JP2019177576A - Production method of transfer printing sheet - Google Patents

Abstract

To provide a production method of a transfer printing sheet for textile material capable of being produced by a simple step, inexpensively in variable cost and fixed cost, excellent in economical efficiency, suppressing environmental load, and having excellent quality.SOLUTION: There is provided an ecological and economical production method of a transfer printing sheet for textile material formed of a paste layer and a dye ink applied to the paste layer provided on a substrate, the paste layer is formed by applying a paste on a pre-stage unit of a multistep gravure printing machine, then, the dye ink is applied in a subsequent stage unit.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a transfer printing paper used for transfer printing of a fiber material. More specifically, it is a method of forming a paste layer as an ink receiving layer on the surface of a substrate and applying a dye ink to the paste layer, and producing a transfer printed paper excellent in economic efficiency and quality stability. Related to the method.
In the present application, the paper or resin film before applying the paste is referred to as “base material”, and in the case of paper, it may be referred to as “base paper”. In addition, the “transfer printing paper” in the present application includes not only a paper using a paper as a base material but also a transfer printing film using a resin film as a base material.

As a textile material printing method, flat screen printing using a color paste, roller printing, rotary screen printing, and the like are known. However, these printing methods require the use of a large amount of color paste and the need to make surplus color paste, so the drainage load is large, the work process is complicated and requires skill, and the incidence of defective products increases. There are problems such as easy.
Therefore, as a method for solving these problems, recently, a paste is applied to a base material to form an ink receiving layer and a transfer printing paper (a base material coated with a paste is called a transfer printing paper). The same shall apply hereinafter), and transfer printing paper to which ink containing a dye (dye ink) is applied on the ink receiving layer by digital printing, gravure printing, etc. (transfer printing paper to which dye ink has been applied is transferred. Transfer textile printing methods for performing wet transfer, dry transfer, sublimation transfer, non-sublimation transfer, and the like on fiber materials have been widely used.

For example, in Patent Document 1 and Patent Document 2, an adhesive layer is formed on a release paper to form an ink receiving layer, dye ink is applied (printed) to the ink receiving layer, and fibers of the ink receiving layer A method is disclosed in which dry transfer to a material, release paper release, and dye fixing by steaming are sequentially performed.
Patent Document 3 discloses a mixed paste solution in which a water-soluble synthetic binder, a natural paste, an auxiliary agent, and the like, which have a temporary adhesive force with a fiber material by heating and pressurization, are added to inexpensive commercial paper. After coating and drying to form an ink receiving layer and adhesive layer, the transfer printed paper obtained by printing the dye ink on the transfer printed paper obtained in this manner is heated and pressed on the fiber material and pasted. In addition, a transfer printing method in which a dye is transferred and fixed is disclosed.
Patent Document 4 discloses a transfer printing method using a non-sublimation type disperse dye of a polyester fiber material.

  In these transfer textile printing methods, conventionally, the production process of the transfer textile paper and the production process of the transfer textile paper have been performed separately, and each has a division of labor system that is performed by different specialists. Specifically, the transfer printing paper production process (the step of applying the glue) is carried out by a paper company having a technology for producing coated paper, and the transfer printing paper production process (transfer printing paper is dyed). The step of applying ink) is performed by a textile processing company that performs transfer printing using the transfer printing paper. That is, a textile processing company having expertise in color patterns, dyes, and dyeing performs a process of applying a dye ink to coated paper to produce a transfer printed paper and transferring and coloring the fiber material.

However, this division of labor had the following problems.
There are many large-scale coating machines in the papermaker's facilities, and it is desirable to apply coatings of tens of thousands of meters per lot. When the coating amount of one lot is small, the loss rate of paper and paste is high, and the unit price of transfer textile printing paper is high.
On the other hand, the processing unit in a textile processing company is relatively small, and in particular due to the recent trend of small quantity and variety, the number of lots is several thousand m or less. Therefore, if the production volume of one lot of coating is large, the stock quantity of transfer printing paper will increase and a long-term inventory will be required, resulting in an increase in storage charges, moisture absorption of glue, and defective products due to alteration , Color development defects) occur.
In addition to the above-mentioned problems, this division of labor system has many cost increasing factors such as a cost increase in a complicated distribution stage and generation of a double processing fee due to production at another factory.
For this reason, the transfer printing method using a substrate has advantages such as the use of water-based dye inks, and a printing method that has a small wastewater load and is friendly to the environment. Not reached.

Japanese Patent No. 4058470 Japanese Patent Laid-Open No. 06-270596 Japanese Patent No. 4778124 Japanese Patent No. 61733641

  As a result of intensive studies to solve the above-described cost problems of the transfer printing method using a substrate, the present inventor has found that if a gravure printing machine or a flexographic printing machine having a multi-stage unit is used, the glue is used. The coating process (transfer textile production process) and the process of applying dye ink to the transfer textile paper (transfer textile production process) can be carried out continuously with the same equipment, that is, at the same line speed, In addition, it has been found that transfer printing paper of the same quality as transfer printing paper manufactured by the conventional division of labor can be manufactured, and as a result, the above problems can be solved and the manufacturing cost of transfer printing paper can be greatly reduced. did.

  Conventionally, a multicolor printed matter is produced by printing each of a plurality of hues of dye ink with each unit using a gravure printing machine or a flexographic printing machine having a multi-stage unit. Printing in each unit is performed continuously, and the feed speed of the printing material is the same in each unit. Therefore, conventionally, it is not considered that a paste coating liquid having a completely different composition from that of a dye ink can be continuously applied with the same apparatus, and it is not considered that the same quality as the conventional one can be obtained. A method of applying continuously (at the same line speed) with the same apparatus has not been adopted. However, the present inventor can apply sufficiently with a gravure printing machine used for printing a dye ink as long as it is a coating solution of a specific paste containing a natural paste and / or a synthetic paste. It has been found that transfer printed paper of the same quality as before can be produced.

The present invention relates to a method for producing a transfer printed paper used for transfer printing of a fiber material, wherein the production of the transfer printed paper and the application of dye ink to the transfer printed paper are continuously performed with one apparatus. Another object of the present invention is to provide a method for producing a transfer printed paper that can reduce production costs.
Another object of the present invention is to provide a printing method characterized by using the transfer printed paper produced by the above production method and a method for producing a dyed product using the textile printing method.

The first of the present invention is
A step of forming a paste layer by applying a paste containing a paste selected from a natural paste and a synthetic paste on a substrate; and a step of applying a dye ink on the paste layer Have
The step of forming the adhesive layer is performed in a front stage unit of a gravure printing machine or a flexographic printing machine having a multistage unit,
The method for producing a transfer printed paper for a fiber material is characterized in that the step of applying the dye ink is performed in a subsequent unit of the gravure printing machine or flexographic printing machine.

A second aspect of the present invention is the first aspect of the present invention, wherein the substrate is a base paper having a basis weight of 20 to 150 g / m ² or a resin film having a thickness of 10 to 100 μm. This is a method for producing a transfer printed paper for a fiber material.

  A third aspect of the present invention is the first or second aspect of the present invention, wherein the paste liquid further comprises a water-soluble dispersant, an alkali metal or alkaline earth metal sulfate, hydrochloride, nitrate, phosphate, A mixed paste containing one or more selected from the group consisting of carbonates, bicarbonates or hydroxides, mineral fine particles, pigments and auxiliaries, and the viscosity of the mixed paste at 25 ° C. Is a method for producing a transfer-printed paper of a fiber material, characterized in that is 10 mPas or more and 3000 mPas or less.

  A fourth aspect of the present invention is the first to third aspects of the present invention, wherein the dye ink is selected from the group consisting of reactive dyes, acid dyes, disperse dyes, gold-containing dyes, direct dyes and cationic dyes. Or it is the manufacturing method of the transfer printing paper for fiber materials characterized by being an aqueous | water-based dye ink containing 2 or more types of dyes.

  A fifth aspect of the present invention is the first to fourth aspects of the present invention, wherein the transfer printing paper is a sublimation transfer printing paper, a dry transfer printing paper, a wet transfer printing paper, a paper printing transfer printing paper, or a non-sublimation. A method for producing a transfer-printed paper for a fiber material, characterized in that it is a transfer-printed paper.

  A sixth aspect of the present invention is the transfer printed paper produced by the method for producing a transfer printed paper for the first to fifth fiber materials of the present invention, in close contact with the fiber material, heated, and the dye ink, A transfer printing method for a fiber material, comprising a step of transferring to a fiber material.

  A seventh aspect of the present invention is the sixth textile material transfer printing method of the present invention, wherein the fibrous material is a natural fiber, a semi-synthetic fiber or a synthetic fiber woven fabric, a knitted fabric, a non-woven fabric, a sheet or a film, or A fiber material transfer printing method characterized by being a blended, mixed, interwoven or composite material of fibers selected from natural fibers, semi-synthetic fibers and synthetic fibers.

  An eighth aspect of the present invention is a method for producing a dyed product, characterized in that the sixth or seventh fibrous material transfer printing method of the present invention is used.

  According to the present invention, an existing multi-color gravure printing machine that is widely used in the printing industry can be used to produce a transfer printed paper for fiber materials without generating a double processing fee in a simple process. Can be manufactured. And the present invention is a manufacturing method that is low in fixed cost and variable cost, is excellent in economic efficiency, has little loss of resources such as paste and base material, and has a small drainage load due to loss of paste and therefore excellent in ecology. is there. In addition, according to the present invention, quality control is easy and it is easy to manufacture excellent products, and the stock of printing paper can be reduced to zero, so that inventory management costs and logistics costs can be greatly reduced.

  Conventionally, in the production of transfer textiles, due to the fact that the production process of transfer textiles and the production process of transfer textiles have become a division of labor, the inventory management cost of transfer textiles increases and the quality deteriorates. There are many cost-up factors such as the generation of defective products due to the above, the cost increase at complicated distribution stages, and the generation of double processing costs due to production at different factories. Expansion of the practical application of the transfer printing method using printing paper has been hindered. However, the present invention solves these problems, and is an epoch-making method for producing transfer printing paper that is both economical and ecological, and is eco-friendly and economical transfer printing paper that is friendly to the earth. The manufacturing method was provided.

It is a schematic cross section which shows typically the printing machine used for the manufacturing method of the transfer textile printing paper of this invention.

The method for producing the transfer printing paper for the fiber material of the present invention,
A step of forming a paste layer by applying a paste containing a paste selected from a natural paste and a synthetic paste on a substrate to form a transfer printing paper; and In addition to having dye ink on the glue layer and producing a transfer printed paper,
Using a gravure printing machine or flexographic printing machine having a multi-stage unit (hereinafter simply referred to as “printing machine” means a gravure printing machine or flexographic printing machine); and
The step of forming the adhesive layer (the step of producing a transfer textile sheet) is performed in the preceding unit of the printing machine,
A step of applying the dye ink (a step of producing a transfer printing paper) is performed in a subsequent unit of the printing machine; and
The step of forming the glue layer and the step of applying the dye ink are performed continuously in the printing press.

Here, the “unit” is composed of a set of means necessary for gravure printing or flexographic printing. In the printing press used in the present invention, a large number of units are connected in series (one continuous workpiece is sequentially passed). Multiple units are lined up). As means necessary for printing constituting one unit, there are an ink pan, a plate cylinder on the ink pan, an impression cylinder, a drying device, and the like. In many cases, a doctor blade is attached to the plate cylinder.
In the manufacturing method for a fiber material of the present invention, a printing machine having a multi-stage unit, that is, a printing machine having a plurality of units is used, and an object to be processed (base material) continuously passes through the plurality of units. The process of forming the said glue layer and the process of providing the said dye ink are performed, and a transfer textile paper is manufactured.
The front-stage unit is a unit on the side where the object to be processed (base material) is taken into the printing press, and the rear-stage unit is a unit on the side where the object to be processed (base material) is taken out from the printing press.
“Consecutively performed” means that after the step of forming the glue layer is performed in the former unit, the transfer textile printing paper is not taken out from the printing machine and is not substantially stored in the printing machine, and is stored in the latter unit. It means that the process of feeding and applying dye ink is performed. Since the transfer textile paper is not taken out from the printing machine, the stock of the transfer textile paper does not occur, and the transfer textile paper does not need to be transferred.

According to the method of the present invention, the transfer printing paper and the transfer printing paper can be continuously produced by one apparatus, so that the manufacturing process is simplified and no double processing fee is generated. Therefore, the method of the present invention is an economical method, but furthermore, there is little loss of resources such as glue and base paper, and transfer printing paper is not invented, greatly increasing inventory management costs and logistics costs. It has an epoch-making feature that it can be reduced.
In addition, as a method of applying the glue in the production of coated paper (printing paper), there is a method using a gravure coater as one of many known coating methods, but it is applied to the production of transfer textile paper. There is no specific description, and there is no description indicating that the same gravure coater can continuously apply the paste and apply the dye ink.

[Step of forming glue layer (production of transfer printing paper)]
A paste layer is formed by applying a paste on the substrate. The application of the paste liquid is performed in the unit on the front side of the printing press. Usually, the paste liquid is put into an ink pan in the unit, and after the paste liquid is applied to the surface of the plate cylinder, It is performed by adhering or laminating (coating) the paste on the substrate by a method in which the substrate is brought into close contact and the paste is transferred from the plate cylinder to the substrate surface. After the paste liquid is transferred to the surface of the base material, the base material is usually dried through a drying device provided in the unit to produce a transfer textile sheet.
The unit used in this process often uses plain gravure printing and plate cylinders used for flexographic printing, and the drying conditions of the drying device are also adjusted appropriately. This is the same as the unit of the printing machine and flexographic printing machine.

The paste applied to the base is usually a component of the paste (components including natural or synthetic pastes and, if necessary, water-soluble dispersants, inorganic salts, mineral compounds, various auxiliaries, etc.) And water are mixed and stirred well to adjust to the optimum viscosity.
As conditions for applying (coating) the paste liquid, the viscosity of the paste liquid at 25 ° C. is 10 to 3000 mPas (more preferably 20 to 1000 mPas), and the base material speed (coating speed) in the printing press is 1 to 100 m. / Min, the plate depth of the plate cylinder is preferably 0 to 500 μm, but when the viscosity or solid content of the paste is high, the coating speed is slowed down, and when the viscosity or solid content is low, the coating speed is fastened. It is possible to adjust the application amount of the paste liquid (the coating amount). In the case of a low coating amount, a plate cylinder of Muku may be used.
Although the preferable range of the application amount of the paste varies depending on the use, it is often ¹ to 30 g / m ^{2 in} terms of solid content, and more preferably ^{2 to} 25 g / m ² .

  Depending on the type of paste liquid and base material, it may be difficult to uniformly apply to the base material due to water repelling or paper shrinkage. It can be controlled by individually adjusting the solid content, viscosity, type of surface tension reducing agent (anionic, nonionic surfactants, alcohols, etc.) and addition amount, type of base material, prescription conditions, and the like.

  The step of forming the adhesive layer may be performed by one unit on the front side, or may be performed by using a plurality of units on the front side. For example, after applying the paste liquid A in the first unit (hereinafter, the first unit on the front side is referred to as the first unit and the nth unit is referred to as the nth unit), the paste liquid B is applied in the second unit. It is possible to make the glue layer into two layers by coating continuously. It is also possible to apply the same paste liquid A in the second unit together with the first unit to adjust the coating amount.

[Process for applying dye ink (production of transfer printing paper)]
The transfer printing paper produced by the former unit is sent to the latter unit, and dye ink is applied by the latter unit to produce the transfer textile paper. The application of the dye ink is performed by printing the dye on the surface of the transfer printing paper in the same manner as in ordinary gravure printing and flexographic printing.
In the case of single color printing (single color printing), this process may be performed by only one unit at the subsequent stage. However, it is usually performed by a plurality of units, and in the case of multicolor printing, printing of each hue is performed by each of the plurality of subsequent units. For example, when performing multicolor printing of three primary colors and black, it is desirable that the printing machine includes a total of 5 to 6 units or more. Since many commercially available multicolor gravure printing presses are provided with 5 to 9 units, it is possible to sufficiently apply the paste liquid and cope with multicolor printing of ink.
As described above, dyes are printed on the surface of transfer printing paper by gravure printing and flexographic printing in each unit subsequent to the printing press, and then dried to obtain transfer printing paper.

[Printer]
As the printing machine used in the present invention, a known gravure printing machine or flexographic printing machine is used. For example, as a gravure printing machine, a gravure printing machine that is frequently used in printing using ink by a known direct gravure printing method, kiss reverse gravure printing method, kiss touch bar coat gravure printing method, offset gravure printing method, etc. is used. it can. When using a gravure printing machine, the feed rate of the substrate is often about 5 to 50 m / min. A combination of a plain plate cylinder (gravure roll) with a deeper plate depth and an impression cylinder can be used for applying (applying) the paste to the base material. A kiss coat method or a bar coat method can also be adopted. As shown in JP 2011-56352 A, the rotation direction of the base material and the roll may be either forward or reverse. The application amount of the paste liquid (coating amount) can be controlled by the plate depth, rotation speed, rotation direction, use of a doctor blade, solid content of the paste liquid, viscosity of the paste liquid, and the like. Normally, a gravure roll is used for the plain plate cylinder. However, when the coating amount is small, a plate cylinder having a plate depth of zero may be used.

[Base material]
As the substrate on which the adhesive layer is formed, paper or a resin film is used. Examples of the paper used as the base material include paper made using unbleached or bleached softwood pulp, hardwood pulp, kraft pulp, grind pulp, recycled pulp using recycled paper, and the like.
These papers include papers made by adding fillers such as sizing agents, paper strength enhancers, pigments, calcium carbonate, talc and clay. Furthermore, the inside or the surface of the paper, bleached or unbleached kraft paper treated with modified starch, CMC, PVA, clay, etc., high quality paper, medium quality paper, single gloss kraft paper, art paper, coated paper, cast coated paper, Carbonless paper, glassine paper, or the like can also be used as a substrate, and paper having excellent smoothness with less ink penetration and bleeding is preferably selected. The basis weight of the paper as the substrate is preferably 10 g / m ² or more and 150 g / m ² or less, more preferably 20 g / m ² or more and 120 g / m ² or less from the viewpoint of strength and flexibility.

Specific examples include coated paper, fine-coated paper, high-quality paper, intermediate and lower grade paper manufactured by Nippon Paper Industries Co., Ltd., for example, pure white roll paper, bleached or unbleached kraft paper, silver-bamboo kraft paper, silver bamboo, silver candy, white silver, etc. , Glassine paper, unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, single-sided kraft paper (golden, bleached dragon king, Nagoya bleached dragon king), NCP base paper, pure white roll paper, various coated papers, Various calendar papers, various coated papers manufactured by Mitsubishi Paper Industries, and the like can be mentioned, but these are only examples.
Various physical properties such as air permeability, density, tensile strength, surface strength, wet strength, etc. are not restricted in particular as physical properties of paper, but there is no particular limitation. Tensile when printing or applying paste Any paper that can ensure strength, elongation, swelling and smoothness can be used. However, when the gravure printing method is adopted, it is preferable for the printability that the paper has a good smoothness, so that a calendar process may be applied to improve the smoothness. In addition, release paper obtained by applying various release agents to paper can also be used.

  Examples of the resin film used as the substrate include synthetic resin films such as polyester, polyamide, polyurethane, polyacrylamide, and polyimide. From the viewpoint of strength, flexibility, and ease of handling, the thickness of the resin film is preferably 10 μm or more and 100 μm or less.

[Glue, paste liquid]
The substrate surface is provided with a dye ink receiving layer for temporarily adhering the transfer printed paper and the fabric (substance to be dyed), increasing the transfer efficiency to promote the color development of the fabric, and preventing dye back-through. For the purpose of preventing ink bleeding and flow and forming a sharp pattern, a glue layer made of glue or the like is provided.
The glue layer is formed by applying a paste liquid containing a glue on the surface of the substrate and drying it. Examples of the paste liquid include a paste liquid consisting of only a paste or a paste and water alone, but also a paste liquid obtained by adding other components to the paste or the paste and water within a range not impairing the gist of the invention. Can be mentioned.
The paste is selected from natural pastes and synthetic pastes. In the case of consisting of one or two or more types selected from only natural pastes, in the case of consisting of one or more types selected from only synthetic pastes, in the case of a mixture of natural pastes and synthetic pastes Either may be sufficient.

(Natural glue)
A natural paste is a paste using a naturally produced paste as it is, or a paste obtained by physically or chemically processing the paste, and as the paste, a plant raw material is used. There are processed plant paste and animal paste processed animal raw materials.

Examples of plant pastes include seaweeds, natural gum pastes, fiber derivatives, polysaccharides and the like.
Examples of seaweeds include low, medium or high viscosity sodium alginate, potassium alginate, ammonium alginate, alginates, and the like.
Examples of the natural gum paste include tamarind seed gum, etherified tamarind gum, etherified locust bean gum, etherified guar gum, gum arabic, and acacia gum.
Examples of the fiber derivative include carboxymethyl cellulose, etherified carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, cellulose sulfate and the like.
Polysaccharides include starch, cationized starch, cationized oxidized cornpropylated phosphate cross-linked starch, phosphorylated starch, starch glycolate sodium, starch acetate, glycogen, dextrin, amylose, hyaluronic acid, chitin, agarose, heparin, pectin, Examples include kuzu, konjac, agar, starch starch, processed starch such as etherified starch and esterified starch.

  Examples of animal pastes include gelatin, collagen peptide, casein peptide, chondroitin sulfate, sodium hyaluronate, and the like obtained by heating and extracting collagen.

(Synthetic glue)
Synthetic pastes include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, cationized polyvinyl alcohol, polyvinyl acetate, ethylene vinyl acetate copolymer, maleated resin, dicarboxylic acid ketene dimer, alkyl ketene dimer, polyacrylamide, acrylic acid latex, acrylic Examples thereof include acid synthetic pastes, vinyl acetate latexes, alkenyl succinic anhydrides, polyacrylate ammonium salts, sodium salts, water-soluble polyester resins having a sulfone group or a carboxyl group.

  The paste forming the glue layer contains natural glue and / or synthetic glue, and also one or more selected from inorganic salts, mineral fine particles, water-soluble dispersants, and auxiliaries. In addition, a mixed paste may be used. The component of the paste liquid is appropriately selected from the blended components exemplified above according to various printing methods in which the transfer printing paper produced according to the present invention is used.

(Inorganic salts)
Examples of the inorganic salts include alkali metal or alkaline earth metal sulfates, hydrochlorides, nitrates, phosphates, and carbonates. Specific examples include sodium sulfate, potassium sulfate, lithium sulfate, calcium sulfate, sodium nitrate, potassium nitrate, calcium nitrate, sodium primary phosphate, sodium secondary phosphate, sodium tertiary phosphate, sodium carbonate, sodium bicarbonate, carbonic acid Calcium, lithium carbonate, etc. can be mentioned. One of these may be blended alone, or two or more may be blended. These compounding amounts are preferably 0 to 20% by mass with respect to the solid content of the paste.

(Mineral fine particles)
Examples of the mineral fine particles include clay, talc, kaolin, titanium dioxide, silica, silica gel, colloidal silica, bentonite, acid clay, zeolite, alumina, magnesium silicate, calcium silicate, aluminum silicate, aluminum hydroxide, barium sulfate, and zinc oxide. , Zinc carbonate, diatomaceous earth, and the like. One of these may be blended alone, or two or more may be blended. These compounding amounts are preferably 0 to 15% by mass with respect to the solid content of the paste.

(Water-soluble dispersant)
Examples of the water-soluble dispersant include a formalin condensate of naphthalene sulfonic acid, a formalin condensate of methyl naphthalene sulfonic acid, a formalin condensate of naphthol sulfonic acid, a formalin condensate of phenol sulfonic acid, and a formalin condensate of cresol sulfonic acid. , Lignin sulfonic acids, orophine PD-003, olfin PD-001, olfin PD-002W, olfin PD-004, olfin PD-005, olfin PD-201, olfin PD-301 and the like And nonionic dispersants. One of these may be blended alone, or two or more may be blended. These compounding amounts are preferably 0 to 30% by mass with respect to the solid content of the paste.

(Auxiliary)
In order to improve various physical properties and stability as an ink-receiving layer formed of the sizing agent, it is preferable to add an auxiliary agent to the sizing solution. Auxiliaries to be added to the paste include water-soluble resins such as acrylic synthetic glue, surfactants, thickeners, moisturizers, pH adjusters, thickening agents, preservatives, antifungal agents, deodorizers A gas agent, an antifoamer, a reduction inhibitor, a dispersant, a sequestering agent, and the like can be given.

  The blending amount of these auxiliaries is 0 to 5% in the case of an anionic or nonionic surfactant blended as a surface tension adjusting agent, a repellent inhibitor, and a penetrant, as an apparent mass% with respect to the total mass of the paste liquid. (More preferably 1 to 3%), polyhydric alcohols such as polyethylene glycol, glycerin, thiodiglycol and diethylene glycol blended as a wetting / humectant, 0 to 20% in the case of urea, thiourea, dicyandiamide, etc. In the case of an acrylic acid synthetic paste compounded for increasing the viscosity of the mixed paste liquid at the time of coating, 0 to 5% (more preferably 0 to 3%) is often preferable, but the purpose of the present invention is impaired. As long as it is not limited to this range.

Some weakly acidic substances such as glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, maleic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, Tartaric acid and its derivatives, sebacic acid, thioglycolic acid, thiodipropionic acid, trichloroacetic acid, hydroxyisobutyric acid, brassylic acid, isobutyric acid, malonic acid, itaconic acid, butyric acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid , P-hydroxybenzoic acid, m-nitrobenzoic acid, vanillic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzenetetracarboxylic acid, stearic acid, ammonium sulfate with respect to the total mass of the paste solution. When it is blended by mass%, the color developability may be improved.
One type of auxiliary agent may be blended alone, or two or more types may be blended.

  Furthermore, synthetic polymers and water-soluble resins (water-soluble synthetic polymers that do not impair the dyeing property in the auxiliaries and do not contaminate the fibers in order to improve the adhesion to the fabric (fiber material). It is also possible to add a small amount of substances other than the above-mentioned synthetic paste. Specific examples of the water-soluble synthetic polymers include polyester resins, polyurethane resins, polyethylene oxide resins, polyamide resins, polyvinyl acetal resins, water-soluble polyether / urethane resins, and the like. Yes, one or more selected from these can be blended. These resins can be blended in the form of an aqueous solution or an emulsion. The blending ratio is preferably 0 to 20% by mass with respect to the total mass of the auxiliary agent.

[Dye / Dye ink]
The dye ink to be applied to the adhesive layer is a dye ink.
Examples of dyes constituting the dye ink include reactive dyes, acid dyes, disperse dyes, metal-containing dyes, direct dyes, and cationic dyes. Among these, depending on the type of fiber material to be processed, etc. It is selected appropriately. It is desirable to use a dye having excellent fastness such as light resistance, friction and washing.
When a disperse dye is used, an S type having excellent sublimation fastness, an intermediate SE type, and an E type dye used for sublimation transfer (for example, disclosed in claim 9 of JP2011-21133A). Can be selected and used according to the fiber material to be processed.

For example, the dye can be converted into an ink by the method described in Japanese Patent No. 5970588.
The dye content (mass% of the chromogen) in the ink is preferably 2 to 20 mass% depending on the color density. Oil-based inks can also be used, but water-based inks are preferable in consideration of workplace safety and health, environmental issues, handling of dangerous goods, and economic efficiency.

Currently, oil-based inks are used for gravure printing on sublimation transfer paper, but oil-based inks use a large amount of volatile organic solvents, so there are many problems such as environmental problems, safety and health problems, and handling of hazardous materials. . On the other hand, the method of the present invention can be used with water-based dye ink, and is therefore an excellent method from the viewpoint of environment and safety.
Conventionally, the conversion to environmentally friendly water-based ink has been hindered by the problem of economic efficiency, but it is considered that the conversion from oil-based ink to water-based ink proceeds by the method of the present invention which is excellent in economic efficiency.

  The method of the present invention can be applied not only to pattern designs but also to plain dyeing using a plain plate cylinder by uniformly applying or printing dye ink on a transfer textile.

For the dye ink for gravure printing (gravure ink), a disperse dye atomized to an average particle size of 0.2 to 10 μm or other water-soluble dye is preferably used together with a dispersant. These dyes can be made into gravure inks by dispersing or dissolving them in a slightly viscous aqueous solution whose viscosity is adjusted to about 20 to 500 mPas with a thickener, and the dye ink used in the present invention can be obtained. it can.
Examples of the dispersant that can be used include naphthalene sulfonic acid formalin condensate, methyl naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, olfin PD-003, olphin PD-001, olphin PD-002W, olphin PD-004, olphin PD-005. , Olfin PD-201, Olfin PD-301, and the like.
More specific examples of the gravure ink as the dye ink used in the present invention include Metroze 65SH · 400 (manufactured by Shin-Etsu Chemical Co., Ltd.), Metroze 65SH · 4000 (manufactured by Shin-Etsu Chemical Co., Ltd.), Poval AP-17 (Nihon Vinegar) Examples include inks that use partially hydrolyzed PVA such as Bi Poval Co., Ltd. as a thickener, contain 1 to 20% by mass of a dye in terms of the original, and adjust the viscosity to 20 to 500 mPas.

The present invention, in addition to the method for producing the transfer printing paper, in addition to the transfer printing paper produced by this production method, closely contacting the fiber material and heating, transferring the dye ink to the fiber material, That is, the present invention provides a transfer printing method for fiber materials characterized by having a transfer printing process.
The present invention further provides a method for producing a dyed product, characterized by using the above-mentioned transfer printing method for fiber materials.

[Transfer printing process]
The printing method in which the transfer printing paper produced by the present invention can be used is not particularly limited, and is applicable to sublimation transfer printing, wet transfer printing, dry transfer printing, paper printing method, non-sublimation transfer printing, and the like. A substrate, a glue layer, a dye ink, and the like are selected according to various printing methods. These transfer textile printing methods can be performed by applying known processing conditions.

For example, in the case of sublimation transfer, when the sublimation transfer printed paper obtained in the present invention is brought into close contact with a polyester fabric and heated at 200 ° C. for about 30 seconds, the sublimation dye can fly to the fabric and color can be developed.
In the case of the paper printing method, a transfer printing paper having a paste layer containing a binder whose temporary adhesive strength becomes stronger by heating and pressurization, and obtained in the present invention is a high temperature, high pressure (150 to 200 ° C., The dye is fixed to the fabric by press-bonding (adhering) to the fabric at ^{20 to} 30 kg / cm ² ) and then steaming, and then the fabric from which the paper has been peeled can be soaped and finished.

(Fiber material)
Examples of the fiber material (fabric) to be transferred and printed using the transfer printed paper produced according to the present invention include polyester fiber materials, polylactic acid fiber materials, cationic dyeable polyesters, polyamide fiber materials, and polyacrylamide fiber materials. , Mainly synthetic fiber materials such as vinylon fiber materials and polyurethane fiber materials, and / or cellulose fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk, wool and villi Examples thereof include woven fabrics, knitted fabrics, nonwoven fabrics, sheets, films and the like, or mixed spinning, mixed fiber, interwoven fabric, or composite materials of the above-mentioned various fiber materials.

  FIG. 1 is a schematic view schematically showing an example of a printing machine used in the method for producing a transfer printed paper of the present invention and an example of a method for producing the transfer printed paper of the present invention performed using this printing machine. It is sectional drawing. The printing press shown in FIG. 1 is a gravure printing press having three or more units in series, but only the first to third units are shown in the figure, and the fourth and subsequent units in series with the third unit are shown below. Not shown. Each unit has an ink pan, a plate cylinder, an impression cylinder, and a drying device, and a doctor blade is provided in contact with the plate cylinder.

  The first unit ink pan contains paste liquid made of glue or the like, and the second unit and subsequent ink pans contain dye inks of the respective hues. A part of the surface of the plate cylinder of each unit is immersed in the paste liquid or dye ink in the ink pan, and the paste liquid or dye ink is applied (printed) to the surface of the plate cylinder. The paste solution or dye ink applied to the surface of the plate cylinder is applied (printed) from the plate cylinder onto a base material (transfer printing paper) that passes between the plate cylinder and the impression cylinder. After the paste liquid or dye ink is applied, the base material (transfer printing paper) passes through a drying device and is dried.

  The base material is first taken into the first unit, and the paste liquid is applied and dried to form a transfer textile sheet. As is apparent from the figure, the produced transfer printing paper is continuously sent to the second unit (without being taken out of the printing press or stored in the printing press), and dye ink 1 (for example, Yellow color) is sent. (Gravure ink) is applied (printed). The transfer textile sheet to which the dye ink 1 is applied (printed) is sent to the third unit, and the dye ink 2 of another hue (for example, a gravure ink of Magenta color) is applied (printed). Thereafter, similarly, the application (printing) of dye inks of other hues (for example, Cyan gravure ink) is repeated to produce multicolor transfer printed paper. That is, with only one gravure printing machine, the process for producing the transfer textile paper and the process for producing the transfer textile paper can be performed from the base material.

The present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to these examples. In the examples, unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”. In the examples and comparative examples, the dyeing power (coloring property of the fiber material (fabric)) and the leveling property after transfer printing were determined according to the following criteria.
The color development (dyeing power) and leveling property of the fiber material after transfer printing are evaluated by 10 panelists, and the coloration (dyeing power) and leveling property of the fiber material are excellent and the quality is good. 3 points for evaluation, color development (dyeing power) and leveling ability are slightly inferior and quality is slightly poor, and 2 points for coloration (dyeing power) and leveling are obvious The case where it was determined that the quality was clearly defective was defined as 1 point, the total evaluation score of the panelists was 25 points or more, ◯, 15 to 24 points were Δ, and 14 points or less were ×.

Example 1
[Preparation of paste liquid]
As a mixed paste, 37.5 g of Piostarch LT (modified starch: manufactured by Nissho Chemical Co., Ltd.) was dissolved in 87.5 g of hot water, 262.5 g of water was added, and fine gum HEL-3 (cellulose derivative: first (Manufactured by Kogyo Kagaku Co., Ltd.) 75 g, sodium sulfate 37.5 g, and tartaric acid 2.5 g were added and stirred well with a high-speed desper type stirrer (3000 rpm) to prepare a uniform and smooth paste. To this paste, 0.1% of a commercially available degassing agent or antifoaming agent is added to the paste to eliminate the foam, diluted with water so that the solid content is 10 to 12%, and further with a viscosity modifier. The viscosity was adjusted to prepare a paste liquid having a viscosity of 120 mPas.
[Coating of paste liquid]
Ink of the first unit of multicolor gravure printing machine (printer that performs normal gravure printing using an impression cylinder and plate cylinder) using single glossy kraft paper with a basis weight of 50 g / m ² as the base paper Put the paste into the pan, use a plain plate Helio plate 54L, plate depth 320μm gravure roll and impression cylinder, 25 ° C, speed of 15m / min. After coating while adjusting to m ² , coated paper was produced through a dryer and fed to the second unit.
[Aqueous dispersion ink]
Yellow, Magenta, and Cyan colors each containing 15% of TERATOP Yellow GWL-01, Pink 2GLA, Blue BGE (dispersed dye manufactured by Huntsman) described in Example 1 of Japanese Patent No. 5970588 as a disperse dye Gravure inks were prepared and the respective viscosities were adjusted to 80 mPas.
[Printing with ink]
Yellow is added to the ink pan of the second unit of the multicolor gravure printing machine, the Magenta is added to the ink pan of the third unit, and the Cyan ink is added to the ink pan of the fourth unit. On the coated paper, a checkered pattern was continuously printed to obtain a transfer printed paper.

[Color of fabric]
The obtained transfer-printed paper is adhered to a polyester taffeta having a basis weight of 35 g and heated (220 ° C., 0.5 Mpa, 40 seconds, using a sublimation flat press HSP-2210 manufactured by HASHIMA Co., Ltd.). Was transferred and fixed, and then the paper was removed.
The polyester taffeta printed fabric thus obtained is dyed densely and delicately (quality judgment such as color developability is ◯), the texture of the fiber is good, and the sublimation fastness according to JISL0854 is (changed) It was grade 4, (dirty) grade 4. Moreover, the light fastness according to JISL0842 was grade 4 or higher.

Example 2
Instead of Piostarch LT and Fine Gum HEL-3, sorbitole C-5 (etherified starch) and EX-100S are used to make a paste, and as a disperse dye, Sumikaron Yellow E-4GL, an E-type sublimation dye. A sublimation transfer printed paper having a patterned pattern was obtained in the same manner as in Example 1 except that ink using Sumikaron Red E-FBL and Sumikaron Blue E-GRL was used.
Using this sublimation transfer printed paper, a polyester taffeta with a weight of 35 g was transferred and printed at a speed of 3 m / min at 200 ° C. using a large drum-type sublimation transfer machine. As a result, it was excellent in light fastness. A fabric was obtained.

Example 3
Pluscoat RZ-142 (water-soluble polyester resin 25% aqueous solution, manufactured by Kyoyo Chemical Co., Ltd.) 500 g, 20% penon JE66 aqueous solution (processed starch: manufactured by Nissho Chemical Co., Ltd.) 100 g, 20% fine gum HEL-3 (cellulose derivative: No. 1) 80 g, 40% demole NL 60 g, Evatex D-23 (aluminum silicate derivative, manufactured by Kyoei Chemical Co., Ltd.) 20 g, dicyandiamide 30 g, and soda ash 50 g to adjust the viscosity by adding water. In the same manner as in the preparation of the mixed paste liquid in No. 1, a mixed paste liquid for paper printing was prepared.
An ink was prepared in the same manner as in Example 1 except that a reactive dye was used instead of the disperse dye. Using the resulting mixed paste and ink, coating of the paste (coating amount 20 g / m ² ) and ink printing are performed consistently to obtain a transfer printed paper for paper printing for reactive dyes on cotton. It was.
The transfer printed paper for paper printing is pressure-bonded to a cotton broad cloth with a basis weight of 65 g at 200 ° C. and 3 Mpa, steamed at 100 ° C. for 10 minutes, and then the transfer paper is peeled off and then soaped. A printed cotton fabric with excellent fastness to wear was obtained.

Example 4
A transfer printing paper (film) for reactive dyes was obtained in the same manner as in Example 3 except that a polyester film having a thickness of 30 μm whose corona discharge was applied to the coated surface was used instead of the base paper in Example 3. It was. Using this transfer printed paper (film), paper printing was carried out in the same manner as in Example 3. As in Example 3, a printed cotton fabric with excellent fastness that was densely and finely dyed was obtained.

Example 5
In place of the gravure printing machine, only the first unit (glue coating process) is carried out except using a kiss touch bar coat gravure printing method in which a plate cylinder is brought into contact with a substrate supported by two rolls. The same process as in Example 1 was performed to obtain a transfer printed paper. The obtained transfer-printed paper is adhered to a polyester taffeta having a basis weight of 35 g and heated (220 ° C., 0.2 Mpa, 40 seconds, using a sublimation flat press HSP-2210 manufactured by HASHIMA Co., Ltd.). Was transferred and fixed, and then the paper was removed.
The polyester taffeta printed fabric thus obtained is dyed densely and delicately (quality judgment such as color developability is ◯), the texture of the fiber is good, and the sublimation fastness according to JISL0854 is (changed) It was grade 4, (dirty) grade 4. Moreover, the light fastness according to JISL0842 was grade 4 or higher.

Claims (8)

A step of forming a paste layer by applying a paste containing a paste selected from a natural paste and a synthetic paste on a substrate; and a step of applying a dye ink on the paste layer Have
The step of forming the adhesive layer is performed in a front stage unit of a gravure printing machine or a flexographic printing machine having a multistage unit,
A method for producing a transfer-printed paper for a fiber material, wherein the step of applying the dye ink is performed in a subsequent unit of the gravure printing machine or flexographic printing machine. The method for producing a transfer-printed paper for a fiber material according to claim 1, wherein the substrate is a base paper having a basis weight of 20 to 150 g / m ² or a resin film having a thickness of 10 to 100 µm. .   The paste liquid further comprises a water-soluble dispersant, an alkali metal or alkaline earth metal sulfate, hydrochloride, nitrate, phosphate, carbonate, bicarbonate or hydroxide, mineral fine particles, pigment and auxiliary agent. 3. A mixed paste containing one or more selected from the group consisting of: wherein the mixed paste has a viscosity at 25 ° C. of 10 mPas to 3000 mPas. 4. A method for producing a transfer-printed paper of the fiber material described in 1.   The dye ink is an aqueous dye ink containing one or more dyes selected from the group consisting of reactive dyes, acid dyes, disperse dyes, gold-containing dyes, direct dyes and cationic dyes. The manufacturing method of the transfer printing paper for fiber materials of any one of Claim 1 thru | or 3.   5. The transfer printing paper according to claim 1, wherein the transfer printing paper is sublimation transfer printing paper, dry transfer printing paper, wet transfer printing paper, transfer printing paper for paper printing, or non-sublimation transfer printing paper. A process for producing a transfer-printed paper for a fiber material according to claim 1.   A transfer printed paper produced by the method for producing a transfer printed paper for a fiber material according to any one of claims 1 to 5, is adhered to the fiber material and heated, and the dye ink is added to the fiber. A method for transferring and printing a fiber material, comprising a step of transferring to a material.   The fiber material is natural fiber, semi-synthetic fiber or synthetic fiber woven fabric, knitted fabric, non-woven fabric, sheet or film, or mixed fiber, mixed fiber, interwoven fabric of natural fiber, semi-synthetic fiber and synthetic fiber, or It is a composite material, The transfer printing method of the fiber material of Claim 6 characterized by the above-mentioned.   A method for producing a dyed product, wherein the method for transferring and printing a fiber material according to claim 6 or 7 is used.

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