WO2017111107A1 - Transfer-printing method for polyester-based fibrous materials - Google Patents
Transfer-printing method for polyester-based fibrous materials Download PDFInfo
- Publication number
- WO2017111107A1 WO2017111107A1 PCT/JP2016/088527 JP2016088527W WO2017111107A1 WO 2017111107 A1 WO2017111107 A1 WO 2017111107A1 JP 2016088527 W JP2016088527 W JP 2016088527W WO 2017111107 A1 WO2017111107 A1 WO 2017111107A1
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- WIPO (PCT)
- Prior art keywords
- group
- polyester
- paste
- transfer
- transfer printing
- Prior art date
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/003—Transfer printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
Definitions
- the present invention relates to a transfer printing method for a polyester fiber material using a non-sublimation type disperse dye.
- Patent Document 1 Patent Document 2, Patent Document 3, Patent Document 4 and the like disclose sublimation transfer methods using printing paper obtained by ink-jet printing an oil-based ink or water-based ink containing an E type sublimation dye on sublimation transfer printing paper. And is industrially implemented.
- Patent Document 4 discloses a method of increasing the residence time at low temperature (140 ° C.) (5 minutes), but this method has a problem in productivity. Therefore, heat treatment is usually performed at 190 to 200 ° C. for 30 seconds to 1 minute.
- sublimation dyes are small molecular weight dyes, and have a problem that they are easily moved and diffused by heat and jump out of the fibers into the air to contaminate other fibers and white spots.
- the transfer temperature is high, the dye once dyed jumps out of the fiber material (fabric), so there is a problem that the pattern is blurred and the transfer device and the environment are contaminated. Therefore, the transfer temperature is generally processed at a temperature of 200 ° C. or lower.
- the method of transfer printing at 190 to 200 ° C. for 30 seconds to 1 minute using a transfer paper printed with a non-sublimation disperse dye ink on a known sublimation transfer printing paper has poor color developability and has practical value. There is no. That is, even when known sublimation transfer conditions are applied to a non-sublimation type disperse dye, good color developability cannot be obtained.
- Patent Documents 5 and 6 disclose that an ink receiving layer is coated on a release paper and dried, and then printed on the ink receiving layer with a disperse dye.
- a method of sequentially performing dye transfer to a fiber material, release of release paper, and fixing of a dye by steaming is disclosed.
- this method cannot transfer 100% of the ink receiving layer if the cost of the release paper (transfer base paper) is high, the humidity of the factory where the transfer is performed, and the storage conditions of the transfer textiles are inappropriate.
- There are problems such as generation of non-defective products, difficulty in recycling paper, and a large number of processes.
- Patent Document 7 a water-soluble synthetic binder, a natural glue, and a mixed glue solution, to which an auxiliary agent is added, are added to an inexpensive commercially available paper, and the temporary adhesive force to the fiber material is increased by heating and pressing. Coating and drying to form an ink-receptive layer and adhesive layer, and then coloring the transfer-printed paper obtained by printing the disperse dye ink on the transfer-printed paper obtained in this way (paper printing method) ) Is disclosed.
- This method is an excellent processing method in that no pre-treatment of the fiber material is necessary, but there is a problem that the number of steps is large because a crimping step, a coloring step (dry heat treatment or steaming), a soaping step, etc. are necessary. .
- a direct method is also known in which disperse dye ink is printed with an inkjet printer on a dried fabric (fiber material) after applying a paste to the fiber material (pretreatment).
- this method requires a pretreatment process, a printing process, a steaming process, and a soaping process of the fiber material, and has a large number of processes and a drainage load, so that there is a problem in economic efficiency and quality stability.
- the dyes that can be used are limited to known sublimation transfer methods, methods of applying known sublimation transfer conditions to non-sublimation type disperse dyes, known dry transfer methods, direct methods, and other known printing methods.
- Problems, product quality problems such as fastness, hue / color development, stability of quality, economic problems such as many processes, high raw material costs, contaminating other fibers and the environment, Problems with the environment (ecology) such as heavy drainage load have been pointed out. Therefore, development of a printing method free from these problems is demanded.
- the present invention provides a product with a small number of processes, low fixed costs and variable costs (thus excellent economy), low drainage load (thus excellent ecology), and excellent quality such as hue and fastness.
- the purpose of the present invention is to provide a printing method for polyester fiber materials.
- the present inventor aims to develop a textile printing method that solves quality problems such as economic efficiency, environmental problems, and fastness, and uses a known printing method such as an ink jet printing method or a gravure printing method for the polyester fiber material.
- a known printing method such as an ink jet printing method or a gravure printing method for the polyester fiber material.
- an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group such as a quaternary ammonium group.
- a glue having a functional group or A transfer printing paper printed with a non-sublimation disperse dye ink on a transfer printing paper selected from natural gum glue, fiber derivatives and polysaccharides and further provided with a paste containing a carboxylic acid compound.
- the transfer printing paper can be completed with all the steps of transfer printing, and the quality can be achieved simply by pressing and heating under specific conditions with the transfer printing paper in close contact with the polyester fiber material.
- the transfer printing method of the present invention was completed.
- the first aspect of the present invention is: A transfer printing method in which transfer printing paper printed with disperse dye ink on a transfer printing paper provided with a paste is applied to a polyester fiber material and pressed and heated to transfer printing,
- the disperse dye ink is a non-sublimation disperse dye ink
- the glue is A paste having a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group;
- a transfer printing method for a polyester fiber material characterized in that it is a paste selected from natural gum paste, fiber derivatives and polysaccharides and further mixed with carboxylic acid compounds (Claim 1).
- Examples of the paste include one or more selected from the group consisting of animal glues and plant glues (Claim 2).
- 1 type or more means that one type of thing may be individual, and 2 or more types may be used together.
- the glue is a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group.
- a carboxylic acid compound may be further added to the paste.
- the carboxylic acid compounds are preferably at least one selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids (Claim 4).
- the paste may further contain one or more selected from the group consisting of weakly acidic compounds that are salts of strong acids and weak bases, mineral acidic compounds, and mineral additives (Claim 5).
- the paste may further contain an auxiliary agent (claim 6).
- non-sublimation type disperse dye ink a gravure ink or a flexo ink prepared using a disperse dye atomized to an average particle diameter of 0.2 to 10 ⁇ m, or an average particle diameter of 0.05 to 0.2 ⁇ m.
- An ink-jet ink produced using a finely divided disperse dye can be mentioned as a preferred embodiment.
- the disperse dye one or more non-sublimation disperse dyes selected from the group consisting of S type or SE type disperse dyes are preferably used.
- the polyester fiber material is a polyester polymer selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, depolymerized polyester, cationic dyeable polyester, room temperature dyeable polyester, and alkali weight loss polyester.
- Transfer printing in the transfer printing method of the first aspect is preferably carried out by applying pressure and heating at a transfer temperature of 150 to 250 ° C. and a transfer pressure of 0.01 MPa or more (claim 9).
- the second aspect of the present invention is: A method for producing a transfer textile used for the transfer textile printing method of the first aspect,
- the base paper has a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group.
- a method for producing a transfer printing paper characterized by applying a paste, or a natural gum paste, a fiber derivative and a polysaccharide, and further adding a paste containing a carboxylic acid compound (claim 10). ).
- the third aspect of the present invention is: A method for producing a polyester fiber material, comprising the step of performing transfer printing on a polyester fiber material by the polyester fiber material transfer printing method according to the first aspect (claim 11).
- the present invention has been completed as a result of research to develop a transfer printing method that uses a non-sublimation type disperse dye excellent in fastness and has a small number of processes and a small drainage load, and is an economically competitive economy. Is a new method that can provide products with excellent quality and ecology, and can provide products with excellent quality. Transfer printing method that can finish polyester fiber materials into fine, robust and good-quality products in one step. It is.
- a dry transfer textile printing method or a paper textile printing method for example, a dry transfer textile printing method or a paper textile printing method, a transfer process or a pressure bonding process, an adhering (steaming) process, and a washing process are indispensable.
- the entire process of transfer printing can be completed in one step (the method of the present invention is referred to as a one-shot method (one-step method)). Therefore, the process is simple and excellent in economic efficiency, and the washing process can be omitted, so that the drainage load can be reduced, and the economic efficiency and ecology are excellent.
- the sublimation transfer method using a sublimation dye is a method having a small number of steps, but this method can be applied only to a dye having low fastness and sublimation by heat, and is not considered to be applicable to a non-sublimation dye. It was. In other words, in order to increase fastness, non-sublimation type disperse dye ink is applied to a commercially available sublimation transfer printing paper, and the color developability is poor even when heated under known conditions in close contact with the fiber material. It has been considered difficult to carry out the sublimation transfer method using a dye.
- a transfer printing paper produced by printing with a non-sublimation type disperse dye ink on a transfer printing paper provided with a specific paste is used, and the transfer printing paper is closely adhered to a fiber material, and a specific range of
- a polyester fiber material having good dyeing power (coloring property) is obtained, and fastness and texture are also good.
- a cleaning process can also be skipped by using a suitable paste.
- the present invention utilizes the existing roller type (also referred to as rotary or continuous type) sublimation transfer machine or flat plate type heat transfer device, which is widely used in the dyeing industry, to provide robust and efficient transfer of polyester synthetic fiber materials.
- good textile printing can be performed and inexpensive base paper and inexpensive paste can be used.
- it is possible to construct a printing method with good quality such as leveling, texture, fineness, color development and fastness, as well as excellent economy and ecology (such as zero drainage load). .
- the present invention provides an ecological and economical transfer printing method that is friendly to the earth.
- a paste that is imparted to a base paper to form a transfer printing paper An acidic group selected from a carboxyl group (—COOH), a sulfone group (—SO 3 H) and a phosphoric acid group (—PO 4 H 2 ), an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group
- a paste mainly composed of a compound having one or more functional groups selected from the group consisting of cationic groups or It is characterized by being a paste containing at least one selected from the group consisting of natural gum paste, fiber derivative and polysaccharide, and further containing carboxylic acid compounds.
- the paste is an aqueous solution of a compound mainly composed of a water-soluble polymer compound, and has a viscosity at 20 ° C. of 3 mPa ⁇ s or more when a 2% by mass aqueous solution is used.
- the thing of 10 mPa * s or more is used.
- the cationic group include a quaternary ammonium group.
- a paste having a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group includes natural glues and synthetic glues, and the following compounds can be mentioned as examples.
- the natural paste is a paste obtained by using a natural paste as it is, or obtained by physically or chemically processing the paste, and a plant paste obtained by processing a plant raw material and an animal paste. There are animal pastes processed from raw materials.
- Plant-based paste processed from plant-based raw materials includes low, medium or high viscosity sodium alginate (included in seaweeds), potassium alginate, ammonium alginate, alginates, gum arabic, glucuronic acid, xanthan gum , Pectin, heparin, carboxymethylcellulose (hereinafter abbreviated as “CMC”), acidic CMC, alkyl etherified CMC, esterified CMC, cellulose sulfate, cationized starch, cationized oxidized corn starch, cationized cellulose, oxidized starch, acetylated Adipic acid cross-linked starch, starch sodium phosphate ester, esterified starch, hydroxypropylated phosphoric acid cross-linked starch, phosphorylated starch, starch sodium glycolate, starch acetate, octenyl succinate starch, rosin soap, etc. That.
- CMC carboxymethylcellulose
- Animal pastes processed from animal raw materials include gelatin obtained by heating and extracting collagen contained in the skin and bones of animals, collagen peptides that are enzymatic degradation products thereof, casein peptides that are degradation products of casein, Examples thereof include egg protein, chondroitin sulfate, sodium hyaluronate, cationized polypeptide, and the like.
- Synthetic glues include carboxy-modified polyvinyl alcohol, cationized polyvinyl alcohol, polyvinyl acetate, ethylene vinyl acetate copolymer, vinyl carboxylate, maleated resin, dicarboxylic acid ketene dimer, alkyl ketene dimer, polyacrylic acid amide, acrylic acid Mention may be made of latex, synthetic synthetic glue, vinyl acetate latex, alkenyl succinic anhydride, polyacrylic ester ammonium salt, sodium salt, water-soluble polyester resin having sulfone group or carboxyl group, and the like.
- the paste is preferably a paste mainly composed of one or more selected from the group consisting of animal glues and plant glues.
- the blending ratio of the natural paste in the total amount of the paste is preferably 1% by mass to 100% by mass in terms of solid content, and more preferably 10% by mass to 90% by mass.
- Natural gum paste, fiber derivatives and polysaccharides are natural glues, usually acidic groups selected from carboxyl groups, sulfone groups and phosphoric acid groups, ester groups of the acidic groups, amides, alkali metal salts or It means things other than the paste having a functional group selected from the group consisting of alkaline earth metal salts and cationic groups.
- 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.
- the fibrin derivative include etherified carboxymethyl cellulose, hydroxyethyl cellulose and the like.
- Polysaccharides include starch, cellulose, glycogen, dextrin, amylose, chitin, agarose, heparin, pectin, kuzu, konjac, agar, starch starch, etherified starch, processed starch, processed starch that uses seaweed as a starting material, hydroxy Examples include processed cellulose such as methylcellulose, etherified starch, esterified starch and the like.
- carboxylic acid compounds are further blended.
- the glue is a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group.
- carboxylic acid compounds compounded in these cases mean a compound having a carboxyl group. Among them, one or more compounds selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids are included. preferable.
- Examples of the aliphatic carboxylic acid and aromatic carboxylic acid as the carboxylic acid compound to be blended in the paste include monocarboxylic acids and polyvalent carboxylic acids, and the following compounds can be given as specific examples. .
- 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, brassic 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 Acid, vanillic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzenetetracarboxylic acid, stearic acid.
- the preferable content in the mixed paste solution of carboxylic acid compounds is solid. In terms of minutes, it is 1 to 50% by mass, and more preferably 3 to 30% by mass.
- the paste is one or more selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group.
- an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group
- an ester body an amide body
- an alkali metal salt or an alkaline earth metal salt of the acidic group and a cationic group.
- the preferred content of the carboxylic acid compounds in the paste is 1% by mass to 50% by mass in terms of solid content, and the more preferred content is 3% by mass to 30% by mass.
- the paste may further contain one or more selected from the group consisting of a weakly acidic compound, a mineral acid compound, and a mineral additive, which are salts of strong acid and weak base.
- the weakly acidic compound blended in the paste is a salt composed of a strong acid and a weak base, which dissolves in water and exhibits acidity. Specific examples thereof include ammonium sulfate, monobasic sodium phosphate, and ammonium chloride. , Calcium chloride, and the like.
- the mineral-based acidic compound blended in the paste is a water-soluble compound obtained from a mineral, a complex of this compound, or the like, and shows acidity when dissolved in water. Examples of mineral acid compounds include sulfuric acid band, alum, kaolin and the like. It is preferable to add a weakly acidic compound or a mineral-based acidic compound since an effect of improving color developability can be obtained.
- Mineral additives blended in the paste are compounds obtained from minerals or composites of these compounds, etc., which are other than the above-mentioned mineral acidic compounds and are water-soluble or uniformly dispersed in water. is there. When a mineral additive dissolves in water, it shows neutrality or alkalinity.
- coating pigments generally used in papermaking applications that is, clay, talc, titanium dioxide, calcium carbonate, silica, silica gel, colloidal silica, alumina, etc., bentonite, porcelain clay, aluminum silicate and Examples thereof include mineral derivatives such as derivatives thereof, diatomaceous earth, kaolin, and acid clay. It is preferable to add a mineral-based additive because it can provide an effect of preventing blocking and improving ink acceptability of a layer formed of a paste on a transfer printing paper.
- Each of the weakly acidic compound, the mineral-based acidic compound, and the mineral-based additive may be blended singly or in combination of two or more. Any one of a weak acidic compound, a mineral acidic compound, and a mineral additive may be blended, or two or more may be used in combination.
- the preferable blending ratio of the weak acidic compound and the mineral acidic compound is 0% to 30% in terms of solid content with respect to the total mass of the paste, and the more preferable blending ratio is 0.5% to 10%.
- a mixed paste containing an aliphatic carboxylic acid, an aromatic carboxylic acid, a weakly acidic compound and / or a mineral acidic compound in the paste exhibits weak acidity, but generally has a pH in the range of 2-6. Often enters.
- auxiliary agent In order to improve various physical properties as an ink receiving layer formed from the paste, it is preferable to further add an auxiliary agent to the paste.
- auxiliary agent such as acrylic synthetic glue, surfactants, thickeners, moisturizers, pH adjusters, thickening agents, preservatives, antifungal agents, demolding agents.
- 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 agent, and a penetrating agent ( More preferably 1 to 3%), polyhydric alcohols such as polyethylene glycol, glycerin, thiodiglycol and diethylene glycol blended as wetting and moisturizing agents, 0 to 10% for urea, thiourea, dicyandiamide, etc., coating
- 0 to 5% is often preferable, but the gist of the present invention is not impaired. As long as it is not limited to this range.
- One type of auxiliary agent may be blended alone, or two or more types may be blended.
- water-soluble 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.
- water-soluble synthetic polymers include polyvinyl alcohol, polyester resin, polyacrylic resin, polyurethane resin, polyethylene oxide resin, polyamide resin, vinyl acetate resin, styrene acrylic acid resin, Styrene maleic acid resins, polyvinyl acetal resins, water-soluble polyether / urethane resins, and the like can be used, and 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 relative to the total mass of the auxiliary agent.
- the base paper used to make transfer textile printing paper by applying glue is kraft paper, fine paper, medium quality paper, lower grade paper, coated paper, sealing paper, smooth paper, glossy paper, etc. Processed paper, unprocessed paper or recycled paper may be used, and generally used inexpensive paper can be used as the base paper. There is no need to use expensive paper such as release paper. A synthetic resin film can also be used as the base paper.
- Examples of the pulp that forms the base paper of the base paper include unbleached or bleached softwood pulp, hardwood pulp, kraft pulp, grind pulp, and recycled pulp made from recycled paper.
- the base paper obtained from these pulps can contain sizing agents, paper strength enhancers, fillers, pigments, etc., and in order to control the water absorption and wrinkle generation of paper, Paper coated with a sealing agent such as synthetic resin may be used.
- the basis weight of the base paper is preferably 10 to 120 g / m 2 , more preferably 25 to 100 g / m 2 in view of workability, and the thickness is preferably about 0.01 to 0.5 mm.
- Specific examples include coated paper, fine coated paper, high quality paper, middle and lower grade paper manufactured by Nippon Paper Industries, Ltd., for example, pure white, bleached or unbleached kraft paper, silver bamboo, silver glaze, white silver, single gloss craft paper, Glassine paper, unbleached kraft paper manufactured by Daio Paper, semi-bleached kraft paper, bleached kraft paper, bleached glazed kraft paper, pure white roll paper, various coated papers, various calendar papers, etc. Only.
- the transfer printing paper used in the transfer printing method of the present invention is produced by applying the paste to the base paper and forming an ink receiving layer and dyeing promoting layer on the surface of the base paper.
- the applied amount of the paste is preferably 1 to 50 g / m 2 in terms of dry, more preferably 2 to 20 g / m 2 with respect to the base paper.
- Application of the paste to the base paper is usually a component containing the components of the paste (essential components, and if necessary, carboxylic acid compounds, weakly acidic compounds, mineral acid compounds, mineral additives, various auxiliary agents, etc. ) And water are mixed and stirred well to prepare a mixed paste, and the mixed paste is absorbed or laminated on the base paper by coating (application), spraying or dipping on the base paper, and then drying. Is done. Among coating, spraying and dipping, the method by coating is most preferable. The optimum viscosity of the mixed paste is either applied, sprayed or dipped, and even in the case of coating, the viscosity can be easily adjusted by adjusting the moisture, although it varies depending on the type of coating machine. is there.
- Application equipment for mixed paste includes various blade coaters, comma direct coaters, lip coaters, gravure coaters, comma reverse coaters, air knife coaters, slot die coaters, jet coaters, bar coaters, curtain coaters, size presses, etc. Can do. If necessary, smoothing processing and gloss finishing processing may be performed using a calendar device such as a machine calendar, a soft calendar, or a super calendar after coating.
- a transfer-printed paper is obtained by applying a non-sublimation type disperse dye to the above-mentioned transfer-printed paper in an ink state by inkjet printing or other methods such as gravure printing or flexographic printing and drying.
- the non-sublimation type disperse dye used here is a dye which does not easily sublime at high temperatures, and corresponds to the S type or SE type disperse dyes having excellent sublimation fastness as shown below.
- S-type or SE-type disperse dyes are disperse dyes with excellent sublimation fastness that make the dye difficult to sublimate by increasing the molecular structure or introducing a polar substituent, and are used in the sublimation transfer method.
- This is a dye excluding sublimable disperse dyes of type E.
- Specific examples of the non-sublimation type disperse dye used in the present invention include the following dyes.
- Disperse Brown 1, 4, 9, 13, 19, 24, 25 etc. Black can be produced by blending the three primary colors + ⁇ of these fast S-type dyes.
- Specific examples of the E type sublimation dyes include the dyes described in claim 9 of JP2011-21133A, but not limited to the sublimation fastness, and the light fastness. There are many dyes with generally low fastness.
- the non-sublimation type disperse dye is converted into an ink so that it can be used as an inkjet ink, a gravure ink, a flexo ink or the like.
- ink is printed (printed) on the transfer textile sheet by inkjet printing, gravure printing, flexographic printing, or the like to produce transfer textile paper.
- the dye content (chromogen) in the ink is preferably 1 to 15% by mass depending on the color density.
- the ink to be used can be oil-based ink, but it is desirable to use water-based ink in consideration of occupational safety and health, environmental problems, handling of dangerous goods, and economy.
- dyes atomized to have an average particle size of 0.05 to 0.2 ⁇ m are preferably used. Atomization can be carried out by a known method using a bead mill or the like in the presence of a dispersant.
- the ink used in the ink jet printer is preferably a finely divided dye, a dispersion stabilizer, a drying inhibitor, and surface tension adjustment. Add and mix agents, viscosity modifiers, pH adjusters, antiseptics, antifungal agents, sequestering agents, antifoaming agents, deaerators, dispersants, etc. Filtered and degassed with a membrane filter. If the average particle size is too small, reaggregation of the particles tends to occur. On the other hand, if the average particle size is too large, the problem of clogging the nozzles of the ink jet printer tends to occur.
- a dye finely atomized to an average particle size of 0.2 to 10 ⁇ m is preferably used together with a dispersant. Whether the average particle size is too small or too large, printability and color developability tend to be poor.
- ink in which the atomized dye is mixed and dispersed in a viscous aqueous solution containing a thickener and the viscosity is adjusted to about 30 to 500 mPa ⁇ s can be used.
- Dispersing agents that can be used include naphthalene sulfonic acid formalin condensate, methyl naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, olfin PD-003, olfin PD-001, olphin PD-002W, olphin PD-004, olphin PD-005.
- Transfer printing process The transfer printing paper obtained as described above and the polyester fiber material (fabric) are overlapped, and the dye is transferred to the fiber material by pressurization and heating, whereby the transfer printing of the present invention is performed.
- the heating temperature (transfer temperature) and the pressurizing pressure (transfer pressure) are in the range of 150 to 250 ° C. and 0.01 MPa or more, respectively, preferably 200 to 230 ° C. and 0, respectively.
- the range is from 0.02 to 4 MPa.
- the temperature or pressure exceeds the upper limit, the texture of the product tends to be inferior.
- the temperature or pressure is less than the lower limit, the color developability tends to be insufficient.
- the pressurizing / heating time is usually in the range of 1 second to 10 minutes.
- processing time transfer time
- the higher the temperature and pressure the better the color developability and the shorter the processing time.
- the higher the temperature and the higher the pressure the better.
- the transfer temperature is 220 ° C. and the transfer pressure is 0.05 MPa, good color developability can be obtained even with a processing time of 30 seconds.
- the polyester fiber material (fabric) transferred and printed by the transfer printing method of the present invention is a woven fabric, a knitted fabric, a nonwoven fabric, a sheet, a film, or the like mainly composed of a polyester polymer material, or the woven fabric, knitted fabric, nonwoven fabric. And fiber materials such as blended fibers, mixed fibers, union products, and composite materials of natural fibers and synthetic fibers other than polyester polymer materials.
- the polyester polymer material include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, depolymerized polyester, cationic dyeable polyester, room temperature dyeable polyester, and polyester material called alkali weight loss polyester. .
- natural fibers examples include cellulosic fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk and wool.
- Synthetic fiber material means all known synthetic fiber materials other than polyester-based polymer materials such as nylon, vinylon, polyacryl, polyurethane, and may be composite fibers.
- Example 1 As a mixed paste for forming an ink receiving layer and a dyeing acceleration layer, 20 g of sorbitole C-5 (etherified starch: manufactured by AVEBE), 20 g of FD algin BL (soda alginate: manufactured by Furukawa Chemical Co., Ltd.), EX-100 (Tamarind gum: manufactured by Tomoe Glue Co., Ltd.) A mixture of 20 g, tartaric acid 40 g and ion-exchanged water 400 g (total 500 g) was thoroughly stirred with a high-speed desper type stirrer (3,000 rpm) to produce a uniform and smooth high-viscosity paste. did.
- a high-speed desper type stirrer 3,000 rpm
- Disperse dye ink liquid (CI Disperse Blue 60: 6%, ethylene glycol 5%, glycerin 15%, nonionic dispersant 5%, anionic dispersant 5%, ion exchange on the obtained transfer textile paper.
- a striped pattern was printed on an ink jet printer (an ink jet printer manufactured by Roland: Soljet EJ-640) and dried to obtain a transfer printed paper.
- the transfer-printed paper thus obtained and the polyester satin fabric are brought into close contact with each other, and heated and pressurized (210 ° C., 0.8 MPa, 40 seconds, using a sublimation flat press HSP-2210 manufactured by HASHIMA Co., Ltd.). After transferring and fixing the dye to the fabric, the paper was removed.
- the maximum pressure (cylinder pressure) of the sublimation press machine manufactured by Hashima is 1 MPa, and this pressure corresponds to a transfer pressure of 0.049 MPa. Therefore, the cylinder pressure of 0.8 MPa in this embodiment corresponds to the transfer pressure of 0.039 MPa.
- HASHIMA high pressure sublimation press manufactured by Hashima
- the polyester 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 (modified) 5 Grade, (dirty) 4-5 grade.
- the light fastness according to JISL0842 was grade 5.
- Example 2 Solbitose C-5 (etherified starch: manufactured by AVEBE) 10 g, FD algin BL (sodium alginate: manufactured by Furukawa Chemical Co., Ltd.) 5 g, EX-100 (tamarind gum: manufactured by Tomoe Glue Co., Ltd.), Penon JE66 (modified starch) : Nissho Chemical Co., Ltd.) 10 g, tartaric acid 10 g and ion-exchanged water 170 g (total 210 g) were thoroughly stirred with a high-speed desper type stirrer (3,000 rpm) to produce a uniform and smooth high-viscosity paste.
- a high-speed desper type stirrer 3,000 rpm
- a small amount of degassing agent and antifoaming agent was added to this high viscosity paste, and a small amount of preservatives and fungicides were added, and water was further added to adjust the viscosity to about 1200 mPa ⁇ s to obtain a mixed paste solution.
- the obtained mixed paste is uniformly coated and dried on a base paper (manufactured by Nippon Paper Industries Co., Ltd., glossy kraft paper, basis weight 60 g / m 2 ), and transfer printing. Got the paper.
- the coating amount (dry weight) of the mixed paste was 10 g / m 2 .
- Disperse dye ink liquid (CI Disperse Blue 60: 6%, ethylene glycol 5%, glycerin 15%, nonionic dispersant 5%, anionic dispersant 5%, ion-exchanged water on the resulting transfer printing paper. 64%) was printed with a pattern using an inkjet printer (an inkjet printer manufactured by Roland: Soljet Pro4XF-640) to obtain a transfer printed paper.
- the obtained transfer printed paper and polyester taffeta fabric are brought into close contact with each other, and heated and pressurized (210 ° C, 0.8 MPa, 40 seconds, HASHIMA sublimation flat press) to transfer and fix the dye to the polyester fabric to remove the paper.
- a polyester printed fabric was obtained.
- the polyester printed fabric obtained in this way is dyed densely and delicately (the judgment of dyeability is ⁇ ), the texture of the fibers is good, the fastness to sunlight (change) and the fastness to sublimation (change) , Dirt) was grade 4 or higher.
- Example 3 Except for adding 20 g of citric acid instead of 40 g of tartaric acid, the same procedure as in Example 1 was carried out to prepare a mixed paste and apply it to paper to obtain a transfer printed paper.
- Disperse dye ink liquid CI Disperse Red 92: 5%, ethylene glycol 5%, glycerin 15%, nonionic dispersant 5%, anionic dispersant 5%, ion-exchanged water on the resulting transfer printing paper. 64%) was printed with a pattern using an inkjet printer (an inkjet printer manufactured by Roland: Soljet ProIIIXJ-640) and dried to obtain a transfer printed paper.
- the obtained transfer printed paper and polyester satin fabric are brought into intimate contact, and heated and pressurized (218 ° C, 1.0 MPa, 30 seconds, HASHIMA sublimation flat press) to transfer and fix the dye to the polyester fabric to remove the paper.
- the polyester printed fabric obtained in this way is dyed densely and delicately (the determination of dyeability is ⁇ ), the texture of the fiber is good, and the fastness to sunlight is high.
- the sublimation fastness was excellent as in Example 1.
- Example 4 As a result of processing in the same manner as in Example 1 except that the amount of tartaric acid was changed from 40 g to 4 g and the heating and pressing conditions were changed to a transfer pressure of 0.05 MPa, a transfer temperature of 195 ° C., and a processing time of 120 seconds. A robust printed product similar to 1 was obtained.
- Example 5 20 g of citric acid was used in place of 40 g of tartaric acid, and treatment was performed in the same manner as in Example 1 except that 1% of microid KM386P (silica gel: manufactured by KD Corp.) was added to the mixed paste.
- microid KM386P silicon gel: manufactured by KD Corp.
- the polyester taffeta printed fabric obtained had a delicate design (judgment was ⁇ ), the fiber texture was soft, and various fastness properties such as light resistance, sublimation, sweat and washing were also good.
- Example 6 As a mixed paste for forming the ink receiving layer and dyeing acceleration layer, Goosenol GL-05 (water-soluble polyvinyl alcohol: manufactured by Nippon Synthetic Chemical Co., Ltd.) 20 g, Fine Gum HEL-3 (cellulose derivative: manufactured by Daiichi Kogyo Kagaku Co., Ltd.) ) 50 g, EX-200 (Tamarind gum: manufactured by Tomoe Glue Co., Ltd.) 50 g, urea 50 g, special A clay KL-18: 20 g, microid KM-386P: 10 g, citric acid 25 g, tartaric acid 25 g, water 750 g The mixture was stirred well with a high-speed despar-type stirrer at 5,000 rpm to prepare a high-viscosity paste.
- a high-speed despar-type stirrer at 5,000 rpm to prepare a high-viscosity paste.
- this high-viscosity paste After adjusting the viscosity of this high-viscosity paste, using a comma coater, it was applied to a base paper (Nippon Paper Industries Co., Ltd., silver bamboo, 50 g / m 2 ) and dried to obtain a transfer printed paper.
- This transfer textile sheet was calendered at a pressure of 3 MPa and smoothed.
- the amount of glue applied was 12 g / m 2 .
- Disperse dye gravure ink liquid (CI Disperse Red86 product: 15% was contained on the obtained transfer printing paper, and the viscosity was adjusted to 120 mPas using water, cellulose thickener, polyvinyl alcohol and isopropanol. Ink) was printed by a gravure printing machine and dried to obtain a transfer printed paper.
- the obtained transfer printed paper is closely attached to the polyester taffeta fabric, and heated and pressed at 210 ° C., 0.8 MPa for 40 seconds using a flat plate press manufactured by Hashima to transfer and fix the dye to the polyester fabric, thereby producing a polyester printed fabric. Obtained.
- This polyester printed fabric is dyed densely and delicately (quality judgment is ⁇ ), the texture of the fiber is good, and the sublimation fastness according to JISL0854 is (Fixed) Grade 5 and (Stained) Grade 4-5 there were. Moreover, the light fastness according to JISL0842 was grade 4 or higher.
- Example 7 Using a drum-type continuous thermo printer manufactured by Inoue Metal Industry Co., Ltd. instead of a flat-type sublimation transfer machine manufactured by Hashima Co., Ltd., a drum surface temperature of 220 ° C and a pressure of 0.5 MPa. As a result of processing in the same manner as in Example 6 except that the time was 30 seconds, the fiber material exhibited good color developability ( ⁇ ).
- Example 8 In place of the flat sublimation transfer machine manufactured by HASHIMA, a two-roll pressurizing / heating machine manufactured by Yuri Roll Co., Ltd. was used, under the conditions of a hot roll surface temperature of 230 ° C, a pressure of 3 MPa, and a feed rate of 1 m / min. As a result of processing in the same manner as in Example 1 except that the heat roll contact residence time of the transfer printed paper was 20 seconds, good color developability ( ⁇ ) of the fiber material was exhibited.
- Comparative Example 1 Printing is performed on four types of commercially available company A's sublimation transfer printing paper, brand a, brand b, brand c, and brand d using the disperse dye ink used in Example 1. As a result of transfer printing in the same manner as in Example 1 except that the color was changed, the color development (determination of dyeing power was ⁇ to ⁇ ) was inferior to that in Example 1 in each case, and it was determined that there was a problem in practical use. It was done.
- Comparative Example 2 Using the commercially available B company sublimation transfer printing paper and the C company sublimation transfer printing paper, except that the transfer printing paper was changed, the transfer printing paper was prepared and the transfer printing was carried out in the same manner as in Example 1. It was remarkably inferior to 1 (stainability was judged as x).
- Comparative Example 3 A sublimation dye C.I. I.
- the color development was good.
- the color developability was poor ( ⁇ ) when treated in the same manner as in Example 1 except that printing was performed with an ink containing Disperse Red 92 and the treatment was performed at a pressure of 0.15 MPa.
- Comparative Example 4 When processed in the same manner as in Example 2 except that tartaric acid was not added, the coloring property of the fiber material was insufficient (judgment determination was ⁇ ), and spots were generated.
- Example 9 Fine gum HEL-3 (sodium carboxymethylcellulose: Daiichi Kogyo Seiyaku Co., Ltd.) 20 parts, FD Algin BL (sodium alginate: Furukawa Chemical Co., Ltd.) 20 parts, EX-100 (Tamarind gum: Tomoe Glue Co., Ltd.) 10 And a mixture of 400 parts of ion-exchanged water (450 parts in total) were sufficiently stirred with a high-speed desper type stirrer (3,000 rpm) to prepare a uniform and smooth high-viscosity paste (mixed paste). Bubbles were extinguished by adding a commercially available degassing agent and antifoaming agent to the mixed paste.
- the prepared mixed paste is uniformly applied to paper (Nippon Paper Industries Co., Ltd., fine paper, basis weight 60 g / m 2 ), dried and transferred. A printed paper was obtained.
- the coating amount (dry weight) of the mixed paste was 8 g / m 2 .
- An ink (CI Disperse Blue 79: 4%, ethylene glycol 5%, ethylene glycol 5%, with a disperse dye atomized by a bead mill to an average particle size of 0.1 ⁇ m on the transfer printed paper thus obtained.
- a striped pattern was printed with an inkjet printer (an inkjet printer manufactured by Roland: Soljet EJ-640) using 15% glycerin, 5% nonionic dispersant, 5% anionic dispersant, and 66% ion exchange water. Thereafter, it was dried to obtain a transfer printed paper.
- the transfer printed paper thus obtained and the polyester satin fabric were brought into close contact with each other and heated and pressurized (215 ° C., cylinder pressure 0.6 MPa, 40 seconds) with a sublimation flat press HSP-2210 manufactured by HASHIMA Co., Ltd. After transferring and fixing the dye to the fabric, the paper was removed to obtain a polyester printed fabric.
- the polyester printed fabric obtained in this way is densely and delicately dyed (good color developability), the texture of the fiber is good, and the sublimation fastness according to JISL0854 is (Fixed) Grade 5, (Stain) It was grade 4-5.
- the light fastness according to JISL0842 was grade 5 or higher.
- Example 10 A mixture of 10 parts of Poval AP-17 (carboxy-modified PVA, manufactured by Nippon Vinegar Pover Co., Ltd.), FD Argin BL: 20 parts, EX-100: 10 parts, and 200 parts of ion-exchanged water (240 parts in total) The mixture was thoroughly stirred with a mold stirrer (3,000 rpm) to prepare a uniform and smooth high-viscosity paste (mixed paste). Since foam was generated, the foam was removed by adding a commercially available degassing agent and antifoaming agent to the mixed paste liquid. Further, a small amount of preservatives and fungicides were added.
- Poval AP-17 carboxy-modified PVA, manufactured by Nippon Vinegar Pover Co., Ltd.
- FD Argin BL 20 parts
- EX-100 10 parts
- ion-exchanged water 200 parts in total
- the mixed paste liquid which is prepared by adding water to the high-viscosity paste to adjust the viscosity to about 1200 mPa ⁇ s, is used as a base paper (manufactured by Nippon Paper Industries Co., Ltd., bleached kraft paper, basis weight 40 g / M 2 ) uniformly and dried to obtain a transfer printed paper.
- the coating amount (dry weight) of the mixed paste was 10 g / m 2 .
- the viscosity is 200 mPa ⁇ s using Metrolose 65SH • 400 (manufactured by Shin-Etsu Chemical Co., Ltd.), Metrolze 65SH • 4000 (manufactured by Shin-Etsu Chemical Co., Ltd.), Poval AP-17 (manufactured by Nippon Vinegar Poval Co., Ltd.) and isopropanol.
- a viscous ink aid was prepared.
- Disperse Red 86 ⁇ 200% product (average particle size 1.5 ⁇ m) was blended 15% (relative to the ink auxiliary agent), and the viscosity of the ink was adjusted to 150 mPa ⁇ s to prepare a Magenta ink for gravure.
- the thus obtained Magenta ink for gravure is solid-printed at a speed of 15 m / min and a temperature of 25 ° C. on the above-mentioned transfer printing paper using an electric gravure printing tester GP-10 (manufactured by Kurabo Industries).
- a transfer printed paper was obtained.
- the transfer printed paper and the polyester taffeta fabric are brought into close contact with each other and heated and pressurized (220 ° C., roll pressure 0.5 MPa, 40 seconds, roller type transfer machine) to remove the paper after transferring the dye to the fabric.
- a polyester printed fabric was obtained.
- the polyester printed fabrics obtained in this way are densely and delicately dyed, the texture of the fibers is good, and both the fastness to sunlight (change) and the fastness to sublimation (change, stain) are both grade 5 That was all.
- Example 11 instead of the mixed paste in Example 9, a mixture of 55 parts of a 10% aqueous solution of FD-Algin BL and 10 parts of a 5% aqueous solution of powdered sulfuric acid band (Daimei Chemical Co., Ltd.) is used as the mixed paste. Except for the above, application to paper was carried out in the same manner as in Example 9 to obtain a transfer textile sheet.
- Disperse dye ink liquid (CI Disperse Red 92: 5%, ethylene glycol 5%, glycerin 15%, nonionic dispersant 5% on ink obtained by using finely divided disperse dyes on the transfer printing paper obtained.
- the obtained transfer printing paper and polyester taffeta fabric are brought into close contact with each other, and heated and pressurized (215 ° C., cylinder pressure 1.0 MPa, 30 seconds) with a sublimation flat press HSP-2210 manufactured by HASHIMA, Inc. After transferring and fixing, the paper was removed to obtain a polyester printed fabric.
- the polyester printed fabric thus obtained was dyed densely and delicately, the texture of the fibers was good, and the fastness to sunlight and the fastness to sublimation were excellent as in Example 9.
- Example 12 instead of the mixed paste in Example 9, a mixed paste consisting of 100 parts of EX-3 (cationized starch, manufactured by Nissho Chemical Co., Ltd.) 10% aqueous solution and 100 parts of 10% aqueous solution of FD-Algin BL was used.
- EX-3 chemically synthesized starch, manufactured by Nissho Chemical Co., Ltd.
- a polyester taffeta printed fabric was obtained.
- the resulting polyester taffeta printed fabric had good color development and a delicate design, the fiber texture was soft, and various fastness properties such as light resistance, sublimation, sweat and washing were also good.
- Example 13 10 parts of brivine (phosphorylated starch, manufactured by Nissho Chemical Co., Ltd.), 50 parts of fine gum HEL-3, 10 parts of EX-200 (manufactured by Tomoe Glue Co., Ltd.), Gohsenol GL-05 (water-soluble polyvinyl alcohol: Nippon Synthetic Chemical Co., Ltd.) 20 parts, Microid KM-386P: 10 parts, tartaric acid 50 parts and water 650 parts were mixed well with a high-speed desper type stirrer at 5,000 rpm to obtain a uniform and smooth high-viscosity paste ( A mixed paste) was prepared.
- brivine phosphorylated starch, manufactured by Nissho Chemical Co., Ltd.
- EX-200 manufactured by Tomoe Glue Co., Ltd.
- Gohsenol GL-05 water-soluble polyvinyl alcohol: Nippon Synthetic Chemical Co., Ltd.
- Microid KM-386P 10 parts, tartaric acid
- Disperse dye gravure ink liquid (CI Disperse Red92 product 15% is blended on the transfer printing paper obtained, and the viscosity is adjusted to 80 mPa ⁇ s using water, cellulose thickener, polyvinyl alcohol and isopropanol. The ink) was printed by a gravure printing machine and dried to obtain a transfer printed paper.
- the obtained transfer-printed paper is brought into close contact with the polyester taffeta fabric, and heated and pressurized (215 ° C., cylinder pressure 0.8 MPa, 40 seconds) using a flat plate press manufactured by HASHIMA, Inc., the dye is transferred and fixed to the fabric. Thereafter, the paper was removed to obtain a polyester printed fabric.
- the polyester printed fabric obtained in this way is densely and delicately dyed, the texture of the fiber is good, and the sublimation fastness according to JISL0854 is (Fixed) Grade 5 and (Stained) Grade 4-5. there were. Moreover, the light fastness according to JISL0842 was grade 5 or higher.
- Example 14 In place of the flat sublimation transfer machine manufactured by Hashima in Example 9, a roll type sublimation transfer machine was used under the conditions of a hot roll surface temperature of 210 ° C. and a roll pressure of 2 MPa (nip width 3 cm). ) And the heat-transfer contact time of the transfer printed paper was 30 seconds. As a result of processing in the same manner as in Example 9, good color development of the fiber material was exhibited.
- Example 15 A mixture prepared by mixing fine gum HEL-3: 20 parts, EX-3: 10 parts, EX-100: 20 parts and water 400 parts instead of the mixed paste liquid (high viscosity paste) in Example 9.
- the paste solution was used, the color of the polyester printed fabric was good and had a delicate design, the texture of the fiber was flexible, and various kinds of light resistance, sublimation, sweat, washing, etc. The fastness was also good.
- Example 16 instead of the mixed paste liquid (high viscosity paste) in Example 9, 100 parts of a 10% aqueous solution of brivain (phosphorylated starch, manufactured by Nissho Chemical Co., Ltd.) and 100 parts of a 10% aqueous solution of FD-Algin BL were prepared.
- the polyester printed fabric had good color development and a delicate design, and the texture of the fiber was flexible, such as light resistance, sublimation, sweat, washing, etc. Various fastnesses were also good.
- Example 17 As a result of processing in the same manner as in Examples 9 and 10 except that the heating and pressurizing conditions were a transfer temperature of 190 ° C., a transfer pressure of 0.01 MPa, and a time of 60 seconds, the color developability was higher than that of Examples 9 and 10. It was inferior. However, when the temperature was 200 ° C., the pressure was 0.02 MPa, and the time was 3 minutes, the color development was good.
- Comparative Example 5 A commercially available sublimation transfer printing paper JetcolTA (manufactured by Caldenhove) was used as the transfer printing paper and printed with the ink comprising the non-sublimation type disperse dye of Example 9 to obtain a transfer printing paper. Next, when this transfer printed paper and polyester taffeta were brought into close contact with each other, a color development test was conducted at 210 ° C. and 0.02 MPa for 40 seconds.
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Abstract
Description
(1)原紙: 糊剤を塗工する前の紙(またはフィルム)
(2)転写捺染用紙:糊剤を塗工した原紙
(3)転写捺染紙: 染料インクが付与された転写捺染用紙 In the present specification and claims, terms relating to paper used for printing may be used in the following meaning.
(1) Base paper: Paper (or film) before applying glue
(2) Transfer printing paper: base paper coated with paste (3) Transfer printing paper: transfer printing paper to which dye ink is applied
ポリエステル系繊維材料に捺染を行うにあたり、
カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩又はアルカリ土類金属塩、及び第4級アンモニウム基等のカチオン基からなる群より選ばれる官能基を有する糊剤、又は、
天然ガム糊、繊維素誘導体及び多糖類から選ばれ、更にカルボン酸化合物類が配合された糊剤
を原紙に付与した転写捺染用紙に、非昇華型分散染料インクを用いて印刷した転写捺染紙を用い、前記転写捺染紙をポリエステル系繊維材料に密着して特定条件で加圧・加熱するだけで、転写捺染の全工程を完結することができ、かつ品質も良好な捺染されたポリエステル系繊維材料が得られる事を見出し、本発明の転写捺染法を完成した。 The present inventor aims to develop a textile printing method that solves quality problems such as economic efficiency, environmental problems, and fastness, and uses a known printing method such as an ink jet printing method or a gravure printing method for the polyester fiber material. As a result of intensive research on printing methods,
When printing on polyester fiber materials,
It is selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group such as a quaternary ammonium group. A glue having a functional group, or
A transfer printing paper printed with a non-sublimation disperse dye ink on a transfer printing paper selected from natural gum glue, fiber derivatives and polysaccharides and further provided with a paste containing a carboxylic acid compound. Used, the transfer printing paper can be completed with all the steps of transfer printing, and the quality can be achieved simply by pressing and heating under specific conditions with the transfer printing paper in close contact with the polyester fiber material. The transfer printing method of the present invention was completed.
糊剤を原紙に付与した転写捺染用紙に、分散染料インクを用いて印刷した転写捺染紙を、ポリエステル系繊維材料に密着して加圧・加熱して転写捺染する転写捺染法であって、
前記分散染料インクが、非昇華型分散染料インクであり、
前記糊剤が、
カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤、又は、
天然ガム糊、繊維素誘導体及び多糖類から選ばれ、更にカルボン酸化合物類が配合された糊剤である事を特徴とするポリエステル系繊維材料の転写捺染法である(請求項1)。 The first aspect of the present invention is:
A transfer printing method in which transfer printing paper printed with disperse dye ink on a transfer printing paper provided with a paste is applied to a polyester fiber material and pressed and heated to transfer printing,
The disperse dye ink is a non-sublimation disperse dye ink,
The glue is
A paste having a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group; Or
A transfer printing method for a polyester fiber material, characterized in that it is a paste selected from natural gum paste, fiber derivatives and polysaccharides and further mixed with carboxylic acid compounds (Claim 1).
前記糊剤が、カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤の場合は、この糊剤には、更にカルボン酸化合物類を配合してもよい(請求項3)。 Examples of the paste include one or more selected from the group consisting of animal glues and plant glues (Claim 2). In addition, 1 type or more means that one type of thing may be individual, and 2 or more types may be used together. The same applies to “one or more” shown below.
The glue is a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group. In the case of a paste having a carboxylic acid compound, a carboxylic acid compound may be further added to the paste.
前記糊剤には、更に強酸と弱塩基からなる塩である弱酸性化合物、鉱物系酸性化合物及び鉱物系添加剤からなる群より選ばれる1種以上を配合してもよい(請求項5)。
前記糊剤には、更に助剤を配合してもよい(請求項6)。 The carboxylic acid compounds are preferably at least one selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids (Claim 4).
The paste may further contain one or more selected from the group consisting of weakly acidic compounds that are salts of strong acids and weak bases, mineral acidic compounds, and mineral additives (Claim 5).
The paste may further contain an auxiliary agent (claim 6).
第1の態様の転写捺染法に用いられる転写捺染用紙の製造方法であって、
原紙に、カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤、又は、天然ガム糊、繊維素誘導体及び多糖類から選ばれ、更にカルボン酸化合物類が配合された糊剤を付与する事を特徴とする転写捺染用紙の製造方法である(請求項10)。 The second aspect of the present invention is:
A method for producing a transfer textile used for the transfer textile printing method of the first aspect,
The base paper has a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group. A method for producing a transfer printing paper, characterized by applying a paste, or a natural gum paste, a fiber derivative and a polysaccharide, and further adding a paste containing a carboxylic acid compound (claim 10). ).
前記第1の態様のポリエステル系繊維材料の転写捺染法により、ポリエステル系繊維材料に転写捺染をする工程を有する事を特徴とするポリエステル系繊維材料の製造方法である(請求項11)。 The third aspect of the present invention is:
A method for producing a polyester fiber material, comprising the step of performing transfer printing on a polyester fiber material by the polyester fiber material transfer printing method according to the first aspect (claim 11).
本発明の第1の態様は、原紙に付与されて転写捺染用紙を形成する糊剤が、
カルボキシル基(-COOH)、スルフォン基(-SO3H)及び燐酸基(-PO4H2)から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩又はアルカリ土類金属塩、及びカチオン基からなる群より選ばれる1種以上の官能基を有する化合物を主成分とする糊剤である事、又は、
天然ガム糊、繊維素誘導体及び多糖類からなる群より選ばれる1種以上からなり、更にカルボン酸化合物類が配合された糊剤である事を特徴とする。なお、糊剤とは、水溶性の高分子化合物を主体とした化合物の水溶液であり、2質量%水溶液としたときの20℃での粘度が、3mPa・s以上のものを言うが、好ましくは10mPa・s以上のものが使用される。又、カチオン基としては、4級アンモニウム基等を挙げることができる。 [Glue]
In the first aspect of the present invention, a paste that is imparted to a base paper to form a transfer printing paper,
An acidic group selected from a carboxyl group (—COOH), a sulfone group (—SO 3 H) and a phosphoric acid group (—PO 4 H 2 ), an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group And a paste mainly composed of a compound having one or more functional groups selected from the group consisting of cationic groups, or
It is characterized by being a paste containing at least one selected from the group consisting of natural gum paste, fiber derivative and polysaccharide, and further containing carboxylic acid compounds. The paste is an aqueous solution of a compound mainly composed of a water-soluble polymer compound, and has a viscosity at 20 ° C. of 3 mPa · s or more when a 2% by mass aqueous solution is used. The thing of 10 mPa * s or more is used. Examples of the cationic group include a quaternary ammonium group.
糊剤が、カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩又はアルカリ土類金属塩、及びカチオン基からなる群より選ばれる1種以上の官能基を有する化合物の場合も、カルボン酸化合物類の糊中の好ましい含有率は固形分換算で1質量%から50質量%、更に好ましい含有率は3質量%から30質量%である。 When the paste is a natural gum paste, a fiber derivative, or a polysaccharide, the preferable content in the mixed paste solution of carboxylic acid compounds (mixed with water as a constituent of the paste to make a uniform solution) is solid. In terms of minutes, it is 1 to 50% by mass, and more preferably 3 to 30% by mass. A mixed paste containing these carboxylic acid compounds shows weak acidity, but generally generally falls within the range of PH = 3-5.
The paste is one or more selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group. Also in the case of a compound having a functional group, the preferred content of the carboxylic acid compounds in the paste is 1% by mass to 50% by mass in terms of solid content, and the more preferred content is 3% by mass to 30% by mass.
糊剤に配合される鉱物系酸性化合物とは、鉱物より得られる水溶性の化合物又はこの化合物の複合体等であって、水に溶解して酸性を示すものである。鉱物系酸性化合物としては、硫酸バンド、ミョウバン、カオリン等を挙げることができる。弱酸性化合物や鉱物系酸性化合物を配合することにより、発色性が向上するとの効果が得られるので好ましい。 The weakly acidic compound blended in the paste is a salt composed of a strong acid and a weak base, which dissolves in water and exhibits acidity. Specific examples thereof include ammonium sulfate, monobasic sodium phosphate, and ammonium chloride. , Calcium chloride, and the like.
The mineral-based acidic compound blended in the paste is a water-soluble compound obtained from a mineral, a complex of this compound, or the like, and shows acidity when dissolved in water. Examples of mineral acid compounds include sulfuric acid band, alum, kaolin and the like. It is preferable to add a weakly acidic compound or a mineral-based acidic compound since an effect of improving color developability can be obtained.
糊剤を付与して転写捺染用紙を作製する為に用いられる原紙は、クラフト紙、上質紙、中質紙、下級紙、コート紙、目止め紙、平滑処理紙、片艶紙等、どの様な加工紙、又は未加工紙や再生紙でも良く、一般的に使用されている安価な紙を原紙として用いることができる。離型紙等の高価な紙を用いる必要はない。なお、合成樹脂フィルムを原紙として用いることもできる。 [Base paper]
The base paper used to make transfer textile printing paper by applying glue is kraft paper, fine paper, medium quality paper, lower grade paper, coated paper, sealing paper, smooth paper, glossy paper, etc. Processed paper, unprocessed paper or recycled paper may be used, and generally used inexpensive paper can be used as the base paper. There is no need to use expensive paper such as release paper. A synthetic resin film can also be used as the base paper.
本発明の転写捺染法に使用される転写捺染用紙は、前記糊剤を、原紙に付与し原紙の表面上にインク受容層兼染着促進層を形成することにより作製される。糊剤の付与量は、原紙に対して、ドライ換算1~50g/m2が好ましく、より好ましくは2~20g/m2である。 [Transfer printing paper]
The transfer printing paper used in the transfer printing method of the present invention is produced by applying the paste to the base paper and forming an ink receiving layer and dyeing promoting layer on the surface of the base paper. The applied amount of the paste is preferably 1 to 50 g / m 2 in terms of dry, more preferably 2 to 20 g / m 2 with respect to the base paper.
前記の転写捺染用紙に、非昇華型分散染料を、インクの状態で、インクジェットプリント又はその他の方法、例えばグラビア印刷、フレキソ印刷法で付与(プリント)して乾燥することにより転写捺染紙が得られる。ここで使用される非昇華型分散染料とは高温で昇華し難い染料であって、以下に示す昇華堅牢度の優れたSタイプ又はSEタイプの分散染料が該当する。Sタイプ又はSEタイプの分散染料とは、分子構造を大きくするか、又は極性置換基を導入する事によって染料が昇華し難くした昇華堅牢度の優れた分散染料であり、昇華転写法に用いられるEタイプの昇華性分散染料を除外した染料である。本発明で用いられる非昇華型分散染料の具体例として以下の染料を挙げることができる。 [Dye, Ink, Transfer Textile Paper]
A transfer-printed paper is obtained by applying a non-sublimation type disperse dye to the above-mentioned transfer-printed paper in an ink state by inkjet printing or other methods such as gravure printing or flexographic printing and drying. . The non-sublimation type disperse dye used here is a dye which does not easily sublime at high temperatures, and corresponds to the S type or SE type disperse dyes having excellent sublimation fastness as shown below. S-type or SE-type disperse dyes are disperse dyes with excellent sublimation fastness that make the dye difficult to sublimate by increasing the molecular structure or introducing a polar substituent, and are used in the sublimation transfer method. This is a dye excluding sublimable disperse dyes of type E. Specific examples of the non-sublimation type disperse dye used in the present invention include the following dyes.
前記のようにして得られた転写捺染紙とポリエステル系繊維材料(布帛)を重ね合わせ、加圧・加熱により繊維材料に染料を移行染着させて、本発明の転写捺染が行われる。一般的には、加熱の温度(転写温度)、加圧の圧力(転写圧)は、それぞれ、150~250℃、0.01MPa以上の範囲であり、好ましくは、それぞれ、200~230℃、0.02~4MPaの範囲である。温度や圧力が上限超える場合は、製品の風合いが劣る傾向があり、一方温度や圧力が下限未満の場合は、発色性が不十分となる傾向がある。 [Transfer printing process]
The transfer printing paper obtained as described above and the polyester fiber material (fabric) are overlapped, and the dye is transferred to the fiber material by pressurization and heating, whereby the transfer printing of the present invention is performed. In general, the heating temperature (transfer temperature) and the pressurizing pressure (transfer pressure) are in the range of 150 to 250 ° C. and 0.01 MPa or more, respectively, preferably 200 to 230 ° C. and 0, respectively. The range is from 0.02 to 4 MPa. When the temperature or pressure exceeds the upper limit, the texture of the product tends to be inferior. On the other hand, when the temperature or pressure is less than the lower limit, the color developability tends to be insufficient.
本発明の転写捺染法により転写捺染されるポリエステル系繊維材料(布帛)とは、ポリエステル系高分子材料を主体とする織物、編物、不織布、シート、フイルム等の単独、又は前記織物、編物、不織布等と、天然繊維やポリエステル系高分子材料以外の合成繊維との混紡、混繊、交織品、複合材料等の繊維材料を言う。ポリエステル系高分子材料としては、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸、解重合ポリエステル、カチオン可染ポリエステル、常温可染ポリエステル、アルカリ減量ポリエステルと呼ばれるポリエステル系材料を挙げることができる。前記天然繊維としては綿、麻、リヨセル、レーヨン、アセテート等のセルロース系繊維材料、絹、羊毛等の蛋白質系繊維材料を挙げることができる。合成繊維材料とは、ナイロン、ビニロン、ポリアクリル、ポリウレタン等、ポリエステル系高分子材料以外の公知の合成繊維材料の全てを意味し、更に複合系繊維でも良い。 [Polyester fiber material]
The polyester fiber material (fabric) transferred and printed by the transfer printing method of the present invention is a woven fabric, a knitted fabric, a nonwoven fabric, a sheet, a film, or the like mainly composed of a polyester polymer material, or the woven fabric, knitted fabric, nonwoven fabric. And fiber materials such as blended fibers, mixed fibers, union products, and composite materials of natural fibers and synthetic fibers other than polyester polymer materials. Examples of the polyester polymer material include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, depolymerized polyester, cationic dyeable polyester, room temperature dyeable polyester, and polyester material called alkali weight loss polyester. . Examples of the natural fibers include cellulosic fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk and wool. Synthetic fiber material means all known synthetic fiber materials other than polyester-based polymer materials such as nylon, vinylon, polyacryl, polyurethane, and may be composite fibers.
○:繊維材料の発色性(染色力)、均染性、堅牢度が優れており品質良好。
△:繊維材料の発色性(染色力)と均染性がやや劣っており品質不良。
×:繊維材料の発色性(染色力)と均染性が明らかに不良で品質明らかに不良。 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 Examples 1 to 7 and Comparative Examples 1 to 4, the dyeing power after transfer printing (coloring property of the fiber material (fabric)) and leveling property were determined according to the following criteria.
○: Good color quality (dyeing power), levelness and fastness of the fiber material and good quality.
(Triangle | delta): The coloring property (dyeing power) and leveling property of a fiber material are a little inferior, and a quality is bad.
X: The coloring property (dyeing power) and leveling property of the fiber material are clearly poor and the quality is clearly poor.
インク受容層兼染着促進層用形成用の混合糊液として、ソルビトーゼC-5(エーテル化澱粉:AVEBE社製)20g、FDアルギンBL(アルギン酸ソーダ:古川化学工業社製)20g、EX-100(タマリンドガム:トモエ製糊社製)20g、酒石酸40g及びイオン交換水400g(計500g)の混合物を、高速デスパー型攪拌機(3,000rpm)でよく攪拌し、均一で滑らかな高粘度ペーストを作製した。この高粘度ペーストに、市販の脱気剤又は消泡剤を、高粘度ペーストに対して0.2%加えて泡を消し、塗工機(横山製作所社製コンマコーター)を使用して紙(日本製紙社製、晒しクラフト紙、坪量60g/m2)に均一に塗工・乾燥した。混合糊液の塗工量(乾燥重量)は8g/m2であった。この様にして転写捺染用紙を得た。 Example 1
As a mixed paste for forming an ink receiving layer and a dyeing acceleration layer, 20 g of sorbitole C-5 (etherified starch: manufactured by AVEBE), 20 g of FD algin BL (soda alginate: manufactured by Furukawa Chemical Co., Ltd.), EX-100 (Tamarind gum: manufactured by Tomoe Glue Co., Ltd.) A mixture of 20 g, tartaric acid 40 g and ion-exchanged water 400 g (total 500 g) was thoroughly stirred with a high-speed desper type stirrer (3,000 rpm) to produce a uniform and smooth high-viscosity paste. did. To this high-viscosity paste, 0.2% of a commercially available degassing agent or antifoaming agent is added to the high-viscosity paste to eliminate the foam, and paper (using a coater manufactured by Yokoyama Seisakusho Co., Ltd.) Nippon Paper Industries Co., Ltd., bleached kraft paper, basis weight 60 g / m 2 ) were uniformly coated and dried. The coating amount (dry weight) of the mixed paste was 8 g / m 2 . In this way, a transfer printed paper was obtained.
ソルビトーゼC-5(エーテル化澱粉:AVEBE社製)10g、FDアルギンBL(アルギン酸ソーダ:古川化学工業社製)5g、EX-100(タマリンドガム:トモエ製糊社製)5g、ペノンJE66(加工澱粉:日澱化学社製)10g、酒石酸10g及びイオン交換水170g(計210g)の混合物を、高速デスパー型攪拌機(3,000rpm)でよく攪拌し、均一で滑らかな高粘度ペーストを作製した。この高粘度ペーストに脱気剤及び消泡剤を少量加え、かつ、防腐剤、防かび剤を微量加え、更に水を加えて粘度を約1200mPa・sに調整し混合糊液を得た。塗工機としてエアナイフコーターを使用して、得られた混合糊液を、原紙(日本製紙社製、片艶クラフト紙、坪量60g/m2)に均一に塗工・乾燥して、転写捺染用紙を得た。混合糊液の塗工量(乾燥重量)は10g/m2であった。 Example 2
Solbitose C-5 (etherified starch: manufactured by AVEBE) 10 g, FD algin BL (sodium alginate: manufactured by Furukawa Chemical Co., Ltd.) 5 g, EX-100 (tamarind gum: manufactured by Tomoe Glue Co., Ltd.), Penon JE66 (modified starch) : Nissho Chemical Co., Ltd.) 10 g, tartaric acid 10 g and ion-exchanged water 170 g (total 210 g) were thoroughly stirred with a high-speed desper type stirrer (3,000 rpm) to produce a uniform and smooth high-viscosity paste. A small amount of degassing agent and antifoaming agent was added to this high viscosity paste, and a small amount of preservatives and fungicides were added, and water was further added to adjust the viscosity to about 1200 mPa · s to obtain a mixed paste solution. Using an air knife coater as a coating machine, the obtained mixed paste is uniformly coated and dried on a base paper (manufactured by Nippon Paper Industries Co., Ltd., glossy kraft paper, basis weight 60 g / m 2 ), and transfer printing. Got the paper. The coating amount (dry weight) of the mixed paste was 10 g / m 2 .
酒石酸40gの代わりにクエン酸20gを加える以外は実施例1と同様に処理して混合糊液の作製と紙への塗工を行い、転写捺染用紙を得た。得られた転写捺染用紙上に、分散染料インク液(C.I.Disperse Red92:5%、エチレングリコール5%、グリセリン15%、ノニオン系分散剤5%、アニオン系分散剤5%、イオン交換水64%)を、インクジェットプリンター(ローランド社製インクジェットプリンター:SoljetProIIIXJ-640)により、柄模様のプリントを行い乾燥し、転写捺染紙を得た。 Example 3
Except for adding 20 g of citric acid instead of 40 g of tartaric acid, the same procedure as in Example 1 was carried out to prepare a mixed paste and apply it to paper to obtain a transfer printed paper. Disperse dye ink liquid (CI Disperse Red 92: 5%, ethylene glycol 5%, glycerin 15%, nonionic dispersant 5%, anionic dispersant 5%, ion-exchanged water on the resulting transfer printing paper. 64%) was printed with a pattern using an inkjet printer (an inkjet printer manufactured by Roland: Soljet ProIIIXJ-640) and dried to obtain a transfer printed paper.
酒石酸の量を40gから4gに変え、加熱・加圧の条件を、転写圧力0.05MPa、転写温度195℃、処理時間120秒に変えた以外は実施例1と同様に処理した結果、実施例1と同様な堅牢な捺染製品を得た。 Example 4
As a result of processing in the same manner as in Example 1 except that the amount of tartaric acid was changed from 40 g to 4 g and the heating and pressing conditions were changed to a transfer pressure of 0.05 MPa, a transfer temperature of 195 ° C., and a processing time of 120 seconds. A robust printed product similar to 1 was obtained.
酒石酸40gの代わりにクエン酸20gを使用し、混合糊液に、更にマイクロイドKM386P(シリカゲル:KDCorp.社製)を、混合糊液に対して1%加える以外は実施例1と同様に処理した結果、得られたポリエステルタフタの捺染布は繊細なデザインを有し(判定は○)、繊維の風合は柔軟で、耐光、昇華、汗、洗濯等の各種堅牢性も良好であった。 Example 5
20 g of citric acid was used in place of 40 g of tartaric acid, and treatment was performed in the same manner as in Example 1 except that 1% of microid KM386P (silica gel: manufactured by KD Corp.) was added to the mixed paste. As a result, the polyester taffeta printed fabric obtained had a delicate design (judgment was ◯), the fiber texture was soft, and various fastness properties such as light resistance, sublimation, sweat and washing were also good.
インク受容層兼染着促進層用形成用の混合糊液として、ゴーセノールGL-05(水溶性ポリビニルアルコール:日本合成化学社製)20g、ファインガムHEL-3(セルロース誘導体:第一工業薬品社製)50g、EX-200(タマリンドガム:トモエ製糊社製)50g、尿素50g、特AクレイKL-18:20g、マイクロイドKM-386P:10g、クエン酸25g、酒石酸25g、水750gの混合物を、5,000rpmの高速デスパー型攪拌機でよく攪拌し、高粘度のペーストを作製した。この高粘度のペーストの粘度を調整した後、コンマコーターを使用して原紙(日本製紙社製、銀竹、50g/m2)に塗工し乾燥して、転写捺染用紙を得た。この転写捺染用紙に3MPaの圧力でカレンダー加工して、平滑処理した。糊塗布量は12g/m2であった。得られた転写捺染用紙上に、分散染料グラビアインク液(C.I.Disperse Red86製品:15%を含有し、水、セルロース系増粘剤、ポリビニルアルコール及びイソプロパノールを用いて粘度を120mPasに調整したインキ)をグラビア印刷機によりプリントを行い乾燥して転写捺染紙を得た。 Example 6
As a mixed paste for forming the ink receiving layer and dyeing acceleration layer, Goosenol GL-05 (water-soluble polyvinyl alcohol: manufactured by Nippon Synthetic Chemical Co., Ltd.) 20 g, Fine Gum HEL-3 (cellulose derivative: manufactured by Daiichi Kogyo Kagaku Co., Ltd.) ) 50 g, EX-200 (Tamarind gum: manufactured by Tomoe Glue Co., Ltd.) 50 g, urea 50 g, special A clay KL-18: 20 g, microid KM-386P: 10 g, citric acid 25 g, tartaric acid 25 g, water 750 g The mixture was stirred well with a high-speed despar-type stirrer at 5,000 rpm to prepare a high-viscosity paste. After adjusting the viscosity of this high-viscosity paste, using a comma coater, it was applied to a base paper (Nippon Paper Industries Co., Ltd., silver bamboo, 50 g / m 2 ) and dried to obtain a transfer printed paper. This transfer textile sheet was calendered at a pressure of 3 MPa and smoothed. The amount of glue applied was 12 g / m 2 . Disperse dye gravure ink liquid (CI Disperse Red86 product: 15% was contained on the obtained transfer printing paper, and the viscosity was adjusted to 120 mPas using water, cellulose thickener, polyvinyl alcohol and isopropanol. Ink) was printed by a gravure printing machine and dried to obtain a transfer printed paper.
ハシマ社製平型昇華転写機の代わりに、井上金属工業社製のドラム型連続式サーモプリンターを用い、ドラム表面温度220℃、圧力0.5MPaでポリエステル繊維材料と転写捺染紙の熱ドラム接触滞留時間が30秒となるようにした以外は、実施例6と同様に処理した結果、繊維材料の良好な発色性(○)を示した。 Example 7
Using a drum-type continuous thermo printer manufactured by Inoue Metal Industry Co., Ltd. instead of a flat-type sublimation transfer machine manufactured by Hashima Co., Ltd., a drum surface temperature of 220 ° C and a pressure of 0.5 MPa. As a result of processing in the same manner as in Example 6 except that the time was 30 seconds, the fiber material exhibited good color developability (◯).
ハシマ社製平型昇華転写機の代わりに、由利ロール社製2本ロール加圧・加熱機を用い、熱ロールの表面温度230℃、圧力3MPa、送り速度1m/minの条件で、繊維材料と転写捺染紙の熱ロール接触滞留時間が20秒となるようにした以外は、実施例1と同様に処理した結果、繊維材料の良好な発色性(○)を示した。 Example 8
In place of the flat sublimation transfer machine manufactured by HASHIMA, a two-roll pressurizing / heating machine manufactured by Yuri Roll Co., Ltd. was used, under the conditions of a hot roll surface temperature of 230 ° C, a pressure of 3 MPa, and a feed rate of 1 m / min. As a result of processing in the same manner as in Example 1 except that the heat roll contact residence time of the transfer printed paper was 20 seconds, good color developability (◯) of the fiber material was exhibited.
市販のA社昇華転写捺染用紙、銘柄a、銘柄b、銘柄c、銘柄dの4種類に実施例1で使用した分散染料インクを用いて印刷して転写捺染紙を作製し、転写捺染紙を変えた以外は実施例1と同様に転写捺染をした結果、発色性(染色力の判定は△~×)は、いずれの場合も実施例1に比べて劣っており実用上問題があると判定された。 Comparative Example 1
Printing is performed on four types of commercially available company A's sublimation transfer printing paper, brand a, brand b, brand c, and brand d using the disperse dye ink used in Example 1. As a result of transfer printing in the same manner as in Example 1 except that the color was changed, the color development (determination of dyeing power was △ to ×) was inferior to that in Example 1 in each case, and it was determined that there was a problem in practical use. It was done.
市販のB社昇華転写捺染用紙、C社昇華転写捺染用紙を用い、転写捺染用紙を変えた以外は実施例1と同様に、転写捺染紙の作製、転写捺染をした結果、発色性は実施例1に比べて著しく劣っていた(染色性の判定は×)。 Comparative Example 2
Using the commercially available B company sublimation transfer printing paper and the C company sublimation transfer printing paper, except that the transfer printing paper was changed, the transfer printing paper was prepared and the transfer printing was carried out in the same manner as in Example 1. It was remarkably inferior to 1 (stainability was judged as x).
市販のA社昇華転写捺染用紙銘柄aに、昇華染料C.I.Disperse Red60を含有するインクで印刷し、圧力を0.15MPaで処理する以外は実施例1と同様に処理したところ、発色性は良好であった。しかし、非昇華染料C.I.Disperse Red92を含有するインクで印刷し、圧力0.15MPaで処理する以外は実施例1と同様に処理したところ発色性は不良(△)であった。 Comparative Example 3
A sublimation dye C.I. I. When printing was performed with an ink containing Disperse Red 60 and the treatment was performed in the same manner as in Example 1 except that the pressure was treated at 0.15 MPa, the color development was good. However, non-sublimation dyes C.I. I. The color developability was poor (Δ) when treated in the same manner as in Example 1 except that printing was performed with an ink containing Disperse Red 92 and the treatment was performed at a pressure of 0.15 MPa.
酒石酸を加えない以外は、実施例2と同様にして加工したところ、繊維材料の発色性は不十分(染色性の判定は△)であり斑が生じていた。 Comparative Example 4
When processed in the same manner as in Example 2 except that tartaric acid was not added, the coloring property of the fiber material was insufficient (judgment determination was Δ), and spots were generated.
ファインガムHEL-3(カルボキシメチルセルロースナトリウム:第一工業製薬社製)20部、FDアルギンBL(アルギン酸ソーダ:古川化学工業社製)20部、EX-100(タマリンドガム:トモエ製糊社製)10部及びイオン交換水400部(計450部)の混合物を、高速デスパー型攪拌機(3,000rpm)でよく攪拌し、均一で滑らかな高粘度ペースト(混合糊液)を作製した。混合糊液に市販の脱気剤、消泡剤を加えて泡を消した。 Example 9
Fine gum HEL-3 (sodium carboxymethylcellulose: Daiichi Kogyo Seiyaku Co., Ltd.) 20 parts, FD Algin BL (sodium alginate: Furukawa Chemical Co., Ltd.) 20 parts, EX-100 (Tamarind gum: Tomoe Glue Co., Ltd.) 10 And a mixture of 400 parts of ion-exchanged water (450 parts in total) were sufficiently stirred with a high-speed desper type stirrer (3,000 rpm) to prepare a uniform and smooth high-viscosity paste (mixed paste). Bubbles were extinguished by adding a commercially available degassing agent and antifoaming agent to the mixed paste.
ポバールAP-17(カルボキシ変性PVA、日本酢ビ・ポバール社製)10部、FDアルギンBL:20部、EX-100:10部、イオン交換水200部(計240部)の混合物を、高速デスパー型攪拌機(3,000rpm)でよく攪拌し、均一で滑らかな高粘度ペースト(混合糊液)を作製した。泡が生じたので、混合糊液に市販の脱気剤、消泡剤を加えて泡を消した。更に防腐剤、防かび剤を微量加えた。 Example 10
A mixture of 10 parts of Poval AP-17 (carboxy-modified PVA, manufactured by Nippon Vinegar Pover Co., Ltd.), FD Argin BL: 20 parts, EX-100: 10 parts, and 200 parts of ion-exchanged water (240 parts in total) The mixture was thoroughly stirred with a mold stirrer (3,000 rpm) to prepare a uniform and smooth high-viscosity paste (mixed paste). Since foam was generated, the foam was removed by adding a commercially available degassing agent and antifoaming agent to the mixed paste liquid. Further, a small amount of preservatives and fungicides were added.
実施例9に於ける混合糊液の代わりに、FDアルギンBLの10%水溶液55部に、粉末硫酸バンド(大明化学工業社製)の5%水溶液10部を加えたものを混合糊液として用いる以外は、実施例9と同様にして紙への塗工を行って転写捺染用紙を得た。 Example 11
Instead of the mixed paste in Example 9, a mixture of 55 parts of a 10% aqueous solution of FD-Algin BL and 10 parts of a 5% aqueous solution of powdered sulfuric acid band (Daimei Chemical Co., Ltd.) is used as the mixed paste. Except for the above, application to paper was carried out in the same manner as in Example 9 to obtain a transfer textile sheet.
実施例9に於ける混合糊液の代わりにEX-3(カチオン化澱粉、日澱化学社製)10%水溶液100部、FDアルギンBLの10%水溶液100部からなる混合糊液を用いる以外は、実施例9と同様にしてポリエステルタフタ捺染布を得た。得られたポリエステルタフタ捺染布の発色性は良好で繊細なデザインを有し、繊維の風合は柔軟で、耐光、昇華、汗、洗濯等の各種堅牢性も良好であった。 Example 12
Instead of the mixed paste in Example 9, a mixed paste consisting of 100 parts of EX-3 (cationized starch, manufactured by Nissho Chemical Co., Ltd.) 10% aqueous solution and 100 parts of 10% aqueous solution of FD-Algin BL was used. In the same manner as in Example 9, a polyester taffeta printed fabric was obtained. The resulting polyester taffeta printed fabric had good color development and a delicate design, the fiber texture was soft, and various fastness properties such as light resistance, sublimation, sweat and washing were also good.
ブリバイン(燐酸化澱粉、日澱化学社製)10部、ファインガムHEL-3:50部、EX-200(タマリンドガム:トモエ製糊社製)10部、ゴーセノールGL-05(水溶性ポリビニルアルコール:日本合成化学社製)20部、マイクロイドKM-386P:10部、酒石酸50部及び水650部の混合物を、5,000rpmの高速デスパー型攪拌機でよく攪拌し、均一で滑らかな高粘度ペースト(混合糊液)を作製した。この高粘度ペーストの粘度を調整した後、コンマコーターを使用して原紙(日本製紙社製、片艶紙50g/m2)に、塗工・乾燥して、分散染料用の転写捺染用紙を作製した。この転写捺染用紙の糊塗布量は7.5g/m2であった。 Example 13
10 parts of brivine (phosphorylated starch, manufactured by Nissho Chemical Co., Ltd.), 50 parts of fine gum HEL-3, 10 parts of EX-200 (manufactured by Tomoe Glue Co., Ltd.), Gohsenol GL-05 (water-soluble polyvinyl alcohol: Nippon Synthetic Chemical Co., Ltd.) 20 parts, Microid KM-386P: 10 parts, tartaric acid 50 parts and water 650 parts were mixed well with a high-speed desper type stirrer at 5,000 rpm to obtain a uniform and smooth high-viscosity paste ( A mixed paste) was prepared. After adjusting the viscosity of this high-viscosity paste, use a comma coater to coat and dry the base paper (manufactured by Nippon Paper Industries Co., Ltd., single glossy paper 50 g / m 2 ) to produce a transfer printing paper for disperse dyes. did. The amount of paste applied to this transfer textile paper was 7.5 g / m 2 .
実施例9に於けるハシマ社製平型昇華転写機の代わりに、ロール型昇華転写機を用い、熱ロールの表面温度210℃、ロール圧力2MPa(ニップ幅3cm)の条件で、生地(繊維材料)と転写捺染紙の熱ロール接触時間が30秒となるようにした以外は、実施例9と同様に処理した結果、良好な繊維材料の発色性を示した。 Example 14
In place of the flat sublimation transfer machine manufactured by Hashima in Example 9, a roll type sublimation transfer machine was used under the conditions of a hot roll surface temperature of 210 ° C. and a roll pressure of 2 MPa (nip width 3 cm). ) And the heat-transfer contact time of the transfer printed paper was 30 seconds. As a result of processing in the same manner as in Example 9, good color development of the fiber material was exhibited.
実施例9に於ける混合糊液(高粘度ペースト)の代わりにファインガムHEL-3:20部、EX-3:10部、EX-100:20部及び水400部を混合して作製した混合糊液を用いる以外は実施例9と同様に処理した結果、ポリエステル捺染布の発色性は良好で繊細なデザインを有し、繊維の風合は柔軟で、耐光、昇華、汗、洗濯等の各種堅牢性も良好であった。 Example 15
A mixture prepared by mixing fine gum HEL-3: 20 parts, EX-3: 10 parts, EX-100: 20 parts and water 400 parts instead of the mixed paste liquid (high viscosity paste) in Example 9. As a result of processing in the same manner as in Example 9 except that the paste solution was used, the color of the polyester printed fabric was good and had a delicate design, the texture of the fiber was flexible, and various kinds of light resistance, sublimation, sweat, washing, etc. The fastness was also good.
実施例9に於ける混合糊液(高粘度ペースト)の代わりにブリバイン(燐酸化澱粉、日澱化学社製)10%水溶液100部、FDアルギンBLの10%水溶液100部を混合して作製した混合糊液を用いる以外は実施例9と同様に処理した結果、ポリエステル捺染布の発色性は良好で繊細なデザインを有し、繊維の風合は柔軟で、耐光、昇華、汗、洗濯等の各種堅牢性も良好であった。 Example 16
Instead of the mixed paste liquid (high viscosity paste) in Example 9, 100 parts of a 10% aqueous solution of brivain (phosphorylated starch, manufactured by Nissho Chemical Co., Ltd.) and 100 parts of a 10% aqueous solution of FD-Algin BL were prepared. As a result of the same treatment as in Example 9 except that the mixed paste was used, the polyester printed fabric had good color development and a delicate design, and the texture of the fiber was flexible, such as light resistance, sublimation, sweat, washing, etc. Various fastnesses were also good.
加熱、加圧の条件を、転写温度190℃、転写圧力0.01MPa、時間60秒とした以外は、実施例9及び10と同様に処理した結果、発色性は実施例9及び10に比べて劣っていた。ただし、温度を200℃、圧力を0.02MPa、時間を3分としたところ発色性は良好となった。 Example 17
As a result of processing in the same manner as in Examples 9 and 10 except that the heating and pressurizing conditions were a transfer temperature of 190 ° C., a transfer pressure of 0.01 MPa, and a time of 60 seconds, the color developability was higher than that of Examples 9 and 10. It was inferior. However, when the temperature was 200 ° C., the pressure was 0.02 MPa, and the time was 3 minutes, the color development was good.
転写捺染紙として市販の昇華転写捺染用紙JetcolTA(コールデンホーブ社製)を用いて実施例9の非昇華型分散染料からなるインクで印刷して転写捺染紙を得た。次いで、この転写捺染紙とポリエステルタフタと密着させて210℃、0.02MPa、40秒間で発色試験したところ発色性は不良であった。 Comparative Example 5
A commercially available sublimation transfer printing paper JetcolTA (manufactured by Caldenhove) was used as the transfer printing paper and printed with the ink comprising the non-sublimation type disperse dye of Example 9 to obtain a transfer printing paper. Next, when this transfer printed paper and polyester taffeta were brought into close contact with each other, a color development test was conducted at 210 ° C. and 0.02 MPa for 40 seconds.
Claims (11)
- 糊剤を原紙に付与した転写捺染用紙に、分散染料インクを用いて印刷した転写捺染紙を、ポリエステル系繊維材料に密着して加圧・加熱して転写捺染する転写捺染法であって、
前記分散染料インクが、非昇華型分散染料インクであり、
前記糊剤が、
カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤、又は、
天然ガム糊、繊維素誘導体及び多糖類から選ばれ、更にカルボン酸化合物類が配合された糊剤である事を特徴とするポリエステル系繊維材料の転写捺染法。 A transfer printing method in which transfer printing paper printed with disperse dye ink on a transfer printing paper provided with a paste is applied to a polyester fiber material and pressed and heated to transfer printing,
The disperse dye ink is a non-sublimation disperse dye ink,
The glue is
A paste having a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group; Or
A transfer printing method for polyester fiber materials, characterized in that it is a paste selected from natural gum paste, fiber derivatives and polysaccharides and further mixed with carboxylic acid compounds. - 前記糊剤が、動物系糊料及び植物系糊料からなる群より選ばれる1種以上である事を特徴とする請求項1に記載のポリエステル系繊維材料の転写捺染法。 The transfer printing method for a polyester fiber material according to claim 1, wherein the paste is at least one selected from the group consisting of animal glues and plant glues.
- 前記糊剤が、カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤であって、更にカルボン酸化合物類が配合されているものである事を特徴とする請求項1又は請求項2に記載のポリエステル系繊維材料の転写捺染法。 The glue is a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester form, an amide form, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group. The transfer printing method for a polyester fiber material according to claim 1 or 2, wherein the paste further comprises a carboxylic acid compound.
- 前記カルボン酸化合物類が、脂肪族系カルボン酸及び芳香族系カルボン酸からなる群より選ばれる1種以上である事を特徴とする請求項1ないし請求項3のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 The polyester according to any one of claims 1 to 3, wherein the carboxylic acid compound is at least one selected from the group consisting of an aliphatic carboxylic acid and an aromatic carboxylic acid. Transfer printing method of fiber materials.
- 前記糊剤に、更に強酸と弱塩基からなる塩である弱酸性化合物、鉱物系酸性化合物及び鉱物系添加剤からなる群より選ばれる1種以上が配合される事を特徴とする請求項1ないし請求項4のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 2. The paste according to claim 1, further comprising at least one selected from the group consisting of a weak acid compound, a mineral acid compound, and a mineral additive, which is a salt composed of a strong acid and a weak base. The transfer printing method of the polyester-type fiber material of any one of Claim 4.
- 前記糊剤に、更に助剤が配合される事を特徴とする請求項1ないし請求項3のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 The transfer printing method for a polyester fiber material according to any one of claims 1 to 3, wherein an auxiliary agent is further added to the paste.
- 前記非昇華型分散染料インクが、平均粒径0.2~10μmに微粒化された分散染料を用いて作製されたグラビアインク若しくはフレキソインク、又は、平均粒径0.05~0.2μmに微粒化された分散染料を用いて作製されたインクジェットインクであり、前記分散染料が、Sタイプ又はSEタイプの分散染料からなる群から選ばれる1種以上の非昇華型分散染料である事を特徴とする請求項1ないし請求項6のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 The non-sublimation type disperse dye ink is a gravure ink or flexo ink prepared using a disperse dye atomized to an average particle size of 0.2 to 10 μm, or fine particles of an average particle size of 0.05 to 0.2 μm An ink-jet ink produced using a disperse dye, wherein the disperse dye is one or more non-sublimation disperse dyes selected from the group consisting of S-type and SE-type disperse dyes. The transfer printing method for polyester fiber materials according to any one of claims 1 to 6.
- 前記ポリエステル系繊維材料が、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸、解重合ポリエステル、カチオン可染ポリエステル、常温可染ポリエステル及びアルカリ減量ポリエステルからなる群から選ばれるポリエステル系高分子の
織物、編物、不織布、シート若しくはフイルム、又は、前記織物、編物若しくは不織布と、天然繊維及び前記ポリエステル系高分子以外の合成繊維から選ばれる繊維との混紡、混繊、交織品若しくは複合材料である事を特徴とする請求項1ないし請求項7のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 The polyester fiber material is a polyester polymer selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, depolymerized polyester, cationic dyeable polyester, room temperature dyeable polyester, and alkali weight loss polyester. A woven fabric, a knitted fabric, a nonwoven fabric, a sheet or a film, or a blend, a mixed fiber, a woven fabric or a composite material of the woven fabric, the knitted fabric or the nonwoven fabric and a fiber selected from natural fibers and synthetic fibers other than the polyester polymer. The transfer printing method for a polyester fiber material according to any one of claims 1 to 7, characterized in that: - 前記転写捺染が、転写温度が150~250℃、転写圧が0.01MPa以上で加圧・加熱して行われる事を特徴とする請求項1ないし請求項8のいずれか1項に記載のポリエステル系繊維材料の転写捺染法。 The polyester according to any one of claims 1 to 8, wherein the transfer printing is performed by applying pressure and heating at a transfer temperature of 150 to 250 ° C and a transfer pressure of 0.01 MPa or more. Transfer printing method of fiber materials.
- 原紙に、
カルボキシル基、スルフォン基及び燐酸基から選ばれる酸性基、前記酸性基のエステル体、アミド体、アルカリ金属塩若しくはアルカリ土類金属塩、及びカチオン基からなる群より選ばれる官能基を有する糊剤、又は、
天然ガム糊、繊維素誘導体及び多糖類から選ばれ、更にカルボン酸化合物類が配合された糊剤を付与する事を特徴とする転写捺染用紙の製造方法。 On the base paper,
A paste having a functional group selected from the group consisting of an acidic group selected from a carboxyl group, a sulfone group and a phosphoric acid group, an ester body, an amide body, an alkali metal salt or an alkaline earth metal salt of the acidic group, and a cationic group; Or
A method for producing a transfer printing paper, characterized by applying a paste selected from natural gum paste, fiber derivatives and polysaccharides and further containing carboxylic acid compounds. - 請求項1ないし請求項9のいずれか1項に記載のポリエステル系繊維材料の転写捺染法により、ポリエステル系繊維材料に転写捺染をする工程を有する事を特徴とするポリエステル系繊維材料の製造方法。 A method for producing a polyester fiber material, comprising a step of performing transfer printing on a polyester fiber material by the transfer printing method for a polyester fiber material according to any one of claims 1 to 9.
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CN108699765A (en) | 2018-10-23 |
JPWO2017111107A1 (en) | 2017-12-21 |
JP6173641B1 (en) | 2017-08-02 |
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