JP7296872B2 - transfer paper - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transfer paper used for transferring a pattern in a transfer printing method for forming a pattern on a textile material. In particular, it relates to a transfer paper suitable when the fiber material is cotton.

In a printing paper that can express fine printing patterns, excellent uniformity of dyeing, and reproducibility of the texture of flexible fibers, a pattern is printed on the printing paper with an ink containing a dye to obtain the printing paper, and the textile material or A printing paper used in a transfer printing method in which a dye is transferred by closely contacting a printing paper to a leather material and applying heat and pressure, and fixing treatment of the dye is performed in a state where the printing paper is attached to a textile material or leather material, After coating, spraying or immersing a base paper with a hydrophilic mixture in which the blending ratio of the natural sizing agent to the water-soluble synthetic binder is in the range of 5% to 0% in terms of solid content and further blended with various auxiliaries, A printing paper having an ink-receiving layer and an adhesive layer that is absorbed or laminated on the paper by drying is known (see, for example, Patent Document 1).

A sublimation ink-jet printing transfer paper that can suppress the strike-through of ink during transfer printing and is less likely to wrinkle even when used in a sheet form, comprising a sublimation-type printing ink-receiving layer formed on a base material. The printing ink-receiving layer is composed of an ink-receiving layer paint containing a water-soluble resin, fine particles A, and fine particles B, and the fine particles A have a tabular crystal structure and have a size of 0.4 to 2.3 μm. Inorganic fine particles having a median diameter d50 and an aspect ratio of 5 or more, the fine particles B being silica particles, and the ratio of the fine particles A to the fine particles B (fine particles A/fine particles B) The weight ratio is 15/85 to 90/10, the water-soluble resin is sodium carboxymethylcellulose, and the sodium carboxymethylcellulose is a total of 100 parts by weight of the fine particles A and the fine particles B in the ink-receiving layer coating material. , and the coating amount (dry) of the ink-receiving layer paint is 3-13 g/m ² , and is measured by the air permeability measurement method in accordance with JIS P 8117:2009. The air permeability is 100 to 10000 seconds, and the time until the ultrasonic transmission intensity of the initial water absorption property measured by a surface/sizing tester (EST12) reaches 100% is 0.1 to 3.0 seconds. Sublimation ink jet printing transfer paper characterized by being a substrate is known (see, for example, Patent Document 2).

JP 2016-102283 A JP 2018-030342 A

In the transfer printing method, the transfer paper and the fiber material are brought into close contact with each other, and the dye received by the transfer paper is transferred to the fiber material. In the textile printing industry using the transfer printing method, the following items are required from the viewpoint of work efficiency and the quality of patterns formed on textile materials.
(1) It must have anti-blocking properties between transfer sheets.
(2) Adhesion of the transfer paper to the fiber material should be good.
(3) The pattern formed on the fiber material has good color density.
(4) The transfer paper should be easily peeled off from the fiber material after the transfer of the dye.
In the absence of (1), when a roll of transfer paper that is commonly used in the textile printing industry is unwound to adhere to a fiber material, the coating layer may be missing due to blocking. If there is a serious defect in the coating layer of the portion where the pattern is formed, there will also be a defect in the pattern of the textile material formed by transfer. Moreover, even if there is no significant omission in the pattern on the transfer paper, the pattern finally formed on the fiber material may have color unevenness. If (2) is not satisfactory, the working efficiency of transfer printing is lowered, or the formed pattern is distorted or out of focus. If the item (3) is not satisfactory, it cannot be used as a product. If (4) is not satisfactory, the working efficiency of transfer printing is lowered or the design formed on the fiber material is missing.

In the textile transfer method as described in Patent Document 1, dye fixation treatment such as steaming treatment is performed while the transfer paper is in close contact with the fiber material. The reason for this is that the steaming treatment softens the water-soluble synthetic binder and the natural sizing agent, making it easier for the transfer paper to separate from the fiber material. However, when the transfer paper is adhered to the fiber material and the dye is fixed, the transfer paper and the fiber material adhered to each other are thick, so there are problems in transporting and handling the transfer paper in the fixing device. Further, when the transfer paper is adhered to the fiber material, the dye remaining on the transfer paper may cause fogging during the dye fixing treatment. "Fog" is a phenomenon in which dye is transferred to an area where there is no original pattern. A representative fog is spot fog in which dye transfer occurs in spots in a pattern-free area. On the other hand, it is difficult to peel off the transfer paper from the fiber material after the transfer paper is brought into close contact with the fiber material and heated and pressurized and before dye fixation treatment such as steaming treatment is performed. Even if the pattern can be peeled off, the pattern formed on the fibrous material may have defects such as missing parts.

A transfer paper as described in Patent Document 2 is used for sublimation-type textile printing ink. Textile materials that can be printed with sublimation printing ink are limited to polyester fibers, and plant-derived fiber materials such as cotton cannot be printed. Inks containing reactive dyes are used for cotton printing. However, plant-derived fiber materials such as cotton are poor in anionic or cationic charge, and dyes that are normally charged are difficult to adsorb. As a result, it is difficult to print plant-derived fiber materials such as cotton.

In view of the above, an object of the present invention is to enable the transfer paper to be separated from the fiber material after the fiber material and the transfer paper are brought into close contact with each other and heated and pressurized and before the dye fixing treatment, that is, the above (4). and to provide a transfer paper that satisfies the above (1) to (3).

As a result of extensive research conducted by the inventors in order to solve the above problems, the objects of the present invention are achieved as follows.

[1] A transfer paper obtained by printing a design with an ink containing a dye is brought into close contact with a fiber material, and heated and pressed to transfer the dye from the transfer paper to the fiber material, and after the transfer, the transfer paper is removed from the fiber material. A transfer paper before printing a pattern, which is used in a transfer printing method in which a dye is fixed to the fiber material after peeling, and one or more non-aqueous resin laminate layers are formed on one side of the base paper. and a substrate having one or more coating layers on the laminate layer of the substrate, and the outermost coating layer positioned outermost relative to the substrate in the coating layer is A white pigment, a binder, and two or more selected from the group consisting of urea, thiourea, and dicyandiamide, wherein the binder contains at least a water-soluble polyester resin, a polyvinyl alcohol resin, an acrylic resin, and a polysaccharide; In the coating layer, the binder is 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, and 20 parts by mass of the white pigment in the outermost coating layer in the outermost coating layer. 0 parts by mass to 3 parts by mass of urea, 20 parts by mass to 50 parts by mass of thiourea, and 20 parts by mass to 50 parts by mass of dicyandiamide, and a permeation time of 4 seconds using water A transfer paper having an ultrasonic transmission attenuation rate of 25% or more.

[2] The transfer paper according to [1], wherein the white pigment in the outermost coating layer contains at least amorphous silica, and the average particle size of the amorphous silica is 10 μm or more and 28 μm or less.
When the average particle size of the white pigment in the outermost coating layer satisfies the above range, the transfer paper improves the adhesion of the transfer paper to the fiber material and/or the peeling of the transfer paper from the fiber material after the dye is transferred. do.

According to the present invention, (1) blocking resistance between transfer papers, (2) good adhesion of the transfer paper to the fiber material, and (3) good color density of the pattern formed on the fiber material. and (4) the transfer paper can be easily peeled off from the fiber material after the transfer of the dye.

The present invention will be described in detail below.
In the present invention, the term “transfer paper” refers to paper in a blank state before a design to be transferred is printed. "Transfer paper" means paper on which a design to be transferred is printed.
In the present invention, "having a layer" means having a distinct layer that can be distinguished from the base paper or base material when the cross section of the transfer paper is observed with an electron microscope. For example, a resin component or a polymer component is coated, and a small amount of the coated component is absorbed by the base paper or base material, and as a result, when the cross section of the transfer paper is observed with an electron microscope, the base paper or base material If it does not have a clear layer that can be distinguished from

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 substrate. Among the coating layers, the coating layer located on the outermost side with respect to the substrate 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 a white pigment, a binder, and two or more selected from the group consisting of urea, thiourea and dicyandiamide. The binder includes at least water-soluble polyester resin, polyvinyl alcohol resin, acrylic resin and polysaccharide. When the coating layer is two or more layers, the coating layer present between the base material and the outermost coating layer is a coating layer conventionally known in the field of coated paper, and contains a white pigment. and type, the presence or absence and type of binder, and the presence or absence of urea, thiourea and dicyandiamide are not particularly limited. In addition, the coating layer present between the substrate and the outermost coating layer can contain various conventionally known additives in the field of coated paper.

From the viewpoint of the manufacturing cost of the transfer paper, the number of coating layers is preferably one. Also, the coating layer may be provided on one side or both sides of the substrate. The coating layer is provided at least on the side of the substrate having the laminate layer. When the transfer paper has the outermost coating layer according to the present invention on one side of the substrate, it may have a conventionally known back coat layer on the back surface of the substrate.

The coating amount of the coating layer is not particularly limited. From the viewpoint of production cost and ease of handling of the transfer paper, the coating amount is preferably 5 g/m ² or more and 70 g/m ² or less in terms of dry solid content per 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 coating layer from falling off when the transfer paper and the fiber material are in close contact, the coating amount is most preferably 10 g/m ² or more and 30 g/m ² or less per side. . The amount of coating is the total value when there are multiple coating layers per side.

The substrate is 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 to be provided.
When the outermost coating layer of the transfer paper and the fibrous material become difficult to separate, all or part of the coating layer is removed by peeling between the substrate and the coating layer including the outermost coating layer. The fiber material can be successfully peeled off from the transfer paper, including the state of adhering to the fiber material. A transfer printing method in which the transfer paper is peeled off from the fiber material and then the dye is fixed to the fiber material is used to improve the transportation problem and the difficulty in handling in the fixing device. Furthermore, when the base material is laminated paper, when a design is printed on the transfer paper with ink containing dye, the non-aqueous resin laminate layer prevents the dye from reaching the base paper, resulting in the design formed on the fiber material being deficient. and the decrease in color density are further suppressed.

The base paper includes chemical pulp 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), At least one pulp selected from mechanical pulps such as CTMP (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp), CGP (ChemiGroundwood Pulp), and waste paper pulp such as DIP (DeInked Pulp), heavy calcium carbonate, light calcium carbonate, Various fillers such as talc, clay, kaolin, and calcined kaolin, and various additives such as sizing agents, fixatives, retention agents, cationizing agents, and paper strength agents. is. Further, the base paper includes fine paper obtained by subjecting paper to calendering, surface sizing treatment with starch, polyvinyl alcohol, or the like, or surface treatment. Further, the base paper includes fine paper that has been calendered after surface sizing or surface treatment.

Paper making is carried out using a conventionally known paper machine by adjusting the stock to be acidic, neutral or alkaline. Examples of paper machines include fourdrinier paper machines, twin wire paper machines, combination 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 ease of paper handling, the basis weight of the base paper is preferably 10 g/m ² or more and 100 g/m ² or less, more preferably 30 g/m ² or more and 100 g/m ² or less.

Other additives in paper materials include binders, pigment dispersants, thickeners, fluidity improvers, defoaming agents, foam inhibitors, release agents, foaming agents, penetrants, coloring dyes, coloring pigments, One or two or more selected from fluorescent brighteners, ultraviolet absorbers, antioxidants, preservatives, anti-baking agents, water-resistant agents, wet paper strength agents and dry paper strength agents, etc. It can be blended as appropriate within a range that does not impair the effect of.

A substrate having a non-aqueous resin laminate layer on at least the side of the base paper on which the outermost coating layer is to be provided can be obtained by providing a non-aqueous resin laminate layer on one side of the base paper. The non-aqueous resin laminate layer has a function of assisting separation between the transfer paper and the fiber material and a function of preventing the permeation of the dye into the base paper.

The non-aqueous resin forming the non-aqueous resin laminate layer is a polyolefin resin, a vinyl resin, or a resin cured by an electron beam, which forms a water-insoluble layer on the base paper. Non-aqueous resins include, for example, polyethylenes such as high density polyethylene, low density polyethylene, medium density polyethylene and linear low density polyethylene; isotactic, syndiotactic, atactic, mixtures thereof, random copolymers with ethylene and block copolymers such as polypropylene; other examples include polymethylpentene, polyethylene glycol terephthalate, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl alcohol copolymer, ethylene vinyl acetate copolymer and the like. One or more selected from the group consisting of these can be used for the non-aqueous resin.

The method of providing the non-aqueous resin laminate layer on the base paper is not particularly limited. For example, a method using a conventionally known laminator device such as a general melt-extrusion die, a T-die, a multi-layer co-extrusion die and the like can be used. One or more non-aqueous resin laminate layers are provided on one side of the base paper. From the viewpoint of manufacturing cost, one non-aqueous resin laminate layer is preferable. The thickness of the non-aqueous resin laminate layer is preferably 10 μm or more, more preferably 15 μm or more. The reason for this is that the non-aqueous resin laminate layer has sufficient covering properties for the base paper and provides the above functions. Moreover, the thickness of the non-aqueous resin laminate layer is preferably 30 μm or less. The reason for this is that the above functions are saturated at 30 μm, and if the thickness exceeds 30 μm, the material cost increases.
When the non-aqueous resin laminate layer is one layer, the thickness of the layer is indicated, and when the non-aqueous resin laminate layer is two or more layers, the total thickness of these layers is indicated.

The coating layer can be provided by applying a coating layer coating solution to the substrate or the underlying coating layer and drying the coating layer.
The method of providing the coating layer is not particularly limited. For example, a method of coating and drying using a conventionally known coating apparatus and drying apparatus in the field of paper manufacturing can be mentioned. Examples of coating equipment include a size press, a gate roll coater, a film transfer coater, a blade coater, a rod coater, an air knife coater, a comma coater (registered trademark), a gravure coater, a bar coater, an E bar coater, and a curtain coater. be able to. Examples of the drying device include hot air dryers such as straight tunnel dryers, arch dryers, air loop dryers, sine curve air float dryers, infrared heating dryers, dryers using microwaves, and the like.
Moreover, the coating layer can be subjected to calendering after coating and drying.

The binder of the outermost coating layer contains at least water-soluble polyester resin, polyvinyl alcohol resin, acrylic resin and polysaccharide. By adding these binders to the coating liquid for the outermost coating layer, the outermost coating layer can contain a water-soluble polyester resin, a polyvinyl alcohol resin, an acrylic resin and a polysaccharide.

A water-soluble polyester resin is a resin obtained by a polycondensation reaction from a polycarboxylic acid and a polyol, and the polycarboxylic acid and the polyol occupy 60% by mass or more of the resin as constituent components. Examples of polyvalent carboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, and the like, and one or two selected from the group consisting of these. It is preferable to select and use the above. Examples of polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, and bisphenol. It is preferable to select and use one or more from the group consisting of. Moreover, the water-soluble polyester resin can be copolymerized with a component having a hydrophilic group such as a carboxyl group or a sulfonic acid group in order to increase the water solubility.
Water-soluble polyester resins are commercially available from GOO Chemical Industry Co., Ltd., Takamatsu Yushi Co., Ltd., Unitika Co., etc., and these commercial products can be used in the present invention. In addition, "water-soluble" refers to being able to finally dissolve in water at 20°C in an amount of 1% by mass or more.

Polyvinyl alcohol resins are various polyvinyl alcohols having various degrees of saponification and various degrees of polymerization, and various modified polyvinyl alcohols. Examples of modified polyvinyl alcohol include carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, phosphoric acid-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol. can be done. Further examples include modified polyvinyl alcohol obtained by copolymerizing ethylene, vinyl ether having a long-chain alkyl group, acrylamide, methacrylamide, and the like.

Polyvinyl alcohol resin is preferably carboxylic acid-modified polyvinyl alcohol. The reason for this is the better adhesion of the transfer paper to the fibrous material and the better release of the transfer paper from the fibrous material. Carboxylic acid-modified polyvinyl alcohol has a polyvinyl alcohol site modified with a carboxylic acid by introducing a carboxyl group.
Examples of the carboxylic acid-modified polyvinyl alcohol include those obtained by graft polymerization or block polymerization of polyvinyl alcohol and a vinyl carboxylic acid compound, those obtained by copolymerizing a vinyl ester compound and a vinyl carboxylic acid compound and then saponifying them. and those obtained by reacting polyvinyl alcohol with a carboxylating agent. Examples of the vinylcarboxylic acid compound include compounds containing carboxyl groups such as acrylic acid, methacrylic acid, (anhydrous) maleic acid, (anhydride) phthalic acid, (anhydride) itaconic acid, and (anhydride) trimellitic acid, or anhydride-containing compounds thereof. can be mentioned. Examples of the vinyl ester compound include vinyl acetate, vinyl formate, vinyl propionate, vinyl versatate, and vinyl bivalate. Examples of the carboxylating agent include succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, glutaric anhydride, hydrogenated phthalic anhydride, and naphthalenedicarboxylic anhydride. can be mentioned.
Carboxylic acid-modified polyvinyl alcohols are commercially available from Nippon Synthetic Chemical Industry Co., Ltd., Nippon Acetate & Poval Co., Ltd., Kuraray Co., Ltd., etc., and these commercial products can be used in the present invention.
The carboxylic acid-modified polyvinyl alcohol preferably has a number average degree of polymerization of 1000 or more and 3000 or less. Moreover, the carboxylic acid-modified polyvinyl alcohol preferably has a degree of saponification of 85 mol % or more and 90 mol % or less. These reasons are because it is excellent in compatibility with other resins.

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

Polysaccharides are conventionally known saccharides that are not classified as monosaccharides or oligosaccharides in which two to several molecules of monosaccharides are condensed by dehydration condensation of several or more monosaccharides through glycosidic bonds. Polysaccharides also include chemically modified ones. Examples of polysaccharides include carrageenan, agar, pectin, xanthan gum, guar gum, gellan gum, alginic acid and its salts, tara gum, tragacanth gum, tamarind seed gum, psyllium seed gum, karaya gum, starch and various modified starches, amylose, pullulan, dextran, Curdlan, lentinan, amylopectin, glycogen, xylan, galactan, mannan, glucomannan, glucomannoglycan, galactoglucomannoglycan, guaran, etc., and hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl starch, Celluloses such as hydroxypropyl starch, methylcellulose, carboxymethylcellulose, hydroxyethylmethylcellulose and hydroxypropylmethylcellulose can be mentioned.

Preferred polysaccharides are starch and various modified starches. Modified starch can be obtained by processing starch refined from natural plants. Examples of modified starch include hydroxyethylated starch, hydroxypropyl starch, oxidized starch, etherified starch, phosphated starch, urea phosphated starch, enzyme-modified starch, and cold water obtained by flash-drying them. Soluble starch.

A preferred polysaccharide is hydroxypropyl starch. The reason for this is that the adhesion of the transfer paper to the fiber material is improved and the color density of the pattern formed on the fiber material is improved. Hydroxypropyl starch is a modified starch obtained by etherifying some or all of the hydroxyl groups of glucose with propylene oxide to introduce hydroxypropyl groups in polysaccharides in which glucose is polymerized through glycosidic bonds.
Hydroxypropyl starch is commercially available from Nippon Starch Chemical Co., Ltd., Matsutani Kagaku Kogyo Co., Ltd., Ingredion Japan Co., etc., and these commercial products can be used in the present invention.

In the outermost coating layer, the content of each of the water-soluble polyester resin, polyvinyl alcohol resin, acrylic resin and polysaccharide is 5 parts by weight of the water-soluble polyester resin per 20 parts by mass of the white pigment in the outermost coating layer. It is preferable to use 10 to 35 parts by mass of polyvinyl alcohol resin, 5 to 25 parts by mass of acrylic resin, and 10 to 50 parts by mass of polysaccharide. In the outermost coating layer, the total binder content is 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.

The outermost coating layer can contain conventionally known binders in the field of coated paper, in addition to water-soluble polyester resins, polyvinyl alcohol resins, acrylic resins and polysaccharides. Examples of binders include water-soluble synthetic resins, water-dispersible synthetic resins, resins derived from natural components, and resins obtained by physically or chemically modifying these resins. Specific examples of binders include urethane resins, polyamide resins, vinyl acetate resins, styrene-butadiene-based copolymer resins, styrene-acrylic acid-based copolymer resins, styrene-maleic acid-based copolymer resins, and styrene-acrylic-maleic acid-based copolymer resins. Coalescent resins, water-insoluble polyester resins, polyvinyl acetal resins, proteins, casein, gelatin and the like can be mentioned.

In the outermost coating layer, the total content of the water-soluble polyester resin, polyvinyl alcohol resin, acrylic resin and polysaccharide preferably accounts for 85 mass % or more of the binder in the outermost coating layer.

White pigments are conventionally known white pigments in the coated paper field. White pigments include, for example, 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, diatomaceous earth, silicic acid Calcium, magnesium silicate, amorphous silica, colloidal silica, aluminum hydroxide, alumina, alumina hydrate, lithopone, zeolite, magnesium carbonate, inorganic pigments such as magnesium hydroxide, styrene plastic pigments, acrylic plastic pigments, styrene - organic pigments such as acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins;

The white pigment in the outermost coating layer preferably contains at least amorphous silica. The reason for this is the better adhesion of the transfer paper to the fibrous material and the better release of the transfer paper from the fibrous material.
Amorphous silica can be broadly classified into wet process silica and vapor phase process silica according to the manufacturing method. Further, wet process silica can be classified into precipitation process silica and gel process silica according to the manufacturing method. Precipitation silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the grown silica particles are aggregated and precipitated, and then filtered, washed with water, dried, pulverized, and classified. Precipitated silicas are, for example, Nipsil® from Tosoh Silica Corporation, Fineseal® and Toxil® from Oriental Silicas Corporation (OSC), and Mizukasil® from Mizusawa Kagaku Kogyo Co., Ltd. marketed as. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. Because fine particles dissolve during aging and re-precipitate to bind other primary particles together, gel-process silica loses distinct primary particles and forms relatively hard agglomerated particles with an internal void structure. do. Gel silica is commercially available, for example, from Tosoh Silica Corporation as Nipgel (registered trademark), and from Grace Japan as Syloid (registered trademark) and Sylojet (registered trademark). Vapor-phase silica is also called a dry method as opposed to a wet method, and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known. Silanes such as methyltrichlorosilane and trichlorosilane can be used alone or in combination with silicon tetrachloride instead of silicon tetrachloride. Vapor-phase silica is commercially available, for example, from Nippon Aerosil Co., Ltd. as Aerosil (registered trademark), and from Tokuyama Corporation as Reolosil (registered trademark).
The white pigment is more preferably precipitated silica.

The amorphous silica preferably has an average particle size of 6 μm or more, more preferably 10 μm or more. The amorphous silica preferably has an average particle size of 40 μm or less, more preferably 35 μm or less. More preferably, the amorphous silica has an average particle size of 10 μm or more and 28 μm or less. The reason for this is that the adhesion of the transfer paper to the textile material and/or the detachment of the transfer paper from the textile material after transfer of the dye is improved. The average particle size of amorphous silica is a volume-based value determined by laser diffraction/scattering particle size distribution measurement. The volume-based average particle size obtained by laser diffraction/scattering particle size distribution measurement can be measured and calculated using, for example, a laser diffraction/scattering particle size distribution analyzer Microtrac MT3000II manufactured by Nikkiso Co., Ltd. Amorphous silica satisfying the above average particle size can be obtained, for example, by dry pulverizing and/or wet pulverizing amorphous silica having relatively large particles and sizing. In addition, as the amorphous silica, commercially available products satisfying the above average particle size can be used.

The outermost coating layer may contain various additives conventionally known in the field of coated paper, if necessary, in addition to the white pigment and the binder. Examples of additives include dispersants, fixing agents, cationizing agents, thickeners, fluidity improvers, antifoaming agents, release agents, foaming agents, penetrating agents, coloring agents, fluorescent whitening agents, and UV absorbers. agents, antioxidants, preservatives, anti-fungal agents and the like.
Further, the outermost coating layer can contain various conventionally known auxiliaries in the transfer printing method. Auxiliary agents are added for the purpose of optimizing various physical properties of the outermost coating layer coating liquid, or improving the dyeability of the material to be printed. Auxiliaries include, for example, various surfactants, pH adjusters, alkaline agents, deep dyeing agents, moisturizing agents, degassing agents and anti-reducing agents.

The outermost coating layer contains two or more selected from the group consisting of urea, thiourea and dicyandiamide. In the outermost coating layer, 0 parts by mass or more and 3 parts by mass or less of urea, 20 parts by mass or more and 50 parts by mass or less of thiourea, and 20 parts by mass of dicyandiamide with respect to 20 parts by mass of the white pigment in the outermost coating layer. part or more and 50 parts by mass or less.
Urea, thiourea and dicyandiamide are conventionally added to textile pretreatment agents or printing inks as hydrotropic agents in the textile sector. The reason for this is that urea, thiourea and dicyandiamide have the effect of promoting the dyeing of the fiber material in the steaming treatment, which is the fixing treatment of the dye. Urea, thiourea and dicyandiamide are particularly suitable for reactive dyes. On the other hand, urea and thiourea are dye solvents that increase the solubility of dyes, and dicyandiamide has the property of polycondensation. Due to these properties, if the outermost coating layer of the transfer paper contains two or more selected from the group consisting of urea, thiourea and dicyandiamide in order to promote the dyeing, problems may occur. there were. The present inventor found a blending ratio when the outermost coating layer of the transfer paper contains urea, thiourea and dicyandiamide, and synergistic with the specific binder and the value of the ultrasonic transmission attenuation rate in the specific range described later. The effect led to the present invention.

If the urea content exceeds 3 parts by mass, the blocking resistance between transfer sheets and/or the color density of the pattern formed on the fiber material deteriorate. If the content of thiourea is less than 20 parts by mass, the adhesion of the transfer paper to the fibrous material and/or the peeling of the transfer paper from the fibrous material deteriorates. If the content of thiourea exceeds 50 parts by mass, the color density of the pattern formed on the fiber material deteriorates. If the content of dicyandiamide is less than 20 parts by mass, the adhesion of the transfer paper to the fiber material and/or the color density of the pattern formed on the fiber material deteriorates. If the content of dicyandiamide is more than 50 parts by mass, the transfer paper will be detached from the fibrous material.

The transfer paper has an ultrasonic wave transmission attenuation rate of 25% or more when permeated with water for 4 seconds. It is preferable that the transfer paper has an ultrasonic transmission attenuation rate of 25% or more and 90% or less when water is permeated for 4 seconds. In general, the value of the ultrasonic transmission attenuation rate is 100%, and the smaller the % value, the more water permeates. means The inventors have found that this value affects the peeling and adhesion between the transfer paper and the fibrous material and the blocking resistance of the transfer paper.
The attenuation rate of ultrasonic transmission through paper changes with time due to water penetration. The ultrasonic transmission attenuation rate can be measured, for example, under conditions of a temperature of 23° C. and a relative humidity of 50%, using a dynamic permeability measuring device (DPM) manufactured by Emco. In DPM, the paper to be tested is placed in a water-filled measurement container, with the paper secured to a sample holder so that water permeates only one side of the paper. Ultrasonic waves emitted from one side of the container pass through the water, the holder, and the test paper fixed to the holder, and reach the receiver installed on the other side. Since the ultrasonic transmission attenuation rate of water and the holder is constant, the change in the ultrasonic transmission attenuation rate over time is caused only by the change in the ultrasonic transmission of the paper under test due to the penetration of water into the paper. The ultrasonic transmission attenuation rate of the transfer paper is measured by fixing the transfer paper to a sample holder so that the surface having the outermost coating layer of the transfer paper faces the water side.

In general, the value of the ultrasonic transmission attenuation rate of coated paper changes with time as follows. In the measurement start time range, as the coated paper surface becomes wet with water, the reflection of ultrasonic waves at the interface between the coated paper and water decreases. Since the ultrasonic transmission of water is better than that of water, the received signal increases, and as a result, the value of the ultrasonic transmission attenuation rate becomes small. After that, as the water permeates the coated paper, the ultrasonic wave is scattered by the air bubbles left inside the coated paper, and the received signal decreases, resulting in attenuation of ultrasonic transmission. The rate value will increase. When water completely permeates the coated paper, the absorption of ultrasonic waves decreases and the received signal increases, resulting in a lower ultrasonic transmission attenuation factor.
The value of the ultrasonic transmission attenuation rate is, for example, the degree of calendering, the basis weight, the amount of coating, the type and content of the white pigment in the coating layer, the type and content of the binder, and the content ratio of the white pigment and the binder. It can be adjusted by the density and sizing degree of the base paper, and the content of ionic compounds such as printability improvers. In calendering, when the linear pressure is light, the large surface voids are crushed and the internal voids are maintained, and when the linear pressure is moderate, the surface voids are crushed and the internal voids are maintained, and the linear pressure is strong. Then, the voids on the surface are crushed and the inside is also densified. In calendering, when the treatment temperature rises, the binder in the coating layer softens, so that the voids tend to decrease and the ultrasonic transmission attenuation value tends to decrease. Water-soluble polyester resins, polyvinyl alcohol resins and acrylic resins are more easily softened than polysaccharides such as starches and celluloses. When the amount of coating is small, when the amount of binder is relatively large, or when the number of voids in the coated paper is reduced, the value of the ultrasonic transmission attenuation rate in the measurement start time region tends to be small. When the content of the binder in the coating layer increases with respect to the content of the white pigment, the number of voids in the coating layer decreases, which tends to reduce the value of the ultrasonic transmission attenuation factor.

In the transfer paper of the present invention, a pattern is printed with an ink containing a dye to form a transfer paper, and the transfer paper and the fiber material are brought into close contact with each other, and the dye is transferred from the transfer paper to the fiber material by applying heat and pressure. After that, the transfer paper is peeled off from the fiber material, and then the fiber material is subjected to dye fixation treatment such as steaming treatment.

Examples of dye-containing inks include inks containing dyes selected from reactive dyes, acid dyes, metal complex 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.

An ink containing a reactive dye can be prepared by adding a reactive dye as a coloring material to various solvents such as water and alcohol. The ink may optionally contain conventionally known auxiliary agents such as dispersants, resins, penetrants, humectants, thickeners, pH adjusters, antioxidants and reducing agents. Inks containing reactive dyes are also commercially available.

The transfer paper can be obtained by printing a design on the transfer paper with ink containing a dye. Printing is performed on the side of the transfer paper having the outermost coating layer. Examples of printing methods include a gravure printing method, a screen printing method, an inkjet printing method, and the like. Inkjet printing is preferable as a method of printing a design because of the relatively high degree of freedom in image quality and the inks to be used.

Heating and pressurizing the transfer paper and the fiber material in close contact is to bring the printing surface of the transfer paper on which the pattern is printed and the textile surface of the fiber material into close contact with each other, and apply heat and pressure in the close contact state. . The heating and pressing conditions for the close contact are conventionally known conditions for the transfer printing method. Examples of the method of applying heat and pressure in close contact include a method in which the transfer paper is brought into close contact with the fibrous material using a press machine, a heating roll, a heating drum, or the like, and then heated and pressurized.

Separation of the transfer paper from the fiber material is to physically separate the transfer paper from the fiber material from the fiber material and the transfer paper that are in close contact with each other. The peeling method is a conventionally known method and is not particularly limited. Examples of the method include a method in which the transfer paper and the fibrous material in a roll state in which the transfer paper and the fibrous material are adhered are separately wound up into rolls to separate them.

The dye fixation process is a process for fixing the dye transferred from the transfer paper to the fiber material, and is a conventionally known processing method in the field of textile printing. The dye fixation treatment includes, for example, steaming treatment, humidification treatment, and dry heat treatment at high temperature. The fixing treatment of the dye is preferably a steaming treatment. The steaming treatment is also called a wet fixing treatment and is a conventionally known treatment. Steaming treatment typically includes normal pressure steaming method, HT steaming method and HP steaming method. In general, wet heat treatment at about 105° C. for 10 minutes to 15 minutes in normal pressure steaming method, wet heat treatment at 150° C. to 180° C. for 5 minutes to 10 minutes in HT steaming method, HP steaming method The dye is fixed to the fiber material by wet heat treatment at 120° C. or higher and 135° C. or lower for 20 minutes or longer and 40 minutes or shorter.

The fiber material may be either natural fiber material or synthetic fiber material. Examples of natural fiber materials include cellulosic fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk, wool and animal hair. Examples of synthetic fiber materials include polyamide fiber (nylon), vinylon, polyester, and polyacryl. Examples of the structure of the fiber material include woven fabrics, knitted fabrics, non-woven fabrics, and the like, single, mixed, mixed, and mixed weaves. Furthermore, these configurations may be compounded.
The transfer paper of the present invention is suitable for natural fiber materials, especially cotton.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Here, "parts by mass" and "% by mass" respectively represent "parts by mass" and "% by mass" of the amount of dry solids and the amount of substantial components. The coating amount of the coating layer represents the dry solid content.

<Base paper>
10 parts by weight of calcium carbonate, 1.2 parts by weight of amphoteric starch, 0.8 parts by weight of aluminum sulfate, and 0.1 parts by weight of an alkylketene dimer type sizing agent are added to a pulp slurry consisting of 100 parts by weight of LBKP with a freeness of 380 mlcsf as fillers. 1.5 g/m ² of oxidized starch per side was applied to both sides with a size press, and machine calendering was performed to prepare a base paper with a basis weight of 50 g/m ² . .

<Base material 1>
One side of the base paper was laminated with high-density polyethylene using a melt extrusion die so as to have a thickness of 15 μm, thereby obtaining a substrate 1 having a non-aqueous resin laminate layer.

<Base material 2>
The base paper was used as the base material 2 .

<Coating layer coating liquid>
In each example and each comparative example, a coating solution for coating layer was prepared using water as a medium according to the following formulation. Finally, the concentration of the coating liquid for the coating layer was set to 15% by mass.
Water-soluble polyester resin The number of parts is listed in Tables 1 to 4 Carboxylic acid-modified polyvinyl alcohol The number of parts is listed in Tables 1 to 4 Acrylic resin The number of parts is listed in Tables 1 to 4 Hydroxypropyl starch The number of parts is listed in Tables 1 to 4 Amorphous silica Types and parts are listed in Tables 1 to 4 Fatty acid ester 10 parts by mass Urea Parts are listed in Tables 1 to 4 Thiourea Parts are listed in Tables 1 to 4 Dicyandiamide Parts are listed in Tables 1 to 4 Antifoaming agent 0.15 mass Part Sodium carbonate 25 parts by mass

In Tables 1 to 4, Pluscoat (registered trademark) RZ-142 manufactured by GOO CHEMICAL INDUSTRY CO., LTD. was used as the water-soluble polyester resin. Kuraray Poval (registered trademark) 25-88KL manufactured by Kuraray Co., Ltd. was used as the carboxylic acid-modified polyvinyl alcohol resin as the polyvinyl alcohol resin. NK Binder M-302HN manufactured by Shin-Nakamura Chemical Co., Ltd. was used as the acrylic resin. Pyostarch (registered trademark) H from Nippon Denkagaku Co., Ltd. was used as hydroxypropyl starch as a polysaccharide, and Mizukasil P-603 (average particle size 6 μm) from Mizusawa Chemical Industry Co., Ltd. was used as amorphous silica A. For the amorphous silica B, Tokusil NP (average particle size: 10.3 µm) manufactured by OSC was used. Mizusawa Chemical Industry Co., Ltd. Mizukasil P-78F (average particle size 18 μm) was used as the amorphous silica C. OSC BM225 (average particle diameter: 20.8 μm) was used as the amorphous silica D. For the amorphous silica E, amorphous silica (average particle size: 28 μm) obtained by subjecting NIPSEAL AQ of Tosoh Silica Co., Ltd. having an average particle size of about 100 μm to wet pulverization and sizing was used. For the amorphous silica F, amorphous silica (average particle size: 35 μm) obtained by subjecting NIPSEAL AQ of Tosoh Silica Co., Ltd. having an average particle size of about 100 μm to wet pulverization and sizing was used.

<Transfer paper>
Coating Layer The coating solution was applied onto one side of the substrate using an air knife coater and dried using a hot air dryer to form the coating layer as the outermost coating layer. After that, a calendering treatment was applied to finally produce a roll-shaped transfer paper. The coating amount of the outermost coating layer was 12 g/m ² for Examples 12 and 13 and Comparative Example 13, and 15 g/m ² for Examples 1 to 11 and 14 to 18 and Comparative Examples 1 to 12. The linear pressure and temperature conditions of the calendering treatment were adjusted so that the value of the transmission attenuation rate was a predetermined value.
In the substrate 1 having the non-aqueous resin laminate layer, the outermost coating layer was provided on the side having the laminate layer.
In Comparative Examples 12 and 13, the ratio of the binder content to the white pigment content in the outermost coating layer does not satisfy the conditions of the present invention. Comparative Example 12 is a design in which the content ratio of the binder in the outermost coating layer is considerably high relative to the content of the white pigment conventionally present in the field of transfer printing. In Comparative Example 13, the coating layer is designed such that the binder is in the range of 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of a white pigment conventionally known in the field of inkjet paper.

<Value of Ultrasonic Transmission Attenuation Rate>
The value of the ultrasonic transmission attenuation rate of the transfer paper to water was measured using DPM manufactured by Emco. The transfer paper was fixed to the sample holder so that the surface of the transfer paper having the outermost coating layer was positioned on the water side. The value was read 4 seconds after the start of measurement with an ultrasonic frequency of 2 MHz.

<Transfer paper>
Using an inkjet printer (ValueJet (registered trademark) VJ-1628TD, manufactured by Muto Kogyo Co., Ltd.) in which ink containing a reactive dye is set on a roll of transfer paper, ink ( Cyan, magenta, yellow, and black) were printed to obtain a sheet-like transfer paper. NOVACRON® MI inks from Huntsman were used for inks containing reactive dyes.

<Evaluation of blocking resistance>
A roll of transfer paper was unwound from an unwinder. Regarding the part of the unwound transfer paper where the pattern is printed, the pattern is missing and formed in the fiber material due to the adhesion of the components of the coating layer to the back surface of the transfer paper where the printed part of the transfer paper is in contact. The state of occurrence of color unevenness was visually observed, and sensory evaluation was performed according to the following criteria. Evaluation results are shown in Tables 1 to 4. In the present invention, if the evaluation is A, B or C, the transfer paper has anti-blocking properties.
A: Good with no adhesion, no chipping, and no color unevenness.
B: Although there is very little adhesion, there is no serious defect and there is no color unevenness, and it is generally good.
C: Adhesion is slightly observed, but there is no serious defect and the color unevenness is very slight, and practical use is possible.
D: Adhesion, missing and color unevenness, impractical.

<Transfer printing>
A roll of cotton cloth without pretreatment was used as the textile material. The printing surface of the transfer paper and the surface of the cotton cloth to be printed were conveyed so as to face each other, and were brought into close contact with each other by a roll nip method equipped with a heating roll, and heated and pressed. The heating and pressing conditions were a temperature of 120° C., a linear pressure of 70 kg/cm, and a time of 0.5 seconds.

<Peeling off the transfer paper>
The transfer paper was peeled off from the cotton cloth to which the transfer paper was adhered by a method in which the transfer paper and the cotton cloth were separately wound around rolls.

<Evaluation of peeling>
The state of the peeled surface of the cotton cloth when the transfer paper was peeled off from the cotton cloth and the state of the peeled surface of the cotton cloth after washing with water were observed. Based on the state of the peeled surface, sensory evaluation was performed according to the following criteria. Evaluation results are shown in Tables 1 to 4. In the present invention, if the evaluation is A or B, the transfer paper is considered to be well peeled from the cotton cloth.
A: It can be easily peeled off, and even if there is adhesion of the components of the outermost coating layer,
It can be easily removed by washing with water afterward, and the pattern formed is free of defects.
B: Although the components of the outermost coating layer are attached, they can be peeled off,
By subsequent washing with water, the adhering components can be removed, and the pattern formed is free of defects.
C: It is difficult or impossible to peel off, and there is a part where the transfer paper is torn and remains in close contact,
It is difficult to remove even after washing with water, or the pattern formed is missing.

<Steaming treatment of cotton cloth>
The roll of cotton cloth from which the transfer paper was peeled off was transported from the unwinder to the winder, during which it was subjected to wet heat treatment at 105° C. for 10 to 15 minutes by normal pressure steaming.

<Flush>
After steaming, the obtained cotton cloth was washed with running water.

<Evaluation of adhesion>
From the viewpoint of distortion and defocusing of the pattern formed on the cotton cloth, the good adhesion between the transfer paper and the fiber material was sensory evaluated according to the following criteria. Evaluation results are shown in Tables 1 to 4. In the present invention, if the evaluation is A, B or C, the transfer paper has good adhesion to the fibrous material.
A: Distortion and out-of-focus are not observed in the pattern. Good.
B: Distortion and/or out-of-focus is very slightly observed in the pattern.
but generally good.
C: Inferior to B above, distortion and/or out-of-focus are slightly observed.
But standard.
D: Inferior to C above, distortion and/or out-of-focus is observed.
but at a practicable level.
E: Inferior to D above, distortion and/or out-of-focus is observed. Impractical level.

<Evaluation of color density>
The color density of the three-color (cyan, magenta, yellow) solid image formed on the cotton cloth was measured using an optical densitometer (X-rite (registered trademark) 530, X-Rite Inc.). The color density values of the colors were summed. Based on the total value, the color density was evaluated according to the following criteria. Evaluation results are shown in Tables 1 to 4. In the present invention, if the transfer paper is evaluated as A, B or C, a fibrous material with good color density can be provided.
A: The total value is 4.8 or more B: The total value is 4.6 or more and less than 4.8 C: The total value is 4.4 or more and less than 4.6 D: The total value is 4.2 or more4. Less than 4 E: Total value less than 4.2

Each evaluation result is described in Tables 1 to 4.

From Tables 1 to 4, the transfer papers of Examples 1 to 18 corresponding to the present invention (1) have blocking resistance between the transfer papers and (2) have good adhesion of the transfer paper to the fiber material. (3) good color density of the pattern formed on the fibrous material; and (4) good release of the transfer paper from the fibrous material after transfer of the dye. On the other hand, Comparative Examples 1 to 13, which do not satisfy the constitution of the present invention, cannot simultaneously satisfy the effects (1) to (4) of the present invention.
Mainly from the comparison between Example 1 and Examples 14 to 18, it can be seen that the average particle size of the white pigment in the outermost coating layer is preferably 10 μm or more and 28 μm or less.

Claims (2)

The dye is transferred from the transfer paper to the fiber material by contacting the transfer paper obtained by printing the pattern with the ink containing the dye and the fiber material and applying heat and pressure, and after the transfer, the transfer paper is peeled off from the fiber material, A transfer paper before printing a pattern for use in a transfer printing method in which a dye is fixed to the fiber material after peeling, and the base paper has 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 base material, wherein the outermost coating layer positioned on the outermost side with respect to the base material in the coating layer is a white pigment. , a binder and two or more selected from the group consisting of urea, thiourea and dicyandiamide , and 0 parts by mass or more and 3 parts by mass or less of urea with respect to 20 parts by mass of the white pigment in the outermost coating layer; Thiourea is 20 parts by mass or more and 50 parts by mass or less, and dicyandiamide is 20 parts by mass or more and 50 parts by mass or less, the binder contains at least a water-soluble polyester resin, a polyvinyl alcohol resin, an acrylic resin and a polysaccharide, and the outermost coating In the work layer, the binder is 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. A transfer paper having an ultrasonic transmission attenuation rate of 25% or more as measured under conditions of a temperature of 23° C. and a relative humidity of 50% . 2. The transfer paper according to claim 1, wherein the white pigment in the outermost coating layer contains at least amorphous silica, and the amorphous silica has an average particle size of 10 [mu]m to 28 [mu]m.