JP5300399B2 - Sublimation type inkjet printing transfer paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide sublimation type inkjet textile printing transfer paper having characteristics of hardly causing waviness when printing using a sublimation type textile printing ink while maintaining quality as the sublimation type inkjet textile printing transfer paper, and suppressing expanding/contracting variation during heating transfer. <P>SOLUTION: The sublimation type inkjet textile printing transfer paper has a base material, a sublimation type textile printing ink receiving layer provided on the surface of the base material, and a back coating layer provided on the back face of the base material. The sublimation type textile printing ink receiving layer contains water soluble resin and fine particles. The fine particles are synthetic amorphous silica. The back coating layer contains water soluble resin, and contains at least polyethylene glycol as the water soluble resin. The expansion rate of the sublimation type inkjet textile printing transfer paper is 0.7% or less in a vertical direction and 0.5% or less in a lateral direction. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a sublimation type ink jet printing transfer paper. Specifically, the sublimation type printing ink is printed on a transfer paper by an ink jet recording method, and the printed image on the transfer paper is transferred to a cloth such as polyester. The present invention relates to a sublimation type ink jet printing transfer paper used for sublimation transfer printing.

  For transfer printing methods, melt-type transfer printing methods using heat softening fixatives such as waxes and resins and inks made of pigments, rubber prints using powders such as polyvinyl chloride and plasticizers and pigments There are a type transfer printing method and a sublimation type printing transfer method using a heat sublimation dye.

  In the melt type transfer printing method, the texture and stretchability of the printed material are insufficient, and the printed material by the rubber print type transfer printing method does not have good air permeability and feel. The sublimation printing transfer method is a transfer printing method that is mainly performed at present because it can print a sharp pattern that cannot be produced by other transfer methods without impairing the texture of the printed matter. Conventionally, a thermal transfer printing sheet has required a printing plate such as a screen plate and a gravure plate and a printing machine corresponding to the thermal transfer printing sheet. However, due to the diversification of individuality, a transfer printing sheet for inkjet printing corresponding to a small lot is required. There has been a report, and sublimation printing transfer corresponding to small lots has become widespread, and demand is increasing.

  The sublimation printing transfer method is a method in which a transfer material such as a polyester fabric and a sublimation ink jet printing transfer paper are placed in close contact with a dryer heated to 180 to 220 ° C. to form a sublimation ink jet printing transfer paper. The printed printing ink is sublimated by heat, and transfer printing is performed on the transfer object.

As the sublimation type ink jet printing transfer paper for ink jet printing, an ink receiving layer containing a pigment such as silica or a binder such as polyvinyl alcohol or a water-soluble cellulose derivative on a substrate is provided. Known (see Patent Documents 1 to 5).
Japanese Patent Laid-Open No. 2002-292995 JP 2003-276309 A JP 2004-255715 A JP 2004-255717 A JP 2003-266919 A

  In the conventional sublimation type ink jet textile transfer paper, when ink jet printing is performed, the liquid (water or organic solvent) in the ink tends to be absorbed, so that the transfer paper tends to be wavy. When a wave is generated, a gap is created between the transfer paper and the transferred object when they are superimposed during heat transfer, making it difficult for them to adhere evenly, and image reproducibility or transfer on the transferred object is difficult. There arises a problem that efficiency decreases. For this reason, there has been a demand for a transfer paper that is less likely to generate waviness after printing, but it has been extremely difficult to effectively suppress waviness.

  In addition, if the sublimation inkjet printing transfer paper after printing is subjected to a heat transfer process, the transfer paper is overdried due to the heating, resulting in significant expansion and contraction fluctuations. There was also a problem that the image reproducibility and the transfer efficiency deteriorated. In particular, in recent years, a temperature condition exceeding 170 to 210 ° C. is applied as a temperature at the time of transfer to improve the transfer efficiency to the transfer object, whereby ink transfer is performed on both surfaces of the transfer object by transfer from one side. However, when transfer is performed at such a high temperature, fluctuations in the expansion and contraction of the transfer paper are more likely to occur. For this reason, there is a need for a sublimation type ink-jet printing transfer paper that is resistant to fluctuations in expansion and contraction even when heated at high temperatures and has excellent dimensional stability.

  In addition to the above, when performing ink jet printing on sublimation type ink jet textile transfer paper, it is possible to prevent so-called back-through, in which ink escapes to the back surface of the transfer paper, and furthermore, the heat resistance required at the time of heat transfer. It was necessary to maintain good characteristics in terms of points.

  In view of the above-described situation, the present invention is less likely to generate ripples when printed with sublimation type printing ink while maintaining the quality as sublimation type ink jet printing transfer paper. It is an object of the present invention to provide a sublimation ink jet printing transfer paper having suppressed characteristics.

  The present invention is a sublimation ink jet printing transfer paper comprising a substrate, a sublimation printing ink receiving layer provided on the surface of the substrate, and a backcoat layer provided on the back surface of the substrate. The sublimation printing ink receiving layer contains a water-soluble resin and fine particles, the fine particles are synthetic amorphous silica, the backcoat layer contains a water-soluble resin, and the water-soluble resin A sublimation type ink jet printing transfer paper comprising at least polyethylene glycol and having a stretching ratio of 0.7% or less in the vertical direction and 0.5% or less in the horizontal direction.

Preferably, the base material is craft paper having a glossy surface on one side, the sublimation printing ink receiving layer is provided on the glossy surface, contains a penetrant in the base material, and the sublimation type the textile ink receiving layer, wherein the fine particles contain 20 to 50 wt%, the coating amount of the backcoat layer is, on a dry weight is ^{0.1g / m 2 ~0.8g / m 2} .

  Preferably, the water-soluble resin constituting the back coat layer contains polyethylene glycol and polyvinyl alcohol, and the weight ratio of the two is in the range of 10:90 to 50:50.

  The sublimation type ink jet printing transfer paper of the present invention is less likely to generate a wave when printing with a sublimation type printing ink while maintaining the quality as a conventional sublimation type ink jet printing transfer paper, and heat transfer Occasionally, fluctuations in expansion and contraction are also suppressed, and the image has excellent characteristics of image reproducibility and transfer efficiency on a transferred object after heat transfer.

  The sublimation type inkjet printing transfer paper of the present invention is provided with a coating layer on both sides of a substrate, and on one side, a sublimation type printing ink receiving layer for printing using a sublimation type printing ink is provided, On the back side, a backcoat layer is provided to prevent the occurrence of waviness when printing is performed using sublimation type printing ink, and to suppress fluctuations in expansion and contraction during heat transfer.

  The sublimation type ink jet printing transfer paper of the present invention comprises a sublimation type printing ink receiving layer composed of a water-soluble resin and predetermined fine particles, and further provided with an appropriate backcoat layer, so that the expansion / contraction ratio under heating and humidification is provided. Specifically, the expansion / contraction rate is 0.7% or less in the vertical direction and 0.5% or less in the horizontal direction. By having the expansion / contraction ratio within this range, it is possible to sufficiently suppress fluctuations during printing and fluctuations during expansion / contraction during heat transfer, and excellent image reproducibility and transfer efficiency after transfer by heating. Can be. Note that the conventional sublimation type inkjet textile transfer paper showed a high value of about 0.9%, so there was a tendency for waves during printing and fluctuations in expansion and contraction during heat transfer to occur very easily. It was.

  The lower the expansion / contraction rate, the more preferable the wave during printing and the expansion / contraction variation during heat transfer are suppressed. Specifically, the expansion / contraction rate is 0.7% or less in the vertical direction and 0.5% or less in the horizontal direction. It is preferable.

  The expansion / contraction rate in the present invention is measured by a measuring instrument: automatic paper extensometer No. Using 2078-III, test conditions: For each transfer paper of 10 × 150 mm, the test piece was set on a measuring instrument, and then kept in an environment of 20 ° C. and 30% RH for 1 hour to determine a reference length. Thereafter, the temperature was raised at a rate of 1 ° C./min to 80 ° C. and 30% RH. After maintaining for 3 hours in this environment, the stretch length of the test piece was measured and used as a measured value. The measurement was performed by averaging 5 samples each in the vertical direction (flow direction) and the horizontal direction (width direction).

  According to the knowledge of the present inventors, there is a high correlation between the expansion ratio and the temperature, and in the sublimation type ink jet printing apparatus using the sublimation type ink jet printing transfer paper, the temperature at the time of transfer is 150 ° C. to 300 ° C., usually Although used in the vicinity of 180 ° C., originally, measurement in an environment at 180 ° C. is necessary, but the expansion / contraction rate in an environment at substantially 20 ° C. to 80 ° C. is 0.7% or less in the vertical direction and 0 in the horizontal direction. By setting the ratio to 5% or less, the expansion / contraction problem at the time of sublimation printing ink transfer can be solved. Therefore, it is adopted as an alternative test means, and the required expansion / contraction rate is specified.

  The expansion / contraction rate within the range specified in the present invention is such that the sublimation type printing ink receiving layer is composed of a water-soluble resin and predetermined fine particles, and an appropriate back coat layer is provided on the back side of the sublimation type ink jet printing transfer paper. Can be achieved.

  The base material used in the practice of the present invention is not limited as long as the base material is provided with a sublimation printing ink receiving layer. That is, paper mainly composed of wood pulp, a porous resin film made of a thermoplastic resin containing inorganic fine particles, non-woven fabric, fabric, resin-coated paper, synthetic paper, and the like can be given. The substrate in which the effects of the present invention are remarkably exhibited is a porous material in which the sublimation printing ink is easily sublimated by heating to the back surface of the sublimation type ink jet printing transfer paper. Paper, non-woven fabric, and fabric.

  As a base material, it is preferable to use paper mainly composed of wood pulp, and it is particularly preferable to use single glossy paper having a glossy surface on one side by performing a drying step using a Yankee dryer.

The glossy paper that the present inventors have found most suitable will be described below as a base material.
Since the glossy surface of single glossy paper has a high surface flatness, it is possible to obtain a sublimation printing ink receiving layer with high homogeneity by providing a sublimation printing ink receiving layer here. It has excellent properties and can also have excellent image reproducibility and transfer efficiency at the time of warm transfer for sublimation printing. It is suitably used as a particularly excellent substrate, and further, by providing a back coat layer on the non-glossy surface, the expansion / contraction rate can be made a lower value.

Single glossy paper is paper that has a Yankee dryer surface as a glossy surface by performing a drying process using a Yankee dryer. Single glossy paper is made by attaching wet paper to a Yankee dryer and drying it. Compared to wet paper drying using a multi-cylinder dryer, it has superior dimensional stability and a glossy surface that is highly smooth. Reproducibility can be achieved. Furthermore, since the back surface is rougher than the glossy surface and has many voids, the heat retention effect is high during heating, and the sublimation printing ink can be sublimated evenly and effectively. Katatsuyashi used therefor is preferably a basis weight is 60 to 150 g / ^{m 2,} more preferably 90~110g / ^{m 2.} If the glossy surface of the glossy paper is less than 60 g / m ² , the tensile strength and tear strength will decrease, and when the paper is cut or recorded on the sublimation printing ink receiving layer, the substrate tends to undergo stretching fluctuations when wavy or heated. At the same time, there is a tendency for the workability to deteriorate. If the plain weight of the glossy paper exceeds 150 g / m ² , heat transfer is deteriorated at the time of heat transfer of the sublimation printing ink to the transfer object, and the transfer efficiency tends to be lowered.

  Moreover, it is preferable that the Beck smoothness based on JISP8119 of the glossy surface of single glossy paper is 40 to 200 second, and 50 to 100 second is more preferable. If the glossy surface has a Beck smoothness of less than 40 seconds, the absorption / drying property of the sublimation printing ink at the time of printing increases, but the image reproducibility deteriorates and the sublimation printing ink is transferred to the transfer object. Image reproducibility and transfer efficiency tend to decrease. On the other hand, if it exceeds 200 seconds, unevenness occurs in the formation of the sublimation printing ink receiving layer comprising the water-soluble resin and fine particles, and the image reproducibility tends to be lowered.

  The smoothness of the back surface, which is a non-glossy surface, is preferably about 18 seconds. If the back surface has a smoothness equal to or higher than that of the glossy surface, heat retention during heating is inferior, and there may be a problem that inferior in terms of image reproducibility and transfer efficiency of a transfer object by transfer. Therefore, high-quality paper or the like dried with a multi-cylinder dryer on both the front and back surfaces may be inferior in terms of image reproducibility and transfer efficiency of the transferred material by transfer compared to single glossy paper.

  Furthermore, by providing a back coat layer on the back side of single glossy paper, it is possible to obtain a back side property with little dimensional change between fibers, similar to tension drying with a Yankee dryer applied to the glossy surface. Together, it can bring out properties with little dimensional change.

  Furthermore, it is preferable that the base material contains a penetrating agent so that the solvent of the sublimation printing ink applied to the sublimation printing ink receiving layer can be quickly obtained when printing is performed using the sublimation printing ink. While impregnating in the material, it suppresses the wave of sublimation type ink jet printing transfer paper, and at the time of heat transfer, it exhibits the characteristics that the expansion and contraction fluctuation is also suppressed.

  The glossy paper according to the present invention is composed of raw materials used in the so-called papermaking field. Although it does not specifically limit as a pulp to be used, For example, chemical pulps, such as a softwood unbleached kraft pulp (NUKP), a softwood bleached kraft pulp (NBKP), a hardwood unbleached kraft pulp (LUKP), and a hardwood bleached kraft pulp (LBKP); Thermomechanical pulp (TMP), Chemithermomechanical pulp (CTMP), Refiner mechanical pulp (RMP), Refiner ground pulp (RGP), Chemiground pulp (CGP), Thermogrand pulp (TGP), Groundwood pulp (GP), Stone Mechanical pulp such as ground pulp (SGP) and pressed stone grand pulp (PGW); waste paper pulp including chemical pulp and mechanical pulp such as deinking pulp (DIP) and waist pulp (WP). 1 type or 2 types from It can be selected and used above. Of these, it is preferable to use a combination of softwood bleached kraft pulp and hardwood bleached kraft pulp as appropriate.

  The penetrant that can be blended into the substrate in the present invention is generally known as a drug that improves the permeability of the oil component to the paper substrate. Specific examples include surfactants such as nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In the present invention, nonionic surfactants are particularly preferably used. be able to.

  In addition to nonionic surfactants that can be suitably used in the present invention as penetrants, cationic, amphoteric, and anionic surfactants are commercially available, but cationic aliphatic amine salts and aromatic quaternary compounds are commercially available. Ammonium salts, heterocyclic quaternary ammonium salts, and the like are surfactants that exhibit a cationically dissociated portion in an aqueous solution, but promote the fixing of the sublimation printing ink and sublimate the ink when heated. May be suppressed.

  Examples of amphoteric surfactants include betaines, aminocarboxylates, imidazoline derivatives, and the like, and both an anionic hydrophilic group and a cationic hydrophilic group are present in the molecule. It also dissociates and acts as anionic on the alkali side, cationic on the acidic side, and a nonionic surfactant near the neutral side. Similarly, sublimation of sublimation type printing ink may be suppressed.

  An anionic surfactant is a substance that ionically dissociates in an aqueous solution and the anion portion exhibits surface activity, causing a problem that not only the solvent of the sublimation printing ink but also the solute portion penetrates into the substrate. There is a case.

  Specific examples of nonionic surfactants include polyalkylene oxide ethers of long-chain or branched alkylphenols, polyalkylene oxide ethers of long-chain alkyl alcohols, fatty acid esters, alkylamines, alkylamides, alkylthioethers, and phosphate esters. Polyoxyethylene glycols, acetylene glycol-based nonionic surfactants; fatty acid anhydrosorbite esters, fatty acid anhydrosorbite ester and ethylene oxide condensates, fatty acid glycerin esters, pentaerythritol esters, fatty acid sucrose esters, Polyhydric alcohols represented by glucoside, gluconamide, fatty acid alkylolamide; propargyl alcohol, butynediol, acetylene alcohol, etc. Door can be.

  As the most preferred nonionic surfactant in the present invention, the reason is not clear. However, since the hydrophilic group is a surfactant exhibiting properties that can increase the hydrophilicity as the number of OH groups increases, an acetylene glycol type surfactant is used. These surfactants and acetylene alcohol surfactants are preferably used for promptly absorbing the solvent of the sublimation printing ink into the substrate and promoting drying.

  In particular, an acetylene glycol nonionic surfactant having an acetylene group in the center and a symmetrical structure is preferably used.

  Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and mixtures thereof. Or an ethylene oxide adduct etc. can be mentioned. Furthermore, an acetylene glycol surfactant having an HLB value of 9 to 13 is preferred.

  Examples of acetylene alcohol surfactants include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 2,4,7,9-tetramethyl-5-decyne-4 , 7-diol, 3,5-dimethyl-1-hexyn-3-ol, a mixture thereof, or an ethylene oxide adduct. Furthermore, acetylene alcohols having an HLB value of 6 or more are preferred.

  The HLB value referred to in the present invention is based on the Griffin method, and is determined by a calculation formula of HLB value = 20 × (weight% of hydrophilic group) based on the formula weight and molecular weight of the hydrophilic group.

  By containing a penetrant, particularly an acetylene alcohol-based and / or acetylene glycol-based nonionic surfactant, in the substrate, the solvent contained in the sublimation printing ink is selectively selected from the sublimation printing ink receiving layer. The absorption and drying properties of the sublimation printing ink are promoted in order to create an effect of permeating into the ink and retaining the sublimation printing ink component hitting the solute in the sublimation printing ink receiving layer.

  Furthermore, by combining with fine particles contained in the sublimation printing ink receiving layer, it is controlled that the sublimation printing ink component (solute) having a particle size larger than the solvent reaches the substrate through the sublimation printing ink receiving layer. In addition, the transfer efficiency of sublimation printing ink and the density of sublimation printing ink to the transfer object can be improved, and the excellent drying property of sublimation printing ink and image reproduction when printing onto sublimation inkjet printing transfer paper. And sublimation type ink jet printing transfer paper having excellent properties in terms of image reproducibility and transfer efficiency of a transferred object by transfer.

  The content of the penetrant is preferably 0.01 to 1.0% by mass (solid content), more preferably 0.05 to 0.8% by mass with respect to the raw material pulp (absolutely dry). . Here, if the content is less than 0.01% by mass, it is difficult to obtain the effect of the penetrating agent on the ink absorption and drying properties of the sublimation printing ink. If the content exceeds 1.0% by mass, the sublimation printing ink is used. In the formation of the receiving layer, the water-soluble resin component is excessively permeated and impregnated in the base material, which causes a problem that the coating layer strength is reduced and paper dust is generated during processing.

  In addition, base materials include various starches such as oxidized starch, acetylated starch, esterified starch, and etherified starch, and additive chemicals such as paper strength enhancer, internal sizing agent, external sizing agent, and yield improving agent. Can be contained as appropriate.

  The sublimation type printing ink receiving layer provided on the substrate contains fine particles and a water-soluble resin as a binder. As will be described later, the surface of the sublimation printing ink receiving layer is coated with irregularities by agglomerates of fine particles, and this property is the absorption / drying property of the sublimation printing ink and the sublimation during printing. In addition to improving the image reproducibility and workability of the ink jet printing transfer paper, it also prevents the sublimation printing ink from penetrating to the back side of the sublimation ink jet printing transfer paper during warm transfer for sublimation printing. In addition, it also exhibits excellent characteristics in terms of image reproducibility of the transferred object by transfer and transfer efficiency.

In the present invention, synthetic amorphous silica is used as the fine particles. Among these synthetic amorphous silicas, porous amorphous particles having a large pore volume and having a three-dimensional structure of SiO ₂ formed by silicic acid gelation, a fine particle of about 10 to 2000 angstroms. Those having a pore size are preferred. By using the synthetic amorphous silica, the absorption and drying properties of the sublimation printing ink of the sublimation type ink jet printing transfer paper of the present invention are improved, and the transfer efficiency of the sublimation printing ink to the transfer object is improved. The image on the transfer can be made clearer. As fine particles, fine particles other than synthetic amorphous silica, such as colloidal silica, can be used in appropriate combination.

  As such synthetic amorphous silica, commercially available ones can be suitably used. For example, Mizukacil P-526, Mizukacil P-801, Mizukacil NP-8, Mizukacil P-802, Mizukacil P-802Y, Mizukacil. C-212, Mizukacil P-73, Mizukacil P-78A, Mizukacil P-78F, Mizukacil P-87, Mizukacil P-705, Mizukacil P-707, Mizukacil P-707D, Mizukacil P-709, Mizukacil C-402, Mizukacil C-484 (manufactured by Mizusawa Chemical Co., Ltd.), Toxeal U, Toxeal UR, Toxeal GU, Toxeal AL-1, Toxeal GU-N, Toxeal N, Toxeal NR, Toxeal PR, Sorex, Fineseal E- 50, fine seal T-32, fine sea X-30, fine seal X-37, fine seal X-37B, fine seal X-45, fine seal X-60, fine seal X-70, fine seal RX-70, fine seal A, fine seal B (above, (Manufactured by Tokuyama Corporation), Sipernato, Carplex FPS-101, Carplex CS-7, Carplex 22S, Carplex 80, Carplex 80D, Carplex XR, Carplex 67 (above, manufactured by DSL Japan Co., Ltd.) ), Syloid 63, Syroid 65, Syloid 66, Syloid 77, Syloid 74, Syloid 79, Syloid 404, Syloid 620, Syloid 800, Syloid 150, Syloid 244, Syroid 266 (manufactured by Fuji Silysia Chemical Co., Ltd.), Nip gel AY-200, nip gel AY-6A2, nip gel AZ-200, nip gel AZ-6A0, nip gel BY-200, nip gel BY-200, nip gel CX-200, nip gel CY-200, nip seal E-150J, nip seal E-220A, Nip seal E-200A (above, manufactured by Tosoh Silica Co., Ltd.).

  The synthetic amorphous silica used in the present invention is preferably an aggregate of fine particles, and the average particle diameter of the aggregate (volume average particle diameter measured by a Coulter counter particle size distribution meter described later) is 1.7 μm. It is preferable to be within a range of ˜13 μm, preferably 2.3 μm to 12.7 μm. By using an aggregate having an average particle size of 1.7 μm to 13.0 μm as the synthetic amorphous silica, high quality color reproducibility and image reproducibility can be obtained. If the average particle size of the fine particle aggregate is less than 1.7 μm, the absorption / drying property of the sublimation printing ink tends to be reduced, and the average particle size of the fine particle aggregate is 13.0 μm. If it exceeds, the color density of the transferred material may be lowered.

  In the present invention, only one kind of aggregate of synthetic amorphous silica can be used, but preferably two or more kinds of synthetic amorphous silica aggregates having different average particle diameters of aggregates are used. It is preferable to use in combination. Particularly, a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm and a synthetic amorphous silica aggregate having an average particle diameter exceeding 5 μm were used in combination. It is preferable to use a mixture of fine particles. Thus, by using together different synthetic amorphous silica aggregates having an average particle diameter of several μm, a mixture is formed in which aggregates of different average particle diameters complement the gaps between the aggregates, Sublimation-type ink-jet printing using sublimation printing ink has excellent dryness of sublimation printing ink, image reproducibility, prevention of back-through, and heat resistance when printing on sublimation ink-jet printing transfer paper. Good characteristics can also be obtained in terms of transfer efficiency.

  More preferably, although the reason is not clear, the use of a combination of two or more kinds of synthetic amorphous silica aggregates facilitates the formation of irregularities described later, and provides excellent sublimation printing ink drying properties and the like. The effects of the invention can be achieved.

  As such a synthetic amorphous silica aggregate, a commercially available one can be used, for example, as a commercial product of a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm. Nipgel AY-200 and the like, and as a commercial product of a synthetic amorphous silica aggregate in which the average particle diameter of the aggregate exceeds 5.0 μm, nipgel AY-6A2 and the like can be mentioned.

  In the present invention, the average particle size is obtained by adding a small amount of sample to a methanol solution and dispersing the solution for 3 minutes with an ultrasonic disperser using a Coulter counter particle size distribution analyzer (TA-II type manufactured by COULTER ELECTRONICS INS). Measurements were made using a 50 μm aperture.

  In a combination of synthetic amorphous silica aggregates having different preferred average particle diameters, a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm and an average particle diameter of 5 The blending ratio of the synthetic amorphous silica aggregate exceeding 0.0 μm is not particularly limited, but is preferably about 10:90 to 50:50 by weight ratio of solid content. By setting the weight ratio of the solid content to about 10:90 to 50:50, the silica aggregate having a small particle diameter fills the gap between the silica aggregate having a large particle diameter, so that the porosity of the resulting mixture increases. In the formation of unevenness on the surface of the sublimation printing ink receiving layer, a uniform agglomerate unevenness coating by the mixture can be obtained, so that excellent absorption and drying properties of the sublimation printing ink, image of sublimation ink jet printing transfer paper Reproducibility, reproducibility of the image on the transfer object, and high transfer efficiency of the sublimation printing ink can be obtained.

  In the present invention, by using a nonionic surfactant that can be suitably used as the penetrant, in particular, an acetylene glycol surfactant and an acetylene alcohol surfactant, the unevenness of the surface of the sublimation printing ink receiving layer can be obtained. In the formation, in order to efficiently impregnate the substrate with the solvent of the sublimation printing ink, the agglomerates formed in the sublimation printing ink receiving layer may be inadvertently reaggregated in response to the penetration of the solvent. In addition, the formation of uneven portions by uniform aggregates of aggregates can be obtained, and sublimation type ink-jet printing that quickly absorbs and dries sublimation type printing ink when printing with sublimation type printing ink and does not show through when transferring. Transfer paper can be obtained.

  As long as the effects of the present invention are exhibited, fine particles other than synthetic amorphous silica can be blended together with synthetic amorphous silica. Other fine particles include, for example, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, magnesium hydroxide, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, Aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, colloidal silica, alumina, colloidal alumina, alumina hydrate (pseudo boehmite, etc.), aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide and other inorganic pigments, styrene And organic pigments such as polyethylene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

  The content of fine particles in the sublimation printing ink receiving layer is preferably 20 to 50% by mass, and more preferably 23 to 45% by mass. When the content is less than 20% by mass, the sublimation printing ink acceptance amount is decreased, and the transfer efficiency tends to be lowered. On the other hand, if it exceeds 50% by mass, the sublimation printing ink acceptance amount increases, but the sublimation efficiency at the time of transfer tends to decrease, which may cause a problem of fouling. Since the water-soluble resin in the sublimation printing ink receiving layer may exhibit thermoplasticity, the heat resistance of the sublimation printing transfer paper can be increased by increasing the content of fine particles in the sublimation printing ink receiving layer. improves.

  In the present invention, the water-soluble resin is mainly used as a binder, for example, starch derivatives such as starch, oxidized starch, cationized starch, etherified starch, and phosphate esterified starch, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate and the like. Cellulose derivatives, various saponified polyvinyl alcohols or their silanol-modified products, carboxylated products, cationized products and other derivatives, water-soluble natural polymers such as casein, gelatin, modified gelatin, soybean protein, polyvinylpyrrolidone, sodium polyacrylate Water-soluble synthetic polymers such as sodium styrene-maleic anhydride copolymer and sodium polystyrene sulfonate. These water-soluble polymers can be used alone or in combination. That.

  Examples of the most preferable water-soluble resin found by the present inventors include polyvinyl alcohol and carboxymethyl cellulose, and it is most preferable to use both in combination.

  It does not specifically limit as polyvinyl alcohol, Although polyvinyl alcohol of various saponification degrees can be used, As a saponification degree, about 87-89 mol% is preferable. The degree of polymerization is not particularly limited, but, for example, those having a degree of polymerization of about 1000 or less are particularly preferred for compatibility with carboxymethylcellulose and for retaining sublimation printing inks in the ink receiving layer. Examples of such commercially available polyvinyl alcohol include Poval PVA-210, Poval PVA-205 (manufactured by Kuraray Co., Ltd.), and the like.

  Dispersibility of the synthetic amorphous silica used in the preparation of the ink-receiving layer coating by using polyvinyl alcohol having a saponification degree of about 87 to 89 mol% and a polymerization degree of about 1000 or less as the water-soluble resin. In particular, the ability to form irregularities when using a combination of two or more types of synthetic amorphous silica aggregates, and excellent sublimation printing ink when printing on sublimation ink jet printing transfer paper using sublimation printing ink In addition to having drying properties, image reproducibility, anti-through-through properties, and heat resistance, it is possible to obtain good characteristics in terms of image reproducibility and transfer efficiency of a transfer object by transfer.

  The blending amount of the polyvinyl alcohol is preferably about 1 to 200 parts by weight, more preferably about 2 to 100 parts by weight with respect to 100 parts by weight of fine particles containing at least synthetic amorphous silica as a solid content. By this range, it is possible to achieve both excellent drying property of sublimation printing ink and high prevention property of sublimation printing ink.

  When the blending amount of polyvinyl alcohol is less than 1 part by weight with respect to 100 parts by weight of fine particles, the binder effect due to polyvinyl alcohol is not sufficiently exerted, and the ink receiving layer is easily peeled off or scratched, thereby reducing image reproducibility. Problems arise.

  When the blending amount of the polyvinyl alcohol exceeds 200 parts by weight with respect to 100 parts by weight of the fine particles, a decrease in the drying property of the sublimation printing ink becomes a problem because a film is formed by the polyvinyl alcohol.

  The carboxymethyl cellulose as the water-soluble resin suitably used is not particularly limited, and those having a degree of etherification in the range of 0.5 to 1.0 are preferable.

  As a water-soluble resin, carboxymethylcellulose having a degree of etherification of 0.5 to 1.0 is preferably used in combination with polyvinyl alcohol, particularly a saponification degree of about 87 to 89 mol% and a polymerization degree of about 1000 or less. Has good compatibility with polyvinyl alcohol and does not hinder the dispersibility of synthetic amorphous silica, particularly the ability to form irregularities when using a combination of two or more types of synthetic amorphous silica aggregates. , Sublimation printing ink using sublimation printing ink Sublimation printing ink has excellent dryness, image reproducibility, anti-through-through resistance and heat resistance when printed on transfer paper, and image reproducibility of transferred object by transfer Also, good characteristics can be obtained in terms of transfer efficiency.

  As a commercially available product, Serogen 7A (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can be used. The blending amount of carboxymethyl cellulose is preferably about 20 to 400 parts by weight, more preferably about 100 to 350 parts by weight, with respect to 100 parts by weight of fine particles containing at least synthetic amorphous silica as a solid content. When the blending amount of carboxymethyl cellulose is less than 20 parts by weight, the transfer efficiency of the sublimation printing ink to the transferred material is lowered, and there may be a problem that the sublimation printing ink in the sublimation type ink jet printing transfer paper is behind. If the amount of carboxymethyl cellulose exceeds 400 parts by weight, the absorption and drying properties of the sublimation printing ink are lowered, and the problem of fouling such as the sublimation printing ink being set off during storage tends to occur.

  Preferably, by using a water-soluble resin in which polyvinyl alcohol and carboxymethyl cellulose are used in the above ranges, it is possible to achieve both excellent drying properties of sublimation printing ink and a high degree of anti-sublimation prevention of sublimation printing ink.

  In the present invention, the stabilization of the dye in the sublimation printing ink is promoted in the sublimation printing ink receiving layer, and the fixing property to the synthetic amorphous silica contained in the sublimation printing ink receiving layer is improved. Amidines and epichlorohydrins are able to control the absorption and drying properties of sublimation printing inks and the excessive impregnation of the ink into the base material to form high-concentration and high-definition printing information in the sublimation printing ink receiving layer. It is preferable to contain a cationic resin consisting of the above in the sublimation type printing ink receiving layer.

  Among amidines, a particularly suitable polyamidine is a water-soluble cationic polymer having a 5-membered amidine structure in the main chain of the polymer, and is synthesized from acrylonitrile and N-vinylformamide. In the fixing action of sublimation type printing ink, it is more hydrophilic than the quaternary ammonium salt type cationic polymer fixing agent that is a commonly used fixing agent for ink jet recording ink, and tends to be re-dissolved. In particular, low molecular weight polyamidine enables high-definition (low bleeding) sublimation printing ink information to be recorded at a high concentration without causing excessive fixing of the sublimation printing ink. Since the sublimation printing ink can be transferred, sublimation ink jet printing transfer paper having excellent drying properties of the sublimation printing ink and good characteristics in terms of image reproducibility and transfer efficiency can be obtained.

  In addition, a cationic resin having reactivity such as epichlorohydrins, in particular, polydimethylamine epichlorohydrin and modified dimethylamine epichlorohydrin condensate, which binds to cellulose and insolubilizes the resin in water can be suitably used. Although the sublimation type printing ink receiving layer is composed of a water-soluble resin and a coating mainly composed of fine particles, it tends to have a relatively high viscosity, but a cationic resin such as polydimethylamine epichlorohydrin or a modified dimethylamine epichlorohydrin condensate. Since it has the effect of reducing the viscosity of the paint, it is possible to easily adjust the viscosity while containing agglomerates in the paint adjustment of the present invention, and the operability of the paint adjustment and coating can be improved.

  The weight average molecular weight of the cationic resin is preferably 10,000 to 500,000, more preferably 10,000 to 400,000, still more preferably 10,000 to 200,000, and particularly preferably 10,000 to 10 It is ten thousand. By being at least the lower limit of the range, the ink absorbability of the sublimation printing ink receiving layer mainly comprising a water-soluble resin and fine particles is improved. On the other hand, when the amount is not more than the upper limit value, the fixing property with the synthetic amorphous silica is good in the combination with the fine particles contained in the sublimation type printing ink receiving layer, particularly with the synthetic amorphous silica.

  The cationic resin that can be used in the present invention is preferably a weak electrolyte having a cation density of 2 to 12 meq / g. The cation density of the cationic resin is determined by a method based on the colloid titration method.

  The cationic layer of the coating layer containing a cationic resin on the coated surface, preferably a polyamidine, a polydimethylamine epichlorohydrin, a cationic resin composed of a modified dimethylamine epichlorohydrin condensate, is added to the cationic resin. Although the reason is not clear by adjusting the paint so that the adjustment is 0.5 to 3.5 Meq / g, more preferably 1.0 to 3.0 Meq / g, the sublimation printing ink is sublimated. Sublimation type printing ink in order to promote the absorption and drying properties of sublimation type printing ink on the surface layer of the type printing ink and to control the dye component of sublimation type printing ink having a particle size larger than that of the solvent to be impregnated to the base material. Can be concentrated and fixed, and can form clear prints. In the sublimation printing process, the transfer efficiency and sublimation type of sublimation printing ink. Can be obtained sublimation inkjet printing transfer paper improved dyeing ink density and high-definition sublimation transfer resistance and the ink print-through preventing property during transfer can be level up.

  The content of the cationic resin is preferably 1 to 25 parts by weight, more preferably 5 to 10 parts by weight with respect to 100 parts by weight of fine particles. Here, if the content is less than 1 part by weight, it is difficult to obtain an effect on the ink absorption and drying property of the sublimation printing ink. If the content exceeds 25 parts by weight, the image reproducibility, drying property and ink penetration during printing are difficult. Although good results are obtained in the cockling suitability by the ink, the dye sublimation failure (transfer defect) to the fabric, the yellowing of the fabric, the dye fixing is performed in the sublimation printing ink receiving layer, and the ink at the time of winding after printing Undesirably, rubbing dirt is generated.

The coating amount of the sublimation printing ink receiving layer is preferably in the range of 3 to 25 g / ^{m 2,} the range of 5 to 15 g / ^{m 2} is more preferable. If it is less than 3 g / m ² , a sufficient absorption capacity of the sublimation ink cannot be secured, the resolution of the transferred image is deteriorated, and unevenness tends to occur in the solid image portion. When the coating amount of the ink receiving layer exceeds 25 g / m ² , the surface strength is relatively lowered, causing powder falling or the like, which causes workability to be lowered.

Furthermore, in relation to the penetrant, if it is less than 3 g / m ² , the effect of the penetrant contained in the base material is sufficient to cause the entire sublimation printing ink component (solute / solvent) to reach the base material, The absorption capacity of the sublimation printing ink cannot be secured, the resolution of the transferred image is deteriorated, and unevenness tends to occur in the solid image portion. When the coating amount of the sublimation printing ink receiving layer exceeds 25 g / m ² , the speed at which the solvent component of the sublimation printing ink reaches the substrate is slow, and the effect of incorporating the penetrant into the substrate becomes difficult to be expressed. At the same time, the surface strength is relatively lowered, and there is a risk that powder fall or the like occurs and workability is lowered.

  The method for coating the sublimation printing ink receiving layer is not particularly limited, and the coating method is not particularly limited. For example, a known coating such as an air knife coater, roll coater, bar coater, comma coater, blade coater, etc. However, among the above-mentioned coating means, the blade coater, in particular, the reproduction of unevenness caused by the synthetic amorphous silica contained in the sublimation type printing ink receiving layer coating and It is preferable to use a vent blade that can form a coating layer with a desired coating amount without causing flatness and streaks on the surface of the sublimation printing ink receiving layer.

  By the above process, it has excellent sublimation printing ink absorption / drying property, good workability, image reproducibility on transfer paper surface, heat resistance during heat transfer, transferred material after transfer A sublimation type ink jet textile transfer paper having good characteristics in terms of image reproducibility on the surface and transfer efficiency can be preferably produced.

  In a particularly preferred embodiment of the sublimation type ink jet printing transfer paper of the present invention, unlike the conventional product, the sublimation type printing ink receiving layer has a unique uneven surface structure. In the conventional product, as shown in FIG. 2, the sublimation printing ink receiving layer has a pigment and binder covering the surface of the substrate with a substantially constant thickness, and as shown in FIG. 3, the sublimation printing ink receiving layer has a pigment on the sublimation printing ink receiving layer. In the preferred embodiment of the present invention, the surface of the sublimation type printing ink receiving layer has irregularities as shown in FIG. The irregularities are preferably aggregates of fine particles, but in particular, the irregularities formed by aggregates obtained by agglomeration of two types of synthetic amorphous silica aggregates having different particle diameters. More preferred. Most preferably, a large number of convex portions having a width of 5 μm or more are formed by the agglomerates, and the sublimation printing ink receiving layer having such irregularities on the surface covers the surface of the substrate, whereby the sublimation of the present invention. A type inkjet textile transfer paper is formed.

  If this irregularity is present, the specific surface area of the substrate surface increases, so that the sublimation printing ink can be instantly absorbed and retained (dried) by the sublimation printing ink receiving layer, and the sublimation printing ink is absorbed and dried. And improved sublimation printing ink absorption / drying properties, good workability, image reproducibility on transfer paper surface, heat resistance during heat transfer, transferred material after transfer A sublimation ink jet printing transfer paper having excellent characteristics in terms of image reproducibility on the surface and transfer efficiency can be produced.

  Here, the unevenness referred to in the present invention means the undulation of the surface of the sublimation printing ink receiving layer due to agglomerates of fine particles, and the formation thereof is at the stirring stage of the coating liquid for forming the sublimation printing ink receiving layer. It can be obtained by adding fine particles to a water-soluble resin and mixing and dispersing it. If the physical shearing force at the time of mixing and dispersion is too strong, uniform dispersion of fine particles will occur and it will be difficult to form irregularities, so it is preferable to adjust the dispersion treatment appropriately so that fine particle aggregates are formed in the coating liquid. When the sublimation type printing ink receiving layer is formed, irregularities are formed. The mechanism for forming the irregularities is not clear, but when the substrate is impregnated with the water-soluble resin, agglomerates of fine particles dispersed in the water-soluble resin appear and the sublimation printing ink is received on the substrate surface. In addition to forming a layer, irregularities due to agglomerates are formed.

  Existence of irregularities can be confirmed using an analytical scanning electron microscope (JSM-6390A type manufactured by JEOL Datum Co., Ltd.) as described later. According to the knowledge of the present inventors, if the width of the convex portion of the agglomerate forming the unevenness tends to be too small, there is a tendency that the prevention of the back-through of the sublimation type printing ink tends to be lowered, so about 30 μm or less is preferable, and 20 μm A degree or less is more preferable. The average value of 60 randomly selected agglomerates from individual long and short widths was actually measured, and 50 actually measured average values excluding 5 minimum values and 5 maximum values were measured.

  Further, the surface roughness of the sublimation type printing ink receiving layer satisfies a mean square roughness of 2 μm or more in a measured value measured with a laser microscope (Color Laser Microscope High Resolution Type VK-9700, manufactured by Keyence Corporation). It is preferable. Preferably it is 2.5 μm or more. The upper limit is preferably about 21 μm or less, or about 20 μm or less. If the surface roughness is too low, less than 2 μm, the drying property of the sublimation printing ink is not sufficient. If the surface roughness is more than 21 μm, the image reproducibility on the sublimation ink jet printing transfer paper is lowered and the image is transferred. In addition to the image reproducibility and transfer efficiency of the object being lowered, it is inconvenient for achieving the effects of the present invention. In addition, the root mean square roughness in a conventional product is less than 3 μm.

  As an example of a specific method for coating the surface of the sublimation type printing ink receiving layer with irregularities by agglomerates of fine particles, the coating liquid is prepared by the following procedure. That is, first, a solution of carboxymethyl cellulose is prepared at a relatively high temperature (for example, about 50 to 80 ° C.). Separately, a slurry of synthetic amorphous silica is prepared at a relatively low temperature (for example, about 20 to 40 ° C.). By adding the silica slurry to the carboxymethylcellulose slurry, the silica is aggregated to obtain a gelled mixture. Thereafter, polyvinyl alcohol is further added. In the obtained mixture, the solid content concentration of the fine particles is adjusted to 2 to 25% by mass, preferably about 3 to 12% by mass. A silica agglomerate having a substantially uniform particle size is obtained by subjecting this mixture to a mixing and dispersing treatment within about 30 minutes, preferably within 20 minutes, at around room temperature (for example, 15 to 45 ° C., 20 to 35 ° C.). Form. By adjusting the physical shearing force so that the size of the silica agglomerates is several tens of μm (specifically, about 10 to 30 μm) at the time of mixing and dispersing, the sublimation type ink jet printing transfer paper of the present invention is obtained. A coating solution suitable for production can be produced.

  Thereafter, in order to adjust the unevenness or the static friction coefficient, a flattening process can be performed using a machine calendar, a soft calendar, or the like. It is also possible to provide a backcoat layer for the purpose of correcting curl or the like.

  In the present invention, a back coat layer is provided on the back surface of the sublimation type ink jet printing transfer paper in combination with the sublimation type ink receiving layer. The backcoat layer is generally a coating layer containing a resin such as a water-soluble resin and a pigment, and is intended to prevent the ink from penetrating during printing. However, in the present invention, by selecting the composition of the backcoat layer, the coating amount, etc., not only prevents back-through, but also lowers the expansion / contraction rate of the sublimation type ink jet textile transfer paper, and causes fluctuations during printing or heat transfer. It is possible to improve the image reproducibility and transfer efficiency of the transferred material after heat transfer by preventing the stretching and contraction of the material.

  Examples of the water-soluble resin used in the backcoat layer of the present invention include starch derivatives such as starch, oxidized starch, cationized starch, etherified starch, and phosphate esterified starch, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and cellulose. Cellulose derivatives such as sulfate, polyvinyl alcohol with various saponification degrees or various derivatives thereof such as silanol modified products, carboxylated products, cationized products, natural polymers such as casein, gelatin, modified gelatin, soybean protein, polyvinyl pyrrolidone, sodium polyacrylate , And water-soluble synthetic polymers such as sodium styrene-maleic anhydride copolymer, sodium polystyrene sulfonate, polyethylene glycol, etc., and these water-soluble polymers can be used alone or in combination. It is possible. Among these, at least polyethylene glycol is used from the viewpoint of effectively preventing waves during printing and fluctuations in expansion and contraction during heat transfer.

  By using polyethylene glycol in the backcoat layer, the backcoat layer has water retention, and the moisture content retained by the base paper as the base material is adjusted to prevent the base paper from being overdried. Therefore, the expansion and contraction fluctuation of the substrate can be suppressed. In addition, since it has a temperature holding effect during heating, the thermal transfer efficiency can be improved. As the polyethylene glycol, those having a polymerization degree of 1,000 or less are preferably used. More preferably, the degree of polymerization is in the range of 200 to 400. When the degree of polymerization is 1,000 or more, the paint cannot be adjusted. As such polyethylene glycol, commercially available products include PEG-200, PEG-300 and PEG-400 (manufactured by Toho Chemical Industry Co., Ltd.).

  In addition, it is preferable to use polyvinyl alcohol together with polyethylene glycol in the back coat layer, so that it is difficult for waviness to occur when printing is performed using sublimation printing ink, and expansion and contraction fluctuations during heat transfer are suppressed. be able to. Polyvinyl alcohol having various saponification degrees can be used as the polyvinyl alcohol, and the saponification degree is preferably about 97 to 99 mol%. The degree of polymerization is not particularly limited, but for example, those having a degree of polymerization of about 1000 or less are preferred for compatibility with polyethylene glycol. Examples of such commercially available products of polyvinyl alcohol include Poval PVA-110 and Poval PVA-105 (manufactured by Kuraray Co., Ltd.).

  In particular, when polyethylene glycol and polyvinyl alcohol are used in combination, both polymers are preferably contained in a weight ratio of 10:90 to 50:50. When the amount of polyvinyl alcohol used is less than 50:50, the binder effect of polyvinyl alcohol is not sufficiently exhibited, and the problem of deterioration in image reproducibility occurs due to deterioration of dimensional stability due to peeling of the backcoat layer. Moreover, since the film formation by polyvinyl alcohol is not made, the effect of preventing the breakthrough is not exhibited. Conversely, if the amount of polyvinyl alcohol used is greater than 10:90, control of film formation becomes difficult.

  The back coat layer of the present invention preferably contains no pigment. When a pigment is contained, a stable film formation is not performed, so that a sufficient suppression effect of expansion / contraction fluctuations cannot be obtained, and a back-through prevention effect is not exhibited.

The coating amount of the backcoat layer is not particularly limited, in order to achieve a predetermined scaling factor by blending at least a polyethylene glycol in the range of 0.1g ^/ m ² ~0.8g / m 2 is preferable in dry weight . If the coating amount is less than 0.1 g / m ² , the effect of providing the back coat layer cannot be sufficiently exerted. Conversely, if it exceeds 0.8 g / m ² , drying after coating is performed. The drying load in the process increases, and not only the productivity decreases due to the decrease in coating speed, but also the curling property deteriorates.

  Polyvinyl alcohol and / or modified polyvinyl alcohol is used as an adhesive that is mixed with polyethylene glycol and blends the backcoat layer with the base material, but styrene-butadiene, acrylic, vinyl acetate, etc. Various proteins such as copolymer latex and casein, starches, and cellulose can be used in combination.

  Although it does not specifically limit as a coating method of a backcoat layer, For example, it can coat using well-known coating machines, such as an air knife coater, a roll coater, a bar coater, a comma coater, a blade coater.

  Hereinafter, the present invention will be described in detail with reference to examples in the case where recording is performed on sublimation type printing type recording paper with sublimation type printing ink using an ink jet recording method, but the present invention is limited to these examples. Is not to be done. In the examples, “parts” and “%” indicate parts by weight and% by weight unless otherwise specified. In addition, the part shown in a mixing | blending is a part of solid content.

  Hereinafter, the present invention will be described in detail with reference to examples in the case where recording is performed on sublimation type printing type recording paper with sublimation type printing ink using an ink jet recording method, but the present invention is limited to these examples. Is not to be done. In the examples, “parts” and “%” indicate parts by weight and% by weight unless otherwise specified. In addition, the part shown in a mixing | blending is a part of solid content.

<Creation of base material>
Freeness 530ml (C.S.F.) hardwood bleached kraft pulp (LBKP) and freeness 580ml (C.S.F.) softwood bleached kraft pulp (NBKP) 50:50 blend, auxiliary (solid content) Cationized starch 0.8 wt%, internal sizing agent 1.1 wt%, anion-modified polyacrylamide 0.3 wt%, acetylene glycol 1 as penetrant (acetylene glycol manufactured by Nissin Chemical Industry Co., Ltd.) system nonionic surfactant, model number: Surfynol 440, HLB 8) a was added 0.10% to prepare a stock, and paper in a paper machine having a Yankee dryer, basis weight 100 g / ^{m 2,} smoothness A 60-second glossy paper was produced.

Example 1
As fine particles, 85 parts by weight of silica A (manufactured by Tokuyama, model number: Fine Seal X37B), which is a synthetic amorphous silica having an average particle diameter of 3.7 μm, and a synthetic amorphous silica having an average particle diameter of 6.2 μm 15 parts by weight of silica B (manufactured by Tokuyama Corporation, model number: Fine Seal X60) and 100 parts by weight of the fine particles, sodium carboxymethyl cellulose (hereinafter abbreviated as CMC) CMC-A (first) 200 parts by weight of Kogyo Seiyaku Co., Ltd., trade name: Serogen PR), 25 parts by weight of PVA-A (trade name: PVA-205, manufactured by Kuraray Co., Ltd.), solid content concentration A 6.6% sublimation printing ink receiving layer coating was prepared. In order to purify the agglomerates of fine particles, a silica dispersion slurry at a low temperature of 20 ° C. to 30 ° C. is added to a high temperature CMC at 65 ° C. to 80 ° C. to agglomerate silica to obtain a gelled mixture. Thereafter, PVA was added and mixed and dispersed at 20 to 45 ° C., and the physical shearing force was adjusted so that the size of the silica agglomerates was 15 μm.

The coating liquid prepared by adjusting the agglomerates of fine particles was applied to the glossy surface of the substrate so that the dry coating amount was 5 g / m ² .
Furthermore, the coating amount of a water-soluble resin containing polyvinyl alcohol (manufactured by Kuraray, trade name: PVA-110) and polyethylene glycol (trade name: PEG-200, manufactured by Toho Chemical Co., Ltd.) in a ratio of 75:25 The non-glossy surface of the base material was coated so as to be 0.5 g / m ² (solid content), a back coat layer was formed, and sublimation printing transfer paper was obtained. The manufactured sublimation printing transfer paper was evaluated according to the evaluation criteria described later.

  In the following examples and comparative examples, as shown in Tables 1 and 2, the sublimation printing transfer paper is manufactured by changing the base material, fine particles, water-soluble resin, and coating amount as shown in Tables 1 and 2. Evaluation was performed in the same manner as in Example 1.

  In Example 2, the basis weight and smoothness were changed as shown in Table 1, and instead of acetylene glycol 1, acetylene glycol 2 (acetylene glycol-based nonionic surfactant manufactured by Nissin Chemical Industry Co., Ltd., model number: Surfynol) 465, HLB 13) 0.50% is used, and instead of silica A, silica C (manufactured by Tosoh Silica Co., Ltd., model number) which is a synthetic amorphous silica aggregate having an average particle diameter of 1.7 μm of aggregates : Nipgel AZ-204) was used.

  In Example 3, the basis weight and smoothness were changed as shown in Table 1, and instead of acetylene glycol 1, acetylene glycol 3 (acetylene glycol-based nonionic surfactant manufactured by Nissin Chemical Industry Co., Ltd., model number: Surfynol) 485, HLB 17) 0.05%, and instead of silica A, silica D (manufactured by DSL Japan Co., Ltd.), which is a synthetic amorphous silica aggregate having an average particle size of 4.3 μm Model number: Carplex BS-312AJ).

  In Example 4, the basis weight and smoothness were changed as shown in Table 1, and instead of acetylene glycol 1, acetylene glycol 4 (acetylene glycol nonionic surfactant manufactured by Nissin Chemical Industry Co., Ltd., model number: Olphine STG) , HLB 9.5) is used in an amount of 0.01%, silica B is used in place of silica A, and instead of silica B, the synthetic amorphous silica aggregate in which the average particle size of the aggregate is 12.7 μm Silica G (manufactured by DSL Japan Co., Ltd., model number: Carplex BS-303) was used.

  In Example 5, the smoothness was changed as shown in Table 1, and in place of acetylene glycol 1, acetylene alcohol 1 (Daiichi Kogyo Seiyaku Co., Ltd. acetylene alcohol-based nonionic surfactant, model number: Neugen ET83, HLB 6. 4) 0.50% is used, and silica F (manufactured by DSL Japan Co., Ltd., model number), which is a synthetic amorphous silica aggregate having an average particle size of 10.1 μm instead of silica B, is used. Carplex BS-304N) was used.

  In Example 6, in place of acetylene glycol 1, 0.50% of acetylene alcohol 2 (Daiichi Kogyo Seiyaku Co., Ltd., acetylene alcohol nonionic surfactant, model number: Neugen ET802, HLB 10.8) was used, and silica was used. The blending amounts of A and silica B were changed as shown in Table 1. Moreover, the brand name: PEG-300 by Toho Chemical Co., Ltd. was used as polyethylene glycol.

  In Example 7, in place of acetylene glycol 1, 0.50% of acetylene alcohol 3 (acetylene alcohol-based nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd., model number: Neugen ET143, HLB 12.6) was used and silica A was used. The amount of silica B was changed as shown in Table 1. Moreover, the brand name: PEG-400 by Toho Chemical Co., Ltd. was used as polyethylene glycol.

  In Example 8, the basis weight and smoothness were changed as described in Table 1, and instead of acetylene glycol 1, acetylene alcohol 4 (acetylene alcohol-based nonionic surfactant manufactured by Daiichi Kogyo Seiyaku, model number: Neugen ET69 0.55% of HLB 5.7) was used, silica C was used instead of silica A, and calcined clay having an average particle size of 6.3 μm was used instead of silica B. As polyethylene glycol, trade name: PEG-300 manufactured by Toho Chemical Co., Ltd. was used.

  In Example 9, the amount of acetylene glycol 1 used was changed to 0.50%, and instead of CMC-A, CMC-B (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen 7A, polymerization degree 120-150) , Molecular weight 27000-33000). Moreover, the brand name: PEG-400 by Toho Chemical Co., Ltd. was used as polyethylene glycol.

  In Example 10, 0.50% of acetylene glycol 2 was used instead of acetylene glycol 1, and instead of 200 parts of CMC-A, CMC-C (Daiichi Kogyo Seiyaku Co., Ltd., trade name: cellogen 5A, polymerization degree) 120 parts or less and a molecular weight of 27,000 or less) was used, and the amount of PVA-A used was changed to 2 parts.

  In Example 11, 0.50% of acetylene alcohol 1 was used instead of acetylene glycol 1, and CMC-D (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen WS-A, polymerization degree) was used instead of CMC-A. 460-500, molecular weight 100,000-110,000).

In Example 12, 0.50% of acetylene alcohol 2 was used instead of acetylene glycol 1, and CMC-E (Daiichi Kogyo Seiyaku, trade name: Cellogen BS-H, polymerization degree) was used instead of CMC-A. 500-800, molecular weight 180,000-190000) 200 parts were used.

  In Example 13, the amount of acetylene glycol 1 used was changed to 0.50%, and instead of PVA-A, PVA-B (manufactured by Kuraray Co., Ltd., trade name: PVA210, saponification degree 87 to 89 mol%, polymerization) Degree 1000) was used.

  In Example 14, 0.50% of acetylene glycol 2 was used instead of acetylene glycol 1, and instead of PVA-A, PVA-C (manufactured by Kuraray, trade name: PVA203, saponification degree 87-89 mol%, A degree of polymerization of 300) was used.

  In Example 15, 0.50% of acetylene alcohol 1 is used instead of acetylene glycol 1, 310 parts of CMC-A is used, and PVA-D (trade name: PVA110, manufactured by Kuraray Co., Ltd.) is used instead of PVA-A. Saponification degree 98-99 mol%, polymerization degree 1000).

In Example 16, 0.50% of acetylene alcohol 2 was used instead of acetylene glycol 1, 400 parts of CMC-A was used, and PVA-E (manufactured by Kuraray Co., Ltd., instead of 25 parts of PVA-A). (Product name: PVA120, saponification degree 98-99 mol%, polymerization degree 2000) 150 parts were used.

  In Example 17, instead of acetylene glycol 1, 0.50% of an amphoteric surfactant (alkylpolei aminoethylerglycine, manufactured by Takemoto Yushi Co., Ltd., model number: Piionin C-156) was used, and the coating amount was expressed. 1 was changed. In addition, oxidized starch (MS3600 manufactured by Nippon Food Processing Co., Ltd.) was used instead of polyvinyl alcohol.

  In Example 18, instead of acetylene glycol 1, 0.60% of a cationic surfactant (Laururpyridinium chloride, manufactured by Takemoto Yushi Co., Ltd., model number: Pionin B-251) was used, and CMC-A and PVA-A were used. The amount used was changed as shown in Table 1. In addition, carboxymethylcellulose (Serogen PR manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of polyvinyl alcohol.

  In Example 19, 0.80% of an anionic surfactant (dodecylbenzenesulfonate, manufactured by Takemoto Yushi Co., Ltd., model number: Piion A-41C) was used in place of acetylene glycol 1, and the coating amount was shown in Table 1. Changed as described in. Moreover, the cationized starch (Castarch M by GSL Japan) was used instead of polyvinyl alcohol.

  In Example 20, high-quality paper to which a sizing agent was externally added was used as the base material, and the amount of acetylene glycol 1 used was changed to 1.00%. Further, silanol-modified polyvinyl alcohol (R1130 manufactured by Kuraray Co., Ltd.) was used instead of polyvinyl alcohol.

  In Comparative Example 1, only the water-soluble resin was applied in the ink receiving layer without using the penetrant and the fine particles. Moreover, only polyvinyl alcohol PVA-110 was applied in the back coat layer.

  In Comparative Example 2, a penetrating agent was not used, and only a calcined clay having an average particle size of 6.3 μm (manufactured by Engelhard Inc., model number: Ancilex) was used as fine particles. As a water-soluble resin, only 25 parts of PVA-A was used. Moreover, only the polyethylene glycol PEG-200 was applied in the backcoat layer.

  Commercially available high-quality paper and kraft paper were purchased and evaluated as commercial products 1 to 3.

<Measurement and evaluation method>
For ink jet recording evaluation using sublimation type textile printing ink, an image for ink jet recording evaluation defined in ISO300 was used by using a JV4 type ink jet printer manufactured by Mimaki Co., Ltd., and sublimation ink (SPC- 370 series).
A polyester cloth material was used for the transfer object.

(A) Basis weight It measured based on JISP8124.

(B) Smoothness Measured according to JIS P 8119.

  (1) Width of convex portion: Using a scanning electron microscope (JSM-6390A type, manufactured by JEOL Datum Co., Ltd.) on the surface of the sublimation printing ink receiving layer of each produced transfer paper, 60 arbitrary aggregates The width was measured, the average value from each long and short width was measured, and 50 actually measured average values excluding 5 minimum values and 5 maximum values were measured.

  (2) Root mean square roughness: The mean square roughness (μm) of the surface roughness of the concavo-convex portion was measured using a laser microscope (Color Laser Microscope VK-9700, manufactured by Keyence Corporation).

(3) Ink dryness: Immediately after black printing on each transfer paper produced by an inkjet printer, the printed surface is rubbed with tissue paper and wiped to visually check the elongation of the sublimation printing ink on the paper surface. The following criteria were used for the 5-level evaluation. Three or more grades are practical levels.
5: Drying is fast. The surface of the paper wiped off with tissue paper does not stretch the ink.
4: Drying is fast. The surface of the paper wiped off with tissue paper has almost no ink growth.
3: Slightly slow drying, but no problem in practical use. The surface of the paper that has been wiped off with tissue paper has a slight ink elongation.
2: Drying is slow and the paper surface rubbed with tissue paper is not practical because of ink elongation.
1: Drying is slow, leading to device stains and print stains, and cannot be used. On the paper surface rubbed with tissue paper, the elongation of the sublimation printing ink is long.

(4) Image reproducibility: Visually, the image reproducibility of the digital image prescribed in ISO300 on the surface of the transfer paper was evaluated in five stages according to the following criteria. Three or more grades are practical levels.
5: Image reproducibility with no difference from the original.
4: Good image reproducibility.
3: Although the image reproducibility is slightly inferior, it can be used.
2: Image reproducibility is inferior and cannot be used.
1: Image reproducibility is poor and cannot be used.

(5) Expansion / contraction variation:
Measuring instrument: Automatic paper extensometer No. 2078-III
Test conditions: For each 10 × 150 mm transfer paper, a test piece was set in a measuring instrument, and then kept for 1 hour in an environment of 20 ° C. and 30% RH to determine a reference length. Thereafter, the temperature was raised at a rate of 1 ° C./min to 80 ° C. and 30% RH. After maintaining for 3 hours in this environment, the stretch length of the test piece was measured and used as a measured value. The measurement was performed by averaging 5 samples each in the vertical direction (flow direction) and the horizontal direction (width direction).
Expansion rate = (measured value / reference length)

(6) Ink back-through (sublimation-proof dye back-off prevention): Print sublimation ink on each manufactured transfer paper, and apply heat (210 ° C.) from a heat source to sublimation ink-jet printing paper. After the transfer, the back-through of the ink on the surface opposite to the ink-receiving layer surface of the sublimation type ink-jet printing paper was visually judged, and the back-through prevention was evaluated in five levels according to the following criteria. Three or more grades are practical levels.
5: No sublimation of sublimation printing ink.
4: Slightly no sublimation of sublimation printing ink.
3: There is a slight penetration of sublimation type printing ink, but there is no practical problem.
2: Back-through of sublimation type printing ink is recognized and the heat source is slightly stained.
1: Many see-throughs of sublimation dyes are observed, and the heat source device is severely soiled.

  (7) Heat resistance: Sublimation ink was printed on each manufactured transfer paper, and the temperature at which the ink receiving layer surface of the manufactured transfer paper began to deteriorate when heat was applied from a heat source with different temperature conditions was measured. 210 ° C. or higher is a practical level.

(10) Corrugation Black solid printing was performed on each manufactured transfer paper with an inkjet printer, and the corrugation of the transfer paper after 60 seconds was judged visually.

(11) Transfer efficiency:
(I) Evaluation of resolution, (ii) Evaluation of solid image portion (image density and uniformity of solid image portion),
The transfer efficiency of the sublimation type printing ink jet recording was evaluated in five levels according to the following criteria. Three or more grades are practical levels.
(I) Evaluation of resolution 5: Good resolution. There is no phenomenon such as distortion on the print surface, and the print tone is comparable to the printed document.
4: Good resolution. Although a phenomenon such as distortion is not recognized on the printing surface, the reproducibility of the printing tone comparable to the printed document is slightly inferior.
3: Although the resolution is slightly inferior, there is no problem in practical use. There is no phenomenon such as distortion on the printing surface, and the reproducibility of the printing tone comparable to that of the printed document is slightly inferior, but there is no problem in using the transferred material.
2: The resolution is slightly poor, but can be used depending on conditions. Phenomena such as distortion are slightly observed on the printing surface, and the reproducibility of the printing tone comparable to the printed document is slightly inferior.
1: Poor resolution and cannot be used. Phenomena such as distortion are recognized on the printing surface, and there is no reproducibility of the printing tone comparable to the printed document.
(Ii) Evaluation of solid image portion 5: The image density is high, and there is no unevenness in the solid image portion.
4: The image density is high, and some unevenness is observed in the solid image portion.
3: The image density is slightly high, and unevenness is observed in the solid image portion, but there is no practical problem.
2: The image density is slightly low, and unevenness is observed in the solid image portion.
1: The image density is low, and a lot of unevenness is observed in the solid image portion.

Electron micrograph showing the case where irregularities are formed on the surface of the sublimation printing ink receiving layer (the preferred embodiment of the present invention) Electron micrograph showing the case where unevenness is not formed on the surface of the sublimation type printing ink receiving layer (comparative example: commercially available inkjet recording paper) Electron micrograph showing the case where unevenness is not formed on the surface of the sublimation type printing ink receiving layer (comparative example: commercially available high quality paper)

Claims (3)

Sublimation type inkjet printing transfer paper having a substrate, a sublimation printing ink receiving layer provided on the surface of the substrate, and a backcoat layer provided on the back surface of the substrate,
The sublimation printing ink receiving layer contains a water-soluble resin and fine particles,
The fine particles are synthetic amorphous silica;
The back coat layer contains a water-soluble resin, and contains at least polyethylene glycol as the water-soluble resin,
A sublimation type ink jet printing transfer paper, wherein the expansion / contraction ratio of the sublimation type ink jet printing transfer paper is 0.7% or less in the vertical direction and 0.5% or less in the horizontal direction. The base material is craft paper having a glossy surface on one side, and the sublimation printing ink receiving layer is provided on the glossy surface,
Containing a penetrant in the substrate,
The sublimation printing ink receiving layer contains 20 to 50% by mass of the fine particles,
Sublimation inkjet printing transfer paper according to claim 1, wherein the coating amount of the backcoat layer is, on a dry weight is ^{0.1g / m 2 ~0.8g / m 2} .   The sublimation ink jet printing transfer paper according to claim 1 or 2, wherein the water-soluble resin constituting the back coat layer contains polyethylene glycol and polyvinyl alcohol, and the weight ratio of the two is in the range of 10:90 to 50:50. .