JP2000025347A - Powder mixture for sublimation type dye thermal transfer image receptor sheet and sublimation type dye thermal transfer image receptor sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder mixture for the manufacture of a sublimation type dye thermal transfer image receptor sheet, excellent in mold releasing property from an ink sheet even though the layer is a single layer and capable of forming a receptor layer providing a high-density heat transfer picture on a substrate, and, further, provide the sublimation type dye thermal transfer image receptor sheet having the receptor layer, consisting of such a powder mixture, on the substrate. SOLUTION: A powder mixture for a sublimation type dye thermal transfer receptor sheet, consisting of 100 pts.wt. of powdered coating composition containing a coloring agent and a saturated polyester resin having acid value of 1.0-20 mgKOH/g and the glass transition temperature of 50-70 deg.C blended with the range of 0.5-15 pts.wt. of hydrophobic inorganic fine grain, is provided. The powdered coating composition is preferable to contain 0.5-15 wt.% of cured substance of reaction curing silicone oil having a functional group, capable of reacting with carboxylic group and/or hydroxylic group contained in the saturated polyester resin, in the terms of a reaction curing 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 forming a receptor layer of an image receiving sheet for forming an image by thermal transfer of a sublimation dye, and a sublimation dye having such a receptor layer on a substrate. Regarding the thermal transfer image receiving sheet, in detail, while being a single layer on the substrate, excellent in releasability, and, furthermore, a sublimation dye thermal transfer image receiving sheet capable of forming a high density image by thermal transfer of the sublimation dye, It relates to a powder mixture for forming such an image receiving sheet.

[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. Preparation, separately, to prepare a thermal transfer image-receiving sheet provided with a receiving layer for receiving the dye on the surface, the dye layer side surface of the ink sheet is superimposed on the receiving layer side surface of the thermal transfer image receiving sheet, The ink sheet is heated according to the image information by a heat-sensitive means such as a head, and the dye is transferred to the receiving layer of the thermal transfer image receiving sheet in accordance with the image information, and the image is transferred from the ink sheet to the thermal transfer image receiving sheet. Is a recording method in which is thermally transferred.

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, the combination of the cured product of the reaction-curable silicone oil and the styrene-acrylic copolymer resin of the resin components makes it practical for ink sheets. It has a good release property.

In such a conventional sublimation type dye thermal transfer image-receiving sheet, all of the above resin components play a role as a binder resin for combining various components of the powder coating composition into powder. In addition, the saturated polyester resin plays an important role in absorbing and receiving a sublimable dye forming an image during thermal transfer of an image from an ink sheet, while a styrene-acrylic copolymer resin is As described above, it is important to provide releasability so that the receiving layer does not fuse to the ink sheet.

[0010] Therefore, the above-mentioned conventional receiving layer, at the expense of the density of the thermal transfer image formed by the sublimable dye,
The releasability of the receiving layer is ensured by the styrene / acrylic copolymer resin, and there is a regret that the density of the thermal transfer image of the sublimation dye is not sufficient. If only the saturated polyester resin is used as the resin component, the density of the thermal transfer image can be increased, but the saturated polyester resin easily fuses with the ink sheet during thermal transfer of the sublimation dye to the image receiving sheet,
Therefore, it is not possible to obtain a practical image-receiving sheet that does not fuse with an ink sheet during thermal transfer of a dye, using only a saturated polyester resin as a resin component.

Further, 2 having a mutually reactive functional group.
As a kind of reaction-curable silicone oil, a reaction-curable silicone oil having an amino group and a reaction-curable silicone oil having an epoxy group are actually used. The powder coating composition obtained by using the one having an amino group turns yellow during storage and colors the receiving layer, which should be originally white, so that it can be used for the production of a thermal transfer image-receiving sheet. Disappears.

[0012]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the sublimation type dye thermal transfer image-receiving sheet and the powder coating composition therefor. A sublimation dye thermal transfer image-receiving sheet capable of forming a receiving layer that gives a high-density thermal transfer image while having excellent releasability from an ink sheet by a single process on a substrate without any change. It is intended to provide a powder mixture for production. A further object of the present invention is to provide a sublimation dye thermal transfer image-receiving sheet 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.
With respect to 100 parts by weight of a powder coating composition containing a saturated polyester resin at 0 to 70 ° C, hydrophobic inorganic fine particles are added in an amount of 0.5 to 0.5%.
A powder mixture for a sublimation dye thermal transfer image-receiving sheet, which is blended in an amount of 15 parts by weight, is provided.

Further, according to the present invention, there is provided a sublimation dye thermal transfer image-receiving sheet comprising a receiving layer for receiving a sublimation dye formed from the above powder mixture.

Further, according to the present invention, a colorant and an acid value of 1.
0-20 mgKOH / g, glass transition temperature 50-70 ° C
A cured product of a saturated polyester resin having a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of the saturated polyester resin is obtained by converting the cured product to 0.5 in terms of the reaction curable silicone oil.
The present invention provides a powder mixture for a sublimation dye thermal transfer image-receiving sheet, wherein hydrophobic inorganic fine particles are blended in a range of 0.5 to 15 parts by weight with respect to 100 parts by weight of a powder coating composition containing 0.1 to 15% by weight. .

Further, according to the present invention, there is provided a sublimation dye thermal transfer image-receiving sheet comprising a receiving layer for receiving a sublimation dye formed from the above powder mixture.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The powder mixture for a sublimation dye thermal transfer image-receiving sheet according to the present invention comprises a powder coating composition and hydrophobic inorganic fine particles.
1.0-20 mgKOH / g, glass transition temperature 50-70
° C saturated polyester resin.

In the present invention, the saturated polyester resin functions as a binder resin for combining various components of the powder coating composition into a powder and forms a resin layer as a sublimable dye receiving layer on a substrate. Then, when recording characters and images by thermal transfer of the sublimable dye, the sublimable dye is diffused in the resin layer and absorbed by the resin layer to enable thermal transfer recording on the image receiving sheet.

The saturated polyester resin used in the present invention is a polymer obtained by the 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, but includes, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A and the like. 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 transfer 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.

According to the present invention, in the powder coating composition, the content of the saturated polyester resin is usually 70 to 95% by weight.
It is blended in the range. In the present invention, the resin component in the powder coating composition preferably comprises only the saturated polyester resin as described above, but in the powder coating composition, the other resin is contained in an amount less than 10% by weight. May be included. 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, which is dry-coated on the surface of the substrate, 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.

According to the present invention, by using substantially only a saturated polyester resin as a resin component in the powder coating composition, a high-density image can be ensured during thermal transfer of the sublimation dye, A hydrophobic inorganic fine particle is blended in the product, and the hydrophobic inorganic fine particle can impart sufficient releasability to the receiving layer.

That is, in the powder mixture for a sublimation dye thermal transfer image-receiving sheet according to the present invention, hydrophobic inorganic fine particles having an average particle diameter in the range of 1 nm to 1 μm are added to 100 parts by weight of the powder coating composition as described above. It is blended 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. When the mixing ratio of the inorganic fine particles is too small,
When the ink sheet is superimposed on the image receiving sheet and heated, the image receiving sheet is easily fused. 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, the proportion of the resin powder coating composition is relatively too small, and 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 releasability of the receiving layer from the ink sheet is poor. Is larger than 1 μm, the powder mixture composed of such inorganic fine particles and the powder coating composition is dry-coated on a substrate, and then fixed on the substrate even by heating and melting. It is difficult and peels off from the substrate to cause a defect in the obtained sublimable dye thermal transfer image-receiving sheet. 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,
Preferably, anhydrous silica, titanium dioxide or aluminum oxide is subjected to a hydrophobic treatment, and in particular, inorganic fine particles surface-treated with hexamethyldisilazane are preferably used. Among such hydrophobic inorganic fine particles, hydrophobic anhydrous silica surface-treated with hexamethyldisilazane is, for example, hydrophobic anhydrous silica H-2000, H-2000 / 4 manufactured by Wacker Chemicals East Japan,
It can be obtained as a commercial product such as H-3004.

According to the present invention, a cured product of 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 is contained in a powder coating composition as a release agent. Can be done. This cured product gives the thermal transfer image-receiving sheet a more excellent releasability when combined with the above-mentioned hydrophobic inorganic fine particles.

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, it is preferable to use an epoxy-modified reaction-curable silicone oil having an epoxy equivalent in the range of 100 to 4000 g / mol.
In the production of the powder coating composition according to the present invention as described below, a saturated polyester resin and an epoxy-modified reaction-curable silicone oil efficiently undergo a crosslinking reaction to produce an effective amount of a cured product, and the resulting thermal transfer image-receiving image is obtained. This is because excellent releasability can be imparted to the receiving layer of the sheet.

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 powder coating composition has a saturated polyester resin, a colorant and, if necessary, a functional group capable of reacting with a carboxyl group and / or a hydroxyl group of the saturated polyester resin. A mixture comprising the reaction-curable silicone oil and, if necessary, together with other additives, is usually at a temperature of about 100 to 200 ° C, preferably about 130 to 180 ° C for several minutes, usually
It can be obtained by melt-kneading for about 3 to 5 minutes, cooling, pulverizing and classifying. The powder coating composition has an average particle size in the range of 0.1 to 30 μm, preferably in the range of 1 to 25 μm, most preferably 5 to 25 μm.
２０20 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, according to the present invention, the hydrophobic inorganic fine particles are used as an external release agent, and the reaction-cured product of the reaction-curable silicone oil and the saturated polyester resin is used as the internal release agent. By using as a resin in the powder coating composition, while substantially using only a saturated polyester resin, in the thermal transfer of the sublimable dye, while ensuring a high density image, sufficient releasability of the receiving layer is obtained. You can give it.

The sublimation type dye thermal transfer image-receiving sheet according to the present invention is obtained by dry-coating a powder mixture comprising the above-described powder coating composition and hydrophobic inorganic fine particles on a substrate, and heating and melting the mixture. It can be obtained by fixing and forming a receiving layer. The thickness of the receiving layer is usually from 1 to 100.
μm, preferably in the range of 2 to 80 μm,
In particular, it is 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 sublimable dye thermal transfer image-receiving sheet 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 a sublimable dye thermal transfer image-receiving sheet according to the present invention by using such an electrostatic spray method. That is, a continuous long base material (for example, plain paper) 2 unwound from the roll 1
Guided into the booth 4 by the conveyor belt 3, where:
As described later, after the powder mixture is dry-coated by an electrostatic spray method, 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 needle electrode (not shown) incorporated at the tip of the spray gun has:
A high negative voltage is applied by the DC power supply 9, and 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 sublimable dye thermal transfer 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 particulate solid compounded in order to give a required triboelectric charge to a so-called 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.

[0046]

As described above, the powder mixture for a sublimable dye thermal transfer image-receiving sheet according to the present invention has a hydrophobic property in a powder coating composition containing a colorant, a resin component and a cured product of a reaction-curable silicone oil. A sublimable dye thermal transfer image-receiving sheet according to the present invention, comprising inorganic fine particles, is prepared by dry-coating such a powder mixture on a substrate, heat-melting, fixing, and forming a receptor layer. Obtainable.

Here, since the resin component in the powder coating composition consists essentially of a saturated polyester resin, a high-density transfer image can be formed by thermal transfer of the sublimation dye. Has a cured product formed by reaction of a reactive curable silicone oil with a carboxyl group and / or a hydroxyl group of a saturated polyester resin, and further has hydrophobic inorganic fine particles. Has high mold release properties.

[0048]

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.) 89 parts by weight, 4 parts by weight of an anti-offset wax (Viscol 550P manufactured by Sanyo Chemical Industry Co., Ltd.) and 7 parts by weight of titanium oxide as a white pigment were mixed with a mixer. After mixing and stirring, the mixture was melt-kneaded at 150 to 160 ° C. for 3 to 5 minutes using a biaxial melt kneader. After cooling, the obtained kneaded material is pulverized and classified,
A white powder coating composition having an average particle size of 10 μm was obtained. 100 parts by weight of this white powder coating composition was added to a hydrophobic anhydrous silica (H-2000 / Wacker Chemicals East Asia).
4, average particle diameter of 16 nm) to obtain a white powder mixture for dry coating by electrostatic spraying.

(Manufacture of Image Receiving Paper for Sublimation Dye Thermal Transfer Recording)
The above-mentioned white powder mixture is adhered to the entire surface of a commercially available plain paper using a commercially available electrostatic spray device, and then heated, melted, and fixed to form a 20 μm-thick receiving layer. An image receiving paper for heat transfer recording of a dye was obtained.

(Thermal Transfer of Sublimable Dye) Using a sublimation type thermal transfer type high-speed printer, under the following thermal transfer conditions, 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 with each other. 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. The results are shown in Evidence 1.

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

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.

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.

◎: Neither peeling of the receiving layer nor adhesion of the ink sheet occurred, and the noise generated during transfer was small. ：: There was no peeling of the receiving layer, but there was some adhesion of the ink sheet. The abnormal noise generated during transfer is small. 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.

Example 2 88 parts by weight of a saturated polyester resin (NE-382, manufactured by Kao Corporation, acid value: 8.9 mg KOH / g, glass transition point: 62.6 ° C.), wax as an offset inhibitor (Sanyo Chemical Industries, Ltd.) 4 parts by weight of Viscol 550P), 7 parts by weight of titanium oxide as a white pigment, and 1 part by weight of an epoxy-modified silicone oil (KF-101 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 350 g / mol) were mixed with a mixer. After stirring, the mixture was melt-kneaded at 150 to 160 ° C. for 3 to 5 minutes using 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. 100 parts by weight of the white powder coating composition was added to a hydrophobic anhydrous silica (Hacker, manufactured by Wacker Chemicals East Asia).
(−2000/4, average particle diameter: 16 nm) 3 parts by weight to obtain a white powder mixture for dry coating by electrostatic spraying.

Using this white powder mixture, an image receiving paper for sublimation dye thermal transfer recording was prepared in the same manner as in Example 1.
The dye was thermally transferred from the ink sheet using a high-speed sublimation thermal transfer printer, and the releasability from the ink sheet and the image density were evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 Saturated polyester resin (FC-5 manufactured by Mitsubishi Rayon Co., Ltd.)
45, acid value 4.1 mgKOH / g, glass transition point 52.5
° C) 88 parts by weight, 4 parts by weight of wax (Viscol 550P manufactured by Sanyo Chemical Industry Co., 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.) −101,
After mixing and stirring 1 part by weight of an epoxy equivalent (350 g / mol) with a mixer, the mixture is mixed at 150 to 160 ° C. with a biaxial melt kneader.
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. 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.

Using this white powder mixture, an image receiving paper for sublimation dye thermal transfer recording was prepared in the same manner as in Example 1.
The dye was thermally transferred from the ink sheet using a high-speed sublimation thermal transfer printer, and the releasability from the ink sheet and the image density were evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 4 88 parts by weight of a saturated polyester resin (NE-382, manufactured by Kao Corporation, acid value: 8.9 mg KOH / g, glass transition point: 62.6 ° C.), wax as an offset inhibitor (Sanyo Chemical Industries, Ltd.) 4 parts by weight of Viscol 550P), 7 parts by weight of titanium oxide as a white pigment, and 1 part by weight of an epoxy-modified silicone oil (KF-101 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 350 g / mol) were mixed with a mixer. After stirring, the mixture was melt-kneaded at 150 to 160 ° C. for 3 to 5 minutes using 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.

Hydrophilic aluminum oxide (aluminum oxide C manufactured by Nippon Aerosil Co., Ltd., average particle diameter 13n)
The surface of m) was treated with hexamethyldisilazane to obtain a hydrophobic aluminum oxide. The white powder coating composition 1
6 parts by weight of this hydrophobic aluminum oxide was mixed with 00 parts by weight to obtain a white powder mixture for dry coating by an electrostatic spray method.

Using this white powder mixture, an image receiving paper for sublimation dye thermal transfer recording was prepared in the same manner as in Example 1.
The dye was thermally transferred from the ink sheet using a high-speed sublimation thermal transfer printer, and the releasability from the ink sheet and the image density were evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 5 88 parts by weight of a saturated polyester resin (NE-382, manufactured by Kao Corporation, acid value: 8.9 mgKOH / g, glass transition point: 62.6 ° C.), wax as an offset inhibitor (Sanyo Chemical Industries, Ltd.) 4 parts by weight of Viscol 550P), 7 parts by weight of titanium oxide as a white pigment, and 1 part by weight of an epoxy-modified silicone oil (KF-101 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 350 g / mol) were mixed with a mixer. After stirring, the mixture was melt-kneaded at 150 to 160 ° C. for 3 to 5 minutes using 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.

Hydrophilic titanium oxide (Nippon Aerosil Co., Ltd.)
(P25, average particle diameter 21 nm) was treated with hexamethyldisilazane to obtain hydrophobic titanium oxide. 9 parts by weight of this hydrophobic aluminum oxide was mixed with 100 parts by weight of the white powder coating composition to obtain a white powder mixture for dry coating by electrostatic spraying.

Using this white powder mixture, an image receiving paper for sublimable dye thermal transfer recording was prepared in the same manner as in Example 1.
The dye was thermally transferred from the ink sheet using a high-speed sublimation thermal transfer printer, and the releasability from the ink sheet and the image density were evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 In Example 1, hydrophilic anhydrous silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was used instead of the hydrophobic anhydrous silica (H-2000 / 4 manufactured by Wacker Chemicals East Asia, average particle diameter: 16 nm). , Average particle size 12 nm) 3
A white powder mixture was prepared in the same manner as in Example 1 except that the parts by weight were used, and an image receiving paper for sublimation dye thermal transfer recording was prepared using the same, and sublimation was performed in the same manner as in Example 1. An attempt was made to thermally transfer a dye from an ink sheet using a high-speed printer of the thermal transfer type. However, the image receiving paper was fused with the ink sheet (level X), and a thermal transfer image could not be obtained.

Comparative Example 2 In Example 1, hydrophobic anhydrous silica (Nippon Aerosil) treated with dimethyldichlorosilane was used in place of the hydrophobic anhydrous silica (H-2000 / 4 manufactured by Wacker Chemicals East Asia, average particle diameter: 16 nm). R97 manufactured by
2, average particle diameter 16 nm) A white powder mixture was prepared in the same manner as in Example 1 except that 3 parts by weight was used, and a sublimation dye thermal transfer recording receiving paper was prepared using the white powder mixture. In the same manner as in Example 1, an attempt was made to perform thermal transfer of the dye from the ink sheet using a high-speed sublimation-type thermal transfer printer, but the image receiving paper was fused to the ink sheet (level of △).
A thermal transfer image could not be obtained.

[0069]

[Table 1]

[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.

[Explanation of symbols]

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 from the front page (72) Fumio Matsui Inventor F-term (reference) 2H111 AA27 CA03 CA31 CA32 CA41 4J038 DD001 DD241 DL032 DL052 GA06 GA07 GA15 HA216 HA446 KA15 KA20 MA02 MA13 MA14

Claims (14)

[Claims] 1. A colorant, having an acid value of 1.0 to 20 mg KOH /
g, 100 parts by weight of a powder coating composition containing a saturated polyester resin having a glass transition temperature of 50 to 70 ° C., and 0.5 to 15 parts by weight of hydrophobic inorganic fine particles having an average particle size of 1 nm to 1 μm. A powder mixture for a sublimation dye thermal transfer image receiving sheet, which is blended. 2. The powder mixture for a sublimation dye thermal transfer 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 a sublimation dye thermal transfer image-receiving sheet according to claim 1, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 4. A colorant and an acid value of 1.0 to 20 mg KOH /
g, a cured product of a saturated polyester resin having a glass transition temperature of 50 to 70 ° C. 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. With respect to 100 parts by weight of a powder coating composition containing 0.5 to 15% by weight in terms of oil, the average particle size is 1 nm to 1%.
A powder mixture for a sublimation dye thermal transfer image-receiving sheet, comprising 0.5 to 15 parts by weight of hydrophobic inorganic fine particles having a particle diameter of 0.5 μm. 5. The powder mixture for a sublimation dye thermal transfer image-receiving sheet according to claim 4, wherein the hydrophobic inorganic fine particles are inorganic fine particles surface-treated with hexamethyldisilazane. 6. The powder mixture for a sublimation dye thermal transfer image-receiving sheet according to claim 4, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 7. 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 a sublimation dye thermal transfer image-receiving sheet according to claim 1, wherein the amount is g / mol. 8. A sublimation dye thermal transfer image-receiving sheet having a sublimation dye-receiving receptor layer on a substrate, comprising: a colorant;
Acid value 1.0-20 mgKOH / g, glass transition temperature 50-
Powder mixture obtained by blending hydrophobic inorganic fine particles having an average particle diameter of 1 nm to 1 μm in a range of 0.5 to 15 parts by weight with respect to 100 parts by weight of a powder coating composition containing a saturated polyester resin at 70 ° C. A sublimation dye thermal transfer image-receiving sheet, characterized in that the above-mentioned receptor layer is formed thereon. 9. The sublimation dye thermal transfer image-receiving sheet according to claim 8, wherein the hydrophobic inorganic fine particles are inorganic fine particles surface-treated with hexamethyldisilazane. 10. The sublimation dye thermal transfer image-receiving sheet according to claim 8, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 11. A sublimation dye thermal transfer image-receiving sheet having a receptor layer for receiving a sublimation dye on a substrate, a colorant, an acid value of 1.0 to 20 mg KOH / g, and a glass transition temperature of 5
A cured product of a saturated polyester resin at 0 to 70 ° C. 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 is converted to a reaction curable silicone oil in an amount of 0%. A powder mixture obtained by blending hydrophobic inorganic fine particles having an average particle diameter of 1 nm to 1 μm in a range of 0.5 to 15 parts by weight with respect to 100 parts by weight of a powder coating composition containing 0.5 to 15% by weight. A sublimation dye thermal transfer image receiving sheet, wherein a receiving layer is formed. 12. The sublimation dye thermal transfer image-receiving sheet according to claim 11, wherein the hydrophobic inorganic fine particles are inorganic fine particles surface-treated with hexamethyldisilazane. 13. The sublimation dye thermal transfer image-receiving sheet according to claim 11, wherein the inorganic fine particles are anhydrous silica, titanium dioxide or aluminum oxide. 14. The reaction-curable silicone oil has an epoxy group as a functional group and has an epoxy equivalent of 100 to 400.
The sublimation dye thermal transfer image-receiving sheet according to claim 11, wherein the amount is 0 g / mol.