JP6488259B2 - Transfer paper - Google Patents

Description

  The present invention relates to a transfer paper used for transferring a pattern in a transfer printing method for forming a pattern on a substrate such as a fiber material.

  As a method of forming a pattern on a printed material such as a textile material, the pattern is printed on a transfer paper using sublimation dye ink to produce a transfer paper, the transfer paper is adhered to the printed material, and the sublimation dye ink is used. A transfer textile printing method for transferring to a substrate is known (see, for example, Patent Document 1 and Patent Document 2).

Transfer paper used for transfer textile printing is known.
For example, a sheet-like substrate can be used as a sublimation transfer sheet that is excellent in water-based ink absorptivity and capable of obtaining a clear recorded image without bleeding and excellent in ink transfer efficiency to a transfer object during sublimation transfer. Material and an ink receiving layer provided on one side or both sides of the sheet-like base material, and the ink receiving layer contains a pigment, a binder, and a cationic resin. Examples of the binder include starch, starch derivatives, A sublimation transfer sheet is known in which any one of polyvinyl alcohol and modified polyvinyl alcohol or a mixture of two or more thereof is used (see, for example, Patent Document 3).
In addition, it has excellent ink absorption and drying properties in ink jet printing using sublimation textile printing ink, and has good workability, image reproducibility on the surface of transfer paper, heat resistance during heat transfer, after transfer As a sublimation type ink jet printing transfer paper having good properties in terms of image reproducibility and transfer efficiency on the surface of the transferred material, the sublimation type printing ink receiving layer has a sublimation type printing ink receiving layer on a substrate. Contains a water-soluble resin and fine particles, contains the synthetic amorphous silica as the fine particles, and in the relative value of the ultrasonic transmission intensity on the sublimation type printing ink receiving layer side of the sublimation type ink jet printing transfer paper. A sublimation type ink jet printing transfer paper having a minimum value peak within a measurement time of 3 seconds is known (see, for example, Patent Document 4).

  As described in Patent Document 3 and Patent Document 4, an inkjet printing method is used as a method for producing a transfer paper by printing a pattern on a transfer paper using an ink containing a sublimation dye or a sublimation printing ink. Often used.

JP2015-168705A Japanese Patent Laying-Open No. 2015-124324 JP 2010-158875 A JP 2010-058335 A

It is necessary to have two contradictory characteristics between a transfer sheet, which is a white paper before the pattern is printed, and a transfer sheet obtained by printing the pattern on the transfer sheet. That is, the transfer paper is required to have an ability to successfully receive the sublimation dye ink, and the transfer paper is required to have an ability to transfer the sublimation dye ink to the printing material.
Since the transfer paper becomes a transfer paper having a sharp image so as not to deteriorate the image quality of the pattern formed on the substrate, it is necessary to improve the acceptability for the sublimation dye ink. Furthermore, the transfer paper must not deteriorate the image quality of the pattern formed on the substrate from the transfer paper having a sharp image.
On the other hand, when the transfer paper has improved acceptability of the transfer paper with respect to the sublimation dye ink, the transfer of the sublimation dye ink may be insufficient at the time of transfer for forming a pattern on the substrate. As a result, the color developability of the substrate is reduced.

  Further, since the transfer is performed by bringing the transfer paper and the printing material into close contact with each other, the transfer paper must be able to make good contact with the printing material. In the case of continuously transferring to a printing material, the transfer is performed by bringing the roll paper-like transfer paper and the printing material into close contact with each other. In particular, in order to proceed the transfer continuously, it is more important that the transfer paper is in close contact with the substrate.

  The quality of the sublimation transfer sheet of Patent Document 3 and the sublimation ink jet printing transfer paper of Patent Document 4 is not always sufficient, and in particular, an improvement in adhesion is desired.

In view of the above, an object of the present invention is to provide a transfer paper that satisfies the following items.
(1) Image degradation can be suppressed on the substrate (image degradation resistance)
(2) The ability to suppress a decrease in color development on the substrate (color development)
(3) The transfer paper and the substrate to be in good contact (adhesion)

As a result of intensive studies to solve the above problems, the inventors of the present invention can achieve the objects of the present invention as follows.
[1] It has a base paper and one or more coating layers containing a pigment and a binder on at least one side of the base paper, the base paper contains urea phosphate esterified starch, and is outermost on the basis of the base paper A transfer paper used in a transfer printing method using a sublimation dye ink, wherein the pigment of the outermost coating layer located is at least kaolin and calcium carbonate.

  [2] The transfer paper according to [1], wherein the base paper contains a water-soluble calcium salt.

  [3] The transfer paper according to [2], wherein the water-soluble calcium salt is at least one selected from the group consisting of calcium chloride and calcium nitrate.

  According to the present invention, it is possible to provide a transfer paper that has good image deterioration resistance, good color developability, and excellent adhesion.

The present invention is described in detail below.
In the present invention, the “transfer sheet” refers to a sheet in a blank state before a pattern to be transferred is printed. “Transfer paper” refers to paper on which a pattern to be transferred to the transfer paper is printed.

The transfer paper has a base paper and one or more coating layers containing a pigment and a binder on at least one side of the base paper. In the case of one coating layer, the coating layer corresponds to the outermost coating layer, and the pigments of the outermost coating layer are at least kaolin and calcium carbonate. When there are two or more coating layers, the pigments of the outermost coating layer located on the outermost side with respect to the base paper are at least kaolin and calcium carbonate. When there are two or more coating layers, the coating layer existing between the base paper and the outermost coating layer is either a coating layer containing a pigment and a binder or a coating layer containing no pigment. There is no particular limitation.
From the viewpoint of production cost, one coating layer is preferable. 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 side of the base paper.

The coating amount of the coating layer is not particularly limited. Terms easily brought into close contact against the manufacturing cost and the substrate of the transfer sheet, the coating weight is preferably 2 g / m ² or more 70 g / m ² or less per side dry solid content. The upper limit is more preferably 30 g / ^{m 2} or less of coating weight, 20 g / ^{m 2} or less is more preferred. Furthermore, for the reason that it is possible to prevent the coating layer is lost during the adhesion and the manufacturing cost and the substrate, the coating weight is per side 2 g / m ² or more 12 g / m ² or less is most preferred. When there are a plurality of coating layers on one side, the coating amount is a total value thereof.

  Base paper is chemical pulp such as LBKP (Leaf Bleached Kraft Pulp), NBKP (Needle Bleached Kraft Pulp), GP (Groundwood Pulp), PGW (Pressure Ground Wood pulp), RMP (Refiner Mechanical Pulp), TMP (ThermoMechanical Pulp), CTMP (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp), CGP (ChemiGroundwood Pulp) and other mechanical pulp, and DIP (DeInked Pulp) and other waste paper pulp, at least one pulp selected from calcium carbonate, talc, clay, kaolin, etc. In addition, various types of fillers, and further, papers made from papers containing various additives such as sizing agents, fixing agents, retention agents, cationizing agents, and paper strength agents as necessary. Further, the base paper includes high-quality paper obtained by subjecting papermaking paper to calendar treatment, surface sizing treatment with starch or polyvinyl alcohol, or the like. Furthermore, the base paper includes high-quality paper that has been subjected to surface sizing or surface treatment and then calendered.

  Paper making is performed using a conventionally known paper machine by adjusting the stock to acid, 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, and a Yankee paper machine.

The basis weight of the base paper is not particularly limited. The basis weight of the base paper is preferably 10 g / m ² or more and 100 g / m ² or less, and more preferably 40 g / m ² or more and 90 g / m ² or less from the viewpoint of easy handling with respect to transfer to the printing material. Further, the thickness of the transfer paper is not particularly limited. From the viewpoint of easy handling with respect to the transfer to the printing material, the thickness of the transfer paper is preferably 0.01 mm or more and 0.5 mm or less, and more preferably 0.05 mm or more and 0.3 mm or less.

  In paper stock, other additives include pigment dispersants, thickeners, fluidity improvers, antifoaming agents, antifoaming agents, mold release agents, foaming agents, penetrating agents, colored dyes, colored pigments, fluorescent enhancers. One or more selected from a whitening agent, an ultraviolet absorber, an antioxidant, an antiseptic, an antibacterial agent, a water resistant agent, a wet paper strength enhancer, a dry paper strength enhancer, and the like according to the present invention. It can mix | blend suitably in the range which does not impair an effect.

The base paper contains urea phosphated starch.
Urea phosphate esterified starch is one type of esterified starch, and is a starch derivative in which starch and urea are heated at high temperature in the presence of phosphoric acid to introduce phosphate groups and carbamic acid groups. Urea phosphate esterified starch includes those having an alkylene group between a phosphate group and a glucose six-membered ring or between a carbamic acid group and a glucose six-membered ring. The alkylene group preferably has 1 to 3 carbon atoms, and more preferably 1 carbon atom. Urea phosphate esterified starch is commercially available from Oji Cornstarch Co., Ltd., Nippon Shokuhin Kako Co., Ltd., GS Japan Ltd., and the like.

The method in which the base paper contains urea phosphated starch is as follows: (A) pulp, filler, urea phosphate esterified starch, and paper containing additives as necessary; (B) pulp, filler and necessary According to the method, a paper material containing an additive is made, and a method in which urea phosphate esterified starch is imparted to the obtained paper by a conventionally known coating apparatus such as a size press can be mentioned. The method is preferably (B) because the adhesiveness is good with a small content.
In the above (A), calendaring or size pressing may be performed after papermaking.
In (B), the papermaking paper obtained by papermaking may be calendered before or after the urea phosphate esterified starch is applied. A sizing agent or the like may be contained in the coating liquid for imparting urea phosphate esterified starch.

The content of urea phosphate esterified starch in the base paper is preferably 0.5 g / m ² or more and 4 g / m ² or less in the case of (A), and 0.25 g / m per side in the case of (B). ² or more and 2 g / m ² or less are preferable.

  The base paper preferably contains a water-soluble calcium salt. This is because the color developability and adhesion are improved.

  The method of adding water-soluble calcium salt to the base paper is as follows: (a) a method of blending the water-soluble calcium salt into the paper material and making the paper material; (b) pulp, filler, urea phosphated starch, and if necessary A paper material containing an additive is made according to the method, and a water-soluble calcium salt is imparted to the resulting paper made by a conventionally known coating device such as a size press, (c) pulp, filler and, if necessary, Examples thereof include a method of making a paper stock containing an additive, and imparting urea phosphate esterified starch and water-soluble calcium salt to the resulting paper by a conventionally known coating apparatus such as a size press. The content of the water-soluble calcium salt is preferably (b) or (c) from the viewpoint of color development.

  The water-soluble calcium salt is a calcium salt that can be finally dissolved in 1% by mass or more in 20 ° C. water. Examples of water-soluble calcium salts include salt compounds such as calcium lactate, calcium nitrate, calcium chloride, calcium formate, and calcium acetate, or complex salts such as calcium ethylenediaminetetraacetate. One or more water-soluble calcium salts are selected from the group consisting of these. Among these, the water-soluble calcium salt is preferably one or two selected from the group consisting of calcium chloride and calcium nitrate.

In the case of (a), the content of the water-soluble calcium salt in the base paper is preferably 1 g / m ² or more and 10 g / m ² or less, and in the case of (b) or (c), 0.5 g / m ² per side. m ² or more and 5 g / m ² or less are preferable.

  Examples of conventionally known coating apparatuses in the above (B), (b) and (c) include size press, gate roll coater, film transfer coater, blade coater, rod coater, air knife coater, comma coater, and gravure coater. , Bar coater, E bar coater, curtain coater and the like. The coating device is preferably a size press, a gate roll coater, or a film transfer coater installed in the paper machine from the viewpoint of manufacturing cost.

The transfer paper has one or more coating layers containing a pigment and a binder. The coating layer can be provided on the base paper by applying and drying a coating layer coating solution on the base paper.
The method for providing the coating layer on the base paper is not particularly limited. Examples thereof include a method of coating and drying using a conventionally known coating apparatus and drying apparatus in the papermaking field. As an example of a coating apparatus, the above-mentioned conventionally well-known coating apparatus can be mentioned. Examples of dryers include various dryers such as straight tunnel dryers, arch dryers, air loop dryers, sine curve air float dryers, hot air dryers, infrared heating dryers, dryers using microwaves, etc. Can do.

The pigments of the outermost coating layer are at least kaolin and calcium carbonate. The content mass ratio of kaolin and calcium carbonate in the outermost coating layer is preferably kaolin: calcium carbonate = 9: 1 to 6: 4, and more preferably 8: 2 to 7: 3.
For reasons of printability for the ink jet printing method, calcium carbonate is preferably heavy calcium carbonate.

The outermost coating layer can contain a conventionally known pigment in addition to kaolin and calcium carbonate. Examples of conventionally known pigments include inorganic pigments such as talc, satin white, lithopone, titanium oxide, zinc oxide, silica, alumina, aluminum hydroxide, zinc oxide, activated clay, diatomaceous earth, and organic pigments such as plastic pigments. Can be mentioned. The outermost coating layer can be used in combination with kaolin and calcium carbonate in combination of one or more of these pigments.
The proportion of kaolin and calcium carbonate in the pigment of the outermost coating layer is preferably 70% by mass or more, and more preferably 80% by mass or more.

The binder of the outermost coating layer is a conventionally known binder and is not particularly limited. Examples of conventionally known binders include starches and various modified starches, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, natural polymer resins such as casein, gelatin, soy protein, pullulan, gum arabic, karaya gum, and albumin or derivatives thereof, Polyvinyl pyrrolidone, polyvinyl alcohol and various modified polyvinyl alcohols, polyacrylamide, polyethyleneimine, polypropylene glycol, polyethylene glycol, maleic anhydride resin, acrylic resin, methacrylate ester-butadiene copolymer, styrene-butadiene copolymer, ethylene- Thermosetting of vinyl acetate copolymers or functional group-modified copolymers with monomers containing functional groups such as carboxy groups of these various copolymers, melamine resins, urea resins, etc. Binders such as synthetic resins, polyurethane resins, unsaturated polyester resins, polyvinyl butyral, can be exemplified alkyd resin latex. The outermost coating layer can contain one or a combination of two or more of these binders.
The content of the binder in the outermost coating layer is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the pigment.

The outermost coating layer can contain various conventionally known additives in the coated paper field as necessary. Examples of additives include dispersants, fixing agents, thickeners, fluidity improvers, antifoaming agents, mold release agents, foaming agents, penetrating agents, coloring pigments, colored dyes, fluorescent whitening agents, UV absorbers , Antioxidants, preservatives, antifungal agents and the like.
Further, the outermost coating layer can contain various conventionally known auxiliaries by a transfer printing method. The auxiliary agent is added to optimize various physical properties of the outermost coating layer coating solution or to improve the dyeing property of the transferred sublimation dye ink. Examples of the auxiliary agent include various surfactants, humectants, wetting agents, pH adjusting agents, alkali agents, thickening agents, deaerating agents and reduction inhibitors.

The transfer paper can be obtained by printing a pattern on the side of the transfer paper having the outermost coating layer using various conventionally known printing methods including sublimation dye ink.
Various printing methods for printing the design on the transfer paper are conventionally known printing methods and are not particularly limited. Examples of the printing method include a gravure printing method, an ink jet printing method, an electrophotographic printing method, a screen printing method, and the like. Among these, the ink jet printing method is preferable in terms of high image quality and downsizing of the apparatus.

  The transfer textile printing method using a sublimation dye ink is a method having a step of obtaining a transfer paper by printing a pattern on a transfer paper and a step of bringing the transfer paper into close contact with a substrate. The process of making it adhere | attach includes heating and pressurization as needed. The conditions for heating and pressurizing in the step of adhering are conventionally known conditions in the transfer printing method. Examples of the step of bringing in close contact include a method in which the transfer paper is brought into close contact with the substrate to be printed with a press or a heating drum and heated and pressurized.

  The substrate 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 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 the synthetic fiber material include polyamide fiber (nylon), vinylon, polyester, and polyacryl. Examples of the configuration of the fiber material include woven fabrics, knitted fabrics, nonwoven fabrics, and the like alone, mixed spinning, mixed fiber, and union. Furthermore, these configurations may be combined. Moreover, you may pre-process a to-be-printed material with the chemical | medical agent effective in dyeing | staining promotion as needed.

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

<Example 1>
(Base paper 1)
In a pulp slurry comprising 100 parts by mass of LBKP having a freeness of 380 mlcsf, 30 parts by mass of calcium carbonate, 1.2 parts by mass of urea phosphated starch, 0.8 parts by mass of sulfuric acid band, 0.1 parts by mass of an alkyl ketene dimer type sizing agent Add a part by weight, make paper with a long paper machine, attach 1.5 g / m ^{2 of} oxidized starch and 1.0 g / m ^{2 of} calcium nitrate per side with a size press, and machine calender The base paper of the basic weight 62g / m < ² > was produced by processing.

(Outermost coating layer coating solution 1)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 75 parts by weight Heavy calcium carbonate 25 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The above contents were mixed and dispersed with water to adjust the concentration to 48% by weight.

(Transfer paper)
A transfer sheet was prepared by the following procedure.
On the base paper, the outermost coating layer coating solution was coated on both sides with an air knife coater, dried, and then subjected to calendar treatment to obtain a transfer paper of Example 1. The coating amount was 9 g / m ² per side.

<Example 2>
A transfer paper of Example 2 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 2.

(Base paper 2)
In a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as filler, 30 parts by mass of calcium carbonate, 9 parts by mass of urea phosphated starch, 0.8 parts by mass of sulfuric acid band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Is added, and the paper is made with a long paper machine, with a size press machine, 1.5 g / m ^{2 of} oxidized starch and 1.0 g / m ^{2 of} calcium nitrate per side are adhered to both sides, and machine calendering is performed. Thus, a base paper having a basis weight of 62 g / m ² was produced.

<Example 3>
A transfer sheet of Example 3 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 3.

(Base paper 3)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Added, made with a long net paper machine, and attached with 0.25 g / m ^{2 of} urea phosphate ester starch and 1.0 g / m ^{2 of} calcium nitrate per side on both sides with a size press machine. A base paper having a basis weight of 59.5 g / m ² was prepared by processing.

<Example 4>
A transfer paper of Example 4 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 4.

(Base paper 4)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Added, made with a long paper machine, and attached with 1.0 g / m ² urea phosphate ester per side and 1.0 g / m ² per side with a size press machine, machine calendar A base paper having a basis weight of 61 g / m ² was prepared by processing.

<Example 5>
A transfer paper of Example 5 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 5.

(Base paper 5)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Added, made with a long paper machine, and attached with 1.5 g / m ^{2 of} urea phosphate ester per side and 1.0 g / m ² per side of calcium phosphate on both sides with a size press machine. The base paper of the basic weight 62g / m < ² > was produced by processing.

<Example 6>
The transfer paper of Example 6 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 6.

(Base paper 6)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Added, made with a long paper machine, and attached with a size press device on both sides, urea phosphate esterified starch 2.0 g / m ² per side and calcium nitrate 1.0 g / m ² per side, machine calendar The base paper of the basic weight 63g / m < ² > was produced by processing.

<Example 7>
The transfer paper of Example 7 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 7.

(Base paper 7)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Add, make paper with a long paper machine, attach urea phosphate esterified starch 1.5g / m ² per side and calcium chloride 1.0g / m ² per side with a size press machine, machine calendar The base paper of the basic weight 62g / m < ² > was produced by processing.

<Example 8>
The transfer paper of Example 8 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 8.

(Base paper 8)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent The paper is made with a long net paper machine, and 1.5 g / m ^{2 of} urea phosphate ester starch and 1.0 g / m ^{2 of} calcium acetate per side are adhered to both sides with a size press machine. The base paper of the basic weight 62g / m < ² > was produced by processing.

<Example 9>
The transfer paper of Example 9 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 9.

(Base paper 9)
In a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as filler, 30 parts by mass of calcium carbonate, 9 parts by mass of urea phosphated starch, 0.8 parts by mass of sulfuric acid band, 0.1 parts by mass of alkyl ketene dimer type sizing agent It was added and papermaking in Fourdrinier, on both sides in a size press apparatus, oxidized starch was per side 1.5 g / m ² adhesion, making the base paper having a basis weight of 60 g / m ² by a machine calendering treatment did.

<Example 10>
The transfer paper of Example 10 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 10.

(Base paper 10)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent It is added and made with a long paper machine, urea phosphate esterified starch is attached to both sides with a size press machine at 1.5 g / m ² per side, machine calendering is performed, and a base paper with a basis weight of 60 g / m ² Was made.

<Example 11>
The transfer paper of Example 11 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 11.

(Base paper 11)
In a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as filler, 30 parts by mass of calcium carbonate, 9 parts by mass of urea phosphated starch, 0.8 parts by mass of sulfuric acid band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Then, 2.5 parts by mass of calcium nitrate was added, the paper was made with a long paper machine, the oxidized starch was attached to both sides with a size press machine at 1.5 g / m ² , and the basis weight was machine calendered. A base paper of 60 g / m ² was prepared.

<Example 12>
A transfer paper of Example 12 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 12.

(Base paper 12)
In a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent, Add 2.5 parts by weight of calcium nitrate, make paper with a long paper machine, attach 1.5g / m ^{2 of} urea phosphate ester starch on both sides with a size press machine, and machine calender A base paper having a basis weight of 60 g / m ² was prepared.

<Example 13>
In Example 5, it carried out similarly except having changed the outermost coating layer coating liquid 1 into the outermost coating layer coating liquid 2, and obtained the transfer paper of Example 13.

(Outermost coating layer coating solution 2)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 90 parts by weight Heavy calcium carbonate 10 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The above contents were mixed, dispersed with water, and adjusted to a concentration of 48% by weight.

<Example 14>
In Example 5, it carried out similarly except having changed the outermost coating layer coating liquid 1 into the outermost coating layer coating liquid 3, and obtained the transfer paper of Example 14.

(Outermost coating layer coating solution 3)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 60 parts by weight Heavy calcium carbonate 40 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The above content was mixed and dispersed with water to adjust the concentration to 48% by weight.

<Example 15>
In Example 5, it carried out similarly except having changed the outermost coating layer coating liquid 1 into the outermost coating layer coating liquid 4, and obtained the transfer paper of Example 15.

(Outermost coating layer coating solution 4)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 60 parts by weight Heavy calcium carbonate 20 parts by weight Synthetic amorphous silica 20 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The above contents are mixed and dispersed with water, The concentration was adjusted to 48% by mass.

<Example 16>
In Example 5, it carried out similarly except having changed the outermost coating layer coating liquid 1 into the outermost coating layer coating liquid 5, and obtained the transfer paper of Example 16.

(Outermost coating layer coating solution 5)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 52.5 parts by weight Heavy calcium carbonate 17.5 parts by weight Synthetic amorphous silica 30 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The dispersion was adjusted to a concentration of 48% by mass.

<Example 17>
The coating layer coating solution 1 was coated on both sides of the base paper 5 with an air knife coater, dried, and then subjected to a calendar process to obtain a coated paper. The coating amount was 3 g / m ² per side.
The outermost coating layer coating solution 1 was applied on both sides of this coated paper with a blade coater, dried, and then subjected to a calendar process to obtain a transfer paper of Example 17. The coating amount was 9 g / m ² per side.

(Coating layer coating solution 1)
The coating layer coating solution was prepared according to the following contents.
Heavy calcium carbonate 100 parts by mass Styrene-butadiene copolymer 15 parts by mass Polyvinyl alcohol 10 parts by mass The above contents were mixed, and mixed and dispersed with water to adjust the concentration to 38% by mass.

<Comparative Example 1>
A transfer sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 13.

(Base paper 13)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent It was added and made with a long paper machine. Oxide starch was attached to both sides with a size press machine at 1.5 g / m ² per side, and machine calendering was performed to prepare a base paper with a basis weight of 60 g / m ² . .

<Comparative example 2>
A transfer sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the base paper 1 was changed to the base paper 14.

(Base paper 14)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, as a filler, 30 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, 0.1 parts by mass of alkyl ketene dimer type sizing agent Add, make paper with a long paper machine, attach 1.5g / m ² phosphate ester per side on both sides with a size press machine, machine calender treatment and base paper of 60g / m ² basis weight Produced.

<Comparative Example 3>
The transfer paper of Comparative Example 3 was obtained in the same manner as in Example 5 except that the outermost coating layer coating solution 1 was changed to the outermost coating layer coating solution 6.

(Outermost coating layer coating solution 6)
The outermost coating layer coating solution was prepared according to the following contents.
Kaolin 100 parts by mass Styrene-butadiene copolymer 10 parts by mass Phosphate esterified starch 10 parts by mass The above contents were mixed, and mixed and dispersed with water to adjust the concentration to 48% by mass.

<Comparative example 4>
The transfer paper of Comparative Example 4 was obtained in the same manner as in Example 5 except that the outermost coating layer coating solution 1 was changed to the outermost coating layer coating solution 7.

(Outermost coating layer coating solution 7)
The outermost coating layer coating solution was prepared according to the following contents.
Heavy calcium carbonate 100 parts by mass Styrene-butadiene copolymer 10 parts by mass Phosphate esterified starch 10 parts by mass The above contents were mixed, mixed and dispersed with water, and adjusted to a concentration of 48% by mass.

<Comparative Example 5>
The transfer paper of Comparative Example 5 was obtained in the same manner as in Example 5 except that the outermost coating layer coating solution 1 was changed to the outermost coating layer coating solution 8.

(Outermost coating layer coating solution 8)
The outermost coating layer coating solution was prepared according to the following contents.
Synthetic amorphous silica 100 parts by weight Styrene-butadiene copolymer 10 parts by weight Phosphate esterified starch 10 parts by weight The above contents were mixed, dispersed and mixed with water, and adjusted to a concentration of 48% by weight.

<Preparation of transfer paper>
For each transfer paper obtained as described above, an ink jet printer (JV2-130II, manufactured by Mimaki Engineering Co., Ltd.) using a sublimation dye ink is used for evaluation with sublimation dye ink (cyan, magenta, yellow, black). Was printed to obtain a transfer paper.

<Printing (cut paper)>
A polyester cloth was used as the substrate. The obtained transfer paper and the polyester cloth were brought into close contact with each other, and heated at 200 ° C. for 1 minute using a thermal transfer press (manual wide swinger Model 221 manufactured by INSTA) to transfer the dye to the polyester cloth. Thereafter, the transfer paper was peeled from the polyester cloth to obtain a polyester cloth on which a pattern was formed.

<Evaluation of image degradation resistance>
From the point of sharpness of the design, the image quality of the polyester cloth on which the design was formed was sensory-evaluated based on the following criteria. In the present invention, if the transfer paper is evaluated as A or B, the image deterioration resistance is good.
A: Good level.
B: Almost no deterioration in image quality is observed, and the level is generally good.
C: Deterioration in image quality is recognized, but there is no practical problem.
D: Level at which deterioration of an image which is practically impossible is recognized.

<Evaluation of color development>
The color density of three solid color sublimation dye ink colors (cyan, magenta, yellow) is measured using an optical densitometer (X-rite 530, manufactured by Sakata Inx Engineering Co., Ltd.). Totaled. The color developability was judged according to the following criteria. In the present invention, the transfer paper has good color developability if the evaluation is A or B.
A: Total value is 4.7 or more B: Total value is 4.4 or more and less than 4.7 C: Total value is less than 4.4

<Printing (roll paper)>
A rolled polyester cloth was used as the substrate. The obtained roll paper-like transfer paper and the polyester cloth were brought into close contact with each other, and the dye was transferred to the polyester cloth using a heating and pressurizing machine (190 ° C., 0.5 MPa, 2.5 m / min, roller type). Thereafter, the transfer paper was peeled from the polyester cloth to obtain a polyester cloth on which a pattern was formed.

<Evaluation of adhesion>
From the viewpoint of the degree of occurrence of color unevenness in the solid image portion, the adhesiveness was subjected to sensory evaluation according to the following criteria for the polyester cloth on which the design was formed. In the present invention, if the transfer sheet is evaluated as A or B, it is excellent in adhesion.
A: Color unevenness is not recognized and good.
B: Color unevenness is slight and good in general.
C: Color unevenness is observed, but there is no practical problem.
D: Color unevenness is recognized, which causes a problem in practical use.

  The evaluation results are shown in Table 1.

From the evaluation results of Table 1, it can be seen that Examples 1 to 17 corresponding to the present invention have image deterioration resistance and color development properties and are excellent in adhesion. However, it can be seen that Comparative Examples 1 to 5 that do not satisfy the configuration of the present invention cannot obtain the effects of the present invention.
Mainly from the comparison between Example 2 and Example 11 and Example 9, and from the comparison between Example 5, Example 7, Example 8, Example 12 and Example 10, the base paper is a water-soluble calcium salt. It turns out that it is preferable to contain.
Also, mainly from the comparison between Example 5 and Example 7 and Example 8, it is understood that the water-soluble calcium salt is preferably at least one selected from the group consisting of calcium chloride and calcium nitrate.

Claims (3)

  A base paper and one or more coating layers containing a pigment and a binder on at least one side of the base paper, and the base paper contains urea phosphate esterified starch and is located on the outermost side with respect to the base paper. A transfer paper used in a transfer printing method using a sublimation dye ink, wherein the pigment of the outer coating layer is at least kaolin and calcium carbonate.   The transfer paper according to claim 1, wherein the base paper contains a water-soluble calcium salt.   The transfer paper according to claim 2, wherein the water-soluble calcium salt is at least one selected from the group consisting of calcium chloride and calcium nitrate.