JP2019195921A - Transfer paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer paper used in a transfer printing method using a sublimation dye ink having excellent image deterioration resistance and printing unevenness resistance. An object is to have a base paper and one or more coating layers on at least one surface of the base paper, and in the coating layers, the outermost coating layer located on the outermost side with respect to the base paper is white. Transfer paper used in a transfer printing method using a sublimation dye ink, which contains at least a pigment, starch, polyvinyl alcohol, a water-soluble calcium salt and a fluorescent dye, and the fluorescent dye is a triazinyl stilbene sulfonic acid compound. Achieved by [Selection diagram] None

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 printing material 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 printing material, it is necessary to improve the receptivity to 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.

  In addition to the deterioration of the image quality of the printing material due to the sharpness of the image on the transfer paper, there is a problem of uneven printing of the printing material. A region having a uniform color on the transfer paper is a phenomenon in which unevenness occurs in the color of the final printed material. Printing unevenness is a phenomenon in which transfer of sublimation dye ink is partially insufficient from a transfer paper. Printing unevenness tends to occur particularly when a transfer paper in a roll shape is continuously transferred to a printing material.

  The quality of the sublimation transfer sheet of Patent Document 3 and the sublimation type ink jet printing transfer paper of Patent Document 4 is not necessarily sufficient, and improvement in printing unevenness is particularly desired.

In view of the above, an object of the present invention is to provide a transfer paper that satisfies the following items.
(1) There is no image degradation on the substrate and the image degradation resistance is good.
(2) Printing unevenness is suppressed in the printing material, and has printing unevenness resistance.

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 on at least one side of the base paper, and the outermost coating layer located on the outermost side with respect to the base paper is a white pigment or starch. Transfer paper used for transfer printing using a sublimation dye ink, comprising at least a polyvinyl alcohol, a water-soluble calcium salt and a fluorescent dye, wherein the fluorescent dye is a triazinyl stilbene sulfonic acid compound.

  [2] The transfer paper according to [1], wherein the outermost coating layer contains a cationic resin in addition to a white pigment, starch, polyvinyl alcohol, a water-soluble calcium salt, and a fluorescent dye.

  According to the present invention, it is possible to provide a transfer paper having good image deterioration resistance and having printing resistance unevenness.

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 on at least one side of the base paper. When the coating layer is one layer, the coating layer corresponds to the outermost coating layer, and the outermost coating layer contains at least a white pigment, starches, polyvinyl alcohols, a water-soluble calcium salt, and a fluorescent dye. contains. When there are two or more coating layers, the outermost coating layer located on the outermost side with respect to the base paper contains at least a white pigment, starches, polyvinyl alcohols, a water-soluble calcium salt, and a fluorescent dye. 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 white pigment and a binder or a coating layer containing no pigment. There may be, and it does not specifically limit.
From the viewpoint of production cost, one coating layer is preferable. Moreover, you may have a coating layer on the single side | surface of a base paper, or both surfaces. 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 of the coating amount is more preferably 30 g / m ² or less, and further preferably 10 g / m ² or less. 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 less per one surface 2 g / m ² or more 8 g / m ² and most preferably. 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 kind of 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. Furthermore, the base paper includes high-quality paper obtained by subjecting papermaking paper to calendar treatment, surface sizing treatment or surface treatment with starch, 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 acidity, neutrality or alkalinity. Examples of the paper machine include a long paper machine, a twin wire paper machine, a combination paper machine, a circular 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 resistance 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 transfer paper has one or more coating layers on at least one side of the base paper.
The coating layer or the outermost coating layer can be provided by coating and drying each coating layer coating solution on the base paper or the coating layer. The method of providing 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. Examples of conventionally known coating apparatuses include size presses, gate roll coaters, film transfer coaters, blade coaters, rod coaters, air knife coaters, comma coaters, gravure coaters, bar coaters, E bar coaters, curtain coaters, and the like. Can do. Examples of drying devices include various types of 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, dryers using microwaves, etc. Can do.

The outermost coating layer contains a white pigment.
White pigments are conventionally known in the coated paper field, such as kaolin, light calcium carbonate, heavy calcium carbonate, talc, satin white, lithopone, titanium oxide, zinc oxide, silica, alumina, alumina hydrate. And inorganic pigments such as aluminum hydroxide, zinc oxide, activated clay and diatomaceous earth, and organic pigments such as plastic pigments. The white pigment is preferably one or more selected from the group consisting of these.

  The white pigment in the outermost coating layer preferably contains at least heavy calcium carbonate. The heavy calcium carbonate is preferably 30 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the white pigment of the outermost coating layer. These reasons are because the printability with respect to an inkjet printing system becomes favorable.

The outermost coating layer contains starch and polyvinyl alcohol as a binder.
Here, starch refers to a generic term for starches including unprocessed and unmodified starch, various modified starches, and various modified starches. Examples of such starches include starch, oxidized starch, enzyme-modified starch, etherified starch, cationic starch, amphoteric starch, dialdehyde starch, phosphate esterified starch and urea phosphate esterified starch, Examples thereof include hydroxyethylated starch and hydroxybutylated starch. It is preferable that starches are 1 type, or 2 or more types chosen from the group which consists of these.
Here, the polyvinyl alcohols are generic names including polyvinyl alcohols having various saponification and polymerization degrees and various modified polyvinyl alcohols. Examples of such polyvinyl alcohols include polyvinyl alcohols of various saponification degrees, various modified polyvinyl alcohols such as silanol-modified or acetoacetyl-modified, and partially introduced functional groups such as carboxyl groups, and these And polyvinyl alcohol having various polymerization degrees. It is preferable that polyvinyl alcohol is 1 type, or 2 or more types chosen from the group which consists of these.

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 white pigment in the outermost coating layer.
Moreover, it is preferable that the content ratio of starch and polyvinyl alcohol in the outermost coating layer is in the range of starch: polyvinyl alcohol = 3: 7 to 7.5: 2.5.

The outermost coating layer can contain a conventionally known binder in addition to starches and polyvinyl alcohols. Examples of conventionally known binders include cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, natural polymer resins such as casein, gelatin, soybean protein, pullulan, gum arabic, karaya gum, and albumin or derivatives thereof, polypropylene glycol, polyethylene glycol, Maleic anhydride resin, acrylic resin, methacrylic acid ester-butadiene copolymer, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, or a functional group-containing monomer such as carboxy group of these various copolymers And functional group-modified copolymers, binders such as thermosetting synthetic resins such as melamine resins and urea resins, polyurethane resins, unsaturated polyester resins, polyvinyl butyral, alkyd resins, and the like.
The outermost coating layer preferably has a total content of starch and polyvinyl alcohol in the outermost coating layer of 80 parts by mass or more with respect to 100 parts by mass of the binder in the outermost coating layer.

The outermost coating layer contains a water-soluble calcium salt.
Here, the water-soluble calcium salt is a calcium salt that can be finally dissolved in water of 20 ° C. by 1% by mass or more. 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. The water-soluble calcium salt is preferably one or more selected from the group consisting of these. Furthermore, the water-soluble calcium salt is preferably one or two selected from the group consisting of calcium chloride and calcium nitrate. This is because the image deterioration resistance is improved.

  The content of the water-soluble calcium salt in the outermost coating layer is preferably 7 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the white pigment in the outermost coating layer.

The outermost coating layer contains a triazinyl stilbene sulfonic acid compound that is a fluorescent dye.
Examples of the triazinyl stilbene sulfonic acid compound include triazinyl stilbene disulfonic acid and its salt, triazinyl stilbene tetrasulfonic acid and its salt, and triazinyl stilbene hexasulfonic acid and its salt. More specific examples of the triazinyl stilbene sulfonic acid compound include CAS No. 4404-43-7, CAS No. 12768-92-2, known as FLUORESCENT BRIGHTTENER under the compound number (CAS No.) used in Chemical Abstracts, CAS number 16324-27-9, CAS number 12224-02-1, CAS number 68971-49-3, CAS number 76482-78-5, CAS number 41098-56-0 etc. can be mentioned. The triazinyl stilbene sulfonic acid compound is preferably one or more selected from the group consisting of these.
The triazinyl stilbene sulfonic acid compound is preferably triazinyl stilbene hexasulfonic acid such as CAS No. 68971-49-3, CAS No. 764822-78-5, CAS No. 41098-56-0, or a salt thereof. This is because the printing unevenness resistance is improved.

The fluorescent dye improves apparent whiteness by being contained in paper. However, the advantage of improving the apparent whiteness of the transfer paper by adding a fluorescent dye to the outermost coating layer of the transfer paper from the use of the transfer paper that finally forms the design on the substrate is the transfer paper. Although the visibility is improved, the technical value is small.
Therefore, when the outermost coating layer containing white pigment, starch, polyvinyl alcohol and water-soluble calcium salt further contains a triazinyl stilbene sulfonic acid compound which is a fluorescent dye, the effect of the present invention can be obtained. That is not expected. The reason for this is unclear, but the inventors believe that this is due to the combined synergistic effect of white pigments, starches, polyvinyl alcohols, calcium ions and triazinyl stilbene sulfonic acid compounds.

  The content of the triazinyl stilbene sulfonic acid compound in the outermost coating layer is preferably 6 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the white pigment in the outermost coating layer.

The outermost coating layer preferably contains a cationic resin. This is because the effect of the present invention is improved.
The cationic resin is a cationic polymer or a cationic oligomer, and conventionally known ones can be used. Cationic resins are polymers or oligomers containing primary to tertiary amines or quaternary ammonium salts that readily coordinate protons and dissociate when dissolved in water to exhibit cationic properties. Examples of cationic resins include polyethyleneimine, polyvinyl pyridine, polyamine sulfone, polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, polydialkylaminoethyl methacrylamide, polydialkylaminoethyl acrylamide, polyepoxyamine, polyamidoamine, dicyandiamide. -Compounds such as formalin condensate, polyvinylamine, polyallylamine and their hydrochlorides, copolymers of diallylamine and acrylamide, polydiallyldimethylammonium chloride and copolymers of diallyldimethylammonium chloride and acrylamide, polydiallyl Methylamine hydrochloride, dimethylamine-epichlorohydrin polycondensate and diethylenetriamine-ethylene Chlorohydrin polycondensate of aliphatic monoamines or aliphatic polyamines with an epihalohydrin compound, such as polycondensates can be mentioned. It is not limited to these. From the viewpoint of commercial availability, dimethylamine-epichlorohydrin polycondensate is preferred. In the present invention, the average molecular weight of the cationic resin is not particularly limited, but is preferably in the range of 500 or more and 20,000 or less.

  The content of the cationic resin in the outermost coating layer is preferably 2 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the white pigment in the outermost coating layer.

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, colored pigments, colored dyes, ultraviolet absorbers, antioxidants, Preservatives, antifungal agents and the like can be mentioned.
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 inkjet 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 sublimation dye ink is a method having a step of printing a pattern on a transfer paper to obtain a transfer paper and a step of bringing the transfer paper into close contact with a substrate. The step of bringing in close contact includes heating and pressurization as necessary. 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 printing material using a press, a heating drum, or the like 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 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, 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. In a general sublimation dye ink, polyester is preferable as the fiber material.

  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.

(Base paper)
To a pulp slurry consisting of 100 parts by mass of LBKP having a freeness of 380 mlcsf, 20 parts by mass of calcium carbonate, 1.2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, and 0.1 parts by mass of alkyl ketene dimer type sizing agent as fillers. 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 . .

(Outermost coating layer coating solution)
The outermost coating layer coating solution was prepared according to the following contents.
White pigment types and parts listed in Table 1 Binder types and parts listed in Table 1 Water-soluble salts Types and parts listed in Table 1 Fluorescent dye types and parts listed in Table 1 Cationic resin Parts listed in Table 1 above And mixed and dispersed with water to adjust the concentration to 48% by mass.

  All the materials used were commercial products. In Table 1, polyvinyl alcohol has a saponification degree of about 98 mol% and a polymerization degree of about 1700, fluorescent dye A is triazinyl stilbene tetrasulfonic acid CAS No. 12224-02-1, and fluorescent dye B is triazinyl stilbene hexasulfone. CAS number 68971-49-3 which is an acid, fluorescent dye C is CAS number 12224-41-8 which is a thiophene compound, and the cationic resin is a dimethylamine-epichlorohydrin polycondensate.

(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 sheet. The coating amount was 6 g / m ² per side.

<Preparation of transfer paper>
By using an ink jet printer (JV2-130II, manufactured by Mimaki Engineering Co., Ltd.) using a sublimation dye ink on the transfer paper obtained as described above, an evaluation pattern using sublimation dye ink (cyan, magenta, yellow, black) is provided. Printing was performed to obtain a transfer paper.

<Printing>
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, 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 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 printing unevenness>
Using a transfer paper that was printed in a roll form at room temperature by printing 50 points of the design, a printed material of a roll on which the 50 points of design was formed as described above. About the obtained to-be-printed material, sensory evaluation was carried out visually according to the following criteria for the degree of occurrence of printing unevenness.
X: Printing unevenness is hardly recognized, and the formed pattern is good.
Y: Printing unevenness is slightly recognized, but the formed pattern has no practical problem.
Z: Printing unevenness is recognized, and the formed pattern becomes a practical problem.
From the result of sensory evaluation, the number of printed materials corresponding to X and Z was determined and evaluated according to the following criteria. In the present invention, if the evaluation is A, B, or C, it has printing unevenness resistance.
A: The number of Z cases is less than 2, and the number of X cases is 30 or more.
B: The number of cases of Z is less than 2, and the number of cases of X is less than 30.
C: The number of Z is 2 or more and less than 6.
D: The number of Z is 6 or more.

  The evaluation results are shown in Table 2.

From the evaluation results in Table 2, it can be seen that Examples 1 to 13 corresponding to the present invention have good image deterioration resistance and have printing unevenness resistance. However, it can be seen that Comparative Examples 1 to 7 which do not satisfy the configuration of the present invention cannot obtain image deterioration resistance and / or printing unevenness.
Mainly from the comparison between Example 5 and Example 13, it can be seen that the outermost coating layer preferably contains a cationic resin.

Claims (2)

  A base paper and at least one coating layer on at least one side of the base paper, wherein the outermost coating layer located on the outermost side with respect to the base paper is a white pigment, starch, polyvinyl alcohol Transfer paper used for transfer printing using a sublimation dye ink, which contains at least a water-soluble calcium salt and a fluorescent dye, and the fluorescent dye is a triazinyl stilbene sulfonic acid compound.   The transfer paper according to claim 1, wherein the outermost coating layer contains a cationic resin in addition to a white pigment, starches, polyvinyl alcohols, a water-soluble calcium salt and a fluorescent dye.