JP2000025348A - Powder mixture for image receiving sheet combinedly used for sublimation type dye thermal transfer and heat fusion type ink thermal transfer, and image receiving sheet thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder mixture for forming an acceptive layer of an image receiving sheet used combinedly for the sublimation type dye thermal transfer and heat fusion type ink thermal transfer. SOLUTION: A powder mixture for an image receiving sheet used combinedly for the sublimation type dye thermal transfer and the heat fusion type ink transfer is manufactured by blending hydrophobic organic fine particles of 1 nm-1 # mm average particle diameter forming the range of 0.5-15 pts.wt. with a 100 pts.wt. powder coating material composition containing a 70-95 wt.% resin mixture as a resin component, which is composed of a coloring agent and 50-90 wt.% saturated polyester resin of 1.0-20 mgKOH/g acid value and 50-70 deg.C glass transition temperature and 50-10 wt.% styrene and acrylic copolymerized resin, and also containing a reaction curative silicone oil cured material, which is provided with a functional group reactive with carboxyl and/or hydroxyl contained in the saturated polyester resin, forming the range of 0.5-15 wt.% when it is converted on the basis of the reaction curative silicone oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder mixture for an image receiving sheet for both thermal transfer of a sublimation type dye and thermal transfer of a hot melt type ink, and an image receiving sheet. In detail, the present invention has a single layer on a substrate, but has excellent releasability from the ink sheet during thermal transfer of the sublimation dye from the ink sheet, and has a high density by thermal transfer of the sublimation dye. Not only can a transfer image be formed, but also during thermal transfer of hot-melt ink from an ink sheet, the ink from the ink sheet can be well received without repelling and a high-density transfer image can be formed. The present invention relates to a powder mixture for forming a receiving layer of an image receiving sheet, and an image receiving sheet having such a receiving layer on a substrate for both sublimation dye thermal transfer and hot-melt ink thermal transfer.

[0002]

2. Description of the Related Art Conventionally, in order to record information such as characters and images on a recording image receiving sheet using various dyes or inks,
Various thermal transfer recording systems are known. However, no matter what thermal transfer recording method is adopted, the image receiving sheet for thermal transfer recording, that is, the thermal transfer image receiving sheet generally prevents bleeding of the dye or ink thermally transferred to the image receiving sheet, A substance having a function of fixing is dissolved or dispersed in an appropriate solvent, and this is applied on an appropriate substrate in a single layer or a multilayer, and dried. Therefore,
On the one hand, such a thermal transfer image-receiving sheet has to be expensive due to the large number of manufacturing steps, and on the other hand, from the characteristics of the respective recording methods,
If a special thermal transfer image-receiving sheet is not used in each case, a high-quality transfer image cannot be obtained.

As a typical one of the thermal transfer recording methods, a method using thermal transfer of a sublimable dye is known. In the sublimation dye thermal transfer system, for example, a thermal transfer sheet (also referred to as an ink sheet or an ink film; hereinafter, referred to as an ink sheet) in which a sublimable dye layer is formed on an appropriate support such as a polyethylene terephthalate film. Prepared, separately, allowing the dye to penetrate into the surface,
A thermal transfer image-receiving sheet having a dye-receiving layer is prepared, the surface of the ink sheet on the dye layer side is superimposed on the surface of the thermal transfer image-receiving sheet on the receiving layer side, and the image is formed by a heat-sensitive means such as a thermal head. A recording method in which an ink sheet is heated according to information, the dye is transferred to a receiving layer of a thermal transfer image receiving sheet in accordance with the image information, and an image is thermally transferred from the ink sheet to the thermal transfer image receiving sheet.

In such a sublimation dye thermal transfer recording system, conventionally, an image receiving sheet is a resin in which a sublimation dye of an ink sheet can be diffused or transferred by heat onto a base material including a synthetic paper or a synthetic resin sheet. A plurality of resin layers consisting of a receiving layer composed of layers and a release layer composed of a resin layer for preventing fusion between the receiving layer and the ink sheet during heating are sequentially laminated by a wet coating method. It is manufactured by:

That is, in the conventional sublimation dye thermal transfer image-receiving sheet, a solution containing the resin constituting the above-described receiving layer is applied onto a substrate, dried to form a receiving layer, Apply a resin layer to form a release layer on
It is manufactured by drying to form a release layer, and thus separating and laminating a plurality of resin layers for each function. If necessary, an undercoat layer or an intermediate layer may be formed between the substrate and the receiving layer. Therefore, such a conventional thermal transfer image receiving sheet has a complicated manufacturing process and a high manufacturing cost.

Therefore, before the resin layers are laminated on the ink sheet in advance and the yellow, magenta, cyan and black dyes are sequentially transferred to the substrate, the resin layer is first thermally transferred onto the substrate. A dye transfer type full color recording system in which a receptor layer is formed and the above dye is thermally transferred on the receptor layer has also been proposed.

However, according to this method, a long time is required for thermal transfer of the resin layer, a long time is required for full-color transfer as a whole, and it is not easy to form a uniform receiving layer on the base material. There is also a problem that the obtained transferred image is inferior in quality. In addition, there are various technical problems in laminating the resin layer for the receiving layer on the surface of the ink sheet.
As described above, in any case, conventionally, the sublimable dye transfer recording method requires a dedicated sheet for that purpose.

Therefore, Japanese Patent Application Laid-Open No. Hei 8-224970 discloses a resin composition comprising a saturated polyester resin and a styrene-acrylic copolymer resin, a colorant, and at least two kinds of reactive curing compounds having functional groups capable of reacting with each other. It describes that a mixture containing a water-soluble silicone oil is melt-kneaded under heating to produce a powder coating composition for a sublimation dye thermal transfer image-receiving sheet. This powder coating composition is dry-coated on a substrate, heated, melted, and fixed to form a sublimation having a receiving layer as a coating film or a resin layer of the powder coating composition on the substrate. Dye thermal transfer image-receiving sheet can be obtained. Although such a receiving layer is a single layer, it has practical releasability with respect to an ink sheet by a combination of the cured product of the reaction-curable silicone oil and a styrene-acrylic copolymer resin. ing.

However, if such a sublimation dye thermal transfer image-receiving sheet is used as an image receiving sheet for thermal transfer of hot-melt ink, it will have releasability from the ink sheet containing the sublimation dye. Further, since the wet ink is inferior in wettability and the molten ink is repelled, a clear and high-density transfer image cannot be formed on the image receiving sheet. Hot-melt ink Thermal transfer recording method is already well-known, and heats and melts ink on an ink sheet,
This is transferred to an image receiving sheet such as plain paper and fixed.

That is, it is preferable that the thermal transfer type ink thermal transfer image-receiving sheet has wettability to the ink in which the receiving layer is melted, and also has irregularities on the surface. The required characteristics of such a thermal melting type ink thermal transfer image receiving sheet are contrary to the required characteristics of the above-described sublimation type dye thermal transfer image receiving sheet.

Accordingly, an inexpensive image-receiving sheet which can be used for both thermal transfer of a sublimation dye and thermal transfer of a hot-melt ink and which is inexpensive has been strongly demanded because of its convenience. However, since these contradictory required characteristics cannot be satisfied at the same time, they have not been conventionally known.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in response to the above-mentioned demands, and is intended to form a single-layer, high-density transfer image upon thermal transfer of a sublimation dye. And has a high release property with respect to the ink sheet, and also has a high wettability with the molten ink during the thermal transfer of the hot-melt ink to form a high-density transfer image. Thus, it is an object of the present invention to provide a powder mixture for forming a receiving layer of an image receiving sheet which can satisfy both of the above-mentioned contradictory requirements and thermal transfer of a sublimation dye and thermal transfer of a hot melt ink. It is a further object of the present invention to provide an image receiving sheet having both a sublimation type dye thermal transfer and a hot melt type ink thermal transfer having a receiving layer comprising such a powder mixture on a substrate.

[0013]

According to the present invention, a colorant, an acid value of 1.0 to 20 mgKOH / g and a glass transition temperature of 5 are provided.
A resin mixture consisting of 50 to 90% by weight of a saturated polyester resin at 0 to 70 ° C and 50 to 10% by weight of a styrene / acrylic copolymer resin is contained as a resin component in an amount of 70 to 95% by weight. To 100 parts by weight of a powder coating composition containing 0.5 to 15% by weight of a cured product of a reactive curable silicone oil having a functional group capable of reacting with a hydroxyl group and / or a hydroxyl group in terms of the reactive curable silicone oil. Average particle size 1 nm
The present invention provides a powder mixture for an image-receiving sheet for heat transfer of a sublimation dye and heat transfer of a hot-melt ink, which comprises blending hydrophobic inorganic fine particles of 1 to 1 μm in a range of 0.5 to 15 parts by weight.

Further, according to the present invention, a sublimation dye thermal transfer and a hot-melt ink thermal transfer comprising a receiving layer capable of receiving both a sublimation dye and a hot-melt ink formed from the above powder mixture. A dual-purpose image receiving sheet is provided.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The powder mixture for an image-receiving sheet for both thermal transfer of a sublimation dye and thermal transfer of a hot-melt ink according to the present invention comprises a powder coating composition and hydrophobic inorganic fine particles. , Colorant, acid value 1.0-20mgKOH
/ G, a resin mixture consisting of 50 to 90% by weight of a saturated polyester resin having a glass transition temperature of 50 to 70 ° C and 50 to 10% by weight of a styrene / acrylic copolymer resin as a resin component, and 70 to 95% by weight. A cured product of a reaction-curable silicone oil having a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of a saturated polyester resin is contained in an amount of 0.5 to 15% by weight in terms of the reaction-curable silicone oil.

In the present invention, among the resin components, the saturated polyester resin, together with the styrene and acrylic copolymer resins, has a role as a binder resin for combining various components of the powder coating composition into a powder, Forming a resin layer as a sublimable dye receiving layer on the surface, and when recording characters and images by thermal transfer of the sublimable dye, the sublimable dye is diffused into the resin layer, absorbed by the resin layer, and transferred to the image receiving sheet. This makes it possible to perform thermal transfer recording.

The saturated polyester resin used in the present invention is a polymer obtained by condensation polymerization of a dihydric carboxylic acid and a dihydric alcohol, and the divalent carboxylic acid is not limited. Aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, and aromatic dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid, and isophthalic acid And the like. If necessary, a tribasic or higher polybasic acid may be used in combination. Examples of such polybasic acids include trimellitic anhydride and pyromellitic anhydride.

The dihydric alcohol is not limited, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, and hydrogenated bisphenol A. be able to. If necessary, a trihydric or higher polyhydric alcohol may be used in combination. Examples of such polyhydric alcohols include glycerin, trimethylolpropane, diglycerin, pentaerythritol, sorbitol and the like.

The saturated polyester resin used in the present invention must have an acid value in the range of 1.0 to 20 mgKOH / g and a glass transition temperature in the range of 50 to 70 ° C. Commercial products can be suitably used as such a saturated polyester resin. Such commercial products include, for example, Byron RV103, RV20
0, RV290 (manufactured by Toyobo Co., Ltd.), KA-1038C
(Manufactured by Arakawa Chemical Co., Ltd.), TP-220, 235 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Diacron ER-101, F
C-005, 344, 545 (Mitsubishi Rayon Co., Ltd.)
NE-382, 1110 (manufactured by Kao Corporation) and the like.

When the saturated polyester resin does not have an acid value, thermal transfer of the sublimation dye is not sufficient, and a high-density transferred image cannot be obtained. However, when the acid value is too high, fusion occurs between the ink sheet and the thermal transfer image receiving sheet during thermal transfer, and thermal transfer itself cannot be performed. Also, when the glass transition temperature of the saturated polyester resin is too low, fusion occurs between the ink sheet and the thermal transfer image receiving sheet during thermal transfer, and thermal transfer itself cannot be performed.

In the present invention, the styrene-acrylic copolymer resin, together with the saturated polyester resin, serves as a binder resin for combining various components of the powder coating composition into powder, and also serves as a sublimation dye from an ink sheet. During the thermal transfer of the ink, it has a role of giving the releasability to the ink sheet to the receiving layer.

The styrene-acrylic copolymer resin is a copolymer of styrene and (meth) acrylic acid ester. Specifically, the (meth) acrylic acid ester includes, for example, ethyl acrylate and butyl acrylate. , Methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like. In particular, in the present invention, as the styrene / acrylic copolymer resin, for example, styrene / butyl acrylate copolymer, styrene / butyl methacrylate copolymer, styrene / methyl methacrylate copolymer, a mixture thereof and the like are preferably used. .

As such a styrene-acrylic copolymer resin, various commercially available products can be suitably used. Commercially available products include, for example, Hymer UNI-3000, TB-
1800, TBH-1500 (Sanyo Chemical Industry Co., Ltd.)
CPR-100, 600B, 200, 300, X
PA4799, 4800 (manufactured by Mitsui Chemicals, Inc.) and the like.

In the present invention, the powder coating composition comprises, as a resin component, a saturated polyester resin 50 as described above.
~ 90% by weight and styrene / acrylic copolymer resin 50 ~ 1
0% by weight of the resin mixture in the range of 70 to 95% by weight.

In the resin component, the saturated polyester resin has excellent dye or ink receptivity when the ink sheet is heated, and, as will be described later, a cured product obtained by the reaction between the reaction-curable silicone oil and the saturated polyester resin. In the thermal transfer, the ink sheet and the sublimation type thermal transfer image receiving sheet are overlapped, and when the ink sheet is heated, the releasability from the ink sheet is imparted to the thermal transfer image receiving sheet. In this case, the amount of the reaction-curable silicone oil may be increased, but if such a large amount of the reaction-curable silicone oil is added, the image density is significantly reduced by thermal transfer. Therefore, according to the present invention, the saturated polyester resin 50 to 90 is used as the resin component.
Styrene / acrylic copolymer resin 50-1
By using 0% by weight, the releasability of the receiving layer is enhanced while ensuring the transfer density of the saturated polyester resin.

Therefore, when the content of the saturated polyester resin exceeds 90% by weight in the resin component, the transfer image obtained at the time of thermal transfer of the sublimation dye has a relatively high density. Fusion is likely to occur. However, when the content of the saturated polyester resin is less than 50% by weight, that is, when the content of the styrene / acrylic copolymer resin exceeds 50% by weight, the releasability of the receiving layer is high but the image density is insufficient.

In the present invention, the resin component in the powder coating composition preferably comprises the above-mentioned saturated polyester resin and styrene-acrylic copolymer resin.
However, the resin component may contain other resins in a range of less than 10% by weight, if necessary. Examples of such a resin include polyamide resin, (meth) acrylic resin, polyurethane resin, polyvinyl alcohol resin, polyvinyl acetal resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride resin, and polystyrene. Resins, styrene resins such as styrene / acrylic copolymer resins and styrene / butadiene copolymer resins, polyethylene resins, ethylene / vinyl acetate copolymer resins, cellulose resins, epoxy resins and the like can be mentioned.

In the present invention, the powder coating composition usually contains a coloring agent. As the colorant, a white colorant is preferably used in order to give a white ground color to the base material. Examples of such a white colorant include zinc white, titanium oxide, tin oxide, antimony white, zinc sulfide,
Barium carbonate, clay, silica, white carbon, talc, alumina, barite and the like are used, and usually, titanium oxide is preferably used. However, if desired, a colored colorant can be used to impart a colored ground color to the substrate. Such a colorant is usually 0.5 to 30% by weight, preferably, in the powder coating composition,
It is blended in the range of 5 to 25% by weight.

According to the present invention, the powder coating composition is formed into a powder mixture with the inorganic fine particles described below, and the powder coating composition is dry-coated on the surface of the base material, melted by heating, and fixed. In addition, an anti-offset agent may be included, if necessary, so as not to cause an offset. As the anti-offset agent, usually, various waxes having a melting point in the range of 50 to 150 ° C. are preferably used. Specific examples include paraffin wax, polyolefin wax such as polyethylene and polypropylene, fatty acid metal salts, fatty acid esters, higher fatty acids, higher alcohols, and the like. Such an offset preventing agent is usually used in the powder coating composition in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

In the present invention, the powder coating composition is a reaction-curable silicone oil having a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of a saturated polyester resin in a resin component, together with a resin component and a colorant. The cured product imparts releasability to the ink sheet when the image receiving sheet receives a sublimation dye from the ink sheet.

According to the present invention, as the reactive curable silicone oil having a functional group capable of reacting with the carboxyl group and / or hydroxyl group of the saturated polyester resin, a reactive curable silicone oil having an epoxy group (epoxy-modified silicone oil) Curable silicone oil) is preferably used. In particular, according to the present invention, when an epoxy-modified reaction-curable silicone oil having an epoxy equivalent in the range of 100 to 4000 g / mol is used, when a powder coating composition according to the present invention as described below is produced, a saturated polyester resin is used. And the epoxy-modified reaction-curable silicone oil efficiently cause a cross-linking reaction to form a cured product, which gives the receptive layer of the resulting thermal transfer image-receiving sheet excellent release properties. When the epoxy equivalent of the epoxy-modified reaction-curable silicone oil is less than 100 g / mol,
In producing a powder coating composition as described below, a sufficient amount of a cured product is not produced between the composition and a saturated polyester resin.

The epoxy-modified reaction-curable silicone oil has an epoxy group introduced into a polysiloxane, usually dimethylpolysiloxane, at a side chain or at a molecular terminal or both, and various types are already commercially available. Also in the present invention, such commercially available products, for example, KF-10
1 (epoxy equivalent 350 g / mol), KF-105 (epoxy equivalent 490 g / mol), X-22-169AS
(Epoxy equivalent 530 g / mol), X-22-163A
(Epoxy equivalent 950 g / mol), X-22-169B
(Epoxy equivalent 1670 g / mol), X-22-163
B (epoxy equivalent 1760 g / mol), X-22-16
3C (epoxy equivalent 2790 g / mol), KF-102
(Epoxy equivalent 3600 g / mol), KF-1001
(An epoxy equivalent of 4000 g / mol) or the like can be suitably used. However, among these, in the present invention, it is particularly preferable to use an epoxy-modified reaction-curable silicone oil having an epoxy equivalent in the range of 100 to 1000 g / mol.

With respect to such silicone oil,
For example, "Silicone Handbook" (published by Nikkan Kogyo Shimbun on August 31, 1990) describes its properties and manufacturing method in detail.

According to the present invention, the powder coating composition comprises a cured product of such an epoxy-modified reaction-curable silicone oil of 0.5 to 1 in terms of the reaction-curable silicone oil.
5% by weight, preferably in the range of 0.5 to 10% by weight. In the present invention, since the cured product is a reaction product of a reaction-curable silicone oil and a saturated polyester resin, the weight of the epoxy-modified reaction-curable silicone oil in the weight of the cured product is the reaction-curable silicone oil. Use the amount in oil conversion.

In the powder coating composition, when the amount of the cured product of the above reaction-curable silicone oil is less than 0.5% by weight in terms of the reaction-curable silicone oil, such a powder coating composition is used. The thermal transfer image-receiving sheet obtained by using is not sufficient in releasability, and at the time of thermal transfer, the ink sheet and the thermal transfer image-receiving sheet are fused to each other, so that a high quality image cannot be obtained. On the other hand, when the amount of the cured product of the reaction-curable silicone oil in the powder coating composition is more than 15% by weight in terms of the reaction-curable silicone oil, the amount of the cured product in the obtained thermal transfer image-receiving sheet is large. Too low, resulting in a transferred image with inferior density.

According to the present invention, the resin composition, the colorant, and a reactive curable silicone oil having a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of the saturated polyester resin are provided. The mixture comprising, if necessary, together with other additives, is usually about 100 to 200 ° C., preferably 130 to 18 ° C.
It can be obtained by melt-kneading at a temperature of about 0 ° C. for several minutes, usually about 3 to 5 minutes, cooling, pulverizing, and classifying. The powder coating composition has an average particle diameter of 0.1 to 0.1.
It is in the range of 30 μm, preferably in the range of 1 to 25 μm, most preferably in the range of 5 to 20 μm.

According to the present invention, while the mixture is heated and melt-kneaded, the epoxy-modified reaction-curable silicone oil reacts with the saturated polyester resin to form a cured product. However, the heating temperature and time are not particularly limited, and in addition to the resin component and the epoxy-modified reaction-curable silicone oil, as well as components such as a colorant and an anti-offset agent are uniformly mixed, Any condition may be used as long as the reaction-curable silicone oil reacts with the saturated polyester to form a cured product.

As described above, the saturated polyester resin is used when the sublimable dye is thermally transferred from the ink sheet.
When the ink sheet and the sublimation type thermal transfer image receiving sheet are stacked and the ink sheet is heated, it has a role of receiving a sublimable dye, while the styrene / acrylic copolymer resin is
It has a role of giving the receptive layer to the ink sheet when the ink sheet is heated, and the cured product obtained by the reaction between the reactive curable silicone oil and the saturated polyester resin also has a releasability for the ink sheet. To the receiving layer.

As described above, according to the present invention, when the resin component in the powder coating composition and the cured product of the reaction-curable silicone oil are used, the receiving layer can form a high-density transfer image upon thermal transfer of the sublimation dye. And has a releasability from the ink sheet, but according to the present invention, further, by adding hydrophobic inorganic fine particles to the powder coating composition, the sublimation type dye is added to the receiving layer. In addition to the above-described properties for thermal transfer, it also gives wettability to hot-melt ink.

The powder mixture according to the present invention has an average particle diameter of 1 nm to 100 parts by weight of the powder coating composition as described above.
It is obtained by blending hydrophobic inorganic fine particles in a range of 1 μm in a range of 0.5 to 15 parts by weight. In particular, according to the present invention, the amount of the hydrophobic inorganic fine particles to be added to the powder coating composition is preferably in the range of 1 to 12 parts by weight based on 100 parts by weight of the powder coating composition. ,Preferably,
It is in the range of 5 to 10 parts by weight. If the blending ratio of the inorganic fine particles is too small, the wet transferability of the hot-melt ink to the ink is insufficient, and a clear transfer image with high density cannot be obtained. On the other hand, when the amount is too large, the fixing property of the receiving layer to the base material is poor. For example, when the base material is bent, the receiving layer peels off from the base material. Furthermore,
Since the proportion of the resin powder coating composition is relatively small, the formed image density may be insufficient.

When the average particle diameter of the inorganic fine particles is smaller than 1 nm, even if a relatively large amount of the inorganic fine particles is used, the effect of improving the wettability to the molten ink is poor, while the average particle diameter is 1 μm. When larger than, after dry-coating a powder mixture composed of such inorganic fine particles and a powder coating composition on a substrate, even if heated and melted, it is difficult to fix on the substrate. In some cases, the heat-meltable ink image-receiving sheet is peeled off from the base material to cause a defect. Therefore, according to such an image-receiving sheet, a high-quality thermal transfer image cannot be obtained.

The hydrophobic inorganic fine particles include, for example,
Anhydrous silica, titanium dioxide or aluminum oxide which has been subjected to a hydrophobic treatment is preferred, and in particular, anhydrous silica surface-treated with hexamethyldisilazane is preferably used.
As such hydrophobic anhydrous silica, for example, commercially available products such as hydrophobic anhydrous silica H-2000, H-2000 / 4, and H-3004 manufactured by Wacker Chemicals East Japan can be suitably used.

The image-receiving sheet for both the thermal transfer of the sublimation type dye and the transfer of the hot-melt type ink according to the present invention is obtained by dry-coating a powder mixture comprising the above-mentioned powder coating composition and hydrophobic inorganic fine particles on a substrate. Then, heat and melt this, fix it,
It can be obtained by forming a receiving layer. The thickness of the receiving layer is usually in the range of 1 to 100 μm,
The range is preferably 80 μm, and particularly preferably in the range of 5 to 50 μm.

In the present invention, the substrate is usually
Paper, synthetic paper, synthetic resin sheet and the like are preferably used.
The paper is not particularly limited as long as it is made of ordinary cellulose fiber, and in addition to plain paper, high-quality paper,
Including coated paper. Examples of plain paper include ordinary PPC copy paper, calender-treated PPC copy paper to enhance the surface smoothness, and thermal transfer word processor paper and coated paper that have already been surface-treated. Can be mentioned. As the synthetic resin sheet, for example, polyester, polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate,
Examples include sheets made of polycarbonate, polyamide, and the like. Examples of the synthetic paper include those obtained by extruding a mixture of a polyolefin resin or another synthetic resin as a resin component, a required inorganic filler, and the like. In particular, by using paper as the base material, the image receiving sheet for both sublimation dye thermal transfer and hot-melt ink transfer according to the present invention can be manufactured at low cost.

In the present invention, in order to dry-coat a powder coating composition containing inorganic fine particles on a substrate, for example, electrostatic coating such as electrostatic spraying or electrostatic immersion, spraying, spraying, etc. Powder coating such as coating method, dispersion method, powder melt lamination method, dusting method, cascade method, magnetic brush developing method,
Electrophotographic methods such as a powder cloud method, an open chamber method, a liquid developing method, a fur developing method, a printing developing method, and a developing method by electrostatic induction can be used.

Among these dry coatings, in the present invention, for example, an electrostatic spray method can be preferably used. This electrostatic spraying method is a kind of powder coating, and specifically, a powder mixture according to the present invention, which is atomized at the tip of a spray gun, that is, a powder comprising a powder coating composition and inorganic fine particles. The body mixture is transported by air, and a negative high voltage (for example, -50 to -90 kV) is applied to a needle electrode incorporated at the tip of the spray gun to negatively charge the powder mixture. A grounded electrode is placed along the back surface of the substrate, and thus the negatively charged powder mixture is carried to the substrate and electrostatically deposited by the electric field present between the spray gun and the grounded electrode. It is.

FIG. 1 shows a preferred embodiment of a method for producing an image-receiving sheet for sublimation dye thermal transfer and hot-melt ink transfer according to the present invention using such an electrostatic spray method. That is, the continuous long base material (for example, plain paper) 2 unwound from the roll 1 is guided into the booth 4 by the conveyor belt 3, and here, as described later, by the electrostatic spray method. After the powder mixture is dry-coated, the powder mixture is heated and melted by a fixing roll 5 and fixed, and then wound around a roll or cut as appropriate. After passing through the fixing roll 5, it is wound around the roll again or cut as appropriate. The transport belt 3 has a grounded (ie, positive) electrode 6 on the back side along the base material to which it is transported. The powder mixture is conveyed from the storage tank 7 to the spray gun 8 by compressed air, while a negative high voltage is applied by a DC power supply 9 to a needle electrode (not shown) incorporated at the tip of the spray gun. The powder mixture is negatively charged. Thus, the powder mixture is carried to and adheres to the base paper by the electric field present between the spray gun and the electrodes along the substrate on the conveyor belt. In this way, the substrate on which the powder mixture is dry-coated is guided to the fixing roll 5, where the powder mixture is heated and melted and fixed on the substrate, and the resin layer (receiving layer) is formed. Once formed, the image receiving sheet 10 according to the present invention can be obtained.

When the powder mixture according to the present invention is dry-coated on a substrate by a dry coating method using various electrostatic recording methods including an electrophotographic method, the powder mixture should contain a charge controlling agent. Is preferred.

The charge control agent is a fine particle solid compounded to give a required frictional charge to a toner in a recording system such as an electrophotographic system or another electrostatic latent image system. Various types are already known. For example, Japanese Patent Application Laid-Open No. 5-323664 discloses various charge control agents according to the polarity. The charge control agent is used in an amount of usually 0.1 to 15% by weight, preferably 1 to 10% by weight in the powder mixture.

[0050]

As described above, the powder mixture for an image-receiving sheet for both heat transfer of a sublimation dye and transfer of a hot-melt ink according to the present invention contains a colorant, a resin component and a cured product of a reaction-curable silicone oil. An image-receiving sheet comprising a powder coating composition and hydrophobic inorganic fine particles, which is used for both sublimation dye thermal transfer and hot-melt ink transfer according to the present invention, is obtained by dry-coating such a powder mixture on a substrate. , By heating, melting and fixing to form a receptor layer.

The receiving layer composed of such a powder mixture comprises:
Despite being a single layer, at the time of thermal transfer of the sublimation dye from the ink sheet, it has excellent releasability from the ink sheet, and can form a high-density transfer image by thermal transfer of the sublimation dye. In the thermal transfer of the hot-melt ink from the ink sheet, the ink from the ink sheet can be well received without repelling and a high-density transfer image can be formed. That is, according to the present invention, it is possible to solve the problem of the contradictory required characteristics of the thermal transfer of the sublimation dye and the thermal transfer of the hot-melt ink, and to obtain an image receiving sheet that is used for both the thermal transfer of the sublimation dye and the thermal transfer of the hot-melt ink. Can be.

[0052]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 (Preparation of powder coating composition and powder mixture) Saturated polyester resin (NE-382, manufactured by Kao Corporation, acid value 8.9 mgK)
OH / g, glass transition point 62.6 ° C) 44 parts by weight, styrene / acrylic copolymer resin (TB- manufactured by Sanyo Chemical Industries, Ltd.)
1804) 44 parts by weight, 4 parts by weight of an anti-offset wax (Viscol 550P manufactured by Sanyo Chemical Industries, Ltd.), 7 parts by weight of titanium oxide as a white pigment, and epoxy-modified silicone oil (KF manufactured by Shin-Etsu Chemical Co., Ltd.) -1
01, an epoxy equivalent of 350 g / mol), 1 part by weight of a mixer was mixed and stirred, and then mixed with a biaxial melt kneader at 150 to 1 part.
Melt kneading was performed at 60 ° C. for 3 to 5 minutes. After cooling, the obtained kneaded product was pulverized and classified to obtain a white powder coating composition having an average particle size of 10 μm. This white powder coating composition 10
0 parts by weight of hydrophobic anhydrous silica (H-2000 / 4 manufactured by Wacker Chemicals East Asia, average particle size 16n)
m) 3 parts by weight were mixed to obtain a white powder mixture for dry coating by an electrostatic spray method.

(Production of Image Receiving Paper) The white powder mixture was applied to the entire surface of a commercially available plain paper using a commercially available electrostatic spray device, and then heated, melted, and fixed to a thickness of 2 mm.
A receiving layer having a thickness of 0 μm was formed to obtain an image receiving paper for thermal transfer recording of a sublimable dye.

(Thermal Transfer of Sublimable Dye) Using a sublimation type thermal transfer high-speed printer, the ink sheet and the thermal transfer image receiving paper are overlapped so that the surface on the dye layer side and the receptor layer are in contact under the following thermal transfer conditions. Then, the ink sheet was heated by a thermal head to transfer the dye to the receiving layer of the thermal transfer image receiving paper. In this transfer image, the image density (yellow, magenta, cyan) and the releasability of the ink sheet were evaluated. Table 1 shows the results.

Transfer conditions of sublimation type thermal transfer type high-speed printer Thermal head: KGT-219-12MPL2 (manufactured by Kyocera) Driving voltage: 17V Line speed: 4ms

Sublimable dye of ink sheet Sublimable dye Yellow: styryl-based yellow dye Sublimable dye magenta: Anthraquinone-based magenta dye Sublimable dye cyan: Indoaniline-based cyan dye

Test Method The image density was measured using a densitometer (PDA-60 manufactured by Konica).
Was used to measure the reflection density.

In order to check the releasability from the ink sheet,
High-speed printability, presence or absence of white spots caused by peeling of the printed image from the receiving layer, presence or absence of ink sheet adhering to the receiving layer, and differences that occur when the ink sheet and the receiving paper are peeled off during printing. The loudness of the sound was comprehensively examined and evaluated in the following three grades.

：: No abnormal noise generated at the time of transfer without peeling of the receiving layer and adhesion of the ink sheet. Δ: There was little peeling of the receiving layer and adhesion of the ink sheet,
Abnormal noise generated during transfer. ×: High-speed printing was not possible, or the receiving layer was peeled off or the ink sheet was remarkably adhered.

(Thermal transfer of hot-melt ink) A commercially available hot-melt thermal transfer printer (G370-7 manufactured by Mitsubishi Electric Corporation)
0), the ink sheet and the thermal transfer image receiving paper are overlapped so that the surface on the ink layer side and the receiving layer of the image receiving paper are in contact with each other under the following transfer conditions, and the ink sheet is heated by a thermal head. Thus, the ink was transferred to the receiving layer of the image receiving paper. For this thermal transfer image, the print density (yellow, magenta, cyan) and the resistance to bleeding of the ink on the image receiving paper were evaluated. Table 2 shows the results.

Test Method The print density was determined using a densitometer (PDA-60 manufactured by Konica).
Was used to measure the reflection density.

In order to examine the bleeding resistance of the ink on the image receiving paper, printability and resolution were comprehensively examined and evaluated in the following three grades. Table 1 shows the results.

○: One dot size on the image receiving paper is about 1.0 to 1.5 times the specified value. Δ: One dot size on the image receiving paper is about 1.5 to 2.0 times the specified value. ×: Ink is popped on the surface of the image receiving paper to form no image, or the size of one dot on the image receiving paper is 2.0 times or more of the specified value.

Example 2 (Preparation of powder coating composition and powder mixture) Saturated polyester resin (FC-545, manufactured by Mitsubishi Rayon Co., Ltd., acid value 4.
75 mg by weight of 1 mg KOH / g, glass transition point 52.5 ° C., 13 parts by weight of styrene / acrylic copolymer resin (TB-1804 manufactured by Sanyo Chemical Industry Co., Ltd.), wax as an anti-offset agent (Sanyo Chemical Industry Co., Ltd.) ) Viscole 5
50P) 4 parts by weight, 7 parts by weight of titanium oxide as a white pigment and epoxy-modified silicone oil (KF-101 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 350 g / mol)
After mixing and stirring 1 part by weight with a mixer, the mixture was melt-kneaded at 150 to 160 ° C. for 3 to 5 minutes with a biaxial melt kneader.
After cooling, the obtained kneaded product was pulverized and classified to obtain a white powder coating composition having an average particle size of 10 μm. To 100 parts by weight of this white powder coating composition, 10 parts by weight of hydrophobic anhydrous silica (H-2000, manufactured by Wacker Chemicals East Asia Co., average particle diameter: 14 nm) is mixed, and dry-coated by electrostatic spraying. White powder mixture.

In the same manner as in Example 1, an image receiving paper was prepared using the white powder mixture, and the ink sheet was transferred from the ink sheet to the image receiving paper using a sublimation type thermal transfer high-speed printer and a fusion type thermal transfer type printer. Thermal transfer of the dye and ink was performed.

The transfer performance of each of the thermal transfer images thus obtained was evaluated in the same manner as in Example 1. Table 1 shows the results of the thermal transfer of the sublimation dye, and Table 2 shows the results of the thermal transfer of the hot-melt ink.

Comparative Example 1 In Example 1, hydrophilic anhydrous silica (Aerosil 20 manufactured by Nippon Aerosil Co., Ltd.) was used instead of hydrophobic anhydrous silica (H-2000 / 4) treated with hexamethyldisilazane.
0, average particle diameter 12 nm) Except for using 3 parts by weight, a white powder mixture was prepared in the same manner as in Example 1, and an image receiving paper was prepared using the white powder mixture. The dye and the ink were thermally transferred from the ink sheet to the image receiving paper using a sublimation type thermal transfer type high-speed printer and a fusion type thermal transfer type printer.

The transfer performance of each of the thus obtained thermal transfer images was evaluated in the same manner as in Example 1. Table 1 shows the results of the thermal transfer of the sublimation dye, and Table 2 shows the results of the thermal transfer of the hot-melt ink.

Comparative Example 2 In Example 1, hydrophobic anhydrous silica treated with dimethyldichlorosilane (manufactured by Nippon Aerosil Co., Ltd.) was used instead of hydrophobic anhydrous silica (H-2000 / 4) treated with hexamethyldisilazane. R972, average particle diameter 16 nm) 3
Except for using parts by weight, a white powder mixture was prepared in the same manner as in Example 1, and an image receiving paper was prepared using the mixture. Dye and ink were thermally transferred from the ink sheet to the image receiving paper, respectively, using a fusion type thermal transfer printer.

The transfer performance of each of the thus obtained thermal transfer images was evaluated in the same manner as in Example 1. Table 1 shows the results of the thermal transfer of the sublimation dye, and Table 2 shows the results of the thermal transfer of the hot-melt ink.

[0072]

[Table 1]

[0073]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an example of an apparatus configuration showing the production of a sublimation dye thermal transfer image receiving sheet according to the present invention.

[Description of Signs] 1 ... roll, 2 ... long base material (for example, plain paper), 3 ...
Conveyor belt, 4 booth, 5 fixing roll, 6 electrode,
7 ... Storage tank, 8 ... Spray gun, 9 ... DC power supply, 10 ...
Sublimation dye thermal transfer image receiving sheet.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Fumio Matsui Inventor F-term in Pioneer Research Institute, 6-1-1-1 Fujimi, Tsurugashima-shi, Saitama F-term (reference) 2H111 AA26 AA27 CA03 CA30 CA31 CA32 CA47 CA48

Claims (8)

[Claims] 1. A colorant, having an acid value of 1.0 to 20 mg KOH /
g, 50 to 90% by weight of a saturated polyester resin having a glass transition temperature of 50 to 70 ° C. and styrene / acrylic copolymer resin 5
A reaction-curable silicone oil containing 70 to 95% by weight of a resin mixture of 0 to 10% by weight as a resin component and having a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of the saturated polyester resin. Hydrophobic inorganic fine particles having an average particle diameter of 1 nm to 1 μm are added to 100 parts by weight of a powder coating composition containing the cured product in an amount of 0.5 to 15% by weight in terms of the reaction curable silicone oil.
A powder mixture for an image-receiving sheet for thermal transfer of a sublimation dye and thermal transfer of a hot-melt ink, which is blended in a range of 0.5 to 15 parts by weight. 2. The powder mixture for an image receiving sheet according to claim 1, wherein the hydrophobic inorganic fine particles are inorganic fine particles surface-treated with hexamethyldisilazane. 3. The powder mixture for an image receiving sheet according to claim 1, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 4. The reaction-curable silicone oil has an epoxy group as a functional group and has an epoxy equivalent of 100 to 4000.
The powder mixture for an image receiving sheet according to claim 1, wherein the amount is g / mol. 5. An image receiving sheet for heat transfer of a sublimation dye and heat transfer of a hot melt ink having a receptor layer for receiving a sublimation dye and a heat melting type ink on a substrate, comprising a colorant, an acid value of 1.0 to 1.0. 20 mg KOH / g, glass transition temperature 50-7
A resin mixture comprising 50 to 90% by weight of a saturated polyester resin at 0 ° C. and 50 to 10% by weight of a styrene / acrylic copolymer resin is contained as a resin component in an amount of 70 to 95% by weight. And / or 100 parts by weight of a powder coating composition containing a cured product of a reactive curable silicone oil having a functional group capable of reacting with a hydroxyl group in an amount of 0.5 to 15% by weight in terms of the reactive curable silicone oil. Average particle size 1nm ~ 1μ
m, wherein the receiving layer is formed from a powder mixture comprising 0.5 to 15 parts by weight of hydrophobic inorganic fine particles for both sublimation dye thermal transfer and hot-melt ink thermal transfer. Image receiving sheet. 6. The image receiving sheet according to claim 5, wherein the hydrophobic inorganic fine particles are inorganic fine particles surface-treated with hexamethyldisilazane. 7. The image receiving sheet according to claim 5, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 8. The reaction-curable silicone oil has an epoxy group as a functional group and has an epoxy equivalent of 100 to 4000.
The image receiving sheet according to claim 5, wherein the amount is g / mol.