TWI732456B - Transfer printing paper and transfer printing method - Google Patents

Abstract

The subject of the present invention is to provide a transfer paper with good adhesion to the fiber material and good color density of the pattern formed on the fiber material, good peeling, and no difference in texture between the pattern area and the non-pattern area of the fiber material. The present invention provides a transfer paper having: a substrate with one or more non-aqueous resin laminated layers on one side of the base paper, and one or more layers on the laminated layer of the base paper The coating layer, the outermost coating layer located on the basis of the substrate in the coating layer contains a white pigment and a binder, the white pigment at least contains amorphous silicon dioxide, and the binder contains at least There are five types of water-soluble polyester resin, carboxylic acid modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch and alginate.

Description

Transfer printing paper and transfer printing method

The present invention relates to a transfer printing paper for transferring patterns in a transfer printing method for forming patterns on fiber materials, and a transfer printing method using the transfer printing paper. In particular, it relates to a transfer printing paper and transfer printing method suitable for the case where the fiber material is cotton.

Regarding the printing paper that obtains the performance of fine printing patterns with good reproducibility and excellent leveling property and soft fiber texture, the following printing papers are known: they are used in transfer printing methods, and the transfer printing method uses The ink containing the dye prints the pattern on the printing paper to obtain the printing paper. The printing paper is adhered to the fiber material or leather material by heating and pressurizing the printing paper to transfer the dye. The dye fixing process is carried out in the state of the printing paper, and the printing paper has an ink receiving layer and an adhesive layer. The ink receiving layer and adhesive layer is made by adjusting the blending ratio of the natural paste to the water-soluble synthetic adhesive. The solid content is converted into the range of 5% to 0%, and the hydrophilic mixture mixed with various additives is coated, sprayed or immersed in the base paper and then dried and absorbed or laminated on the paper (for example, refer to the patent document 1). Prior art literature Patent literature

[Patent Document 1] JP 2016-102283 A

[The problem to be solved by the invention]

In the transfer printing method, the transfer paper is in close contact with the fiber material, and the dye accepted by the transfer paper is transferred to the fiber material. In the printing industry that effectively utilizes the transfer printing method, in terms of work efficiency and the quality of the pattern formed on the fiber material, the following items are required. (1) The transfer paper adheres well to the fiber material. (2) The color density of the pattern formed on the fiber material is good. (3) The transfer paper peels well from the fiber material after the dye transfer. (4) There is little difference in texture between the patterned fiber material area and the unpatterned fiber material area. Regarding (1) When the situation is not good, the work efficiency of transfer printing is reduced, or the formed pattern produces distortion or image blur that becomes a problem in practical aspects. Regarding (2) In the case of unsatisfactory circumstances, it is not valid as a commodity. Regarding (3) When the situation is not good, the work efficiency of transfer printing is reduced, or the pattern formed on the fiber material is defective. Regarding (4), if the difference in texture is large, the value of the product decreases. Especially when the fiber material is cotton, in the area where the pattern is formed, the soft skin touch of cotton is impaired, so it is not good.

In the printing transfer method described in Patent Document 1, in a state where the transfer paper is in close contact with the fibrous material, dye fixing treatment such as steaming treatment is performed. The reason is that the water-soluble synthetic adhesive and natural paste are softened by the steaming treatment, and the transfer paper becomes easy to peel from the fiber material. However, in the dye fixing process in the state where the transfer paper is in close contact with the fibrous material, the adhesion between the transfer paper and the fibrous material is rich in thickness, so there are problems in the transportation and operation of the fixing treatment device. In addition, in the fixing process of dyes in a state where the transfer paper is in close contact with the fibrous material, there are cases where the dye remaining on the transfer paper causes fog during the fixing process of the dyes. "Fog" is the phenomenon of dye transfer in areas where there is no original pattern. The representative fog is the spot fog that produces the transfer of the dye in the form of spots in the area where there is no pattern. On the other hand, it is difficult to peel the transfer paper from the fiber material after the transfer paper is adhered to the fiber material and heated and pressurized, and before the dye fixing process such as steaming treatment is performed. Even in the case of peeling, there are also cases where defects such as defects are generated in the pattern formed on the fiber material.

In view of the above, the object of the present invention is to provide a transfer paper that can be peeled from the fiber material after the fiber material is closely attached to the transfer paper and heated and pressurized and before the dye fixation process, that is, meets the above (3) and satisfies The transfer paper of (1), (2) and (4) above. [Technical means to solve the problem]

The inventors of the present invention made repeated efforts to solve the above-mentioned problems, and as a result, the object of the present invention was achieved by the following.

[1] A transfer paper, which is a transfer paper before printing a pattern used in a transfer printing method, the transfer printing method including the step of printing the pattern on the transfer paper using an ink containing a dye to obtain the transfer paper , The step of transferring the dye from the transfer paper to the fiber material by adhering the above transfer paper to the fiber material and heating and pressing, the step of peeling the transfer paper from the fiber material after the transfer step, and the step of peeling off the transfer paper after the peeling step Steps of dye fixing treatment of fiber material; The transfer paper has: a substrate having one or more non-aqueous resin laminate layers on one side of the base paper, and one or more coating layers on the laminate layer of the above-mentioned substrate; Among the above-mentioned coating layers, the outermost coating layer on the basis of the above-mentioned substrate contains a white pigment and a binder, The above-mentioned white pigment contains at least amorphous silicon dioxide, The adhesive includes at least five types: water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate.

[2] The transfer paper as described in [1] above, wherein, in at least one aspect, the outermost coating layer includes a water-soluble polyester resin, a carboxylic acid-modified polyvinyl alcohol resin, and an acrylic resin The content of each of hydroxypropyl starch and alginate is as follows: relative to 20 parts by mass of the white pigment in the outermost coating layer, the water-soluble polyester resin is 5 parts by mass or more and 30 parts by mass or less, modified by carboxylic acid Polyvinyl alcohol resin is 10 parts by mass or more and 35 parts by mass or less, acrylic resin is 5 parts by mass or more and 25 parts by mass or less, hydroxypropyl starch is 10 parts by mass or more and 35 parts by mass or less, and alginate is 3 parts by mass Part or more and 15 parts by mass or less. As the content of each meets their respective ranges, the adhesion between the fiber material of the transfer paper and the transfer paper, the peeling of the transfer paper from the fiber material, the color density of the pattern formed on the fiber material, and/or the pattern area of the fiber material No difference in texture between non-patterned areas is optimized.

[3] The transfer paper as described in [1] or [2] above, wherein, in at least one aspect, the outermost coating layer contains fatty acid ester. Since the outermost coating layer contains fatty acid esters, the transfer paper optimizes the color density of the pattern formed on the fiber material and the peeling of the transfer paper from the fiber material. [4] A transfer printing method, including the step of obtaining a transfer paper, the transfer paper having a substrate having one or more non-aqueous resin laminated layers on one side of the base paper, and the substrate One or two or more coating layers on the laminated layer. Among the coating layers, the outermost coating layer on the basis of the substrate contains a white pigment and a binder, and the white pigment is at least Containing amorphous silicon dioxide, the above-mentioned adhesive includes at least five types of water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate; The step of printing a pattern on the above transfer paper by using an ink containing a dye to obtain a transfer paper; The step of transferring the dye from the transfer paper to the fiber material by closely adhering the transfer paper to the fiber material and heating and pressing; The step of peeling off the transfer paper from the fiber material after the above transfer step; and The step of fixing the dyestuff on the fiber material after the above-mentioned peeling step. [Effects of Invention]

By means of the present invention, it is possible to provide a transfer paper and transfer printing method that meet the following conditions: (1) the transfer paper has good adhesion to the fiber material, (2) the color density of the pattern formed on the fiber material is good, (3) the transfer printing The printing paper peels well from the fiber material after the dye transfer, and (4) there is no difference in texture between the patterned fiber material area and the unpatterned fiber material area.

The present invention will be described in detail below. In the present invention, "transfer paper" refers to paper in the state of white paper before the transferred pattern is printed. "Transfer paper" refers to the paper in a state where the transferred pattern is printed on the transfer paper. In addition, in the present invention, "having a layer" means having a clear layer that can be distinguished from the base paper or the base material when the cross-section of the transfer paper is observed by an electron microscope. For example, when a resin component or a polymer component is coated, the amount of the above-mentioned components coated is small and is absorbed by the base paper or the substrate. As a result, when the cross-section of the transfer paper is observed by an electron microscope, it is not distinguishable from the base paper or the substrate. The situation of the clear layers does not conform to the "having layers".

[Transfer Paper] The first embodiment of the present invention is transfer paper. The transfer paper has a substrate having one or more non-aqueous resin laminate layers on one side of the base paper, and one or more coating layers on the laminate layer of the above-mentioned substrate. Among the coating layers, the coating layer located on the outermost side based on the base material is referred to as the outermost coating layer. When the coating layer is one layer, the coating layer becomes the outermost coating layer. The outermost coating layer contains white pigments and adhesives. The white pigment includes at least amorphous silica. The adhesive includes at least five types: water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate. In the case of two or more coating layers, the coating layer existing between the substrate and the outermost coating layer is a previously known coating layer in the field of coated paper. Regarding the presence and type of white pigment, and adhesion There are no special restrictions on the availability and types of agents. In addition, the coating layer existing between the substrate and the outermost coating layer may contain various additives previously known in the field of coated paper.

From the viewpoint of the production cost of the transfer paper, the coating layer is preferably one layer. In addition, the coating layer may exist on one side or both sides of the substrate. The coating layer is provided at least on the side of the substrate with the laminated layer. When the outermost coating layer of the present invention is present on one side of the substrate, the transfer paper may have a previously known post-coating layer on the back of the substrate.

The coating amount of the coating layer is not particularly limited. From the viewpoint of the production cost of the transfer paper and the ease of use, the coating amount is preferably 5 g/m ² or more and 70 g/m ² or less in terms of the amount of dry solid content per single side. The upper limit of the coating amount is more preferably 30 g/m ² or less. Furthermore, from the viewpoint of reducing the manufacturing cost and preventing the defect of the coating layer when the transfer paper and the fibrous material are in close contact, the coating amount is preferably 10 g/m ² or more and 30 g/m per side ² or less. When there are multiple coating layers on each single side, the coating amount is the total value.

The substrate is a laminated paper having one or more non-aqueous resin laminated layers on at least the side of the base paper on which the outermost coating layer is provided. In the present invention, since the transfer paper has the non-aqueous resin laminate layer and the outermost coating layer, when it is difficult to peel the outermost coating layer of the transfer paper from the fiber material, the substrate and the outermost coating layer are included. Peeling between the coating layers of the cloth layer can smoothly peel the fiber material from the transfer paper. After peeling, it may include a state where all or part of the coating layer is attached to the fiber material, but the coating layer can be removed by washing with water. As long as it is a transfer printing method that performs dye fixing treatment on the fiber material after the transfer paper is peeled from the fiber material, the transportation problems and operation difficulties in the fixing treatment device can be improved. Furthermore, when the substrate is laminated paper, when a pattern is printed on transfer paper using ink containing dye, the non-aqueous resin laminated layer prevents the dye from reaching the base paper, thereby further suppressing the formation on the fiber material. The pattern is defective and the color density is reduced.

The above-mentioned base paper pairs are selected from chemical pulps such as LBKP (Leaf Bleached Kraft Pulp) and NBKP (Needle Bleached Kraft Pulp), GP (Groundwood Pulp), PGW (Pressure GroundWood pulp), RMP (Refiner Mechanical Pulp), TMP (ThermoMechanical Pulp) , CTMP (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp), CGP (ChemiGroundwood Pulp) and other mechanical pulps and DIP (DeInked Pulp) and other waste paper pulps are blended with heavy calcium carbonate, light calcium carbonate, Papermaking made of various fillers such as talc, clay, kaolin and calcined kaolin, and then blended with various additives such as sizing agent, fixing agent, yield agent, cationizing agent, paper strength agent, etc., as necessary. . Furthermore, the base paper includes Dawlin paper that has been subjected to calendering treatment for papermaking, surface sizing treatment with starch or polyvinyl alcohol, or surface treatment. Furthermore, the base paper includes road forest paper that has been subjected to surface sizing treatment or surface treatment and then calendering treatment.

The papermaking system adjusts the paper stock to be acidic, neutral or alkaline, and is performed using a previously known papermaking machine. Examples of paper machines include Fourdrinier paper machines, two-wire paper machines, combined paper machines, cylinder paper machines, Yankee paper machines, and the like.

The basis weight of the base paper is not particularly limited. From the viewpoint of the ease of use of the paper, the basis weight of the base paper is preferably 10 g/m ² or more and 100 g/m ² or less, and more preferably 30 g/m ² or more and 100 g/m ² or less .

In the paper material, within the range that does not impair the desired effect of the present invention, it can be appropriately blended selected from other additives such as binders, pigment dispersants, tackifiers, fluidity improvers, defoamers, and foam inhibitors. Agents, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent brighteners, ultraviolet absorbers, antioxidants, preservatives, mold inhibitors, water resistance agents, wet paper strength enhancers and drying One or two or more of paper strength enhancers.

A substrate having a non-aqueous resin laminated layer on at least the side where the outermost coating layer is provided on the base paper can be obtained by providing a non-aqueous resin laminated layer on one side of the base paper. The non-aqueous resin laminated layer has the function of supporting the peeling of the transfer paper and the fiber material and the function of preventing the dye from penetrating into the base paper.

The non-aqueous resin laminated layer is mainly formed of a non-aqueous resin. The non-aqueous resin forming the non-aqueous resin laminated layer is a polyolefin resin, an ethylene resin, or a resin hardened by electron beam to form a water-insoluble layer on the base paper. Regarding non-aqueous resins, for example, polyethylenes such as high-density polyethylene, low-density polyethylene, medium-density polyethylene, and linear low-density polyethylene; same row, opposite row, miscellaneous row, mixtures of these, and Polypropylene such as random copolymers and block copolymers of ethylene; and polymethylpentene, polyethylene glycol terephthalate, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl alcohol copolymers, Ethylene-vinyl acetate copolymer, etc. Regarding the non-aqueous resin, one or two or more selected from the group consisting of these can be used.

The method of providing the non-aqueous resin laminated layer on the base paper is not particularly limited. For example, a method using a conventionally known laminating machine device such as a general melt extrusion die, a T-die, and a multi-layer simultaneous extrusion die can be cited. On one side of the base paper, the non-aqueous resin laminated layer is 1 layer or 2 layers or more. From the viewpoint of manufacturing cost, the non-aqueous resin laminated layer is preferably one layer. The non-aqueous resin laminated layer preferably has a thickness of 10 μm or more, more preferably 15 μm or more. The reason is that it has sufficient covering properties to base paper and has the above-mentioned function of obtaining a non-aqueous resin laminated layer. In addition, the thickness of the non-aqueous resin laminated layer is preferably 30 μm or less. The reason is that the above functions are saturated at 30 μm, and the material cost increases if it exceeds 30 μm. Regarding the thickness of the non-aqueous resin laminated layer, if the non-aqueous resin laminated layer is one layer, it means the thickness of the layer, and if the non-aqueous resin laminated layer is two or more layers, it means the total thickness of the layers.

The coating layer can be provided by applying the coating layer coating liquid to the substrate or the lower coating layer and drying it. The method of providing the coating layer is not particularly limited. For example, a method of coating and drying using a previously known coating device and drying device in the papermaking field can be cited. Examples of coating devices include: sizing press, gate roll coater, film transfer coater, knife coater, rod coater, air knife coater, and corner wheel coater (Comma Coater) (registered trademark), gravure coater, bar coater, E bar coater, curtain coater, etc. Examples of drying devices include hot air dryers such as linear tunnel dryers, arch dryers, air circulation dryers, and sinusoidal air flotation dryers, infrared heating dryers, and microwave dryers. In addition, the coating layer may be calendered after coating and drying.

The outermost coating layer contains at least five binders: water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch and alginate. Since the coating liquid of the outermost coating layer is blended with these five binders, the outermost coating layer can contain water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, Hydroxypropyl starch and alginate.

The water-soluble polyester resin is obtained by the polycondensation reaction of a polycarboxylic acid and a polyol, and the polycarboxylic acid and polyol as constituent components account for 60% by mass or more of the resin. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, etc., preferably It is free to choose one or two or more of these groups to use. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, di Phenols, etc., are preferably selected from one kind or two or more kinds from the group consisting of them. In addition, in order to improve water solubility, the water-soluble polyester resin may copolymerize a component having a hydrophilic group such as a carboxyl group or a sulfonic acid group. Water-soluble polyester resins are commercially available from Interaction Chemical Industry Co., Ltd., Takamatsu Oil Co., Ltd., Unitika Co., etc., and these commercial products can be used in the present invention. Furthermore, "water-soluble" means that it can finally dissolve more than 1% by mass in water at 20°C.

The carboxylic acid-modified polyvinyl alcohol resin has polyvinyl alcohol sites that are modified by carboxylic acid by introducing carboxyl groups. Examples of carboxylic acid-modified polyvinyl alcohol resins include those obtained by graft polymerization or block polymerization of polyvinyl alcohol and a vinyl carboxylic acid compound, and those obtained by copolymerizing a vinyl ester compound and a vinyl carboxylic acid compound. Those obtained by saponification, those obtained by reacting polyvinyl alcohol with a carboxylating agent, and the like. Examples of the above vinyl carboxylic acid compounds include acrylic acid, methacrylic acid, maleic acid (anhydride), phthalic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), etc. Compounds of anhydrides. As said vinyl ester compound, vinyl acetate, vinyl formate, vinyl propionate, vinyl tetradeca carbonate, vinyl pivalate, etc. are mentioned. Examples of the carboxylation agent include: succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic dianhydride, glutaric anhydride, hydrogenated phthalic anhydride, and naphthalene dicarboxylic acid Acid anhydride and so on. The carboxylic acid-modified polyvinyl alcohol resin is commercially available from Nippon Synthetic Chemical Industry Co., Ltd., JAPAN VAM&POVAL Co., Ltd., and Kuraray Co., Ltd., and these commercially available products can be used in the present invention. The carboxylic acid-modified polyvinyl alcohol resin preferably has a number average degree of polymerization of 1,000 or more and 3,000 or less. In addition, the carboxylic acid-modified polyvinyl alcohol resin preferably has a saponification degree of 85 mol or more and 90 mol or less. The reason for this is that it has excellent compatibility with other resins.

Acrylic resin is a general term for polymers or copolymers mainly composed of derivatives such as acrylic acid and its esters, and derivatives such as methacrylic acid and its esters. Examples of acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, and the like. In addition, examples of methacrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and 2-dimethylamino methacrylate. Ethyl and 2-hydroxyethyl methacrylate, etc. In the present invention, copolymers such as acrylonitrile, acrylamide, and N-methylol acrylamide are also included in the acrylic resin. Acrylic resins are commercially available from Toagosei Co., Ltd., Nippon Shokubai Co., Ltd., Shin-Nakamura Chemical Industry Co., Ltd., Idemitsu Kosan Co., Ltd., and Mitsubishi Chemical Co., Ltd., and these commercially available products can be used in the present invention.

Hydroxypropyl starch is a modified starch in which glucose is polymerized by glycosidic bonds. A part or all of the hydroxyl groups of glucose are etherified by propylene oxide to introduce hydroxypropyl modified starch. Hydroxypropyl starch is commercially available from Nidodo Chemical Co., Matsutani Chemical Industry Co., Ltd., and Ingredion Japan Co., Ltd., and these commercially available products can be used in the present invention.

The alginate is known in the past and is not particularly limited. In terms of the liquid stability of the coating layer coating liquid or the strength of the coating layer, the degree of polymerization of the alginate is preferably in the range of 80 or more and 1100 or less. The alginate is preferably one or two or more selected from the group consisting of potassium salt, sodium salt, and ammonium salt. The reason is that these are water-soluble. The alginate is preferably sodium alginate as the sodium salt. The reason is that it is commercially available. Alginates represented by sodium alginate are commercially available from Furukawa Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., and Kimika Co., Ltd., and these commercially available products can be used in the present invention. Commercially available alginates are classified into various grades according to the viscosity of a 1% by mass aqueous solution or the viscosity of a 10% by mass aqueous solution. In addition, they are also classified according to gel strength, degree of purification, and the like. In the present invention, the alginate can be of any grade or classification.

In the outermost coating layer on each single side of the substrate, the content of the water-soluble polyester resin is preferably 5 parts by mass or more and 30 parts by mass or less relative to 20 parts by mass of the white pigment in the outermost coating layer. The content of the carboxylic acid-modified polyvinyl alcohol resin in the outermost coating layer on each single side of the substrate is preferably 10 parts by mass or more and 35 parts by mass relative to 20 parts by mass of the white pigment in the outermost coating layer The following. In the outermost coating layer on each single side of the substrate, the content of the acrylic resin is preferably 5 parts by mass or more and 25 parts by mass or less relative to 20 parts by mass of the white pigment in the outermost coating layer. In the outermost coating layer on each single side of the substrate, the content of hydroxypropyl starch is preferably 10 parts by mass or more and 35 parts by mass or less relative to 20 parts by mass of the white pigment in the outermost coating layer. In the outermost coating layer on each single side of the substrate, the content of the alginate is preferably 3 parts by mass or more and 15 parts by mass or less relative to 20 parts by mass of the white pigment in the outermost coating layer. Furthermore, the content of each of the water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate in the outermost coating layer on each single side of the substrate is preferably As follows: With respect to 20 parts by mass of the white pigment in the outermost coating layer, the water-soluble polyester resin is 5 parts by mass or more and 30 parts by mass or less, and the carboxylic acid-modified polyvinyl alcohol resin is 10 parts by mass or more and 35 parts by mass. Hereinafter, the acrylic resin is 5 parts by mass or more and 25 parts by mass or less, the hydroxypropyl starch is 10 parts by mass or more and 35 parts by mass or less, and the alginate is 3 parts by mass or more and 15 parts by mass or less. In addition, in the outermost coating layer on each single side of the substrate, the total content of the binder is preferably 50 parts by mass or more and 125 parts by mass or less with respect to 20 parts by mass of the white pigment in the outermost coating layer. If the water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate in the outermost coating layer meet the above ranges, the fiber material and the transfer paper The adhesion, peeling of the transfer paper from the fibrous material, the color density of the pattern formed on the fibrous material, and/or the no difference in texture between the patterned area and the non-patterned area of the fibrous material are optimized.

In the outermost coating layer, in addition to water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate, it may also contain a previously known adhesive in the field of coated paper. Binders are, for example, water-soluble synthetic resins, water-dispersible synthetic resins, resins derived from natural ingredients, and resins obtained by physical or chemical modification. Specific examples of the adhesive include: polyvinyl alcohol resins other than carboxylic acid-modified polyvinyl alcohol resins and various modified derivatives of these, urethane resins, polyamide resins, and vinyl acetate Ester resin, styrene-butadiene copolymer resin, styrene-acrylic copolymer resin, styrene-maleic acid copolymer resin, styrene-acrylic acid-maleic acid copolymer resin, water-insoluble Polyester resin, polyvinyl acetal resin, protein, casein, gelatin, etherified tamarind gum, etherified locust bean gum, etherified guar gum and acacia gum and other rubbers, cellulose and carboxymethyl cellulose And modified derivatives of cellulose such as hydroxyethyl cellulose, modified starches other than starch and hydroxypropyl starch, and alginate salts.

The outermost coating layer is preferably water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate. The total mass of the adhesive in the outermost coating layer is 85 mass. %the above.

The outermost coating layer contains white pigment. White pigments are previously known white pigments in the field of coated paper. Examples of white pigments include: heavy calcium carbonate, light calcium carbonate, various kaolins, clays, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatoms Earth, calcium silicate, magnesium silicate, amorphous silica, colloidal silica, aluminum hydroxide, aluminum oxide, aluminum oxide hydrate, lithopone, zeolite, magnesium carbonate, magnesium hydroxide and other inorganic pigments, benzene Vinyl plastic pigments, acrylic plastic pigments, styrene-acrylic plastic pigments, polyethylene, microcapsules, urea resins, melamine resins and other organic pigments.

The white pigment of the outermost coating layer contains at least amorphous silica. Amorphous silicon dioxide can be roughly divided into wet-process silicon dioxide and vapor-phase silicon dioxide according to the manufacturing method. Furthermore, wet-process silicon dioxide can be classified into precipitation silicon dioxide and gel silicon dioxide according to the manufacturing method. Precipitation method Silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the grown silica particles are aggregated and precipitated, and then go through the steps of filtration, water washing, drying, crushing, and classification And manufacturing. Precipitation method silicon dioxide is marketed by TOSOH SILICA as Nipsil (registered trademark), Oriental Silicas Corporation as Finesil (registered trademark) and Tokusil (registered trademark), and Mizusawa Chemical Industry as Mizukasil (registered trademark) The company is commercially available. Gel-method silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. The fine particles dissolve in the aging process to re-precipitate in a way that other primary particles are combined with each other. Therefore, the clear primary particles of gel-method silica disappear, forming relatively hard agglomerated particles with internal void structure. Gel-method silica is commercially available from TOSOH SILICA Co., Ltd. as Nipgel (registered trademark), and from Grace Japan Co., Ltd. as SYLOID (registered trademark) and SYLOJET (registered trademark). Compared with the wet method, the vapor-phase silicon dioxide is also called the dry method, and is generally produced by the flame hydrolysis method. Specifically, it is generally known that silicon tetrachloride is produced by combusting it with hydrogen and oxygen. Instead of silicon tetrachloride, silanes such as methyltrichlorosilane or trichlorosilane can be used alone or in combination with silicon tetrachloride. Vapor-phase silicon dioxide is marketed, for example, by Aerosil (registered trademark) by AEROSIL, Japan, and REOLOSIL (registered trademark) by Tokuyama, Inc. The amorphous silicon dioxide is more preferably deposited silicon dioxide. The amorphous silica in the outermost coating layer preferably accounts for 85% by mass or more of the white pigment in the outermost coating layer.

In addition to the white pigment and adhesive, the outermost coating layer may optionally contain various additives previously known in the field of coated paper. Examples of additives include: dispersing agents, fixing agents, cationizing agents, tackifiers, fluidity improvers, defoamers, mold release agents, foaming agents, penetrants, colorants, fluorescent whitening Agents, UV absorbers, antioxidants, preservatives, antifungal agents, etc. In addition, the outermost coating layer may contain various auxiliary agents previously known in the transfer printing method. The auxiliary agent is added in order to optimize the various physical properties of the coating liquid for the outermost coating layer or to improve the dyeability to the printed matter. Examples of the auxiliary agent include various surfactants, pH adjusters, alkali agents, thick dyeing agents, moisturizers, degassing agents, reduction inhibitors, and the like.

The outermost coating layer preferably contains fatty acid ester. The reason is that the color density of the pattern formed on the fiber material is optimized and the peeling of the transfer paper from the fiber material is optimized. Fatty acid esters esterify fatty acids such as saturated fatty acids, unsaturated fatty acids, higher fatty acids, and lower fatty acids with alcohols such as primary alcohols, secondary alcohols, tertiary alcohols, higher alcohols, lower alcohols, monohydric alcohols, and polyhydric alcohols. Compound obtained. Examples of fatty acid esters include: esters of fatty acids and monohydric alcohols, esters of fatty acids and ethylene glycol, esters of fatty acids and propylene glycol, and esters of fatty acids and glycerol, and esters of fatty acids and polyhydric alcohols, and polyoxyethylene additions of these And other derivatives. The fatty acid may be an aliphatic fatty acid, an aromatic fatty acid, or a compound partially having a cyclic structure. The alcohol may be an aliphatic alcohol, an aromatic alcohol, or a compound partially having a cyclic structure. Fatty acid esters are sold by Kao Corporation, Riken Vitamin Corporation, Nikka Chemical Corporation, Chuo Kasei Corporation, Kawaken Fine Chemicals, etc., and can be used. Fatty acid esters are preferably esters of fatty acids and polyhydric alcohols. Relative to 100 parts by mass of the adhesive of the outermost coating layer, the content of fatty acid ester in the outermost coating layer is preferably 5 parts by mass or more and 25 parts by mass or less, more preferably 8 parts by mass or more and 20 parts by mass the following.

[Transfer Printing Method] The transfer printing paper of the present invention is used in a transfer printing method including the following steps: a step of obtaining a transfer paper by printing a pattern on a transfer paper using an ink containing a dye, and heating the transfer paper by adhering the above-mentioned transfer paper to a fiber material And press to transfer the dye from the transfer paper to the fiber material, the step of peeling the transfer paper from the fiber material after the above transfer step, the steaming treatment of the fiber material after the above peeling step, and the dye fixing treatment. step. The second embodiment of the present invention is a transfer printing method. The transfer printing method of the present invention includes: The step of obtaining a transfer paper, which has a substrate with one or more non-aqueous resin laminate layers on one side of the base paper, and one or more layers on the laminate layer of the above-mentioned substrate The coating layer, in the coating layer, the outermost coating layer located on the basis of the substrate contains a white pigment and a binder, and the white pigment at least includes amorphous silicon dioxide and the binder Contain at least five kinds of water-soluble polyester resin, carboxylic acid modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch and alginate; The step of printing a pattern on the above transfer paper by using an ink containing a dye to obtain a transfer paper; The step of transferring the dye from the transfer paper to the fiber material by closely adhering the transfer paper to the fiber material and heating and pressing; The step of peeling off the transfer paper from the fiber material after the above transfer step; and The step of fixing the dyestuff on the fiber material after the above-mentioned peeling step. The transfer paper obtained in the step of obtaining the transfer paper is the same as the transfer paper of the first embodiment of the present invention described above, so the description is omitted.

Examples of inks containing dyes include inks containing dyes selected from reactive dyes, acid dyes, metal complex salt type dyes, direct dyes, disperse dyes, sulfur dyes, vat dyes, and cationic dyes. The transfer paper of the present invention is suitable for inks containing reactive dyes.

Inks containing reactive dyes can be prepared by adding reactive dyes as colorants to various solvents such as water and alcohol. The ink may optionally contain previously known dispersants, resins, penetrants, humectants, tackifiers, pH adjusters, antioxidants, and reducing agents. In addition, inks containing reactive dyes are commercially available and available.

The transfer paper can be obtained by printing a pattern on the transfer paper using an ink containing a dye. Printing is performed on the side with the outermost coating layer of the transfer paper. The printing method can include: gravure printing method, screen printing method and inkjet printing method, etc. Regarding the method of printing a pattern, the inkjet printing method is preferred in terms of image quality and relatively high degree of freedom of the ink used.

The heating and pressurizing to make the transfer paper and the fibrous material tightly contact the printing surface of the printed transfer paper and the fibrous material for printing, and heat and press in a tightly adhered state. The conditions of heating and pressing for close bonding are previously known conditions in the transfer printing method. As a method of heating and pressurizing the adhesive by heating and pressurizing, for example, a method of heating and pressurizing the transfer paper by adhering the transfer paper to the fibrous material using a pressing machine, a heating roller, a heating drum, or the like.

The peeling of the transfer paper from the fiber material is performed after the transfer step and before the fixing step. The peeling of the transfer paper from the fibrous material is to physically peel the transfer paper from the fibrous material for the fibrous material and the transfer paper in a tightly bonded state. The peeling method is a previously known method and is not particularly limited. For example, a method of peeling off the roll-shaped transfer paper and the fiber material in a state where the transfer paper and the fiber material are attached by a method of respectively winding them into a roll shape. In the present invention, since the transfer paper has the non-aqueous resin laminate layer and the outermost coating layer, when it is difficult to peel the outermost coating layer of the transfer paper from the fiber material, the substrate and the outermost coating layer are included. Peeling between the coating layers of the cloth layer can smoothly peel the fiber material from the transfer paper. After peeling, it may include the state where all or part of the coating layer is attached to the fiber material, but the coating layer can be removed by washing with water. As long as it is a transfer printing method that performs dye fixing treatment on the fiber material after the transfer paper is peeled from the fiber material, the transportation problems and operation difficulties in the fixing treatment device can be improved. Furthermore, when the substrate is laminated paper, when printing patterns on transfer paper with ink containing dyes, the non-aqueous resin laminated layer prevents the dyes from reaching the base paper and further suppresses the pattern formation on the fiber material. Defects and reduced color density. The transfer printing method of the present invention may optionally include the step of washing the fiber material with water after the peeling step and before the color fixing treatment.

The dye fixing treatment is a treatment to fix the dye transferred from the transfer paper to the fiber material to the fiber material, and is a previously known treatment method in the printing field. Examples of dye fixing treatment include steaming treatment, humidification treatment, and dry heat treatment at high temperature. The dye fixing treatment is preferably steaming treatment. Steaming treatment is also called wet fixation treatment, which is a previously known treatment. The representative steaming treatments are atmospheric steaming method, HT steaming method and HP steaming method. Generally speaking, the normal pressure steaming method uses moist heat treatment at about 105°C for 10 minutes or more and 15 minutes or less, and the HT steam method uses moist heat treatment for 150°C or more and 180°C or less, 5 minutes or more and 10 minutes or less. , The HP steaming method is to fix the dye to the fiber material by the moist heat treatment at 120°C or more and 135°C or more, 20 minutes or more and 40 minutes or less. The transfer printing method of the present invention may optionally include the step of washing the fiber material with water after the fixation treatment.

The fiber material may be any one of natural fiber material and synthetic fiber material. Examples of natural fiber materials include cellulose fiber materials such as cotton, hemp, Lyocell, rayon, and acetate, protein fiber materials such as silk, wool, and animal hair. Examples of synthetic fiber materials include polyamide fibers (nylon), vinylon, polyester, polypropylene, and the like. Examples of the structure of the fiber material include woven fabrics, knitted fabrics, non-woven fabrics, etc., alone, blended, blended, or interwoven. Furthermore, these structures can be combined. The transfer paper of the present invention is suitable for natural fiber materials, especially cotton. [Example]

The following examples illustrate the present invention in further detail. Furthermore, the present invention is not limited to these embodiments. Here, "parts by mass" and "% by mass" represent the respective "parts by mass" and "% by mass" of the dry solid content or the actual content. The coating amount of the coating layer represents the dry solid content.

<Base paper> To a pulp slurry composed of 100 parts by mass of LBKP with a drainage degree of 380 ml csf, add 10 parts by mass of calcium carbonate as filler, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of aluminum sulfate, and alkyl ketene dimer type 0.1 parts by mass of sizing agent, papermaking using a Fourdrinier paper machine, using a sizing press device to ^{attach oxidized starch on both sides at 1.5 g/m 2} per single side, and mechanically calendering to make a basis weight of 80 g/m ² of the original paper.

＜Substrate 1＞ On one side of the aforementioned base paper, high-density polyethylene was laminated to a thickness of 15 μm using a melt extrusion die to obtain a base material 1 having a non-aqueous resin laminated layer.

＜Substrate 2＞ The above-mentioned base paper is used as the base material 2.

<Coating Layer Coating Liquid> Using water as a medium, a coating layer coating liquid was prepared in the following mixing ratio. Finally, the concentration of the coating layer coating liquid was 15% by mass. Water-soluble polyester resin The number of copies is recorded in Table 1~Table 5 Polyvinyl alcohol Types and number of copies are described in Table 1~Table 5 Acrylic The number of copies is recorded in Table 1~Table 5 Starch Types and number of copies are described in Table 1~Table 5 Alginate (Sodium Alginate) The number of copies is recorded in Table 1~Table 5 Styrene-butadiene copolymer The number of copies is recorded in Table 1~Table 5 White paint Types and number of copies are described in Table 1~Table 5 Fatty acid ester (glycerol monostearate) 10 parts by mass/0 parts by mass Humectant (thiourea) 25 parts by mass Humectant (Dicyandiamide) 25 parts by mass Defoamer 0.15 parts by mass Sodium carbonate 25 parts by mass

In Table 1~Table 5, the water-soluble polyester resin uses Pluscoat (registered trademark) RZ-142 of Intercord Chemical Industries, and the carboxylic acid-modified polyvinyl alcohol resin uses Kuraray poval (registered trademark) of Kuraray 25- 88KL, other polyvinyl alcohol resins use Kuraray poval 22-88 from Kuraray, acrylic resins use NK BINDER M-302HN from Shinnakamura Chemical Industry Co., and hydroxypropyl starch use PIOSTARCH (registered trademark) H from Nisdom Chemical Co., Ltd. Other starches use Neotack (registered trademark) 40T from Japan Food Processing Corporation, sodium alginate uses FD Argin BL from Furukawa Chemical Industry Co., Ltd., styrene-butadiene copolymer resin uses JSR Company's JSR0693, and amorphous silica Mizukasil P-603 from Mizusawa Chemical Industry Co., Ltd. was used, and Ultra White 90 from ENGELHARD Co., Ltd. was used for kaolin. Only in Example 25, the fatty acid ester was set to 0 parts by mass.

[Table 1] Outermost coating layer Mass parts Substrate Peel off Close Color density texture material Water-soluble polyester resin 5 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 1 Starch ：Hydroxypropyl starch 15 8 A A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 2 Starch ：Hydroxypropyl starch 15 8 A A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 30 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 3 Starch ：Hydroxypropyl starch 15 8 A A B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 10 Acrylic 10 Substrate 1 Example 4 Starch ：Hydroxypropyl starch 15 8 B A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 35 Acrylic 10 Substrate 1 Example 5 Starch ：Hydroxypropyl starch 15 8 A A B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Hydroxypropyl starch 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 5 Substrate 1 Example 6 Starch ：Hydroxypropyl starch 15 8 A A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 25 Substrate 1 Example 7 Starch ：Hydroxypropyl starch 15 8 A A A B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20

[Table 2] Outermost coating layer Mass parts Substrate Peel off Close Color density texture material Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Example 8 Acrylic 10 10 8 Substrate 1 A A B A Starch ：Hydroxypropyl starch Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Example 9 Acrylic resin starch 10 35 8 Substrate 1 A A B A ：Hydroxypropyl starch Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 10 Starch ：Hydroxypropyl starch 15 3 A A B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Hydroxypropyl starch 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 11 Starch ：Hydroxypropyl starch 15 15 A A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 28 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 35 Acrylic 20 Substrate 1 Example 12 Starch ：Hydroxypropyl starch 28 14 A A B B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 11 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 15 Acrylic 7 Substrate 1 Example 13 Starch ：Hydroxypropyl starch 11 6 B B A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 15 Acrylic 10 Substrate 1 Example 14 Starch ：Hydroxypropyl starch 15 10 B B A A Sodium Alginate Styrene-butadiene copolymer resin 10 White paint ：Amorphous silicon dioxide 20

[table 3] Outermost coating layer Mass parts Substrate Peel off Close Color density texture material Water-soluble polyester resin 3 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 15 Starch ：Hydroxypropyl starch 15 8 A B A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 45 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 16 Starch ：Hydroxypropyl starch 15 8 A A B B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 5 Acrylic 10 Substrate 1 Example 17 Starch ：Hydroxypropyl starch 15 8 B B A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 55 Acrylic 10 Substrate 1 Example 18 Starch ：Hydroxypropyl starch 15 8 B A B B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 3 Substrate 1 Example 19 Starch ：Hydroxypropyl starch 15 8 A B A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 45 Substrate 1 Example 20 Starch ：Hydroxypropyl starch 15 8 A A B B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20

[Table 4] Outermost coating layer Mass parts Substrate Peel off Close Color density texture material Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 21 Starch ：Hydroxypropyl starch 5 8 B B B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Example 22 Acrylic 10 55 8 Substrate 1 B A B A Starch ：Hydroxypropyl starch Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 23 Starch ：Hydroxypropyl starch 15 1 A B B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 24 Starch ：Hydroxypropyl starch 15 35 B A A A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Example 25 Starch ：Hydroxypropyl starch 15 8 B A B A Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20

[table 5] Outermost coating layer Mass parts Substrate Peel off Close Color density texture material Water-soluble polyester resin 0 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 1 Starch ：Hydroxypropyl starch 15 8 B C A B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol 0 Acrylic 10 Substrate 1 Comparative example 2 Starch ：Hydroxypropyl starch 15 8 C C A B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Comparative example 3 Acrylic 0 15 8 Substrate 1 B C A B Starch ：Hydroxypropyl starch Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 4 Starch Sodium Alginate 0 8 B C C B Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 5 Starch ：Hydroxypropyl starch 15 0 B C C B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 6 Starch ：Hydroxypropyl starch 15 8 B C C B Sodium Alginate Styrene-butadiene copolymer resin 0 White paint : Kaolin 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Other polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 7 Starch ：Hydroxypropyl starch 15 C C A B Sodium Alginate 8 Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 1 Comparative example 8 Starch ：Other starch 15 B C C B Sodium Alginate 8 Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20 Water-soluble polyester resin 15 Polyvinyl alcohol ：Carboxylic acid modified polyvinyl alcohol resin 20 Acrylic 10 Substrate 2 Comparative example 9 Starch ：Hydroxypropyl starch 15 C A C C Sodium Alginate 8 Styrene-butadiene copolymer resin 0 White paint ：Amorphous silicon dioxide 20

<Transfer Paper> The coating liquid for the coating layer was applied to one side of the substrate using an air knife coater, and dried using a hot air dryer, to make this coating layer the outermost coating layer. After that, calendering is performed to finally produce roll-shaped transfer paper. The coating amount of the outermost coating layer was set to 18 g/m ² . In the substrate 1 with a non-aqueous resin laminated layer, the outermost coating layer is provided on the side with the laminated layer.

＜Transfer paper＞ On roll-shaped transfer paper, use an inkjet printer (ValueJet (registered trademark) VJ-1628TD, manufactured by Muto Kogyo Co., Ltd.) containing ink containing reactive dyes, and use inks (indigo, magenta, yellow, Black) The evaluation pattern is printed on the side of the transfer paper with the outermost coating layer, and finally a sheet-like transfer paper is obtained. The ink containing reactive dyes uses NOVACRON (registered trademark) MI ink manufactured by Huntsman.

＜Transfer printing＞ Use unpretreated rolled cotton cloth as the fiber material. The printing surface of the transfer paper and the printing surface of the cotton cloth are conveyed facing each other, and the roller nip method equipped with a heating roller is used to make it close and heat and pressurize it. The conditions of heating and pressurization are temperature 120°C, linear pressure 70 kg/cm, and time 0.5 seconds.

＜Peeling off transfer paper＞ For the cotton cloth in the state where the transfer paper is attached, the transfer paper is peeled off from the cotton cloth by winding the transfer paper and the cotton cloth into rolls respectively.

＜Evaluation of peeling＞ When the transfer paper is peeled from the cotton cloth, observe the state of the peeling surface of the cotton cloth and the state of the peeling surface of the cotton cloth after washing. The sensory evaluation was performed based on the state of the peeled surface based on the following criteria. The evaluation results are described in Tables 1 to 5. In the present invention, if the evaluation is A or B, it is considered that the transfer paper peels off from the cotton cloth well. A: It can be easily peeled off, even if there is adhesion of the components of the outermost coating layer, It can also be easily removed by washing with water, and the pattern formed has no defects. B: Although there is adhesion of the components of the outermost coating layer, it can be peeled off, As long as it is washed with water, the attached components can be removed, and the pattern formed will not be defective. C: It is not easy to peel off or cannot be peeled off, the transfer paper is broken, and there is still a part in a close state, which is not easy to remove by washing with water, or the formed pattern is defective.

＜Steaming treatment of cotton cloth＞ The rolled cotton cloth with the peeled transfer paper is transported from the unwinding machine to the winding machine, during which the wet heat treatment is performed at 105°C for 10-15 minutes by the atmospheric steaming method.

＜Washing＞ After steaming, wash the obtained cotton cloth in running water.

＜Evaluation of close bonding＞ From the viewpoint of distortion and image blurring of the pattern formed on the cotton cloth, sensory evaluation of the goodness of the adhesion between the transfer paper and the fiber material was carried out on the basis of the following criteria. The evaluation results are described in Tables 1 to 5. In the present invention, if the evaluation is A or B, it is considered that the adhesion between the transfer paper and the fiber material is good. A: Distortion and blurring of the image are not confirmed, which is good. B: It is inferior to the above A, but distortion and/or image blur are not clearly confirmed, and it is generally good. C: Inferior to the above B, distortion and/or image blur are slightly confirmed, which is the upper and lower practical limit. D: It is inferior to the above C, and distortion and/or blurring of the image are confirmed.

＜Evaluation of color density＞ An optical densitometer (X-rite (registered trademark) 530, X-rite-Incorporated) was used to measure the color density of the three-color (indigo, magenta, and yellow) solid image formed on the cotton cloth. Color density value. Based on the total value, the color density was evaluated based on the following criteria. The evaluation results are described in Tables 1 to 5. In the present invention, it is considered that as long as it is evaluated as A or B, the transfer paper can provide a fiber material with good color density. A: The total value is 4.8 or more B: The total value is 4.5 or more and less than 4.8 C: The total value is 4.2 or more and less than 4.5 D: The total value does not reach 4.2

＜Evaluation of texture＞ In the patterned cotton cloth, the texture of the area where the black solid image portion is formed and the area where there is no transfer image is evaluated by sensory evaluation by palpation with human hands. The evaluation results are described in Tables 1 to 5. In the present invention, as long as it is evaluated as A or B, it is considered that the transfer paper can provide a fibrous material with no difference in texture between the area where the pattern is formed and the area where the pattern is not formed. A: There is no difference in skin feel between regions, and the texture is good. B: A slight difference in skin touch between areas is confirmed, and no difference in texture is felt. C: Compared with the above-mentioned B, the difference in skin touch between regions is more clearly recognized.

According to Tables 1 to 5, it can be seen that the transfer paper corresponding to Examples 1 to 25 of the present invention satisfies (1) the adhesion of the transfer paper to the fiber material is good, (2) the color density of the pattern formed on the fiber material is good, ( 3) The transfer paper peels well from the fiber material after the dye transfer, and (4) There is no difference in texture between the patterned fiber material area and the unpatterned fiber material area. On the other hand, it can be seen that Comparative Examples 1 to 9 that do not satisfy the structure of the present invention cannot simultaneously satisfy the effects of the present invention. Mainly based on the comparison of Examples 1 to 3 and Examples 15 and 16, it is preferable that the content of the water-soluble polyester resin in the outermost coating layer of each single side of the substrate is relative to that in the outermost coating layer. 20 parts by mass of the white pigment is 5 parts by mass or more and 30 parts by mass or less. Mainly based on the comparison of Examples 2, 4 and 5 with Examples 17 and 18, it is preferable that the content of the carboxylic acid-modified polyvinyl alcohol resin in the outermost coating layer of each single side of the substrate is relative to the outermost 20 parts by mass of the white pigment in the coating layer is 10 parts by mass or more and 35 parts by mass or less. Mainly based on the comparison between Examples 2 and 6 and Example 19, it can be seen that in Examples 2 and 6, the content of acrylic resin in the outermost coating layer of each single side of the substrate is relative to the whiteness in the outermost coating layer. 20 parts by mass of the pigment is 5 parts by mass or more, and the adhesion between the fiber material and the transfer paper is excellent. Mainly based on the comparison between Examples 2 and 7 and Example 20, it can be seen that in Examples 2 and 7, the content of acrylic resin in the outermost coating layer of each single side of the substrate is relative to the whiteness in the outermost coating layer. 20 parts by mass of the pigment is 25 parts by mass or less, and the color density of the pattern formed on the fiber material is excellent. Therefore, the content of the acrylic resin in the outermost coating layer is preferably 5 parts by mass or more and 25 parts by mass or less with respect to 20 parts by mass of the white pigment in the outermost coating layer. Mainly based on the comparison of Examples 2, 8 and 9 with Examples 21 and 22, it is preferable that the content of hydroxypropyl starch in the outermost coating layer of each single side of the substrate is relative to that in the outermost coating layer 20 parts by mass of the white pigment is 10 parts by mass or more and 35 parts by mass or less. Mainly based on the comparison between Examples 2 and 10 and Example 23, it can be seen that in Examples 2 and 10, the content of alginate in the outermost coating layer on each single side of the substrate is relative to that in the outermost coating layer. 20 parts by mass of the white pigment is 3 parts by mass or more, and the adhesion between the fiber material and the transfer paper is excellent. Mainly based on the comparison between Examples 2 and 11 and Example 24, it can be seen that in Examples 2 and 11, the content of alginate in the outermost coating layer on each single side of the substrate is relative to that in the outermost coating layer. 20 parts by mass of the white pigment is 15 parts by mass or less, and the transfer paper is excellent in peeling from the fiber material after the dye transfer. Therefore, the content of the alginate in the outermost coating layer is preferably 3 parts by mass or more and 15 parts by mass or less with respect to 20 parts by mass of the white pigment in the outermost coating layer. Mainly based on the comparison between Example 2 and Example 25, it can be known that the outermost coating layer preferably contains fatty acid esters.

The disclosures of Japanese Patent Application No. 2019-058089 (application date: March 26, 2019) and Japanese Patent Application No. 2019-225616 (application date: December 13, 2019) are incorporated herein by reference in their entirety. In the manual. All the documents, patent applications, and technical specifications described in this specification are to the same extent that they are incorporated by reference into each document, patent application, and technical specifications specifically and separately, and are incorporated into this by reference. In the manual.

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no

Claims (6)

A transfer printing paper, which is a transfer printing paper used in a transfer printing method before printing a pattern. The transfer printing method includes a step of printing the pattern onto the transfer paper using an ink containing a dye to obtain the transfer paper. The step of making the above-mentioned transfer paper and the fibrous material tightly adhered and heating and pressurizing to transfer the dye from the transfer paper to the fibrous material, the step of peeling the transfer paper from the fibrous material after the transfer step, and the fibrous material after the peeling step Steps of dye fixing treatment; The transfer paper has: a substrate having one or more non-aqueous resin laminate layers on one side of the base paper, and one or more coating layers on the laminate layer of the above-mentioned substrate; Among the above-mentioned coating layers, the outermost coating layer on the basis of the above-mentioned substrate contains a white pigment and a binder, The above-mentioned white pigment contains at least amorphous silicon dioxide, The adhesive includes at least five types: water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate. The transfer paper of claim 1, wherein, in the outermost coating layer, the content of each of water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate is as follows : Relative to 20 parts by mass of the white pigment in the outermost coating layer, the water-soluble polyester resin is 5 parts by mass or more and 30 parts by mass or less, and the carboxylic acid-modified polyvinyl alcohol resin is 10 parts by mass or more and 35 parts by mass or less , The acrylic resin is 5 parts by mass or more and 25 parts by mass or less, the hydroxypropyl starch is 10 parts by mass or more and 35 parts by mass or less, and the alginate is 3 parts by mass or more and 15 parts by mass or less. The transfer paper of claim 1 or 2, wherein the outermost coating layer contains fatty acid ester. A transfer printing method, which includes the step of obtaining transfer paper, the transfer paper having a substrate with one or more non-aqueous resin laminated layers on a single side of the base paper, and a laminated layer on the above-mentioned substrate The upper one or two or more coating layers. Among the coating layers, the outermost coating layer on the basis of the substrate contains a white pigment and a binder, and the white pigment contains at least an amorphous High-quality silicon dioxide, the above-mentioned adhesive includes at least five types of water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch and alginate; The step of printing a pattern on the above transfer paper by using an ink containing a dye to obtain a transfer paper; The step of transferring the dye from the transfer paper to the fiber material by closely adhering the transfer paper to the fiber material and heating and pressing; The step of peeling off the transfer paper from the fiber material after the above transfer step; and After the above-mentioned peeling step, the fiber material after peeling is subjected to the step of dye fixing treatment. Such as the transfer printing method of claim 4, wherein the content of each of the water-soluble polyester resin, carboxylic acid-modified polyvinyl alcohol resin, acrylic resin, hydroxypropyl starch, and alginate in the outermost coating layer is as follows : Relative to 20 parts by mass of the white pigment in the outermost coating layer, the water-soluble polyester resin is 5 parts by mass or more and 30 parts by mass or less, and the carboxylic acid-modified polyvinyl alcohol resin is 10 parts by mass or more and 35 parts by mass or less , The acrylic resin is 5 parts by mass or more and 25 parts by mass or less, the hydroxypropyl starch is 10 parts by mass or more and 35 parts by mass or less, and the alginate is 3 parts by mass or more and 15 parts by mass or less. The transfer printing method of claim 4 or 5, wherein the outermost coating layer contains fatty acid esters.