JP2010024442A - Ink set for textile printing inkjet and textile printing inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for textile printing inkjet satisfactorily preventing feathering and obtaining high color-developing density without using a glue agent or the like as pretreatment to a cloth, and further simplifying a post-treatment process and obtaining a recorded article in which the versatile correspondence cloth kinds are used, and to provide a recording method of textile printing inkjet. <P>SOLUTION: The ink set for textile printing inkjet comprises: an ink composition (C) which comprises at least a reactive dye, water, a hydrophobic monomer as a polymerizable component, a water-soluble copolymer containing an isolated polymer by 0.5-5.0 mass% for ink total amount and at least one kind selected from glycol ether and 1,2-alkane diol; and an alkali supply ink composition (A) which comprises water, at least one kind selected from glycol ether and 1,2-alkane diol, and an alkali supply material. Further, the recording method of textile printing inkjet is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a textile ink jet ink set and a textile ink jet recording method.

  Textile printing is a general term for a method of dyeing multicolored patterns on fibers (mainly fabrics or knitted fabrics), and there are various methods.

  For example, the direct printing method is the most common printing method, and is a method of drawing a pattern by sequentially printing a printing paste according to the number of colors of a white cloth or a dyed cloth. Examples of the printing machine include a rotary screen printing machine, a roller printing machine, a fully automatic flat screen printing machine, and a hand flat screen printing stand. In addition, various methods such as an anti-dyeing method, an anti-discharge method, a discharging method, a transfer printing method, and a bucket dyeing are used.

  However, each time the design is changed, it is necessary to create a plurality of plates in which the image is newly separated for each color, and to replace the screen, engraving roller, etc. The production usually requires a period of one month or longer. In recent years, due to the diversification of consumer needs, demands for small-lot, multi-product production and quick response have increased, and it has become difficult to satisfy these demands with conventional textile printing methods.

  In response to such market demands, a printing ink jet method has been proposed as a new printing method, and commercialization is progressing by each manufacturer.

  The textile printing ink jet method is a method in which fine droplets of an ink jet recording liquid (hereinafter, also simply referred to as ink) are ejected by various operating principles and adhered to a recording medium (in this case, mainly a fabric or woven fabric). This image formation is performed and has the following advantages.

  Since a design pattern can be generated from a CD-ROM, MO, or a photograph read by a scanner, and the information can be printed directly on a recording medium (fabric, woven fabric), it is necessary to prepare a plate for each color as in the conventional printing method. There is no. In addition, it has a feature that it can be made from design to finishing in a short time because many sample variations can be produced with less production time and the entire process can be processed by a personal computer.

  However, even in the textile printing inkjet method, a pretreatment process in which a water-soluble polymer such as an anti-bleeding paste is preliminarily applied to a cloth, a printing process in which an image is inkjet-recorded, a drying process, a coloring process by steaming or high-temperature processing, an unreacted process A cleaning process that removes chemicals such as dyes and pre-treatment agents, and a fixing process that improves various fastnesses are essential, and this requires specialized technology and large-scale equipment. The problem remains that it is a drag on the law.

  For example, when dyeing cotton or silk fabric as a recording medium by a printing ink jet method, a water-soluble metal salt, an alkaline substance (see, for example, Patent Document 1) for preventing bleeding and improving dye fixing property, A pretreatment step (for example, see Patent Documents 2, 3, and 4) in which a pretreatment agent such as a water-soluble polymer is applied to the fabric in advance is performed, so that not only the pretreatment step but also the pretreatment after printing A post-treatment process for washing and removing the agent is essential, and a considerable work and time burden is generated. Furthermore, for the raised fabric or knitted fabric, when water-soluble polymer or the like is applied, when the pretreatment agent is applied, the raised portion of the surface is processed in a crushed state. In other words, it is difficult to obtain a uniform image.

  In addition, regarding a method for imparting a bleeding prevention effect by including a resin or the like in the ink itself, an application for an ink composition using a water-soluble resin in a pretreatment effect ink has been published (for example, Patent Documents). 5). However, this aims at adhesion on a glass substrate and prevention of clogging by ink jet ejection, and there is no technical idea such as prevention of bleeding on the fabric or impossibility of reduction to the post-treatment process.

  As described above, with regard to the pretreatment process in which the paste or the like is preliminarily applied to the medium to be recorded, it is necessary to prepare time for the fabric that has been pretreated in advance. Because large-scale equipment is required, specialized knowledge and experience are required for preparation of medicines to be applied in pretreatment, and pretreated fabrics cannot be stored for a long time due to the effects of chemical deterioration, yellowing, etc. Therefore, a system that does not require a pretreatment process is desired.

Japanese Examined Patent Publication No. 4-33913 Japanese Examined Patent Publication No. 63-31594 Japanese Patent Laid-Open No. 5-148777 Japanese Patent Application Laid-Open No. 5-179579 Japanese Patent Laid-Open No. 2001-200182

  It is an object of the present invention to suppress bleeding without using a glue or the like as a pre-treatment on a fabric, to have a high color density, and to simplify the post-treatment process. The present invention provides a textile ink jet ink set and a textile ink jet recording method.

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

  1. A water-soluble copolymer containing at least a reactive dye, water, a hydrophobic monomer as a polymerization component, and a free polymer in an amount of 0.5 to 5.0% by mass based on the total amount of the ink, glycol ether, and 1,2 -Alkali supply ink containing an ink composition (C) containing at least one selected from alkanediol, at least one selected from water, glycol ether and 1,2-alkanediol, and an alkali supply substance A textile ink jet ink set comprising the composition (A).

  2. The water-soluble copolymer having a hydrophobic monomer as a polymerization component is a copolymer obtained by polymerizing unsaturated vinyl having a carboxyl group as at least a monomer component, and is neutralized and dissolved with an amine. The ink set for textile printing ink jet according to 1.

  3. 3. The textile ink jet ink set as described in 1 or 2 above, wherein the ink composition (C) contains a fluorine-based or silicon-based surfactant.

  4). 4. The ink set for textile printing ink jet according to any one of 1 to 3, wherein the alkali supply substance is carbonate.

  5. The alkali supply ink composition (A) contains a water-soluble copolymer containing a hydrophobic monomer as a polymerization component and a free polymer in an amount of 0.5 to 5.0% by mass based on the total amount of the ink. 5. The textile ink jet ink set according to any one of 1 to 4 above.

  6). A textile printing ink jet recording method, wherein printing is performed while heating a fabric or a knitted fabric using the textile ink jet ink set described in any one of 1 to 5 above.

  7). The water-soluble copolymer having a hydrophobic monomer as a polymerization component is a copolymer obtained by polymerizing unsaturated vinyl having a carboxyl group as at least a monomer component, and is neutralized and dissolved with an amine. The textile printing inkjet recording method of 6.

  8). 8. The printing inkjet recording method according to 6 or 7 above, wherein the printing is performed while heating the fabric or the knitted fabric in a temperature range of 40 ° C to 60 ° C.

  9. The printing ink jet according to any one of 6 to 8, wherein the alkali supply material is printed on a fabric or a knitted fabric so as to adhere to a hydroxyl concentration of 0.05 to 0.4 mol per square meter. Recording method.

  According to the present invention, the color density is good and bleeding can be suppressed without using a paste or the like as a pretreatment for the fabric or woven fabric, and the post-treatment process can be simplified. Even a uniform image can be obtained.

  The present invention will be described in more detail.

  According to the configuration of the present invention, it is possible to suppress bleeding at the time of printing without obtaining a pretreatment agent such as a glue on the fabric in advance, and to obtain an image sample having a high color density and no unevenness of dyeing. The effect of the present invention has not yet been clearly interpreted, but is considered as follows.

  Heating the ink containing the ink-soluble resin to accelerate drying is an effective printing means that suppresses image bleeding when ink droplets land on the fabric as a result of contributing to a rapid increase in viscosity. On the other hand, if the viscosity increases immediately after ink landing, penetration of the liquid droplets into the fabric fibers is suppressed, and sufficient color development efficiency cannot be obtained, resulting in an image with low image density. Also, due to insufficient permeability, the fiber surface is not uniformly dyed, and dyeing unevenness called “irritation” in the textile printing industry tends to occur.

  For this problem, it is considered to be a preferable requirement to increase the permeability to the fibers by keeping the viscosity increase rate low immediately after the ink landing and to increase the viscosity increase rate in the drying process. That is, a water-soluble copolymer (hereinafter, dissolved resin) having a hydrophobic monomer present as a soluble resin as a polymerization component is selected as the ink-soluble resin, which is a constitution of the present invention, and a water-soluble solvent used in the present invention. It is presumed that it was realized by a combination with a certain glycol ether and / or 1,2-alkanediol.

  The dissolved resin of the present invention is such that after the ink has landed on the recording medium, the water evaporates in the drying stage and the concentration of glycol ether and / or 1,2-alkanediol, which is a relatively hydrophobic water-soluble solvent, increases. It is believed that the molecular chain of the dissolved resin having a hydrophobic part spreads and viscosity is developed to prevent bleeding. In addition, it is believed that water-soluble solvents with high fiber penetration promoted penetration into the fiber, increased color development efficiency, and prevented uneven dyeing.

  The present invention will be described in detail below.

<Water-soluble copolymer>
A water-soluble copolymer having a hydrophobic monomer as a polymerization component (hereinafter also abbreviated as a water-soluble copolymer) is used for printing ink-jet ink (in order to improve image fastness (abrasion resistance, washing resistance, etc.)) Hereinafter, it is preferably a resin that can be stably dissolved in the ink) but can be given water resistance after drying on a recording medium. The water-soluble copolymer as used in the field of this invention means the copolymer which melt | dissolves 10 mass% or more with respect to water.

  As such a resin, a resin having a hydrophobic component and a hydrophilic component is designed and used. At this time, as the hydrophilic component, either an ionic or nonionic component may be used, but an ionic component is more preferable, and an anionic component is more preferable. In particular, those which are rendered water-soluble by neutralizing anionic substances with a volatile base component are preferred.

  In particular, at least one of the water-soluble copolymers has a carboxyl group or a sulfonic acid group as an acidic group, and a resin having an acid value of 80 or more and less than 300 is preferable in view of the effects of the present invention.

  Hydrophobic monomers of the water-soluble copolymer include acrylic acid esters (n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc.), methacrylic acid esters (ethyl methacrylate, butyl methacrylate, methacrylic acid). Glycidyl acid) and styrene.

  Examples of the hydrophilic monomer of the water-soluble copolymer include acrylic acid, methacrylic acid, acrylamide and the like, and those having an acidic group such as acrylic acid can preferably be those neutralized with a base after polymerization. .

  As a molecular weight of the water-soluble copolymer, a weight average molecular weight of 3000 to 30000 can be used, and a more preferable range of the weight average molecular weight is 7000 to 20000.

  The water-soluble copolymer having a Tg of about -30 ° C to 100 ° C can be used, and a more preferable Tg range is -10 ° C to 80 ° C.

  As a more preferable acid value of the water-soluble copolymer, one having about 90 to 250 can be used, and as the polymerization method, solution polymerization is preferably used.

  The acidic group derived from the acidic monomer of the water-soluble copolymer is preferably partially or completely neutralized with a base component. As the neutralizing base in this case, an alkali metal-containing base such as Na, K hydroxide, or an amine (ammonia, alkanolamine, alkylamine or the like can be used) can be used.

  In particular, neutralization with amines having a boiling point of less than 200 ° C. is particularly preferable from the viewpoint of improving image fastness.

  The water-soluble copolymer having a hydrophobic monomer as a polymerization component has a free polymer content of 0.5% by mass or more and 5.0% by mass or less based on the total mass of the ink composition from the viewpoint of expressing the object effect of the present invention. It is contained in a range. More preferably, it is the range of 1.0 mass% or more and 3.0 mass% or less. In the present invention, the water-soluble copolymer is preferably contained in an amount of 1.0% by mass or more and 10.0% by mass or less based on the total mass of the ink composition.

  The free polymer as used in the field of this invention is a polymer melt | dissolved in the ink. Even if it is a water-soluble copolymer, the solubility of a water-soluble copolymer may fall depending on an ink composition, and the prescribed water-soluble copolymer is not necessarily completely dissolved. In the present invention, the polymer component dissolved in the ink is a free polymer. In the present invention, the amount of free polymer can be quantified by treating the color ink with a centrifuge and precipitating insoluble components in the ink and then quantitatively analyzing the supernatant.

As a condition for the centrifugal separation, a centrifugal force of 15690 m / sec ² or more is applied to precipitate the ink insoluble component. For example, using a cooling high-speed centrifuge H-2100M2 (manufactured by Kokusan Co., Ltd.), the mixture was centrifuged at 3000 rpm (equivalent to 15690N) for 2 hours, and the supernatant was collected. The supernatant is dried and concentrated, and then dissolved in tetrahydrofuran, and GPC (HLC-8220 GPC Tosoh Corporation) measurement is performed to determine the free polymer content.

<Water-soluble organic solvent>
The ink of the present invention must contain at least a water-soluble organic solvent selected from glycol ether and / or 1,2-alkanediol.

  Specific examples of the glycol ether include ethylene glycol monoethyl, ethylene glycol monobutyl, diethylene glycol monobutyl, triethylene glycol monobutyl, propylene glycol monopropyl, dipropylene glycol monomethyl, and tripropylene glycol monomethyl.

  Examples of the 1,2-alkanediol include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and the like. The addition amount is preferably 7% to 20%, and more preferably 7% to 12%. Within this range, high quality image quality can be obtained. Further, within this range, the ink can be used stably even when stored for a long period of time. In particular, it is preferable in terms of storage stability of the ink to contain 1,2-alkanediol.

  In addition to glycol ether or 1,2-alkanediol, a solvent can be added to the ink of the present invention.

  Specifically, as the solvent according to the present invention, an aqueous liquid medium is preferably used, and examples include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol). , 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), amine (For example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine) , Morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine), amides (eg, formamide, N, N-dimethylformamide, N , N-dimethylacetamide, etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides ( Examples thereof include dimethyl sulfoxide).

  The water, which is a requirement of the present invention, is preferably contained in an amount of 50% or more from the viewpoint of improving the drying property and the storage stability of the ink, and more preferably 60% or more.

<Reactive dyestuff>
The inkjet ink of the present invention uses a reactive dye. Preferably, in consideration of dyeability and fastness to the fabric, the reactive group type of the reactive dye is preferably a monochromatic triazine type.

  Examples of reactive dyes that can be used in the present invention include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, and diphenylmethane dyes.

  Specific examples of reactive dyes that can be applied to the inkjet ink of the present invention will be listed below, but the present invention is not limited to these exemplified reactive dyes.

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. are mentioned.

<Surfactant>
In the present invention, the surface tension of the ink is preferably 30 mN / m or less and more preferably 28 mN / m or less because of the need to have permeability to fabrics and knitted fabrics and sufficient wettability. In order to adjust to this surface tension, various surfactants can be preferably used. In particular, it is effective to use at least one selected from a silicon surfactant and a fluorine surfactant having a perfluoroalkenyl group.

  The silicon-based surfactant according to the present invention is a product obtained by modifying the side chain or terminal of dimethylpolysiloxy acid with a polyether, such as KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd., BYK347 and BYK348 manufactured by Big Chemie. Are commercially available.

  The fluorosurfactant having a perfluoroalkenyl group according to the present invention is a dimer, trimer or pentamer obtained by anionic polymerization of 4-fluorinated ethylene or hexafluoropropylene. Any of a nonionic type having a polyoxyethylene ether in a hydrophilic group, an anionic type having a sulfonic acid or a carboxylic acid, and a betaine type having a quaternary ammonium salt and a carboxylic acid can be preferably used. It is marketed as the footage series made by the company Neos.

  In addition to the fluorine-based or silicon-based surfactant, the following surfactant may be used or used in combination with the ink of the present invention. For example, anionic surfactants such as alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, fatty acid salts, polyoxyethylene alkyl Nonionic surfactants such as ethers, polyoxyalkylene alkylphenyl ethers, acetylene glycols, polyoxyethylene-polyoxypropylene block copolymers, activities such as glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides, amine oxides Agents, cationic surfactants such as alkylamine salts and quaternary ammonium salts.

<Alkali supply material>
As the dyeing mechanism of the reactive dye, dyeing efficiency can be increased by dyeing in an alkaline atmosphere. Monochlorotriazine-based reactive dyes are used in particular, but the reaction mechanism causes a dehydrochlorination reaction with cellulose molecules and binds to the fibers, so that the hydrochloric acid is neutralized by the alkali supply substance, and the reaction proceeds and the dyeing proceeds. Wearing is promoted.

  The alkali supplying substance is not particularly limited as long as a necessary amount of alkali can be supplied at the time of dyeing. Commonly used in printing are sodium silicate, caustic soda, sodium carbonate, sodium bicarbonate, potassium carbonate, etc., but sodium bicarbonate or sodium bicarbonate is particularly preferred for reasons such as dyeability and storage stability.

  In the present invention, the alkali amount is preferably printed so that 0.05 to 0.4 mol of a hydroxyl group concentration per square meter adheres to the fabric or knitted fabric. As for the adhesion amount, there are a method of adjusting the concentration of the alkali supply substance in the alkali supply ink and a method of adjusting an appropriate amount of liquid at the time of printing (droplet size, print resolution, etc.). You can go there. When the alkali adhesion amount is less than 0.05 mol, not only the amount of alkali necessary for color development is insufficient, but also the color density is lowered, and the dyeing effect (aggregation effect) of the dye by the alkali is also lowered, and the image density and blur suppression are reduced. Resulting in. On the other hand, when the amount is more than 0.4 mol, the coagulation effect is excessively increased, and the permeation into the fibers is hindered and the flickering increases.

<Various additives>
The effect of the present invention is remarkably exhibited in a refined fabric (P-processed product in terms of the textile industry), a textile ink used for textile printing, or a textile used for textile printing, which is used for dyeing by a hot steam method. Even if a dyeing aid is contained in the fabric, the effect of the present invention is not suppressed. The dyeing aid has the effect of making eutectic mixture with the water condensed in the form of cloth when steaming the printed fabric, reducing the amount of water that re-evaporates, and shortening the heating time. Further, this eutectic mixture has the effect of dissolving the dye on the fiber and promoting the diffusion rate of the dye into the fiber. Urea is mentioned as a dyeing assistant.

  In the present invention, other conventionally known additives can be contained. For example, optical brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid bases, pH adjusters such as buffer solutions, antioxidants, surface tension It is a regulator, a non-resistance modifier, a rust inhibitor, an inorganic pigment, a reduction inhibitor, and the like. Since these additives are preferably removed in the washing step, it is preferable to use them in a range that does not impose a load on the washing step and waste water contamination.

<Fabric and knitted fabric>
The fiber material constituting the fabric or knitted fabric mainly used in the textile printing inkjet recording method of the present invention is not particularly limited as long as it contains fibers that can be dyed with a reactive dye. Those containing fibers such as wool, silk, rayon and polyamide are preferred. Among them, it is particularly preferable that cotton and silk fibers are contained.

  As a medium for printing, the above-described fibers may be in any form such as woven fabric, knitted fabric, and non-woven fabric. Further, as a fabric that can be used in the present invention, it is preferable that the fiber that can be dyed with a reactive dye is 100%. However, a mixed woven fabric or a mixed non-woven fabric with polyester, acetate or the like is also used as a textile for printing. Can be used. 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, a fabric or knitted fabric as a recording medium is heated for printing. By heating the recording medium, the drying and thickening speed of the ink is remarkably improved, and high image quality can be obtained. Also, the durability of the image is improved.

  The heating temperature is preferably such that the recording surface temperature of the recording medium is 40 ° C. to 90 ° C. Heating below 40 ° C. is not preferable because the image quality is insufficient and sufficient image durability cannot be obtained, and it takes time to dry. If the temperature exceeds 90 ° C., ink ejection is greatly affected, and stable printing cannot be performed.

  More preferably, the recording surface temperature of the recording medium is 40 ° C. to 60 ° C.

  As a heating method, a heating method can be selected by incorporating a heat generating heater in the recording medium conveyance system or platen member and heating from the lower side of the recording medium, or from the lower side or the upper side by a lamp or the like. .

<Coloring process>
The coloring process is a dye fixing process (also referred to as a fixing process or a coloring process). The ink droplets applied onto the recording medium by the textile printing ink jet method exhibit the original hue of the ink by being adsorbed and fixed on the fabric. The reactive dye is fixed by the covalent bonding of the fabric fiber as a recording medium and the reactive group of the dye, and the original hue and fastness can be obtained. As the fixing method, steaming by steam, baking by dry heat, thermosol, HT steamer by superheated steam, HP steamer by pressurized steam, or the like is 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 or may be heat-treated after a while and may be dried and colored according to the intended use, and any method may be used in the present invention.

  The reactive dye is preferably fixed mainly by atmospheric pressure steaming. In this method, the recorded material is fixed in saturated steam at 100 ° C. to 104 ° C. In the case of acid dyes, high pressure steaming is often used. This is a method of fixing a recorded material in a high-temperature and high-pressure saturated steam at 110 ° C. to 130 ° C. The steaming time varies depending on the conditions of the dye type, fabric type, etc., but it is usually preferable to carry out in about 10 to 20 minutes because of the dye fixing rate.

<Washing process>
After the heat treatment, washing may be performed for the purpose of removing the dye that was not involved in the dyeing. The method is selected according to the material to be printed, the ink type, and the pre-processing contents for the printed matter. There are many cases that end with water washing, but when fastness is required, it is effective to perform water washing, hot water washing and soaping (40 to 50 ° C. for 5 to 10 minutes, cleaning agent 1 to 2 g / L). . You may dry after washing | cleaning. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

<Fix processing>
In order to improve the fastness, a fixing process may be performed after the cleaning process. Although the fixing agent used varies depending on the dye type and the fabric type, quaternary ammonium salts, polyamine compounds, pyridinium salts, tannins, and the like are usually used.

<Drainage>
The waste water quality regulations caused by washing, fixing, etc. use a large amount of water in dyeing factories and the like, so the load on the processing equipment is large. Water pollutants need to be separated from water or changed to non-pollutants, and each dyeing factory wants to reduce pollutants as much as possible. However, it is difficult to reduce the amount of glue used to reduce the image quality performance. As a result, the cleaning load for de-glue increases, and the amount of waste water and waste liquid treatment increase. By using the ink of the present invention, it is possible to reduce the use of the paste and, in some cases, to satisfy a sufficient image quality without using it, and to greatly reduce the drainage load.

  Examples of the present invention will be specifically described below, but the embodiments of the present invention are not limited thereto. In the examples, “%” represents mass% unless otherwise specified.

Example 1
[Preparation of ink composition]
An ink composition (C) and an alkali supply ink composition (A) were produced as follows.

(Synthesis of water-soluble copolymer having hydrophobic monomer as polymerization component)
50 g of methyl ethyl ketone was added to a flask equipped with a dropping funnel, a nitrogen introducer, a reflux condenser, a thermometer and a stirring device, and heated to 75 ° C. while bubbling nitrogen. Thereto, a mixture of 40 g of n-butyl methacrylate, 40 g of styrene, 20 g of acrylic acid, 50 g of methyl ethyl ketone, and 500 mg of initiator (AIBN) was dropped from a dropping funnel over 3 hours. It heated and refluxed for 6 hours after dripping. After allowing to cool, the mixture was heated under reduced pressure to distill off methyl ethyl ketone.

  The polymer residue was dissolved in a solution in which dimethylaminoethanol corresponding to 1.05 mol of acrylic acid added as a monomer was dissolved in 450 ml of ion-exchanged water. An aqueous solution of a water-soluble copolymer having a solid content of 20% and having a hydrophobic monomer as a polymerization component was prepared with ion-exchanged water.

<Ink composition (C1)>
C. I. Reactive Red 245 9.5%
Water-soluble copolymer aqueous solution having hydrophobic monomer as polymerization component 16.0%
Diethylene glycol monobutyl ether 8.0%
Diethylene glycol 16.8%
Glycerin 4.8%
Olphine E1010 (Nisshin Chemical Industries) 0.3%
Ion exchange water was added to make the total amount 100% to obtain an ink composition (C1).

<Alkali supply ink composition (A1)>
Sodium bicarbonate 9.5%
Diethylene glycol monobutyl ether 8.0%
Diethylene glycol 23.0%
Glycerin 4.5%
Orphin E1010 (Nisshin Chemical Co., Ltd.) 5.3%
Ion exchange water was added to make the total amount 100% to obtain an alkali supply ink composition (A1).

  Similarly, C2 to C14 (color ink) which are ink compositions (C) in which the respective components are changed as shown in Table 1, and A2 which are alkali supply ink compositions (A) which are changed as shown in Table 2. A10 (alkali ink) was prepared.

(Measurement of free polymer amount)
Each produced ink was centrifuged at 3000 rpm for 2 hours with a centrifuge (cooling high-speed centrifuge H-2100M2 manufactured by Kokusan Co., Ltd.), and the supernatant was collected. The supernatant was dried and concentrated, then dissolved in tetrahydrofuran, and GPC (HLC-8220 GPC Tosoh Corp.) measurement was performed to determine the free polymer content.

  Ink jet ink sets (ink sets) 1 to 31 in which the inks obtained as described above are combined are prepared, and the evaluation results are shown in Tables 3 to 6.

<Recording medium>
Fabric 1 (cotton, no pretreatment)
A cotton fabric made of 100% cotton with a plain weave of 20cm / P under processing (print base processing).

Fabric 2 (cotton, with pretreatment)
Padded with a liquid containing 30 g / l carboxymethylcellulose (Sunrose S, manufactured by Nippon Paper Chemicals) as a paste and 30 g / l baking soda on a plain-woven silk fabric made of 100% cotton Rate: 80%) and dried at 40 ° C. for 30 minutes.

Fabric 3
A plain weave 12cm / P-finished silk fabric made of 100% silk and knitted fabric pre-treated.

Fabric 4 (silk, with pretreatment)
Padded with a liquid containing 30 g / l of sodium carboxymethylcellulose (Sunrose S, manufactured by Nippon Paper Chemicals) as a paste and 30 g / l baking soda on a silk fabric with a plain weave of 12% / P made of 100% silk Rate: 70%) and dried at 40 ° C. for 30 minutes.

<Coloring process>
The ink-jet print product was completely dried and fixed at 103 ° C. for 15 minutes in a normal pressure saturated steam using a simple color developing device for textile printing.

<Washing process 1>
After the color development step, the recording medium was washed with cold water for 5 minutes, using a soaping solution in which a 3% soaping agent was dissolved, at 80 ° C. for 5 minutes, rinsed with cold water for 5 minutes, and then dried.

<Washing process 2>
After the color development step, the recording medium is rinsed with cold water for 10 minutes and at 40 ° C. for 10 minutes, and then washed with a soaping solution containing 3% soaping agent at 80 ° C. for 10 minutes, again at 40 ° C. for 10 minutes, and cold water. Rinse for 10 minutes and dry.

(Image formation)
Equipped with a piezo-type head with a nozzle diameter of 28 μm, drive frequency of 18 kHz, number of nozzles of 512, minimum liquid amount of 14 pl, nozzle density of 180 dpi (where dpi represents the number of nozzles per inch, ie 2.54 cm), and maximum recording density Each ink was loaded into an on-demand ink jet printer having a 1440 × 1440 dpi (dpi represents 1 dot, that is, the number of dots per 2.54 cm).

  Next, each ink was ejected onto fabrics 1 to 3 serving as recording media under the conditions of printing resolution: 720 dpi × 720 dpi, head conveyance speed: 200 mm / sec bidirectional printing, a solid image of 10 cm × 10 cm, a width of 250 μm, and a length. A 5 cm thin line was printed to form a recorded image. After printing, the coloring process and washing process 1 or 2 were performed.

  During printing on the recording medium, the recording medium was heated from the back side, and the surface temperature of the recording medium during image recording was controlled with a heater as shown in the table. The surface temperature of the recording medium was measured using a non-contact thermometer (IT-530N type, manufactured by Horiba, Ltd.).

(Evaluation of color density)
Fix the unprinted cloth in the same manner as the printed cloth, place the printed cloth on the 20 sheets, measure the image density at the response T using the X-Rite 938 Spectrodensitometer, and measure the image density according to the following criteria. Judgment was made.

A: Image density is 1.5 or more and no problem in quality ○: Image density is 1.0 or more and less than 1.5 and quality problem △: Image density is 0.5 or more and less than 1.0 Quality problems x: Image density is less than 0.4.

(Evaluation of bleeding)
Images were visually observed, and feathering was evaluated according to the following criteria.

◎: Fine lines are reproduced without blurring due to bleeding ○: Fine lines are reproduced without blurring due to bleeding △: Lines are not thickened due to bleeding, but less than 10 Ink bleeding along the fiber is observed. X: Line thickening due to bleeding is intense, and ink bleeding along the fiber is observed at 20 or more points. Of these, x is a level at which there is a problem as a product.

(Evaluation of irritability)
Images were visually observed to evaluate image uniformity.

◎: No white spots, high-quality level that can be confirmed as a uniform image even when magnified with a magnifying glass ○: Level without white spots and can be confirmed visually as a uniform image △: White spots are observed in some places in the fiber, and the uniform image The quality is low but acceptable level ×: Many white spots are observed in the fiber, and the quality as a uniform image is very low. Among these, × is a level having a problem as a product.

(Evaluation of ink storage stability)
Ejection evaluation apparatus with a single head equipped with a piezo-type head with a known nozzle volume of 25 μm, drive frequency 12 kHz, nozzle number 128, nozzle density 180 dpi after ink is placed in a thermostatic bath at 50 ° C. for 30 days Was used for continuous discharge for 60 minutes in an environment of a temperature of 25 ° C. and a humidity of 40%, and the discharge stability was evaluated in five stages. This evaluation method was used because ink having better ink storage stability is more stably ejected without affecting inkjet ejection.

◎: No problem ○: All nozzles are ejected but ink is slightly scattered on the head surface △: All nozzles are ejected, but ink is slightly scattered on the head surface ×: No ejecting nozzles are generated and ink on the head surface Xx; all nozzles are not emitted. Of these, x and xx are levels that are problematic as products.

(Evaluation of cleaning process load)
The obtained image was subjected to the washing step 1 or 2 after the color development step, and the friction fastness was evaluated according to JIS standard (JIS L 0849I).

○: fastness to dry friction 3rd grade in cleaning process 1 △: fastness to dry friction 3rd grade in cleaning process 1, 3rd grade or higher in cleaning process 2 ×: fastness to dry friction in cleaning process 1 or 2 Less than 3rd grade.

  Among these, x is a level which has a problem as a product.

  As described above, according to the present invention, it is possible to obtain a high-density image with high density and no unevenness of dyeing without causing any special pretreatment to the fabric, and further, the burden on waste liquid treatment is significantly reduced. It became possible to do.

Claims (9)

A water-soluble copolymer containing at least a reactive dye, water, a hydrophobic monomer as a polymerization component, and a free polymer in an amount of 0.5 to 5.0% by mass based on the total amount of the ink, glycol ether, and 1,2 -Alkali supply ink containing an ink composition (C) containing at least one selected from alkanediol, at least one selected from water, glycol ether and 1,2-alkanediol, and an alkali supply substance A textile ink jet ink set comprising the composition (A). The water-soluble copolymer having the hydrophobic monomer as a polymerization component is a copolymer obtained by polymerizing an unsaturated vinyl having a carboxyl group as at least a monomer component, and is neutralized and dissolved with an amine. Item 2. The ink set for textile printing inkjet according to item 1. The ink set for textile printing ink jet according to claim 1 or 2, wherein the ink composition (C) contains a fluorine-based or silicon-based surfactant. The textile ink jet ink set according to any one of claims 1 to 3, wherein the alkali supply substance is a carbonate. The alkali supply ink composition (A) contains a water-soluble copolymer containing a hydrophobic monomer as a polymerization component and a free polymer in an amount of 0.5 to 5.0% by mass based on the total amount of the ink. The textile ink jet ink set according to any one of claims 1 to 4. A textile printing inkjet recording method comprising printing a fabric or a knitted fabric while heating using the textile ink jet ink set according to any one of claims 1 to 5. The water-soluble copolymer having the hydrophobic monomer as a polymerization component is a copolymer obtained by polymerizing an unsaturated vinyl having a carboxyl group as at least a monomer component, and is neutralized and dissolved with an amine. Item 7. The textile inkjet recording method according to item 6. The printing inkjet recording method according to claim 6 or 7, wherein the printing is performed while heating the fabric or knitted fabric in a temperature range of 40 ° C to 60 ° C. The textile printing according to any one of claims 6 to 8, wherein the alkali supply substance is printed on a fabric or knitted fabric so as to adhere to 0.05 to 0.4 mol of hydroxyl group per square meter. Inkjet recording method.