JP2010089393A - Transfer paper for sublimable ink-jet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide transfer paper for sublimable ink-jet printing, which has an excellent property of drying sublimable printing ink when printing is performed on the transfer paper for sublimable ink-jet printing by using the sublimable printing ink and which is excellent in image reproducibility and transfer efficiency. <P>SOLUTION: The transfer paper for sublimable ink-jet printing is provided with: a base material; and a sublimable printing ink receiving layer arranged on the surface of the base material and is characterized in that transfer information is recorded on the sublimable printing ink receiving layer by ink-jet recording and the recorded transfer information is heated and sublimed into the object to be transferred to form a transferred image. The sublimable printing ink receiving layer comprises a water-soluble resin, a minute particle based on synthetic amorphous silica, and a cationic compound and has 0.5-3.5 Meq/g cation density. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to sublimation type ink jet textile transfer paper, and more specifically, printing using sublimation type textile ink on the transfer paper, and transferring the printed image on the transfer paper to a cloth such as polyester to perform sublimation transfer. The present invention relates to a sublimation type ink jet printing transfer paper used for printing.

  The transfer printing method includes a melt transfer printing method using an ink composed of a heat-softening fixing agent such as wax or resin and a pigment, and a rubber print transfer using a plastisol ink composed of a powder such as polyvinyl chloride and a plasticizer and a pigment. There are printing methods and sublimation printing transfer methods using heat sublimation dyes.

  In the melt transfer printing method, the texture and stretchability of the printed material are insufficient, and the printed material by the rubber print transfer printing method does not have good air permeability and feel. The sublimation printing transfer method is a printing transfer method that is mainly used 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 requires a printing plate such as a screen plate or a gravure plate and a printing machine corresponding to the printing plate. However, due to the diversification of individuality, for example, a transfer printing sheet for inkjet printing corresponding to a small lot. As a result, sublimation transfer for small lots has spread and demand is growing.

  The sublimation printing transfer method is a method of printing on a sublimation inkjet printing transfer paper by attaching a transfer material such as polyester fabric and sublimation inkjet printing transfer paper to a dryer heated to 180-220 ° C. The printed ink is sublimated with heat to perform transfer printing on the transfer object.

As the sublimation type ink jet printing transfer paper for ink jet printing, there is known one in which an ink receiving layer containing a pigment such as silica or a binder such as polyvinyl alcohol is provided on a substrate ( (See Patent Documents 1 and 2).
JP 2003-276309 A Japanese Patent Laid-Open No. 2002-292995

  However, in the conventional sublimation type ink jet printing transfer paper, particularly when ink jet printing is performed, the sublimation type printing ink is insufficiently dry and the print image tends to bleed, causing undesirable image defects and print stains on the print surface. There was something to do. On the other hand, when transferring and printing on a transfer object, fine design details may not be expressed due to bleeding of the design portion.

  Further, the back side of the sublimation type ink jet printing transfer paper, which is different from the sublimation type printing ink receiving layer, is exposed to the back side or passes through the fabric to be transferred (back side), and is transferred to the transfer press machine. There was a problem that the printing ink adhered. This drying property of sublimation type printing ink and the prevention of reverse exposure of sublimation type printing ink are contradictory properties, which are compatible with each other, that is, the sublimation type printing ink is rapidly absorbed while expressing a clear image without blurring during printing. It was difficult to produce a sublimation type ink jet printing transfer paper that was dried and did not show through during transfer. Furthermore, the transfer efficiency (transfer image density level and uniformity thereof, etc.) to the transfer object on the sublimation type ink jet textile transfer paper has to be of a sufficient level.

  In view of the above situation, the present invention has excellent sublimation printing ink drying properties during printing on sublimation ink jet printing transfer paper using sublimation printing ink, and also has good image reproducibility and transfer efficiency. An object of the present invention is to provide a sublimation type ink jet textile transfer paper having characteristics.

  The present invention has a substrate and a sublimation printing ink receiving layer provided on the surface of the substrate, and after transferring transfer information by ink jet recording on the sublimation printing ink receiving layer, the transfer is performed by heating. A sublimation type ink jet printing transfer paper that sublimates information on a transfer object to form a transfer image, wherein the sublimation type ink receiving layer is composed mainly of a water-soluble resin and synthetic amorphous silica. A sublimation ink jet printing transfer paper comprising fine particles and a cationic compound, wherein the sublimation printing ink receiving layer has a cation density of 0.5 to 3.5 Meq / g.

  Preferably, the base material is single-glazed kraft paper, the sublimation-type printing ink receiving layer is provided on the glossy surface of the single-glazed kraft paper, and the fine particles are contained in the sublimation-type printing ink receiving layer in an amount of 20 to 50. Contains by mass%.

  Preferably, the cationic compound is composed of one or more selected from amidines and epichlorohydrins.

  The sublimation type ink jet printing transfer paper of the present invention has excellent drying property of sublimation type printing ink at the time of printing on sublimation type ink jet printing transfer paper using sublimation type printing ink, and also in terms of image reproducibility and transfer efficiency. Has good characteristics.

  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 effect of the present invention is remarkably exhibited is a porous material in which the sublimation type printing ink is easily sublimated by heating to the back surface of the sublimation type ink jet printing transfer paper. Specifically, wood pulp is mainly used. It is paper, a nonwoven fabric, or a fabric as a component.

  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. Single glossy paper, unlike conventional paper, has excellent dimensional stability, unlike film, can be recycled, and has the characteristics of excellent absorption and drying properties of sublimation printing ink.

  The substrate of the sublimation type ink jet printing transfer paper of the present invention is not limited as long as it is a support provided with a sublimation type printing ink receiving layer, but is based on single glossy paper that the present inventors have found most suitable. The material will be described below.

Katatsuyashi used in the practice of the present invention preferably has a basis weight is 60 to 150 g / m ^2, more preferably 90~110g / m ^2. In the sublimation printing type transfer paper obtained in the present invention, the dimensional stability of the substrate may be impaired by the sublimation printing ink when printing is performed with the sublimation printing ink. Since it has the process which passes, when the tsubo of a glossy paper is less than 60 g / m < ² >, while dimensional stability is inferior, it will become easy to generate | occur | produce paper cutting by the fall of tensile strength and tear strength. When 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 transfer efficiency is lowered.

  Further, the Bekk smoothness described in JISP8119 on the glossy surface of glossy paper is preferably 40 to 200 seconds, and more preferably 60 to 100 seconds. If the Beck smoothness of the glossy surface is 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 image reproduction at the time of transferring the sublimation printing ink to the transfer object. Performance and transfer efficiency are significantly reduced. On the other hand, if it exceeds 200 seconds, unevenness occurs in the formation of the ink receiving layer composed of the water-soluble resin and fine particles, and the image reproducibility is 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 and the like flattened by a multi-cylinder dryer having high flatness on both the front and back surfaces are inferior in terms of image reproducibility and transfer efficiency of the transferred material by transfer compared to single glossy paper.

  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 pulp, 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); chemical pulp such as deinking pulp (DIP) and waist pulp (WP) and waste paper pulp including mechanical pulp 1 type or 2 types from It can be selected and used above. Of these, softwood bleached kraft pulp and hardwood bleached kraft pulp are preferably used in combination as appropriate in terms of paper strength, flatness of the substrate surface, and quality confirmation of sublimation ink-jet printing paper for sublimation printing ink.

  The sublimation type ink jet printing transfer paper of the present invention preferably has an air permeability of 1,500 to 25,000 seconds, more preferably 8,000 to 21,5, according to JIS P 8117. 000 seconds, more preferably 9,000 to 20,000 seconds. If the air permeability is less than 1,500 seconds, there arises a problem that the transfer efficiency and the prevention of back-through of the sublimation printing ink are lowered. If the air permeability exceeds 25,000 seconds, the heat transfer is lowered and the transfer of the sublimation printing ink is performed. As efficiency decreases, image reproducibility deteriorates.

  For adjustment of air permeability, known means such as selection of raw material pulp used for the base material, beating treatment, etc. can be used, and in glossy paper that can be suitably used as the base material in the present invention, the Yankee dryer surface The air permeability can be adjusted more suitably by the contact pressure. By containing the penetrant suitably used in the present invention in the base material, it is possible to form uneven portions by uniform agglomerates, so that the air permeability can be further adjusted.

  In addition, various starches such as oxidized starch, acetylated starch, esterified starch, etherified starch, additive chemicals such as paper strength enhancer, internal sizing agent, external sizing agent, yield improver, etc. can be further adjusted. In the range, a filler such as titanium oxide, clay, talc, calcium carbonate may be contained.

  For adjustment of air permeability, in addition to known means such as selection of raw material pulp used for the base material, beating treatment, etc., in the glossy paper that can be suitably used as the base material in the present invention, It can adjust more suitably by contact pressure.

  More preferably, a penetrating agent is preferably contained in the substrate. Suitable penetrants include nonionic surfactants. In particular, acetylene glycol surfactants and acetylene alcohol surfactants are used to form uniform aggregates and lumps in forming irregularities on the surface of a sublimation printing ink receiving layer. In addition to the formation of the concavo-convex portions of the aggregate, it is possible to quickly absorb and dry the sublimation type printing ink when printing with the sublimation type printing ink, and to obtain a sublimation type ink jet printing transfer paper that does not show through when transferring. .

  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. As well as excellent image reproducibility and transfer efficiency at the time of warm transfer for sublimation printing, and the sublimation ink jet printing transfer paper of the present invention. It is suitably used as a particularly excellent substrate.

  The sublimation printing ink receiving layer provided on the substrate contains fine particles and a water-soluble resin as a binder, and further contains the penetrant in an amount that does not cause excessive penetration of the sublimation printing ink. You can also do things. As will be described later, it is preferable from the combination with the penetrant that the surface of the sublimation type printing ink receiving layer is coated with unevenness by agglomerates of fine particles. With this property, the absorption and drying properties of the sublimation printing ink during printing are improved due to the synergistic effect with the penetrant, and the image reproducibility on the transfer paper surface, heat resistance during heat transfer, and transferred image after transfer Better characteristics can be obtained in terms of image reproducibility on the surface of the object and transfer efficiency.

In the present invention, synthetic amorphous silica is used as a main component as fine particles. Such a synthetic amorphous silica is a porous and amorphous fine particle having a large pore volume, in which a three-dimensional structure of SiO ₂ is formed by the gelation of silicic acid, and has a fineness of about 10 to 2000 angstroms. Has a pore size. By using the synthetic amorphous silica, the absorption and drying properties of the sublimation type printing ink of the sublimation type ink jet printing transfer paper of the present invention are improved, and the transfer efficiency of the sublimation type printing ink to the transfer object is also improved. The image on the transfer object can be made clearer. If only fine particles other than synthetic amorphous silica produced by a gel method, such as colloidal silica, are used as the fine particles, the effects of the present invention cannot be achieved.

  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 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 is in the range of 1.7 μm to 13.0 μm, preferably 2.3 μm to 12.7 μm. It is preferable to be within. 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 lowered, and the average particle size of the fine particle aggregate is 13.0 μm. If it exceeds 1, the color density of the transferred printed matter 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. In this way, by using together different synthetic amorphous silica aggregates having an average particle diameter in the range of several μm, aggregates are formed in which aggregates of different average particle diameters complement the gaps between the aggregates and the aggregates, Excellent sublimation printing ink absorption and drying properties when printing onto sublimation inkjet printing transfer paper using sublimation printing ink, better image reproducibility on transfer paper surface, heat resistance during heat transfer, Better characteristics can be obtained in terms of image reproducibility and transfer efficiency on the surface of the transferred material after transfer.

  More preferably, although the reason is not clear, the use of a combination of two or more kinds of synthetic amorphous silica aggregates makes it easy to achieve the water absorption rate defined in the present invention, and the base material by the penetrating agent is used. The effects of the present invention, such as excellent sublimation printing ink absorption and drying properties, can be achieved by a synergistic effect with the effect of improving the water absorption rate.

  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 suitable average particle sizes, the synthetic amorphous silica aggregates having an average particle size of 1.7 to 5.0 μm, preferably 2.3 to 4.1 μm, are preferable. The blending ratio of the aggregate and the synthetic amorphous silica aggregate having an average particle diameter of more than 5.0 μm, preferably 6.0 to 12.7 μm is not particularly limited, but is preferably solid The weight ratio of the minute is preferably about 10:90 to 50:50. By setting the weight ratio of solids to about 10:90 to 50:50, the silica aggregates having a small particle diameter fill the gaps between the silica aggregates having a large particle diameter, thereby increasing the porosity of the obtained aggregate. It can achieve better absorption and drying properties of sublimation printing inks, and also has high image reproducibility on sublimation ink jet printing transfer paper, heat resistance during heat transfer, and image reproducibility on transferred material. The transfer efficiency of the sublimation printing ink 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 the amount 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. In addition, since the water-soluble resin in the sublimation printing ink receiving layer exhibits thermoplasticity, the heat resistance of the sublimation printing transfer paper is improved by increasing the content of fine particles in the sublimation printing ink receiving layer. .

  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 preferable for compatibility with carboxymethyl cellulose and for sublimation printing inks to be retained in a sublimation printing 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.

  As a water-soluble resin, by using polyvinyl alcohol having a saponification degree of about 87 to 89 mol% and a polymerization degree of about 1000 or less for the sublimation printing ink receiving layer, excellent sublimation printing ink absorption / drying property at the time of printing. In addition, the penetrant produces a control function that allows the solute of the sublimation printing ink to permeate the substrate through the sublimation printing ink receiving layer and the effect of promptly bringing the solvent component to the substrate. It can also have better characteristics in terms of image reproducibility on the surface of transfer paper, heat resistance during heat transfer, image reproducibility on the surface of the transferred material after transfer, and transfer efficiency.

  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 better absorption and drying properties of the 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 exhibited, and the sublimation printing ink receiving layer is easily peeled off and scratched, and image reproducibility. The problem of lowering occurs. When the blending amount of polyvinyl alcohol exceeds 100 parts by weight with respect to 100 parts by weight of fine particles, a decrease in absorption and drying properties of the sublimation printing ink becomes a problem due to the formation of a film by polyvinyl alcohol.

  In the sublimation type printing ink receiving layer of the sublimation type ink jet printing transfer paper, the degree of polymerization or molecular weight of carboxymethyl cellulose that can be suitably used as a water-soluble resin is necessary for the rapid development and absorption of the sublimation type printing ink. In order to exert an influence, it is preferable to control the temperature by using a product having a predetermined polymerization degree and molecular weight.

  As carboxymethylcellulose as a water-soluble resin suitably used, those having a polymerization degree of 120 to 500 and a molecular weight of 27000 to 110000 are preferable. As a water-soluble resin, carboxymethylcellulose having a degree of polymerization of 120 to 500 and a molecular weight of 27,000 to 110000 is easy to form agglomerates of fine particles due to viscosity and workability, and is important for facilitating coating of the formed agglomerates. It becomes a big factor. If the degree of polymerization is less than 120 and the molecular weight is less than 27000, the viscosity of the water-soluble resin is low, and it is difficult to form an aggregate. On the other hand, if the degree of polymerization is greater than 500 and the molecular weight is greater than 110,000, the coating solution is poor in workability for coating agglomerates. For example, if the viscosity is too high to be applied, or if the solid content is lowered to lower the viscosity, a drying load is applied. If the temperature is too high for lowering the viscosity, the film formation is adversely affected.

  Carboxymethyl cellulose has a good compatibility with polyvinyl alcohol, preferably a combination of polyvinyl alcohol having a saponification degree of about 87 to 89 mol% and a polymerization degree of about 1000 or less, and a synthetic amorphous form. Printing on sublimation ink jet printing transfer paper using sublimation printing ink without impairing the ability to form irregularities when using two or more types of synthetic amorphous silica aggregates in combination. In addition to better absorption and drying properties of sublimation printing inks at the time, image reproducibility on the transfer paper surface, heat resistance during heat transfer, image reproducibility and transfer efficiency on the surface of the transferred material after transfer In this respect, it can have better characteristics.

  As a commercial item, Serogen PR (above, Dai-ichi Kogyo Seiyaku Co., Ltd. product) etc. can be used. The blending amount of carboxymethyl cellulose is preferably about 100 to 400 parts by weight, and 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 amount of carboxymethyl cellulose is less than 100 parts by weight, there may be a problem that the transfer efficiency of the sublimation printing ink to the transfer object is lowered. If the amount of carboxymethylcellulose exceeds 400 parts by weight, the absorption and drying properties of the sublimation printing ink are lowered, and the sublimation printing ink is liable to cause problems such as show-through during storage.

  A suitable sublimation type printing ink receiving layer on the transfer paper surface according to the present invention contains a water-soluble resin and fine particles, and in addition to containing the synthetic amorphous silica as the fine particles, the water-soluble resin. It is preferable to contain carboxymethylcellulose and polyvinyl alcohol in a ratio of 100: 1 to 400: 200 on a weight basis. Furthermore, by controlling the preparation conditions of the coating liquid used when forming the sublimation printing ink receiving layer, the surface of the sublimation printing ink receiving layer is covered with the agglomerates of the fine particles. A sublimation ink jet printing transfer paper having the above water absorption rate can be obtained.

In the present invention, the cationic compound contained in the sublimation ink-receiving layer is a so-called fixing agent used for improving the fixability of the ink to the surface of the sublimation printing ink-receiving layer by interaction with the ink. Examples thereof include cationic resins, water-soluble metal salts such as zinc sulfate, and cationic surfactants. Among these, cationic resins are preferable, and examples thereof include the following.
1) Polyalkylene polyamines such as polyethylene polyamine and polypropylene polyamine, and derivatives thereof.
2) An acrylic resin having a secondary amino group, a tertiary amino group, and / or a quaternary ammonium group.
3) Amidines For example, polyvinylamine (co) polymer, polyvinylamidine, and 5-membered ring amidine.
4) Dicyan cation resin such as dicyandiamide-formalin polycondensate.
5) Polyamine cationic resins such as dicyandiamide-diethylenetriamine polycondensate.
6) Epichlorohydrins For example, polydimethylamine epichlorohydrin, modified dimethylamine epichlorohydrin condensate.
7) Dimethyl diallylammonium chloride polymer.
8) Dimethyl diallylammonium chloride-SO ₂ copolymer.
9) Diallylamine-SO ₂ copolymer.
10) Polymer of allylamine salt.
11) Dialkylaminoethyl (meth) acrylate quaternary ammonium salt polymer.
12) Acrylamide-diallylamine salt copolymer.
13) Aminoorganosilane compounds such as 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
14) Polyaluminum salts such as polyaluminum chloride, polyaluminum acetate, and polyaluminum lactate.

One cationic resin may be used, or two or more cationic resins may be mixed and used.
Among the above-mentioned cationic resins that can be suitably used in the present invention, in particular, the above-mentioned 3) and 6) are the dyes in the sublimation type printing ink, in the sublimation type printing ink receiving sublimation type printing ink layer. , And improved fixing of the synthetic amorphous silica contained in the sublimation printing ink receiving layer, absorption drying of the sublimation printing ink, and excessive impregnation of the ink into the substrate. It is more preferable because high density and high definition printing information can be formed on the sublimation type printing ink receiving layer by controlling.

  Among the amidines described in 3), 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 transfer of the sublimation printing ink can be achieved, a sublimation ink jet printing transfer paper having excellent drying properties of the sublimation printing ink and excellent image reproducibility and transfer efficiency can be obtained.

  Further, a cationic resin having a reactivity such as polydimethylamine epichlorohydrin and modified dimethylamine epichlorohydrin condensate, and binding to cellulose and insolubilizing the resin in water is also preferably used. I can do things. 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 mass 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 100,000. It is. 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 compound 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 compound is determined by a method based on the colloid titration method.

  The cationic layer of the coating layer containing an ink jet fixing agent comprising a cationic compound, preferably polyamidine, polydimethylamine epichlorohydrin, or a modified dimethylamine epichlorohydrin condensate on the coating surface is the amount of the cationic compound added. Although the reason is not clear by adjusting the coating material 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 receiving layer is not clear. Concentrate and fix the sublimation printing ink to promote the absorption and drying properties of the sublimation printing ink on the surface layer and to control that the dye component of the sublimation printing ink having a particle size larger than the solvent is impregnated to the substrate. It is possible to form clear prints and transfer efficiency of sublimation printing ink and sublimation printing in the sublimation printing process. It can be obtained sublimation inkjet printing transfer paper capable of leveling up the anti-ink print at improving the density and high-definition sublimation transfer and transferability.

  When the cation density of the coating layer is less than 0.5 Meq / g, it is not possible to obtain an appropriate fixing of the sublimation printing ink, so that excellent drying property of the sublimation printing ink and image when printing on the sublimation ink jet printing transfer paper are obtained. It is difficult to obtain good characteristics in terms of reproducibility and transfer efficiency, and if it exceeds 3.5 Meq / g, the fixing of the sublimation printing ink proceeds excessively, resulting in a problem that the image reproducibility and transfer efficiency are lowered.

  It is preferable that content of the said cationic compound is 1-25 weight part with respect to 100 weight part of fine particles, More preferably, it is 5-10 weight part. 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 can be obtained in the cockling suitability due to ink, sublimation failure of the dye to the fabric (transfer failure), yellowing of the fabric, and dye staining on the surface cause ink scuffing stains when winding after printing This is not preferable.

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 type printing ink receiving layer is not particularly limited, but in order to achieve the effect of the present invention efficiently, the coating amount adjusted as described above is applied in a coating weight of 3 to 3 by dry weight. A method of coating on the substrate so as to be 25 g / cm ² is preferable. Although it does not specifically limit as a coating method, For example, although it can coat using well-known coating machines, such as an air knife coater, a roll coater, a bar coater, a comma coater, and a blade coater, Among them, use a blade coater, especially a vent blade that can ensure the reproduction of irregularities caused by the synthetic amorphous silica contained in the sublimation printing ink receiving layer coating and the flatness of the surface of the sublimation printing ink receiving layer. Is preferred.

  In addition, since streaks are likely to occur due to agglomerates contained in the coating liquid, the coating layer can be applied at a desired coating amount without causing streaks by using a vent blade as a suitable coating means. Can be formed. 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.

  Furthermore, unlike the conventional product, the sublimation type ink jet printing transfer paper of the present invention is provided with a surface structure having specific irregularities on the sublimation type printing ink receiving layer, so that the ultrasonic transmission strength on the sublimation type printing ink receiving layer side is improved. It is preferable that the peak of the minimum value in the relative value has a unique property that the measurement time is within 3 seconds.

  The ultrasonic transmission intensity is the intensity of the ultrasonic signal received by the receiver after the transmitted ultrasonic signal has passed through the sample. Generally, ultrasonic waves have no intensity attenuation in the solvent, but are strong when passing through the sample. Attenuation occurs. The transmission of ultrasound by paper changes as the paper absorbs liquid and is influenced by a series of mechanisms. (i) Increased received signal due to attenuation of ultrasonic reflection at the paper-liquid interface due to wet paper, (ii) left locally in the paper due to non-uniform liquid penetration Reduced received signal due to scattering of ultrasonic waves by bubbles, (iii) Elasticity of fibers due to the mechanism of increase in received signal due to decreased absorption of ultrasonic waves by completely filling pores and capillaries with liquid Changes and the attenuation of the ultrasonic wave changes.

The relative value of the ultrasonic transmission intensity can be calculated from the following equation so that the minimum value of the received signal is 100%.
Relative value of ultrasonic transmission intensity (%) = Minimum value of ultrasonic reception signal / Ultrasonic reception signal at each measurement time × 100 (The ultrasonic reception signal is a negative value.)

  The ultrasonic transmission intensity is measured by attaching a double-sided tape to the sample holder so that no air bubbles enter, and sticking the sample on the double-sided tape. The sample holder can be set in the test machine, measurement can be started, and ultrasonic transmission intensity data can be obtained. In the case of this paper, the relative value of the ultrasonic transmission intensity is almost the same data regardless of the measurement area and the measurement frequency, so it is not specified.

  The dynamic liquid permeability measuring apparatus used to calculate the relative value of the ultrasonic transmission intensity in the present invention is DPM33 and DPM3-2-T manufactured by EMCO, Germany.

  In the sublimation type ink jet printing transfer paper of the present invention, when the relative value of the ultrasonic transmission intensity is measured, a peak of the minimum value appears within a measurement time of 3 seconds as shown in FIG. Specifically, the relative value of ultrasonic transmission intensity changes over time after the start of measurement, but the relative value continues to decrease immediately after the start of measurement, and the decrease gradually increases within 3 seconds. Turn to. The time point when the decrease starts to increase is defined as the time at which the peak of the relative value of the ultrasonic transmission intensity appears.

  On the other hand, in the conventional sublimation type ink jet printing transfer paper, as shown in FIG. 1, the ultrasonic transmission intensity once increases due to wetting at the interface with the coating layer surface as time passes. Even if the relative value of the transmission intensity continues to decrease and does not have a minimum value peak, or has a minimum value peak, it has the peak in about 3 seconds, for example, around 10 seconds. .

  If the sublimation ink jet printing transfer paper has a minimum peak value in the relative value of ultrasonic transmission intensity within 3 seconds, the water absorption speed is very fast, so the sublimation printing ink absorbs and dries very quickly. Even when the transfer paper is wound up after printing, problems such as show-through, dirt, and scumming are less likely to occur, and workability during high-speed printing can be improved. If the minimum value peak does not exist or the measurement time exceeds 3 seconds, the absorption and drying properties of the sublimation type printing ink are insufficient, and show-through and stains may occur during winding after printing. Scratch is likely to occur, and workability during high-speed printing is significantly deteriorated. Specifically, when ink-jet printing is performed at a high speed such that the printing speed exceeds 1 m / min and the transfer paper after printing is wound at a high speed, the surface of the sublimation printing ink receiving layer on which the printing has been performed is dried. It will be wound up inadequately, resulting in problems of show-through, dirt, and cosmetics. In addition, the sublimation-type printing ink unnecessary for show-through, dirt, and rusting caused in this way adheres to the transfer equipment and the transferred material during heat transfer, and the quality of the final transferred product is likely to deteriorate and become dirty. . If an attempt is made to avoid the above problem without using the sublimation type ink jet textile transfer paper of the present invention, it becomes necessary to separately install a drying facility during printing, leading to an increase in cost. In other words, by using the sublimation type ink jet textile transfer paper of the present invention, it is possible to perform high-speed printing while winding up without causing problems of show-through, dirt, and scum without providing a drying facility or the like. become. In addition, if equipment is provided, it becomes possible to perform further high-speed printing.

Also, if the measurement time exceeds 3 seconds, the sublimation printing ink that sublimates the sublimation printing ink in the direction opposite to the transfer target during heat transfer will stain the transfer machine and adhere to the transfer machine. Is further sublimated, and the mechanism different from the above tends to cause the quality of the final transfer product to deteriorate and stains.

  From the above, it is preferable that the peak of the minimum value appears in a shorter time after the start of measurement, specifically, it is preferable to have the measurement time within 2 seconds, and particularly preferably within the measurement time of 1 second.

  A suitable means for producing a sublimation type ink jet printing transfer paper having a minimum peak in relative value of ultrasonic transmission intensity within a measurement time of 3 seconds includes water solubility in the sublimation type ink receiving layer described above. In addition to containing a resin and fine particles, and the fine amorphous particles containing synthetic amorphous silica in a predetermined ratio, more preferably, the surface of the sublimation printing ink receiving layer is uneven by fine particle aggregates. In addition to improving the absorption and drying properties of sublimation-type printing inks and workability, the image reproducibility on the transfer paper surface, the heat resistance during heat transfer, and the coating after transfer are possible. A sublimation ink jet printing transfer paper having good characteristics in terms of image reproducibility and transfer efficiency on the surface of the transfer 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 10 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, when the surface roughness of the sublimation printing ink receiving layer is measured with a laser microscope (Color Laser Microscope High Resolution Type VK-9700, manufactured by Keyence Corporation), it is preferable that the root mean square roughness satisfies 2 μm or more. . 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 (eg, 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.

  Further, the sublimation type ink jet printing transfer paper of the present invention preferably has a contact angle of 50 to 85 degrees on the surface of the sublimation type printing ink receiving layer according to the sessile drop method of the wettability test method according to JIS R 3257.

  The contact angle is defined as the angle between the tangent line and the solid surface when a tangent line is drawn on the curved surface of the liquid from the part where solid, liquid and gas (generally air) are in contact. Is a method of obtaining a contact angle by placing a droplet on a solid surface. In order to measure the contact angle of the surface of the sublimation printing ink receiving layer, it is sufficient to comply with JIS R 3257, but it is appropriate to use 4 μl or less of pure water for the liquid droplets to be left on the solid surface. is there. Moreover, the measurement needs to be measured within 10 seconds immediately after the water droplet is left on the test piece. This is because if the measurement exceeds 10 seconds, moisture penetrates the surface of the coating layer and the contact angle cannot be measured accurately. By controlling the contact angle to 50 to 85 degrees, it is possible to ensure faster absorption and drying of the sublimation printing ink and to prevent the sublimation printing ink from bleeding on the surface of the sublimation printing ink receiving layer. Can do. Furthermore, at the time of heat transfer, heat compatibility is high, and transfer efficiency can be improved. When the contact angle is less than 50 degrees, the sublimation printing ink permeates too much, so that the transfer efficiency in heat transfer becomes low. On the other hand, if it exceeds 85 degrees, the ink absorption / drying property of the sublimation textile printing ink is insufficient, and it is easy to cause show-through, dirt, and scumming during winding after printing. Sexually deteriorates. Preferably it is 50-75 degree | times. In the conventional sublimation type ink jet textile transfer paper, the contact angle was about 60 degrees.

  In order to produce a sublimation ink jet printing transfer paper having such a contact angle, carboxymethyl cellulose and polyvinyl alcohol to be blended in the sublimation printing ink receiving layer on the surface of the transfer paper are 100: 1 to 400: 200 on a weight basis. It is preferable to contain by a ratio. Furthermore, when the preparation conditions of the coating liquid and the coating conditions are controlled in the same manner as described above so that the surface of the sublimation printing ink receiving layer is covered with the agglomerates of the fine particles, In addition, it has excellent sublimation printing ink absorption / drying properties, good workability, image reproducibility on the surface of transfer paper, heat resistance during heat transfer, and 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.

  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 530 ml (C.S.F.) hardwood bleached kraft pulp (LBKP) and freeness 580 ml (C.S.F.) softwood bleached kraft pulp (NBKP) 50:50 blended, auxiliary (solid content) A paper machine equipped with a Yankee dryer to prepare a paper stock by adding 0.8% by weight of cationized starch, 1.1% by weight of internal sizing agent and 0.3% by weight of anion-modified polyacrylamide Was used to produce a piece of glossy paper having a basis weight of 100 g / m ² and a smoothness of 60 seconds.

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 of silica B (manufactured by Tokuyama Co., Ltd., model: Fine Seal X60) and 100 parts of the fine particles, sodium carboxymethyl cellulose (hereinafter abbreviated as CMC) as a water-soluble resin CMC-A (Daiichi Kogyo Seiyaku) 200 parts of polyvinyl alcohol (hereinafter abbreviated as PVA) PVA-A (trade name: PVA-205, saponification degree 87-89 mol%, polymerization degree 500) manufactured by Kuraray Co., Ltd. 25 parts, SC-700 as a cationic compound (trade name, polyamidine manufactured by Hymo Co., Ltd., cation density: 1.4 to 1.6 Meq / g, mass average molecule 80,000) using 8 parts, to prepare a solid concentration of 6.6% of sublimation printing ink-receiving layer coating. In order to form an agglomerate of fine particles, a silica dispersion slurry at a low temperature of 20 ° C. to 30 ° C. was added to a high temperature CMC at 65 ° C. to 80 ° C. to agglomerate the 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 in which the agglomerates of fine particles were adjusted was applied to the glossy surface of the substrate so that the dry coating amount was 5 g / m ² , 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, sublimation printing by changing the base material, fine particles, water-soluble resin, cationic compound and coating amount based on the conditions of Example 1 A transfer paper was produced and evaluated 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 silica A, silica C (a synthetic amorphous silica aggregate having an average particle diameter of 1.7 μm) ( Tosoh Silica Co., Ltd., Model No .: Nipgel AZ-204) was used, and instead of CMC-A, CMC-C (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen 5A, polymerization degree 120 or less, molecular weight 27000 or less) It was used.

  In Example 3, the basis weight and the smoothness were changed as shown in Table 1, and instead of silica A, silica D (a synthetic amorphous silica aggregate having an average particle diameter of 4.3 μm) ( DSL Japan Co., Ltd., model number: Carplex BS-312AJ), instead of CMC-A, CMC-D (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen WS-A, polymerization degree 460) 500, molecular weight 100,000-110,000).

  In Example 4, the basis weight and smoothness were changed as shown in Table 1, and silica B was used instead of silica A, and instead of silica B, the aggregate had an average particle diameter of 12.7 μm. Silica G (manufactured by DSL Japan Co., Ltd., model number: Carplex BS-303), which is an amorphous silica aggregate, was used, and the amount of SC-700 used was changed to 5 parts.

  In Example 5, the smoothness was changed as shown in Table 1, and instead of silica B, silica F (DSL. Japan), which is a synthetic amorphous silica aggregate having an average particle diameter of 10.1 μm, was used. Co., Ltd., model number: Carplex BS-304N) was used, and the amount of SC-700 used was changed to 10 parts.

  In Examples 6 and 7, the blending amounts of silica A and silica B were changed as shown in Table 1.

  In Example 8, the basis weight and smoothness were changed as shown in Table 1, 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. The amount of SC-700 used was changed to 0.8 parts.

  In Example 9, CMC-B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen 7A, polymerization degree 120-150, molecular weight 27000-33000) was used instead of CMC-A, and instead of SC-700. SC-700L (trade name, polyamidine manufactured by Hymo Co., Ltd., cation density: 1.4 to 1.6 Meq / g, mass average molecular weight 100,000) was used.

  In Example 10, instead of 200 parts of CMC-A, 90 parts of CMC-C (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen 5A, polymerization degree 120 or less, molecular weight 27000 or less) was used, and PVA-A was used. 10 parts were used, and SC-700M (trade name, polyamidine manufactured by Hymo Co., Ltd., cation density 1.8 to 2.4 Meq / g, mass average molecular weight 30,000) was used instead of SC-700.

  In Example 11, instead of CMC-A, CMC-D (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen WS-A, degree of polymerization 460 to 500, molecular weight 100000 to 110000) was used. Instead, 1 part of PDMAE-A (polydimethylamine epichlorohydrin, CAS No. 7-24, cation density 7.41, mass average molecular weight 29,300) was used.

  In Example 12, 10 parts of PDMAE-B (polydimethylamine epichlorohydrin, CAS No. 7-24, cation density 7.03, mass average molecular weight 15,200) was used instead of SC-700.

  In Example 13, PVA-B (manufactured by Kuraray Co., Ltd., trade name: PVA210, saponification degree 87 to 89 mol%, polymerization degree 1000) was used instead of PVA-A, and PDMAE- was used instead of SC-700. 10 parts of C (polydimethylamine epichlorohydrin, CAS No. 7-1518, cation density 7.32, mass average molecular weight 25,000) were used.

  In Example 14, PVA-C (manufactured by Kuraray Co., Ltd., trade name: PVA203, saponification degree 87 to 89 mol%, polymerization degree 300) was used instead of PVA-A, and PDMAE- was used instead of SC-700. 25 parts of D (polydimethylamine epichlorohydrin, CAS No. 7-1517, cation density 6.00, mass average molecular weight 16,700) was used.

  In Example 15, PVA-D (manufactured by Kuraray Co., Ltd., trade name: PVA110, saponification degree 98 to 99 mol%, polymerization degree 1000) was used instead of PVA-A.

  In Example 16, 300 parts of CMC-A was used, and 100 parts of PVA-E (manufactured by Kuraray Co., Ltd., trade name: PVA120, saponification degree 98 to 99 mol%, polymerization degree 2000) was used instead of PVA-A. did.

  In Example 17, high-quality paper was used as a base material, and 15 parts of tertiary ammonium salt (trade name: DK 6852, manufactured by Seiko PMC) was used instead of SC-700.

  In Comparative Example 1, the water-soluble resin and SC-700L were applied without using fine particles. However, instead of CMC-A, CMC-E (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen BS-H, polymerization degree 500-800, molecular weight 180000-190000) is used, and the amount of SC-700L used is changed. Changed to 0.2 parts.

  In Comparative Example 2, only a calcined clay having an average particle diameter of 6.3 μm (manufactured by Engelhard, model number: Ansilex) was used as the fine particles, and PVA- Only 50 parts of A were used. Further, 27 parts of the above-mentioned tertiary ammonium salt was used in place of SC-700.

  Commercially available high-quality paper, kraft paper, and inkjet recording coated paper were purchased and evaluated as a commercial product 1, a commercial product 2, and a commercial product 3.

<Measurement and evaluation method>
For ink jet recording evaluation using sublimation type textile printing ink, an image for ink jet recording evaluation specified in ISO 300 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.
(1) Presence / absence and width of projection: Arbitrary aggregate 60 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 transfer paper produced. The width of each piece 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) Surface roughness of concavo-convex portion: The surface roughness of the concavo-convex portion was measured by measuring the root mean square roughness (μm) using a laser microscope (Color Laser Microscope VK-9700, manufactured by Keyence Corporation).

  (3) Static friction coefficient: In accordance with “Friction coefficient test method for paper and paperboard” described in JIS P 8147 for each manufactured transfer paper, static friction between sublimation printing ink receiving layer surfaces of transfer paper (paper flow direction) The coefficient was measured. The weight used was a dimension (width 60 mm, length 100 mm) and mass (1000 g), and the average value of 5 times in total was taken as the coefficient of static friction.

(4) Cation Density of Coating Layer Sublimation-type printing ink-receiving layer coating solid content 1 g obtained by peeling the sublimation-type printing ink-receiving layer with a razor was stirred with ion-exchanged water 1000 ml (10 ° C.) for 30 minutes. Thereafter, the solution was filtered through a glass filter, and the filtrate was subjected to colloidal titration with a 1/400 normal potassium potassium sulfate solution. The volume ml (CV) at the time when the color changed from blue to magenta using a toluidine blue-0.1% solution as an indicator. (Referred to as “value”) is an equivalent value per active ingredient weight divided by 4.

(5) Ink dryness: Immediately after black printing on each transfer paper produced by an inkjet printer, the print 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 off with tissue paper has ink elongation and is not at a practical level.
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.

(6) 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.

(7) Dimensional stability:
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.
Expansion rate (%) = (measured value / reference length) x 100
The following criteria were used for the 5-level evaluation. Three or more grades are practical levels.
5: Conversion value is less than 30 4: Conversion value is 30 or more and less than 35 3:35 or more and less than 40 2:40 or more and less than 50 1:50 or more

(8) Back-through ink (prevention of back-through of sublimation type printing ink): Sublimation type printing ink of transfer paper produced when sublimation type printing ink is printed on each produced transfer paper and heat is applied from a heat source. The back-through of the sublimation type printing ink on the surface opposite to the receiving layer surface was visually judged, and the back-through prevention property was evaluated according to the following criteria based on 5 levels. Three or more grades are practical levels.
5: No sublimation of sublimation type printing ink.
4: Slightly no sublimation of sublimation printing ink.
3: There is a slight penetration of sublimation printing ink, but there is no problem in practical use.
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.
(9) Heat resistance: Sublimation ink was printed on each manufactured transfer paper, and when heat was applied from a heat source with different temperature conditions, the temperature at which the ink receiving layer surface of the manufactured transfer paper began to deteriorate was measured. 210 ° C. or higher is a practical level.

(10) Yellowing of Transferred Material In the heat resistance evaluation in (9), the yellowing of the transferred material at a temperature condition of 210 ° C. was visually evaluated.

(11) Transfer efficiency:
The transfer efficiency of the sublimation printing ink-jet recording was evaluated in five stages according to the following criteria by visual determination in terms of resolution evaluation and solid image portion evaluation. 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 (image density and uniformity 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 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) Graph measuring ultrasonic transmission intensity

Claims (3)

A substrate and a sublimation printing ink receiving layer provided on the surface of the substrate. After recording the transfer information on the sublimation printing ink receiving layer by ink jet recording, the transfer information is transferred by heating. Sublimation type ink jet textile transfer paper that sublimates a transfer product to form a transfer image,
The sublimation type printing ink receiving layer contains a water-soluble resin, fine particles mainly composed of synthetic amorphous silica, and a cationic compound.
A sublimation type ink jet printing transfer paper, wherein the sublimation type ink receiving layer has a cation density of 0.5 to 3.5 Meq / g. The base material is single-sided kraft paper, and the glossy surface of the single-sided craft paper has the sublimation type printing ink receiving layer;
2. The sublimation ink jet printing transfer paper according to claim 1, wherein the fine particles are contained in the sublimation printing ink receiving layer in an amount of 20 to 50% by mass.   The sublimation ink jet printing transfer paper according to claim 1 or 2, wherein the cationic compound comprises one or more selected from amidines and epichlorohydrins.