JP2010158875A - Sublimation transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sublimation transfer sheet which is used for a sublimation transfer print system, has excellent aqueous ink absorbency in obtaining clear recorded images without bleeding, and is also excellent in ink transfer efficiency to a transferring object when carrying out sublimation transfer. <P>SOLUTION: The sublimation transfer sheet is applied in the sublimation transfer print system, and contains a sheet base material and an ink acceptance layer laid out on one side or both sides of the sheet base material. A pigment, a binder, and a cationic resin are contained in the ink acceptance layer, sedimentation method silica is used as a pigment, and, as to the binder, either one or more of blends among from starch, a starch inductor, polyvinyl alcohol and modified polyvinyl alcohol is used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sublimation transfer sheet used in a sublimation transfer printing system, and more particularly to a sublimation transfer sheet applied to an ink jet printer.

  2. Description of the Related Art Conventionally, a sublimation transfer printing system has been used as an image recording method for cloth products such as sports competition uniforms, T-shirts, tapestry, and banners. FIG. 1 schematically shows the mechanism of such a sublimation transfer printing system. In the figure, 11 is a sublimation transfer sheet, 12 is a sublimation ink, and 13 is a transfer object.

  In the sublimation transfer printing system, a reverse image is printed on the sublimation transfer sheet 11 with the sublimation ink 12 (see FIG. 1A), and then the sublimation transfer sheet 11 and the transfer object 13 are brought into contact with each other to generate heat. By performing the pressure treatment (see FIG. 1B), the image formed on the sublimation transfer sheet 11 is transferred to the transfer object 13 such as a cloth by using the sublimation property of the sublimation ink 12, and the target is obtained. The image is printed on the transfer object (see FIG. 1C).

  Recording methods such as screen printing, gravure printing, and offset printing have been used as recording methods for transfer sheets used in the sublimation transfer printing system. However, these recording methods require plate making and time and In recent years, the inkjet recording method has attracted attention because of its high cost. Since the inkjet recording method does not require plate preparation, it has the advantages of cost reduction and shortening of the preparation period as compared with a printing method that requires a plate, and is suitable for printing on a small lot for on-demand use. For example, in Japanese Patent Laid-Open No. 10-58638 (Patent Document 1), a mirror image is recorded on an ink receiving sheet by an ink jet recording method using an ink containing a sublimation dye, and then an arbitrary transfer object and ink receiving is performed. A method is disclosed in which a sublimation dye is sublimated and transferred from an ink receiving sheet to an arbitrary transfer object by heating in a state where it is superposed on a conductive sheet.

  Further, as one of the performances required for a transfer sheet used for sublimation transfer printing, there is a high color density of an image transferred to a transfer object. In order to increase the color density of the image transferred to the transfer object, the ink received on the transfer sheet must be efficiently transferred to the transfer object in the sublimation transfer process. That is, the smaller the amount of ink remaining on the transfer sheet after the sublimation transfer is, the higher the ink transfer efficiency to the transfer object, and the more ink is transferred to the transfer object, the transfer The color density of the image transferred to the object increases. Therefore, the transfer sheet is also required to have a characteristic of efficiently transferring ink to the transfer object.

  As an invention that pays attention to the transfer efficiency of ink onto a transfer object, Japanese Patent Application Laid-Open No. 2003-266919 (Patent Document 2) discloses an ink receiving layer containing a water-soluble cellulose derivative and inorganic fine particles having an average particle diameter of 1 μm or less. An ink jet recording medium for sublimation ink provided with is disclosed. In addition, Japanese translations of PCT publication No. 2002-521245 (Patent Document 3) discloses a transfer paper for ink-jet printing provided with a relatively high density carboxymethylcellulose layer having a porosity of 100 ml / min or less.

JP-A-10-58638 (refer to claim 1) JP 2003-266919 A (refer to claim 1) Special Table 2002-521245 (refer to claim 1 and [0031])

  The transfer sheet is required to have a characteristic for transferring the ink efficiently, but is also required to have ink absorbability and adhesion. In a sublimation transfer printing system, when recording is performed with an ink jet printer, printing is performed by adding a sublimation dye to the ink jet recording ink. However, the ink for ink jet recording is a water-based ink and contains a large amount of moisture. It is included. For this reason, when performing multicolor solid printing or the like where the printing density exceeds 200%, there is a possibility that problems such as image distortion and defective drying may occur if the transfer sheet does not have sufficient ink absorption capability. . Further, if there is no ability to sufficiently fix a large amount of ink, there is a possibility that the image is blurred and a clear recorded image cannot be obtained.

  However, if the ink absorptivity and adhesiveness are too high, the other necessary characteristic of efficiently transferring the ink can be impaired. That is, if the ink is excessively absorbed and fixed to the transfer sheet, the ink may not be released efficiently during sublimation transfer, and conversely, the ink is absorbed so that the ink is efficiently released during sublimation transfer. When the property and the fixing property are limited, there is a possibility that the image is disturbed or poorly dried when printed on the transfer sheet, or the image is blurred and a clear recorded image cannot be obtained.

  The present invention has been made in view of such problems, and the object of the present invention is to be used in a sublimation transfer printing system for recording information on a transfer sheet by an ink jet printer and absorbs water-based ink. It is an object of the present invention to provide a sublimation transfer sheet that can obtain a clear recorded image that is excellent in color and has no bleeding, and that is excellent in the efficiency of ink transfer onto a transfer object during sublimation transfer.

  Other objects and operational effects of the present invention will be easily understood by those skilled in the art by referring to the following description.

  In order to achieve the above object, the sublimation transfer sheet of the present invention uses ink containing a sublimation dye, and prints desired information on a predetermined sublimation transfer sheet by an ink jet printer. Applied to a sublimation transfer printing system in which the desired information is transferred and printed from the sublimation transfer sheet to the transfer object by pressing and heating the printed sublimation transfer sheet against an arbitrary transfer object. This is a sublimation transfer sheet.

  A specific configuration includes a sheet-like substrate and an ink receiving layer provided on one or both sides of the sheet-like substrate.

  The ink receiving layer includes a pigment, a binder, and a cationic resin. As the pigment, precipitated silica is used. As the binder, starch, starch derivatives, polyvinyl alcohol, and modified polyvinyl alcohol are used. Any one or a mixture of two or more thereof is used.

  According to such a configuration, a sublimation transfer sheet can be obtained that is excellent in water-based ink absorbability during printing on a sublimation transfer sheet and can provide a clear image without bleeding. In addition, the efficiency of ink transfer to the transfer object is high during sublimation transfer, and a clear image can be transferred to the transfer object.

  In a preferred embodiment of the present invention, the precipitated silica has a pore volume ratio having a pore radius of 100 mm or less in the pore distribution measured by mercury porosimetry, with respect to the total pore volume. % Or less is desirable. According to such a configuration, it is possible to obtain a sublimation transfer sheet that is more excellent in the efficiency of ink transfer to a transfer object during sublimation transfer.

  In a preferred embodiment of the present invention, precipitated silica having an oil absorption of 120 to 180 ml / 100 g is used as the precipitated silica, and 100 to 250 parts by weight of 100 to 100 parts by weight of the binder is incorporated in the ink receiving layer. It is desirable to do. According to such a configuration, it is possible to obtain a sublimation transfer sheet having further excellent ink transfer efficiency to a transfer object during sublimation transfer.

  In a preferred embodiment of the present invention, it is desirable to use a polydimethylamine epichlorohydrin condensate as the cationic resin. According to such a configuration, it is possible to obtain a sublimation transfer sheet that is further excellent in the efficiency of ink transfer to a transfer object during sublimation transfer.

In preferable embodiment of this invention, the said sheet-like base material has a pulp as a main component, and it is desirable that basic weight is 50-200 g / m < ² >. According to such a configuration, it is possible to obtain a sublimation transfer sheet having excellent transportability in an ink jet printer.

  ADVANTAGE OF THE INVENTION According to this invention, the sublimation transfer sheet which can provide the clear recorded image which is excellent in the absorptivity of water-based ink at the time of the printing to a sublimation transfer sheet, and does not have a bleeding is obtained. Further, the ink transfer efficiency to the transfer object is high during sublimation transfer, and a clear image can be transferred to the transfer object. That is, by applying the sublimation transfer sheet of the present invention to a sublimation transfer printing system that records information on a transfer sheet by an ink jet printer, the sublimation ink is transferred with high transfer efficiency, and the color density on the transfer object is increased. High transfer images can be obtained.

  Moreover, in the pore distribution measured by the mercury intrusion method, the ratio of the pore volume having a pore radius of not more than 100 mm is 1% or less of the sedimentation method silica with respect to the total pore volume. In this way, the ink transfer efficiency to the transfer object during sublimation transfer is further improved, and by applying to a sublimation transfer print system in which information is recorded on a transfer sheet by an ink jet printer, the transfer object is transferred to the transfer object. It becomes possible to transfer a transfer image having a higher color density.

  In addition, as the precipitated silica, precipitated silica having an oil absorption of 120 to 180 ml / 100 g is used, and the ink receiving layer contains 100 to 250 parts by weight with respect to 100 parts by weight of the binder. It is possible to obtain a sublimation transfer sheet excellent in the efficiency of ink transfer to a transfer object. By applying it to a sublimation transfer printing system that records information on a transfer sheet using an ink jet printer, it is possible to transfer a transfer image having a higher color density onto a transfer object.

  Furthermore, by using a polydimethylamine epichlorohydrin condensate as the cationic resin, it is possible to obtain a sublimation transfer sheet having a high ink transfer efficiency to a transfer object during sublimation transfer. By applying it to a sublimation transfer printing system that records information on a transfer sheet using an ink jet printer, it is possible to transfer a transfer image having a higher color density onto a transfer object.

It is the figure which represented typically the mechanism of the sublimation transfer printing system. It is a pore distribution table | surface of the silica 1 (micropore diameter ratio: 12.77%). It is a pore distribution table | surface of the silica 2 (micropore diameter ratio: 13.74%). 3 is a pore distribution table of silica 3 (fine pore diameter ratio: 0.65%). It is a pore distribution table of silica 4 (fine pore diameter ratio: 0.52%). It is a pore distribution table of silica 5 (fine pore diameter ratio: 0.1%). It is a pore distribution table | surface of the silica 6 (micropore diameter ratio: 0.2%). It is a pore distribution table of silica 7 (micropore diameter ratio: 0.2%). It is the evaluation result (the 1) of an Example and a comparative example. It is the evaluation result (the 2) of an Example and a comparative example.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

  As described above, the sublimation transfer sheet of the present invention is required to have sufficient ink absorbability and ink fixing property, and in addition to this, it has the property of efficiently transferring once received ink to a transfer object. Is also required. That is, the ink jet ink ejected from the ink nozzles can be sufficiently absorbed and fixed when ink jet recording is performed, and the sublimation ink is easily released from the transfer sheet during sublimation transfer. Needed. The property of sufficiently absorbing and fixing ink and the property of easily releasing the ink once received are seemingly contradictory properties, and it has been considered difficult to satisfy both of these properties at the same time.

  However, as a result of diligent research, the inventors of the present application have combined the specific pigment and binder in the ink receiving layer provided on the sheet-like base material, and further contained a cationic resin, whereby the ink absorbability during printing can be increased. It has been found that a sublimation transfer sheet satisfying simultaneously seemingly contradictory properties such as fixing property and ink release property at the time of transfer can be obtained.

  Based on this knowledge, in the sublimation transfer sheet of the present invention, an ink receiving layer is provided on at least one surface of the sheet-like substrate, and in the ink receiving layer, precipitated silica is used as a pigment, starch as a binder, starch Any one of a derivative, polyvinyl alcohol, and modified polyvinyl alcohol, or a mixture of two or more of them was further added with a cationic resin. In this way, combining a specific pigment and a binder and further containing a cationic resin makes it possible to achieve both the characteristics of sufficiently absorbing and fixing the ink and the characteristic of easily releasing the ink once received. It becomes important.

[Types of silica]
First, the precipitated silica used in the ink receiving layer in the present invention will be described. Although silica varies depending on the amount of oil absorption, the ink absorbability is superior to other general inorganic pigments such as kaolin, talc and calcium carbonate. For this reason, sufficient ink absorption performance can be maintained in the sublimation transfer sheet by including silica in the ink receiving layer. Furthermore, as a result of the verification by the inventors of the present application, by setting the type of silica to precipitated silica, it is possible to easily release the ink that is heated and sublimated during sublimation transfer, and as a result, the object to be transferred during sublimation transfer. It was found that the ink transfer efficiency to the object can be improved.

  Here, precipitated silica is silica produced by a precipitation method (precipitation method), which is one of the wet methods, and the primary particle grows faster as the reaction proceeds in an alkaline pH region. It is called sedimentation silica because the particles aggregate in a floc form and settle. On the other hand, there is a gel method as a production method classified into the same wet method, and silica produced by this production method is called gel method silica because a reaction aggregate becomes a gel. Silica produced by the gel method causes the reaction to proceed in an acidic pH region, thereby causing aggregation in a state in which the growth of primary particles is suppressed, and the reaction aggregate becomes a gel.

  The reason why the transfer efficiency of the ink is improved by adopting the precipitation method silica is not clear, but it is presumed that the difference in pore diameter due to the production method has an influence. In general, when the precipitated silica and the gel silica are compared, the pore diameter of the primary particles is larger in the precipitated silica.

  Here, as the precipitated silica used in the present invention, in the pore distribution measured by the mercury intrusion method, the ratio of the pore volume having a pore radius of 100 mm or less is 1% or less with respect to the total pore volume. Precipitation silica is more preferred. By using precipitated silica having a pore volume satisfying this condition, it is possible to further improve the efficiency of ink transfer to a transfer object during sublimation transfer. This is because, among the precipitated silicas that tend to have a relatively large pore size between primary particles, the smaller the proportion of pore volume having a small pore size, the more efficient the ink transfer to the transfer object during sublimation transfer. It is effective for improvement.

[About Binder]
Next, the binder used in the present invention will be described. In the sublimation transfer sheet of the present invention, the ink receiving layer contains, as a binder, any one of starch, starch derivatives, polyvinyl alcohol, and modified polyvinyl alcohol, or a mixture of two or more thereof.

  As described above, the sublimation transfer sheet of the present invention contains precipitated silica in the ink-receiving layer. By using the precipitated silica and these binders in combination, ink transfer to a transfer object during sublimation transfer is performed. Efficiency can be improved. The reason why the efficiency of ink transfer to the transfer object during sublimation transfer is improved by using the precipitated silica in combination with these specific binders is not clear, but the pore size between the primary particles of the precipitated silica is relatively It seems that this is because of the large size and the compatibility between the precipitated silica and these binders, the heat required for sublimation of the ink is easily conducted and the sublimation of the ink itself is not easily inhibited. Due to such factors, heat is easily transferred to the ink held in the ink receiving layer during sublimation transfer, and the ink is smoothly sublimated, and the structure of the ink receiving layer makes it easy to release the sublimated ink. It is presumed that

  In general ink jet recording paper, latex such as acrylic resin or SBR, ethylene-vinyl acetate resin, or the like may be used as a binder used in the ink receiving layer. However, precipitated silica and acrylic resin or SBR may be used. As a result of using a binder such as latex and ethylene-vinyl acetate resin together with these binders, it was not possible to improve the efficiency of ink transfer to the transfer object during sublimation transfer.

  The starch derivative that can be used here is not particularly limited, and it is possible to select a starch derivative that is used as a binder for general coating agents such as oxidized starch, etherified starch, and esterified starch. Of these, phosphate esterified starch is particularly preferred because of the stability of the paint properties.

  Further, the polyvinyl alcohol and the modified polyvinyl alcohol that can be used here are not particularly limited, regardless of whether they are a complete saponification type or a partial saponification type, and silanol modification, carboxyl group modification, Various modified polyvinyl alcohols such as acetoacetyl group-modified and cation-modified can be used.

  In the sublimation transfer sheet of the present invention, the blending amount of the pigment and binder in the ink receiving layer is not particularly limited, and may be appropriately determined according to the oil absorption amount of the precipitated silica used as the pigment. Here, the oil absorption amount of the precipitated silica is a value measured by a method defined in JIS K5101, and the same applies to the following.

  When using precipitated silica with a relatively large amount of oil absorption, it is easy to satisfy the absorbability of water-based ink even if the amount of precipitated silica is small, but on the other hand, the strength of the ink receiving layer tends to be weak, so the binder It is necessary to add a relatively large amount. On the other hand, when using precipitated silica with a relatively small oil absorption amount, if the precipitated silica content is too small, sufficient ink absorbability cannot be obtained. It is necessary to relatively increase the amount of precipitated silica to satisfy the water-based ink absorbability.

  As an example of a specific blending amount, when using precipitated silica having an oil absorption amount exceeding 200 ml / 100 g, it is desirable to blend 50 to 150 parts by weight of precipitated silica with respect to 100 parts by weight of the binder. Here, if the blending amount of the precipitation method silica is less than 50 parts by weight, the blending proportion of the precipitation method silica may be too small to satisfy the absorptivity of the water-based ink. There is a possibility that the strength of the falling ink receiving layer is weakened.

  When using precipitated silica having an oil absorption of 200 ml / 100 g or less, it is desirable to mix 100 to 300 parts by weight of precipitated silica with 100 parts by weight of the binder. Here, if the blending amount of the precipitation method silica is less than 100 parts by weight, the blending proportion of the precipitation method silica may be too small to satisfy the absorptivity of the water-based ink. There is a possibility that the strength of the falling ink receiving layer is weakened.

  When using precipitated silica having an oil absorption of 120 to 180 ml / 100 g, the blending amount is desirably about 100 to 250 parts by weight with respect to 100 parts by weight of the binder. Here, if the compounding amount of the precipitated silica is less than 100 parts by weight, the water-based ink absorbability may not be satisfied. Conversely, if it exceeds 250 parts by weight, the strength of the ink receiving layer may be weakened. When using precipitated silica with a relatively small oil absorption amount, the blending ratio of precipitated silica in the ink-receiving layer can be made higher than when using precipitated silica with a large oil absorption amount. As a result, it is possible to further improve the efficiency of ink transfer to the transfer object during sublimation transfer.

  In the sublimation transfer sheet of the present invention, the ink receiving layer further contains a cationic resin in addition to the precipitated silica and the binder. By including a cationic resin in the ink receiving layer, the sublimation transfer sheet can retain sufficient ink fixing properties, and blurring or the like does not occur in the image by inkjet recording, and a clear recorded image can be obtained. . By fixing the ink to the ink receiving layer, it may be difficult to release the ink at the time of sublimation transfer and the ink transfer efficiency to the transfer target may be reduced. As a result, the ink transfer efficiency to the transfer object was improved.

  The reason for this is not clear, but when ink jet recording is performed, the cationic resin contained in the ink receiving layer as the surface layer keeps the ink in the ink receiving layer, and the ink reaches the sheet-like substrate of the sublimation transfer sheet. In order to prevent permeation, it is presumed that the ink is retained on the surface layer and easily released during the sublimation transfer, and the ink transfer efficiency is improved.

  In the present application, the content of the cationic resin contained in the ink receiving layer is not particularly limited, but is preferably 5 to 80 parts by weight with respect to 100 parts by weight of the binder. When the blending amount of the cationic resin is less than 5 parts by weight, the ink fixing property cannot be satisfied, and as a result, the ink transfer efficiency may not be improved satisfactorily. On the other hand, if the blending amount of the cationic resin exceeds 80 parts by weight, the binder ratio in the ink receiving layer is relatively lowered, and the strength of the ink receiving layer may be weakened.

  Moreover, as a kind of cationic resin used by this application, the cationic resin used as an ink fixing agent in a normal inkjet recording paper can be used. For example, polydimethylammonium resin, polydiallyldimethylammonium resin, polyamine resin, polyamide resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, polydiallylamine resin, polydimethylamine epichlorohydrin resin, polyethyleneimine resin, Cationic polymer resins such as polyallylamine resins, dicyandiamide condensates, and polyamidine resins can be selected and used as appropriate. There is no particular limitation as to which of these cationic polymer resins is used, but polydimethylamine epichlorohydrin condensate is used in terms of good ink transfer efficiency to a transfer object during sublimation transfer. It is particularly desirable to use it.

  In the ink receiving layer of the present invention, the antifoaming agent, the thickening agent, the pH adjusting agent, the lubricant, the dispersing agent, the wetting agent, the dye, etc. are used in the technical field as long as the intended effect is not impaired. You may use the well-known additive used suitably.

  In the present invention, the coating apparatus for forming the ink receiving layer on the sheet-like substrate is not particularly limited, and a known coating apparatus generally used in the technical field can be used as appropriate. For example, a blade coater, an air knife coater, a roll coater, a reverse roll coater, a curtain coater, a bar coater, a gravure coater, a bill blade coater, or the like can be used.

In the sublimation transfer sheet of the present invention, the coating amount of the ink receiving layer is preferably ³ to 12 g / m ² per side as the solid content of the ink receiving layer. If the coating amount of the ink receiving layer is less than 3 g / m ² , there is a possibility that image recording suitability by the ink jet printer cannot be satisfied, for example, sufficient absorbability of the ink jet ink cannot be secured. On the other hand, when the coating amount of the ink receiving layer exceeds 12 g / m ² , the thickness of the coating layer increases, so that the flexibility may be impaired and it may be difficult to handle as a sublimation transfer sheet.

The sheet-like base material used for the sublimation transfer sheet of the present invention is not particularly limited, and a sheet-like base on which an ink receiving layer can be provided, such as paper mainly composed of pulp, film, nonwoven fabric, and synthetic paper. Although it is possible to select appropriately from the material, it is preferable to use paper containing pulp as a main component in consideration of transportability in an ink jet printer. Further, the basis weight of the sheet-like substrate is not particularly limited, and may be appropriately selected within a range applicable to an inkjet printer that performs printing. In the case of using paper containing pulp as a main component as a sheet-like substrate, it is preferable to set it in the range of 50 to 200 g / m ² in consideration of various strengths.

  Examples of the sublimation transfer sheet according to the present invention will be specifically described below, but the present invention is not limited thereto. Moreover, unless otherwise indicated, the part and% in an Example show a dry weight part and weight%. In addition, the ratio (hereinafter referred to as the fine pore diameter ratio) of the precipitated silica used in each Example and Comparative Example to the total pore volume of the oil absorption amount and the pore volume having a pore radius of 100 mm or less is: It calculated | required with the following method.

[Oil absorption]
The oil absorption was measured by a measuring method using refined linseed oil according to JIS K5101-13.

[Fine pore size ratio]
The pore distribution of each precipitated silica was measured by a mercury intrusion method using a mercury porosimeter (Pascal 440 / manufactured by AMCO Corporation) within a pore radius of 22 to 60000 mm. The fine pore size ratio was determined from the obtained pore distribution table. The pore distribution table of each precipitated silica is shown in FIGS. The pore distribution tables shown in FIGS. 2 to 8 are the following pore distribution tables of precipitated silica.
Fig. 2: Silica 1 (Nip seal K-500 / manufactured by Tosoh Silica Co., Ltd., fine pore size ratio: 12.77%)
Fig. 3: Silica 2 (Nip Seal HD / Tosoh Silica Co., Ltd., fine pore size ratio: 13.74%)
FIG. 4: Silica 3 (Nip seal E-200A / manufactured by Tosoh Silica Co., Ltd., fine pore diameter ratio: 0.65%)
FIG. 5: Silica 4 (Nip seal E-150J / manufactured by Tosoh Silica Co., Ltd., fine pore diameter ratio: 0.52%)
Fig. 6: Silica 5 (Nip seal E-75 / manufactured by Tosoh Silica Co., Ltd., fine pore size ratio: 0.1%)
FIG. 7: Silica 6 (Nip seal E-743 / manufactured by Tosoh Silica Co., Ltd., fine pore diameter ratio: 0.2%)
FIG. 8: Silica 7 (Nip seal E-74P / Tosoh Silica Co., Ltd., fine pore diameter ratio: 0.2%)

  2 to 8, the horizontal axis is the pore radius (半径). The scale indicated on the right axis of the vertical axis is a scale of a bar graph representing the pore volume (%), and the bar graph represents a numerical value obtained by accumulating the pore volume of each pore for each pore radius. The scale indicated on the left axis of the vertical axis is a scale of a line graph representing the cumulative volume (cc / g), and the line graph is calculated based on the proportion of pores for each pore radius. This indicates the cumulative volume of the pores, which are accumulated in order from the largest pore radius. Of silicas 1-7 shown in FIGS. 2-8, it can be seen that for silicas 3-7 with a fine pore size ratio of 1% or less, the proportion of fine pore diameters with a pore radius of 100 mm or less is small, Among them, it is clear that the ratio of the fine pore diameter is particularly small for silicas 5 to 7.

<Example 1>
After adding 100 parts by weight of precipitated silica (Nipseal K-500 / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 12.77% and an oil absorption of 300 ml / 100 g as a pigment and sufficiently stirring , 100 parts by weight of oxidized starch (SK-20 / manufactured by Nippon Corn Starch Co., Ltd.) as a binder, and 30 parts by weight of polyamidine resin (Himax SC-700 / manufactured by Himo Co., Ltd.) as a cationic resin are added, and a thickener is further added. 1 part by weight was added and mixed to obtain a paint for an ink receiving layer. The obtained coating material for ink-receiving layer was coated on a surface of 80 g / m ² bleached kraft paper (bleached kraft paper / manufactured by Kishu Paper Co., Ltd.) with a coating rod in a solid content of 8.0 g. / M ² to obtain a target sublimation transfer sheet. The “coating rod” used for coating the ink-receiving layer paint is a hand-painting tool used in the trial production of paper, and has a length of about 30 cm with fine grooves dug on the surface. The metal rod.

<Example 2>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1 except that the binder was changed to 100 parts by weight of completely saponified polyvinyl alcohol (JF-17 / Nippon Acetate / Poval).

<Example 3>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1, except that the binder was changed to 100 parts by weight of phosphate esterified starch (Ace P-260 / Oji Cornstarch Co., Ltd.).

<Example 4>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1 except that the binder was changed to 100 parts by weight of silanol-modified polyvinyl alcohol (Kuraray R Polymer / Kuraray Co., Ltd.).

<Example 5>
In Example 1, the binder was changed to 50 parts by weight of oxidized starch (SK-20 / manufactured by Nippon Corn Starch Co., Ltd.) and 50 parts by weight of completely saponified polyvinyl alcohol (JF-17 / manufactured by Nihon Ventures & Poval Co., Ltd.). A sublimation transfer sheet was obtained in the same manner as Example 1 except for the above.

<Example 6>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1 except that the addition amount of the polyamidine resin (Himax SC-700 / manufactured by Hymo Co., Ltd.), which is a cationic resin, was changed to 5 parts by weight. It was.

<Example 7>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1, except that the addition amount of the polyamidine resin (Himax SC-700 / manufactured by Hymo Co., Ltd.), which is a cationic resin, was changed to 80 parts by weight. It was.

<Example 8>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1 except that the cationic resin was changed to 30 parts by weight of polydiallyldimethylammonium chloride condensate (Unisense CP-102 / Senka Co., Ltd.).

<Example 9>
As a pigment, 100 parts by weight of precipitated silica (Nipseal HD / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 13.74% and an oil absorption of 240 ml / 100 g was added to water and stirred sufficiently, and then the binder was added. Add 100 parts by weight of silanol-modified polyvinyl alcohol (Kuraray R Polymer / Kuraray Co., Ltd.) and 30 parts by weight of polydiallyldimethylammonium chloride condensate (Unisense CP-102 / Senka Co., Ltd.) as a cationic resin. 1 part by weight of a sticking agent was added and mixed to obtain a paint for an ink receiving layer. The obtained coating material for ink-receiving layer was coated on a surface of 80 g / m ² bleached kraft paper (bleached kraft paper / manufactured by Kishu Paper Co., Ltd.) with a coating rod in a solid content of 8.0 g. / M ² to obtain a target sublimation transfer sheet.

<Example 10>
In Example 9, the binder was changed to 50 parts by weight of oxidized starch (SK-20 / manufactured by Nippon Corn Starch Co., Ltd.) and 50 parts by weight of completely saponified polyvinyl alcohol (JF-17 / manufactured by Nihon Ventures & Poval Co., Ltd.). A sublimation transfer sheet was obtained in the same manner as Example 9 except that.

<Example 11>
In Example 1, the pigment was changed to 100 parts by weight of precipitated silica (Nipseal E-200A / manufactured by Tosoh Silica Co., Ltd.) having a fine pore ratio of 0.65% and an oil absorption of 230 ml / 100 g. In the same manner as in No. 1, a sublimation transfer sheet was obtained.

<Example 12>
In Example 9, the pigment was changed to 140 parts by weight of precipitated silica (Nipseal E-150J / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.52% and an oil absorption of 200 ml / 100 g. In the same manner as in Example 9, a sublimation transfer sheet was obtained.

<Example 13>
In Example 9, the pigment was changed to 300 parts by weight of precipitated silica (Nipseal E-150J / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.52% and an oil absorption of 200 ml / 100 g, and the binder was changed to phosphorus. A sublimation transfer sheet was obtained in the same manner as in Example 9, except that the content was changed to 100 parts by weight of acid esterified starch (Ace P-260 / Oji Cornstarch Co., Ltd.).

<Example 14>
In Example 1, a sublimation transfer sheet was obtained in the same manner as in Example 1 except that the cationic resin was changed to 30 parts by weight of a polydimethylamine epichlorohydrin condensate (WSC-173 / Meisei Chemical Co., Ltd.).

<Example 15>
In Example 9, a sublimation transfer sheet was obtained in the same manner as in Example 9 except that the cationic resin was changed to 30 parts by weight of a polydimethylamine epichlorohydrin condensate (WSC-173 / Meisei Chemical Co., Ltd.).

<Example 16>
After adding 250 parts by weight of precipitated silica (Nipseal E-75 / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.1% and an oil absorption of 120 ml / 100 g as a pigment and sufficiently stirring 100 parts by weight of phosphate esterified starch (Ace P-260 / Oji Cornstarch Co., Ltd.) as a binder, and 30 parts by weight of polydiallyldimethylammonium chloride condensate (Unisense CP-102 / Senka Co., Ltd.) as a cationic resin Further, 1 part by weight of a thickening agent was added and mixed to obtain a paint for an ink receiving layer. The obtained coating material for ink-receiving layer was coated on a surface of 80 g / m ² bleached kraft paper (bleached kraft paper / manufactured by Kishu Paper Co., Ltd.) with a coating rod in a solid content of 8.0 g. / M ² to obtain a target sublimation transfer sheet.

<Example 17>
In Example 16, the blending amount of precipitated silica (Nipseal E-75 / manufactured by Tosoh Silica Co., Ltd.) having a fine pore diameter ratio of 0.1% and an oil absorption of 120 ml / 100 g used as a pigment was 170 parts by weight. A sublimation transfer sheet was obtained in the same manner as Example 16 except for the change.

  <Example 18>

  In Example 16, the pigment was changed to 160 parts by weight of precipitated silica (Nipseal E-743 / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.2% and an oil absorption of 155 ml / 100 g. In the same manner as in No. 16, a sublimation transfer sheet was obtained.

<Example 19>
In Example 16, the pigment was changed to 150 parts by weight of precipitated silica (Nipseal E-74P / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.2% and an oil absorption of 180 ml / 100 g. In the same manner as in No. 16, a sublimation transfer sheet was obtained.

<Example 20>
In Example 16, the pigment was changed to 100 parts by weight of precipitated silica (Nipseal E-74P / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.2% and an oil absorption of 180 ml / 100 g. In the same manner as in No. 16, a sublimation transfer sheet was obtained.

<Example 21>
In Example 1, the pigment was changed to precipitated silica (Nipseal E-200A / manufactured by Tosoh Silica Co., Ltd.) having a fine pore ratio of 0.65% and an oil absorption of 230 ml / 100 g, and the cationic resin was polydimethyl A sublimation transfer sheet was obtained in the same manner as in Example 1 except that it was changed to an amine epichlorohydrin condensate (WSC-173 / Meisei Chemical Co., Ltd.).

<Example 22>
In Example 1, the pigment was changed to 140 parts by weight of precipitated silica (Nipseal E-150J / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.52% and an oil absorption of 200 ml / 100 g, and the binder was silanol. Except for changing to 100 parts by weight of modified polyvinyl alcohol (Kuraray R Polymer / Kuraray Co., Ltd.) and changing the cationic resin to 30 parts by weight of polydimethylamine epichlorohydrin condensate (WSC-173 / Maisei Chemical Co., Ltd.) In the same manner as in Example 1, a sublimation transfer sheet was obtained.

<Example 23>
After adding 170 parts by weight of precipitated silica (Nipseal E-75 / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.1% and an oil absorption of 120 ml / 100 g as a pigment and sufficiently stirring 100 parts by weight of phosphate esterified starch (Ace P-260 / manufactured by Oji Cornstarch Co., Ltd.) as the binder, and 30 parts by weight of polydimethylamine epichlorohydrin condensate (WSC-173 / manufactured by Meisei Chemical Co., Ltd.) as the cationic resin Further, 1 part by weight of a thickening agent was added and mixed to obtain a paint for an ink receiving layer. The obtained coating material for ink-receiving layer was coated on a surface of 80 g / m ² bleached kraft paper (bleached kraft paper / manufactured by Kishu Paper Co., Ltd.) with a coating rod in a solid content of 8.0 g. / M ² to obtain a target sublimation transfer sheet.

<Example 24>
After adding 150 parts by weight of precipitated silica (Nipseal E-74P / manufactured by Tosoh Silica Co., Ltd.) having a fine pore size ratio of 0.2% and an oil absorption of 180 ml / 100 g as a pigment and sufficiently stirring 100 parts by weight of phosphate esterified starch (Ace P-260 / manufactured by Oji Cornstarch Co., Ltd.) as the binder, and 30 parts by weight of polydimethylamine epichlorohydrin condensate (WSC-173 / manufactured by Meisei Chemical Co., Ltd.) as the cationic resin Further, 1 part by weight of a thickening agent was added and mixed to obtain a paint for an ink receiving layer. The obtained coating material for ink-receiving layer was coated on a surface of 80 g / m ² bleached kraft paper (bleached kraft paper / manufactured by Kishu Paper Co., Ltd.) with a coating rod in a solid content of 8.0 g. / M ² to obtain a target sublimation transfer sheet.

<Comparative Example 1>
A sublimation transfer sheet was obtained in the same manner as in Example 23 except that in Example 23, the pigment was changed to 150 parts by weight of gel method silica (Gasyl IJ45 / Ineos Silica) having an oil absorption of 180 ml / 100 g.

<Comparative example 2>
In Example 23, a sublimation transfer sheet was obtained in the same manner as in Example 23, except that the pigment was changed to 100 parts by weight of gel silica (nip gel BY6A1 / Tosoh Silica Co., Ltd.) having an oil absorption of 215 ml / 100 g. It was.

<Comparative Example 3>
In Example 23, a sublimation transfer sheet was obtained in the same manner as in Example 23 except that the binder was changed to 100 parts by weight of an ethylene-vinyl acetate copolymer resin (Sumikaflex 305HQ / manufactured by Sumitomo Chemical Co., Ltd.).

<Comparative example 4>
In Example 23, a sublimation transfer sheet was obtained in the same manner as in Example 23, except that the binder was changed to 100 parts by weight of a styrene-acrylic copolymer (Cybinol UC-404 / Syden Chemical Co., Ltd.).

<Comparative Example 5>
In Example 23, a sublimation transfer sheet was obtained in the same manner as in Example 23 except that the binder was changed to 100 parts by weight of styrene-butadiene copolymer latex (RL-500 / Asahi Kasei Co., Ltd.).

<Comparative Example 6>
In Example 23, a sublimation transfer sheet was obtained in the same manner as in Example 23 except that the cationic resin was not added.

The evaluation results of the ink transfer efficiency of the sublimation transfer sheets obtained in Examples 1 to 24 and Comparative Examples 1 to 6 are shown in FIGS. The types of binders in FIGS. 9 and 10 are as follows.
A: Oxidized starch (SK-20 / manufactured by Nippon Corn Starch Co., Ltd.)
B: Completely saponified polyvinyl alcohol (JF-17 / Nippon Vinegar / Poval)
C: Phosphate esterified starch (Ace P-260 / Oji Cornstarch Co., Ltd.)
D: Silanol-modified polyvinyl alcohol (Kuraray R polymer / Kuraray Co., Ltd.)
E: Ethylene-vinyl acetate copolymer resin (Sumikaflex 305HQ / Sumitomo Chemical Co., Ltd.)
F: Styrene-acrylic copolymer (Cybinol UC-404 / Syden Chemical Co., Ltd.)
G: Styrene-butadiene copolymer latex (RL-500 / Asahi Kasei Corporation)
Ink transfer efficiency was evaluated by the following method.

[Ink transfer efficiency]
An image was recorded on the ink receiving layer forming surface of the sublimation transfer sheet obtained in each of Examples and Comparative Examples using an inkjet printer (PX-9500 / manufactured by Seiko Epson Corporation). As the ink, sublimation type ink-jet ink (SPC-0493Y, M, C, K / Mimiki Engineering Co., Ltd.) was used. Next, in a state where the image portion recorded on the ink receiving layer of the sublimation transfer sheet and the cloth made of polyester are overlapped, a hot press machine (SHINTO type press machine / manufactured by Shinto Metal Industries Co., Ltd.) is used at 200 ° C. The image recorded on the sublimation transfer sheet was sublimated and transferred onto a cloth by heat and pressure treatment for 5 minutes under the condition of × 2.5 kg / cm ² . Both the color density of the image transferred to the cloth and the density of the ink remaining on the sublimation transfer sheet were visually confirmed and evaluated in six stages (1-6). The color transferred to the cloth has a high color density, the density of the ink remaining on the sublimation transfer sheet is low, and the ink transfer efficiency can be determined to be particularly good. A density of 1 was determined to indicate that the density of the ink remaining on the sublimation transfer sheet was low and the ink transfer efficiency was particularly poor. In this evaluation, a sublimation transfer sheet having an ink transfer efficiency evaluation of 2 or more was regarded as acceptable.

[Verification of composition]
As is clear from FIGS. 9 and 10, the sublimation transfer sheets obtained in Examples 1 to 24 have ink transfer efficiencies of 2 to 6, and the ink transfer efficiencies are at acceptable levels. The sublimation transfer sheet obtained in Example 6 had a relatively low ink transfer efficiency because the amount of the cationic resin added was relatively small, but it was a pass level with no practical problems. The sublimation transfer sheet obtained in Example 7 had a relatively large addition amount of the cationic resin, so that the binder ratio was relatively lowered and the coating layer strength was slightly weak, but there was no practical problem. The ink transfer efficiency was also acceptable.

  On the other hand, in Comparative Example 1 and Comparative Example 2, gel method silica having an oil absorption of 180 to 215 ml / 100 g was used, but the sublimation transfer sheets obtained in these Comparative Examples were almost the same except for the production method of silica. As compared with the sublimation transfer sheet obtained in Example 24, the transfer efficiency was significantly inferior. This is presumably because gel silica was used as the pigment used in the ink receiving layer.

  Further, as a binder used for the ink receiving layer, Comparative Example 3 using ethylene-vinyl acetate copolymer resin, Comparative Example 4 using styrene-acrylic copolymer, Comparative Example using styrene-butadiene copolymer latex The sublimation transfer sheet obtained in No. 5 resulted in significantly inferior ink transfer efficiency in spite of the same conditions as in Example 23 except for the binder. It is presumed that this is due to the fact that each binder of ethylene-vinyl acetate copolymer resin, styrene-acrylic copolymer, and styrene-butadiene copolymer latex is incompatible with precipitated silica.

  Further, the sublimation transfer sheet obtained in Comparative Example 6 in which no cationic resin was blended in the ink receiving layer was also subjected to the ink transfer in spite of the same conditions as in Example 23 except for the presence or absence of the cationic resin. The result was very inefficient. This seems to be because the cationic resin was not blended.

  From the above results, the ink receiving layer uses precipitated silica as a pigment, and uses any one of starch, starch derivatives, polyvinyl alcohol, and modified polyvinyl alcohol as a binder, or a mixture of two or more thereof, and is further cationic. It turns out that it is preferable to contain resin. In any of the sublimation transfer sheets obtained in Examples 1 to 24, since a pigment was blended in the ink receiving layer, it was excellent in water-based ink absorbability and a clear recorded image free from bleeding could be obtained. It was.

[Verification of the fine pore diameter ratio of silica]
Next, the fine pore size ratio of the precipitated silica is verified. Examples 1 and 11 are the same conditions except for the fine pore diameter ratio and oil absorption of the precipitated silica, but the sublimation transfer obtained in Example 11 using the precipitated silica with a fine pore ratio of 0.65%. The resulting sheet was superior in ink transfer efficiency to the sublimation transfer sheet obtained in Example 1 using precipitated silica having a fine pore size ratio of 12.77%.

  Similarly, Example 9 and Example 12 were obtained in Example 12 using precipitated silica having a fine pore diameter ratio of 0.52%, although the same conditions except for the fine pore diameter ratio and oil absorption amount of the precipitated silica. The sublimation transfer sheet was superior in ink transfer efficiency to the sublimation transfer sheet obtained in Example 9 using precipitated silica having a fine pore size ratio of 13.74%.

  Further, the sublimation transfer sheet obtained in Example 13 using the precipitated silica having a fine pore diameter ratio of 0.52% also uses the precipitated silica having a fine pore diameter ratio of 12.77 to 13.74%. As a result, the ink transfer efficiency was superior to the sublimation transfer sheets obtained in Examples 1 to 10.

  From these results, it is considered that the smaller the pore diameter ratio of the precipitated silica used in the ink receiving layer, the more effective the ink transfer efficiency is, and the precipitated silica having a fine pore diameter ratio of 1% or less is used. It seems most preferable.

[Verification of oil absorption and blending amount of silica]
Next, the oil absorption amount of the precipitated silica and the blending amount in the ink receiving layer will be verified. In Examples 16 to 20, silica having an oil absorption of 120 to 180 ml / 100 g is blended in an amount of 100 to 250 parts by weight per 100 parts by weight of binder. In Examples 11 to 13, the oil absorption is 200 to 230 ml / 100 g. Some silica is blended in an amount of 100 to 300 parts by weight per 100 parts by weight of the binder. As a result, the sublimation transfer sheets obtained in Examples 16 to 20 were excellent in ink transfer efficiency as compared with the sublimation transfer sheets obtained in Examples 11 to 13.

  From the above results, it is considered that the ink transfer efficiency is further improved by using precipitated silica having an oil absorption amount of 120 to 180 ml / 100 g. In this case, the added amount of precipitated silica is 100 parts by weight of binder. From 100 to 250 parts by weight is considered preferable.

[Verification of cationic resin types]
Next, the type of cationic resin added to the ink receiving layer is verified. Example 1 and Example 14 are the same conditions except for the kind of the cationic resin used, but the sublimation transfer sheet obtained in Example 14 using polydimethylamine epichlorohydrin condensate as the cationic resin is a cationic resin. As a result, the ink transfer efficiency was superior to that of the sublimation transfer sheet obtained in Example 1 using a polyamidine resin. From this, it can be said that a polydimethylamine epichlorohydrin condensate is more suitable as a cationic resin used in the present application than a polyamidine resin.

  Similarly, Example 9 and Example 15 are the same conditions except for the type of the cationic resin used, but the sublimation transfer sheet obtained in Example 15 using polydimethylamine epichlorohydrin condensate as the cationic resin was As a result, the ink transfer efficiency was superior to that of the sublimation transfer sheet obtained in Example 9 using polydiallyldimethylammonium chloride condensate as the cationic resin. From this, it can be said that the polydimethylamine epichlorohydrin condensate is more suitable than the polydiallyldimethylammonium chloride condensate as the cationic resin used in the present application.

  Further, Example 11 and Example 21 were the same except for the type of the cationic resin used, but the sublimation transfer sheet obtained in Example 21 using polydimethylamine epichlorohydrin condensate as the cationic resin was As a result, the ink transfer efficiency was superior to that of the sublimation transfer sheet obtained in Example 11 using a polyamidine resin as the conductive resin. Further, Example 12 and Example 22 were the same conditions except for the type of the cationic resin used, but the sublimation transfer sheet obtained in Example 22 using polydimethylamine epichlorohydrin condensate as the cationic resin was As a result, the ink transfer efficiency was superior to that of the sublimation transfer sheet obtained in Example 12 using a polyamidine resin as the conductive resin. From these, it can be said that a polydimethylamine epichlorohydrin condensate is more suitable as a cationic resin used in the present application than a polyamidine resin.

  From these results, in the sublimation transfer sheet of the present application, it seems that the use of polydimethylamine epichlorohydrin condensate as the cationic resin is effective in further improving the ink transfer efficiency.

  In Examples 1 to 24 and Comparative Examples 1 to 6, the ink transfer efficiency was particularly excellent in the ink receiving layer having a fine pore diameter ratio of 0.1% and an oil absorption of 120 ml / 100 g. To the sublimation transfer sheet obtained in Example 23 using a polydimethylamine epichlorohydrin condensate as a cationic resin, and 170 parts by weight of precipitated silica per 100 parts by weight of the binder, and a fine pore size In Example 24, 150 parts by weight of precipitated silica having a ratio of 0.2% and an oil absorption of 180 ml / 100 g was added per 100 parts by weight of binder, and polydimethylamine epichlorohydrin condensate was used as the cationic resin. It was the obtained sublimation transfer sheet.

  As described above, according to the present invention, it is possible to obtain a clear recorded image that is excellent in water-based ink absorbability and has no bleeding, and further, the ink transfer efficiency to the transfer object during sublimation transfer is improved. It is possible to obtain a good sublimation transfer sheet. An image printed on the transfer object using the sublimation transfer sheet of the present application is very clear because the transfer efficiency of ink from the sublimation transfer sheet to the transfer object is high.

  Further, since it is printed by an ink jet printer, it is suitable for small lot applications such as on-demand, and is suitable for various uses such as sports competition uniforms, T-shirts, tapestry, and banners.

11 Sublimation transfer sheet 12 Sublimation ink 13 Transfer object

Claims (5)

After using ink containing a sublimation dye and printing desired information on a predetermined sublimation transfer sheet by an ink jet printer, the printed sublimation transfer sheet is pressed against an arbitrary transfer object and heated. Thus, a sublimation transfer sheet applied to a sublimation transfer printing system adapted to transfer print the desired information from the sublimation transfer sheet to the transfer object,
A sheet-like substrate;
Including an ink receiving layer provided on one side or both sides of the sheet-like base material,
The ink receiving layer contains a pigment, a binder, and a cationic resin,
As the pigment, precipitated silica is used, and as the binder, any one of starch, starch derivatives, polyvinyl alcohol, modified polyvinyl alcohol, or a mixture of two or more thereof is used.
Sublimation transfer sheet characterized by the above.   The sedimentation silica is characterized in that, in the pore distribution measured by mercury porosimetry, the proportion of pore volume having a pore radius of 100 mm or less is 1% or less with respect to the total pore volume. Item 2. The sublimation transfer sheet according to Item 1.   The precipitated silica is an precipitated silica having an oil absorption of 120 to 180 ml / 100 g, and 100 to 250 parts by weight are blended in the ink receiving layer with respect to 100 parts by weight of the binder. Item 3. The sublimation transfer sheet according to Item 1 or 2.   4. The sublimation transfer sheet according to claim 1, wherein a polydimethylamine epichlorohydrin condensate is used as the cationic resin. 5. The sheet-like base material is mainly composed of pulp, sublimation transfer sheet according to any one of claims 1 to 4 the basis weight is characterized by a 50 to 200 g / m ^2.

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