JP2013159647A - Pretreating agent for inkjet textile printing and ink set for inkjet textile printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreating agent for inkjet textile printing, which allows fixability of ink to be made excellent and preservation stability thereof to be improved much more.SOLUTION: The pretreating agent for inkjet textile printing contains 3-8C carboxylic acid-derived polyvalent metallic salt and a water-dispersible resin (A) having ≤10°C glass transition temperature.

Description

  The present invention relates to a pretreatment agent for textile inkjet and an ink set in which the pretreatment agent and ink are set.

  2. Description of the Related Art As a method for printing images such as characters, pictures, designs, etc. on fabrics such as textiles and non-woven fabrics, a textile printing ink jet method that can perform image processing with a computer and perform printing substantially without plate is known. When an image is printed on a cloth by the textile printing ink jet method, there is a problem that the image is disturbed due to the fluff of the cloth surface fibers. In addition, since the printed ink is dried and fixed when the solvent evaporates and dries, the printed ink bleeds along the fiber and the image quality of the printed matter is lowered. In order to solve such a problem, the applicant has proposed a pretreatment agent using a water-dispersible resin and an ink set including the pretreatment agent and ink in Patent Document 1.

  This ink set uses a water-dispersible resin in the pretreatment agent to suppress the fluffing of the fabric surface fibers, and through a relatively soft water-dispersible resin pretreatment agent, it fixes the printed material and ink. Can improve the fastness to washing. The water-dispersible resin contained in the pretreatment agent is applied and dried on the cloth surface by spraying or the like, and then plasticized by heating / pressing operation using an iron to be integrated with the cloth surface fibers. By the action of the water dispersible resin, it is possible to provide a fabric surface having a high smoothness while suppressing the fluff of the fabric surface fibers and to improve the image quality of the printed matter.

  Further, by including a polyvalent metal salt in the pretreatment agent, it is possible to promote the action of aggregating the pigment in the ink and precipitating the resin emulsion to form an ink film on the printing material. When the pretreatment agent contains a polyvalent metal salt, when an image is printed with the inkjet ink for textile printing, the ink droplets that land on the surface of the cloth are polyvalent metal salt contained in the pretreatment agent deposited on the cloth. Is re-dissolved with the solvent (water) contained in the ink, and the dissolved polyvalent metal ions react with the water-dispersible resin contained in the ink to change the ink into a gel and fix it on the cloth. It is thought that the image quality can be improved. Therefore, when the pretreatment agent contains a polyvalent metal salt, it becomes easier to obtain a high-definition image with more ink bleeding and less ink penetration.

JP 2010-150454 A

  However, while the polyvalent metal salt is for gelling the water-dispersible resin in the ink, it also attacks the water-dispersible resin contained in the pretreatment agent, causing the pretreatment agent to aggregate and separate. I understood. In order to gel and fix the water-dispersible resin in the ink, the polyvalent metal salt contained in the pretreatment agent needs to be a polyvalent metal ion. In order to suppress the ionization, it is necessary to suppress ionization, and the polyvalent metal salt is required to have different properties in the storage stage and the stage that functions as a pretreatment agent. In other words, if the storage stability is pursued, the ink fixability must be sacrificed to some extent, and if the ink fixability is pursued, the storage stability must be sacrificed to some extent. This is a trade-off, and this is extremely difficult to achieve.

  The present invention has been made in view of the above circumstances, and provides a printing inkjet pretreatment agent having excellent ink fixability and improved storage stability, and an ink set in which the pretreatment agent and ink are set. It is for the purpose.

The pretreatment agent for textile printing inkjet according to the present invention comprises a polyvalent metal salt derived from a carboxylic acid having 3 to 8 carbon atoms and a water dispersible resin (A) having a glass transition temperature of 10 ° C. or less. It is characterized by.
The polyvalent metal salt is preferably a calcium salt.
The carboxylic acid is preferably propionic acid, lactic acid or phthalic acid.

The ink set for textile printing inkjet of the present invention is
(1) a pretreatment agent for textile inkjet;
(2) A combination of a pigment, a water-dispersible resin (B) having a film elongation of 400% to 1500%, and an ink-jet ink containing water.
More preferably, the textile ink jet ink set of the present invention includes the textile ink jet pretreatment agent (1) and the ink jet ink (2).
(3) a middle coating agent containing a resin (C) having a film elongation of 400% to 1500%;
(4) an overcoat agent containing a resin (D) having a film elongation of 100% to 400%;
It is preferable to consist of the combination which added.

  Since the pretreatment agent for printing ink jet according to the present invention is derived from a carboxylic acid having 3 to 8 carbon atoms in the polyvalent metal salt, ionization is suppressed in the storage state and water in the pretreatment agent for printing ink jet is used. High storage stability can be maintained without attacking the dispersible resin (A). On the other hand, after being coated and dried in an appropriate amount and integrated with the fabric surface fibers, it is possible to suppress the fluffing of the fabric surface fibers, and when the image is printed with the inkjet ink for printing, the ink droplets landed on the fabric surface The ink solvent inside dissolves and ionizes the polyvalent metal salt deposited on the cloth quickly, and the water dispersible resin (B) in the ink can be gelled and fixed by the action of the polyvalent metal ion. . That is, the polyvalent metal salt contained in the pretreatment agent for textile ink jet printing of the present invention is suppressed in ionization in the storage state, but functions as a polyvalent metal ion when in contact with the solvent of the ink. Both fixing property and storage stability can be achieved.

The pretreatment agent for textile ink jet printing of the present invention (hereinafter also simply referred to as pretreatment agent) is a polyvalent metal salt derived from a carboxylic acid having 3 to 8 carbon atoms and water having a glass transition temperature of 10 ° C. or less. Dispersible resin (A) is included.
Examples of polyvalent metal salts include calcium, magnesium, copper, nickel, zinc, barium, and other salts, but they are sprayed on a cloth and fixed with an iron as a pre-treatment agent. In view of the possibility of touching, etc., a calcium salt having no influence is more preferable.

  Preferred examples of the carboxylic acid having 3 to 8 carbon atoms include saturated fatty acids such as propionic acid, butanoic acid, pentanoic acid, hexanoic acid and octanoic acid, hydroxy acids such as lactic acid, and aromatic carboxylic acids such as phthalic acid. be able to. The carbon chain may be linear or branched, and may be saturated or unsaturated.

  When the carbon number is 2 or less, the pretreatment agent is easily ionized in the preservation step and the preservation step, and easily reacts with the resin in the pretreatment liquid. The effect of gelling and fixing (B) is reduced. On the other hand, when the number of carbon atoms is 9 or more, the molecular weight increases, and the amount of polyvalent metal salt in the molecule becomes relatively small, so that the amount of polyvalent metal ions necessary for gelling and solidifying the ink is secured. The required amount of carboxylate increases, causing problems such as an increase in the viscosity of the pretreatment agent. In addition, the storage stability is lowered due to poor solubility.

  The concentration of the polyvalent metal salt in the pretreatment agent is preferably about 1% by mass to 25% by mass, and more preferably about 5% by mass to 15% by mass. If it is less than 1% by mass, it may be difficult to form an ink film properly, and ink fixability may be difficult to improve. On the other hand, even if it exceeds 25 mass%, the effect beyond it cannot be expected.

  The water dispersible resin (A) has a glass transition temperature (hereinafter sometimes referred to as “Tg”) of 10 ° C. or less, and more preferably 5 ° C. or less (Tg is a value after drying). The resin is measured with a differential scanning calorimeter (DSC8230L2, manufactured by Rigaku Corporation) at a heating rate of 10 ° C./min). By applying such a pretreatment agent to a printing material before printing with ink, the adhesion between the printing material and the ink film is improved, and excellent washing and friction fastness can be obtained. Moreover, the fuzz of a fabric can also be suppressed.

The water dispersible resin (A) of the pretreatment agent preferably has an absolute value of zeta potential of less than 10 mV from the viewpoint of stability with the coexisting polyvalent metal salt.
The water-dispersible resin (A) may be a self-emulsifying type into which a hydrophilic component necessary for stably dispersing in water is introduced, or may be water-dispersible by using an external emulsifier.

  The water dispersible resin (A) is not particularly limited as long as it has the above Tg. For example, an acrylic resin, an acrylic-styrene resin, a urethane resin, a vinyl acetate resin, an acrylic-vinyl acetate resin, and the like. Two or more combinations can be used. Specifically, for example, 107M, 300, 361, E2000, E4000, E4800 in the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adekabon titer HUX-950 in the Adekabon titer series manufactured by Adeka Corporation. 290H, Takelac W-512A6 manufactured by Mitsui Chemicals Polyurethane Co., Ltd., Vinibrand 1225, 1245L manufactured by Nissin Chemical Industry Co., Ltd., and the like may be used, and a plurality of types may be used in combination.

  The content of the water-dispersible resin (A) with respect to the total amount of the pretreatment agent (when the water-dispersible resin other than the resin having the physical properties defined in the present invention is contained in the pretreatment agent), In order to appropriately exhibit the effect, the content is preferably 1% by mass to 20% by mass with respect to the total amount of the pretreatment agent. If the amount exceeds 20% by mass, it becomes difficult to remove the pretreatment agent adhering to the non-printing area by washing, and there is a fear that the commerciality of the finished printed product may be lowered.

  The pretreatment agent is an aqueous solution containing water, and this water is not particularly limited, but water with few impurities, such as pure water such as ion exchange water and distilled water, and ultrapure water, is preferable. The water content is not particularly limited and is preferably adjusted as appropriate from the viewpoint of viscosity adjustment. In addition, a water-soluble organic solvent can also be added from a viewpoint of viscosity adjustment and a moisturizing effect. The water-soluble organic solvent that can be used for the pretreatment agent is the same as the water-soluble organic solvent blended in the ink described later.

  Furthermore, additives that are generally blended in inks, such as preservatives, viscosity adjusters, antioxidants, and surfactants, may optionally be added to the pretreatment agent. As such additives, those similar to those blended in the ink described later can be used.

  The textile ink jet ink set of the present invention is characterized by comprising a combination of the textile ink jet pretreatment agent and (2) ink jet ink (hereinafter also simply referred to as ink). More preferably, it comprises a combination of (1) the textile pretreatment inkjet pretreatment agent and (2) ink jet ink plus (3) a middle coat agent and (4) an overcoat agent. preferable. Hereinafter, it demonstrates in order.

(2) The ink includes a pigment, a water-dispersible resin (B) having a film elongation of 400% to 1500%, and water.
In order to ensure washing and friction fastness for a substrate such as a fabric that easily stretches, the ease of stretching of the ink film, that is, the film elongation is important. That is, since the ink film has an elongation that can expand and contract following the expansion and contraction of the fabric, the ink film can be prevented from being broken and cracked, and washing and friction fastness can be ensured. On the other hand, if the elongation of the resin is too large, the adhesion of the ink film to the printing material is reduced, and washing / friction fastness is lowered, which is not preferable. This is presumably because the viscosity of the ink film becomes too strong to exert a sufficient anchor effect on the fiber surface.

From such a viewpoint, the film elongation of the water-dispersible resin (B) is preferably in the range of 400% to 1500%, more preferably 500% to 1100%, and more preferably 400% to 1000%. Even more preferred. Here, the film elongation is such that the water-dispersible resin (B) is applied on the polytetrafluoroethylene sheet so that the film thickness after drying is 500 μm, dried at room temperature for 15 hours, and further at 6 ° C. at 6 ° C. After drying for 20 minutes at 120 ° C., a water dispersible resin film obtained by peeling off from the sheet was measured using a Tensilon universal testing machine RTC-1225A (manufactured by Orientec Co., Ltd.) at a measurement temperature of 20 The length of the water-dispersible resin film stretched until the water-dispersible resin film breaks at a measurement speed of 200 mm / min at 0 ° C. is measured, and the ratio is expressed in percentage (hereinafter referred to as resin). The same applies to (C) and (D)).
The water-dispersible resin (B) may be a self-emulsifying type into which a hydrophilic component necessary for stable dispersion in water is introduced, or may be water-dispersible by using an external emulsifier.

  The type of the water-dispersible resin (B) is not particularly limited as long as it has the above-described film elongation. For example, acrylic resin, acrylic-styrene resin, urethane resin, vinyl acetate resin, acrylic-vinyl acetate resin, etc. , And combinations of two or more thereof can be used. Specifically, for example, Superflex 460, 460s, 470, 500M, 610, 700 in the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adekabon titer HUX in the Adekabon titer series manufactured by Adeka Corporation -380, 290K, 290H, Takelac W-512A6 manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and the like. These are water-dispersible resins having a urethane skeleton. These resins can be used alone or in combination of two or more.

The content of the water-dispersible resin (B) with respect to the total amount of the ink (the total amount including the water-dispersible resin other than the resin having the physical properties defined in the present invention when the ink is included) is a mass ratio. And it is preferably in the range of 0.5 to 2.5 with respect to the pigment 1. Thereby, the compounding effect of water-dispersible resin (B) can be exhibited appropriately. That is, if the mass ratio is less than 0.5 with respect to the pigment 1, there is a fear that sufficient washing and friction fastness cannot be ensured. On the other hand, if it exceeds 2.5, the viscosity of the ink is affected and printability may be hindered.
Further, from the viewpoint of avoiding clogging of the head after leaving the ink and ensuring ease of return, the content of the water-dispersible resin (B) is preferably 30% by mass or less based on the total amount of ink. The content is more preferably 15% by mass or less, and further preferably 10% by mass or less.

  The water dispersible resin (B) is preferably an anionic resin having a characteristic that the absolute value of the zeta potential is 40 mV or more. By having such a zeta potential, the resin is likely to be precipitated by contact with the polyvalent metal salt of the pretreatment agent, and the concealability and the fastness to washing and friction can be improved. The anionic group of the anionic resin is preferably a carboxy group from the viewpoint of easy precipitation due to the action of the polyvalent metal salt when the pretreatment agent is used.

As the pigment, those generally used in the technical field can be arbitrarily used. A white pigment is used for white ink, and a color pigment other than white is used for color ink. Specific examples of the white pigment include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. Besides the inorganic pigment, hollow resin fine particles or polymer fine particles can also be used.
The average particle size of the pigment is preferably 100 nm to 500 nm. When the average particle diameter of the pigment is less than 100 nm, the hiding power tends to be insufficient, and when it exceeds 500 nm, the ejection stability tends to be insufficient.

  Of these, titanium oxide is preferably used from the viewpoint of hiding power. Similarly, the average particle diameter of titanium oxide is preferably 100 nm to 500 nm. When titanium oxide is used, it is preferable to use one that has been surface-treated with alumina or silica in order to suppress the photocatalytic action. The surface treatment amount is preferably about 5% by mass to 20% by mass in the pigment.

  Examples of color pigments include azo, condensed polycyclic, nitro, and nitroso organic pigments (brilliant carmine 6B, lake red C, watching red, disazo yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc. ), Metals such as cobalt, iron, chromium, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides, and inorganic pigments such as ocher, ultramarine, and bitumen, furnace carbon black, lamp black, Carbon blacks such as acetylene black and channel black can be used. Any one of these pigments may be used alone, or two or more of these pigments may be used in combination.

  The pigment content (solid content) varies depending on the type of pigment used, but is preferably 1 to 30% by mass in the ink from the viewpoint of ensuring necessary color development. It is more preferable that it is mass%-15 mass%.

In order to stably disperse the pigment in the ink, it is preferable to use a pigment dispersant represented by a polymer dispersant or a surfactant. The following pigment dispersants can be used in combination of two or more.
As the polymer dispersant, for example, as a commercial product, Solsperse series (Solsperse 20000, 27000, 41000, 41090, 43000, 44000) manufactured by Nippon Lubrizol Co., Ltd., Johncrill series (Johncrill 57, manufactured by Johnson Polymer Co., Ltd.) 60, 62, 63, 71, 501), polyvinyl pyrrolidone K-30, K-90 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and the like.

Examples of the surfactant include anionic surfactants such as the Kao Corporation Demall series (Demol N, RN, NL, RNL, T-45), and Kao Corporation Emulgen series (Emulgen A-60, A). Nonionic surfactants such as -90, A-500, B-40, L-40, 420).
Considering the interaction with the polyvalent metal salt contained in the pretreatment agent, the pigment dispersant is preferably anionic.

  The blending amount in the ink when a pigment dispersant is used varies depending on the type and is not particularly limited, but is generally 0.005 to 0.005 based on the pigment 1 in terms of the mass ratio of the active ingredient (solid content). It is preferably used in the range of 5.

Furthermore, a self-dispersing pigment whose surface is modified with a hydrophilic functional group can also be used. Examples of commercially available products include CAB-O-JET series (CAB-O-JET200, 300, 250C, 260M, 270C) manufactured by Cabot Corporation, CW-1, CW-2 manufactured by Orient Chemical Co., Ltd., and the like.
Moreover, you may use the microencapsulated pigment which coat | covered the pigment with resin.

  The water contained in the ink is not particularly limited, but water with few impurities, such as pure water such as ion exchange water and distilled water, and ultrapure water, is preferable. From the viewpoint of viscosity adjustment, water is preferably contained in the ink in an amount of 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass.

The ink of the present invention preferably contains a water-soluble organic solvent that is liquid at room temperature and can be dissolved in water, from the viewpoints of viscosity adjustment and moisturizing effect. Examples of such water-soluble organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and other glycols, glycerin, acetins, Glycol derivatives such as triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, triethanolamine, 1-methyl-2-pyrrolidone, β-thioglycol, Sulfolane and the like can be used. These water-soluble solvents can be used alone or in combination of two or more.
The water-soluble organic solvent is preferably contained in the ink in an amount of 1% by mass to 80% by mass, and more preferably 10% by mass to 60% by mass, from the viewpoints of viscosity adjustment and a moisturizing effect.

In the ink of the present invention, in addition to the above-mentioned components, a wetting agent (humectant), a surface tension adjusting agent (surfactant), an antifoaming agent, a fixing agent, and a pH adjusting agent within the range not impairing the effects of the present invention. , Antioxidants, preservatives and the like can be optionally contained.
As the wetting agent, polyhydric alcohols can be used.

  As the surface tension adjusting agent, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, or polymer-based, silicone-based, and fluorine-based surfactants may be used. it can. By blending this surfactant, it is preferable because ink can be stably ejected by an ink jet method and ink permeation can be appropriately controlled. The amount added varies depending on the type of surfactant, but is preferably in the range of 0.1% by mass to 10% by mass in the ink. When a large amount of the surfactant is added beyond this range, the surface tension of the ink is lowered, and as a result, the penetration of the ink on the fabric becomes too fast, and there is a fear that the hiding property and the coloring property may be hindered.

  Specifically, as an anionic surfactant, Kao Corporation Emar series (Emar 0, 10, 2F, 40, 20C), Neopelex series (Neopelex GS, G-15, G-25, G- 65), Pelex series (Pelex OT-P, TR, CS, TA, SS-L, SS-H), demole series (demole N, NL, RN, MS) and the like.

  Examples of the cationic surfactant include Acetamine series (Acetamine 24, 86) manufactured by Kao Corporation, Coatamine series (Coatamine 24P, 86P, 60W, 86W), Sanizol series (Sanisol C, B-50), and the like. Is mentioned.

Nonionic surfactants include acetylene glycol surfactants such as Surfynol series (Surfinol 104E, 104H, 420, 440, 465, 485) manufactured by Air Products, and Emulgen Series (Emulgen 102KG manufactured by Kao Corporation). , 103, 104P, 105, 106, 108, 120, 147, 150, 220, 350, 404, 420, 705, 707, 709, 1108, 4085, 2025G) and the like. It is done.
Examples of the amphoteric surfactants include the Amphitol series (Amphithol 20BS, 24B, 86B, 20YB, 20N) manufactured by Kao Corporation.

  In order to adjust the viscosity and pH of the ink, an electrolyte can be added to the ink. Examples of the electrolyte include sodium sulfate, potassium hydrogen phosphate, sodium citrate, potassium tartrate, and sodium borate, and two or more kinds may be used in combination. Sulfuric acid, nitric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, and the like can also be used as an ink thickening aid or pH adjuster.

  By blending an antioxidant, it is possible to prevent the ink components from being oxidized and improve the storage stability of the ink. As the antioxidant, for example, L-ascorbic acid, sodium L-ascorbate, sodium isoascorbate, potassium sulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, sodium pyrosulfite can be used.

  By blending a preservative, the ink can be prevented from being spoiled and the storage stability can be improved. Examples of the preservative include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 1 Isothiazolone preservatives such as 1,2-benzisothiazolin-3-one; triazine preservatives such as hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine; 2-pyridinethiol sodium-1- Pyridine / quinoline preservatives such as oxide and 8-oxyquinoline; Dithiocarbamate preservatives such as sodium dimethyldithiocarbamate; 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitro-1,3 -Propanediol, 2,2-dibromo-2-nitroethanol, 1,2-dibromo-2,4-dicyano Brominated organic preservatives such as Tan; p-hydroxybenzoate, p- hydroxybenzoate ethyl, potassium sorbate, sodium dehydroacetate, can be used salicylic acid.

  The viscosity of the ink can be adjusted as appropriate, but is preferably 1 mPa · s to 30 mPa · s, for example, from the viewpoint of ejection properties. This viscosity is the ink viscosity at 10 Pa when the shear stress is increased from 0 Pa at a rate of 0.1 Pa / s at 23 ° C.

(3) The middle coat agent has a composition containing a resin (C) having a film elongation of 400% to 1500%.
The middle coating agent is used by applying the ink onto a printing material and then applying it to a printing surface including at least a printing area.

  The ink of the present invention can increase the fastness of washing and friction to some extent by using only the ink, but it can further increase the fastness of friction by protecting the printing surface with an overcoat agent described later. However, since the film elongation of the resin of the overcoat agent is set low, the overcoat agent cannot follow the ink film, and may be peeled off by washing. Therefore, peeling can be prevented by using a middle coat agent between the ink film and the overcoat agent.

  Such an effect cannot be obtained when the middle coat agent and the overcoat resin are mixed to form a single layer, and it is important to form the resin layers separately. In addition, it is conceivable to include a middle coat agent component in the ink, but since the amount of resin that can be added to the ink is limited from the viewpoint of viscosity, an independent layer may be provided as the middle coat agent. preferable.

  The film elongation of the resin (C) of the middle coat agent is preferably 400% to 1500%, more preferably 500% to 1100%, and still more preferably 400% to 1000%. By being 400% or more, the middle coating agent can expand and contract following the expansion and contraction of the fabric and the ink film, so that the middle coating agent can be prevented from being broken or cracked. If it exceeds 1500%, from the viewpoint of adhesion between the middle coat agent and the ink film, it is not preferable because sufficient washing and friction fastness cannot be ensured.

  The middle coat agent is preferably water based from the viewpoint of environmental load and safety. The resin (C) used for the middle coating agent is preferably a water-dispersible resin from the viewpoint of water resistance. In this case, the middle coating agent contains a water-dispersible resin and water. The water-dispersible resin may be a self-emulsifying type into which a hydrophilic component necessary for stably dispersing in water is introduced, or may be water-dispersible by using an external emulsifier.

  The type of the resin (C) of the middle coating agent is not particularly limited in view of the object of the present invention as long as it has the above film elongation. For example, acrylic resin, acrylic-styrene resin, urethane resin, vinyl acetate resin , Acrylic-vinyl acetate resin, and the like, and combinations of two or more thereof can be used. Specifically, for example, Superflex 460, 460s, 470, 610, 700 in Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adekabon titer HUX-380 in Adekabon titer series manufactured by Adeka Co., Ltd. 290K, 290H, Takelac W-512A manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and the like. These are water-dispersible resins having a urethane skeleton. These resins can be used alone or in combination of two or more.

  The content of the resin relative to the total amount of the middle coat agent (when the resin other than the resin having the physical properties defined in the present invention is included in the middle coat agent, the total amount including them) is to appropriately exert its effect. It is preferable that it is 1 mass%-60 mass%, and it is more preferable that it is 3 mass%-40 mass%. If it is added in a large amount exceeding 60% by mass, it becomes difficult to uniformly apply to the fabric, and there is a fear that the commercial properties of the finished printed product may be lowered.

Although it does not specifically limit as water, Water with few impurities, such as pure water, such as ion-exchange water and distilled water, and ultrapure water, is preferable. The water content is not particularly limited and is preferably adjusted as appropriate from the viewpoint of viscosity adjustment.
Moreover, a water-soluble organic solvent can be added from a viewpoint of viscosity adjustment and a moisturizing effect. As such a water-soluble organic solvent, those similar to those blended in the ink can be used.

  In the middle coat agent, additives generally blended in the ink, such as preservatives, viscosity adjusting agents, antioxidants, and surfactants, may be optionally added. As such additives, the same additives as those blended into the ink can be used.

(4) An overcoat agent is a composition containing resin (D) whose film elongation is 100%-400%.
The overcoat agent is used by applying the above-described middle coat agent to a substrate to be printed and then applying it to a printing surface including at least a printing region.

  The film frequency of the resin (D) of the overcoat agent is 100% to 400%, and more preferably 150% to 350%. By being 400% or less, it is possible to prevent the ink film from being scraped by a frictional force, and to improve the fastness to friction. On the other hand, if it is less than 100%, the flexibility of the ink film is deteriorated and the texture may be lowered. In addition, if the film elongation of the overcoat film is too low, when the ink film expands and contracts with the fabric, the overcoat film cannot follow and expand and contract, and the ink film breaks and cracks. Sometimes. Therefore, it is preferably 100% or more.

  The resin (D) of the overcoat agent is preferably an aqueous system from the viewpoint of environmental load and safety. The resin (D) used for the overcoat agent is preferably a water-dispersible resin from the viewpoint of water resistance. In this case, the overcoat agent contains a water-dispersible resin and water. The water-dispersible resin may be a self-emulsifying type into which a hydrophilic component necessary for stably dispersing in water is introduced, or may be water-dispersible by using an external emulsifier.

  The type of resin (D) of the overcoat agent is not particularly limited in view of the object of the present invention as long as it has the above-mentioned film elongation. For example, acrylic resin, acrylic-styrene resin, urethane resin, vinyl acetate resin , Acrylic-vinyl acetate resin, and the like, and combinations of two or more thereof can be used. Specifically, Superflex 150, 410, 420, 650, E2500, R5002 in the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , And combinations thereof.

  The content of the resin (the total amount including the resin when the resin other than the resin having the physical properties specified in the present invention is included in the overcoat agent) with respect to the total amount of the overcoat agent appropriately exhibits the effect. Therefore, the content is preferably 1% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass. If it is added in a large amount exceeding 60% by mass, it becomes difficult to uniformly apply to the fabric, and there is a fear that the commercial properties of the finished printed product may be lowered.

  Although it does not specifically limit as water, Water with few impurities, such as pure water, such as ion-exchange water and distilled water, and ultrapure water, is preferable. The water content is not particularly limited and is preferably adjusted as appropriate from the viewpoint of viscosity adjustment.

  A water-soluble organic solvent can be added to the overcoat agent from the viewpoint of viscosity adjustment and a moisturizing effect. As such a water-soluble organic solvent, those similar to those blended in the ink can be used.

  In the overcoat agent of the present invention, additives generally blended in inks such as preservatives, viscosity adjusting agents, antioxidants, surfactants and the like may be optionally added. As such additives, the same additives as those blended into the ink can be used.

  Next, a method for producing a printed matter (printed printed matter) using the ink set of the present invention will be described. As the cloth, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, polyester, nylon, rayon, acetate, cupra and the like can be used. The ink set of the present invention can provide a printed material excellent in washing and friction fastness to fabrics of various materials. In particular, according to the present invention, even when a woven fabric composed of long fibers such as polyester, nylon, rayon, acetate, and cupra is used as a fabric, excellent washing and friction fastness can be obtained.

  The printed matter using the ink set of the present invention includes (1) a step of applying a pretreatment agent to at least a printing region of the fabric, (2) a step of printing the fabric with an inkjet ink by an inkjet recording method, and (3) A step of applying a middle coat agent to at least a print region of the fabric, and (4) a step of applying an overcoat agent to at least the print region of the fabric. According to such a production method, it is possible to obtain a printed matter having excellent washing and friction fastness.

In the step (1), a pretreatment agent is applied to at least the printing region of the fabric that is the substrate. The application area may be the entire fabric including the printing area.
The coating amount of the pretreatment agent, per unit area of the fabric is preferably ^{1g / m 2 ~500g / m 2} , and more preferably ^{10g / m 2 ~200g / m 2} . If it is applied in a large amount exceeding 200 g / m ² , it is difficult to selectively remove the pretreatment agent adhering to the non-printing portion, and there is a fear that the commerciality of the finished printed product may be lowered.

  In step (2), printing is performed by an inkjet recording method. The ink jet printer to be used may be of any method such as a piezo method, an electrostatic method, a thermal method, etc., and ink droplets ejected from an ink jet head based on digital signals are ejected. Can be allowed to adhere to the fabric to which the pretreatment agent has been applied.

If the fabric is a dark color, the color development of the ink may be reduced. Therefore, by first printing white ink on the printing area on the fabric and overlaying the color ink on the printed area, a printed matter with good color development can be obtained. On the other hand, for the case where the fabric is white, it is possible to obtain a printed matter having excellent color developability simply by printing the color ink. Excellent texture and breathability.
The amount of ink applied is not particularly limited, but it is preferably 500 g / m ² or less per unit area of the fabric from the viewpoint of texture.

In the step (3), a middle coat agent is applied to at least the printing region of the fabric on which the ink is printed in the step (2). The application region may be the entire fabric including the print region.
The coating amount of the middle coating agent, per unit area of the fabric is preferably ^{1g / m 2 ~500g / m 2} , and more preferably ^{10g / m 2 ~100g / m 2} . By being in this range, both improvement in fastness and suppression of texture deterioration can be achieved.

In step (4), the overcoat agent is applied to at least the printing region of the fabric to which the middle coat agent is applied in step (3). The application region of the overcoat agent may be the entire fabric including the printing region.
The coating amount of the overcoating agent is per unit area of the fabric is preferably ^{1g / m 2 ~500g / m 2} , and more preferably ^{10g / m 2 ~100g / m 2} . By being in this range, both improvement in fastness and suppression of texture deterioration can be achieved.

  The method for applying the above pretreatment agent, middle coat agent, and overcoat agent to the fabric is not particularly limited, and any method such as a spray method, a dipping method, a pad method, or a coating method can be used. An ink jet recording method or a screen printing method may be used.

  After the pretreatment step in step (1), the printing step in step (2), and the application of the overcoat agent in step (4), it is preferable to perform heat treatment on the fabric at about 100 ° C. to 180 ° C., respectively. . After application of the middle coating agent in step (3), the overcoat agent may be applied as it is without performing heat treatment.

  The heat treatment after the step (1) is to dry the moisture in the pretreatment agent, so that the moisture in the pretreatment agent may be mixed with the ink when the ink is printed and the image may be blurred. In addition, the fluffing of the cloth surface can be corrected. By heat treatment after the step (2), the ink can be dried and a water-dispersible resin can be formed to form a strong ink film. The heat treatment after the step (4) is to form a strong resin film by forming a resin of the middle coat agent and the overcoat agent, and when the middle coat agent and the overcoat agent contain water. Is also for drying moisture. When printing white ink and color ink in step (2), it is only necessary to perform heat treatment after printing color ink.

The heat treatment conditions are not particularly limited. For example, the heat treatment after step (1) is performed at 160 ° C. for about 30 seconds, the heat treatment after step (2) and the heat treatment after step (4) are both 160 ° C. It is preferable to carry out in about 60 seconds.
Hereinafter, the present invention will be described in more detail with reference to examples.

(Examples and Comparative Examples)
A pretreatment liquid was prepared with the formulation shown in Table 1 below (the numerical values shown in Table 1 are parts by mass).

(Evaluation)
(Left stability)
10 cc of the prepared aqueous solution was placed in an SV-20 bottle, the cap was closed, and the mixture was allowed to stand in an environment of 60 ° C. for 2 weeks. The sedimentation state of the resin was visually observed and evaluated according to the following criteria.
◎: No sedimentation ○: The resin settles and the upper part is divided into the lower part, but it is easily homogenized by stirring. △: The resin settles and the upper part is divided into the lower part. X: Resin separates and settles at the bottom, re-sediments even after shaking

(Ink fixability)
After spraying the pretreatment agent uniformly to such an extent that the cloth surface was moistened using a spray, the pretreatment agent was dried while applying pressure with an iron (120 ° C.). A black ink (self-dispersed pigment CW-2 manufactured by Orient Chemical Co., Ltd., 4.5% by mass, Daiichi Kogyo Seiyaku Co., Ltd.) was pre-treated using a textile printing IJ apparatus (Mastermind, Inc .: MMP813BT). Superflex 460 manufactured by Co., Ltd. is 4.5% by mass in solid content, Surfynol 465 manufactured by Air Products is 3.0% by mass, ethylene glycol and glycerin are each 10.0% by mass, and the remaining amount of ion-exchanged water. 1440 dpi × 720 dpi, 80 mm × 80 mm solid printing was performed, and after printing, it was press dried with an iron (120 ° C.) and fixed. It was visually confirmed whether fixing failure, blurring or image distortion occurred, and evaluation was performed according to the following criteria.
○: No blurring of the image or fine characters △: Although blurring can be seen in the fiber method, fine characters can be distinguished ×: Small letters and small characters are broken, making it difficult to distinguish characters

(Discoloration due to UV)
The pretreatment liquid was sprayed on white cotton and fixed with an iron. Using a handy UV irradiation device (OHD-320M) manufactured by Oak Manufacturing Co., Ltd., irradiate from a distance of 30 cm for 30 seconds, repeat the cooling-irradiation, and irradiate until the total irradiation time is 5 minutes. And evaluated according to the following criteria.
○: No discoloration is observed ×: Discoloration is present Table 1 shows the results of the pretreatment agent formulation and evaluation.

  As shown in Table 1, in Examples 1 to 3 using the pretreatment agent for textile ink jet printing of the present invention, it can be seen that both ink fixing properties and storage stability can be achieved. In Comparative Examples 1 and 2 using calcium nitrate or calcium chloride as the metal salt, the ink fixing property was good, but the storage stability was poor. Further, in Comparative Example 1, yellowing occurred due to light, and it was not suitable as a pretreatment agent for textile printing ink jet. On the other hand, Comparative Example 3 containing calcium stearate, which is a polyvalent metal salt, was extremely poor in storage stability and could not be used for ink fixing experiments.

  As described above, since the polyink metal salt is derived from a carboxylic acid having 3 to 8 carbon atoms in the pretreatment agent for textile printing of the present invention, ionization is suppressed in the storage state. When contacted with the solvent, the water-dispersible resin (B) in the ink is gelled and fixed as polyvalent metal ions, thereby making it possible to achieve both ink fixability and storage stability.

Claims (5)

  A pretreatment agent for textile printing inkjet, comprising a polyvalent metal salt derived from a carboxylic acid having 3 to 8 carbon atoms and a water-dispersible resin (A) having a glass transition temperature of 10 ° C. or less.   2. The pretreatment agent for printing ink jet according to claim 1, wherein the polyvalent metal salt is a calcium salt.   The printing ink-jet pretreatment agent according to claim 1 or 2, wherein the carboxylic acid is propionic acid, lactic acid or phthalic acid. (1) The pretreatment agent for textile printing inkjet according to any one of claims 1, 2, and 3
(2) A textile ink jet ink set comprising a combination of a pigment, a water dispersible resin (B) having a film elongation of 400% to 1500%, and an ink jet ink containing water. further,
(3) a middle coating agent containing a resin (C) having a film elongation of 400% to 1500%;
(4) an overcoat agent containing a resin (D) having a film elongation of 100% to 400%;
The textile ink jet ink set according to claim 4, comprising a combination of