JP2022046414A - Transfer sheet and transfer printing method - Google Patents

Abstract

To provide a transfer sheet used in a transfer printing method that uses printing ink, wherein the transfer sheet offers favorable adhesiveness and transfer efficiency and can be smoothly peeled off from a printing object.SOLUTION: The present invention discloses a transfer sheet used in a transfer printing method, the transfer sheet comprising a base sheet and one or more coating layers on at least one surface of the base sheet, wherein an outermost coating layer, located farthest out relative to the base sheet, is free of a white inorganic pigment and contains carboxymethyl cellulose and polyvinyl alcohol.SELECTED DRAWING: None

Description

The present invention relates to a transfer paper used for transferring a pattern in a transfer printing method using a printing ink for forming a pattern on a printed matter such as a textile material. In particular, the present invention relates to a transfer paper suitable for a transfer printing method using a sublimation type printing ink. The present invention also relates to a transfer printing method using the transfer paper.

It has excellent dryness and image reproducibility, strike-through prevention and heat resistance of the sublimation printing ink when printing on sublimation type printing transfer paper using the sublimation printing ink, and also has the image reproducibility of the transferred material by transfer. As a sublimation type printing transfer paper having good characteristics in terms of transfer efficiency, a sublimation printing ink receiving layer is provided on a substrate, and the sublimation printing ink receiving layer contains a water-soluble resin and fine particles, and the fine particles are contained. The particles are synthetic amorphous silica, and the water-soluble resin is polyvinyl alcohol in an amount of 1 to 200 parts by weight based on 100 parts by weight of the fine particles, and carboxymethyl cellulose in an amount of 20 to 399 parts by weight based on 100 parts by weight of the fine particles. It is characterized in that the water absorption of the sublimation type printing ink receiving layer conforming to JIS P 8140 is 15 g / m ² or more, and the surface of the sublimation printing ink receiving layer is uneven. Sublimation type printing transfer paper is known (see, for example, Patent Document 1).

Japanese Patent No. 5420209

The transfer paper, in which the design is printed on the transfer paper, needs to have two contradictory characteristics in the process of transferring the design to the printed matter. One is the characteristic that it adheres well to the printed matter at the time of transfer. The other is the property that it can be successfully peeled off from the printed matter after transfer. If the transfer paper is inferior in the property of being in close contact with each other, the image quality of the pattern formed on the printed matter is deteriorated due to misalignment or the like in the transfer process. If the transfer paper is inferior in the peelable property, the coloring material in the printing ink transferred to the printed matter is peeled off when the transfer paper is peeled from the printed matter, and defects and / or color unevenness occur.

Recently, as a printed matter, there is a fiber material having extensibility as typified by sportswear. When the stretchable fiber material is a printed matter, a shadow-like pattern on the original pattern called "ghost" is generated on the pattern formed on the printed matter. This phenomenon occurs because when the coloring material in the printing ink is transferred from the transfer paper to the printed matter, the printed matter is stretched with respect to the transfer paper while the transfer paper and the printed matter are in close contact with each other. When the conventional fiber material with almost no extensibility is a printed matter, if the transfer paper adheres well to the printed matter, the pattern formed by transferring from the transfer paper to the printed matter with respect to the image quality of the pattern printed on the transfer paper. Deterioration of image quality is suppressed. However, when the stretchable fiber material is a printed matter, the adhesiveness alone is not sufficient. The present inventor needs that when the stretchable fiber material is a printed matter, the transfer paper has a certain degree of adhesive strength and adheres to the printed matter (this is referred to as "adhesiveness" in the present specification). I found that. When the stretchable fiber material is a printed matter, the transfer paper is required to have not only adhesion to the printed matter but also adhesiveness. Moreover, the transfer paper must be removable from the printed matter.

Further, in order to efficiently transfer from the transfer paper to the printed matter, it is desired that the transfer paper and the coloring material in the printing ink have a low affinity. If the affinity between the transfer paper and the color material contained in the printing ink is not low, relatively large energy is required to transfer the color material in the printing ink from the transfer paper to the printed matter. For example, when transferring under the same temperature conditions, it takes a relatively long time to transfer the coloring material from the transfer paper to the printed matter.

In view of the above, an object of the present invention is to provide a transfer paper used for a transfer printing method and to provide a transfer printing method using the transfer paper, which have the following items.
(1) The transfer paper has good adhesion to the printed matter.
(2) The transfer efficiency of the transfer paper is good.
(3) The transfer paper can be successfully peeled off from the printed matter.

The present inventor has conducted extensive research to solve the above problems. As a result, the object of the present invention is achieved by the following.

[1] The base paper has one layer or two or more coating layers on at least one side of the base paper, and the outermost coating layer located on the outermost side of the base paper contains a white inorganic pigment. A transfer paper used in a transfer printing method that contains no or substantially no carboxymethyl cellulose and polyvinyl alcohol.

[2] In the outermost coating layer, the content mass ratio of the carboxymethyl cellulose to the polyvinyl alcohol is 200 parts by mass or more and 400 parts by mass or less of polyvinyl alcohol with respect to 100 parts by mass of the carboxymethyl cellulose. The described transfer paper.

[3] The transfer paper according to the above [1] or the above [2], wherein the polyvinyl alcohol is a carboxy group-modified polyvinyl alcohol.

[4] The transfer paper according to the above [3], wherein the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less, and a saponification degree of 80 mol% or more and 90 mol% or less.

[5] The transfer paper according to any one of [1] to [4] above, wherein the carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 770000 or less and an etherification degree of 0.6 or more and 1.27 or less.

[6] The transfer according to any one of the above [1], [3], [4] and [5], wherein the static friction coefficient is 0.4 or more and 0.6 or less on the side having the outermost coating layer. Paper.

[7] The step of printing a pattern on the transfer paper according to any one of the above [1] to [6] to obtain a transfer paper, and the surface on which the design of the transfer paper is printed is brought into close contact with the printed matter. Transfer printing method including steps.

INDUSTRIAL APPLICABILITY According to the present invention, a transfer paper used for a transfer printing method, which has good adhesiveness and transfer efficiency in a transfer paper and can be successfully peeled from a printed matter, is provided, and a transfer printing method using the transfer paper is provided. can do.

The present invention will be described in detail below.
In the present invention, the "transfer paper" refers to a paper that is in a blank state before the pattern to be transferred is printed. The "transfer paper" refers to a paper in which a pattern to be transferred is printed on the transfer paper.

The transfer paper has a base paper and one or more coating layers on at least one side of the base paper layer.
The base paper is 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), CTMP. (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp), mechanical pulp such as CGP (ChemiGroundwood Pulp), and waste paper pulp such as DIP (DeInked Pulp). Fillers for talc, clay, various kaolin, etc., as well as binders, sizing agents, fixing agents, yield agents, cationizing agents, pulp strength agents, pigment dispersants, thickeners, fluidity improving agents, defoaming agents, foam suppressants. Various additives such as agents, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent whitening agents, ultraviolet absorbers, antioxidants, preservatives, antibacterial agents and water resistant agents are added as needed. It consists of a paper pulp obtained by making a paper material mixed with the above. Further, the base paper includes high-quality paper obtained by subjecting the draft paper to a calendar treatment, a surface size treatment with starch, a styrene acrylic resin, or the like, or a surface treatment. Further, the base paper includes high-quality paper that has been subjected to surface size treatment or surface treatment and then calendar-treated.

In some embodiments, the abstracted paper has a density of 0.75 g / cm ³ or more and 0.85 g / cm ³ as required in accordance with ISO 534: 2011 "Paper and board-Determination of sickness, density and specific volume". It is as follows. The reason for this is that the adhesiveness is improved.

Paper making is performed using a conventionally known paper machine by adjusting the paper material to be acidic, neutral or alkaline. Examples of the paper machine include a long net paper machine, a twin wire paper machine, a combination paper machine, a circular net paper machine, a Yankee paper machine and the like.
The calendar processing is performed using a conventionally known calendar processing device. Examples of the calendar processing device include a machine calendar, a soft nip calendar, a super calendar, a multi-stage calendar, a multi-nip calendar, and the like.

In some embodiments, the pulp has a total of 80% by mass or more of LBKP and NBKP and 75% by mass or more and 95% by mass of LBKP having a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp of the base paper. % Or less, and NBKP in the range of a drainage degree of 400 ml or more and 480 ml or less is 5% by mass or more and 25% by mass or less. These reasons are that the adhesiveness and transfer efficiency are improved. Adhesion is related to the elongation of the paper. Although NBKP can obtain strength, it has many interfiber bonds due to its long fiber length and is difficult to stretch. Compared to NBKP, LBKP has a shorter fiber length and is easier to stretch, but has a water-retaining ability and adversely affects transfer efficiency. When the drainage degree is, for example, a small value, the water retention capacity and the specific surface area of the paper increase. As a result, the affinity for the printing ink becomes high, which adversely affects the transfer efficiency. If the combination of LBKP and NBKP, which is the range of the above-mentioned drainage degree, is used, the transfer paper can obtain appropriate stretchability and does not adversely affect the transfer efficiency. Here, the drainage degree is a CSF drainage degree obtained according to ISO5267-2: 2001 "Pulps-Determination of drainability-Part 2 Canadian Standard freeens method".

In the above-mentioned coating layer, the coating layer located on the outermost side with respect to the base paper is referred to as the outermost coating layer. When there is only one coating layer, the coating layer is the outermost coating layer. The outermost coating layer contains carboxymethyl cellulose and polyvinyl alcohol as a binder. When there are two or more coating layers, the coating layer existing between the base paper and the outermost coating layer is a white color such as the type and quantity of the binder and the synthetic amorphous silica described in Patent Document 1. The presence / absence, type and quantity of the inorganic pigment, and the presence / absence and quantity of other conventionally known additives are not particularly limited. In some embodiments, the coating layer is one layer. The reason for this is that the manufacturing cost of the transfer paper becomes advantageous. Further, the coating layer may be provided on one side or both sides of the base paper. When the outermost coating layer according to the present invention is provided on one side of the base paper, the transfer paper may have a conventionally known back coat layer on the back surface of the base paper, for example, for the purpose of preventing curling of the paper.

The coating layer including the outermost coating layer can be obtained by coating and drying the coating layer coating liquid on the base paper or the coating layer using a conventionally known coating device and drying device. Can be done. In some embodiments, the coating layer is in a state where the components of the coating layer coating liquid are present on the surface of the base paper as a coating layer region and / or the components of the coating layer coating liquid have penetrated into the inside of the base paper. Includes a state that exists as a diffusion layer region. That is, the coating layer is one of a state in which it exists as a coating layer region, a state in which it exists as a diffusion layer region, and a state in which it exists as both a coating layer region and a diffusion layer region with respect to the base paper. .. The state of the coating layer can be confirmed by observing the cross section of the paper with an electron microscope having an elemental analysis function such as an energy dispersive X-ray spectroscope and analyzing the elemental distribution.
The state existing as the coating layer region and / or the state existing as the diffusion layer region includes the density of the base paper, the type and content of the binder in the base paper, the type and content of the sizing agent in the base paper, and the paper strength in the base paper. It can be controlled by the type and content of the agent, the calendar processing conditions for the base paper, and the presence / absence and components of the coating layer between the base paper and the outermost coating layer.
In at least one embodiment, the outermost coated layer is a state in which it exists as a coating layer region or a state in which it exists as both a coating layer region and a diffusion layer region with respect to the base paper. The reason for this is that the adhesiveness is improved.

Examples of conventionally known coating devices include size presses, gate roll coaters, film transfer coaters, blade coaters, rod coaters, air knife coaters, gravure coaters, bar coaters, E bar coaters, curtain coaters and the like. Examples of conventionally known drying devices include various drying devices such as straight tunnel dryers, arch dryers, air loop dryers, hot air dryers such as sine curve air float dryers, infrared heating dryers, and dryers using microwaves. Can be mentioned.
Coating layer After coating and drying the coating liquid, the coating layer can be subjected to calendar treatment.

In some embodiments, the coating amount of the coating layer is 2 g / m ^{2 or more and 6 g / m 2 or} less per one side of the base paper in terms of dry solid content. The reason for this is that the adhesiveness and / or the peeling from the printed matter is improved.

Carboxymethyl cellulose is a kind of cellulose ether, which is conventionally known and is not particularly limited. Carboxymethyl cellulose contains alkali metal salts. Carboxymethyl cellulose can be obtained, for example, by reacting sodium monochloroacetate and sodium hydroxide with pulp as a raw material (direct method). In addition to the direct method, it can be obtained by the Arcel method and the solvent method. Carboxymethyl cellulose can be produced with various molecular weights or degrees of polymerization depending on the properties of the pulp used and the production method. Generally, carboxymethyl cellulose is industrially produced and sold as a carboxymethyl cellulose alkali metal salt. Most of the carboxymethyl celluloses are sodium carboxymethyl cellulose or potassium carboxymethyl cellulose. Conventionally, the description of sodium and potassium is often omitted. In at least one embodiment, the carboxymethyl cellulose is sodium carboxymethyl cellulose. The reason for this is that sodium carboxymethyl cellulose is commercially available. Carboxymethyl cellulose is commercially available from, for example, Sigma-Aldrich, Daicel FineChem, Dai-ichi Kogyo Seiyaku, CPKelco, Nippon Paper Industries, Ashland, and the like.

In some embodiments, carboxymethyl cellulose is a low molecular weight type obtained by gel permeation chromatography (GPC method) having a weight average molecular weight of less than 1 million in terms of polyethylene glycol. In some embodiments, carboxymethyl cellulose has a weight average molecular weight of 770000 or less. Also, in some embodiments, carboxymethyl cellulose has a weight average molecular weight of 27,000 or more. Further, in at least one embodiment, carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 770000 or less. These reasons are because the transfer efficiency is improved.
In some embodiments, the degree of etherification of carboxymethyl cellulose is 0.6 or more and 1.27 or less. The reason for this is that the adhesiveness is improved. The degree of etherification refers to the number (mean value) of the hydroxyl groups substituted with carboxymethyl groups among the three hydroxyl groups on the glucose ring constituting cellulose. The degree of etherification can theoretically have a value between 0 and 3, and generally, the higher the degree of substitution, the more hydrophilic the material.
In at least one embodiment, the carboxymethyl cellulose has a polyethylene glycol-equivalent weight average molecular weight obtained by the GPC method of 27,000 or more and 770000 or less, and an etherification degree of 0.6 or more and 1.27 or less.

Polyvinyl alcohol is a general term that includes general polyvinyl alcohol and various modified polyvinyl alcohols. The polyvinyl alcohol is a conventionally known polyvinyl alcohol and various modified polyvinyl alcohols. Examples of polyvinyl alcohol include polyvinyl alcohol having various degrees of saponification and various average degree of polymerization, modified polyvinyl alcohol having various functional groups such as silyl group, carboxy group, amino group and acetoacetyl group introduced, and other polyvinyl alcohol such as ethylene. Examples thereof include modified polyvinyl alcohol in which a monomer is randomly, grafted or blocked. In some embodiments, the polyvinyl alcohol is one or more selected from the group consisting of polyvinyl alcohols having various saponification degrees and various average degrees of polymerization and modified polyvinyl alcohols.
Polyvinyl alcohol is commercially available from Mitsubishi Chemical Corporation, Kuraray Corporation, Japan Vam & Poval Corporation, Denka Corporation and the like.

In some embodiments, the polyvinyl alcohol is a carboxy group modified polyvinyl alcohol. The reason for this is that the peeling from the printed matter is improved. The carboxy group-modified polyvinyl alcohol is a polyvinyl alcohol having a site in which a carboxy group is introduced and carboxylic acid-modified.
The carboxy group-modified polyvinyl alcohol is obtained by graft polymerization or block polymerization of polyvinyl alcohol and a vinyl carboxylic acid compound, or obtained by copolymerizing a vinyl ester compound and a vinyl carboxylic acid compound and then saponifying the compound. , And those obtained by reacting polyvinyl alcohol with a carboxylating agent. Examples of the vinyl carboxylic acid compound include (anhydrous) carboxy group-containing compounds such as (meth) acrylic acid, (maleic) maleic acid, (anhydrous) phthalic acid, and (anhydrous) itaconic acid. Examples of the vinyl ester compound include vinyl acetate, vinyl formate, vinyl propionate, vinyl versatic acid, vinyl vivalate and the like. Examples of the carboxylating agent include succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, glutaric anhydride, hydrogenated phthalic anhydride, naphthalenedicarboxylic acid anhydride and the like. Can be mentioned.
In some embodiments, the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less, which is determined according to JIS K6726: 1994 "Testing methods for polyvinyl alcohol". Further, in some embodiments, the carboxy group-modified polyvinyl alcohol has a saponification degree of 80 mol% or more and 90 mol% or less, which is obtained according to JIS K6726: 1994 "Testing methods for polyvinyl alcohol". .. In at least one embodiment, the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less and a saponification degree of 80 mol, which are obtained according to JIS K6726: 1994 "Testing methods for polyvinyl alcohol". % Or more and 90 mol% or less. The reason for these is that the coating of the outermost coating layer becomes uniform due to the excellent compatibility with carboxymethyl cellulose, and as a result, the adhesiveness of the transfer paper is improved and the peeling from the printed matter is improved. ..

In some embodiments, the carboxy group-modified polyvinyl alcohol has a modification amount of 0.5 mol% or more and 5 mol% or less. The reason for this is that the transfer efficiency of the transfer paper is improved. The degree of denaturation is, for example, a numerical value obtained from measurement by ¹ H-NMR method.
Further, in at least one embodiment, the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less and a saponification degree obtained according to JIS K6726: 1994 "Testing methods for polyvinyl alcohol". Is 80 mol% or more and 90 mol% or less, and the modification amount is 0.5 mol% or more and 5 mol% or less.

In some embodiments, the mass ratio of carboxymethyl cellulose to polyvinyl alcohol in the outermost coated layer is 200 parts by mass or more and 400 parts by mass of polyvinyl alcohol with respect to 100 parts by mass of carboxymethyl cellulose in the outermost coated layer. It is less than a part. In at least one embodiment, the content mass ratio of carboxymethyl cellulose and polyvinyl alcohol in the outermost coated layer is 200 parts by mass or more and 400 parts by mass of polyvinyl alcohol with respect to 100 parts by mass of carboxymethyl cellulose in the outermost coated layer. The polyvinyl alcohol is a carboxy group-modified polyvinyl alcohol.
The reason for these is that adhesiveness and good peeling from the printed matter can be obtained moderately.

The outermost coating layer can contain a conventionally known binder in addition to carboxymethyl cellulose and polyvinyl alcohol. Conventionally known binders are, for example, starches such as starch, processed starch and modified starch, celluloses such as hydroxyethyl cellulose excluding carboxymethyl cellulose, and naturally derived binders such as casein, gelatin, soybean protein, purulan, Arabica rubber, Karaya rubber and albumin. Resin or its derivative, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polypropylene glycol, polyethylene glycol, maleic anhydride resin, (meth) acrylic acid resin, (meth) acrylic acid ester resin, (meth) acrylic acid ester-butadiene Copolymer resins such as polymers, styrene-butadiene copolymers and ethylene-vinyl acetate copolymers, and functional group-modified copolymer resins using functional group-containing monomers such as carboxy groups of these various copolymers. , Binders such as heat-curable synthetic resins such as melamine resin and urea resin, polyurethane resins, unsaturated polyester resins, polyvinyl butyral, alkyd resin latex and the like can be mentioned.
In some embodiments, the outermost coated layer has a total of 80 parts by mass or more of carboxymethyl cellulose and polyvinyl alcohol with respect to 100 parts by mass of the binder in the outermost coated layer. In at least one embodiment, the outermost coating layer contains no conventionally known binder other than carboxymethyl cellulose and polyvinyl alcohol.

The outermost coating layer does not contain or substantially does not contain a white inorganic pigment. The reason for this is that the content of the white inorganic pigment deteriorates the adhesiveness and the transfer efficiency. "Substantially free" means that the outermost coating layer can contain a white inorganic pigment as long as the adhesiveness and transfer efficiency are not deteriorated. The range in which the white inorganic pigment is substantially not contained is, for example, 5% by mass or less with respect to the dry solid content forming the outermost coating layer coating layer. The white inorganic pigment adsorbs carboxymethyl cellulose and polyvinyl alcohol, which reduces the flexibility of the outermost coating layer. As a result, the adhesiveness of the transfer paper deteriorates. Further, for example, the white inorganic pigment easily adsorbs the coloring material in the printing ink. As a result, the transfer efficiency of the transfer paper deteriorates.

White inorganic pigments include, for example, kaolin, heavy calcium carbonate, light calcium carbonate, talc, satin white, lithopone, titanium oxide, zinc oxide, amorphous silica, colloidal silica, alumina, aluminum hydroxide, zinc oxide, and active white clay. And calcium soil and the like.

The outermost coated layer can contain various additives conventionally known in the field of coated paper, if necessary. Examples of additives include dispersants, fixers, thickeners, fluidity improvers, defoamers, mold release agents, foaming agents, penetrants, colorants, printability improvers, optical brighteners, UV rays. Examples thereof include absorbents, antioxidants, preservatives, antifoaming agents and the like.
Further, the outermost coating layer can contain various conventionally known auxiliaries by the transfer printing method. The auxiliary agent is added to optimize various physical properties of the coating layer coating liquid, or to improve the dyeing property of the coloring material contained in the printing ink such as the sublimation type printing ink. Examples of the auxiliary agent include various surfactants, moisturizers, wetting agents, pH adjusting agents, alkaline agents, deep dyeing agents, deaeration agents, anti-reduction agents and the like.

In some embodiments, the transfer paper, on the side with the outermost coating layer, is ISO 15359: 1999 "Paper and board-Determination of the static and kinetic cofections of friction" -Horizontal coefficient. Is 0.4 or more and 0.6 or less. The reason for this is that the adhesiveness of the transfer paper is improved and the peeling from the printed matter is improved. The coefficient of static friction can be controlled from the viewpoints of smoothness, coating amount and composition of the outermost coating layer, density and hydrophilicity of the outermost coating layer, for example. As the coating amount, smoothness and density of the outermost coating layer increase, the value of the static friction coefficient decreases. As the hydrophilicity of the outermost coating layer increases, the value of the static friction coefficient increases. If a lubricant and a surfactant are contained as the components of the outermost coating layer, the value of the static friction coefficient becomes small. When an inorganic pigment and a resin are contained as the components of the outermost coating layer, the value of the static friction coefficient becomes large. The density of the outermost coating layer can be somewhat controlled by the coating and drying conditions of the coating layer coating liquid. For example, the density of the outermost coating layer tends to increase with the use of contact coating equipment and slower drying rates.

In some embodiments, the transfer paper is such that the polyvinyl alcohol contained in the outermost coating layer is a carboxy group-modified polyvinyl alcohol, and the static friction coefficient on the side having the outermost coating layer is 0.4 or more and 0.6. It is as follows. Further, in some embodiments, in the transfer paper, the polyvinyl alcohol contained in the outermost coating layer is a carboxy group-modified polyvinyl alcohol, and the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less and a saponification degree. It is 80 mol% or more and 90 mol% or less, and the static friction coefficient on the side having the outermost coating layer is 0.4 or more and 0.6 or less. In at least one embodiment, in the transfer paper, the polyvinyl alcohol contained in the outermost coating layer is a carboxy group-modified polyvinyl alcohol, and the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less and a saponification degree of 80 mol%. 90 mol% or less, and the carboxymethyl cellulose contained in the outermost coating layer has a weight average molecular weight of 27,000 or more and 770000 or less, an etherification degree of 0.6 or more and 1.27 or less, and static friction on the side having the outermost coating layer. The coefficient is 0.4 or more and 0.6 or less.

The transfer paper can be obtained by printing a pattern on the surface side of the transfer paper having the outermost coating layer by using various conventionally known printing methods including a printing ink such as a sublimation type printing ink.
Various printing methods for printing a pattern on transfer paper are conventionally known printing methods and are not particularly limited. Examples of the printing method include a gravure printing method, an inkjet printing method, an electrophotographic printing method, a screen printing method, and the like. In at least one embodiment, the printing method for printing a pattern on transfer paper is an inkjet printing method.

The transfer printing method is a method including a step of printing a pattern on a transfer paper to obtain a transfer paper, and a step of bringing the printed surface of the transfer paper into close contact with the printed matter. The step of bringing them into close contact includes heating or heating and pressurizing, if necessary. Each condition of heating or heating and pressurizing in the step of bringing them into close contact is a condition conventionally known in the transfer printing method. Examples of the step of bringing the transfer paper into close contact with the printed matter include a method of bringing the transfer paper into close contact with the printed matter by a press machine, a heating drum, or the like to heat or pressurize the printed matter.
In at least one embodiment, the printing ink used in the transfer printing method is a sublimation type printing ink.

The printed matter is a fiber material and is not particularly limited. The fiber material may be either a natural fiber material or a synthetic fiber material. Examples of the natural fiber material 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 the synthetic fiber material include polyamide fiber (nylon), vinylon, polysell, and polyacrylic acid. In at least one embodiment, when a sublimation type printing ink is used, the fiber material is polyester. Further, if necessary, the printed matter may be pretreated with a chemical or the like effective for promoting dyeing.

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

(Base paper)
A pulp slurry in which a total of 1000 parts by mass of LBKP and NBKP whose drainage degree was adjusted by beating was dispersed in water, 25 parts by mass of talc and 50 parts by mass of light calcium carbonate, 10 parts by mass of cationized starch, and 9 parts by mass of aluminum sulfate were used as fillers. 0.7 parts by mass of an alkyl ketene dimer type sizing agent was added, and papermaking was performed with a long net paper machine to obtain papermaking. The obtained paper was subjected to machine calendar processing to obtain a calendar-processed paper. The density of the paper thus obtained was 0.81 g / cm ³ . A base paper was prepared by applying a size press to both sides of the calendar-treated papermaking so that the amount of the oxidized starch applied to one side was 1 g / m ² . The drainage degrees of LBKP and NBKP and the contents of LBKP and NBKP in 1000 parts by mass are shown in Tables 1 to 3. Here, the degree of drainage was CSF degree of drainage, and was determined according to ISO5267-2: 2001.

(Coating layer coating liquid of the outermost coating layer)
The coating layer coating liquid was prepared according to the following contents.
Cellulose by mass is shown in Tables 1 to 5. Polyvinyl alcohol by mass is shown in Tables 1 to 5. White inorganic pigments by mass are shown in Tables 1 to 5. Mix and disperse with water. , The concentration was adjusted to 10% by mass.

The materials listed in the table using the coating layer coating liquid of the outermost coating layer are as follows.
(cellulose)
Ce1: Carboxymethyl cellulose
(Weight average molecular weight 260000, degree of etherification 0.7)
Ce2: Hydroxymethyl cellulose
(Weight average molecular weight 278,000, degree of etherification 0.9)
Ce3: Carboxymethyl cellulose
(Weight average molecular weight 10000, degree of etherification 0.65)
Ce4: Carboxymethyl cellulose
(Weight average molecular weight 27,000, degree of etherification 0.6)
Ce5: Carboxymethyl cellulose
(Weight average molecular weight 360000, degree of etherification 1.2)
Ce6: Carboxymethyl cellulose
(Weight average molecular weight 770000, degree of etherification 1.27)
Ce7: Carboxymethyl cellulose
(Weight average molecular weight 1400000, degree of etherification 1.1)
Ce8: Carboxymethyl cellulose
(Weight average molecular weight 250,000, degree of etherification 0.55)
Ce9: Carboxymethyl cellulose
(Weight average molecular weight 550000, degree of etherification 1.3)
(Polyvinyl alcohol)
Po1: Polyvinyl alcohol
(Saponification degree 88 mol%, average polymerization degree 300)
Po2: Carboxy group modified polyvinyl alcohol
(Saponification degree 86 mol%, average polymerization degree 300)
Po3: Carboxy group modified polyvinyl alcohol
(Saponification degree 81 mol%, average polymerization degree 350)
Po4: Carboxy group modified polyvinyl alcohol
(Saponification degree 90 mol%, average polymerization degree 200)
Po5: Carboxy group modified polyvinyl alcohol
(Saponification degree 74 mol%, average polymerization degree 350)
Po6: Carboxy group modified polyvinyl alcohol
(Saponification degree 98 mol%, average polymerization degree 200)
Po7: Carboxy group modified polyvinyl alcohol
(Saponification degree 85 mol%, average polymerization degree 3000)
Po8: Carboxy group modified polyvinyl alcohol
(Saponification degree 84 mol%, average polymerization degree 3600)
Po9: Carboxy group modified polyvinyl alcohol
(Saponification degree 88 mol%, average polymerization degree 150)
Po10: Sulfonic acid group-modified polyvinyl alcohol
(Saponification degree 88 mol%, average polymerization degree 300)
(White inorganic pigment)
Pg1: Synthetic amorphous silica (average particle size 2.3 μm aggregated particles)

(Transfer paper)
The transfer paper was prepared by the following procedure.
On one side of the base paper, the coating layer coating liquid of the outermost coating layer was coated with an air knife coater and dried with a hot air dryer. After drying, a calendar process was applied to obtain transfer paper. Except for Examples 39 and 41 to 43, and Examples 44 and 46 to 48, the coating amount was 4 g / m ² . In Examples 39 and 41 to 43, and Examples 44 and 46 to 48, the static friction coefficient was adjusted according to the coating amount, the drying condition and the calendar condition. Examples 39 and 44 have a coating amount of 3 g / m ² , Examples 41 and 46 have a coating amount of 5 g / m ² , Examples 42 and 47 have a coating amount of 7 g / m ² , and Examples 43 and 48. The coating amount was 10 g / m ² .

(Transfer paper)
Using an inkjet printer (JV2-130II, manufactured by Mimaki Engineering Co., Ltd.) using sublimation type printing ink on the obtained transfer paper, each ink single color of sublimation type printing ink (cyan, magenta, yellow, black) and yellow Print and transfer an evaluation pattern consisting of green, which is a mixture of cyan and magenta, red, which is a mixture of yellow and magenta, blue, which is a mixture of cyan and magenta, and black, which is a mixture of yellow, cyan, and magenta. I got a piece of paper.

(Transfer printing)
As a printed matter, a white polyester cloth having 2-way stretchability (stretchability) was used. The surface of the transfer paper having the coated layer and the white polyester cloth faced each other and adhered to each other. The transfer paper in which the white polyester cloth was in close contact was heated at a temperature of 190 ° C. for 30 to 60 seconds using a thermal transfer press (INSTA, USA, heat press model 204).

(Adhesiveness)
The evaluation pattern formed on the white polyester cloth by the transfer printing method was observed with the naked eye and a magnifying glass with the transfer printing time set to 45 seconds, and evaluated according to the following criteria. In the present invention, it is assumed that the transfer paper has good adhesiveness if the evaluation is 3 to 5.
5: Moderate adhesive strength to the printed matter is recognized, and the followability to the printed matter is good.
Ghosts are not seen with a magnifying glass.
4: Some adhesive strength to the printed matter is recognized, and it has the ability to follow the printed matter.
Ghosts are generally not seen with a magnifying glass.
3: Slight adhesive strength to the printed matter is recognized, and it has a slight followability to the printed matter.
Ghosts are not visible to the naked eye and are slightly visible with a magnifying glass.
2: There is no adhesiveness to the transferred matter, and the followability to the printed matter is extremely small.
Ghosts are slightly visible to the naked eye.
1: There is a difficulty in adhesion to the printed matter, and there is no followability to the printed matter.
Ghosts are visible to the naked eye.

(Transfer efficiency)
The color density of the pattern in the white polyester on which the pattern was formed was visually observed by changing the heating time at the time of transfer printing, and evaluated according to the following criteria. The heating time was 30 seconds, 45 seconds and 60 seconds. In the present invention, it is assumed that the transfer paper has a good transfer efficiency if the evaluation is 3 to 5.
There is no change in color density at 5:30 seconds, 45 seconds and 60 seconds.
A slight change in color density is observed between 4:30 seconds and 45 seconds.
No change in color density is observed between 45 seconds and 60 seconds.
A slight change in color density is observed between 3:30 seconds and 45 seconds.
No change in color density is observed between 45 seconds and 60 seconds.
A slight change in color density is observed between 2:45 and 60 seconds.
A change in color density is observed between 1:45 and 60 seconds.

(Peeling)
The state of the printed matter when the transfer paper was peeled off from the printed matter was observed. The surface of the printed matter was visually observed and evaluated according to the following criteria. In the present invention, if the evaluation is 3, 4 or 5, the transfer paper can be successfully peeled off from the printed matter.
5: Can be peeled off smoothly, and there is no adhesion of the outermost coating layer to the printed matter.
No defects or uneven color are observed in the formed pattern.
4: Can be peeled off, and there is very little adhesion of the outermost coating layer.
No defects or uneven color are observed in the formed pattern.
3: It can be peeled off more slowly than 4 above, and there is some adhesion of the outermost coating layer.
No defects or uneven color are observed in the formed pattern.
2: It can be peeled off more slowly than 3 above, and the outermost coating layer is attached.
Defects or uneven color are slightly observed in the formed pattern.
1: It is difficult to peel off, and there is a lot of adhesion of the outermost coating layer.
Defects or uneven color are observed in the formed pattern.

The evaluation results are shown in Tables 1 to 5.

From the evaluation results of Tables 1 to 5, the transfer papers of Examples 1 to 48 according to the present invention have good adhesiveness and transfer efficiency in the transfer paper, and the transfer paper can be successfully peeled off from the printed matter. On the other hand, the transfer papers of Comparative Examples 1 to 4 which do not satisfy the configuration of the present invention cannot satisfy at least one of the effects according to the present invention.

Mainly, from the comparison between Examples 1 to 10, the content mass ratio of carboxymethyl cellulose and polyvinyl alcohol in the outermost coating layer is 200 parts by mass or more and 400 parts by mass with respect to 100 parts by mass of carboxymethyl cellulose. It can be seen that the transfer paper can be moderately adhesive and peeled off from the printed matter well when the amount is less than or equal to the part.

Mainly, from the comparison between Examples 1 to 5 and Examples 6 to 10, it can be seen that when the polyvinyl alcohol is a carboxy group-modified polyvinyl alcohol, the transfer paper is better peeled from the printed matter.

Mainly, from the comparison between Examples 11 to 23, the base paper has a drainage degree of 380 ml or more and a range of 480 ml or less, and LBKP has a drainage degree of 75% by mass or more and 95% by mass or less and a drainage degree of 400 ml or more and 480 ml or less. It can be seen that when the NBKP is 5% by mass or more and 25% by mass or less, the transfer paper has improved adhesiveness and transfer efficiency.

Mainly, from the comparison between Examples 8 and 24 to 30, the carboxymethyl cellulose of the outermost coated layer has a weight average molecular weight of 27,000 or more and 770000 or less in terms of polyethylene glycol obtained by the GPC method and a degree of etherification of 0. It can be seen that when the content is 6 or more and 1.27 or less, the adhesiveness and transfer efficiency of the transfer paper are improved.

Mainly, from the comparison between Examples 8 and 31 to 38, it is said that the carboxy-modified polyvinyl alcohol of the outermost coated layer has an average degree of polymerization of 200 or more and 3000 or less and a saponification degree of 80 mol% or more and 90 mol% or less. It can be seen that the transfer paper has improved adhesiveness and can be successfully peeled off from the printed matter.

Mainly, from the comparison between Examples 39 to 43 or between Examples 44 to 48, when the static friction coefficient on the side having the outermost coating layer is 0.4 or more and 0.6 or less, the transfer paper is determined. It can be seen that the adhesiveness is improved and the printed matter can be peeled off well.

Further, the following additional notes are disclosed with respect to the above-described embodiment of the present invention.

<1>
The base paper has one layer or two or more coating layers on at least one side of the base paper, and the outermost coating layer located on the outermost side of the base paper does not contain or substantially contains a white inorganic pigment. A transfer paper used in a transfer printing method using a printing ink, which does not contain carboxymethyl cellulose and polyvinyl alcohol.

<2>
The transfer according to <1>, wherein in the outermost coating layer, the content mass ratio of the carboxymethyl cellulose to the polyvinyl alcohol is 200 parts by mass or more and 400 parts by mass or less of polyvinyl alcohol with respect to 100 parts by mass of carboxymethyl cellulose. Paper.

<3>
The transfer paper according to <1> or <2>, wherein the polyvinyl alcohol is a carboxy group-modified polyvinyl alcohol.

<4>
The transfer paper according to <3>, wherein the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less, and a saponification degree of 80 mol% or more and 90 mol% or less.

<5>
The transfer paper according to any one of <1> to <4>, wherein the carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 770000 or less and an etherification degree of 0.6 or more and 1.27 or less.

<6>
The transfer paper according to any one of <1>, <3>, <4> and <5>, wherein the static friction coefficient is 0.4 or more and 0.6 or less on the side having the outermost coating layer.

<7>
The base paper contains pulp, and the pulp in the base paper has a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp in the base paper. The transfer paper according to <1> above, wherein NBKP in the range of 5% by mass or more and 25% by mass or less.

<8>
The base paper contains pulp, and the pulp in the base paper has a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp in the base paper. The transfer paper according to <3> above, wherein NBKP in the range of 5% by mass or more and 25% by mass or less.

<9>
The base paper contains pulp, and the pulp in the base paper has a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp in the base paper. The transfer paper according to <4> above, wherein NBKP in the range of 5% by mass or more and 25% by mass or less.

<10>
The base paper contains pulp, and the pulp in the base paper has a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp in the base paper. The transfer paper according to <5> above, wherein NBKP in the range of 5% by mass or more and 25% by mass or less.

<11>
The base paper contains pulp, and the pulp in the base paper has a drainage degree of 380 ml or more and 480 ml or less with respect to the pulp in the base paper. The transfer paper according to <6> above, wherein NBKP in the range of 5% by mass or more and 25% by mass or less.

<12>
A step of printing a pattern on the transfer paper according to any one of [1] to [11] to obtain a transfer paper and a step of bringing the printed surface of the transfer paper into close contact with the printed matter are included. Transfer printing method.

Claims (7)

The base paper has one layer or two or more coating layers on at least one side of the base paper, and the outermost coating layer located on the outermost side of the base paper does not contain a white inorganic pigment or is substantially. A transfer paper used in a transfer printing method that does not contain carboxymethyl cellulose and polyvinyl alcohol. The transfer paper according to claim 1, wherein in the outermost coating layer, the content mass ratio of the carboxymethyl cellulose to the polyvinyl alcohol is 200 parts by mass or more and 400 parts by mass or less of polyvinyl alcohol with respect to 100 parts by mass of carboxymethyl cellulose. .. The transfer paper according to claim 1 or 2, wherein the polyvinyl alcohol is a carboxy group-modified polyvinyl alcohol. The transfer paper according to claim 3, wherein the carboxy group-modified polyvinyl alcohol has an average degree of polymerization of 200 or more and 3000 or less, and a saponification degree of 80 mol% or more and 90 mol% or less. The transfer paper according to any one of claims 1 to 4, wherein the carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 770000 or less and an etherification degree of 0.6 or more and 1.27 or less. The transfer paper according to any one of claims 1, 3, 4, and 5, wherein the static friction coefficient is 0.4 or more and 0.6 or less on the side having the outermost coating layer. A transfer printing method including a step of printing a pattern on the transfer paper according to any one of claims 1 to 6 to obtain a transfer paper, and a step of bringing the printed surface of the transfer paper into close contact with the printed matter. ..