JP2018059252A - Transfer paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer paper having image deterioration resistance, excellent color development, and excellent adhesion.SOLUTION: The problem is solved by a transfer paper used in a transfer printing method using a sublimable printing ink, wherein the transfer paper has a base paper, and at least one coating layer on at least one side of the base paper, and wherein an outermost coating layer, at the outermost position with respect to the base paper, contains at least a pigment, a binder, a polyacrylic acid salt and an acetylene glycol derivative.SELECTED DRAWING: 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 substrate such as a fiber material.

  As a method of forming a pattern on a printed material such as a textile material, a pattern is printed on a transfer paper using sublimation printing ink to produce a transfer paper, the transfer paper is brought into close contact with the printed material, and the sublimation printing 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 or both sides of the sheet-like base material, and the ink receiving layer contains a pigment, a binder, and a cationic resin, and precipitated silica is used as the pigment. In addition, as the binder, a sublimation transfer sheet is known in which any one of starch, starch derivatives, polyvinyl alcohol, modified polyvinyl alcohol or a mixture of two or more thereof is used (for example, And Patent Document 3).
In addition, it has a sublimation printing ink receiving layer on a substrate as a sublimation printing type transfer paper that has excellent ink drying properties and anti-through-through properties, and also has good properties in terms of transfer image reproducibility and transfer efficiency. A sublimation printing type transfer paper, wherein the sublimation printing ink receiving layer comprises a water-soluble resin and fine particles dispersed as a main component, a nonionic surfactant, and a surface of the sublimation printing ink receiving layer. Sublimation printing type transfer paper characterized by forming irregularities 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 2009-131958 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 type printing ink, and the transfer paper is required to have an ability to transfer the sublimation type printing ink onto the substrate.
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 type printing 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 printing ink, the transfer of the sublimation printing 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 addition to the above-described deterioration in image quality during image formation, there is a problem of image quality that occurs because the transfer paper and the printing material do not adhere well. In a region where the transfer paper and the printing material are not in close contact with each other, image blurring or distortion occurs.
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 disclosed in Patent Document 3 and the sublimation printing type transfer paper disclosed in Patent Document 4 are not necessarily sufficient. In particular, 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] 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 pigment, a binder, a polyacrylate, and acetylene A transfer paper used in a transfer printing method using a sublimation printing ink, which contains at least a glycol derivative.

  [2] The transfer paper according to [1], wherein in the outermost coating layer, the content of the polyacrylate with respect to 100 parts by mass of the binder is 0.1 parts by mass or more and 3.5 parts by mass or less.

  [3] The transfer paper according to [1] or [2], wherein the polyacrylate is ammonium polyacrylate.

  [4] The transfer paper according to [3], wherein the weight average molecular weight of the ammonium polyacrylate measured by a gel permeation chromatography method is 5000 or more and 30000 or less.

  According to the present invention, it is possible to provide a transfer paper having image deterioration resistance, good color development, 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 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 pigment, a binder, a polyacrylate, and an acetylene glycol derivative. 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 pigment, a binder, a polyacrylate, and an acetylene glycol derivative. 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. Further, the presence or absence of polyacrylate or acetylene glycol is not particularly limited.
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 30 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 transfer paper has one or more coating layers on at least one side of the base paper. 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. Examples of the coating apparatus include a size press, a gate roll coater, a film transfer coater, a blade coater, a rod coater, an air knife coater, a comma coater, a gravure coater, a bar coater, an E bar coater, and a curtain coater. 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 outermost coating layer contains at least a pigment, a binder, a polyacrylate, and an acetylene glycol derivative.
In the outermost coating layer, the content ratio of pigment to binder is preferably pigment: binder = 20: 80 to 80:20. Further, when the specific surface area of the pigment is relatively large, pigment: binder = 20: 80 to 40:60 is preferable, and when the specific surface area of the pigment is relatively small, pigment: binder = 50: 50 to 80:20 is satisfied. preferable. Here, when the BET specific surface area is 150 m ² / g or less, the specific surface area of the pigment is relatively small, and when the BET specific surface area exceeds 150 m ² / g, the specific surface area of the pigment is relatively large.
The content of the polyacrylate in the outermost coating layer is preferably 0.1 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass in total of the pigment and the binder. In the outermost coating layer, the content of the polyacrylate with respect to 100 parts by mass of the binder is preferably 0.1 parts by mass or more and 3.5 parts by mass or less.
The content of the acetylene glycol derivative in the outermost coating layer is preferably 0.1 parts by mass or more and 0.5 parts by mass or less with respect to a total of 100 parts by mass of the pigment and the binder.
In the present invention, the content of the polyacrylate according to the present invention is not included in the content of the binder.

The pigment of the outermost coating layer is not particularly limited and is a conventionally known pigment in the coated paper field. The pigment is preferably a white pigment. Examples of white pigments include kaolin, heavy calcium carbonate, light calcium carbonate, talc, satin white, lithopone, titanium oxide, zinc oxide, silica, alumina, aluminum hydroxide, activated clay, and diatomaceous earth. And inorganic pigments such as, and organic pigments such as plastic pigments. The outermost coating layer contains one or more selected from these pigments.
For pigments having a relatively small specific surface area, kaolin and light calcium carbonate are preferred. For pigments having a relatively large specific surface area, silica is preferred.

  The binder of the outermost coating layer is a conventionally known binder and is not particularly limited. However, in the present invention, polyacrylate is excluded from conventionally known binders. 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 contains one or more selected from these binders.

  The polyacrylate of the outermost coating layer contains one or more structural units derived from the acrylate represented by the following general formula, and is a homopolymer or copolymer, or as required It is a copolymer containing other structural units. The polyacrylate of the present invention is preferably a polymer in which structural units derived from the acrylate represented by the following general formula account for 50 mol% or more of the whole.

In the above general formula, M is Na, K or NH ₄ .

  The polyacrylate is preferably ammonium polyacrylate. This is because the image deterioration resistance is particularly improved.

The weight average molecular weight of ammonium polyacrylate measured by gel permeation chromatography is preferably 1500 or more and 50000 or less, and more preferably 5000 or more and 30000 or less. This is because the adhesion is improved. Ammonium polyacrylate having a weight average molecular weight of 1500 or more and 50000 or less is excellent as a protective colloid for the pigment, so that the flexibility of the outermost coating layer is increased. As a result, it is considered that the adhesion is improved. If the weight average molecular weight is less than 1500, it is considered that the protective colloid is insufficient, and if it exceeds 50,000, it is difficult to obtain flexibility.
The weight average molecular weight of the present invention is a polyethylene glycol conversion value of the gel permeation chromatography method.

  The acetylene glycol derivative of the outermost coating layer is a compound represented by the following general formula (1) or (2).

R ₁ , R ₂ , R ₃ and R ₄ in the general formula (1) each represents an alkyl group having 1 to 5 carbon atoms. R ₁ , R ₂ , R ₃ and R ₄ preferably have a bilaterally symmetric structure around the acetylene group.

R ₅ , R ₆ , R ₇ and R ₈ in the general formula (2) each represents an alkyl group having 1 to 5 carbon atoms. m and n are each an integer of 1 to 25, and m + n is 2 to 40. OE is an oxyethylene chain (—O—CH ₂ —CH ₂ —), and OP is an oxypropylene chain (—O—CH ₂ —CH [CH ₃ ] —). OE and OP may each be a single chain or a mixed chain. R ₅ , R ₆ , R ₇ and R ₈ preferably have a bilaterally symmetric structure centering on the acetylene group.

  The acetylene glycol derivative is commercially available from Nissin Chemical Industry Co., Ltd. under the name “Surfynol (registered trademark)” or “Olfine (registered trademark)” and from Kawaken Fine Chemical Co., Ltd. under the name “Acetylenol (registered trademark)”.

  In the present invention, the acetylene glycol derivative is 2,4,7,9-tetramethyl-5-decyne-4,7-diol or 2,4,7,9-tetramethyl-5-decyne-4,7-diol. The ethoxylate is preferred. This is because it is easily available commercially.

The outermost coating layer can contain various conventionally known additives in the coated paper field, if necessary, in addition to the polyacrylate and the acetylene glycol derivative. 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 printing 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 type printing 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 sublimation textile printing 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 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.
In the transfer printing method using the sublimation type printing ink, the printed material is preferably a synthetic fiber material. Natural fiber materials often require pretreatment.

  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, 10 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 as fillers It was added and made with a long paper machine. Oxidized 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 62 g / m ² . .

<Outermost coating layer coating solution>
The outermost coating layer coating solution was prepared by mixing and dispersing in water using the materials shown in Table 1.
Table 1 also shows the amount of each material in the outermost coating layer coating solution.

  In Table 1, the silica A is NIPGEL (registered trademark) AY-200 manufactured by Tosoh Silica. Silica B is MIZUKASIL (registered trademark) P-527 manufactured by Mizusawa Chemical. Light calcium carbonate is Tama Pearl (registered trademark) TP221F manufactured by Okutama Kogyo. The acetylene glycol derivative A is Surfynol 104E (structure of general formula (1)) manufactured by Nissin Chemical Industry. The acetylene glycol derivative B is Olfine E1010 (structure of the general formula (2)) manufactured by Nissin Chemical Industry Co., Ltd. The acetylene alcohol is Olfine B manufactured by Nissin Chemical Industry. Except for Examples 24 and 25, ammonium polyacrylate having a weight average molecular weight of about 22,000 as measured by gel permeation chromatography was used. As the ammonium polyacrylates of Examples 24 and 25, those having a weight average molecular weight of about 6000 measured by gel permeation chromatography method were used.

<Transfer paper>
A transfer sheet was prepared by the following procedure.
On the base paper, the outermost coating layer coating solution was coated on one side with an air knife coater, dried with a hot air dryer, and then calendered to obtain a transfer paper. The coating amount is shown in Table 1.

  “Polyacrylate content mass ratio” in Table 1 is the content of polyacrylate with respect to 100 parts by mass of the binder in the outermost coating layer.

<Preparation of transfer paper>
On the obtained transfer paper, using an ink jet printer (JV2-130II, manufactured by Mimaki Engineering Co., Ltd.) using sublimation printing ink, an evaluation pattern using sublimation printing ink (cyan, magenta, yellow) is printed and transferred. I got 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, the transfer paper has an image deterioration resistance if the evaluation is A, B or C.
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>
On the printed material, the color density of a solid image portion of three colors of sublimation type printing ink (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 are brought into close contact with each other, using a heating and pressurizing machine (200 ° C., 0.5 MPa, 2.5 m / min, roller type, contact time with roller 30 seconds), The dye was transferred to a polyester fabric. Thereafter, the transfer paper was peeled from the polyester cloth to obtain a polyester cloth on which a pattern was formed.

<Evaluation of adhesion>
For the polyester cloth on which the design was formed, the adhesiveness was subjected to sensory evaluation according to the following criteria in terms of the degree of out-of-focus and distortion of the design. In the present invention, if the transfer sheet is evaluated as A or B, it is excellent in adhesion.
A: Good level without blurring or distortion.
B: Almost no blur or distortion is observed, and the level is generally good.
C: Defocus and distortion are recognized, but there is no practical problem.
D: A level at which out-of-focus and distortion are recognized, causing a problem in practical use.

  The evaluation results are shown in Table 1 above.

From the evaluation results in Table 1, it can be seen that Examples 1 to 21 corresponding to the present invention have image deterioration resistance, good color developability, and excellent adhesion. However, it can be seen that Comparative Examples 1 to 10 that do not satisfy the configuration of the present invention cannot obtain the effects of the present invention.
In the outermost coating layer, the content of the polyacrylate with respect to 100 parts by mass of the binder is mainly based on the comparison between Examples 4 to 6 and Example 11 and the comparison between Examples 14 to 16 and Example 23. It is understood that a range of 0.1 parts by mass or more and 3.5 parts by mass or less is preferable.
From the comparison between Example 4 and Example 7 and the comparison between Example 14 and Example 17, it can be seen that the polyacrylate is preferably ammonium polyacrylate.

Claims (4)

  A base paper and at least one coating layer 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 contains a pigment, a binder, a polyacrylate, and an acetylene glycol derivative. A transfer paper used in a transfer printing method using at least a sublimation printing ink.   The transfer paper according to claim 1, wherein in the outermost coating layer, the content of the polyacrylate with respect to 100 parts by mass of the binder is 0.1 parts by mass or more and 3.5 parts by mass or less.   The transfer paper according to claim 1 or 2, wherein the polyacrylate is ammonium polyacrylate.   The transfer paper according to claim 3, wherein the weight average molecular weight of the ammonium polyacrylate measured by a gel permeation chromatography method is 5000 or more and 30000 or less.