut oil fatty acid amidopropyldimethyl Betaine aminoacetate, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc.

Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene. Ethers such as lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbose Esters such as alcohol anhydride monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5- Acetylene diols such as decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. (alcohols), such as Surfynol 104, 105, 82, 465, Olfine STG, etc. manufactured by Nissin Chemical Industry Co., Ltd., polyglycol ethers (such as Tergitol 15-S-7 manufactured by SIGMA-ALDRICH, etc.), etc. .

Examples of the silicone surfactant include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane), BYK-345, and BYK-348 (polyether-modified polydimethylsiloxane), all manufactured by BYK Chemical Co., Ltd. Oxane) etc. Examples of fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ethylene oxide adducts. Polyoxyalkylene ether polymer compounds (polyoxyalkylene ether polymers) having a perfluoroalkyl ether group in the chain, etc. Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, and FS-31 (manufactured by DuPont), PF-151N, PF-154N (manufactured by OMNOVA Co., Ltd.), etc.

--Chelating reagent--

Specific examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentacetate, and sodium uracil diacetate. wait.

--Rust inhibitor--

Examples of the rust preventive include hydrogen sulfite, sodium thiosulfate, ammonium thiocholate, diisopropyl ammonium nitrate, pentaerythritol tetranitrate, and dicyclohexyl ammonium nitrate.

--Water-soluble UV absorber--

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

--Water-soluble polymer compounds--

Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine or polyimine.

--Viscosity regulator--

Examples of the viscosity modifier include, in addition to water-soluble organic solvents, water-soluble polymer compounds, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines, and the like.

--Pigment dissolving agent--

Examples of the dye dissolving agent include urea, ε-caprolactam, and ethylene carbonate.

--Anti-fading agent--

The above-mentioned anti-fading agent is used to improve the preservation properties of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, and heterocyclic compounds. wait. Examples of metal complex compounds include nickel complex compounds, zinc complex compounds, and the like.

--Antioxidants--

As the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxy Anilines, heterocyclics, etc.

[Preparation method of water-based white ink composition]

An example of a method for preparing the white ink composition according to this embodiment is a method of preparing an aqueous dispersion containing each of the above components and further adding the above additives as necessary.

Examples of methods for preparing the aqueous dispersion include the use of a sand mill (bead mill), a roller mill, a ball mill, a paint oscillator, an ultrasonic disperser, a microjet mill, etc., together with a pigment, a dispersant, water or an aqueous dispersion. A method of dispersing solvents together, among which a sand mill (bead mill) is preferred. As for the preparation of a pigment dispersion using a sand mill (bead mill), it is preferable to use beads with small diameters (about 0.01 to 1 mm in diameter) and perform treatment under conditions that improve dispersion efficiency by increasing the filling rate of beads, for example. By dispersing under such conditions, the particle size of the pigment can be reduced and a dispersion liquid with good dispersibility can be obtained. In addition, after preparing the dispersion, it is preferable to remove components with large particle sizes by filtration and/or centrifugation. In addition, when violent foaming occurs during preparation of the dispersion, a very small amount of antifoaming agents such as silicones and acetylene glycols may be added in order to suppress the foaming. However, since some defoaming agents inhibit the dispersion or micronization of the pigment, it is preferable to appropriately select and use a defoaming agent that does not have such adverse effects.

The dispersant may be adsorbed on a part of the pigment surface, or may be in a state covering the entire pigment surface (called microencapsulated pigment, etc.). The latter is preferred.

When the entire surface of the pigment is covered with a dispersant (which may also be the case in microencapsulation of the pigment), any known microencapsulation method can be used. The methods are roughly divided into two types: physical and mechanical methods and chemical methods. As the latter chemical method, surface precipitation method, kneading method, interfacial polymerization method (also called surface polymerization method), etc. have been proposed. Among them, surface precipitation methods include acid precipitation method and phase inversion emulsification method. When performing microencapsulation, any method can be used without particular limitation, but among them, the surface precipitation method is preferred, and the phase inversion emulsification method is particularly preferred.

Examples of the phase inversion emulsification method include mixing a solution of a hydrophobic organic solvent in which a dispersant is dissolved and a liquid containing a neutralizer and water to form an emulsion (emulsion or microemulsion), and then adding a pigment and mixing. A method of obtaining an aqueous pigment dispersion by removing the solvent after dispersion. The average particle size of the pigment in the pigment dispersion prepared as described above is usually 200 nm or less, preferably 50 to 150 nm, and more preferably 60 to 120 nm. By setting the average particle diameter within this range, dispersion stability and discharge stability are excellent, and the dyeing concentration becomes high. In addition, the average particle diameter can be measured using the laser scattering method.

The above-mentioned white ink composition can be subjected to ultrafiltration (microfiltration) using a membrane filter or the like. In particular, when used as an ink for inkjet printing, ultrafiltration is preferably performed in order to prevent nozzle clogging. The pore size of the filter used for ultrafiltration is usually 0.1 to 1 μm, preferably 0.1 to 0.8 μm.

According to the white ink composition of this embodiment, the problem that particles in the ink composition agglomerate during storage and the average particle diameter becomes larger can be effectively suppressed, and the problem of particle sedimentation during storage can also be effectively suppressed. That is, according to the white ink composition of this embodiment, the dispersed state of the particles in the ink composition can be stably maintained.

In addition, the white ink composition of this embodiment has good initial filling properties for the inkjet print head, and also has good continuous printing stability. In addition, images with no unevenness and high whiteness and hiding properties can be obtained.

The viscosity of the white ink composition of the present embodiment at 25° C. is preferably about 2 to 20 mPa·s when measured with an E-type viscometer from the viewpoint of ejection responsiveness at high speed. In addition, the surface tension of the white ink composition of this embodiment at 25° C. is preferably about 20 to 45 mN/m when measured using the plate method. In practice, the ejection volume, response speed, ink droplet flying characteristics, etc. of the inkjet printer used are taken into consideration, and the physical property values are adjusted to appropriate values.

[cloth]

The fabric used in the present embodiment is not particularly limited, and examples thereof include natural fibers or synthetic fibers such as silk, cotton, wool, cellulose, nylon, polyester, and rayon. The fabric may also be a blend containing two or more fibers.

<Printing component>

The above-mentioned pretreatment composition is preferably used in the form of a printing assembly (also called an "ink assembly" [also called an "ink set", etc.]) in combination with one or more aqueous ink compositions. The components of the aqueous ink composition constituting the printing unit are as described above.

A printing component according to one embodiment of the present invention has a pretreatment composition and an aqueous white ink composition. The pretreatment composition includes water, a cationic polymer, and a cross-linking agent. The aqueous white ink composition Materials include water, white pigments, polyurethane resin, and water-soluble organic solvents. The components of the aqueous white ink composition constituting the printing unit are as described above.

Conventionally, in the method of using a pretreatment liquid to agglomerate the resin in the ink composition, the color development can be improved because the aggregation of the resin in the ink composition and the penetration of the pigment into the fabric fibers can be suppressed. However, since the resin Early aggregation occurs before contact with the recording medium, so the adhesiveness (adhesion) decreases. On the other hand, the printing module of this embodiment includes a pretreatment composition containing a cationic polymer and a cross-linking agent, so that the adhesion can be improved while maintaining high color rendering properties.

In addition, in order to speed up printing and dyeing, if the ink composition is adhered to the fabric without drying after applying the pretreatment composition, the above-mentioned decrease in adhesion will become more significant. However, in this embodiment The printing unit can improve the adhesion even when achieving such high speed.

Furthermore, in order to not only retain the texture of the fabric but also achieve fixation (fixation) of the ink composition during printing and dyeing, even when the surface of the fabric to which the ink composition is attached is heated without applying pressure, it is different from applying pressure. The above-mentioned decrease in adhesion will also become more significant compared with the case of the printing module of this embodiment. However, the printing module of this embodiment can also improve the adhesion even when this printing and dyeing method is used.

[Inkjet printing and dyeing method]

The inkjet printing method of this embodiment includes a pretreatment step of applying a pretreatment composition on a fabric to form a wet precoat layer, and applying aqueous ink to at least a part of the area where the wet precoat layer is formed. Composition process.

The inkjet printing and dyeing method of a preferred embodiment of the present invention (hereinafter also referred to as the printing and dyeing method) includes: a pretreatment step of coating the above-mentioned pretreatment composition on the fabric to form a wet precoat layer. After the pretreatment step Without drying the fabric, aqueous ink containing water, pigment, resin emulsion (resin particles), water-soluble organic solvent, and surfactant is applied by inkjet to at least a part of the area where the wet precoat layer is formed. The recording process in which a composition is attached to form an image area.

Among the printing and dyeing methods using a pretreatment composition, there are the following methods: a dry-on-wet method in which an ink composition is adhered after applying a dry pretreatment composition, and a method in which the ink composition is applied without applying a dry pretreatment composition. Wet-on-wet method of attachment. In the dry-on-wet method, although the dry part takes time for printing, it has the advantage of being able to obtain an image with high adhesion.

On the other hand, in the wet-on-wet method, although the printing and dyeing time in the non-drying part can be shortened, the ink components will not agglomerate on the fabric fibers due to the large amount of moisture, and the ink components will easily separate from the fibers in the moisture on the fabric. comes out, so there is a problem of reduced adhesion.

In contrast, the inkjet printing method according to the embodiment of the present application uses a pretreatment composition containing a cationic polymer and a cross-linking agent to improve the adhesion and non-uniformity of the printed matter obtained in a wet-on-wet manner. occurrence decrease. In addition, by using the inkjet printing method according to the embodiment of the present application, when using polyester fiber or fiber with a thin texture or fiber with a thick stitch, it is possible to suppress printout (phenomenon) and obtain high-density and dense printing. It is particularly useful for printing materials with high compatibility.

In addition, when two or more ink compositions are sequentially attached to the same recording area, the ink compositions attached later can be effectively aggregated. Specifically, printing may be performed by attaching color ink to a base for attaching a white ink composition to dark fibers containing black. In such a case, the inkjet printing method according to the embodiment of the present application is particularly useful.

Furthermore, in order to not only retain the texture of the fabric but also achieve fixation (fixation) of the ink composition during printing and dyeing, even when the surface of the fabric to which the ink composition is attached is heated without applying pressure, it is different from applying pressure. Compared with the case, there is also the above-mentioned problem of reduced covering and adhesion. According to the inkjet printing method of this embodiment, even when such a non-contact heating method is used, hiding properties and adhesion can be improved.

[Pretreatment process]

The above-mentioned pretreatment process refers to a process of applying the pretreatment composition to the fabric. There is no particular limitation on the method of applying the pretreatment composition. For example, roller coating, spray coating, and ink-jet coating can be used. Among them, it is preferable to apply the pretreatment composition on the above-mentioned fabric in a non-contact manner, and more preferably to apply it by spray coating or inkjet coating. By applying the pretreatment composition in a non-contact manner, it is easier to control the coating amount of the pretreatment composition and the quality of the resulting image tends to be further improved.

In one embodiment, the coating amount of the above-mentioned pretreatment composition per unit area of the above-mentioned fabric is greater than 0.035g/cm ² and less than 0.070g/cm ² for forming a wet pre-coat layer. The above-mentioned coating amount is preferably 0.039 to 0.063 g/cm ² , more preferably 0.040 to 0.060 g/cm ² .

In addition, in another embodiment (especially an embodiment using the above-mentioned aqueous white ink composition), the coating amount of the above-mentioned pretreatment composition per unit area of the above-mentioned fabric is preferably more than 0.035 g/cm ² and less than 0.070g/cm ² for forming a wet pre-coat. The above-mentioned coating amount is more preferably 0.039 to 0.063 g/cm ² , and further preferably 0.040 to 0.060 g/cm ² .

By making the coating amount of the pretreatment composition exceed 0.035g/cm ² , when polyester fiber (reticular texture used for sportswear, etc.) or fiber with a thin texture, fiber with a thick stitch, etc. is used, For fabrics in which ink droplets ejected by the inkjet method easily penetrate (easy to penetrate) to the side opposite to the side where fiber printing is not performed, there is a method that can suppress the ink bleeding and improve the performance when setting the base with white ink. Trends in whiteness and coverage. In addition, when color inks are printed without providing a white base, ink bleeding can be suppressed and a color image with high color rendering properties tends to be obtained. In addition, by setting the coating amount of the pretreatment composition to less than 0.070 g/cm ² , it is possible to suppress the tendency for “traces” of the pretreatment composition to remain.

The inkjet printing method of this embodiment preferably includes a pressurizing step of applying pressure to the area where the wet precoat layer is formed after the pretreatment step. By having such a process, especially when using cotton fibers with large fluff, or raw materials for knitted fabrics with raised back (fleece), it is possible to form a uniform, moist precoat layer with little fluff, and it is possible to suppress the occurrence of lint on the white base. Uneven phenomenon, tendency to improve whiteness, covering properties, scratch resistance, and adhesion. In addition, unevenness of images printed with color ink and deterioration in color rendering tend to be suppressed.

The method used in the above-mentioned pressurizing step is not particularly limited, and examples thereof include methods using commercially available rollers, scrapers, and the like, and methods using a flat plate press, a roller press, and the like.

[Recording process]

In one embodiment, the recording step involves ejecting the at least one aqueous ink composition from a nozzle on at least a part of a region where the wet precoat layer is formed without drying the fabric after the pretreatment step. The process of applying an aqueous ink composition to form an image area.

In addition, in the embodiment using the above-mentioned aqueous white ink composition, the recording step is to spray the fabric from the nozzle on at least a part of the area where the wet precoat layer is formed without drying the fabric after the pretreatment step. The step of extracting the aqueous white ink composition and adhering the aqueous white ink composition to form an image area. In addition, as a recording step using a printing unit further containing an aqueous ink composition, the fabric is ejected from the nozzle on at least a part of the area where the wet precoat layer is formed without drying the fabric after the pretreatment step. The above-mentioned aqueous white ink composition forms a white image area and the aqueous ink composition is ejected from the nozzle head to form a colored image area for part or all of the area where the aqueous white ink composition is ejected to form an image. process.

After the pretreatment step, the recording step is preferably performed in a state where 20% by mass or more of volatile components of the pretreatment composition applied to the fabric remain. That is, in the printing and dyeing method of this embodiment, heating, air blowing, and leaving to dry the pretreatment composition can be omitted. Therefore, when the preprocessing process and the recording process are connected in series, a drying process does not need to be provided in between, thereby simplifying the apparatus and improving production efficiency. In the case of a normal ink composition, the adhesiveness of the cohesive resin in the aqueous ink composition tends to decrease as the pretreatment composition remains. However, according to the printing and dyeing method of this embodiment using the above-mentioned pretreatment composition, even if the recording process is performed in a state where 20 mass % or more of volatile components of the pretreatment composition remain, the decrease in adhesiveness can be suppressed. The residual rate of volatile components of the pretreatment composition is the amount (mass) of the volatile components contained in the pretreatment composition applied to the fabric that remains on the fabric when the recording process is performed. The ratio. The amount of volatile components of the pretreatment composition can be measured by the method described in the Examples. Volatile components are components that do not remain in the fabric after the pretreatment composition is dried, and are water or water-soluble organic solvents.

[Drying process]

The printing and dyeing method of this embodiment preferably further includes a drying step of heating the fabric after the recording step. By heating, the resin emulsion contained in the pretreatment composition or the aqueous ink composition can be bonded (intertwined) to the surface of the fabric, and the cross-linking reaction between the cross-linking agent and the resin emulsion can be promoted while evaporating water. In addition, by performing the drying process, the resulting image tends to have better rub resistance and adhesion.

In the drying step, even if the surface on which the aqueous ink composition adheres to is not subjected to pressure treatment, the surface on which the aqueous ink composition is adhered to may be subjected to pressure treatment. However, it is preferred that the aqueous ink composition-adhering surface on the fabric is not subjected to pressure treatment. A non-contact heating method that pressurizes the surface to which the ink composition adheres. Examples of the non-contact heating method include oven drying (methods that do not apply pressure, such as conveyor ovens and intermittent ovens). By having such a drying process, production efficiency is further improved. In addition, for dark-colored polyester fibers containing black and polyester fiber-containing blends, when the base is set with white ink, the color of the dye can be suppressed by drying the surface where the white ink adheres using a non-contact heating method. Reduction in whiteness caused by migration. In addition, the contact heating method for performing a pressure treatment on the surface on which the aqueous ink composition adheres to the cloth is not particularly limited, and an example thereof is a heat press (thermal transfer machine).

In addition, the heat source for heating is not particularly limited, and an example thereof includes infrared rays (lamp). As for the temperature during drying, it suffices as long as it can join the resin emulsion that can be contained in the ink composition and promote the cross-linking reaction between the above-mentioned cross-linking agent and the resin emulsion and evaporate the water. However, when using dark colors containing black, In the case of polyester fibers or blends containing polyester fibers, from the viewpoint of preventing color migration of dyes, the temperature is preferably 130°C or lower, and more preferably 120 to 130°C. By setting the temperature during drying to the above range, it is possible to suppress a decrease in whiteness due to dye color migration and to improve abrasion resistance and adhesion. In addition, when using fibers other than polyester (for example, cotton, nylon, etc.), the temperature is preferably 150°C or higher, more preferably 150 to 190°C, and particularly preferably 150 to 180°C. By setting the temperature during drying to the above range, abrasion resistance and adhesion tend to be improved. In addition, by setting the temperature to 190° C. or lower, it is possible to prevent fibers and components contained in the pretreatment composition from being deteriorated by heat.

The drying time is preferably 3 to 20 minutes, more preferably 5 to 16 minutes. When using dark-colored polyester fibers containing black or blends containing polyester fibers, from the viewpoint of preventing dye color migration, the time is preferably 3 to 10 minutes, more preferably 4 to 8 minutes, and particularly preferably 5 to 7 minutes. minute.

After the above drying process, the fabric can be washed and dried. At this time, if necessary, you can also perform soaping treatment, that is, a treatment in which unfixed pigments are washed away with hot soapy liquid or the like.

The pretreatment composition of the present invention has high whiteness and hiding properties when setting a base with white ink, has excellent adhesion to fabrics, and has few traces of pretreatment, so it can perform high-quality white printing and dyeing. In addition, the storage stability is also excellent. Since the whiteness and hiding properties of the base can be improved, the color rendering of an image printed with color ink on the base can be improved, and a printed matter with a high-quality color image can be obtained. In addition, printed matter obtained using the pretreatment composition of the present invention is also excellent in various fastnesses such as light resistance, water resistance, and color fastness to washing.

The printing unit of the present invention has high whiteness and hiding properties when the base is set with white ink, has excellent adhesion to fabrics, and has few traces of preprocessing. Therefore, high-quality white printing can be performed. In addition, since the whiteness and hiding properties of the base can be improved, the color rendering of an image printed with color ink on the base can be improved, and a printed matter with a high-quality color image can be obtained.

The printing and dyeing method of the present invention can perform high-quality white printing and dyeing because it has high whiteness and hiding properties when using white ink to set the base, has excellent adhesion to the fabric, and has few traces of pretreatment. In addition, since the whiteness and hiding properties of the base can be improved, the color rendering of an image printed with color ink on the base can be improved, and a printed matter with a high-quality color image can be obtained.

Example

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. In addition, unless otherwise specified, the preparation of the pretreatment composition and the aqueous ink composition is performed under stirring. In addition, "water" used in the examples is ion-exchanged water.

[Preparation Example 1]: Preparation of Dispersion 1

HIROS XVS-1202 (9 parts) manufactured by Starlight PMC Co., Ltd. was dissolved in 2-butanone (30 parts). To this solution, a solution obtained by dissolving 0.9 parts of sodium hydroxide in ion-exchange water (76 parts) was added, and the mixture was stirred for 1 hour to obtain an emulsion. C.I. Pigment Black 7 (30 parts) was added to the obtained liquid, and dispersion processing was performed using a sand mill at 1500 rpm for 15 hours. Ion-exchange water (150 parts) was added dropwise to the obtained liquid, and the beads for dispersion were filtered out. Part of the 2-butanone and water in the obtained mother liquid was removed by distillation under reduced pressure using an evaporator and concentrated to obtain a dispersion with a solid content of 11.9%. Let this be "dispersion 1". In addition, the solid content in the aqueous solution was determined by the dry weight method using MS-70 manufactured by A&D Co., Ltd. The average particle diameter of the pigment contained in dispersion 1 is 88 nm, and the viscosity of dispersion 1 at 25°C is 4.6 mPa·s.

[Preparation Examples 2 to 3]: Preparation of aqueous white ink composition and aqueous ink composition.

The ingredients listed in Table 1 below were thoroughly stirred and mixed to obtain inks 1 to 2. The obtained ink was filtered through a mixed cellulose ester filter with a pore diameter of 5 μm, and then degassed using a vacuum pump to obtain test inks 1 to 2.

The content of each description in Table 1 below is as follows. In addition, the numerical values in Table 1 are "parts".

Ink 1: Aqueous white ink composition prepared in Preparation Example 2

Ink 2: Aqueous ink composition prepared in Preparation Example 3

FUJI SP SAMPLE 138 (white pigment dispersion, 50% solid content, manufactured by Fuji Color Co., Ltd.)

Dispersion 1 (Dispersion 1 obtained in Preparation Example 1)

Hidran WLS-201 (polyurethane resin emulsion, solid content: 35%, freezing point -11°C, glass transition temperature -79°C, manufactured by DIC Co., Ltd.)

JSR0568 (styrene-butadiene resin latex, solid content: 50%, manufactured by JSR Co., Ltd.)

Olfine EXP-4001 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)

Surfynol 420 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)

Surfynol DF-110D (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)

PROXEL GXL(S) (preservative, manufactured by LONZA Co., Ltd.)

TEA: Triethanolamine manufactured by Junsei Chemical Co., Ltd.

Table 1

Element ink 1 ink 2 FUJI SP SAMPLE 138 20 Dispersion 1 50 Hidran WLS-201 43 JSR0568 6 glycerin 18 diglycerin 15 propylene glycol 10 Butyldiglycol 3 Olfine EXP-4001 0.8 Surfynol 420 0.1 Surfynol DF-110D 0.1 PROXEL GXL(S) 0.1 0.1 25% NaOH aqueous solution 0.6 TEA 0.4 0.1 water 17.1 15.6 total 100 100

[Examples 1 to 5, Comparative Examples 1 to 7]: Preparation of pretreatment composition.

Each component described in Table 2 below was mixed to obtain a pretreatment composition with a total amount of 100 parts. The obtained liquid was filtered through a membrane filter with an average pore diameter of 3 μm, and pretreatment compositions 1 to 8 for evaluation tests were obtained.

The abbreviations in Table 2 below have the following meanings. In addition, the numerical values in Table 1 are "parts".

DK6850: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 1703, cationic polymer containing epihalohydrin structural units, active ingredient is 70%)

DK6854: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 5853, cationic polymer containing epihalohydrin structural units, active ingredient is 50%)

PAA-HCL-03: Allylamine hydrochloride polymer (manufactured by NITTOBO MEDICAL CO., LTD.), a cationic polymer with a weight average molecular weight of 6611 and containing allylamine structural units, and the active ingredient is 40%)

MEIKANATE FM-1: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

MEIKANATE ST: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

Mass % of cationic polymer: Mass content (%) of cationic polymer relative to the total mass of the pretreatment composition

Coating amount [g/cm ² ]: Coating amount of pretreatment composition per unit area of fabric

[Weight average molecular weight of cationic polymer]

Gel permeation chromatography using an aqueous solution of acetic acid (500mM) and Na ₂ NO ₃ (200mM) as a developing solvent [GPC device manufactured by Tosoh Corporation (HLC-8320GPC EcoSEC), column manufactured by Tosoh Corporation (connected to TSKgel SuperAW4000 , TSKgel Super AW3000×2 pieces), flow rate 0.6mL/min] and measured using polystyrene as the standard material.

Table 2

[How to make records]

[Pretreatment process]

The pretreatment compositions 1 to 8 obtained above were applied to polyester fabric (dry T-shirt, black 00300-ACT [made by GLIMMER Co., Ltd.]) in A4 Dimensions are applied to form a wet precoat. At this time, pretreatment compositions 1 to 8 were applied using a commercially available sprayer (manufactured by MITSUGIRON Co., Ltd., fine spray). Immediately after applying the pretreatment composition, the following recording process is performed.

[Remaining amount of pretreatment composition]

The remaining amount of the pretreatment composition before the recording process is determined by the following formula. Both the Example and the Comparative Example were 95% or more.

Remaining amount of the pretreatment composition (%) = (weight of the fabric before the recording process - weight of the fabric before the pretreatment process) / (weight of the fabric just after coating in the pretreatment process - after the pretreatment process weight of the previous fabric) × 100%

[Recording process]

The aqueous white ink composition (ink 1) prepared as described above was filled in an industrial inkjet evaluation device (expansion coating device EV2500: manufactured by Ricoh Corporation). Then, under the conditions of an ink droplet weight of 29 pl/dot, a nozzle temperature of 25°C, a resolution of 600×1200 dpi, and repeated printing 6 times, the aqueous ink composition (ink 1) was adhered to the above-mentioned surface. The obtained wet pre-coated portion of the area to form a white solid pattern image. In Examples and Comparative Examples, after the ink composition was attached, it was dried by heating and drying at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO).

In addition, the pretreatment process and the recording process were performed at room temperature 25°C.

In addition, in each of the Examples and Comparative Examples, a pretreatment process was performed on the fabric without ink adhesion, and a recorded matter obtained by heating and drying in the same manner as when ink adhesion was performed was produced.

[BaiDu]

The L* value of the printed surface of the printed material obtained above was recorded using an aqueous white ink composition (ink 1) and measured. As a colorimeter, a spectrophotometer (X-Rite Ci62, manufactured by X-Rite Corporation) was used to measure the CIE/L*a*b* color under the measurement conditions of D65 light source and 2° viewing angle. L* value in the system. Each printed material was measured five times, and the average value is shown in Table 2 as the measurement results. The larger the L* value is, the higher the whiteness is shown, which is preferable. In addition, the L* value represents the numerical value obtained by rounding off the first decimal place.

[coverage]

The hiding properties of the printed surface of the printed matter obtained as described above were recorded using the aqueous white ink composition (Ink 1), and the area ( Solid area) Analysis tool's graininess [%] (Graininess). The average particle size [%] of each of the measured colors Cyan, Magenta, Yellow, and Black was calculated and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2. The smaller the value of graininess [%] (Graininess), the higher the hiding power.

(evaluation criteria)

A: Particle size [%] is less than 4.5.

B: Particle size [%] is 4.5 or more and less than 6.0.

C: Particle size [%] is 6.0 or more and less than 8.5.

D: The particle size [%] is 8.5 or more.

[Tightness]

The adhesion of the printed surface of the printed matter obtained above by recording with the aqueous white ink composition (Ink 1) was judged by a color fastness to washing test. The color fastness to washing test was repeated three times in accordance with "AATCC61 2A" and evaluated according to the following evaluation standards. The evaluation results are shown in Table 2.

(evaluation criteria)

A: The coating did not fall off even after three repeated tests.

B: Although the coating peeled off after three repeated tests, more than half of the film still remained.

C: After two repeated tests, the coating peeled off.

D: After one test, the coating peeled off.

[Trace of preprocessing]

Using a recorded matter that has been subjected to the pretreatment process without ink adhesion, visually compare the pretreatment coated portion (no ink adhesion) and the non-coated portion (the fabric itself) of the recorded matter to confirm the pretreatment coating. White traces from the pretreatment composition remain in the area. The evaluation results are shown in Table 2.

(evaluation criteria)

A: No trace remains.

B: Some traces remain.

C: Considerable traces remain.

[Storage stability test]

Each sample for the test was prepared by weighing 10 g of the pretreatment compositions 1 to 9 prepared above into a 30 mL glass vial (SV-30A, manufactured by Nichiden Rika Glass Co., Ltd.), capping and sealing. Each of the obtained samples was stored at 60° C. for one week, and evaluated according to the following criteria based on changes in appearance after storage. The evaluation results are shown in Table 2.

(evaluation criteria)

A: After saving, the appearance has not changed and is good.

B: After storage, slight aggregation was observed, but no precipitation occurred.

C: Significant aggregation occurs after storage, and there is a precipitate with a thickness of more than 1 mm in a liquid with a height of 2 cm.

From the results in Table 2 above, it can be seen that the results of comparing the pretreatment compositions containing a cross-linking agent and a cationic polymer containing a specific structural unit of the Examples with the pretreatment compositions of Comparative Examples 1 to 4 are whiteness, It has good hiding and adhesion, no trace of pre-treatment and excellent storage stability. On the other hand, it can be seen that in Comparative Example 1, which does not contain a cross-linking agent, the whiteness, hiding properties, and adhesion are reduced, and in Comparative Example 2, which contains a small amount of the cationic polymer, the whiteness and adhesiveness are reduced; In Comparative Example 3 in which the added amount of the cationic polymer was large, traces became worse. In addition, in Comparative Example 4 in which a large amount of crosslinking agent was added, storage stability deteriorated.

[Examples 6 to 18, Comparative Examples 8 to 13]: Preparation of pretreatment composition.

Each component described in Table 3 below was mixed to obtain a pretreatment composition with a total amount of 100 parts. The obtained liquid was filtered through a membrane filter with an average pore diameter of 3 μm, and pretreatment compositions 9 to 24 for evaluation tests were obtained.

The abbreviations in Table 3 below have the following meanings. In addition, the numerical values in Table 1 are "parts".

DK6850: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 1703, cationic polymer containing epihalohydrin structural units, active ingredient is 70%)

DK6854: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 5853, cationic polymer containing epihalohydrin structural units, active ingredient is 50%)

DK6885: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 2038, cationic polymer containing epihalohydrin structural units, active ingredient is 70%)

PAA-HCL-01: Allylamine hydrochloride polymer (manufactured by NITTOBO MEDICAL CO., LTD.), a cationic polymer with a weight average molecular weight of 1955 and containing allylamine structural units. The active ingredient is 34%)

PAA-HCL-03: Allylamine hydrochloride polymer (manufactured by NITTOBO MEDICAL CO., LTD.), a cationic polymer with a weight average molecular weight of 6611 and containing allylamine structural units. The active ingredient is 40%)

UNISENSE KHE100L: Epihalohydrin-modified polyamine resin (manufactured by SENKA, a cationic polymer with a weight average molecular weight of 2191, containing epihalohydrin structural units, and an active ingredient of 60%)

Carbodilite E-02: Carbodiimide cross-linking agent (manufactured by Nisshinbo Chemical Co., Ltd., cationic, 40% active ingredient)

EPOCROS WS-700: oxazoline cross-linking agent (manufactured by Nippon Shokubai Co., Ltd., cationic, active ingredient: 25%)

Trixene Aqua BI522: Blocked isocyanate cross-linking agent (manufactured by Baxenden, cationic, 40% active ingredient)

Mass % of cationic polymer: Mass content (%) of cationic polymer relative to the total mass of the pretreatment composition

Coating amount [g/cm ² ]: Coating amount of pretreatment composition per unit area of fabric

table 3

[Methods for producing recorded matter of Examples 6 to 18 and Comparative Examples 8 to 13]

[Pretreatment process]

The pretreatment compositions 9 to 24 obtained above were applied to polyester fabric (dry T-shirt, black 00300-ACT [made by GLIMMER Co., Ltd.]) in A4 amounts according to the coating amounts listed in Table 3. Dimensions are applied to form a wet precoat. At this time, pretreatment compositions 9 to 24 were applied using a commercially available sprayer (fine spray manufactured by MITSUGIRON Co., Ltd.). Immediately after applying the pretreatment composition, the following recording process is performed.

[Recording process]

The aqueous ink composition (ink 1) prepared as described above was filled in an industrial inkjet evaluation device (expansion coating device EV2500: manufactured by Ricoh Corporation). Then, under the conditions of an ink droplet weight of 29pl/dot, a nozzle temperature of 25°C, a resolution of 600×1200dpi, and repeated printing 6 times, the aqueous ink composition (ink 1) was adhered to the above-mentioned Get a portion of the wet pre-coated area to form a white solid pattern image. After the ink composition was attached, it was dried by heating at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO).

The recorded materials of Examples 6 to 18 and Comparative Examples 8 to 13 were used to perform various evaluations of the above-mentioned whiteness, hiding properties, adhesion, traces of pretreatment, and storage stability tests. The results are shown in Table 3.

It can be seen from the results in Table 3 above that the results of comparing the pretreatment compositions of the Examples including a cross-linking agent and a cationic polymer containing a specific structural unit with the pretreatment compositions of Comparative Examples 8 to 10 are whiteness, It has good hiding and adhesion, no trace of pre-treatment and excellent storage stability. In Comparative Example 8 with a small amount of the cationic polymer added, the whiteness and adhesion decreased; in Comparative Example 9 with a large amount of the cationic polymer added, the traces became worse. In addition, in Comparative Example 10 in which a large amount of crosslinking agent was added, storage stability deteriorated. In Comparative Example 11 where a large amount of the pretreatment composition was applied, the traces became worse; in Comparative Examples 12 and 13 where a small amount of the pretreatment composition was applied, the whiteness, hiding properties and adhesion decreased.

[Examples 19 to 22, Comparative Examples 14 to 17]: Preparation of pretreatment composition.

Each component described in Table 4 below was mixed to obtain a pretreatment composition with a total amount of 100 parts. The obtained liquid was filtered through a membrane filter with an average pore diameter of 3 μm, and pretreatment compositions 1, 2, and 4 to 8 for evaluation tests were obtained.

Each description in Table 4 below is as follows. In addition, the numerical values in Table 4 are "parts".

DK6850: Epihalohydrin-modified polyamine resin (manufactured by Starlight PMC Co., Ltd., weight average molecular weight is 1703, cationic polymer containing epihalohydrin structural units, active ingredient is 70%)

PAA-HCL-03: Allylamine hydrochloride polymer (manufactured by NITTOBO MEDICAL CO., LTD.), a cationic polymer with a weight average molecular weight of 6611 and containing allylamine structural units. The active ingredient is 40%)

MEIKANATE FM-1: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

MEIKANATE ST: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

Table 4

[How to make records]

[Pretreatment process]

Pretreatment compositions 1, 2, 4 to 8 were applied to polyester fabric (dry T-shirt, black 00300-ACT (manufactured by GLIMMER Co., Ltd.)) at the coating amounts listed in Table 4 in A4 size to form a wet Precoating. At this time, pretreatment compositions 1, 2, 4 to 8 were applied using a commercially available sprayer (fine spray manufactured by MITSUGIRON Co., Ltd.). Immediately after application of the pretreatment composition, the following recording process was performed.

[Residual amount of pretreatment composition]

The remaining amount of the pretreatment composition before the recording process is determined by the following formula. Both the Example and the Comparative Example were 95% or more.

Remaining amount of the pretreatment composition (%) = (weight of the fabric before the recording process - weight of the fabric before the pretreatment process) / (weight of the fabric just after coating in the pretreatment process - after the pretreatment process weight of the previous fabric) × 100%

[Recording process]

The aqueous white ink composition (Ink 1) and the aqueous ink composition (Ink 2) prepared as above were filled in an industrial inkjet evaluation device (expansion coating device EV2500: manufactured by Ricoh Corporation) . Then, under the conditions of an ink droplet weight of 29pl/dot, a nozzle temperature of 25°C, a resolution of 600×1200dpi, and repeated printing 6 times, an aqueous white ink composition (ink 1) was attached to the A portion of the wet precoated area obtained as described above to form a white solid pattern image. Then, the aqueous ink composition (Ink 2) was adhered to the provided paper under the conditions of the ink droplet weight of 27pl/dot, the nozzle temperature of 25°C, the resolution of 600×1200dpi, and repeated printing 6 times. Fill half of the area with the aqueous white ink composition (Ink 1) to form a black solid pattern image. After the aqueous ink composition (ink 2) was attached, the obtained printed matter was heated and dried using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO) at 130° C. for 3 minutes. The pretreatment process and recording process were performed at room temperature 25°C.

In each of the Examples and Comparative Examples, recorded matter was also produced in which a pretreatment process was performed on a fabric and the fabric was heated and dried in the same manner as when ink adhesion was performed without ink adhesion.

The recorded materials of Examples 19 to 22 and Comparative Examples 14 to 17 were used to evaluate whiteness, hiding properties, adhesion, traces of preprocessing, and storage stability tests by the above methods. In addition, the solid printing unevenness (solid printing unevenness) of the aqueous ink composition was evaluated by the following method. The results are shown in Table 4.

[Full-page unevenness of aqueous ink composition]

The solid unevenness of the aqueous ink composition was evaluated based on the following evaluation criteria by visually observing the black solid pattern image obtained as described above. The evaluation results are shown in Table 4.

(evaluation criteria)

A: The water-based ink composition fills the entire page evenly.

B: The aqueous ink composition filled the entire page unevenly, and some density unevenness was observed.

C: The aqueous ink composition was filled unevenly across the entire page, and considerable concentration unevenness was observed.

As can be seen from the results in Table 4 above, the printing unit of the Example compared with the printing unit of the Comparative Example has good whiteness, hiding properties, and adhesion, and the aqueous ink composition (color ink) does not have a full page. Less uniformity and no traces of pre-treatment.

On the other hand, it can be seen that in Comparative Example 14 using a pretreatment composition containing no cross-linking agent, and in Comparative Example 15 using a pretreatment composition with a small amount of cationic polymer added, the whiteness, hiding properties, and adhesiveness were found to be With the decrease, the full-color unevenness becomes significantly worse. It can be seen that the traces in Comparative Example 16 using a pretreatment composition with a large amount of cationic polymer added became worse. In addition, it was found that the storage stability in Comparative Example 17 using a pretreatment composition with a large amount of cross-linking agent was deteriorated.

[Examples 23 to 30, Comparative Examples 18 to 29]: Preparation of pretreatment composition.

Each component listed in Table 5 below was mixed to obtain a pretreatment composition with a total amount of 100 parts. The obtained liquid was filtered through a membrane filter with an average pore diameter of 3 μm, and pretreatment compositions 1, 2, and 4 to 8 for evaluation tests were obtained.

Each description in Table 5 below is as follows. In addition, the numerical values in Table 5 are "parts".

DK6850: Epihalohydrin-modified polyamine resin (made by Starlight PMC Co., Ltd., weight average molecular weight is 1703, cationic polymer containing epihalohydrin structural unit, active ingredient is 70%)

PAA-HCL-03: Allylamine hydrochloride polymer (manufactured by NITTOBO MEDICAL CO., LTD.), a cationic polymer with a weight average molecular weight of 6611 and containing allylamine structural units, and the active ingredient is 40%)

MEIKANATE FM-1: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

MEIKANATE ST: Blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature is 120°C or above, active ingredient is 30%)

table 5

[How to make records]

[Pretreatment process]

Pretreatment compositions 1, 2, 4 to 8 were applied to cotton fabric 1 (heavyweight T-shirt, black 00085-CVT [manufactured by PrintStar]) and cotton fabric 2 (sheet fabric, ( 10000L) 300. Black (B) [Shinjuku Okadaya]), cotton 3 (Daily fine pique, (KOF-14) BK. black (B) [Shinjuku Okadaya]), cotton 35%/polyester 65% blend (T/CBroad, (AD40000) 300. Black (B) [Shinjuku Okadaya]), polyester fabric (dry T-shirt, black 00300-ACT [made by GLIMMER Co., Ltd.]) are applied in A4 size to form a moist of pre-coating. At this time, the pretreatment compositions 1, 2, and 4 to 8 were applied using a commercially available sprayer (fine spray manufactured by MITSUGIRON Co., Ltd.).

In Example 30, after applying the pretreatment composition, a roller (wallpaper construction tool roller manufactured by YAYOI Chemical Industry Co., Ltd.) was used to lay down the nap of the fabric on the wet precoat layer, and then the next step was performed immediately. Describe the recording process.

In addition, in Comparative Examples 25 to 29, after applying the pretreatment composition, a desktop automatic flat press (AF-65TEN manufactured by Asahi Textile Machinery Co., Ltd.) was used to heat and dry at 170° C. for 60 seconds, and then the following recording was performed process. In addition, in other Examples and Comparative Examples, the following recording process was performed immediately after applying the pretreatment composition.

[Remaining amount of pretreatment composition]

The remaining amount of the pretreatment composition before the recording process is determined by the following formula. In Comparative Examples 25 to 29 before the recording process, the remaining amount of the pretreatment composition was less than 20%, and in the other Examples and Comparative Examples, it was 95% or more.

Remaining amount of the pretreatment composition (%) = (weight of the fabric before the recording process - weight of the fabric before the pretreatment process) / (weight of the fabric just after coating in the pretreatment process - after the pretreatment process weight of the previous fabric) × 100%

[Recording process]

The aqueous white ink composition (Ink 1) and the aqueous ink composition (Ink 2) prepared as above were filled in an industrial inkjet evaluation device (expansion coating device EV2500: manufactured by Ricoh Corporation) . Then, under the conditions of an ink droplet weight of 29pl/dot, a nozzle temperature of 25°C, a resolution of 600×1200dpi, and repeated printing 6 times, an aqueous white ink composition (ink 1) was attached to the A portion of the wet precoated area obtained as described above to form a white solid pattern image.

Then, the aqueous ink composition (Ink 2) was adhered to the provided paper under the conditions of the ink droplet weight of 27pl/dot, the nozzle temperature of 25°C, the resolution of 600×1200dpi, and repeated printing 6 times. Fill half of the area with the aqueous white ink composition (Ink 1) to form a black solid pattern image.

In Examples 28 to 30 and Comparative Examples 27 to 29, after the aqueous ink composition (Ink 2) was attached, the obtained printing and dyeing was performed at 150° C. using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO). Heat and dry the material for 10 minutes to dry it. In other Examples and Comparative Examples, after the aqueous ink composition (Ink 2) was attached, the resulting printed material was dried at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO). Heat and dry to dry. The pretreatment process and recording process were performed at room temperature 25°C.

In addition, in each of the Examples and the Comparative Examples, recorded matter was also produced in which a pretreatment process was performed on the fabric and heat and drying was performed in the same manner as when ink adhesion was performed without ink adhesion. .

The recordings of Examples 23 to 30 and Comparative Examples 18 to 29 were used to conduct whiteness, hiding properties, adhesion, full-page unevenness of the aqueous ink composition, traces of pretreatment, and storage stability tests using the above methods. various evaluations. The results are shown in Table 5.

It can be seen from the results in Table 5 above that the pretreatment compositions of the Examples compared with the printing and dyeing methods of the Comparative Examples have good whiteness, hiding properties, and adhesion to various fabrics, and the aqueous ink compositions (color Ink) has less unevenness across the entire page and no traces of pre-processing.

On the other hand, it can be seen that in Comparative Example 18, which does not contain a cross-linking agent, the whiteness, hiding properties, and adhesiveness are reduced, and in Comparative Example 19, in which the added amount of the cationic polymer is small, the whiteness and adhesiveness are reduced. In Comparative Example 20, in which the added amount of the cationic polymer was large, the traces became worse. In addition, it was found that the storage stability deteriorated in Comparative Example 21 in which the added amount of the crosslinking agent was large.

It can be seen that in Comparative Example 22 in which the coating amount of the pretreatment composition is 0.070 g/cm ² or more, the traces of pretreatment deteriorate, and in Comparative Example 23 in which the coating amount of the pretreatment composition is 0.035 g/cm ² or less, 24 will cause a decrease in whiteness, hiding properties, and adhesion. In addition, it was found that in Comparative Examples 25 to 29, which were dried after pretreatment, the reduction in whiteness was poor, resulting in a reduction in whiteness and hiding properties, resulting in significant full-color unevenness.

Industrial applicability

The pretreatment composition of the present invention has good whiteness, hiding properties, and adhesion, has no trace of pretreatment, can obtain excellent printed matter, and has good storage stability, so it can be used as a variety of fabric-like materials. The pre-treatment composition is extremely useful.

The printing assembly based on the present invention has good whiteness, hiding properties, and adhesion to various fabrics without traces of pretreatment, and can also obtain excellent printed matter, and the storage stability of the pretreatment composition is good, so it can be used as a A wide variety of fabric printing components are extremely useful.

The inkjet printing and dyeing method of the present invention has good whiteness, hiding properties, and adhesion for various fabrics without traces of pretreatment, and can also obtain excellent printed matter, and the pretreatment composition has good storage stability. Therefore It can expand the applicable range of fabrics and is extremely useful as an inkjet printing and dyeing method for various fabrics.

Claims (39)

1. A pretreatment composition used to form a wet precoat layer that contains an aqueous ink composition for forming an image on a fabric by an inkjet method; wherein, The pretreatment composition meets all of the following requirements [1] to [4]: [1] The aqueous ink composition contains water, pigment, resin emulsion, water-soluble organic solvent, and surfactant; [2] Used to form a moist pre-coating layer with a coating amount of the pre-treatment composition per unit area greater than 0.035 g/cm ² and less than 0.070 g/cm ² ; [3] The pretreatment composition contains water, a cationic polymer greater than 1.4% by mass and less than 10.5% by mass relative to the total mass of the pretreatment composition, and 0.1% by mass relative to the total mass of the pretreatment composition. Mass% or more and less than 2.7 mass% of cross-linking agent; [4] The cationic polymer contains at least any one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and epihalohydrin structural units. 2. The pretreatment composition according to claim 1, wherein the cross-linking agent comprises a compound selected from the group consisting of a blocked isocyanate group-containing compound, a carbodiimide group-containing compound, and an oxazoline group-containing compound. A group consisting of more than one cationic cross-linking agent. 3. The pretreatment composition according to claim 2, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher. 4. The pretreatment composition according to any one of claims 1 to 3, wherein the surface tension at 25°C is 35 mN/m to 60 mN/m. 5. A printing component comprising an aqueous ink composition and the pretreatment composition of any one of claims 1 to 4, the aqueous ink composition comprising water, pigment, resin emulsion, water-soluble organic Solvents, surfactants. 6. An inkjet printing and dyeing method, which includes: The pretreatment process of applying the pretreatment composition according to any one of claims 1 to 4 on the fabric to form a wet precoat layer; and A recording process of applying an aqueous ink composition containing water, pigment, resin emulsion, water-soluble organic solvent, and surfactant to at least a part of the area where the wet precoat layer is formed by an inkjet method, and forming an image area. . 7. The inkjet printing method according to claim 6, wherein after the pretreatment step, the remaining amount of the pretreatment composition coated on the fabric is relative to the amount of the pretreatment composition coated in the pretreatment step. The recording step is performed in a state where the total amount of cloth is 20% by mass or more. 8. A printed matter in which the aqueous ink composition is printed on a fabric coated with the pretreatment composition according to any one of claims 1 to 4. 9. A printing component having a pretreatment composition and an aqueous white ink composition, the pretreatment composition comprising water, a cationic polymer, a cross-linking agent, the aqueous white ink composition comprising water , white pigment, polyurethane resin, water-soluble organic solvent; among them, The content of the cationic polymer in the pretreatment composition is greater than 1.4 mass% and less than 10.5 mass% relative to the total mass of the pretreatment composition, and the content of the cross-linking agent relative to the total mass of the pretreatment composition is 0.1 mass% or more and less than 2.7 mass%. 10. The printing component of claim 9, wherein the cationic polymer is a group selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and epihalohydrin structural units. A polymer with at least any structural unit in it. 11. The printing component according to claim 9 or 10, wherein the cross-linking agent comprises a compound selected from the group consisting of a blocked isocyanate group-containing compound, a carbodiimide group-containing compound and an oxazoline group-containing compound. More than one cationic cross-linking agent in the group. 12. The printing component according to claim 11, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher. 13. The printing component of any one of claims 9 to 12, wherein the pretreatment composition has a surface tension of 35 mN/m to 60 mN/m at 25°C. 14. The printing component according to any one of claims 9 to 13, wherein the polyurethane resin contains at least any one selected from the group consisting of polyether polyurethane resin and polycarbonate polyurethane resin. 15. The printing component according to any one of claims 9 to 14, wherein the polyurethane resin has a glass transition temperature of 0°C or lower. 16. The printing assembly of any one of claims 9 to 15, wherein the aqueous white ink composition further contains a base. 17. The printing component according to any one of claims 9 to 16, further comprising an aqueous ink composition containing water, a pigment, and a polymer dispersant. 18. The printing component according to claim 17, wherein the polymer dispersant is selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1) at least two polymers constituting monomers; The monomer A: a monomer in which R in the formula (1) is a hydrogen atom; The monomer B: a monomer in which R in the formula (1) is a C1-C4 alkyl group; The monomer C: a monomer in which R in the formula (1) is an aryl group or an aryl C1-C4 alkyl group. 19. The printing component according to claim 17 or 18, wherein the aqueous ink composition further contains at least any one selected from the group consisting of polyurethane resin, styrene-butadiene resin and acrylic resin. . 20. An inkjet printing and dyeing method, which includes: A pretreatment process of coating the fabric with the pretreatment composition contained in the printing assembly according to any one of claims 9 to 19 to form a wet precoat layer; Without drying the fabric after the pretreatment process, the printing component according to any one of claims 9 to 19 is sprayed onto part or all of the wet pre-coat layer using an inkjet method. The process of forming an image using an aqueous white ink composition. 21. An inkjet printing and dyeing method, which includes: A pretreatment process of coating the fabric with the pretreatment composition contained in the printing assembly according to any one of claims 9 to 19 to form a wet precoat layer; Without drying the fabric after the pretreatment process, the printing component according to any one of claims 9 to 19 is sprayed onto a part or all of the wet precoat layer using an inkjet method. Process of forming an image using an aqueous white ink composition: The aqueous ink contained in the printing unit according to any one of claims 17 to 19 is ejected by an inkjet method to a part or all of the area where the image is formed by ejecting the aqueous white ink composition. The process of composition to form an image. 22. The inkjet printing method according to claim 20 or 21, wherein the fabric is polyester or a blend containing polyester. 23. The inkjet printing method according to claim 22, further comprising a step of drying the fabric on which the image is formed at 130° C. or lower after the step of applying the aqueous ink composition. 24. The inkjet printing method according to any one of claims 20 or 21, wherein the fabric is cotton or a blend containing cotton. 25. The inkjet printing method according to claim 24, further comprising a pressurizing step of applying pressure to the area where the wet precoat layer is formed after the pretreatment step. 26. An inkjet printing and dyeing method, which is an inkjet printing and dyeing method that uses a pretreatment composition containing water, a cationic polymer, a cross-linking agent, and at least one aqueous ink composition to form an image on a fabric; wherein, The method includes: a pretreatment process of coating the pretreatment composition on the fabric to form a wet precoat layer; and without drying the fabric after the pretreatment step, applying the at least one aqueous ink composition to the wet precoat area, and The coating amount per unit area of the pretreatment composition of the fabric is greater than 0.035g/cm ² and less than 0.070g/cm ² , and the content of the cationic polymer in the pretreatment composition is relative to the pretreatment The total mass of the composition is greater than 1.4 mass% and less than 10.5 mass%, the content of the cross-linking agent is 0.1 mass% or more and less than 2.7 mass% relative to the total mass of the pretreatment composition, and the aqueous ink composition contains water , pigments, resin emulsions, water-soluble organic solvents and surfactants. 27. The inkjet printing method according to claim 26, wherein the resin emulsion contains at least any one selected from the group consisting of polyurethane resin, styrene-butadiene resin and acrylic resin. 28. The inkjet printing method according to claim 26 or 27, wherein the aqueous ink composition further contains a polymer dispersant. 29. The inkjet printing method according to claim 28, wherein the polymer dispersant is selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1) A polymer containing at least two constituent monomers; The monomer A: a monomer in which R in the formula (1) is a hydrogen atom; The monomer B: a monomer in which R in the formula (1) is a C1-C4 alkyl group; The monomer C: a monomer in which R in the formula (1) is an aryl group or an aryl C1-C4 alkyl group. 30. The inkjet printing method according to any one of claims 26 to 29, wherein the pigment is a white pigment. 31. The inkjet printing method according to any one of claims 27 to 30, wherein the polyurethane resin contains at least any one selected from the group consisting of polyether polyurethane resin and polycarbonate polyurethane resin. kind. 32. The inkjet printing method according to any one of claims 26 to 31, wherein the cationic polymer is selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units and cyclic A polymer of at least any structural unit in the group consisting of oxyhalohydrin structural units. 33. The inkjet printing method according to any one of claims 26 to 32, wherein the cross-linking agent comprises a compound selected from the group consisting of a blocked isocyanate group-containing compound, a carbodiimide group-containing compound, and an oxonium-containing compound. One or more cationic cross-linking agents in the group consisting of oxazoline-based compounds. 34. The inkjet printing method according to claim 33, wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher. 35. The inkjet printing method according to any one of claims 26 to 34, wherein the surface tension of the pretreatment composition at 25°C is 35mN/m˜60mN/m. 36. The inkjet printing method according to any one of claims 26 to 35, wherein the fabric is polyester or a polyester-containing blend. 37. The inkjet printing method according to claim 36, further comprising a step of drying the fabric on which the image is formed at 130°C or lower after the step of applying the aqueous ink composition. 38. The inkjet printing method according to any one of claims 26 to 35, wherein the fabric is cotton or a blend containing cotton. 39. The inkjet printing method according to any one of claims 26 to 38, further comprising a pressurizing step of applying pressure to the area where the wet precoat layer is formed after the pretreatment step.