JP2023008466A - Image formation set, image formation device, and image formation method - Google Patents

Abstract

To solve the problem that when an image is formed by imparting a pretreatment liquid to a fabric containing a synthetic resin, and imparting ink to a region where the pretreatment liquid of the fabric is imparted, color development property of the image can be improved, but fastness of the image is insufficient, and to solve the problem that decap property of ink deteriorates when fastness of the image intends to be improved.SOLUTION: An image formation set has a pretreatment liquid imparted to a fabric containing a synthetic fiber, and ink imparted to a region where the pretreatment liquid is imparted of the fabric, wherein the pretreatment liquid contains calcium chloride, the ink contains a water-soluble organic solvent, a pigment, and resin particles, the water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250°C or higher, a content of the water-soluble organic solvent is 25.0 mass% or more and 45.0 mass% or less with respect to the mass of the ink, and a content of the water-soluble organic solvent having a boiling point of 250°C or higher is 5.0 mass% or less and 20.0 mass% or less with respect to the mass of the ink.SELECTED DRAWING: None

Description

The present invention relates to an image forming set, an image forming apparatus, and an image forming method.

2. Description of the Related Art Inkjet printers are widely used in general households as digital signal output devices because they have the advantage of being able to easily form color prints on demand. In recent years, not only for home use, but also for slow permeable media such as coated paper, non-absorbent media such as plastic films, and fabric media such as woven fabrics and knitted fabrics, ink jet recording methods have achieved the same level of performance as conventional analog printing. There is a growing demand to obtain image quality.

For example, in the textile printing field, the so-called DTG (Direct to Garment) field, which prints directly on clothing such as T-shirts, is expanding year by year. Demand for inkjet recording systems capable of forming images with excellent color development properties on fabrics is increasing more and more due to trends such as active collaboration with fine art recognized in the textile field.

Unlike screen printing and other conventional textile printing, the textile printing method, in which ink containing pigments as colorants is used to create an image directly on the fabric, does not require the preparation, storage, cleaning, etc. of the printing plate. , it is suitable for small-lot, high-mix production, it does not include processes such as transfer, so it can be delivered in a short time, and it has excellent light resistance. is coming.

In recent years, there is an increasing need for image formation on fabrics containing synthetic fibers such as polyester materials. In addition, there is an increasing need for image formation not only on plain fabrics but also on fabrics that have already been colored by printing or the like. As for the image formation on colored fabric, there is a method of coating the fabric with white ink and landing color ink on it. Sufficient color developability can be imparted by the ink layer serving as a base for the color ink. Therefore, in the above image forming method, it is important for the white ink to cover the dark color of the fabric, and it is required to have a high degree of whiteness.

Patent Document 1 discloses a treatment liquid composition containing a cationic compound, an emulsifier, and water for the purpose of improving the graininess of an image formed by a textile printing ink composition.

In Patent Document 2, an ink jet printer is disclosed for the purpose of recording an image of sufficient density on a fabric without bleeding, and forming a clear image on the fabric for a long period of time without staining the white area even after washing. In an inkjet printing method for recording on a fabric by a method, a pretreatment liquid is applied to at least a part of the fabric prior to the recording, and after recording with ink, the fabric is washed, and the pretreatment liquid contains a divalent or higher metal salt and has a surface tension of 35 mN/m or less.

However, when an image is formed by applying a pretreatment liquid to a fabric containing synthetic fibers and applying ink to a region of the fabric to which the pretreatment liquid is applied, it is difficult to improve the color developability of the image. However, there is a problem that the fastness of the image is insufficient. Further, when an attempt is made to improve the fastness of the image, there is a problem that the decapping property of the ink is lowered.

The present invention provides an image forming set comprising a pretreatment liquid applied to a fabric containing synthetic fibers, and an ink applied to a region of the fabric to which the pretreatment liquid has been applied, The pretreatment liquid contains calcium chloride, the ink contains a water-soluble organic solvent, a pigment, and resin particles, and the water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250° C. or higher. , the content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink, and the content of the water-soluble organic solvent having a boiling point of 250°C or more is It relates to an image forming set characterized by containing 5.0% by mass or more and 20.0% by mass or less with respect to the mass of ink.

According to the present invention, when an image is formed by applying a pretreatment liquid to a fabric containing synthetic fibers and applying ink to a region of the fabric to which the pretreatment liquid has been applied, the image is colored. It is possible to provide an imaging set capable of improving the durability and fastness, and further improving the ink decap property.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus. FIG. 2 is a schematic diagram showing an example of a housing means.

An embodiment of the present invention will be described below.

<<Image forming set>>
The image forming set of the present invention has a pretreatment liquid and an ink, and if necessary, may have a fabric and other liquid compositions. Also, the number of pretreatment liquids and inks may be one or more.
The "image forming set" in the present disclosure may contain the pretreatment liquid and the ink in an independent state. For example, the pretreatment liquid containing means containing the pretreatment liquid and the ink It is not limited to the case where the ink containing means is manufactured and sold in an integrated state. For example, even if the pretreatment liquid containing means and the ink containing means are manufactured and sold independently, if the pretreatment liquid and the ink are assumed to be used together, or if the pretreatment liquid and the ink are used together. The image forming set includes the case where it is substantially induced to do so.
The “pretreatment liquid” in the present disclosure is applied to a fabric containing synthetic fibers, and by coming into contact with the ink that is applied later to the area to which the pretreatment liquid is applied, aggregates or increases in the ink. It is a viscous liquid composition.
The "ink" in the present disclosure is applied to the area of the fabric containing synthetic fibers to which the pretreatment liquid is applied, and when it comes into contact with the area to which the pretreatment liquid is applied, it aggregates or thickens to form an image. It is the liquid composition that forms. Ink colors include white ink and color ink. A “white ink” is an ink that forms a white image when applied to a fabric containing synthetic fibers. By forming a white image on a fabric containing synthetic fibers, the white ink functions as a base for a color image formed by color ink that is applied later to the area to which the white ink is applied, for example. It is possible to improve the color development of the image. In addition, "white" is a color commonly referred to as white, white, etc., and includes a slightly colored one. In addition, "color ink" is ink that forms a color image by being applied to a fabric containing synthetic fibers. In addition, from the viewpoint of improving the color developability, it is preferable to form a color image by applying the color ink to a region of the fabric containing the synthetic fiber to which the white ink has been applied. In addition, "color" represents a color that is not included in the above "white", and includes, for example, black, cyan, magenta, and yellow.
"Fabric" in the present disclosure refers to fibers in the form of woven fabrics, knitted fabrics, non-woven fabrics, and the like.

<Pretreatment liquid>
The pretreatment liquid contains calcium chloride, and if necessary, polyvalent metal salts other than calcium chloride (hereinafter also referred to as "other polyvalent metal salts"), water, organic solvents, resins, surfactants, etc. It is preferable to contain other components. In addition, it is preferable that the pretreatment liquid does not contain a coloring material in view of its use.

-calcium chloride-
Calcium chloride is a type of polyvalent metal salt, and when contained in the pretreatment liquid, it improves the color development and fastness of the image formed by the ink applied to the area to which the pretreatment liquid is applied. can be improved.

First, since the pretreatment liquid contains calcium chloride, the color development of the image formed by the ink later applied to the area of the fabric to which the pretreatment liquid has been applied (for example, when the ink is white ink The reason why the whiteness) is improved will be explained.
This is because when the calcium chloride contained in the pretreatment liquid applied to the fabric first comes into contact with the colorant contained in the ink applied later, an aggregate of the colorant is formed by the action of charge. This is because the coloring material is separated from the liquid phase to promote fixing to the surface of the fabric. By including calcium chloride in the pretreatment liquid, even if a medium with large voids such as fabric is used, the colorant can be retained on the surface of the fabric by forming a layer of aggregates, resulting in high color development. An image can be formed. In particular, when it is desired to apply ink to a fabric containing colored fibers and hide the color of the fabric with an image formed by the ink (specifically, when forming a base for a white image with white ink). In , it is preferable because a highly colored image can be formed and the color of the fabric can be more concealed. In addition, by forming an aggregate of the coloring material, it is possible to suppress beading that may occur when a fabric having low liquid absorbency is used, and to form a high-quality image. In addition, unlike a flocculant such as a cationic polymer, calcium chloride is a contact member such as a conveying member in the area to which the pretreatment liquid is applied during the period from the application of the pretreatment liquid to the fabric until the ink is applied. It is possible to suppress the pretreatment liquid from being transferred to the contact member even when the contact member is in contact with the contact member.

Next, the reason why the pretreatment liquid containing calcium chloride improves the fastness of the image formed by the ink later applied to the area of the fabric to which the pretreatment liquid has been applied will be described.
This is because calcium chloride is superior to other polyvalent metal salts in absorbing water-soluble organic solvents. Specifically, by applying a pretreatment liquid containing calcium chloride to the fabric, calcium chloride is arranged in the fabric, and then the area of the fabric to which the pretreatment liquid is applied is contacted with the ink applied. By doing so, the calcium chloride absorbs the water-soluble organic solvent contained in the ink. As a result, the content of the water-soluble organic solvent in the image formed by the ink is reduced, and as a result, the fastness of the image is improved and the stickiness of the image can be suppressed. In addition, the absorbability of the water-soluble organic solvent in the ink by calcium chloride is further improved by having a drying step between the application of the pretreatment liquid to the fabric and the application of the ink.
In the present disclosure, the term “fastness” refers to the extent to which an image is transferred to another image when the image formed by the ink is rubbed with another member. is judged to be excellent, and a large amount of transfer is judged to be inferior in fastness.

The content of calcium chloride is preferably 3.0% by mass or more and 20.0% by mass or less, more preferably 10.0% by mass or more and 15.0% by mass or less, relative to the mass of the pretreatment liquid. preferable. When the amount is 3.0% by mass or more and 20.0% by mass or less, the ability of the calcium chloride to absorb the water-soluble organic solvent is sufficiently exhibited, the fastness of the image is further improved, and the stickiness of the image is further suppressed. In addition, the aggregating ability of the coloring material due to calcium chloride is sufficiently exhibited, and the coloring property of the image is further improved.

-Other polyvalent metal salts-
Other polyvalent metal salts in the present disclosure represent polyvalent metal salts other than calcium chloride described above. Other polyvalent metal salts are contained in the pretreatment liquid, so that the color development of the image formed by the ink applied to the area to which the pretreatment liquid is applied (for example, when the ink is white ink, whiteness) can be improved.

The reason why the addition of the polyvalent metal salt to the pretreatment liquid improves the color developability of the image formed by the ink later applied to the area of the fabric to which the pretreatment liquid has been applied will be described.
This is because when the other polyvalent metal salt contained in the pretreatment liquid previously applied to the fabric comes into contact with the colorant contained in the ink applied later, the colorant aggregates due to the action of charge. is formed, and the colorant is separated from the liquid phase to promote fixing to the surface of the fabric. By adding another polyvalent metal salt to the pretreatment liquid, even if a medium with large voids such as a fabric is used, the colorant can be retained on the surface of the fabric by forming a layer of aggregates. A highly colored image can be formed. In particular, when it is desired to apply ink to a fabric containing colored fibers and hide the color of the fabric with an image formed by the ink (specifically, when forming a base for a white image with white ink). In , it is preferable because a highly colored image can be formed and the color of the fabric can be more concealed. In addition, by forming an aggregate of the coloring material, it is possible to suppress beading that may occur when a fabric having low liquid absorbency is used, and to form a high-quality image. In addition, unlike coagulants such as cationic polymers, other polyvalent metal salts are used in areas where the pretreatment liquid is applied, such as transport members, during the period from the application of the pretreatment liquid to the fabric until the ink is applied. Even if the contact members are in contact with each other, the pretreatment liquid can be prevented from being transferred to the contact members.

Examples of other polyvalent metal salts include salts such as titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, zinc compounds, and nickel compounds. be done. Among these, salts of calcium compounds, magnesium compounds, and nickel compounds are preferable, and alkaline earth metal salts of calcium compounds and magnesium compounds are more preferable, since they can effectively aggregate the pigment.

Examples of magnesium compounds include magnesium chloride, magnesium acetate, magnesium sulfate, magnesium nitrate, and magnesium silicate.
Examples of calcium compounds include calcium carbonate, calcium nitrate, calcium acetate, calcium sulfate, calcium silicate and the like.
Barium compounds include, for example, barium sulfate.
Examples of zinc compounds include zinc sulfide and zinc carbonate.
Examples of aluminum compounds include aluminum silicate and aluminum hydroxide.

-water-
As water, for example, ion-exchanged water, ultrafiltrated water, reverse osmosis water, pure water such as distilled water, and ultrapure water can be used.

The content of water is not particularly limited and can be appropriately selected according to the purpose. % by mass or less is preferable, and 20.0% by mass or more and 60.0% by mass or less is more preferable.

-Organic solvent-
Examples of organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.

Specific examples of organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2 ,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1, Polyhydric alcohols such as 3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. polyhydric alcohol alkyl ethers, ethylene glycol monophenyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1 Nitrogen-containing heterocyclic compounds such as ,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropion amides such as amides, 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol; mentioned.

The content of the organic solvent is not particularly limited and can be appropriately selected depending on the purpose. It is more preferably 70.0% by mass or less, and even more preferably 5.0% by mass or more and 50.0% by mass or less.

-resin-
Examples of resins include urethane resins, polyester resins, acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and the like. is mentioned.

The form of the resin in the pretreatment liquid is not particularly limited, but may be resin particles. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the purpose. More preferred. The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and can be appropriately selected according to the purpose. % or more and 20.0 mass % or less is more preferable.

-Other ingredients-
The pretreatment liquid may contain other components such as surfactants, antifoaming agents, antiseptic and antifungal agents, antirust agents, and pH adjusters.

--Surfactant--
Any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.

The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferred. Examples of silicone-based surfactants include side chain-modified polydimethylsiloxane, both-end-modified polydimethylsiloxane, single-end-modified polydimethylsiloxane, and side-chain both-end-modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.

Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of perfluoroalkylsulfonic acid compounds include perfluoroalkylsulfonic acids, perfluoroalkylsulfonates, and the like. Examples of perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. Examples of polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains include sulfuric acid ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in side chains, and polyoxyalkylene ether polymers having perfluoroalkyl ether groups in side chains. Examples thereof include salts of oxyalkylene ether polymers. Counter ions of salts in these _{fluorosurfactants} include Li, Na, K, _NH4 , _NH3CH2CH2OH , _{NH2 ( CH2CH2OH} ) ₂ , and _{NH ( CH2CH2OH} ). ₃ and the like.

Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.

Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.

Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both ends, and polyether-modified silicone surfactants having polyoxyethylene groups or polyoxyethylene polyoxypropylene groups as modifying groups are particularly preferred because they exhibit good properties as water-based surfactants. .
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples include those introduced into the side chain of the Si portion of siloxane.

(However, in general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)
Commercially available products can be used as the above polyether-modified silicone-based surfactants. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Corporation), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like.

上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。

上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられる。 As the fluorosurfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular, fluorine-based compounds represented by general formulas (F-1) and (F-2) Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.

In the compound represented by the above general formula (F-2), Y is H, or CmF _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ -CmF _2m+1 and m is 4 to 6 Integer, or CpH _2p+1 where p is an integer from 1-19. n is an integer of 1-6. a is an integer from 4 to 14;
Commercially available products may be used as the fluorosurfactant. Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both manufactured by Dainippon Ink and Chemicals); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) etc.

The content of the surfactant is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.001% by mass or more and 5% by mass or less with respect to the mass of the pretreatment liquid.

-- Defoamer --
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

-- Antiseptic and antifungal agents --
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

--anti-rust--
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

--pH adjuster--
Any pH adjusting agent can be used without particular limitation as long as it can adjust the pH to 7 or higher.

<Ink>
The ink preferably contains a water-soluble organic solvent, a pigment, and resin particles, and optionally other components such as water and a surfactant. As for other components such as water and a surfactant, the same ones as those of the above pretreatment liquid can be used, so description thereof will be omitted.

-Water-soluble organic solvent-
The ink contains a water-soluble organic solvent from the standpoint of being readily absorbed by the calcium chloride pre-positioned in the fabric to which it is applied. In the present disclosure, the term "water-soluble organic solvent" refers to an organic solvent that is easily dissolved in water. Represents an organic solvent. Examples of water-soluble organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. be done.

Specific examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, nitrogen-containing heterocyclic compounds such as γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N- Amides such as dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine, and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol, propylene carbonate, and ethylene carbonate. etc.

The water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250° C. or higher. By containing a water-soluble organic solvent having a boiling point of 250° C. or more in the ink, drying of the ink is suppressed, and the decap property and ejection stability of the ink are improved. Moreover, the boiling point of the water-soluble organic solvent is preferably 350° C. or less from the viewpoint of the drying property of the image formed by the ink.
In the present disclosure, the term “decapping property” refers to when ink is supplied to a nozzle and ejected after the inkjet head is left in a state where a protective cap that suppresses drying of the ink is not attached (decapping state). It represents the degree of the number of non-ejection nozzles that occur, and when the number of non-ejection nozzles is small, the decap performance is judged to be excellent, and when the number of non-ejection nozzles is large, the decap performance is judged to be poor.
In the present disclosure, "ejection stability" refers to the number of non-ejection nozzles that occur when ink is continuously ejected from the inkjet head. If there are many non-ejecting nozzles, it is determined that the ejection stability is poor.

Examples of water-soluble organic solvents having a boiling point of 250° C. or higher include triethylene glycol (boiling point: 285° C.), 1,6-hexanediol (boiling point: 250° C.), tripropylene glycol n-propyl ether (boiling point: 261° C. ), diethylene glycol n-hexyl ether (boiling point: 259° C.), glycerin (boiling point: 290° C.), etc. Among these, it is preferable to use tripropylene glycol n-propyl ether or glycerin.

The content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink, and the content of the water-soluble organic solvent having a boiling point of 250° C. or more is relative to the mass of the ink is 5.0% by mass or more and 20.0% by mass or less, the water-soluble organic solvent is sufficiently absorbed by the calcium chloride pre-positioned in the fabric to which the ink is applied, and the image fastness is improved. Improves ink decap and jetting stability without sacrificing properties

-Pigments-
An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.

Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.

As inorganic pigments, in addition to titanium oxide, iron oxide, tin oxide, zirconium oxide, iron titanate which is a composite oxide of iron and titanium, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, Carbon black produced by known methods such as contact method, furnace method, thermal method, etc. can be used.

Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.

Specific examples of pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).

Further, for color, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52: 2, 53:1, 57:1 (brilliant carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (red red), 104, 105, 106, 108 ( cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15:1, 15:2, 15:3, 15:4 (phthalocyanine blue), 16, 17:1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.

The content of the pigment in the ink is preferably 0.1% by mass or more and 15.0% by mass or less, based on the mass of the ink, from the viewpoints of improvement in image density, good fixability and ejection stability, and 1.0% by mass. % or more and 10.0% or less by mass is more preferable.

In order to disperse the pigment and obtain an ink, there are a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin for dispersion, and a method of dispersing using a dispersant. method, etc.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with resin, and uncoated pigments or partially coated pigments may be dispersed in the ink.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants. As the dispersant, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be used depending on the pigment. RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant. A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

-Resin particles-
By including resin particles in the ink, both fastness and texture are improved in an image formed by the ink. Materials constituting the resin particles include, for example, urethane resins, polyester resins, acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, Examples include acrylic silicone resins, but urethane resins are preferable from the viewpoint of further improving fastness and texture in images formed with ink.
In the present disclosure, the “texture” represents the evaluation of the image formed by the ink when touched, and the texture is judged to be excellent when the texture is soft, and the texture is judged to be poor when the texture is hard.

When the material constituting the resin particles is a urethane resin, the glass transition temperature (Tg) of the urethane resin is 0° C. or lower, preferably −5° C. or lower. When the glass transition temperature (Tg) of the urethane resin is 0° C. or less, the texture of the image formed by the ink is improved.

The resin particles are preferably dispersed and contained in the ink. The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the purpose. More preferred. The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited, and can be appropriately selected according to the purpose. 20.0% by mass or less is more preferable.

- Physical properties of ink -
The physical properties of the ink can be appropriately selected depending on the purpose. For example, viscosity, surface tension, pH, etc. are preferably within the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoint of improving image density and character quality and obtaining good ejection properties. More preferably, it is 8 mPa·s or more and 15 mPa·s or less. When the viscosity is 8 mPa·s or more, it is possible to suppress the generation of mist when the ink is ejected by an inkjet method, and a high-quality image can be obtained. When the viscosity is 15 mPa·s or less, ejection can be performed at room temperature without heating the inkjet head or the like, so high ejection stability and decapping properties can be obtained. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., from the viewpoint that the ink is appropriately leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

<Fabric>
Fabrics include fibers and represent fibers in the form of wovens, knits, nonwovens, and the like.

Fibers constituting the fabric include synthetic fibers, and if necessary, fibers other than synthetic fibers may be included. The reason why synthetic fibers are used as the fibers constituting the fabric will be described below.
In general, synthetic fibers such as polyester fibers have few voids in the fibers, unlike natural fibers such as cotton fibers. Therefore, when an image is formed by applying ink to a fabric containing synthetic fibers, the water-soluble organic solvent contained in the ink is less likely to be absorbed into the fibers and tends to remain in the image. If the water-soluble organic solvent remains in the image, the fastness of the image is lowered as described above. Also, if the content of the water-soluble organic solvent contained in the ink is reduced in order to maintain the fastness of the image, the decapping property of the ink is lowered.
On the other hand, in the present invention, since the ink is applied to the area to which the pretreatment liquid is applied (the area to which the calcium chloride is placed), even if the fibers constituting the fabric are synthetic fibers, the ink does not contain the ink. The water-soluble organic solvent is absorbed by the calcium chloride, suppressing the residual of the water-soluble organic solvent in the image, and as a result, the fastness of the image is improved. Further, the content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink, and the content of the water-soluble organic solvent having a boiling point of 250° C. or more is the mass of the ink By being 5.0% by mass or more and 20.0% by mass or less with respect to the ink, the wettability of the ink is maintained, and the water-soluble organic solvent is sufficiently absorbed by calcium chloride after the ink is applied. It is possible to achieve both an improvement in fastness and an improvement in ink decapping properties.

Synthetic fibers include, for example, polyester, polyamide, acrylic, polyolefin, polyvinyl alcohol, polyvinyl chloride, polyurethane, and polyimide fibers, among which polyester fibers are preferred.

A biodegradable polyester fiber containing a biodegradable polyester composition can be used as the polyester fiber. The biodegradable polyester composition contains, for example, a biodegradable aliphatic-aromatic polyester or polylactic acid, and if necessary, may contain an organic filler or an inorganic filler. Examples of biodegradable aliphatic-aromatic polyesters include polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and the like. Examples of organic fillers include natural starch, plasticized starch, modified starch, natural fiber, and wood flour. Inorganic fillers include talc powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicates, mica, and glass fibers. , mineral fibers, and the like.

Examples of fibers other than synthetic fibers include semi-synthetic fibers, regenerated fibers, and natural fibers. Semi-synthetic fibers include, for example, fibers of acetate, diacetate, triacetate, and the like. Regenerated fibers include, for example, fibers such as polynosic, rayon, lyocell, and cupra. Natural fibers include, for example, fibers such as cotton, linen, silk, and wool.

<<Image Forming Method>>
The image forming method of the present invention includes a pretreatment liquid application step of applying a pretreatment liquid to a fabric containing synthetic fibers, and an ink application step of applying ink to a region of the fabric to which the pretreatment liquid has been applied. ,including. In addition, the image forming method of the present invention may optionally include other steps, for example, a drying step for drying the pretreatment liquid applied to the fabric between the pretreatment liquid application step and the ink application step. may contain.

<Pretreatment liquid application step>
The pretreatment liquid applying step is a step of applying a pretreatment liquid to a fabric containing synthetic fibers.
A method for applying the pretreatment liquid is not particularly limited, and examples thereof include a liquid ejection method and a coating method.
The liquid ejection method is not particularly limited and can be appropriately selected according to the purpose. For example, a method using a charge control type head of the type. Specifically, a method using an inkjet system is mentioned.
Examples of coating methods include blade coating, gravure coating, gravure offset coating, wire bar coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, four or five roll coating method, dip coating method, curtain coating method, slide coating method, die coating method and the like.

The amount of the pretreatment liquid applied to the fabric in the pretreatment liquid application step is preferably 10 mg/cm ² or more and 50 mg/cm ² or less, more preferably 20 mg/cm ² or more and 40 mg/cm ² or less. When the application amount is 10 mg/cm ² or more, the image quality can be improved, and when it is 50 mg/cm ² or less, the occurrence of precipitation due to the solid content of the pretreatment liquid during drying can be suppressed. can be done.

<Drying process>
The drying step is a step of drying the pretreatment liquid applied to the fabric between the pretreatment liquid application step and the ink application step.
The method of drying the pretreatment liquid applied to the fabric is preferably a method of drying by heating, and known heating means such as a roll heater, a drum heater, hot air, and a heat press can be used. . The heating temperature by the heating means is preferably 60° C. or higher.

<Ink application process>
The ink applying step is a step of applying ink to the area of the fabric to which the pretreatment liquid has been applied.
The method of applying the ink is not particularly limited, and examples thereof include an inkjet method, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spraying method. A coating method or the like may be mentioned, but an inkjet method is preferred.

<<Image forming apparatus>>
The image forming apparatus of the present invention comprises pretreatment liquid containing means containing a pretreatment liquid, ink containing means containing ink, and pretreatment for applying the pretreatment liquid to a fabric containing synthetic fibers. It has liquid applying means and ink applying means for applying ink to the area of the fabric to which the pretreatment liquid has been applied. Further, the image forming apparatus of the present invention may have other means as necessary, for example, drying means for drying the pretreatment liquid applied by the pretreatment liquid applying means. Drying by the drying means is performed before applying ink by the ink applying means.

An image forming apparatus will be described with reference to FIGS. FIG. 1 is a schematic diagram showing an example of an image forming apparatus. FIG. 2 is a schematic diagram showing an example of storage means (pretreatment liquid storage means, ink storage means).

An image forming apparatus 400 shown in FIG. 1 is an image forming apparatus having a serial type inkjet head. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . The storage portion 411 in the pretreatment liquid storage means 410p for the pretreatment liquid, the white ink storage means 410w for the white ink, the black ink storage means 410k for the black ink, and the cyan ink storage means 410c for the cyan ink is, for example, an aluminum laminate. It is formed by a packaging member such as a film. The accommodating portion 411 is accommodated in, for example, a plastic container case 414 . Thereby, each containing means 410 is used as a cartridge.

On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. Each accommodating means 410 is detachably attached to the cartridge holder 404 . As a result, the discharge port 413 of each storage means 410 and the inkjet ejection head 434 (an example of pretreatment liquid application means and ink application means) are communicated via each supply tube 436, and the inkjet ejection head 434 forwards to the fabric. It becomes possible to eject the treatment liquid and each ink.
In addition, in the image forming apparatus 400 shown in FIG. 1, the pretreatment liquid is applied to the fabric by the inkjet ejection method, but the method for applying the pretreatment liquid is not limited to this. For example, it may be applied by a blade coating method, a roll coating method, a spray coating method, or the like.

Note that the image forming apparatus 400 may have heating means (an example of a drying means) for drying a liquid such as a pretreatment liquid or ink applied to the fabric. Examples of the heating means include known heating means such as a roll heater, a drum heater, a hot air generator, and a heat press.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation example of pretreatment liquid>
Pretreatment liquids 1 to 7 were obtained by a conventional method using materials having the formulations shown in Table 1 below. In addition, the unit of the numerical value of various prescriptions shown in following Table 1 is "mass %." The content of resin particles shown in Table 1 below is indicated as a solid content. In addition, the content of the polyvalent metal salt shown in Table 1 below is indicated as the amount of the polyvalent metal salt including the water of hydration, and the content in parentheses is the content of the polyvalent metal salt excluding the water of hydration. It is a representation as a quantity.

Further, the details (product name, manufacturer name, etc.) of each material shown in Table 1 below are as follows.

-Organic solvent-
・Propylene glycol (manufactured by Kanto Chemical Co., Ltd.)
・Glycerin (manufactured by Kanto Chemical Co., Ltd.)

-Resin particles (resin emulsion)-
・ 951HQ (Sumikaflex 951HQ, manufactured by Sumika Chemtex Co., Ltd., active ingredient 55% by mass)

- Polyvalent metal salt -
・ Calcium chloride dihydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
・ Calcium nitrate tetrahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
・Magnesium nitrate hexahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

<Preparation example of urethane resin particles 1>
In a 1 L separable flask equipped with a stirrer, thermometer, and reflux tube, 100 g of polymer polyol (T-5651, manufactured by Asahi Kasei Chemicals Corp.), 5.6 g of 2,2-bis(hydroxymethyl)propionic acid, hexa 27 g of methylene diisocyanate, 4.2 g of triethylamine, and 70 g of acetone as an organic solvent were charged while introducing nitrogen, one drop of the catalyst (di(2-ethylhexanoic acid) tin (II) was added, and the temperature was raised to 60°C. After refluxing for about 3 hours, the temperature was lowered to and maintained at 40° C. While stirring at 300 rpm, 250 g of pure water was slowly added to micronize the mixture, and after heating and stirring for 30 minutes, 3.5 g of isophoronediamine was added. was added and stirred for about 3 hours.The solvent was distilled off so that the active ingredient content was 30% to obtain a dispersion liquid of urethane resin particles 1. The glass transition point (Tg) of the urethane resin particles 1 was measured by Thermo plus. When measured using EVO2 (manufactured by Rigaku), it was -25°C.

<Preparation example of urethane resin particles 2>
100 g of methyl ethyl ketone, polyester polyol (iPA/AA = 6/4 (molar ratio) and EG/NPG = 1/9 (molar ratio) were added to a 2 L reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser. ), number average molecular weight = 2,000, average functional group number = 2, provided that iPA: isophthalic acid, AA: adipic acid, EG: ethylene glycol, NPG: neopentyl glycol), 345 g, 2, 9.92 g of 2-dimethylolpropionic acid (DMPA) was charged and uniformly mixed at 60°C. Thereafter, 45.1 g of triethylene glycol diisocyanate (TEGDI) and 0.08 g of dioctyltin dilaurate (DOTDL) were added and reacted at 72° C. for 3 hours to obtain a polyurethane solution. To this polyurethane solution, 80 g of isopropyl alcohol (IPA), 220 g of methyl ethyl ketone (MEK), 3.74 g of triethanolamine (TEA), and 596 g of water were charged to effect phase inversion, and then MEK and IPA were separated using a rotary evaporator. After removing and cooling to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to obtain a dispersion liquid of urethane resin particles 2 adjusted to 30% active ingredient and pH 8. When the glass transition point (Tg) of the urethane resin particles 2 was measured using Thermo plus EVO2 (manufactured by Rigaku), it was -5°C.

<Preparation example of urethane resin particles 3>
1500 g of polycarbonate diol (reaction product of 3-methyl-1,5-pentanediol and diphenyl carbonate) (number average molecular weight Mn=1200), 2,2- 220 g of dimethylolpropionic acid (DMPA) and 1347 g of N-methylpyrrolidone (NMP) were charged under a nitrogen stream and heated to 60° C. to dissolve DMPA. Next, 1445 g of 4,4'-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) were added and the mixture was heated to 90°C for urethanization reaction over 5 hours to obtain an isocyanate-terminated urethane prepolymer. The reaction mixture was cooled to 80° C., 149 g of triethylamine was added thereto, and 4340 g of the mixture was taken out and added to a mixed solution of 5400 g of water and 15 g of triethylamine under strong stirring. Next, 1500 g of ice is added, 626 g of a 35% 1,6-hexamethylenediamine aqueous solution is added to carry out a chain extension reaction, the solvent is distilled off so that the active ingredient becomes 30%, and the urethane resin particles 3 are dispersed. I got the liquid. When the glass transition point (Tg) of the urethane resin particles 3 was measured using Thermo plus EVO2 (manufactured by Rigaku), it was 10°C.

<Example of preparation of pigment dispersion>
In a beaker, 37.5 parts by mass of acrylic copolymer (DISPERBYK-2008: manufactured by BYK, active ingredient 60% by mass) was dissolved in 100.0 parts by mass of high-purity water, and titanium oxide (JR-600A: manufactured by Tayca (primary particle diameter 250 nm, Surface treatment: Add 30.0 parts by mass of Al)) and stir with an Excel Auto Homogenizer manufactured by Nippon Seiki Seisakusho at 5000 rpm for 30 minutes to disperse until there are no lumps. Stirred for 1 minute. The resulting titanium dioxide pigment dispersion was treated with an ultrasonic homogenizer US-300T (tip φ26) manufactured by Nippon Seiki Seisakusho for 1 hour at 200 μA while being cooled with water, and filtered through a 5 μm membrane filter (cellulose acetate membrane). , a pigment dispersion having a titanium dioxide pigment content of 17.9% by weight was obtained.

<Example of white ink adjustment>
White inks 1 to 17 were obtained using materials having the formulations shown in Table 2 below. Specifically, components other than the resin particle dispersion and the pigment dispersion are dissolved in ion-exchanged water to prepare a vehicle, which is then mixed with the resin particle dispersion and finally mixed with the pigment dispersion. After filtering through a filter with a pore size of 0.8 μm, white inks 1 to 17 were obtained. In addition, the unit of the numerical value of various prescriptions shown in following Table 2 is "mass %." In addition, the resin particle and pigment contents shown in Table 2 below are indicated as solid content. The viscosities of white inks 1 to 17 at 25° C. are also shown in Table 2 below.

Further, the details (product name, manufacturer name, etc.) of each material shown in Table 2 below are as follows.

-Water-soluble organic solvent-
・ Propylene glycol (boiling point: 188 ° C., manufactured by Kanto Chemical Co., Ltd.)
・ 1,2-butanediol (boiling point: 194 ° C., manufactured by Kanto Chemical Co., Ltd.)
・Tripropylene glycol-n-propyl ether (boiling point: 261 ° C., manufactured by Kanto Chemical Co., Ltd.)
・ Glycerin (boiling point: 290 ° C., manufactured by Kanto Chemical Co., Ltd.)

-Surfactant-
・BYK-348 (manufactured by BYK)
・ FS-300 (manufactured by Dupont)

-Resin particles (resin emulsion)-
・ AE982 (acrylic-silicone resin emulsion, manufactured by E-Tech Co., Ltd., active ingredient: 30%)

-Additive-
・Proxel LV (manufactured by Avecia)

<Image sample preparation method>
(Examples 1 to 17, Comparative Examples 1 to 6)
First, image forming sets of Examples 1 to 17 and Comparative Examples 1 to 6 were prepared by combining pretreatment liquids and white inks as shown in Table 3 below.
Next, a hand sprayer was filled with the pretreatment liquid for each image forming set, and the pretreatment liquid was applied to a black polyester fabric manufactured by Tom's Co., Ltd. in an amount of 25 mg/cm ² , and then heated at 130°C. Allow to dry for 90 seconds.
Next, the white ink in each image forming set was filled in an inkjet recording device (Ri6000, manufactured by Ricoh Co., Ltd.), and the amount of adhesion was 25 mg/cm at 600 × 600 dpi on the area of the black polyester fabric coated with the pretreatment liquid. ² , and then dried at 130° C. for 90 seconds to obtain a solid image sample.

(Example 18)
An image sample of Example 18 was obtained in the same manner as in Example 1 except that the cloth used was changed from a black polyester cloth to a cloth formed of a biodegradable polyester fiber composed of a homogeneous mixture having the following composition.
-Composition of biodegradable polyester fiber-
・Polybutylene adipate terephthalate: 84.1 parts by mass ・Polylactic acid: 10.0 parts by mass ・Talc powder: 1.6 parts by mass ・ADR4370 (manufactured by BASF): 0.3 parts by mass ・Stearamide: 0.5 parts by mass - Carbon black: 5 parts by mass (relative to the entire composition)
・ Tetrahydrofuran: 15 ppm (relative to the entire composition)
- Cyclopentanone: 10 ppm (relative to the entire composition)

Using the obtained image samples, "fastness", "texture" and "whiteness" were evaluated as follows. The results are shown in Table 3 below.
Also, using the produced white ink, "discharge stability" and "decapping property" were evaluated as follows. The results are shown in Table 3 below.

[Robustness]
The image sample was rubbed with a cotton cloth 10 times, and the degree of pigment transfer to the cotton cloth was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: Pigment transfer to cotton cloth is hardly observed B: Pigment transfer is observed to some extent C: Pigment is clearly transferred

[Texture]
The image samples were touched and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Soft to the touch B: Slightly hard to the touch C: Hard to the touch

[Whiteness]
The L value of the solid image portion of the image sample was measured with a spectrophotometer (X-Rite) and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: L value is 70 or more B: L value is 60 or more and less than 70 C: L value is less than 60

[Ejection stability]
An inkjet recording apparatus having an inkjet head (MH2420, manufactured by Ricoh Co., Ltd.) was filled with white ink, and the white ink was continuously ejected at a frequency of 5 kHz for 1 minute under the condition that the flying speed of the white ink was 7 m / s ± 1 m / s. The number of nozzles causing ejection failure was counted and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The number of ejection failure nozzles is 0 or more and 2 or less B: The number of ejection failure nozzles is 3 or more and 9 or less C: The number of ejection failure nozzles is 10 or more

[Decap property]
An inkjet recording device (Ri6000, manufactured by Ricoh Co., Ltd.) was filled with white ink, and under the environment of 25°C and 40% RH, the head cleaning was executed from the maintenance command of the inkjet recording device, and a test chart was printed. It was confirmed that all channels were in the discharge state. Next, the ink jet head was left uncapped for 10 minutes, and then the test chart was printed again. The number of non-ejection channels was counted from the test chart after the standing, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The number of ejection failure channels is 1 or less B: The number of ejection failure channels is 2 or more and 9 or less C: The number of ejection failure channels is 10 or more

400 image forming apparatus 401 exterior of image forming apparatus 401c cover of apparatus main body 404 cartridge holder 410p pretreatment liquid storage means 410w white ink storage means 410k black ink storage means 410c cyan ink storage means 411 storage section 413 outlet 414 storage container case 420 Mechanism 434 Ink jet ejection head 436 Supply tube

JP 2019-167657 A JP 2006-124843 A

Claims (8)

An image forming set comprising: a pretreatment liquid applied to a fabric containing synthetic fibers; and an ink applied to a region of the fabric to which the pretreatment liquid has been applied,
The pretreatment liquid contains calcium chloride,
The ink contains a water-soluble organic solvent, a pigment, and resin particles,
The water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250° C. or higher,
The content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink,
The image forming set, wherein the content of the water-soluble organic solvent having a boiling point of 250° C. or higher is 5.0% by mass or more and 20.0% by mass or less with respect to the mass of the ink. 2. The image forming set according to claim 1, wherein the content of said calcium chloride is 3.0% by mass or more and 20.0% by mass or less with respect to the mass of said pretreatment liquid. 3. The image forming set according to claim 1, wherein the resin particles contain a urethane resin having a glass transition temperature of 0[deg.] C. or lower. The image forming set according to any one of claims 1 to 3, wherein the viscosity of the ink at 25°C is 8.0 mPa·s or more and 15.0 mPa·s or less. 5. The imaging set of any one of claims 1-4, wherein the synthetic fibers are polyester fibers. 5. The imaging set of any one of claims 1-4, wherein the synthetic fibers are biodegradable polyester fibers. pretreatment liquid containing means for containing the pretreatment liquid;
an ink containing means containing ink;
pretreatment liquid application means for applying the pretreatment liquid to a fabric containing synthetic fibers;
and an ink applying unit for applying the ink to a region of the fabric to which the pretreatment liquid has been applied, wherein
The pretreatment liquid contains calcium chloride,
The ink contains a water-soluble organic solvent, a pigment, and resin particles,
The water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250° C. or higher,
The content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink,
The image forming apparatus, wherein the content of the water-soluble organic solvent having a boiling point of 250° C. or higher is 5.0% by mass or more and 20.0% by mass or less with respect to the mass of the ink. A pretreatment liquid applying step of applying a pretreatment liquid to a fabric containing synthetic fibers;
and an ink application step of applying ink to the area of the fabric to which the pretreatment liquid has been applied,
The pretreatment liquid contains calcium chloride,
The ink contains a water-soluble organic solvent, a pigment, and resin particles,
The water-soluble organic solvent contains a water-soluble organic solvent having a boiling point of 250° C. or higher,
The content of the water-soluble organic solvent is 25.0% by mass or more and 45.0% by mass or less with respect to the mass of the ink,
The image forming method, wherein the content of the water-soluble organic solvent having a boiling point of 250° C. or higher is 5.0% by mass or more and 20.0% by mass or less with respect to the mass of the ink.

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