WO2011078068A1

WO2011078068A1 - Fabric pretreatment agent for inkjet textile printing, method for pretreating fabric, and textile printing method

Info

Publication number: WO2011078068A1
Application number: PCT/JP2010/072737
Authority: WO
Inventors: 真也渡辺; 正幸牛久
Original assignee: コニカミノルタＩｊ株式会社
Priority date: 2009-12-24
Filing date: 2010-12-17
Publication date: 2011-06-30

Abstract

Disclosed are: pretreatment of fabric by an inkjet method, wherein a bleeding prevention effect or the like is effectively achieved by applying a small amount of a pretreatment agent to the fabric; and a pretreatment agent which is free from deterioration over time and can survive long-term storage. Specifically disclosed is a fabric pretreatment agent for inkjet textile printing, which is characterized by containing at least one compound that is selected from the group consisting of 2-imidazolidinone and derivatives thereof.

Description

Fabric pretreatment agent for inkjet textile printing, fabric pretreatment method and textile printing method

The present invention relates to a novel pretreatment agent for ink jet textile printing, and a pretreatment method and a textile printing method of a fabric using the same, and more specifically, a pretreatment agent containing 2-imidazolidinone and / or a derivative thereof is used. The present invention relates to a textile printing method for pre-treating a fabric.

Conventional textile printing is performed using a printing method using a plate or a screen printing method. On the other hand, a textile printing method using an inkjet method is known. This textile printing method is non-printing, suitable for a small quantity and a wide variety, and has a feature that a printed matter can be produced with a short delivery time.

When printing on a fabric by an ink jet method, there is a case where bleeding occurs. Usually, the fabric is pretreated for the purpose of preventing bleeding and improving the fixing property between the colorant and the fabric. Specifically, as a pretreatment agent, after dipping or coating an aqueous solution containing a polymer compound for preventing bleeding, an acid or alkali for improving fixability, urea as a hydrotropic agent, Processing to dry is given.

Such a fabric pretreatment step is indispensable for inkjet textile printing, but the current method has various problems as shown below.

1) Pre-processing takes time and the delivery time of the print is delayed 2) The cost for the pre-processing step is high 3) The pre-processed fabric deteriorates with time and cannot be stored for a long time. On the other hand, a method has been proposed in which the fabric is pretreated in the pre-printing process. For example, Patent Literature 1 and Patent Literature 2 disclose a method of performing fabric pretreatment by an inkjet method.

Thus, it is said that the above-mentioned problems can be solved by performing the fabric pretreatment by the ink jet method. However, when the pretreatment agent is applied to the fabric by the inkjet method, since the amount of the pretreatment agent applied to the fabric is smaller than the conventional method of applying by dipping or coating, bleeding cannot be prevented. Problems such as insufficient fixability between the colorant and the fabric are likely to occur. On the contrary, if it is going to give many pretreatment agents, processing capacity will fall or the dry load after giving a pretreatment agent will become high, and will become impractical. In addition, since urea that has been conventionally used as a hydrotropic agent is hydrolyzed, the pretreatment agent deteriorates with time and cannot be stored for a long time. Since ammonia and carbon dioxide gas are generated by hydrolysis of urea, bubbles are generated in the pretreatment agent, and the emissivity of the pretreatment agent from the inkjet head becomes unstable. For this reason, the pretreatment agent set in the ink jet printer must be frequently replaced, which is not practical.

No solution is shown in Patent Document 1 for such a problem. Patent Document 2 discloses a method of applying a fixing accelerating composition containing an alkali agent to a fabric by an ink jet method. According to this method, it is said that the fabric deterioration with time (yellowing) due to the alkaline agent can be prevented, and the above-mentioned problem 3) can be solved. However, this method is not sufficient to solve the above-mentioned problems 1) and 2) because the entire fabric needs to be previously treated with a non-alkali pretreatment liquid. Moreover, the above-mentioned problem resulting from urea hydrolysis cannot be prevented.

JP-A-2005-232633 JP 2006-2104030 A

The present invention has been made in view of the above problems, and an object of the present invention is to provide a fabric by an ink jet method by obtaining an effect of preventing bleeding efficiently by applying a small amount of a pretreatment agent to the fabric. Is to realize the pre-processing. Another object of the present invention is to obtain a pretreatment agent that does not deteriorate with time and can withstand long-term storage.

As a result of intensive studies, the present inventor used 2-imidazolidinone or a derivative thereof in place of urea that has been used for a pretreatment agent in the past, so that a small amount of pretreatment agent can be imparted to the fabric. The present inventors have found that a pretreatment agent that can effectively prevent blurring and the like and that does not deteriorate with time and can withstand long-term storage can be obtained, thereby completing the present invention.

The above object of the present invention is achieved by the following configuration.

1.2-A fabric pretreatment agent for ink-jet printing, comprising at least one compound selected from the group consisting of imidazolidinone and derivatives thereof.

2.2 The fabric pretreatment agent for ink-jet printing according to 1 above, wherein the imidazolidinone or a derivative thereof is represented by the following general formula (I):

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, which may be substituted, respectively. )
3. The fabric pretreatment agent for inkjet printing according to 1 or 2 above, wherein at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof is 2-imidazolidinone.

4. The inkjet according to any one of 1 to 3 above, wherein the content of at least one compound selected from the group consisting of 4.2-imidazolidinone and derivatives thereof is 5 to 30% by mass. Fabric pretreatment agent for textile printing.

5. 5. A fabric pretreatment method, comprising applying the fabric pretreatment agent for inkjet textile printing according to any one of 1 to 4 to a fabric by an inkjet method.

6). 6. The method for pretreating a fabric according to 5 above, wherein the amount of the fabric pretreatment agent for inkjet textile printing applied to the fabric is 5 to 20 ml / m ² .

7. A textile printing method comprising applying a fabric pretreatment agent for inkjet textile printing to a fabric by the fabric pretreatment method described in 5 or 6 above, and then applying an ink containing a coloring material to the fabric within 10 seconds. .

According to the present invention, an effect such as efficient bleeding prevention can be obtained by applying a small amount to a fabric, and a pretreatment agent that does not deteriorate with time and can withstand long-term storage can be obtained.

It is a partial schematic diagram showing an example of a configuration of a textile printing apparatus. It is the partial schematic diagram which looked at the carriage of the textile printing apparatus shown in Drawing 1 from the upper part. It is the partial schematic diagram which looked at the carriage of the textile printing apparatus shown in Drawing 1 from the upper part. It is a partial schematic diagram which shows another example of a structure of a textile printing apparatus. FIG. 5 is a partial schematic view of the carriage of the textile printing apparatus shown in FIG. 4 as viewed from above.

The present invention will be described in more detail.

(Pretreatment agent)
The fabric pretreatment agent for ink jet textile printing of the present invention (hereinafter also simply referred to as pretreatment agent) contains at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof. In addition, a polymer compound for preventing bleeding, an acid or an alkali agent for improving the fixing property of the colorant, and other additives as required can be contained. In addition, when the pretreatment agent is applied to the fabric by the inkjet method, a water-soluble organic solvent can be contained. In the present invention, at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof mainly acts as a hydrotropic agent. The hydrotropic agent has the effect of accelerating re-dissolution of the once dried dye in the color development step after printing and improving the color density.

(2-imidazolidinone and its derivatives)
As 2-imidazolidinone and derivatives thereof used in the pretreatment agent of the present invention, compounds represented by the following general formula (I) are preferable.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a substituted alkyl group, or a substituted alkenyl group. Represents a group, a substituted aryl group or a substituted alkoxy group.

The alkyl group, alkenyl group, and alkoxy group are preferably groups having 1 to 8 carbon atoms, and these may be substituted. Specific examples of these include methyl group, ethyl group, propyl group, isopropyl group and the like, and ethenyl group, allyl group, methoxy group, ethoxy group, propoxy group and the like. Examples of the substituent that may be substituted include these groups, and groups such as a hydroxy group, a carboxy group, a sulfo group, a halogen atom, an amide group, and a carbamoyl group.

The aryl group includes a phenyl group and a naphthyl group, and is preferably a phenyl group, which may be substituted, and preferable substituents include the above-described groups.

Examples of 2-imidazolidinone derivatives include 1-methyl-2-imidazolidinone, 1-ethyl-2-imidazolidinone, 1,1′-dimethyl-2-imidazolidinone, 1,3-dimethyl- 2-imidazolidinone, 1,1'-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 4,5-dimethyl-2 -Imidazolidinone, 4,5-diethyl-2-imidazolidinone, 1-tert-butyl-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone, 4,5-diethoxy-2-imidazolidone Lidinone, 1,3-dimethyl-4,5-dimethoxy-2-imidazolidinone, 1,3-dimethyl-4,5-diethoxy-2-imidazolidinone, 1- (2-hydroxyethyl) ) -2-imidazolidinone, 4- (2-hydroxyethyl) -2-imidazolidinone, 4,5-di (2-hydroxyethyl) -2-imidazolidinone, 1-acetyl-2-imidazolidinone Etc. As the compound selected from the group consisting of 2-imidazolidinone and derivatives thereof used in the pretreatment agent of the present invention, 2-imidazolidinone is preferable.

The content of a compound selected from the group consisting of 2-imidazolidinone and its derivatives is preferably 5 to 30% by mass. In this case, the amount of 2-imidazolidinone and its derivative per unit area applied to the cloth is represented by the following formula.

Amount of 2-imidazolidinone and its derivatives to the fabric [g / m ² ] = Amount of pretreatment agent to the fabric [g / m ² ] × 2-imidazolidinone and its derivatives in the pretreatment agent Content [mass%] / 100
If the content is less than 5% by mass, the effects of the present invention may be difficult to obtain. On the other hand, if it exceeds 30% by mass, the amount of 2-imidazolidinone and its derivative applied to the fabric becomes too large, and it tends to spread during steaming, and the viscosity of the pretreatment agent becomes too high. When trying to apply, it may be difficult to discharge stably from the inkjet head.

Incidentally, as a method for imparting 2-imidazolidinone and its derivative to a cloth, a method of incorporating them in a recording ink containing a colorant is conceivable. In this case, the recording ink cloth is intended to increase the image density. Increasing the amount applied to the fabric increases the amount of 2-imidazolidinone and its derivative applied to the fabric in proportion to it, so that bleeding tends to occur during printing and steaming. By adding 2-imidazolidinone and its derivatives to the pretreatment agent, the amount of the ink can be optimized regardless of the amount of the recording ink applied to the cloth, so that the occurrence of bleeding can be prevented. .

(Polymer compound)
The pretreatment agent of the present invention preferably contains a polymer compound as a paste. Examples of the polymer compound include natural gums such as guar gum and locust bean gum, starches, seaweeds such as sodium alginate, funari, plant skins such as pectic acid, cellulose such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose. Derivatives, roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, and other processed starches, processed natural gums, roast bean gum, and other processed natural gums, alginic acid derivatives, or polyvinyl alcohol, polyacrylic esters Synthetic glues such as, emulsions and the like can be used.

When applying the pretreatment agent by the inkjet method, the polymer compound is polyvinyl pyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, diglycerin polyethylene oxide adduct. It is preferable to use a polypropylene adduct of diglycerin.

In the pretreatment agent for inkjet textile printing, the content of the polymer compound is preferably 1 to 10% by mass.

(Alkaline agent)
The pretreatment agent of the present invention can contain an alkali agent. This is particularly preferred when the recording ink uses a reactive dye as a colorant. The alkali agent can be selected from an organic base and an inorganic base, but a water-soluble inorganic base is preferable in terms of color development, odor, solubility in recording ink, drainage load, and the like. Examples of inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonium acetate, lithium acetate, sodium acetate, Potassium acetate, sodium triphosphate, etc. can be used.

When applying the pretreatment agent by the ink jet method, it is preferable to use a potassium salt because precipitation from the pretreatment agent hardly occurs and ejection from the ink jet head is stable.

The content of the alkali agent is preferably 1 to 10% by mass in the pretreatment agent.

(PH adjuster)
The pretreatment agent of the present invention can contain a pH adjusting agent. This is particularly preferred when the recording ink uses an acid dye or a disperse dye as a colorant. As the pH adjuster, ammonium sulfate, ammonium tartrate, dibasic sodium phosphate, sodium tripolyphosphate, citric acid, tartaric acid, lactic acid and the like can be used.

The content of the pH adjusting agent is preferably 1 to 10% by mass in the pretreatment agent.

(Water-soluble organic solvent)
When the pretreatment agent of the present invention is applied by an ink jet method, it is preferable to contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol). Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), glycol ethers (eg, ethylene glycol alkyl ether, diethylene glycol alkyl ether, tri Ethylene glycol alkyl ether, propylene glycol alkyl ether, dipropylene glycol Alkyl ether, tripropylene glycol alkyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, Ethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.) Sulfoxide compounds (e.g., dimethyl sulfoxide) and the like.

The content of the water-soluble organic solvent is preferably 5 to 40% by mass in the pretreatment agent.

(Surfactant)
The pretreatment agent of the present invention can contain a surfactant. As the surfactant, any of cationic, anionic, amphoteric and nonionic can be used. Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like can be mentioned. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, acyl Peptide, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate ester, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol Sulfate ester, secondary higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkylphenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphorus acid Examples thereof include ester salts and alkyl phosphate ester salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether (for example, Emulgen 911), polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, Polyoxyethylene polyoxypropylene alkyl ether (for example, Newpol PE-62), polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene Glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fat Esters, sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkyl amine oxides, acetylene glycol, acetylene alcohol, and the like.

When these surfactants are used, they can be used alone or in combination of two or more, and can be added in the range of 0.001 to 1.0% by mass with respect to the total mass of the pretreatment agent.

(Reduction inhibitor)
The pretreatment agent of the present invention can contain a reduction inhibitor. As the reduction inhibitor, nitrobenzene sulfonate is preferably used, and an alkali metal salt of metanitrobenzene sulfonic acid, particularly a sodium salt is preferably used.

The content of the reducing inhibitor is preferably 0.1 to 7% by mass in the pretreatment agent.

(Other additives)
An antiseptic and an antifungal agent can be added to the pretreatment agent of the present invention. Examples of the antiseptic and antifungal agent include aromatic halogen compounds (for example, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL) and the like. Is mentioned.

(Degassing of pretreatment agent)
When the pretreatment agent of the present invention is applied to the fabric by the ink jet method, if dissolved gas is contained in the pretreatment agent, fine bubbles are generated in the pretreatment agent when ejected from the ink jet head. It becomes a factor causing a defect. Therefore, it is preferable to remove such dissolved gas from the pretreatment agent, and the degassing method is roughly divided into a method of degassing by a physical method such as boiling or reduced pressure, and a pretreatment of the absorbent. There is a chemical method of adding and mixing in the agent.

In the present invention, it is possible to perform deaeration by any means, but in particular, the pretreatment agent is passed through the gas-permeable hollow fiber membrane, and the outer surface side of the hollow fiber membrane is decompressed. Thus, the method of permeating and removing the dissolved gas in the pretreatment agent is preferable because the dissolved gas in the pretreatment agent can be efficiently removed without adversely affecting the physical properties of the pretreatment agent.

(Granting of pretreatment agent)
In the present invention, as a method for applying the pretreatment agent to the fabric, a conventionally known application method such as a pad method, a coating method, a spray method, or the like can be used. Moreover, the method of providing a pretreatment agent to a fabric using an inkjet head can also be used.

In the present invention, it is preferable to use a method of applying a pretreatment agent to a fabric using an inkjet head.

In this case, it is preferable that an ink jet head for applying the pretreatment agent is mounted on the printer and applied to the fabric in-line with the recording ink containing the coloring material.

Specifically, (1) applying the pretreatment agent to the fabric, (2) drying the applied pretreatment agent, and (3) applying the recording ink to form an image, this series of operations is one unit. Configure to be completed within the printer.

In the present invention, the structure of the printer can be simplified and compacted by applying the recording ink containing the coloring material to the fabric within 10 seconds after the pretreatment agent is applied to the fabric. However, if the time from application of the pretreatment agent to application of the recording ink is short, sufficient time for drying the pretreatment agent cannot be taken, and drying of the pretreatment agent may be insufficient. is there.

In such a case, bleeding may occur when the recording ink is applied, or the pretreatment agent applied to the fabric may diffuse in the thickness direction of the fabric, resulting in a decrease in efficacy and color development. By using the pretreatment agent of the present invention, even in such a case, bleeding of the recording ink can be prevented and sufficient color development can be obtained.

When the pretreatment agent of the present invention is applied to a fabric by an ink jet method, the viscosity of the pretreatment agent is preferably 3 to 20 mPa · s. The surface tension is preferably 25 to 70 mN / m. The viscosity and surface tension can be adjusted with the above-described polymer compound, water-soluble organic solvent and surfactant, and the amount of pretreatment agent applied to the fabric is preferably 5 to 20 ml / m ^2. . If the applied amount is less than 5 ml / m ² , the effect of the present invention may be difficult to obtain. Conversely, if the applied amount is more than 20 ml / m ² , the drying load increases.

(Recording ink)
Next, the recording ink that can be used in the textile printing method of the present invention will be described.

The recording ink in the present invention preferably contains at least a coloring material, a water-soluble organic solvent, and water.

(Coloring material)
Examples of the color material include disperse dyes, reactive dyes, acid dyes, direct dyes, pigments, oil-soluble dyes, among which disperse dyes, reactive dyes, or acid dyes are preferably used. .

Hereinafter, specific compounds of the colorant that are preferably used in the present invention are shown, but the present invention is not limited to these exemplified compounds.

As a disperse dye preferably used in the present invention,
C. I. Disperse Yellow; 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224 227, 231, 232,
C. I. Disperse Orange; 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130 139, 142,
C. I. Disperse Red; 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184 , 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 22 5, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328,
C. I. Disperse Violet; 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63 69, 77,
C. I. Disperse Green; 9,
C. I. Disperse Brown; 1, 2, 4, 9, 13, 19,
C. I. Disperse Blue; 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143 146, 148, 149, 153, 154, 158, 165, 167, 167: 1, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205 , 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 29 3, 295, 297, 301, 315, 330, 333,
C. I. Disperse Black 1, 3, 10, 24,
Etc.

In the ink-jet printing method using disperse dyes, when developing colors at high temperatures, disperse dyes on the white background of machines and fabrics will not cause contamination, so select disperse dyes with good sublimation fastness. It is preferable.

As a reactive dye preferably used in the present invention,
C. I. Reactive Yellow; 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95 , 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176,
C. I. Reactive Orange; 1, 4, 5, 7, 11, 12, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91 , 92, 93, 95, 107,
C. I. Reactive Red; 2, 3, 3: 1, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66 78, 83, 84, 106, 111, 112, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187 , 190, 193, 194, 195, 198, 218, 220, 222, 223, 226, 228, 235,
C. I. Reactive Violet; 1, 2, 4, 5, 6, 22, 23, 33, 36, 38,
C. I. Reactive Blue; 2, 3, 4, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191 , 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236,
C. I. Reactive Green; 8, 12, 15, 19, 21,
C. I. Reactive Brown; 2, 7, 9, 10, 11, 17, 18, 19, 21, 23, 31, 37, 43, 46,
C. I. Reactive Black 5, 8, 13, 14, 31, 34, 39,
Etc.

As an acid dye preferably used in the present invention,
C. I. Acid Yellow; 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246,
C. I. Acid Orange; 3, 7, 8, 10, 19, 22, 24, 51, 51S, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127 140, 142, 144, 149, 152, 156, 162, 166, 168,
C. I. Acid Red; 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415,
C. I. Acid Violet; 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126,
C. I. Acid Blue; 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350,
C. I. Acid Green; 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109,
C. I. Acid Brown; 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413,
C. I. Acid Black; 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 63S, 107, 109, 112, 119, 132, 140, 155, 172 187, 188, 194, 207, 222,
As the direct dye preferably used in the present invention,
C. I. Direct Yellow; 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 86, 87, 98, 105, 106, 130, 137, 142, 147, 153,
C. I. Direct Orange; 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118,
C. I. Direct Red; 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243 254,
C. I. Direct Violet; 9, 35, 51, 66, 94, 95,
C. I. Direct Blue; 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291,
C. I. Direct Green; 26, 28, 59, 80, 85,
C. I. Direct Brown; 44, 44: 1, 106, 115, 195, 209, 210, 212: 1, 222, 223,
C. I. Direct Black; 17, 19, 22, 32, 51, 62, 108, 112, 113, 117, 118, 132, 146, 154, 159, 169,
As a pigment preferably used in the present invention,
Carbon black,
C. I. Pigment Yellow; 1, 3, 12, 13, 14, 16, 17, 43, 55, 74, 81, 83, 109, 110, 120, 138, 150,
C. I. Pigment Orange; 13, 16, 34, 43,
C. I. Pigment Red; 2, 5, 8, 12, 17, 22, 23, 41, 112, 114, 122, 123, 146, 148, 149, 150, 166, 170, 220, 238, 245, 258,
C. I. Pigment Violet; 19, 23,
C. I. Pigment Blue; 15, 15: 1, 15: 3, 15: 4, 15: 5, 15: 6, 29,
C. I. Pigment Brown 22,
C. I. Pigment Black; 1, 7,
C. I. Pigment White 6,
Etc.

In the present invention, the content of the color material contained in the ink is preferably 0.1 to 20% by mass, and more preferably 0.2 to 13% by mass.

(Water-soluble organic solvent)
As the water-soluble organic solvent used in the recording ink according to the present invention, the same water-soluble organic solvent as that used in the above-mentioned pretreatment agent can be used. The content of the water-soluble organic solvent is preferably 10 to 60% by mass with respect to the total ink mass.

(Surfactant)
As the surfactant used in the recording ink according to the present invention, the same surfactants as those used in the pretreatment agent described above can be used.

When these surfactants are used, they can be used singly or in combination of two or more. By adding the surfactant in the range of 0.001 to 1.0% by mass with respect to the total mass of the recording ink, The surface tension can be arbitrarily adjusted, which is preferable.

(Inorganic salt)
In the recording ink according to the present invention, an inorganic salt can be added to the ink in order to keep the ink viscosity and the dye stable and improve the color development. Examples of the inorganic salt include sodium chloride, sodium sulfate, magnesium chloride, magnesium sulfate and the like. The present invention is not limited to these.

(Other additives)
In the ink according to the present invention, an antiseptic and an antifungal agent can be added to the ink in order to maintain long-term storage stability of the ink. Examples of antiseptics and antifungal agents include aromatic halogen compounds (for example, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL), etc. Is mentioned. The present invention is not limited to these.

(Dispersion of coloring material)
In the recording ink according to the present invention, when a disperse dye or pigment is used as a color material, it can be dispersed by mixing a color material, a dispersant, a wetting agent, a medium and any additive and using a disperser. As the disperser, conventionally known dispersing means such as a ball mill, a sand mill, a line mill, a high-pressure homogenizer, and the like can be used.

The average particle size of the disperse dye or pigment is preferably 300 nm or less as the average particle size and 900 nm or less as the maximum particle size. This is because if the average particle size or the maximum particle size exceeds the range specified above, clogging is likely to occur in an ink jet printing method in which light is emitted from a fine nozzle, and stable emission cannot be performed. The average particle diameter can be determined by a commercially available particle size measuring instrument using a light scattering method, an electrophoresis method, a laser Doppler method or the like. Specific examples of the particle diameter measuring apparatus include Zetar Sizer 1000 manufactured by Malvern.

Dispersants preferably used in the ink according to the present invention include, for example, a formalin condensate of sodium creosote oil sulfonate (eg, demole C), a formalin condensate of sodium cresolsulfonate and sodium 2-naphthol-6-sulfonate. , Formalin condensate of sodium cresol sulfonate, formalin condensate of sodium phenol sulfonate, formalin condensate of sodium β-naphthol sulfonate, sodium β-naphthalene sulfonate (eg demole N) and sodium β-naphthol sulfonate Formalin condensate, lignin sulfonate (eg, Vanillex RN), sodium paraffin sulfonate (eg, Efcol 214), copolymer of α-olefin and maleic anhydride (eg, Florene G-7) 0), acrylic polymer active agent (for example, Joncryl series) and the like.

The amount of the dispersant used is preferably 20 to 200% by mass with respect to the color material. If the amount of the dispersant is small, it is difficult to make fine particles, and the dispersion stability is also lowered. If the amount of the dispersant is too large, the formation of fine particles and the dispersion stability is inferior, and the viscosity becomes high. These dispersants may be used alone or in combination.

In the present invention, preferable wetting agents for dispersion include, for example, sodium dodecylbenzenesulfonate, sodium 2-ethylhexylsulfosuccinate, sodium alkylnaphthalenesulfonate, ethylene oxide adduct of phenol, ethylene oxide adduct of acetylenic diol, etc. It is.

Depending on the structure of the coloring material used, foaming, gelation, and fluidity may be deteriorated during dispersion. Therefore, the dispersing agent and wetting agent may be used in addition to the wetting ability, atomization ability, and dispersion stability. It is necessary to select in consideration of foaming during dispersion, gelation of the dispersion, fluidity of the dispersion, and the like. Dispersants and wetting agents affect the dyeability, dyeing rate, leveling, transferability, color tone, fastness, etc. of the fabric, and when developing at high temperatures, It is preferable to select in consideration of non-uniform dyeing due to tarring of the agent. Since there is no dispersant that satisfies all of the above requirements, it is necessary to select an optimal dispersant according to the color material to be dispersed and to add an antifoaming agent or the like as necessary.

(Fabric)
In the present invention, the material constituting the fabric to be used is not particularly limited as long as it contains fibers that can be dyed with a colorant. Among them, cotton, silk, hemp, wool, nylon fibers, rayon fibers, among others. At least one selected from acetate fiber, polyester fiber, and blends thereof is preferable. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. The fabric that can be used in the present invention is preferably 100% of fibers that can be dyed with a coloring material, but a mixed woven fabric or a mixed non-woven fabric can also be used as a textile for printing. Further, the thickness of the yarn constituting the fabric as described above is preferably in the range of 10 to 100d.

In the present invention, in order to obtain a uniform dyed product, natural impurities (oils, waxes, pectic substances, natural pigments, etc.) adhering to the fabric fibers, residues of the chemicals used in the fabric production process (such as glue), It is desirable to wash dirt and the like in advance. Examples of the cleaning agent used for cleaning include alkalis such as sodium hydroxide and sodium carbonate, surfactants such as anionic surfactants and nonionic surfactants, enzymes, and the like.

(Inkjet printing method)
In the ink jet textile printing method for printing on a cloth, it is desirable to wind up the printed cloth after emitting the ink, develop a color by heating (coloring step), and wash and dry the cloth. In ink-jet textile printing, ink is printed on a cloth and simply left unattended, it does not dye well. Also, when printing on a long fabric for a long time, the fabric will come out endlessly, so the fabric printed on the floor will take up some space, which is unsafe and unexpectedly dirty. May end up. Therefore, it is necessary to perform a winding operation after printing. During this operation, a medium not related to printing, such as paper, cloth, or vinyl, may be sandwiched between the cloths. However, it is not always necessary to wind up when cutting in the middle or short fabric.

The color development step is a step of developing the original hue of ink by adhering and adhering to the fabric the dye in the ink that has only adhered to the fabric surface after printing and is not sufficiently adsorbed and fixed to the fabric. As the method, steaming by steam, baking by dry heat, thermosol, HT steamer by superheated steam, HP steamer by pressurized steam, etc. are used. They are appropriately selected depending on the material to be printed, ink, and the like. Further, the printed fabric may be immediately heat-treated, heat-treated after a while, or may be dried / colored according to the application, and any method may be used in the present invention.

In the inkjet printing method of the present invention, when dyeing with a disperse dye, not only a method of developing a color at a high temperature but also a carrier may be used. The compound used as the carrier is preferably a compound having characteristics such as large dyeing acceleration, simple use, stable, low burden on human body and environment, easy removal from the fiber, and no influence on dye fastness. Examples of the carrier include o-phenylphenol, p-phenylphenol, methylnaphthalene, alkyl benzoate, alkyl salicylate, chlorobenzene, diphenyl such as diphenyl, ethers, organic acids, hydrocarbons and the like. These promote the swelling and plasticization of difficult-to-dye fibers that are difficult to dye at temperatures around 100 ° C. like polyester, and make it easier for disperse dyes to enter the fibers. The carrier may be preliminarily adsorbed on the fibers of the fabric used for inkjet printing, or may be included in the inkjet ink.

After the heat treatment, a cleaning process is necessary. This is because a dye that has not participated in the dyeing remains, resulting in poor color stability and low fastness. It is also necessary to remove the pretreatment agent applied to the fabric. If left as it is, not only the fastness is lowered, but also the fabric is discolored. Therefore, cleaning according to the object to be removed and the purpose is essential. The method is selected according to the material and ink to be printed. For example, in the case of polyester, treatment is generally performed with a mixed solution of caustic soda, a surfactant, and hydrosulfite. The method is usually carried out in a continuous type such as an open soaper or a batch type using a liquid dyeing machine, and any method may be used in the present invention.

After drying, drying is necessary. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like. Infrared heaters can also be used.

(Textile printing device)
An example of a textile printing apparatus applicable to the textile printing method of the present invention will be described.

(Inkjet head)
In the textile printing method of the present invention, the pretreatment agent can be applied onto the fabric using an inkjet head (hereinafter also simply referred to as a head). By applying the pretreatment agent with the head, it is possible to uniformly apply the necessary amount evenly to the necessary site.

The head for applying the pretreatment agent can be mounted on a carriage separate from the carriage on which the head for applying the recording ink is mounted, or can be mounted on the same carriage. When a head for applying a pretreatment agent is mounted on another carriage, it is preferable to provide a drying device for drying the pretreatment agent after applying the pretreatment agent and before applying the recording ink. Further, when a head for applying a pretreatment agent is mounted on the same carriage, it is preferable to mount a drying device for drying the pretreatment agent on the carriage.

The head used for discharging the pretreatment agent and the recording ink can be selected from various methods such as a piezo method, a thermal method, and a continuous method. The piezo method and the continuous method are preferable because they are highly likely to be stably ejected even with an ink containing a polymer material. In particular, the piezo method is preferable because of its small size and high integration.

(Drying means)
The textile printing apparatus of the present invention preferably has a drying means for drying the fabric after applying the pretreatment agent on the fabric.

In the present invention, in the drying step of the pretreatment agent, it is preferable to dry to the extent that the function of the applied pretreatment agent is expressed to the maximum. In many cases, the pretreatment agent is applied to the fabric as much as possible because the application of the pretreatment agent increases the total ink amount in combination with the subsequent recording ink recording, thereby facilitating bleeding. It is preferable to dry the moisture of the agent and the organic solvent. In the present invention, it is preferable to set the temperature suitable for each composition of the fabric and the pretreatment agent in the range of the fabric surface temperature from 30 ° C to 80 ° C.

In the above drying process, if moisture or organic solvent retained by the pretreatment agent is filled inside the printer, not only will the drying speed decrease, but the electrical system such as the sensor inside the printer may be corroded. Therefore, it is preferable to discharge these volatile components to the outside of the printer. For example, it is preferable to provide an exhaust tower and forcibly exhaust using a fan or the like.

Specific methods of drying means applicable to the textile printing apparatus used in the present invention include temperature-controllable air or drying means using hot air, drying means using a hot plate, visible light or far-infrared light. The drying means used, the drying means using a heat roller, the drying means using a means for irradiating microwaves, etc. can be appropriately selected and used.

(Configuration of textile printing device)
Hereinafter, the textile printing apparatus applicable to the present invention described above will be described with reference to the drawings. However, the present invention is not limited only to the exemplified configurations.

FIG. 1 is a partial schematic diagram showing an example of the configuration of a textile printing apparatus.

FIG. 1 shows an adhesive belt of a textile printing apparatus, a roller for driving the adhesive belt, a carriage equipped with an ink jet head for applying a pretreatment agent, and drying for drying the fabric after applying the pretreatment agent to the fabric. Textile printing apparatus capable of being used in the present invention, showing only means, a carriage equipped with an ink jet head for applying recording ink to the cloth, and a drying means for drying the cloth after applying the recording ink to the cloth. In addition, a control means for applying a pretreatment agent and recording ink is provided.

In FIG. 1, an adhesive belt 1 is an adhesive belt that is held by a support roll 2 and a transport roll 3 and has an adhesive means, particularly preferably a base paste, on an endless base material belt.

The fabric P conveyed from the right direction is sandwiched between the nip roll 4 and the adhesive belt 1 and fixed to the adhesive belt 1. Next, the pretreatment agent is applied to the fabric from the pretreatment agent discharge head mounted on the carriage 5A and then blown with temperature-controllable air or warm air. The fan 7A and the heating element 8A are provided inside. The applied pretreatment agent is dried by the provided warm air applying means 6A. Next, the recording ink is applied onto the fabric from the recording ink discharge head mounted on the carriage 5B to form an image, and then the fabric is dried by the warm air applying means 6B.

FIG. 2 is a partial schematic view of the carriage 5A of the textile printing apparatus shown in FIG. 1 as viewed from above.

In FIG. 2, in the drawing, the pretreatment agent is applied to the fabric conveyed from the upper side by the pretreatment agent discharge head. In Figure, PT denotes a pre-processing agent ejection head, X ₁ represents a main scanning direction of the carriage, X ₂ represents a conveyance direction of the fabric.

FIG. 3 is a partial schematic view of the carriage 5B of the textile printing apparatus shown in FIG. 1 as viewed from above.

In FIG. 3, recording ink is applied to the fabric conveyed from the upper side of the drawing by a recording ink discharge head. C, M, Y, and K indicate recording ink ejection heads corresponding to cyan, magenta, yellow, and black inks, respectively. X ₁ is also expressed in the main scanning direction of the carriage, X ₂ represents a conveyance direction of the fabric.

FIG. 4 is a partial schematic diagram showing another example of the configuration of the textile printing apparatus.

The textile printing apparatus shown in FIG. 4 is an example in which an ink jet head for applying a pretreatment agent and an ink jet head for applying recording ink are mounted on the same carriage with respect to the textile printing apparatus shown in FIG. The carriage 5 is equipped with both an inkjet head for applying a pretreatment agent and a recording ink ejection head for applying recording ink. In this example, since only one set of carriage, its driving means, etc. is prepared, the structure of the textile printing apparatus can be made simple and compact.

FIG. 5 is a partial schematic view of the carriage 5 of the textile printing apparatus shown in FIG. 4 as viewed from above. Recording ink discharge heads C to Y and a pretreatment agent discharge head PT are arranged on the carriage.

In FIG. 5, after the pretreatment agent is applied to the fabric conveyed from the upper side of the drawing by the pretreatment agent ejection head disposed upstream from the recording ink ejection head, it is provided as drying means on both sides of the carriage. The obtained far infrared heater IR is dried. Next, after the recording ink is applied to the fabric by the recording ink discharge head, it is dried by a far infrared heater in the same manner as the pretreatment agent. Incidentally, in FIG., X ₁ is also expressed in the main scanning direction of the carriage, X ₂ represents a conveyance direction of the fabric.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

(Preparation of reactive dye ink)
Each material shown in Table 1 was mixed by stirring and dissolved, then filtered through a 0.2 μm PTFE filter, and then degassed to prepare inks RY, RM, RC, and RBk.

Y dye: C.I. I. Reactive Yellow95
M dye: C.I. I. Reactive Red24
C dye: C.I. I. Reactive Blue 72
Bk dye: C.I. I. Reactive Black39
+ C. I. Reactive Brown11
EG: Ethylene glycol PG: Propylene glycol Gly: Glycerin E1010: Olphine E1010
(Acetylene glycol-based activator, manufactured by Nissin Chemical Industry Co., Ltd.)
(Preparation of acid dye ink)
Each material shown in Table 2 was mixed by stirring and dissolved, then filtered through a 0.2 μm PTFE filter, and then degassed to prepare inks AY, AM, AC, and ABk.

Y dye: C.I. I. Acid Yellow 79
M dye: C.I. I. Acid Red 249
C dye: C.I. I. Direct blue 87
Bk dye: C.I. I. Acid Black 52: 1
DEG: Diethylene glycol Gly: Glycerin (Preparation of disperse dye ink)
(Preparation of dye dispersion)
The following compositions were dispersed using a sand grinder to prepare dye dispersions Y1, M1, C1, and K1, respectively. Dispersion stopped when the average particle size reached 200 nm.

Disperse dye (dispersed dye species listed in Table 3) 25 parts Glycerin 25 parts Ion-exchanged water 25 parts Dispersant A (sodium lignin sulfonate, Vanillex RN, Nippon Paper Industries)
12 parts Dispersant B (Floren G-700, manufactured by Kyoeisha Chemical Co., Ltd.) 3 parts

(Preparation of ink)
Each material shown in Table 4 was stirred and mixed, filtered through a 0.2 μm PTFE filter, and then degassed to prepare inks DY, DM, DC, and DBk.

EG: Ethylene glycol DES: Diethylhexyl sulfosuccinate sodium GXL: Proxel GXL (S) (Avisia)
The reactive dye ink, acid dye ink, and disperse dye ink prepared according to the above method are used to pass the ink through a gas-permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and the outer surface side of the hollow fiber membrane is covered. The dissolved gas in the ink was removed by reducing the pressure with a water flow aspirator. After degassing, these inks were filled into vacuum packs to prevent air from entering.

(Examples 1 to 10)
(Pretreatment agent preparation)
Pretreatment agents PT-1 to PT-10 having the formulations shown in Table 5 were prepared by the following procedure.

First, after a hydrotropic agent was dissolved in water, sodium alginate was dissolved. Next, sodium hydrogen carbonate, register liquid, sodium hexametaphosphate, and sunflorene SN were added in this order and mixed well with stirring. The obtained pretreatment agent was divided into two and filled in an aluminum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature.

(Pretreatment of fabric)
Each pretreatment agent prepared according to the above method was applied to the fabric by the following procedure.

After immersing the fabric (cotton loan) in the pretreatment agent, the excess pretreatment agent is squeezed using a mangle (VPM-1SUS type, manufactured by Sakurai Dyeing Machine Co., Ltd.) so that the squeeze rate becomes 70%. And then dried at 40 ° C. for 30 minutes to obtain a fabric provided with a pretreatment agent.

(Preparation of print sample)
The prepared reactive dye ink was loaded into a textile printer Nassenger-V manufactured by Konica Minolta IJ, and an evaluation image was printed on a fabric provided with the pretreatment agent.

The evaluation image is a solid single-color image that outputs 100% of each color of yellow, magenta, cyan, and black when ink is ejected to all pixels at 540 dpi × 540 dpi, and yellow and magenta. 2-color mixed solid image that outputs 100% of each color to the same area, magenta, cyan 2-color mixed solid image that outputs 100% of each color to the same area, yellow and cyan each color of 100% to the same area The output two-color solid image and the three-color mixed solid image in which each color of yellow, magenta, and cyan was output 100% in the same area were used. In the present invention, dpi represents the number of dots per 2.54 cm.

Next, the printed fabric was steamed at a temperature of 100 ° C. for 15 minutes, washed with water, soaped at 60 ° C., further washed with water and dried to obtain print samples 1 to 10.

(Evaluation of print samples)
(Evaluation of color development)
The reflection density of each color solid image prepared according to the above method was measured using a reflection densitometer (X-rite 938), and the color development was evaluated according to the following criteria.

◎: A sufficient concentration can be obtained ○: Slightly inferior to ◎, but a practically sufficient concentration can be obtained Δ: A practically insufficient concentration can be obtained ×: A practically insufficient concentration can be obtained ( Evaluation of bleed resistance)
The boundary area between the printed solid image part and the white background part was observed for the occurrence of blur using a loupe, and the blur resistance was evaluated according to the following criteria. No occurrence of image formation is observed at all, and the image is extremely clear. O: No occurrence of blur is observed up to the boundary portion of the solid image of the two colors, and the image is extremely clear. Slight blurring is observed at the boundary of the solid image of the three colors, but the image is clear and good. Δ: No blurring is observed at the boundary of the solid monochrome image, and the image is extremely clear. It is. Slight blurring is observed at the boundary of the solid image of the two-color mixture, but the image is clear and good. ×: Strong blurring is observed at the boundary of the solid monochrome image Result obtained as described above Is shown in Table 6.

From the results shown in Table 6, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention was used, the recording ink fabric was compared with the case of using the pretreatment agent containing the urea derivative of the comparative example. It can be seen that the spread of wetting is suppressed and the bleeding resistance is improved. In addition, when the pretreatment agent containing the urea derivative of the comparative example was used, the pretreatment agent stored at 60 ° C. for 1 week had a significantly deteriorated color developability as compared with that stored at room temperature. It can be seen that when the pretreatment agent containing the 2-imidazolidinone derivative of the invention is used, the color developability is not deteriorated and the storage stability is greatly improved.

(Examples 11 to 18)
(Pretreatment agent preparation)
Pretreatment agents PT-11 to PT-18 having the formulations shown in Table 7 were prepared in the same procedure as in Examples 1 to 10.

Sodium alginate (ULV-L3G, manufactured by Kimika)
Resistor liquid: Sodium metanitrobenzenesulfonate solution (Senka)
Sunfloren SN: Polyhydric alcohol fatty acid ester (manufactured by Nikka Chemical Co., Ltd.)
(Pretreatment of fabric)
Each pretreatment agent prepared according to the above method was applied to the fabric in the same manner as in Examples 1 to 10.

(Preparation of print sample)
In the same manner as in Examples 1 to 10, the recording ink was printed on the fabric to which the pretreatment agent was applied to produce print samples 11 to 18.

(Evaluation of print samples)
(Evaluation of bleeding resistance during printing)
After printing, before the steaming process, the boundary area between the printed solid image portion and the white background portion was observed for the occurrence of blur using a loupe, and the blur resistance was evaluated according to the following criteria. Occurrence of blurring is not recognized at all at the boundary of the solid image of the three-color mixture, and the image is extremely clear. It is. Slight blurring is observed at the boundary of a solid image of three colors, but the image is clear and good. Δ: No blurring is observed at the boundary of a solid monochrome image, and the image is extremely clear. It is. Slight blurring is observed at the boundary of a solid image of two colors, but the image is clear and good. ×: Strong blurring is observed at the boundary of a solid monochrome image. In some cases, for example, △△ was written.

(Evaluation of bleeding resistance during steaming)
After the steaming process and before washing with water, the boundary area between the printed solid image part and the white background part was observed with a loupe for the occurrence of bleeding, and the bleeding resistance was evaluated according to the following criteria. Occurrence of blurring at the boundary of the solid image of the three-color mixture is not recognized at all, and the image is extremely clear. ○: Generation of bleeding at the boundary of the solid image of the mixture of two colors is not observed at all, and the image is extremely clear. It is. Slight blurring is observed at the boundary of the solid image of the three colors, but the image is clear and good. Δ: No blurring is observed at the boundary of the solid monochrome image, and the image is extremely clear. It is. Slight blurring is observed at the boundary of the solid image of the two-color mixture, but the image is clear and good. ×: Strong blurring is observed at the boundary of the solid monochrome image. In some cases, for example, △△ was written.

(Evaluation of color development)
The color development was evaluated in the same procedure as in Examples 1-10.

Table 8 shows the results obtained as described above.

From the results of Table 8, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be slightly deteriorated. Moreover, when content exceeds 30 mass%, it turns out that there exists a tendency for the bleeding tolerance at the time of a steaming process to deteriorate a little.

(Examples 19 to 28)
(Pretreatment agent preparation)
Pretreatment agents PT-19 to PT-28 having the formulations shown in Table 9 were prepared by the following procedure.

First, after dissolving the hydrotropic agent and sodium tripolyphosphate in water, fine gum SA-M was dissolved. Next, Nikka Silicon ATS-10 and Resistor Liquid were added in this order and mixed well with stirring. The obtained pretreatment agent was divided into two and filled in an aluminum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature.

(Pretreatment of fabric)
Each pretreatment agent prepared according to the above method was applied to the fabric in the same manner as in Examples 1 to 10.

(Preparation of print sample)
The acid dye ink prepared by the above-described procedure was loaded into a textile printer Nassenger-V manufactured by Konica Minolta IJ, and the evaluation image was printed on the fabric to which the pretreatment agent was applied in the same procedure as in Examples 1 to 10. did.

Next, the printed fabric was steamed at a temperature of 100 ° C. for 30 minutes, washed with water, soaped at 40 ° C., further washed with water and dried to obtain print samples 19 to 28.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The obtained results are shown in Table 10.

From the results shown in Table 10, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention was used, the recording ink fabric was compared with the case of using the pretreatment agent containing the urea derivative of the comparative example. It can be seen that the spread of wetting is suppressed and the bleeding resistance is improved. In addition, when the pretreatment agent containing the urea derivative of the comparative example was used, the pretreatment agent stored at 60 ° C. for 1 week had a significantly deteriorated color developability as compared with that stored at room temperature. It can be seen that when the pretreatment agent containing the 2-imidazolidinone derivative of the invention is used, the color developability is not deteriorated and the storage stability is greatly improved.

(Examples 29 to 36)
(Pretreatment agent preparation)
Pretreatment agents PT29 to PT36 having the formulations shown in Table 11 were prepared in the same procedure as in Examples 19 to 28.

Sodium tripolyphosphate (57% active ingredient, manufactured by Kanto Chemical Co., Inc.)
Fine gum SA-M: Carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd.)
Nikka Silicon ATS-10 (manufactured by Nikka Chemical)
(Pretreatment of fabric)
Each pretreatment agent prepared according to the above method was applied to the fabric in the same manner as in Examples 19 to 28.

(Preparation of print sample)
Print samples 29 to 36 were prepared in the same procedure as in Examples 19 to 28.

(Evaluation of print samples)
In the same procedure as in Examples 11 to 18, the bleeding resistance at the time of printing, the bleeding resistance at the time of the steaming process, and the color development were evaluated. Table 12 shows the obtained results.

From the results shown in Table 12, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be slightly deteriorated. Moreover, when content exceeds 30 mass%, it turns out that there exists a tendency for the bleeding tolerance at the time of a steaming process to deteriorate a little.

(Examples 37 to 46)
(Pretreatment agent preparation)
Pretreatment agents PT-37 to PT-46 having the formulations shown in Table 13 were prepared by the following procedure.

First, after the hydrotropic agent and citric acid were dissolved in water, sodium alginate was dissolved. Next, Sunfloren SN, Nice Paul FE22, NK Guard NDN-7E and EDTA-2Na were added in this order and mixed well with stirring. The obtained pretreatment agent was divided into two and filled in an aluminum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature.

(Preparation of print sample)
The disperse dye ink prepared in the above procedure was loaded into a textile printer Nassenger-V manufactured by Konica Minolta IJ, and the evaluation image was printed on the fabric to which the pretreatment agent was applied in the same procedure as in Examples 1 to 10. did.

Next, the printed fabric was steamed at a temperature of 130 ° C. for 30 minutes, washed with water, soaped at 80 ° C., further washed with water and dried to obtain print samples 37 to 46.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. Table 14 shows the obtained results.

From the results shown in Table 14, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention was used, the recording ink fabric was compared with the case of using the pretreatment agent containing the urea derivative of the comparative example. It can be seen that the spread of wetting is suppressed and the bleeding resistance is improved. In addition, when the pretreatment agent containing the urea derivative of the comparative example was used, the pretreatment agent stored at 60 ° C. for 1 week had a significantly deteriorated color developability as compared with that stored at room temperature. It can be seen that when the pretreatment agent containing the 2-imidazolidinone derivative of the invention is used, the color developability is not deteriorated and the storage stability is greatly improved.

(Examples 47 to 54)
(Pretreatment agent preparation)
Pretreatment agents PT-47 to PT-54 having the formulations shown in Table 15 were prepared in the same manner as in Examples 37 to 46.

Sodium alginate (ULV-L3G, manufactured by Kimika)
Nicepol FE22: Nonionic compound, softener (Nikka Chemical Co., Ltd.)
NK guard NDN-7E: fluorinated water repellent (manufactured by Nikka Chemical Co., Ltd.)
(Pretreatment of fabric)
Each pretreatment agent prepared according to the above method was applied to the fabric in the same manner as in Examples 37 to 46.

(Preparation of print sample)
Print samples 47 to 54 were produced in the same procedure as in Examples 37 to 46.

(Evaluation of print samples)
In the same procedure as in Examples 11 to 18, the bleeding resistance at the time of printing, the bleeding resistance at the time of the steaming process, and the color development were evaluated. The obtained results are shown in Table 16.

From the results shown in Table 16, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be slightly deteriorated. Moreover, when content exceeds 30 mass%, it turns out that there exists a tendency for the bleeding tolerance at the time of a steaming process to deteriorate a little.

(Examples 55 to 70)
(Pretreatment agent preparation)
A pretreatment agent having the formulation shown in Table 17 was prepared by the following procedure.

First, after potassium carbonate was dissolved in water, the hydrotropic agent was dissolved. Next, propylene glycol and triethylene glycol monobutyl ether were dissolved, and further polyethylene glycol 6000 was dissolved. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, then divided into two and filled in a vacuum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature. The pretreatment agent was deaerated by the same method as that for the recording ink described above.

(Preparation of print sample)
Print samples were prepared using the printer shown in FIGS.

First, the pretreatment agent prepared according to the above method is introduced into the pretreatment agent ejection head of the carriage 5A, and the above-described reactive dye inks RY, RM, RC, RBk are used as the recording inks in the recording ink ejection head of the carriage 5B. Was introduced.

Next, while conveying the fabric in the direction of the arrow in FIG. 1, the pretreatment agent was uniformly applied to the entire surface of the fabric from the pretreatment agent discharge head of the carriage 5 </ ^b > A so as to give an amount of 12 ml / m ² . It was made to dry with the warm air provision means 6A.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge head of the carriage 5B, the evaluation image was printed, and then dried by the hot air applying means 6B. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . As the fabric, cotton lawn and canvas were used. Further, the interval between the carriage 5A and the carriage 5B was adjusted so that the interval from when the pretreatment agent was applied to the fabric until the recording ink was applied to the same position was 60 seconds.

Next, the printed fabric was steamed at a temperature of 100 ° C. for 15 minutes, washed with water, soaped at 60 ° C., further washed with water and dried to obtain a print sample.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The obtained results are shown in Table 18.

(Examples 71 to 86)
(Preparation of print sample)
Print samples were prepared using the printer shown in FIGS.

First, the pretreatment agent prepared in Examples 55 to 70 is introduced into the pretreatment agent discharge head PT of the carriage 5, and the above-described reactive dye ink is used as the recording ink in the recording ink discharge heads Y, M, C, and K. RY, RM, RC and RBk were introduced.

Next, after the fabric is conveyed in the direction of the arrow in FIG. 4, the pretreatment agent is uniformly applied to the entire surface of the fabric from the pretreatment agent discharge head PT of the carriage 5 so as to give an amount of 12 ml / m ² . And dried by a far infrared heater IR.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge heads Y, M, C, and K, and the evaluation image was printed, and then dried by the far infrared heater IR. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . As the fabric, cotton lawn and canvas were used. Further, the pretreatment agent ejection head and the recording ink ejection head are arranged so that the interval between the application of the pretreatment agent to the fabric and the application of the recording ink to the same position is 5 seconds and 10 seconds. The interval a was adjusted.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 19.

From the results shown in Tables 18 and 19, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention is used, a thin cloth, such as a cotton lawn, which has a small ink holding amount and easily bleeds ink, is used. In addition, it can be seen that the bleeding resistance is improved. In addition, in the case of the pretreatment agent using the urea derivative of the comparative example, the pretreatment agent stored at 60 ° C. for 1 week has greatly deteriorated color developability as compared with that stored at room temperature. It can be seen that when a pretreatment agent containing a 2-imidazolidinone derivative is used, the color developability is not deteriorated and the storage stability is greatly improved. Further, as in this example, even when the time from application of the pretreatment agent to application of the recording ink is short and sufficient time for drying the pretreatment agent cannot be taken, the 2-imidazo of the present invention is used. It can be seen that sufficient color developability can be obtained when a pretreatment agent containing a ridinone derivative is used.

(Examples 87 to 95)
(Pretreatment agent preparation)
Pretreatment agents having the formulations shown in Table 20 were prepared in the same procedure as in Examples 55 to 70. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, and then filled into a vacuum pack.

PG: Propylene glycol TEGBE: Triethylene glycol monobutyl ether (Butizenol 30, manufactured by Kyowa Hakko Chemical Co., Ltd.)
PEG 6000: polyethylene glycol 6000
(Preparation of print sample)
Print samples were prepared in the same procedure as in Examples 71 to 86 using the printer shown in FIGS. However, the amount of pretreatment agent was as shown in Table 21.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 21.

From the results shown in Table 21, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be somewhat deteriorated. When the content exceeds 30% by mass, 2- The solubility of imidazolidinone becomes severe. Moreover, when the application amount of the pretreatment agent to the fabric is less than 5 ml / m ² , the bleeding resistance and the color developability tend to be slightly deteriorated. When the application amount exceeds 20 ml / m ² , the pretreatment agent is dried. It becomes insufficient and penetrates and diffuses into the fabric, the effect is lowered, and the bleeding resistance and color developability tend to be slightly deteriorated.

(Examples 96 to 111)
(Pretreatment agent preparation)
A pretreatment agent having the formulation shown in Table 22 was prepared by the following procedure.

First, after sodium tripolyphosphate was dissolved in water, the hydrotropic agent was dissolved. Next, propylene glycol and triethylene glycol monobutyl ether were dissolved, and further, resist liquid and polyethylene glycol 6000 were dissolved in this order. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, then divided into two and filled in a vacuum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature.

First, the pretreatment agent prepared according to the above method is introduced into the pretreatment agent discharge head of the carriage 5A, and the acid dye inks AY, AM, AC, ABk described above are used as the recording ink in the recording ink discharge head of the carriage 5B. Was introduced.

Next, while conveying the fabric in the direction of the arrow in FIG. 1, the pretreatment agent was uniformly applied to the entire surface of the fabric from the pretreatment agent discharge head of the carriage 5 </ ^b > A so as to give an amount of 12 ml / m ² . It was made to dry with warm air provision means 6A.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge head of the carriage 5B, the evaluation image was printed, and then dried by the hot air applying means 6B. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . The fabric used was 12 シルク and 20 匁 satin silk. Further, the interval between the carriage 5A and the carriage 5B was adjusted so that the interval from when the pretreatment agent was applied to the fabric until the recording ink was applied to the same position was 60 seconds.

Next, the printed fabric was steamed for 30 minutes at a temperature of 100 ° C., washed with water, soaped at 40 ° C., further washed with water and dried to obtain a print sample.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 23.

(Examples 112 to 127)
(Preparation of print sample)
Print samples were prepared using the printer shown in FIGS.

First, the pretreatment agent prepared in Examples 96 to 111 is introduced into the pretreatment agent discharge head PT of the carriage 5, and the above-described acidic dye ink is used as the recording ink in the recording ink discharge heads Y, M, C, and K. AY, AM, AC, ABk were introduced.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge heads Y, M, C, and K, and the evaluation image was printed, and then dried by the far infrared heater IR. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . The fabric used was 12 シルク and 20 匁 satin silk. Further, the pretreatment agent ejection head and the recording ink ejection head are arranged so that the interval between the application of the pretreatment agent to the fabric and the application of the recording ink to the same position is 5 seconds and 10 seconds. The interval a was adjusted.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 24.

From the results shown in Tables 23 and 24, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention was used, a thin fabric such as satin silk 12 mm, which has a small ink holding amount and easily blots ink, was used. It can be seen that the bleed resistance is improved. In addition, in the case of the pretreatment agent using the urea derivative of the comparative example, the pretreatment agent stored at 60 ° C. for 1 week has greatly deteriorated color developability as compared with that stored at room temperature. It can be seen that when a pretreatment agent containing a 2-imidazolidinone derivative is used, the color developability is not deteriorated and the storage stability is greatly improved. Further, as in this example, even when the time from application of the pretreatment agent to application of the recording ink is short and sufficient time for drying the pretreatment agent cannot be taken, the 2-imidazo of the present invention is used. It can be seen that sufficient color developability can be obtained when a pretreatment agent containing a ridinone derivative is used.

(Examples 128 to 136)
(Pretreatment agent preparation)
Pretreatment agents having the formulations shown in Table 25 were prepared in the same procedure as in Examples 96-111. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, and then filled into a vacuum pack.

Sodium tripolyphosphate (57% active ingredient, manufactured by Kanto Chemical Co., Inc.)
PG: Propylene glycol TEGBE: Triethylene glycol monobutyl ether (Butizenol 30, manufactured by Kyowa Hakko Chemical Co., Ltd.)
PEG 6000: polyethylene glycol 6000
(Preparation of print sample)
Print samples were produced using the printer shown in FIGS. 4 and 5 in the same procedure as in Examples 112 to 127. However, the amount of pretreatment agent applied was as shown in Table 26.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 26.

From the results shown in Table 26, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be slightly deteriorated. When the content exceeds 30% by mass, 2- The solubility of imidazolidinone becomes severe. Moreover, when the application amount of the pretreatment agent to the fabric is less than 5 ml / m ² , the bleeding resistance and the color developability tend to be slightly deteriorated. When the application amount exceeds 20 ml / m ² , the pretreatment agent is dried. It becomes insufficient and penetrates and diffuses into the fabric, the effect is lowered, and the bleeding resistance and color developability tend to be slightly deteriorated.

(Examples 137 to 152)
(Pretreatment agent preparation)
A pretreatment agent having the formulation shown in Table 27 was prepared by the following procedure.

First, citric acid was dissolved in water, and then the hydrotropic agent was dissolved. Next, propylene glycol and triethylene glycol monobutyl ether were dissolved, and EDTA-2Na and polyethylene glycol 6000 were dissolved in this order. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, then divided into two and filled in a vacuum pack, and one was stored at 60 ° C. for 1 week. The other was stored at room temperature.

First, the pretreatment agent prepared according to the above method is introduced into the pretreatment agent discharge head of the carriage 5A, and the above-mentioned disperse dye inks DY, DM, DC, DBk are used as recording inks in the recording ink discharge head of the carriage 5B. Was introduced.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge head of the carriage 5B, the evaluation image was printed, and then dried by the hot air applying means 6B. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . As the fabric, polyester decine and polyester double picket (both handled by Color Dyeing Co., Ltd.) were used. Further, the interval between the carriage 5A and the carriage 5B was adjusted so that the interval from when the pretreatment agent was applied to the fabric until the recording ink was applied to the same position was 60 seconds.

Next, the printed fabric was steamed at a temperature of 130 ° C. for 30 minutes, washed with water, soaped at 80 ° C., further washed with water and dried to obtain a print sample.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 28.

(Examples 153-168)
(Preparation of print sample)
Print samples were prepared using the printer shown in FIGS.

First, the pretreatment agent prepared in Examples 137 to 152 is introduced into the pretreatment agent discharge head PT of the carriage 5, and the above-mentioned disperse dye ink is used as the recording ink in the recording ink discharge heads Y, M, C, and K. DY, DM, DC, DBk were introduced.

Subsequently, the recording ink was applied to the fabric from the recording ink discharge heads Y, M, C, and K, and the evaluation image was printed, and then dried by the far infrared heater IR. The evaluation images were the same as those used in Examples 1 to 10, and the amount of recording ink applied to the single-color solid image was 9 ml / m ² . As the fabric, polyester decine and polyester double picket (both handled by Color Dyeing Co., Ltd.) were used. Further, the pretreatment agent ejection head and the recording ink ejection head are arranged so that the interval between the application of the pretreatment agent to the fabric and the application of the recording ink to the same position is 5 seconds and 10 seconds. The interval a was adjusted.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 29.

From the results shown in Tables 28 and 29, when the pretreatment agent containing the 2-imidazolidinone derivative of the present invention is used, a thin cloth such as polyester decine, which has a small ink holding amount and easily bleeds, is used. In addition, it can be seen that the bleeding resistance is improved. In addition, in the case of the pretreatment agent using the urea derivative of the comparative example, the pretreatment agent stored at 60 ° C. for 1 week has greatly deteriorated color developability as compared with that stored at room temperature. It can be seen that when a pretreatment agent containing a 2-imidazolidinone derivative is used, the color developability is not deteriorated and the storage stability is greatly improved. Further, as in this example, even when the time from application of the pretreatment agent to application of the recording ink is short and sufficient time for drying the pretreatment agent cannot be taken, the 2-imidazo of the present invention is used. It can be seen that sufficient color developability can be obtained when a pretreatment agent containing a ridinone derivative is used.

(Examples 169 to 177)
(Pretreatment agent preparation)
Pretreatment agents having the formulations shown in Table 30 were prepared in the same procedure as in Examples 137 to 152. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, and then filled into a vacuum pack.

PG: Propylene glycol TEGBE: Triethylene glycol monobutyl ether (Butizenol 30, manufactured by Kyowa Hakko Chemical Co., Ltd.)
PEG 6000: polyethylene glycol 6000
NK guard NDN-7E: fluorinated water repellent (manufactured by Nikka Chemical Co., Ltd.)
(Preparation of print sample)
Print samples were prepared using the printer shown in FIGS. 4 and 5 in the same procedure as in Examples 153 to 168. However, the amount of pretreatment agent applied was as shown in Table 31.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 31.

From the results shown in Table 31, when the content of 2-imidazolidinone is less than 3% by mass, the color developability tends to be slightly deteriorated, and when the content exceeds 30% by mass, The solubility of imidazolidinone becomes severe. Moreover, when the application amount of the pretreatment agent to the fabric is less than 5 ml / m ² , the bleeding resistance and the color developability tend to be slightly deteriorated. When the application amount exceeds 20 ml / m ² , the pretreatment agent is dried. It becomes insufficient and penetrates and diffuses into the fabric, the effect is lowered, and the bleeding resistance and color developability tend to be slightly deteriorated.

(Preparation of reactive dye ink)
Each material shown in Tables 32, 33 and 34 was mixed by stirring and dissolved, then filtered through a 0.2 μm PTFE filter, and then degassed to prepare each ink.

Y dye: C.I. I. Reactive Yellow95
M dye: C.I. I. Reactive Red24
C dye: C.I. I. Reactive Blue 72
Bk dye: C.I. I. Reactive Black39 + C. I. Reactive Brown11
EG: ethylene glycol PG: propylene glycol Gly: glycerin E1010: olphine E1010 (acetylene glycol-based activator, manufactured by Nissin Chemical Industry Co., Ltd.)
(Examples 178 to 180)
(Pretreatment agent preparation)
Pretreatment agents PT-94 to PT-96 having the formulations shown in Table 35 were prepared by the following procedure.

First, urea was dissolved in water, and then sodium alginate was dissolved. Next, sodium hydrogen carbonate, register liquid, sodium hexametaphosphate, and sunflorene SN were added in this order and mixed well with stirring.

(Preparation of print sample)
In the same manner as in Examples 1 to 10, the recording ink was printed on the fabric to which the pretreatment agent was applied to produce print samples 178 to 180.

(Evaluation of print samples)
(Evaluation of bleeding resistance during printing)
The bleeding resistance at the time of printing was evaluated in the same procedure as in Examples 11-18.

(Evaluation of bleeding resistance during steaming)
The bleeding resistance at the time of the steaming treatment was evaluated in the same procedure as in Examples 11-18.

Table 36 shows the results obtained as described above.

From the results shown in Table 36, when the recording ink containing the coloring material contains 2-imidazolidinone, bleeding tends to occur during the steaming process particularly in a portion where the amount of the recording ink applied to the cloth is large. I understand. In Examples 178 to 180, although the amount of 2-imidazolidinone applied to the fabric is smaller than that in Examples 14 to 18, the bleeding at the time of the steaming process is deteriorated. This is thought to be due to the localization of 2-imidazolidinone in the vicinity of the dye by adding 2-imidazolidinone to the recording ink and applying it to the cloth.

(Examples 181 to 183)
(Pretreatment agent preparation)
A pretreatment agent having the formulation shown in Table 37 was prepared by the following procedure.

First, after dissolving potassium carbonate in water, urea was dissolved. Next, propylene glycol and triethylene glycol monobutyl ether were dissolved, and further polyethylene glycol 6000 was dissolved. The obtained pretreatment agent was filtered through a 0.2 μm PTFE filter, then degassed, and then filled into a vacuum pack. The pretreatment agent was deaerated by the same method as that for the recording ink described above.

PG: Propylene glycol TEGBE: Triethylene glycol monobutyl ether (Butizenol 30, manufactured by Kyowa Hakko Chemical)
PEG 6000: polyethylene glycol 6000
(Preparation of print sample)
Print samples were prepared in the same procedure as in Examples 71 to 86 using the printer shown in FIGS. However, the amount of the pretreatment agent was 10 ml / m ^2, and a cotton lawn was used as the fabric.

(Evaluation of print samples)
In the same procedure as in Examples 1 to 10, color development and bleeding resistance were evaluated. The results obtained are shown in Table 38.

From the results in Table 38, it can be seen that when 2-imidazolidinone is added to the recording ink containing the color material, bleeding tends to occur particularly in a portion where the amount of the recording ink applied to the cloth is large.

DESCRIPTION OF SYMBOLS 1 Adhesive belt 2 Support roll 3 Conveyance roll 4

Nip roll

5, 5A,

5B Carriage

7, 7A,

7B Fan

8, 8A,

8B Heating element

6, 6A, 6B Hot air provision means PT Pretreatment agent discharge head C, M , Y, K Recording ink ejection head

Claims

2. A fabric pretreatment agent for inkjet printing, comprising at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof.
The fabric pretreatment agent for ink-jet printing according to claim 1, wherein 2-imidazolidinone or a derivative thereof is represented by the following general formula (I).

(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, which may be substituted, respectively. )
The fabric pretreatment agent for inkjet printing according to claim 1 or 2, wherein at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof is 2-imidazolidinone.
The inkjet printing according to any one of claims 1 to 3, wherein the content of at least one compound selected from the group consisting of 2-imidazolidinone and derivatives thereof is 5 to 30% by mass. Fabric pretreatment agent.
A fabric pretreatment method comprising applying the fabric pretreatment agent for inkjet textile printing according to any one of claims 1 to 4 to the fabric by an inkjet method.
The method for pretreating a fabric according to claim 5, wherein the amount of the pretreatment agent for inkjet textile printing applied to the fabric is 5 to 20 ml / m 2 .
A textile print comprising: applying a cloth pretreatment agent for inkjet textile printing to a cloth by the cloth pretreatment method according to claim 5 or 6; and applying an ink containing a coloring material to the cloth within 10 seconds. Method.