JP7155564B2 - Treatment liquid composition, ink set, fabric and inkjet printing method - Google Patents

Description

The present invention relates to a treatment liquid composition, an ink set, a fabric, and an inkjet textile printing method.

The inkjet recording method is a method of recording by ejecting droplets of ink from fine nozzles and depositing them on a recording medium. This method is characterized in that high-resolution, high-quality images can be recorded at high speed with a relatively inexpensive device. In the inkjet recording method, there are a great many factors to consider, including the properties of the ink to be used, the stability in recording, and the quality of the resulting image, and extensive research is being conducted on various compositions to be used.

Moreover, dyeing (textile printing) of fabrics and the like is also performed using an inkjet recording method. Conventionally, screen textile printing, roller textile printing, etc. have been used as textile printing methods for fabrics (woven fabrics and non-woven fabrics). is advantageous, so various studies have been made.

So-called pigment printing, in which an ink composition is mixed with a pigment and a fixing resin to print a fabric, has also been studied. In the case of pigment printing, it is important to physically fix the pigment to the fibers of the fabric.

In Patent Document 1, in pigment textile printing, a treatment liquid containing a polyvalent metal salt or the like, which is called a reaction liquid or a pretreatment liquid, is attached to the fabric before the ink composition is attached to the fabric, thereby improving the color development of the image. Attempts to improve are disclosed.

JP 2015-083629 A

In pigment printing, the use of a pretreatment liquid containing a polyvalent metal salt reacts with the ink composition to quickly fix the coloring material, thereby preventing the ink composition from permeating into the fabric and enhancing the color developability. can be expected. However, in such a technique, as a result of progress in aggregation of pigments, graininess may occur in the image, and graininess may occur in the image particularly in an area where the amount of ink applied is small. One of the objects of the present invention is to provide a treatment liquid composition, an ink set, and an inkjet textile printing method capable of improving the granularity of an image formed on a fabric by the textile printing ink composition, and To provide a fabric capable of forming an image with good graininess.

[Application Example 1] One aspect of the treatment liquid composition according to the present invention is
In textile printing, a treatment liquid composition used by adhering to a fabric,
a cationic compound;
one or more selected from an anionic compound represented by the following general formula (1) as an emulsifier and a nonionic compound represented by the following general formula (2);
water and,
contains

R ¹ -OX-A (1)
(In general formula (1),
R ¹ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms,
X is a polyoxyethylene skeleton or a polyoxypropylene skeleton,
A represents —SO ₃ M, —PO ₃ HM, or —CH ₂ COOM;
M represents an alkali metal, ammonium or alkanolamine. )
R ⁴ —O—X—H (2)
(In general formula (2),
R ⁴ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms,
X is a polyoxyethylene skeleton or a polyoxypropylene skeleton. )

[Application Example 2] In Application Example 1,
The HLB value of the nonionic compound represented by the general formula (2) may be 12 or more.

[Application Example 3] In Application Example 1 or Application Example 2,
The treatment liquid composition may be used for inkjet pigment printing.

[Application Example 4] In any one of Application Examples 1 to 3,
The fabric may be polyester.

[Application Example 5] In any one of Application Examples 1 to 4,
Further, it may contain resin particles.

[Application Example 6] In any one of Application Examples 1 to 5,
A content of the emulsifier may be 0.3% by mass or more and 1.0% by mass or less with respect to the total mass of the treatment liquid composition.

[Application Example 7] In any one of Application Examples 1 to 6,
The content of the cationic compound may be 10 or more and 100 or less in mass ratio with respect to the content of the emulsifier.

[Application Example 8] In any one of Application Examples 1 to 7,
The cationic compound may be a polyvalent metal salt.

[Application Example 9] In one aspect of the ink set according to the present invention,
the treatment liquid composition according to any one of Application Examples 1 to 8;
a textile printing ink composition containing a coloring material, resin particles, and water;
including.

[Application Example 10] In Application Example 9,
The coloring material may be a pigment, and the textile printing ink composition may be an inkjet pigment textile printing ink composition.

[Application Example 11] One aspect of the inkjet textile printing method according to the present invention is
A step of applying the treatment liquid composition according to any one of Application Examples 1 to 8 to a fabric is provided.

[Application Example 12] One aspect of the inkjet textile printing method according to the present invention is
A step of applying an inkjet pigment textile printing ink composition to the region to which the treatment liquid composition according to any one of Application Examples 1 to 8 has been applied.

[Application Example 13] One aspect of the fabric according to the present invention is
The treatment liquid composition according to any one of Application Examples 1 to 8 adheres thereto.

Several embodiments of the present invention are described below. The embodiments described below describe examples of the present invention. The present invention is by no means limited to the following embodiments, and includes various modifications implemented within the scope of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

1. Treatment Liquid Composition The treatment liquid composition according to the present embodiment is used by adhering it to a fabric in textile printing. The treatment liquid composition of the present embodiment is selected from a cationic compound, an anionic compound represented by the following general formula (1) as an emulsifier, and a nonionic compound represented by the following general formula (2). and water.

1.1. The material constituting the fabric is not particularly limited, and examples include natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, and biodegradable materials such as polylactic acid. fibers and the like, and mixed fibers of these may also be used. As the fabric, the above fibers may be in any form such as woven fabric, knitted fabric, or non-woven fabric. Among these, the fabric used in the present embodiment is more preferably made of fibers containing polyester (polyester fabric). By using such a fabric, the excellent effects of the treatment liquid composition of the present embodiment can be obtained more remarkably.

In addition, the basis weight of the fabric used in this embodiment is 1.0 oz or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, and even more preferably. is in the range of 4.0 oz or more and 7.0 oz or less. If the fabric has a basis weight within such a range, the cationic compound can be appropriately arranged when the treatment liquid composition is applied. In other words, if the basis weight of the fabric is within this range, better textile printing can be performed.

1.2. Water The treatment liquid composition according to this embodiment contains water. The treatment liquid composition is preferably an aqueous treatment liquid. Aqueous systems are compositions that contain water as one of the primary solvent components. Water may be included as a main solvent component of the treatment liquid composition, and is a component that evaporates and scatters upon drying. The water is preferably pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water from which ionic impurities are removed as much as possible. Moreover, it is preferable to use water sterilized by ultraviolet irradiation, addition of hydrogen peroxide, or the like, since the generation of mold and bacteria can be suppressed when the composition is stored for a long period of time. The water content is preferably 45% by mass or more, more preferably 50% by mass or more and 98% by mass or less, and still more preferably 55% by mass or more and 95% by mass or less with respect to the total amount of the treatment liquid composition. .

1.3. Cationic Compound The treatment liquid composition of the present embodiment contains a cationic compound. The cationic compound has the effect of aggregating the coloring material and resin particles by reacting with components such as the coloring material contained in the textile printing ink composition and the resin particles contained in the textile printing ink composition. However, the degree of aggregation of the pigment and resin particles by the cationic compound varies depending on the types of the cationic compound, colorant, and resin particles, and can be adjusted. In addition, the cationic compound reacts with the coloring material and resin particles contained in the textile printing ink composition, thereby aggregating the coloring material and resin particles. Such aggregation can, for example, enhance the color development of the coloring material, enhance the fixability of the resin particles, and/or increase the viscosity of the ink composition.

Examples of cationic compounds include, but are not limited to, metal salts, inorganic acids, organic acids, cationic compounds, and the like. Cationic compounds include cationic resins (cationic polymers), cationic interfaces, An activator or the like can be used. Among these, polyvalent metal salts and cationic resins are preferred as cationic compounds. Furthermore, it is particularly preferable to use a polyvalent metal salt as the cationic compound. Moreover, a cationic compound can also use multiple types together.

A polyvalent metal salt is a compound composed of a divalent or higher valent metal ion and an anion. Examples of divalent or higher metal ions include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. Among the metal ions constituting these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferable from the viewpoint of excellent cohesion of the components of the ink composition. Moreover, when the polyvalent metal salt is a magnesium salt or a calcium salt, the stability of the treatment liquid composition is improved. Although polyvalent metal salts generate not only cations but also anions upon hydration, they are treated as "cationic compounds" in this specification.

Anions (counter ions of polyvalent metals) constituting polyvalent metal salts are inorganic ions or organic ions. Polyvalent metal salts are composed of inorganic ions or organic ions and polyvalent metals. Examples of such inorganic ions include chloride ions, bromide ions, iodine ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of organic ions include organic acid ions, such as carboxylate ions.

Specific examples of polyvalent metal salts include calcium carbonate such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, aluminum acetate and the like. These polyvalent metal salts may be used singly or in combination of two or more. Among these, at least one of calcium nitrate and calcium chloride is preferable because sufficient solubility in water can be ensured and traces left by the treatment liquid composition are reduced (marks are less noticeable), and calcium chloride is preferable. more preferred. These polyvalent metal salts may have water of hydration in the raw material form.

Examples of cationic compounds other than polyvalent metal salts include monovalent metal salts such as sodium salts and potassium salts. Examples include sodium sulfate and potassium sulfate. Examples of organic acids as cationic compounds include poly(meth)acrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, Tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, or derivatives of these compounds, or these Preferred examples include salts. An organic acid may be used individually by 1 type, and may use 2 or more types together. Salts of organic acids that are metal salts are included in the above metal salts.

Suitable examples of inorganic acids as cationic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and salts thereof. An inorganic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of cationic resins (cationic polymers) include cationic urethane-based resins, cationic olefin-based resins, and cationic amine-based resins.

As the cationic urethane-based resin, a known one can be appropriately selected and used. As the cationic urethane resin, commercially available products can be used, for example, Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name , manufactured by Dainippon Ink and Chemicals Co., Ltd.), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.) and the like can be used.

The cationic olefin resin has an olefin such as ethylene, propylene, or the like in its structural skeleton, and known resins can be appropriately selected and used. Moreover, the cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

As the cationic amine-based resin (cationic polymer), any one having an amino group in the structure can be used, and known ones can be appropriately selected and used. Examples include polyamine resins, polyamide resins, polyallylamine resins, and the like. A polyamine resin is a resin having an amino group in the main skeleton of the resin. A polyamide resin is a resin having an amide group in the main skeleton of the resin. A polyallylamine resin is a resin having a structure derived from an allyl group in the main skeleton of the resin.

Polyallylamine resins include, for example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride/diallylamine hydrochloride copolymer, allylamine acetate/diallylamine acetate copolymer, allylamine acetate/diallylamine acetate copolymer, allylamine hydrochloride/dimethyl allylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallyl methylethylammonium ethylsulfate/sulfur dioxide copolymer, methyldiallylamine hydrochloride/sulfur dioxide copolymer, diallyldimethylammonium chloride/sulfur dioxide copolymer, diallyldimethylammonium chloride/acrylamide copolymer and the like. Commercially available products can be used as such cationic allylamine resins, such as 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 (trade name, manufactured by Nittobo Medical), Hymo Neo-600, Hymolock Q-101, Q-311 , Q-501, Himax SC-505, SC-505 (trade name, manufactured by Hymo Co., Ltd.) and the like can be used.

In addition, as a cationic polyamine resin, Senka Co., Ltd. Unisense KHE103L (hexamethylenediamine / epichlorohydrin resin, 1% aqueous solution pH about 5.0, viscosity 20 to 50 (mPa s), solid content concentration 50 mass% aqueous solution), Unisense KHE104L (dimethylamine/epichlorohydrin resin, 1% aqueous solution pH of about 7.0, viscosity 1 to 10 (mPa s), solid content concentration 20% by mass aqueous solution). .

Cationic surfactants include, for example, primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, Quaternary alkylammonium salts, alkylpyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts and the like. Specifically, for example, hydrochlorides and acetates of laurylamine, coconut amine, rosinamine, etc., lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammonium ethyl sulfate, Dimethylethyloctylammonium ethyl sulfate, trimethyllaurylammonium hydrochloride, cetylpyridinium chloride, cetylpyridinium bromide, dihydroxyethyllaurylamine, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylammonium chloride, hexadecyldimethylammonium chloride , octadecyldimethylammonium chloride and the like.

These cationic compounds may be used in combination. Among these cationic compounds, polyvalent metal salts have better aggregating action, so that images of higher quality (especially good color development) can be formed.

The total content of the cationic compounds in the treatment liquid composition is, for example, 0.1% by mass or more and 20% by mass or less, or 0.5% by mass or more and 15% by mass, relative to the total mass of the treatment liquid composition. % or less, more preferably 2% by mass or more and 15% by mass or less. Even when the cationic compound is supplied in the form of a solution or a dispersion, the solid content is preferably within the above range. When the content of the cationic compound is 0.1% by mass or more, the ability of the cationic compound to aggregate the components contained in the textile printing ink composition is sufficiently obtained. Further, when the content of the cationic compound is 30% by mass or less, the solubility and dispersibility of the cationic compound in the treatment liquid composition are improved, and the storage stability and the like of the treatment liquid composition are improved. can improve.

1.4. Emulsifier The treatment liquid composition of the present embodiment contains, as an emulsifier, one or more selected from an anionic compound having a specific structure and a nonionic compound having a specific structure.

1.4.1. Anionic Compound The anionic compound that can be contained in the treatment liquid composition has a structure represented by the following general formula (1).

R ¹ -OX-A (1)
(In the general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, X represents a polyoxyethylene skeleton or a polyoxypropylene skeleton, A is —SO ₃ M, —PO ₃ HM or —CH ₂ COOM, and M represents an alkali metal, ammonium, or alkanolamine.)

Among the compounds having the structure represented by the general formula (1), those having the structure represented by the following general formula (1-1) are also preferable.
R ¹ —O—(CHR ² —CHR ³ —O) _n —A (1-1)
(In general formula (1-1), R ¹ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, R ² and R ³ each independently represent hydrogen or a methyl group, and R ² and One of R ³ is hydrogen, A represents —SO ₃ M, —PO ₃ HM, or —CH ₂ COOM, M represents an alkali metal, ammonium or alkanolamine, n is 2 or more and 20 represents the following integers.)

In the compound represented by the general formula (1) and the anionic compound represented by the general formula (1-1), one end of the condensed chain of ethylene oxide or propylene oxide is a monoalkyl ether, and the other end is an acid. It has become salt. In such an anionic compound, mainly the anionic group (acid) and the condensed chain portion are hydrophilic, and mainly the alkyl group (R ¹ ) of the alkyl ether portion is hydrophobic. This makes it possible to exhibit activity as an emulsifier.

In the compound represented by the general formula (1) and the compound represented by the general formula (1-1), since R ¹ has 16 or more carbon atoms, it has sufficient hydrophobicity and can function as an emulsifier. Conceivable. Moreover, it is more preferable that R ¹ has 18 or more carbon atoms. The upper limit of the number of carbon atoms is preferably 20 or less.

By using such a compound, image quality problems such as image graininess and occurrence of wind ripples can be satisfactorily improved. This is presumed to be due to the fact that the above emulsifier stabilizes the dispersion system in the ink and suitably suppresses the reactivity with the cationic compound. Pigment printing inks have good color development and abrasion resistance by reacting and aggregating the resin, which is a dispersion system in the ink, with cationic compounds. The particles may clump together in advance, resulting in graininess in the image and wind ripples. And when the ink is applied at a low duty, this tendency is perceived as more pronounced. By containing the above-mentioned emulsifier, the reaction between the dispersion system in the ink and the cationic compound is suitably suppressed, and the graininess of the image and the occurrence of wind ripples are suitably suppressed by sufficiently spreading and spreading. It is speculated that

By reducing the content of the cationic compound, the reactivity between the dispersion system and the cationic compound in the ink does not change, and the content of the cationic compound improves graininess while maintaining good color development. It is difficult to

1.4.2. Nonionic compound and its HLB
A nonionic compound that can be contained in the treatment liquid composition has a structure represented by the following general formula (2).

R ⁴ —O—X—H (2)
(In general formula (2), R ⁴ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, and X represents a polyoxyethylene skeleton or a polyoxypropylene skeleton.)

Among the compounds having the structure represented by the general formula (2), those having the structure represented by the following general formula (2-1) are also preferred.
R ⁴ —O—(CHR ⁵ —CHR ⁶ —O) _m —H (2-1)
(In general formula (2-1), R ⁴ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, R ⁵ and R ⁶ each independently represent hydrogen or a methyl group, and R ⁵ and One of R6 is hydrogen, and m represents an integer of ² or more and 20 or less.)

In the compound represented by the general formula (2) and the nonionic compound represented by the general formula (2-1), one end of the condensed chain of ethylene oxide or propylene oxide is a monoalkyl ether, and the other end is a hydroxyl group. It has become. In such an anionic compound, the condensed chain portion is mainly hydrophilic, and the alkyl group (R ⁴ ) of the alkyl ether portion is mainly hydrophobic. This makes it possible to exhibit activity as an emulsifier.

In the compound represented by the general formula (2) and the compound represented by the general formula (2-1), since R ⁴ has 16 or more carbon atoms, it has sufficient hydrophobicity and can function as an emulsifier. Conceivable. Moreover, it is more preferable that R ⁴ has 18 or more carbon atoms. The upper limit of the number of carbon atoms is preferably 20 or less.

By using such a compound, image quality problems such as image graininess and occurrence of wind ripples can be satisfactorily improved. This is presumed to be due to the fact that the above emulsifier stabilizes the dispersion system in the ink and suitably suppresses the reactivity with the cationic compound. Pigment printing inks have good color development and abrasion resistance by reacting and aggregating the resin, which is a dispersion system in the ink, with cationic compounds. The particles may clump together in advance, resulting in graininess in the image and wind ripples. And when the ink is applied at a low duty, this tendency is perceived as more pronounced. By containing the above-mentioned emulsifier, the reaction between the dispersion system in the ink and the cationic compound is suitably suppressed, and the graininess of the image and the occurrence of wind ripples are suitably suppressed by sufficiently spreading and spreading. It is speculated that

By reducing the content of the cationic compound, the reactivity between the dispersion system and the cationic compound in the ink does not change, and the content of the cationic compound improves graininess while maintaining good color development. It is difficult to

Further, for the nonionic compound represented by the general formula (2), the HLB value can be defined, and when using the nonionic compound represented by the general formula (2), the HLB value is 12 It is preferably 13 or more, more preferably 13 or more, and even more preferably 15 or more. Here, the HLB value is the HLB value defined by the Griffin method.

1.4.3. Emulsifier content The total content of the emulsifier in the treatment liquid composition of the present embodiment is 0.10% by mass or more and 1.50% by mass or less, preferably 0.30% by mass, relative to the entire treatment liquid composition. % or more and 1.00 mass % or less, more preferably 0.50 mass % or more and 0.80 mass % or less. Within such a range, the treatment liquid composition can be appropriately permeated into the fabric, and the cationic compound can be appropriately arranged on the surface and inside of the fabric. Moreover, such an effect becomes particularly remarkable when the fibers constituting the fabric are highly hydrophobic. Such fabrics include polyester fabrics.

Moreover, the content of the emulsifier contained in the pretreatment composition of the present embodiment has a relatively preferable range with respect to the content of the cationic compound described above. The content of the emulsifier relative to the content of the cationic compound is preferably 0.083 or more and 0.154 or less, more preferably 0.010 or more and 0.154 or less, and more preferably 0.020. It is more preferable to be 0.100 or less. In other words, the content of the cationic compound is preferably 6.5 or more and 120 or less, more preferably 6.5 or more and 100 or less, and 10 or more and 100 or less in terms of mass ratio with respect to the emulsifier content. More preferably, it is 10 or more and 50 or less. When the relative contents of the cationic compound and the emulsifier are within this range, the arrangement of the cationic compound on the fabric to which the treatment liquid composition is applied can be more appropriately arranged, so that when the textile printing ink composition is applied, In addition, the components can be moderately aggregated, and the graininess of the image can be suppressed, and the color developability of the image can be easily improved.

1.5. Other Substances The treatment liquid composition may contain the following substances in addition to the water, cationic compound, and emulsifier described above.

1.5.1. Resin Particles The treatment liquid composition may contain resin particles. The resin particles can improve the adhesion of the treatment liquid composition adhered to the fabric. In addition, since it has a filling effect and makes it easier to retain the ink on the surface of the fabric, it becomes easier to obtain more suitable color development. Examples of such resin particles include urethane-based resins, acrylic resins, styrene-acrylic resins, fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, and epoxy-based resins. , vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate-based resins, and the like. These resin particles are often handled in the form of an emulsion, but may be in the form of powder. Also, the resin particles can be used singly or in combination of two or more.

When resin particles are contained in the treatment liquid composition, it is preferable to select resin particles of a type that is less likely to be aggregated by the cationic compound in the treatment liquid composition. When the treatment liquid composition contains resin particles, it is preferable to select and use non-aggregating resin particles among the resin particles exemplified below.

Urethane-based resin is a general term for resins having urethane bonds. In addition to urethane bonds, urethane-based resins include polyether-type urethane resins containing ether bonds in the main chain, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. You may As the urethane resin, commercially available products may be used, for example, Superflex 460, 460s, 840, E-4000 (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D -4080, D-4200, D-6300, D-6455 (trade name, manufactured by Dainichiseika Kogyo Co., Ltd.), Takelac WS-6021, W-512-A-6 (trade name, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) , Sancure 2710 (trade name, manufactured by LUBRIZOL), and Permalin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.) may be selected and used.

Acrylic resin is a general term for polymers obtained by polymerizing at least acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid ester as one component. Examples include resins obtained, copolymers of acrylic monomers and other monomers, and the like. Examples include acryl-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Further examples include copolymers with vinyl monomers such as styrene.

Acrylamide, acrylonitrile and the like can also be used as acrylic monomers. For resin emulsions made from acrylic resins, commercially available products may be used, such as FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Movinyl 952B, 718A (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). , Nipol LX852, LX874 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like.

In this specification, the acrylic resin may be a styrene-acrylic resin, which will be described later. Moreover, in this specification, the notation of (meth)acrylic means at least one of acrylic and methacrylic.

Styrene acrylic resins are copolymers obtained from styrene monomers and acrylic monomers, and include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-methacrylic acid-acrylic acid esters. copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers, and the like. Commercially available products may be used as styrene acrylic resins, such as Joncryl 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600. , 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (product name, manufactured by BASF), Movinyl 966A, 975N (product name, Japan (manufactured by Synthetic Chemical Industry Co., Ltd.), Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

Polyolefin-based resins have olefins such as ethylene, propylene, and butylene in their structural skeletons, and known resins can be appropriately selected and used. As the olefin resin, a commercially available product can be used, and for example, it may be selected from Arrowbase CB-1200, CD-1200 (trade name, manufactured by Unitika Ltd.) and the like.

In addition, the resin particles may be supplied in the form of an emulsion. Commercially available examples of such resin emulsions include Microgel E-1002 and E-5002 (manufactured by Nippon Paint Co., Ltd. under the trade name of styrene-acrylic resin emulsion), Boncoat 4001 (manufactured by DIC, trade name, acrylic resin emulsion), Boncoat 5454 (manufactured by DIC, trade name, styrene-acrylic resin emulsion), Polysol AM-710, AM-920, AM-2300, AP -4735, AT-860, PSASE-4210E (acrylic resin emulsion), POLYSOL AP-7020 (styrene/acrylic resin emulsion), POLYSOL SH-502 (vinyl acetate resin emulsion), POLYSOL AD-13, AD-2, AD -10, AD-96, AD-17, AD-70 (ethylene/vinyl acetate resin emulsion), Polysol PSASE-6010 (ethylene/vinyl acetate resin emulsion) (manufactured by Showa Denko Co., Ltd.), Polysol SAE1014 (trade name, Styrene-acrylic resin emulsion, manufactured by Zeon Corporation), Saibinol SK-200 (trade name, acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.), AE-120A (trade name, acrylic resin emulsion manufactured by JSR), AE373D (Etec carboxy-modified styrene/acrylic resin emulsion), Seikadyne 1900W (manufactured by Dainichiseika Kogyo Co., Ltd., ethylene/vinyl acetate resin emulsion), Vinyblan 2682 (acrylic resin emulsion), Vinyblan 2886 (vinyl acetate/acrylic resin) Emulsion), Vinyblan 5202 (Acrylic Acetate Resin Emulsion) (manufactured by Nissin Chemical Industry Co., Ltd.), Vinyblan 1008 (Vinyl Acetate Resin Emulsion), Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT- 8904, KT-0507 (product name manufactured by Unitika Co., Ltd., polyester resin emulsion), Hitec SN-2002 (product name manufactured by Toho Chemical Co., Ltd., polyester resin emulsion), Takelac W-6020, W-635, W-6061, W-605 , W-635, W-6021 (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane resin emulsion), Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), per Marine UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion), Sancure 2710 (manufactured by Nippon Lubrizol, urethane resin emulsion), NeoRez R-9660, R-9637, R-940 (Kusumoto Kasei Co., Ltd. company, urethane-based resin emulsion), ADEKA BONDITATER HUX-380, 290K (made by ADEKA Corporation, urethane-based resin emulsion), Movinyl 966A, Movinyl 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.), Joncryl 7100, 390, 711 , 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631 , 790, 780, 7610 (above, manufactured by BASF), NK Binder R-5HN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Hydran WLS-210 (non-crosslinkable polyurethane: manufactured by DIC Corporation), Joncryl 7610 (BASF company) and the like.

The glass transition temperature (Tg) of the resin particles is preferably −50° C. or higher and 200° C. or lower, more preferably 0° C. or higher and 150° C. or lower, and still more preferably 50° C. or higher and 100° C. or lower. When the glass transition temperature (Tg) of the resin particles is within the above range, clogging resistance tends to be more excellent when the treatment liquid composition is applied by an inkjet method. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Science Co., Ltd., according to JIS K7121 (method for measuring transition temperature of plastics).

The volume average particle diameter of the resin particles (before mixing the treatment liquid) is preferably 10 nm or more and 300 nm or less, more preferably 50 nm or more and 250 nm or less, still more preferably 100 nm or more and 230 nm or less, and particularly preferably 150 nm or more and 210 nm or less. When the volume average particle diameter is within the above range, it is preferable in terms of easy availability of desired resin particles and favorable characteristics of the resin particles. The volume-average particle size can be measured by a particle size distribution measuring apparatus based on a laser diffraction scattering method. Examples of the particle size distribution analyzer include a particle size distribution meter (for example, "Microtrac UPA" manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle.

When the treatment liquid composition of the present invention contains resin particles, the content of the resin particles is 0.1% by mass or more and 20% by mass or less, preferably 1% by mass, as a solid content with respect to the total mass of the treatment liquid composition. 15 mass % or less, more preferably 2 mass % or more and 10 mass % or less.

1.5.2. Surfactant The treatment liquid composition may contain a surfactant. The surfactant has the function of reducing the surface tension of the treatment liquid composition and improving the wettability with the fabric. Among surfactants, for example, acetylene glycol-based surfactants, silicone-based surfactants, and fluorine-based surfactants can be preferably used.

The acetylene glycol surfactant is not particularly limited, but for example, Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE- F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all trade names, manufactured by Air Products & Chemicals), Olphine B, Y, P, A, STG, SPC, E1004 , E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), Acetylenol E00, E00P, E40, E100 (all trade names, river (manufactured by Ken Fine Chemical Co., Ltd.).

The silicone-based surfactant is not particularly limited, but preferably includes a polysiloxane-based compound. Examples of the polysiloxane-based compound include, but are not particularly limited to, polyether-modified organosiloxane. Examples of commercial products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (trade names of BYK-Chemie Japan). ), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22 -4515, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer. Specific examples include BYK-3440 (manufactured by BYK-Chemie Japan), Surflon S-241, S-242, and S-243 (trade names, (manufactured by AGC Seimi Chemical Co., Ltd.), Futergent 215M (manufactured by Neos Co., Ltd.), and the like.

When the treatment liquid composition contains a surfactant, a plurality of surfactants may be contained. When the treatment liquid composition contains the surfactant, the content thereof is 0.1% by mass or more and 1.5% by mass or less, preferably 0.2% by mass or more, based on the total mass of the treatment liquid composition. 0% by mass or less, more preferably 0.3% by mass or more and 0.8% by mass or less.

1.5.3. Others The treatment liquid composition may contain ureas, amines, sugars, etc. as additives. Ureas include urea, ethylene urea, tetramethyl urea, thiourea, 1,3-dimethyl-2-imidazolidinone, etc., and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N , N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, etc.).

Amines include diethanolamine, triethanolamine, triisopropanolamine, and the like. Ureas and amines may function as pH adjusters.
Sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

The treatment liquid composition according to the present embodiment further contains components such as antiseptic/antifungal agents, antirust agents, chelating agents, viscosity modifiers, antioxidants, and antifungal agents, if necessary. good too.

1.5.4. Physical properties of the treatment liquid composition The treatment liquid composition according to the present embodiment has a surface tension of 40 mN/m or less, preferably 38 mN at 25°C, from the viewpoint of appropriate penetration and wetting spreadability into the fabric. /m or less, more preferably 35 mN/m or less, and even more preferably 30 mN/m or less. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) to confirm the surface tension when the platinum plate is wetted with the composition in an environment of 25 ° C. can do.

1.5.5. Techniques for Adhering the Treatment Liquid Composition to the Fabric Methods for applying the treatment liquid composition to the fabric include a method of ejecting and applying fine droplets by an inkjet method, and applying the treatment liquid composition to the fabric using various sprays. a method of coating the fabric by immersing it in the treatment liquid composition; and a method of applying the treatment liquid composition to the fabric with a brush, roller, or the like. mentioned.

When the treatment liquid composition is applied to the fabric by a method other than the inkjet method, the viscosity at 20° C. may be higher than that by the inkjet method. is preferably 1.5 mPa·s or more and 50 mPa·s or less, more preferably 1.5 mPa·s or more and 20 mPa·s or less. The viscosity was measured using a viscoelasticity tester MCR-300 (manufactured by Pysica) under an environment of 20°C, increasing the shear rate from 10 to 1000, and reading the viscosity at a shear rate of 200. can be measured.

In addition, the treatment liquid composition may be applied to the fabric by an inkjet method. 5 mPa·s or more and 5 mPa·s or less, and more preferably 1.5 mPa·s or more and 3.6 mPa·s or less.

1.6. Effects, Etc. The treatment liquid composition of the present embodiment contains a cationic compound, one or more selected from the above-described anionic compounds and nonionic compounds as an emulsifier, and water. As a result, when the ink composition is applied to the fabric to which the treatment liquid composition of the present embodiment is applied, the graininess of the image can be improved, and the color developability of the image can be improved. can be done. Such an effect is particularly remarkable in a region where the ink composition is applied in a small amount, and becomes remarkable when polyester is used for the fabric. One of the mechanisms for producing such an effect is that when the treatment liquid composition contains the specific emulsifier described above, the emulsifier stabilizes the dispersion system in the ink when the ink is applied, and the cationic compound It is presumed that this is because the reactivity with is suitably suppressed. Pigment printing inks have good color development and abrasion resistance by reacting and aggregating the resin, which is a dispersion system in the ink, with cationic compounds. Agglomerate before, resulting in graininess in the image. And when the ink is applied at a low duty, this tendency is perceived as more pronounced. It is presumed that the inclusion of a specific emulsifier suitably suppresses the reaction between the dispersion system in the ink and the cationic compound, and the sufficient wetting and spreading of the ink contributes to the favorable graininess of the image.

In addition, by blending an emulsifier in the treatment liquid composition, when the treatment liquid composition permeates the fabric or diffuses in the fabric, the association of the cationic compound is suppressed, and the cationic compound is dispersed on the surface of the fabric. It is thought that this is also due to the fact that they can be appropriately and uniformly arranged inside and inside.

1.7. Fabric Adhered with Treatment Liquid Composition A fabric obtained by adhering the above-described treatment liquid composition to the above-described fabric can form an image with good graininess when used with the textile printing ink composition attached. The fabric to which the treatment liquid composition of the present embodiment has been applied has graininess by adhering the textile printing ink composition to the fabric, whether it is in a dry state or in a non-dry state. , an image with good color development can be formed. Therefore, as the aspect of the fabric to which the treatment liquid composition of the present embodiment is attached, there are aspects of the fabric to which the treatment liquid composition is attached and dried, and the fabric to which the treatment liquid composition is attached and before drying. exist. The former can be used, for example, for applying the textile ink composition by an inkjet method. The latter corresponds to, for example, a state before the treatment liquid composition is applied by the inkjet method and dried, and can be used for applications in which the textile printing ink composition is applied by the inkjet method.

2. Ink Set The ink set of the present embodiment includes the treatment liquid composition described above and the textile printing ink composition described below.

2.1. Textile Ink Composition The textile ink composition contains a colorant, resin particles, and water.

2.1.1. Colorant The textile printing ink composition of the present embodiment contains a colorant. The textile printing ink composition according to the present embodiment can be used as a colored textile printing ink composition by containing a coloring material. At least one of pigments and dyes can be used as the coloring material.

(pigment)
By using a pigment as a coloring material, the lightfastness of the textile ink composition and the printed material can be improved. As the pigment, both inorganic pigments and organic pigments can be used. Pigments include, for example, color pigments such as cyan, yellow, magenta, and black, and special color pigments such as white pigments and luster pigments.

Examples of organic pigments include quinacridone-based pigments, quinacridone-quinone-based pigments, dioxane-based pigments, dioxazine-based pigments, phthalocyanine-based pigments, anthrapyrimidine-based pigments, anthanthrone-based pigments, indanthrone-based pigments, flavanthrone-based pigments, and perylene-based pigments. , diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, thioindigo pigments, isoindolinone pigments, azomethine pigments, dye chelates, dye lakes, Examples include nitro-based pigments, nitroso-based pigments, aniline black, and azo-based pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments.

Specific examples of organic pigments include the following.
As a cyan pigment, C.I. I. Pigment Blue 1, 2, 3, 15:3, 15:4, 16, 22, 60, etc.; C.I. I. Bat Blue 4, 60 and the like, preferably C.I. I. Pigment Blue 15:3, 15:4, and 60, either singly or as a mixture of two or more.

As a magenta pigment, C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, C.I. I. pigment violet 19, preferably C.I. I. Pigment Red 122, 202 and 209, C.I. I. Pigment Violet 19, either alone or in a mixture of two or more.

As a yellow pigment, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, 185, etc., preferably C.I. I. Pigment Yellow 74, 109, 110, 128, and 138, either singly or as a mixture of two or more.

As an orange pigment, C.I. I. Pigment Orange 36 or 43 or mixtures thereof.

As a green pigment, C.I. I. Pigment Green 7 or 36 or mixtures thereof.

Examples of black pigments include furnace black, lamp black, acetylene black, channel black (C.I. Pigment Black 7), commercial products such as No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No2200B, etc. (trade name, manufactured by Mitsubishi Chemical Corporation), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, special Black 6, 5, 4A, 4, 250, etc. (trade name, manufactured by Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700, etc. (all trade names, manufactured by Columbia Carbon) , Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12, etc. (trade name, manufactured by Cabot). These carbon blacks may be used alone or as a mixture of two or more.

The luster pigment is not particularly limited as long as it can exhibit luster when attached to a fabric. Examples include aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and Examples include metal particles of one or more alloys (also referred to as metal pigments) selected from the group consisting of copper, and pearl pigments having pearl luster. Representative examples of pearl pigments include pigments having pearl luster and interference luster such as titanium dioxide-coated mica, fish scale foil, and bismuth oxide. Moreover, the bright pigment may be subjected to a surface treatment for suppressing reaction with water.

Moreover, metal compounds, such as a metal oxide, barium sulfate, and calcium carbonate, are mentioned as a white pigment. Examples of metal oxides include titanium dioxide, zinc oxide, silica, alumina, and magnesium oxide. Particles having a hollow structure may also be used as the white pigment.

The above pigments may be used singly or in combination of two or more. The pigment is preferably an organic pigment from the viewpoint of storage stability such as light resistance, weather resistance and gas resistance.

The volume-based average particle diameter (D50) of the pigment (also referred to as “volume average particle diameter”) (before mixing the treatment liquid) is preferably 10 nm or more and 200 nm or less, more preferably 30 nm or more and 170 nm or less, and 50 nm or more and 150 nm or less. It is more preferable, and 70 nm or more and 120 nm or less is particularly preferable. If the volume-average particle size is within this range, it is easy to obtain, and it is easy to obtain favorable characteristics. In addition, when the volume average particle diameter of the pigment is within the above range, the pigment particles are less likely to settle, the dispersion stability can be improved, and clogging of nozzles is less likely to occur when applied to an inkjet recording apparatus. can do. Further, if the volume average particle diameter of the pigment is within the above range, the color density of the image can be sufficiently satisfied.

The volume-average particle size of the pigment can be measured by a particle size distribution analyzer based on a laser diffraction scattering method. Examples of the particle size distribution analyzer include a particle size distribution meter (for example, "Microtrac UPA" manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle.

It is preferable that the pigment can be stably dispersed in the ink. For example, by modifying the surface of the pigment particles by oxidizing or sulfonating the pigment surface with ozone, hypochlorous acid, fuming sulfuric acid, etc., it may be used as a self-dispersing pigment, or with a resin dispersant. It may be used in a distributed manner.

Examples of resin dispersants include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer. , styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer , styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-maleic ester copolymer, vinyl acetate-croton acid copolymers, vinyl acetate-acrylic acid copolymers, and salts thereof. Among these, a copolymer of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and a polymer composed of a monomer having both a hydrophobic functional group and a hydrophilic functional group are preferable. As the form of the copolymer, any form of random copolymer, block copolymer, alternating copolymer and graft copolymer can be used.

(dye)
A dye may be used as the coloring material. As dyes, acid dyes, direct dyes, reactive dyes, and basic dyes can be used without particular limitation. Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. direct red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Direct Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned. These dyes may be used individually by 1 type, and may use 2 or more types together.

The total content of the coloring materials is preferably 1% by mass or more and 20% by mass or less with respect to the total mass (100% by mass) of the textile printing ink composition.

2.1.2. Resin Particles The textile printing ink composition contains resin particles. The resin particles have a function of fixing the coloring material of the textile printing ink composition adhered to the fabric. Examples of such resin particles include urethane-based resins, acrylic resins, styrene-acrylic resins, fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, and epoxy-based resins. , vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate-based resins, and the like. These resin particles are often handled in the form of an emulsion, but may be in the form of powder. Also, the resin particles can be used singly or in combination of two or more.

As the resin particles contained in the textile printing ink composition, it is preferable to select a type of resin particles that has an aggregating action due to the cationic compound in the treatment liquid composition adhered to the fabric.

2.1.3. Water The textile printing ink composition contains water. The textile ink composition is preferably water-based. Water is the same as described in the explanation of the treatment liquid composition.

2.1.4. Water-Soluble Organic Solvent The textile printing ink composition may contain a water-soluble organic solvent. One of the functions of the water-soluble organic solvent is to improve the wettability of the textile printing ink composition to the fabric and to enhance the moisturizing property of the textile printing ink composition. Examples of water-soluble organic solvents include esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, and polyhydric alcohols. Examples of nitrogen-containing solvents include cyclic amides and non-cyclic amides. Examples of non-cyclic amides include alkoxyalkylamides.

Esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Glycol monoacetates such as ether acetate, methoxybutyl acetate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate glycol diesters such as diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, and dipropylene glycol acetate propionate.

Alkylene glycol ethers may be monoethers or diethers of alkylene glycol, and alkyl ethers are preferred. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol. monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether and other alkylene glycol monoalkyl ethers, and ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, alkylene glycol dialkyl ethers such as tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dimethyl ether; be done.

Cyclic esters include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone , δ-hexanolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ - Cyclic esters (lactones) such as nonalactone, ε-nonalactone, ε-decanolactone, and compounds in which the hydrogen of the methylene group adjacent to the carbonyl group thereof is substituted with an alkyl group having 1 to 4 carbon atoms. can be done.

Alkoxyalkylamides include, for example, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy- N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n -butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-
n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N -diethylpropionamide, 3-iso-propoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3- Examples include tert-butoxy-N,N-methylethylpropionamide.

Cyclic amides include lactams such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, and pyrrolidones such as These are preferred from the viewpoint of promoting film formation of the resin particles, and 2-pyrrolidone is particularly preferred.

Polyhydric alcohols include 1,2-alkanediol (e.g., ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2- alkanediols such as hexanediol, 1,2-heptanediol and 1,2-octanediol), polyhydric alcohols other than 1,2-alkanediols (polyols) (e.g., diethylene glycol, dipropylene glycol, 1,3 -propanediol, 1,3-butanediol (alias: 1,3-butylene glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl- 1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl- 1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, trimethylolpropane, glycerin, etc.). be done.

Polyhydric alcohols can be divided into alkanediols and polyols. Alkanediols are diols of alkanes having 5 or more carbon atoms. The alkane preferably has 5 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms. 1,2-alkanediols are preferred.

Polyols are polyols of alkanes having 4 or less carbon atoms or intermolecular condensates of hydroxyl groups of polyols of alkanes having 4 or less carbon atoms. The alkane preferably has 2 to 3 carbon atoms. The number of hydroxyl groups in the molecule of the polyol is 2 or more, preferably 5 or less, more preferably 3 or less. When the polyols are the above intermolecular condensation products, the number of intermolecular condensations is 2 or more, preferably 4 or less, and more preferably 3 or less.

Alkanediols and polyols can function primarily as penetrating and/or moisturizing solvents. However, alkanediols tend to have strong properties as penetrating solvents, and polyols tend to have strong properties as moisturizing solvents.

When the textile printing ink composition contains a water-soluble organic solvent, it may be used alone or in combination of two or more. The total content of the water-soluble organic solvent relative to the total mass of the textile printing ink composition is, for example, 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 45% by mass or less, and 15% by mass or more and 40% by mass. % by mass or less is more preferable, and 20% by mass or more and 30% by mass or less is even more preferable. When the content of the water-soluble organic solvent is within the above range, the balance between wet spreadability and drying property is further improved, and high-quality images can be easily formed.

2.1.5. Other Components The textile printing ink composition may contain ureas, amines, sugars and the like as additives. In addition, the textile ink composition further contains components such as a chelating agent, a pH adjuster, an antiseptic/antifungal agent, an antirust agent, a viscosity adjuster, an antioxidant, and an antifungal agent, if necessary. may

The chelating agent includes, for example, ethylenediaminetetraacetate (EDTA), nitrilotriacetate, hexametaphosphate, pyrophosphate, or metaphosphate of ethylenediamine.

Examples of preservatives include Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, and Proxel TN (all manufactured by Lonza).

Examples of pH adjusters include morpholines, piperazines, and aminoalcohols such as triethanolamine.

2.2. Physical Properties of Textile Ink Composition The textile ink composition according to the present embodiment has a surface tension of 40 mN/m or less, preferably 38 mN at 25° C., from the viewpoint of appropriate penetration into fabric and wet spreadability. /m or less, more preferably 35 mN/m or less, and even more preferably 30 mN/m or less.

2.3. Method of Adhering the Textile Ink Composition to the Fabric As a method of adhering the textile ink composition to the fabric, there is a method of ejecting and applying fine droplets by an inkjet method. In this case, the viscosity at 20° C. is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 5 mPa·s or less, and 1.5 mPa·s or more and 3.5 mPa·s or more. It is more preferable to set it to 6 mPa·s or less. In this specification, when the textile printing ink composition contains a pigment and is applicable to the inkjet method, it may be referred to as an inkjet pigment textile printing ink composition.

3. Inkjet Textile Printing Method The inkjet textile printing method of the present embodiment includes a step of adhering the treatment liquid composition described above to a fabric. As already mentioned, the treatment liquid composition can be applied to the fabric by various methods, but is preferably applied by an inkjet method. An inkjet recording apparatus that can be used in the inkjet textile printing method will be described.

3.1. Ink Jet Recording Apparatus Both serial type and line type ink jet recording apparatuses can be used. These types of inkjet recording apparatuses are equipped with a recording head, and while changing the relative positional relationship between the fabric and the recording head, the treatment liquid composition and the textile printing ink composition are discharged from the nozzle holes of the recording head. A predetermined image can be formed by ejecting liquid droplets at a predetermined timing and in a predetermined volume (mass) to adhere the treatment liquid composition or the textile printing ink composition to the fabric.

For the inkjet recording apparatus used in this embodiment, for example, a known configuration such as a drying unit, a roll unit, and a winding device can be arbitrarily adopted. In addition, the inkjet recording apparatus includes a conveying means for conveying a cloth, an image layer forming means for recording an image using a treatment liquid composition or a textile printing ink composition, a drying means, an overall drying means for heating and blowing air on a recording surface, and the like. can have

The conveying means can be constituted by rollers, for example. The conveying means may have a plurality of rollers. The position and the number of conveying means to be provided are arbitrary as long as the fabric can be conveyed. The transport means may include paper feed rolls, paper feed trays, paper discharge rolls, paper discharge trays, various platens, and the like.

The image layer forming means ejects the treatment liquid composition or the textile printing ink composition of the present embodiment onto the recording surface of the fabric to record an image layer. The image layer forming means has a recording head having nozzles, and the recording head may be different for each composition, or a nozzle row may be assigned for each composition.

The drying means can be used for drying the image layer formed on the recording surface or removing volatile components on the recording medium. The drying means may be provided at any position, or may be provided in any number, taking into account the timing of the adhesion step, the transport path of the fabric, and the like. Examples of the image layer drying means include a method of applying heat to the fabric by platen heating, a method of blowing air onto the image on the recording medium, and a combination of these methods. Specifically, the means used in these methods may be forced air heating, radiant heating, conductive heating, high frequency drying, microwave drying, and the like.

3.2. Other Steps The inkjet textile printing method of the present embodiment may have a step of attaching the inkjet pigment textile printing ink composition to the fabric. The step of applying the textile ink composition to the fabric can be performed using the above-described inkjet recording apparatus.

In addition, the step of applying the inkjet pigment textile printing ink composition to the fabric may be included a plurality of times, and the order and number of steps are not limited, and can be appropriately performed as necessary. Also, the treatment liquid composition and the textile ink composition can be applied to the same area on the fabric with each other.

For example, if the step of applying the textile printing ink composition is performed after the step of applying the treatment liquid composition, and the textile printing ink composition is applied to the area of the fabric to which the treatment liquid composition has been applied, the treatment can be achieved. The cationic compound in the liquid composition can reliably act on the textile printing ink composition.

Further, the inkjet textile printing method of the present embodiment may appropriately include a step of heating the fabric. The step of heating the fabric can be performed using the drying means described above, for example, when an inkjet recording apparatus is used. In addition, it can be carried out not only by the inkjet recording apparatus, but also by any appropriate drying means. This allows the resulting image to dry and fix better, so that, for example, the print is ready for use. Although the temperature of the fabric in this case is not particularly limited, it can be set in consideration of the Tg of the resin component that constitutes the resin particles contained in the textile printing ink composition and the like. When considering the Tg of the resin component composing the resin particles, the temperature should be set to 5° C. or higher, preferably 10° C. or higher than the Tg of the resin component composing the resin particles.

More specifically, the temperature of the fabric reached by heating in the heating step is 30°C or higher and 120°C or lower, preferably 40°C or higher and 100°C or lower, and more preferably 50°C or higher and 80°C or lower. When the temperature of the fabric is within this range, the resin particles contained in the printed material can be formed into a film and flattened, and the resulting image can be dried and fixed more sufficiently.

The inkjet of the present embodiment can further include other steps as appropriate, and may include, for example, a step of applying clear ink to fabric.

4. EXAMPLES AND COMPARATIVE EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

4.1. Preparation of Printed Material Each component described in Examples and Reference Examples in Table 1 and Comparative Examples in Table 2 was placed in a container and mixed and stirred for 2 hours with a magnetic stirrer to thoroughly mix. After stirring for 1 hour, the treatment liquid composition of each example was obtained by filtering using a 5 μm PTFE membrane filter. The unit of numerical values in the table is % by mass. Concentrations of active ingredients (for example, in the case of resin particles, resin solid content concentration) are indicated for those described other than compound names.

The treatment liquid composition of each example was sufficiently soaked in a sponge roller, and the roller was placed on a polyester fabric (glimmer ACTIVE WEAR 3.5 oz interlock dry T-shirt 001 white) or cotton fabric (printstar heavy weight (white) 5). 0.6 oz) was rolled up and down and left and right 3 to 4 times to apply the treatment liquid composition as uniformly as possible.

The coating amount of the treatment liquid composition was about 20 g per area of A4 size. The fabric coated with the treatment liquid composition was heat-treated at 165° C. for 45 seconds with a heat press and dried.

Using a printer (SC-F200) manufactured by Seiko Epson Corporation, the fabric after drying is printed with a textile printing ink composition shown in Table 3 at a resolution of 1440 dpi × 1440 dpi and a coating amount of 200 mg / inch ² as 100% duty. did Further, printing was performed with a resolution of 1440 dpi×1440 dpi and a coating amount of 40 mg/inch ² at a duty of 20%. After the printing, heat treatment was performed again at 165° C. for 5 minutes in a conveyor oven (hot air drying method) to fix the printed material.

Substances other than compound names in Tables 1 and 2 are as follows.
Emulgen 350 (manufactured by Kao Corporation): Polyoxyethylene stearyl ether. R ⁴ in formula (2) has 18 carbon atoms. Also, HLB is 17.8.
Emulgen 420 (manufactured by Kao Corporation): polyoxyethylene oleyl ether. R ⁴ in formula (2) has 18 carbon atoms. Moreover, HLB is 13.6.
- Newcoal 1860 (manufactured by Nippon Nyukazai Co., Ltd.): Polyoxyethylene stearyl ether. R ⁴ in formula (2) has 18 carbon atoms. Also, the HLB value is 18.1.
- Newcol 1210 (manufactured by Nippon Nyukazai Co., Ltd.): Polyoxyethylene oleyl ether. R ⁴ in formula (2) has 18 carbon atoms. Also, the HLB value is 12.4.
- Newcole 1204 (Nippon Nyukazai Co., Ltd.): polyoxyethylene oleyl ether. R ⁴ in formula (2) has 18 carbon atoms. Also, the HLB value is 7.9.
- Latemul WX (manufactured by Kao Corporation): Sodium polyoxyethylene oleyl ether sulfate. R ¹ in formula (1) has 18 carbon atoms.
Emulgen 103 (manufactured by Kao Corporation): polyoxyethylene lauryl ether. HLB is 8.1.
- Newcol 1006 (manufactured by Nippon Nyukazai Co., Ltd.): Polyoxyethylene 2-ethylhexyl ether. The HLB value is 13.4.
・Newcol 1020 (manufactured by Nippon Nyukazai Co., Ltd.): Polyoxyethylene 2-ethylhexyl ether. The HLB value is 17.4.
Sanded EN (manufactured by Sanyo Chemical Industries, Ltd.): Sodium polyoxyethylene lauryl ether sulfate.
・ Latemul E-50 (manufactured by Kao Corporation): Sodium polyoxyethylene lauryl ether sulfate
.
- Vinyblan 1008 (manufactured by Nissin Chemical Industry Co., Ltd.): Vinyl acetate resin emulsion.
Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.): acetylenic surfactant.

Substances other than compound names in Table 3 are as follows.
- Cyan pigment dispersion C.I. I. Pigment Blue 15:3 20% by mass liquid; resin dispersant is Joncryl 611 (trade name: styrene acrylic resin manufactured by BASF Japan Ltd.) containing 4% by mass.
- Urethane resin emulsion (Takelac WS6021): (manufactured by Mitsui Chemicals, anionic urethane resin emulsion, self-emulsifying type, solid content concentration 30%)
· Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.): acetylenic surfactant · Proxel XL2: (manufactured by Lonza: preservative)

4.2. Evaluation of prints 4.2.1. Evaluation of graininess
For the high-duty and low-duty printed fabrics of each example, the degree of graininess of the image was visually observed, and the graininess was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
S: No rough feeling is observed in the entire area.
A: Slight roughness is observed in some areas, but the graininess is generally good.
B: Roughness is conspicuous in some regions, but within a practically acceptable range.
C: Grainy roughness is conspicuous over the entire area, and the quality poses a practical problem.

4.2.2. Evaluation of color development (high duty)
The OD value of the high-duty (100% duty) printed fabric of each example was measured with a colorimeter (trade name “Gretag Macbeth Spectrolino”, manufactured by X-RITE), and based on the obtained OD value, The color developability was evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.
SS: OD value is 1.45 or more.
S: OD value is 1.40 or more and less than 1.45.
A: The OD value is 1.35 or more and less than 1.40.
B: OD value is less than 1.35.

4.2.3. Evaluation of color development (low duty)
The OD value of the low-duty (20% duty) printed fabric of each example was measured with a colorimeter (trade name “Gretag Macbeth Spectrolino”, manufactured by X-RITE), and based on the obtained OD value, The color developability was evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.
SS: OD value is 0.29 or more.
S: OD value is 0.28 or more and less than 0.29.
A: OD value is 0.27 or more and less than 0.28.
B: OD value is less than 0.27.

4.3. Evaluation Results From the above results, the following was found.
A cationic compound, an anionic compound represented by the general formula (1) as an emulsifier, or one or more selected from a nonionic compound represented by the general formula (2), and water. All of the printed materials prepared using the treatment liquid compositions of Examples had good graininess and color development (density) at both high duty and low duty.

On the other hand, the treatment liquids of Comparative Examples 1 and 7 containing no emulsifier and Comparative Examples 2-6 containing an anionic compound that does not satisfy general formula (1) or a nonionic compound that does not satisfy general formula (2) All of the printed materials prepared using the composition were poor in graininess and color development (density) at low duty.

Comparing Reference Examples 3 and 16 and Comparative Examples 1 and 7, it was found that the treatment liquid composition of the present invention exhibited a higher effect when the target fabric was polyester rather than cotton.

From Reference Examples 1-4 and 1-6, it was found that when the blending amount of the nonionic compound represented by the general formula (2) was increased, the color development slightly decreased. This is because if too much of the nonionic compound represented by the general formula (2) is added, the textile ink composition tends to permeate the fabric in the depth direction, resulting in a decrease in the color density of the printed material. suggesting.

Further, from Examples 1-3 , it was found that the addition of resin particles further improved the color development. This is partly because the components of the treatment liquid composition tend to be localized on the surface side of the fabric due to the presence of the resin particles, thereby making it easier for the coloring material of the textile printing ink composition to stay on the surface side of the fabric. Conceivable.

The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same function, method, and result, or configurations that have the same purpose and effect). Moreover, the present invention includes configurations in which non-essential portions of the configurations described in the embodiments are replaced. In addition, the present invention includes a configuration that achieves the same effects or achieves the same purpose as the configurations described in the embodiments. In addition, the present invention includes configurations obtained by adding known techniques to the configurations described in the embodiments.

Claims (11)

In textile printing, a treatment liquid composition used by adhering to a fabric,
a polyvalent metal salt ;
one or more selected from an anionic compound represented by the following general formula (1) as an emulsifier and a nonionic compound represented by the following general formula (2);
water and,
contains
A treatment liquid composition containing resin particles made of a vinyl acetate resin .
R ¹ -OX-A (1)
(In general formula (1),
R ¹ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms,
X is a polyoxyethylene skeleton or a polyoxypropylene skeleton,
A represents —SO ₃ M, —PO ₃ HM, or —CH ₂ COOM;
M represents an alkali metal, ammonium or alkanolamine. )
R ⁴ —O—X—H (2)
(In general formula (2),
R ⁴ represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms,
X is a polyoxyethylene skeleton or a polyoxypropylene skeleton. ) In claim 1,
A treatment liquid composition, wherein the nonionic compound represented by the general formula (2) has an HLB value of 12 or more. In claim 1 or claim 2,
The treatment liquid composition is a treatment liquid composition used for inkjet pigment textile printing. In any one of claims 1 to 3,
A treatment liquid composition, wherein the fabric is polyester. In any one of claims 1 to 4 ,
The treatment liquid composition, wherein the content of the emulsifier is 0.3% by mass or more and 1.0% by mass or less with respect to the total mass of the treatment liquid composition. In any one of claims 1 to 5 ,
The treatment liquid composition, wherein the content of the cationic compound is 10 or more and 100 or less by mass with respect to the content of the emulsifier. The treatment liquid composition according to any one of claims 1 to 6 ;
a textile printing ink composition containing a coloring material, resin particles, and water;
ink set, including In claim 7 ,
An ink set wherein the coloring material is a pigment and the textile printing ink composition is an inkjet pigment textile printing ink composition. An inkjet textile printing method comprising a step of applying the treatment liquid composition according to any one of claims 1 to 6 to a fabric. An inkjet printing method comprising the step of applying an inkjet pigment printing ink composition to a region to which the treatment liquid composition according to any one of claims 1 to 6 has been applied. A fabric to which the treatment liquid composition according to any one of claims 1 to 6 is adhered.