JP2010037700A - Inkjet printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet printing method excellent in ink ejecting stability, suppressing bleeding, and capable of obtaining inkjet printing print excellent in image endurance and having high quality image. <P>SOLUTION: The inkjet printing method includes carrying out printing on a fabric in using an inkjet water-base pigment ink, which contains a pigment, a surfactant, and a glycol ether or a 1,2-alkanediol and contains as an aqueous solvent a 1.0-10 mass% water-soluble copolymer obtained by neutralizing and dissolving with an amine a copolymer obtained by polymerizing a carboxyl group-containing unsaturated vinyl as a monomer ingredient, based on the ink total weight, and heating the fabric to record under the condition of 40-90°C surface temperature, the fabric comprising at least polyester fiber A having a thickness of 1.0-10 d and a polyester fiber B having a thickness of not less than 0.001 d and less than 1.0 d wherein the mixing ratio (A:B) of the polyester fiber A to the polyester B is 1:0.1-1:10. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an inkjet printing method, and in particular, an inkjet aqueous pigment ink containing a specific fixing resin by heating an inkjet printing fabric formed of a twisted yarn mainly composed of two or more kinds of polyester fibers having different thicknesses. The present invention relates to an ink-jet textile printing method for recording using an ink.

  The image recording method by the ink jet method is a method in which micro droplets of ink are ejected and adhered to a recording medium. The mechanism is relatively simple and inexpensive, and has an advantage that a high-definition and high-quality image can be formed. .

  So-called inkjet printing, in which recording is performed on a fabric by taking advantage of the inkjet method, is also performed. Ink-jet printing, unlike conventional printing methods, does not require the production of a plate and is suitable for producing a small amount of various images. In addition, since only an amount of ink necessary for image formation is used, the image forming method has little waste liquid and is excellent in environmental suitability.

  The ink-jet textile fabric is required to have performances such as ink coloring property, fixing property, drying property, and suppression of ink bleeding. Conventionally, in order to satisfy these required performances, the fabric has been preliminarily treated in advance. However, through the complicated pretreatment process, the advantage of the simplicity of the ink jet system cannot be fully utilized. In addition, the superiority or inferiority of the printed image after the final process is often due to the basic characteristics of the fabric used and the basic characteristics of the ink.

  That is, an ink-jet printing method for forming an image by using a water-based ink-jet ink having a much lower viscosity than that of a conventional printing paste, and representing the dots of this ink, is a physical property of the fabric as compared with the conventional printing method. In particular, in the case of a fabric including yarns mainly composed of polyester fibers, the restriction is large.

  Various pigment inks have been proposed in order to remove the above-described restrictions and form a high-quality image with less bleeding. For example, Patent Document 1 discloses a method in which a reaction liquid containing a reactive agent is attached to a cloth in advance, and then a pigment ink is ejected. It is complicated.

On the other hand, Patent Document 2 discloses a method of using a colorant including a pigment in a polymer having a crosslinked structure for inkjet printing, but even with this technique, the problem of bleeding cannot be solved. is the current situation.
JP 2003-55886 A JP 2002-338859 A

  The present invention has been made in view of the above problems, and its purpose is to obtain an ink jet textile print having a high-quality image that is excellent in ink ejection stability, suppresses bleeding, and has excellent image durability. An object of the present invention is to provide an ink jet textile printing method.

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

  1. A copolymer containing a pigment, a surfactant, a glycol ether or 1,2-alkanediol as a water-soluble solvent and polymerized with at least an unsaturated vinyl having a carboxyl group as a monomer component is added with an amine. Using an aqueous pigment ink for inkjet containing 1.0% by mass or more and 10% by mass or less of the water-soluble copolymer dissolved in the sum, at least the thickness is 1.0d (denier) or more, The polyester fiber A is 10d or less and the polyester fiber B is 0.001d or more and less than 1.0d in thickness, and the mixing ratio (A: B) of the polyester fiber A and the polyester fiber B is 1: 0. It is characterized in that inkjet recording is performed on a fabric in the range of 1 to 1:10 by heating the fabric at a surface temperature of 40 ° C. or higher and 90 ° C. or lower. Ink-jet printing process according to.

  2. 2. The inkjet printing method according to 1 above, wherein inkjet recording is performed using an aqueous pigment ink for inkjet containing water-based dispersed polymer fine particles.

In the present invention, as a more preferred embodiment,
3. 2. The ink-jet printing method according to 1 above, wherein the fabric is a mixed woven yarn of two or more kinds of polyester fibers having different thicknesses.

  4). 2. The ink jet printing method according to 1 above, wherein the fabric is a twisted yarn formed by twisting two or more types of multifilament yarns respectively formed from two or more types of polyester fibers having different thicknesses.

  5. 2. The ink-jet printing method according to 1 above, wherein the fabric is a mixed woven fabric formed from two or more types of twisted yarns formed from two or more types of polyester fibers having different thicknesses.

  6). Inkjet recording is performed using an aqueous pigment ink for inkjet containing 2 to 20% by mass of glycol ethers or 1,2-alkanediols, which are water-soluble solvents, based on the total amount of the ink. 6. The inkjet printing method according to any one of 1 to 5 above.

  7). 7. The ink-jet printing method according to any one of 1 to 6, wherein the water-soluble copolymer has an acid value of 80 or more and less than 300.

  According to the present invention, it is possible to provide an ink jet printing method capable of obtaining an ink jet textile print having a high quality image having excellent ink ejection stability, suppressing bleeding, and having excellent image durability.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventor,
1) Pigment,
2) surfactant,
3) Glycol ethers or 1,2-alkanediols as water-soluble solvents,
4) A water-soluble copolymer obtained by neutralizing and dissolving a copolymer obtained by polymerizing an unsaturated vinyl having at least a carboxyl group as a monomer component with an amine is 1.0% by mass or more and 10% by mass or less based on the total mass of the ink. Using the aqueous pigment ink for ink-jet containing
5) The polyester fiber A having a thickness of at least 1.0d (denier) and 10d or less and a polyester fiber B having a thickness of 0.001d and less than 1.0d,
6) In a fabric in which the mixing ratio (A: B) of the polyester fiber A and the polyester fiber B is in the range of 1: 0.1 to 1:10,
7) According to an inkjet printing method, wherein the fabric is heated under a condition where the surface temperature is 40 ° C. or higher and 90 ° C. or lower to perform inkjet recording.
It has been found that an ink jet textile printing method can be obtained that is excellent in ink ejection stability, suppresses bleeding, has excellent image durability, and can provide an ink jet textile print having a high quality image. .

  The inventor presumes the reason why a desired printed matter can be obtained by inkjet printing on a specific polyester fiber using the inkjet water-based pigment ink according to the present invention.

  In general, inkjet printing, which uses an ink having a much lower viscosity than conventional printing pastes and applies only the minimum amount of colorant to a fabric to form an image by dot expression, is particularly polyester. When recording on a fabric having fiber as the main constituent, there are very many restrictions on the physical conditions of the fabric compared to other methods. According to the inkjet textile printing method of the present invention, it is possible to easily obtain a high-quality image excellent in durability by suppressing bleeding even when a fabric made of polyester fiber is not subjected to pretreatment or the like. Is.

  The water-based pigment ink for inkjet according to the present invention contains a specific water-soluble copolymer, and the water-soluble copolymer is neutralized with an amine and stably dissolved in the ink. When the fabric containing the polyester fiber according to the present invention is heated and recorded using the ink, the solvent in the ink and the amine as the neutralizing agent volatilize, whereby the concentration of the water-soluble copolymer is reduced. To increase. As a result, the landed ink is thickened more than before being ejected from the head, and the color material does not diffuse unnecessarily on the fabric, so that the occurrence of bleeding can be suppressed. Further, the ink having a high viscosity is entangled with the fibers constituting the fabric and strongly fixes the color material, thereby satisfying image durability.

  At this time, the thickness of the polyester fiber constituting the fabric greatly affects the suppression of bleeding and the pigment fixing property, which are functions of the aqueous pigment ink according to the present invention.

  If the thickness of the polyester fiber is small, the surface area of the fiber is large, and the pigment is strongly entangled with the fiber, so that durability such as fixability is improved. On the other hand, if the fiber is too thin, a problem may occur in the conveyance strength of the fabric, and an appropriate thickness is required. However, if the fiber thickness is large, bleeding is likely to occur, and in terms of fixability of the coloring material. Anxiety about image durability.

  Therefore, in the fabric according to the present invention, the polyester fiber A of 1.0 or more and 10d or less and the polyester fiber B having a thickness of 0.001d or more and less than 1.0d are mixed at a mass ratio of 1: 0. .1 to 1:10 in the same fabric.

  Furthermore, the ink according to the present invention uses a specific water-soluble solvent and a surfactant together with the water-soluble copolymer, and quickly penetrates into the yarn constituting the fabric as described above. It is possible to suppress spreading of the gap between the yarns and reduce bleeding.

  Further, in the water-soluble copolymer in which the coloring material is fixed to the fabric according to the present invention, the amine used for neutralizing the material volatilizes with the solvent by heating the fabric during recording. It is considered that even if moisture adheres to the fabric, it can adhere to the fabric without being re-dissolved and can form a printed matter having excellent durability.

  As described above, it is possible to provide an ink jet textile printing method that suppresses bleeding and forms a printed matter having excellent image durability.

<Water-based pigment ink for inkjet>
The aqueous pigment ink for inkjet according to the present invention (hereinafter also simply referred to as ink) is mainly composed of 1) pigment, 2) surfactant, 3) glycol ether or 1,2-alkanediol as water-soluble solvent, 4) It is composed of a water-soluble copolymer obtained by neutralizing and dissolving a copolymer obtained by polymerizing an unsaturated vinyl having at least a carboxyl group as a monomer component with an amine.

[Pigment]
The pigment applicable to the present invention is not particularly limited as long as it can be stably dispersed in an aqueous system. A pigment dispersion dispersed with a polymer resin, a capsule pigment coated with a water-insoluble resin, a dispersion resin modified with a pigment surface is used. It is possible to select from self-dispersing pigments that can be dispersed without such. When emphasis is particularly placed on the storage stability of the ink, it is preferable to select a capsule pigment coated with a water-insoluble resin.

  When a pigment dispersion dispersed with a polymer resin is used, a polymer resin preferably used is a styrene-acrylic acid-alkyl acrylate copolymer, a styrene-acrylic acid copolymer, or a styrene-maleic acid copolymer. Polymer, styrene-maleic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic Resins such as acid copolymers, vinyl naphthalene-maleic acid copolymers, and the like.

  Various methods such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used as a pigment dispersion method.

  In order to prepare the pigment dispersion according to the present invention, it is preferable to use a centrifugal separator or a filter for the purpose of removing coarse particles of the pigment dispersion.

  The water-insoluble resin in the case of using a capsule pigment coated with a water-insoluble resin is a resin that is insoluble in weakly acidic or weakly basic water, and preferably has a solubility in an aqueous solution of pH 4 to 10. The resin is less than mass%.

  Such resins include acrylic, styrene-acrylic, acrylonitrile-acrylic, vinyl acetate, vinyl acetate-acrylic, vinyl acetate-vinyl chloride, polyurethane, silicon-acrylic, acrylic silicon, polyester Examples thereof include epoxy resins and epoxy resins.

  In the present invention, a resin prepared using a hydrophobic monomer and a hydrophilic monomer as constituent components can be used as the resin used for dispersing the pigment.

  Examples of the hydrophobic monomer include acrylic acid esters (for example, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc.), methacrylic acid esters (for example, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate). Etc.), styrene and the like.

  Examples of the hydrophilic monomer 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 molecular weight of resin, the thing of 3000-500000 can be used with the weight average molecular weight Mw. Preferably, the thing of 7000-200000 can be used.

  The Tg of the resin can be about −30 to 100 ° C., preferably about −10 to 80 ° C.

  As the polymerization method, solution polymerization or emulsion polymerization can be used. The polymerization may be performed separately from the pigment in advance, or may be performed by supplying a monomer into the system in which the pigment is dispersed.

  As a method of coating the pigment with the resin, various known methods can be used. Preferably, in addition to the phase inversion emulsification method and the acid precipitation method, the pigment is dispersed using a polymerizable surfactant. It is preferable to select from a method in which a monomer is supplied thereto and coating is performed while polymerizing. As a more preferable method, a water-insoluble resin is dissolved in an organic solvent such as methyl ethyl ketone, and after partially or completely neutralizing an acidic group in the resin with a base, a pigment and ion-exchanged water are added and dispersed. A production method in which an organic solvent is removed and water is added as necessary is preferable.

  The mass ratio of the pigment and the resin can be selected from 100/40 to 100/150 as a pigment / resin ratio. Particularly, 100/60 to 100/110 have good image durability, injection stability, and ink storage stability.

  The average particle diameter of the pigment particles coated with the water-insoluble resin is preferably about 80 to 150 nm from the viewpoint of ink storage stability and color development.

  The average particle diameter of the pigment particles 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. It is also possible to obtain a particle image with a transmission electron microscope on at least 100 particles and perform statistical processing on the image using image analysis software such as Image-Pro (manufactured by Media Cybernetics). Is possible.

  Further, as the self-dispersing pigment, commercially available products that have been surface-treated can be used, and examples thereof include CABO-JET200, CABO-JET300 (above, manufactured by Cabot Corporation), Bonjet CW1 (manufactured by Orient Chemical Industry Co., Ltd.) and the like. be able to.

  As the pigment that can be used in the present invention, conventionally known organic and inorganic pigments can be used. For example, azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment azo pigment, phthalocyanine pigment, perylene and perylene pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, thioindigo pigment, isoindolinone pigment, quinophthalone pigment, etc. Examples include polycyclic pigments, dye lakes such as basic dye-type lakes and acid dye-type lakes, organic solvents such as nitro pigments, nitroso pigments, aniline black and daylight fluorescent pigments, and inorganic pigments such as carbon black.

  Specific organic pigments are exemplified below.

  Examples of pigments for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the orange or yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. And CI Pigment Yellow 138.

  Examples of pigments for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

[Surfactant]
The surfactant according to the present invention is not particularly limited, and examples thereof include silicon surfactants, fluorine surfactants, and acetylene surfactants.

  The silicon surfactant is preferably a dimethylpolysiloxane whose side chain or terminal is polyether-modified (polyether-modified polysiloxane compound). For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. and Big Chemie BYK347, BYK348 and the like.

  In addition, the fluorine-based surfactant means a compound in which a part or all of the surfactant is substituted with fluorine in place of hydrogen bonded to carbon of a hydrophobic group of a normal surfactant. Of these, those having a perfluoroalkyl group in the molecule are preferred.

  Some of the fluorosurfactants are commercially available, for example, under the trade name Megafac F from Dainippon Ink Chemical Co., Ltd. and under the trade name Surflon from Asahi Glass Co., Ltd. EI Dupont Nemeras and Company, Inc. under the trade name Fluorad FC from Minnesota Mining and Manufacturing Company, and Monfloor from Imperial Chemical Industry Are sold under the trade name Zonyls, and under the trade name Licobet VPF from Farbeberke Hoechst.

  Examples of nonionic fluorosurfactants include Megafax 144D manufactured by Dainippon Ink and Surflon S-141 and 145 manufactured by Asahi Glass Co., and amphoteric fluorosurfactants. Examples of the agent include Surflon S-131 and 132 manufactured by Asahi Glass Co., Ltd.

  The acetylene surfactant that can be used in the present invention is an acetylene glycol surfactant, which has a triple bond in the molecule, a hydroxyl group and an alkyl group on the adjacent carbon atom, and In other words, a symmetrical structure is preferable. The acetylene glycol compound and acetylene alcohol compound that can be used in the present invention can be obtained as commercially available products, such as Surfynol, Orphine manufactured by Nissin Chemical Industry Co., Ltd., and acetylenol manufactured by Kawaken Fine Chemical Co., Ltd. It is done.

(Water-soluble solvent)
One feature of the aqueous pigment ink for inkjet according to the present invention is that it contains glycol ethers or 1,2-alkanediols as a water-soluble solvent.

  By using glycol ethers and 1,2-alkanediols together with the water-soluble copolymer, these water-soluble solvents cause hydrophobic interaction with the pigment dispersion and the water-soluble copolymer. After the ink has landed on the heated fabric, the moisture decreases and acts more strongly as the concentration of glycol ethers and the like increases, resulting in an ink thickening effect. Therefore, it is considered that the bleeding prevention effect is remarkably exhibited by using the water-soluble polymer and glycol ethers in combination.

  On the other hand, the glycol ethers and the like are solvents having a relatively small surface tension, and exhibit sufficient affinity for the ink-jet printing fabric according to the present invention due to a synergistic effect with the surfactant used in combination. As a result, the aqueous pigment ink quickly penetrates into the polyester fiber having a specific range of thickness, so that the phenomenon of spreading through the gap between the yarns is suppressed, and the pigment is sufficiently fixed to the fabric. The inventor thinks.

  Examples of glycol ethers according to the present invention include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. Etc. Examples of 1,2-alkanediols include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and the like.

  The glycol ether or 1,2-alkanediol organic solvent according to the present invention is particularly preferably contained in an amount of 2 to 20% by mass with respect to the total mass of the ink from the viewpoint that the effects of the present invention are remarkably exhibited.

(Water-soluble copolymer)
The water-soluble copolymer according to the present invention is designed and used having a hydrophilic component that is a carboxyl group and a hydrophobic component in an appropriate balance. At this time, the water-soluble copolymer according to the present invention to which water solubility is imparted by neutralizing the carboxyl group with a volatile base component sufficiently exhibits the above-described function. Examples of such water-soluble copolymers include acrylic resins, styrene-acrylic resins, acrylonitrile-acrylic resins, vinyl acetate-acrylic resins, polyurethane resins, and polyester resins.

  Examples of the hydrophobic monomer constituting the water-soluble copolymer according to the present invention include acrylic acid esters (for example, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc.), methacrylic acid esters. (For example, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc.), styrene and the like.

  Examples of the hydrophilic monomer constituting the water-soluble copolymer according to the present invention include acrylic acid, methacrylic acid, and acrylamide.

  The acidic group such as a carboxyl group contained in the water-soluble copolymer according to the present invention needs to be partially or completely neutralized with an amine. Examples of the amine include ammonia, triethylamine, 2-dimethylaminoethanol, 2-di-n-butylaminoethanol, methyldiethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, triethanolamine, and 2-methyl. Aminoethanol or the like can be preferably used.

  In particular, neutralization with an amine having a boiling point of less than 200 ° C. is more preferable because the amine is easily volatilized at the time of drying, and the hydrophobicity is rapidly increased to contribute to the improvement of image durability.

  The water-soluble copolymer according to the present invention is contained in an amount of 1.0% by mass or more and 10% by mass or less, more preferably 2.0% by mass or more and 7.0% by mass with respect to the total mass of the ink. It is as follows. When the content of the water-soluble copolymer according to the present invention is 1.0% by mass or more, bleeding can be remarkably prevented and a high-quality image can be obtained. When the content is 10% by mass or less, the storage stability of the ink is remarkably good, stable emission is possible, and a print can be stably obtained over a long period of time.

  In addition, the water-soluble copolymer according to the present invention preferably has an acid value of 80 mgKOH / g or more and less than 300 mgKOH / g, but this significantly increases the viscosity of the water-soluble copolymer upon drying. In addition, the pigment solidifies more firmly after drying, and the fixability of the pigment is good. A more preferred acid value is about 90 to 250 mg KOH / g. The acid value defined in the present invention can be measured according to JIS K0070.

  The polymerization method of the water-soluble copolymer according to the present invention is preferably solution polymerization. As a molecular weight of the water-soluble copolymer according to the present invention, an average molecular weight of 3000 to 30000 can be preferably used, and more preferably 7000 to 20000.

  The Tg of the water-soluble copolymer according to the present invention is preferably about -30 ° C to 100 ° C, more preferably -10 ° C to 80 ° C.

[Aqueous dispersion type polymer fine particles]
The aqueous pigment ink for ink jet according to the present invention preferably contains water-based dispersed polymer fine particles in addition to the above-described constituent elements.

  The water-soluble copolymer according to the present invention has a function of preventing ink bleeding by thickening the ink at the time of drying, and the amine as a neutralizing agent volatilizes, so that it is difficult to be re-dissolved in moisture, and the pigment fixing property is improved. Although it is excellent, it can contribute to the improvement of abrasion resistance by making the pigment fixing property stronger by further containing the water-dispersible polymer fine particles. Also, combined use with water-dispersible polymer fine particles controls the speed at which the ink is thickened, and the ink droplets at the time of landing are appropriately leveled to prevent unevenness on the image surface and improve image clarity. There is an advantage that it can be satisfied in combination with maintenance, suppression of bleeding, and pigment fixing property.

  The Tg of the water-based dispersed polymer fine particles is preferably 35 ° C. or higher in view of particularly exhibiting an image scratch resistance effect, and more preferably 49 ° C. or higher. The upper limit of Tg is not particularly limited, but is preferably about 100 ° C. or less because a flexible ink film can be obtained and cracking of an image due to bending of a printed matter can be suppressed.

  The acid value of the aqueous dispersion type polymer fine particles is preferably 44 mgKOH / g or more, and more preferably 60 mgKOH / g or more. The upper limit of the acid value is not particularly limited, but is preferably less than 110 mgKOH / g from the viewpoint of easily obtaining a more stable dispersion.

  The average particle size of the water-dispersible polymer fine particles is preferably 300 nm or less, more preferably 130 nm or less, from the viewpoint that there is no clogging in the nozzle of the ink jet recording head and a good gloss feeling is obtained. The lower limit of the average particle diameter is preferably 30 nm from the viewpoint of production stability of fine particles.

  The content of the water-based dispersed polymer fine particles is preferably 0.7% to 6%, particularly preferably 1% to 3% from the viewpoints of the fixing property of the color material and the storage stability of the ink.

  The aqueous dispersion type polymer fine particles may be used as it is or after treatment of a dispersion polymerized in an aqueous system, or a dispersion of a polymer polymerized in a solvent system may be used in an acrylic, It can be selected from urethane, styrene, vinyl acetate, vinylidene chloride, vinyl chloride, styrene-butadiene, styrene-acrylonitrile, polybutadiene, polyethylene, polyisobutylene, polyester, and the like.

  In addition, the water-based dispersed polymer particles are preferably soap-free dispersed polymer particles from the viewpoint of ejection stability. Particularly preferred aqueous dispersion polymer fine particles are self-dispersion dispersions of a copolymer obtained by polymerizing unsaturated vinyl having a carboxyl group as a monomer component. For example, acrylic monomers such as ethyl acrylate alone or acrylic Mechanically sheared after a dispersion obtained by emulsion polymerization or suspension polymerization of acrylic acid or maleic acid as a carboxylic acid monomer in a composition comprising an ethylenically unsaturated monomer that can be copolymerized with a monomer is swelled with alkali, and then mechanically sheared. Is an acrylic hydrosol obtained by dividing the particles. Among acrylic hydrosols, it is preferable to contain styrene in the monomer composition from the viewpoint of increasing the refractive index of the resin and obtaining high glossiness.

  As the acrylic hydrosol, Jonkrill (trade name) manufactured by Johnson Polymer Co., Ltd. is commercially available.

[Other solvents]
In addition to the water-soluble solvent according to the present invention, various liquid media can be used for the ink according to the present invention. As the liquid medium, a mixed solvent such as water and a water-soluble organic solvent is more preferably used. For example, alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary 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.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyl) Diethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenedi Amine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (for example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) and the like. It is done.

[Ink set]
In the inkjet textile printing method according to the present invention, the aqueous pigment ink for inkjet may be an ink set including a light inkjet ink and a dark inkjet ink having the same pigment type and different pigment concentrations.

  That is, at least one color ink is composed of a light color ink jet ink and a dark color ink jet ink. Further, in two or more color inks, an ink set including the light color ink jet ink and the dark color ink jet ink can be used.

  By using a light color ink having a low pigment concentration, it is possible to reduce graininess and form a high-quality image without so-called “roughness”. In particular, a high-quality image can be obtained by using at least two inks having different densities in magenta ink or cyan ink having high human visibility.

  The pigment concentration ratio between the light-color ink jet ink and the dark ink-jet ink having different densities may be an arbitrary value. However, in order to reproduce the gradation smoothly, the ratio of the light-color ink to the dark-color ink (the light-color ink pigment) Density / pigment density of dark ink) is preferably between 0.1 and 1.0, more preferably between 0.2 and 0.5, and between 0.25 and 0.4. More preferably.

<< Fabric >>
In the inkjet textile printing method of the present invention, when image formation is performed using the above-described inkjet aqueous pigment ink, the polyester fiber A having a thickness of 1.0 d (denier) or more and 10 d or less and a thickness of 0.001 d are used. As described above, a fabric composed of polyester fiber B of less than 1.0d and having a mixing ratio (A: B) of the polyester fiber A and the polyester fiber B in the range of 1: 0.1 to 1:10 is used. Is a feature.

  Hereinafter, the fabric according to the present invention will be described.

  In the fabric according to the present invention, it is essential to use two or more kinds of polyester fibers having different thicknesses.

  In the fabric according to the present invention, it is necessary to control the polyester fiber group of 1d or more and the polyester fiber group of less than 1d to a specific range of 1: 0.1 to 1:10 in order to achieve various properties. It is based on the knowledge that there is.

  For the measurement of the thickness of the fibers, the fibers cut to a certain length were weighed, the number of fibers and the mass were obtained, converted to the mass per 9000 m, and expressed in d (denier) units.

  Each of the polyester fibers is twisted into a yarn, and the thickness of the yarn at that time is preferably 5 to 200d, more preferably 10 to 100d.

  A method for combining these two or more kinds of polyester fibers constituting the fabric according to the present invention is not particularly limited, and for example, a mixed woven yarn, a twisted yarn, a mixed woven fabric, or the like is preferable.

  Here, the fabric made of mixed woven yarn is a fabric formed by forming a twisted yarn using two or more types of filament fibers. A cloth made of twisted yarn is a twisted yarn obtained by combining two or more types of multifilament yarns (cross-twisted yarn) and made into a fabric. Furthermore, the mixed woven fabric refers to a fabric formed from two or more types of twisted yarns at the weaving stage.

  The fabric according to the present invention is mainly composed of a polyester yarn, but the polyester is a synthetic fiber having an ester bond, and the polyester yarn has high tensile strength, friction strength and heat resistance, and is blended with natural fiber or recycled fiber. It is comfortable to wear and has excellent blendability.

  The polyester according to the present invention is mainly, but not limited to, a condensate of ethylene glycol and terephthalic acid. Further, a condensate of a linear diol having 3 to 8 carbon atoms and terephthalic acid, or a condensate of ethylene glycol, terephthalic acid and a linear dicarboxylic acid having 3 to 8 carbon atoms is preferable.

  The fabric printed by the ink jet textile recording method according to the present invention is then cut into a desired size, and the cut piece is a process for obtaining a final processed product such as sewing, adhesion, or welding. It is possible to obtain clothing such as one piece, dress, tie, swimsuit, duvet cover, sofa cover, handkerchief, curtain, etc. Alternatively, a high-quality image can be formed in the same manner even when a shape such as clothing such as a T-shirt is created and then recorded by the inkjet printing method according to the present invention.

<Inkjet printing method>
[Heating fabric]
One of the features of the ink-jet printing method of the present invention is that the fabric is heated to 40 to 90 ° C. for printing.

  By heating the fabric, the drying and thickening speed of the ink is remarkably improved, and high image quality is obtained. Also, the durability of the image is improved. If it is 40 ° C. or higher, the image quality is sufficient and sufficient image durability is obtained, and the drying time is relatively short. On the other hand, when the temperature is 90 ° C. or lower, it is possible to ensure stable ink ejection and stably print. More preferably, the recording surface temperature of the recording medium is 40 to 60 ° C. As a heating method, it is possible to select a method in which a heating heater is incorporated in the recording medium conveyance system or the platen member and heated from the lower side of the recording medium in a contact manner, or a method of heating in a non-contact manner from the lower side or the upper side by a lamp or the like. In the present invention, as a post-processing after printing, the printed portion of the fabric may be reheated at 70 ° C. or higher for 10 seconds or longer to obtain a final image.

[Inkjet head]
The ink-jet head used in the ink-jet printing method of the present invention may be an on-demand method or a continuous method, and as an ejection method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type). , Piston type, shear mode type, shared wall type, etc.), and any discharge method such as an electro-thermal conversion method (for example, thermal ink jet type, bubble jet (registered trademark) type) may be used.

  EXAMPLES 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.

<< Production of Fabric >>
[Production of Fabric A: Present Invention]
A woven fabric was prepared by blending 10 pieces of 0.5d filamentous polyester fiber A and 10 pieces of 2.0d filamentous polyester fiber B made of a condensate of ethylene glycol and terephthalic acid. It was. The mass ratio (A: B) of the filamentous polyester fiber A and the filamentous polyester fiber B in the fabric A is 1: 4.

[Production of Fabric B: Present Invention]
15 0.4d filamentary polyester fibers A made of a copolymer of ethylene glycol, terephthalic acid and pimelic acid (molar ratio 3: 1: 2) and 20 2d filamentous polyester fibers B were mixed. A woven fabric was produced using the woven yarn as Fabric B. The mass ratio (A: B) of the filamentous polyester fiber A and the filamentous polyester fiber B in the fabric B is 1: 6.7.

[Production of Fabric C: Present Invention]
A woven fabric is prepared by using 20 pieces of 0.3d multifilament-like polyester fibers A made of a condensate of ethylene glycol and terephthalic acid and 12 pieces of 3.0d multifilament-like polyester fibers B. Fabric C was designated. The mass ratio (A: B) of the multifilament polyester fiber A and the multifilament polyester fiber B in the fabric C is 1: 6.

[Production of Fabric D: Present Invention]
A twisted yarn made from 100 pieces of 0.2d filamentary polyester fiber A made of a condensate of ethylene glycol and terephthalic acid was used as the weft, and a twisted yarn made from 6 pieces of 3.0d filamentous polyester fiber B was used as the warp. A mixed woven fabric was prepared and designated as fabric D. The mass ratio (A: B) of the filamentous polyester fiber A and the filamentous polyester fiber B in the fabric D is 1: 0.9.

[Production of Fabric E: Comparative Example]
A woven fabric was produced using only 50 polyester fibers having a 0.2d multifilament shape and a circular cross section made of a condensate of ethylene glycol and terephthalic acid.

[Production of Fabric F: Comparative Example]
A woven fabric was produced using only 13 polyester fibers having a 2.0 d multifilament shape and a circular cross section made of a condensate of ethylene glycol and terephthalic acid.

<< Preparation of pigment dispersion >>
[Preparation of Pigment Dispersion-C]
As a pigment dispersant, 3 parts of a styrene-acrylic acid copolymer (John Cryl 678, molecular weight 8500, acid value 215), 1.3 parts of dimethylaminoethanol, and 80.7 parts of ion-exchanged water are stirred and mixed at 70 ° C to dissolve. did.

  Next, C.I. I. After adding 15 parts of Pigment Blue 15: 3 and premixing, the mixture was dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads, and a pigment dispersion having a cyan pigment content of 15% -C was prepared.

[Preparation of Pigment Dispersion-Y, M, Bk]
In the preparation of Pigment Dispersion-C, cyan pigment C.I. I. Instead of CI Pigment Blue 15: 3, C.I. I. Pigment Yellow-74, C.I. I. Pigment Dispersion-Y, Pigment Dispersion-M, and Pigment Dispersion-Bk were prepared in the same manner except that Pigment Red 122 and carbon black were used as the black pigment.

<Synthesis of water-soluble copolymer>
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 stirrer, and heated to 75 ° C. while bubbling nitrogen.

  Thereto, a mixture composed of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of methyl ethyl ketone, and 500 mg of a polymerization initiator (AIBN) was added dropwise from a dropping funnel over 3 hours. After the dropwise addition, the mixture was further refluxed for 6 hours. After allowing to cool, the mixture was heated under reduced pressure, and methyl ethyl ketone was distilled off to obtain a polymer residue.

  In 450 ml of ion-exchanged water, dimethylaminoethanol corresponding to 1.05 moles of acrylic acid added as a monomer was dissolved, and the polymer residue was added and dissolved therein. Next, the concentration was adjusted with ion-exchanged water to obtain an aqueous solution of water-soluble copolymer 1 (acid value 117 mgKOH / g) having a water-soluble copolymer content of 20%.

[Synthesis of water-soluble copolymers 2, 3]
In the synthesis of the water-soluble copolymer 1, a water-soluble copolymer 2 (acid value 155 mgKOH / g), a water-soluble copolymer 3 and a monomer other than those used in Table 1 were used in the same manner. (Acid value 194 mgKOH / g) was synthesized to obtain an aqueous solution of water-soluble copolymers 2, 3 having a content of each water-soluble copolymer of 20%.

[Synthesis of water-soluble copolymer A for comparison]
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 stirrer, and heated to 75 ° C. while bubbling nitrogen.

  Thereto, a mixture of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of methyl ethyl ketone, and 500 mg of a polymerization 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 to obtain a polymer residue.

  Sodium hydroxide equivalent to 1.05 moles of acrylic acid added as a monomer was dissolved in 450 ml of ion-exchanged water, and the polymer residue was dissolved therein. The concentration was adjusted with ion-exchanged water to obtain an aqueous solution of water-soluble copolymer A having a water-soluble copolymer content of 20%.

<Characteristic value measurement of water-soluble copolymer>
The acid value and weight average molecular weight of each water-soluble copolymer prepared above were measured according to the following method.

(Measurement of acid value)
The acid value of the water-soluble copolymer was measured according to JIS K0070.

[Measurement of weight average molecular weight Mw]
The weight average molecular weight Mw of the water-soluble copolymer was measured using high performance liquid chromatography.

  The results obtained as described above are shown in Table 1.

<Preparation of ink set>
[Preparation of ink set 1: the present invention]
(Preparation of ink C1)
While stirring 46.6 parts of the pigment dispersion-C prepared above, the aqueous solution 15.0 of the water-soluble copolymer 1 having a content of the water-soluble copolymer having a hydrophobic monomer as a polymerization component is 20%. Then, the following compounds were sequentially added to prepare an ink composition, which was filtered through a 0.8 μm filter to obtain an ink C1.

Pigment dispersion-C 46.6 parts Aqueous solution of water-soluble copolymer 1 (water-soluble copolymer content: 20%) 15.0 parts PDX-7664A (manufactured by BASF, acrylic particle content: 46%) 2 .9 parts Triethylene glycol monobutyl ether 10.0 parts 1,2-hexanediol 5.0 parts Diethylene glycol 11.2 parts Acetylene surfactant: Orphine 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.6 parts Ion-exchanged water Was added to prepare 100 parts in total. In addition, the content of the water-soluble copolymer 1 in the ink C1 is 3.0% by mass, and the content of the aqueous dispersion polymer fine particles is 1.9% by mass.

(Preparation of ink Y1, M1, Bk1)
Ink Y1, ink M1, and ink Bk1 were similarly prepared except that pigment dispersion-Y, M, and Bk were used instead of pigment dispersion-C in the preparation of ink C1.

  Ink set 1 was composed of ink C1, ink Y1, ink M1 and ink Bk1 prepared as described above.

[Preparation of ink set 2: the present invention]
In the preparation of the ink set 1, each color ink (ink C2, ink Y2, ink) was used in the same manner except that the water-soluble copolymer 2 was used instead of the water-soluble copolymer 1 used to prepare each color ink. M2 and ink Bk2) were prepared, and this was designated as ink set 2.

[Preparation of ink set 3: the present invention]
In the preparation of the ink set 1 described above, each color ink (ink C3, ink Y3, ink) was similarly obtained except that the water-soluble copolymer 3 was used instead of the water-soluble copolymer 1 used for the preparation of each color ink. M3 and ink Bk3) were prepared, and this was designated as ink set 3.

[Preparation of ink set 4: comparative example]
In the preparation of the ink set 1, each color ink (ink C4, ink Y4) was prepared in the same manner except that the addition amount of the water-soluble copolymer 1 used for the preparation of each color ink was 0.8% by mass. Ink M4 and Ink Bk4) were prepared and used as Ink Set 4.

[Preparation of ink set 5: the present invention]
In the preparation of the ink set 1, each color ink (ink C5, ink Y5) was similarly prepared except that the addition amount of the water-soluble copolymer 1 used for the preparation of each color ink was 1.2% by mass. Ink M5 and Ink Bk5) were prepared and used as Ink Set 5.

[Preparation of ink set 6: the present invention]
In the preparation of the aqueous solution of the water-soluble copolymer 1 having a water-soluble copolymer content of 20%, the concentration of the ion-exchanged water is adjusted to change the content of the water-soluble copolymer 1 to 40%. An aqueous solution of the water-soluble copolymer 1A thus prepared was prepared.

  In the preparation of the ink set 1, instead of the aqueous solution (20%) of the water-soluble copolymer 1 used for the preparation of each color ink, the water-soluble copolymer having a content of the water-soluble copolymer 1 of 40%. Each color ink (Ink C6, Ink Y6, Ink M6, and Ink Bk6) was similarly used except that 1A aqueous solution was used and the content of the water-soluble copolymer 1 was 9.0% by mass with respect to the total mass of the ink. This was designated as Ink Set 6.

[Preparation of ink set 7: comparative example]
In the preparation of the ink set 1, in place of the aqueous solution (20%) of the water-soluble copolymer 1 used for the preparation of each color ink, the water-soluble copolymer having a content of the water-soluble copolymer 1 of 40%. Each color ink (Ink C7, Ink Y7, Ink M7, and Ink Bk7) was similarly obtained except that an aqueous solution of the product 1A was used and the content of the water-soluble copolymer 1 was 11.0% by mass relative to the total mass of the ink. ) Was prepared, and this was designated as ink set 7.

[Preparation of ink set 8: the present invention]
In the preparation of the ink set 1, each color ink (ink C8, ink Y8, ink) was the same except that PDX-7664A (manufactured by BASF, acrylic particle content: 46%) used for the preparation of each color ink was removed. M8 and ink Bk8) were prepared, and this was designated as ink set 8.

[Preparation of ink set 9: comparative example]
In the preparation of the ink set 1 described above, each color ink (ink C9, ink Y9, ink) was used in the same manner except that the water-soluble copolymer A was used instead of the water-soluble copolymer 1 used to prepare each color ink. M9 and ink Bk9) were prepared and used as ink set 9.

<< Image formation and evaluation >>
Images were formed by the recording methods 1 to 14 in which the produced fabric and the prepared inkjet set were combined as shown in Table 2, and the following evaluations were made. At the same time, the ejection stability of each ink set was also evaluated.

[Injection stability]
Using a piezo head having a nozzle diameter of 15 μm, a driving frequency of 10 kHz, and a nozzle number of 64, the light emission was evaluated. The drive voltage was adjusted so that each ink volume was 60 pl. In an environment of 25 ° C. and a relative humidity of 40%, 500 ml of each ink of each ink set is continuously ejected. The injection stability was evaluated.

◎: Normal emission for all nozzles ○: Bending is observed at 1 to 7 nozzles ×: Bending is observed at nozzles of 8 or more [Evaluation of image quality: bleeding resistance]
A contact heater was attached to the inkjet printer Nassenger KS-1600II, and a solid image was printed while the fabrics 1 to 6 were being conveyed at a speed of 10 m / h to produce a print. The heater temperature was adjusted so that the surface temperature of the fabric was 50 ° C.

  About each solid image produced for each ink of each ink set, the occurrence of bleeding of each color ink image in the boundary region between the printing portion and the non-printing portion was visually observed, and the bleeding resistance was evaluated according to the following criteria.

◎: No blur is observed at the boundary between the print portion and the non-print portion in all ink images. ○: Some blur is observed at the boundary between the ink print portion and the non-print portion in some ink images. Ink images of the inks show significant bleeding at the boundary between the printed and non-printed areas. [Evaluation of image durability]
A solid image was prepared for each ink of each ink set by the same method as the above-described evaluation of bleeding resistance, and image durability was evaluated according to the following criteria.

◎: Even if all the ink images are wiped with a cloth soaked in water, there is almost no stain on the wiped cloth. ○: Even if some of the ink images are wiped with a cloth soaked in water, the image will change in appearance. No, but the wiped cloth is colored and dirty ×: All the ink images are wiped with a dry polyester cloth, but the image will not change visually, but the wiped cloth will be colored and dirty [Drying Evaluation)
After creating each color solid image in the same manner as the evaluation of display durability, heating was continued at 50 ° C. from the bottom of the recording medium, and the solid image portion formed with a cotton swab was rubbed every 20 seconds until the swab no longer colored. Time was measured and used as a measure of dryness.

  Table 2 shows each evaluation result excluding the drying property obtained as described above.

  As is clear from the results shown in Table 2, the image formed by the inkjet printing method of the present invention using the aqueous pigment ink for inkjet and the fabric having the structure defined in the present invention is blurred compared to the comparative example. It turns out that it is excellent in tolerance and image durability. In addition, it can be seen that the water-based pigment ink for ink jet having the configuration defined in the present invention is superior in ejection stability to the comparative example.

  Further, as a result of evaluating the drying property according to the above method, all images formed by the ink jet printing method of the present invention had a drying time of 3 minutes or less, and showed a good drying property.

Claims (2)

A copolymer containing a pigment, a surfactant, a glycol ether or 1,2-alkanediol as a water-soluble solvent and polymerized with at least an unsaturated vinyl having a carboxyl group as a monomer component is added with an amine. Using an aqueous pigment ink for inkjet containing 1.0% by mass or more and 10% by mass or less of the water-soluble copolymer dissolved in the sum, at least the thickness is 1.0d (denier) or more, The polyester fiber A is 10d or less and the polyester fiber B is 0.001d or more and less than 1.0d in thickness, and the mixing ratio (A: B) of the polyester fiber A and the polyester fiber B is 1: 0. It is characterized in that inkjet recording is performed on a fabric in the range of 1 to 1:10 by heating the fabric at a surface temperature of 40 ° C. or higher and 90 ° C. or lower. Ink-jet printing process according to. 2. The ink jet printing method according to claim 1, wherein ink jet recording is performed using an aqueous pigment ink for ink jet containing water-based dispersed polymer fine particles.