JPH07195836A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording medium capable of sharply expressing the hue originally possessed by the medium without receiving the effect of receiving paper having any hue and generating a color mixture even in lap-printing. CONSTITUTION:A thermal transfer recording medium has such a structure that a transparent color ink layer is provided on a base material 1 and a gloss preventing layer 3 is provided on the layer 2 and, further, a concealing layer 4 containing a non-leafing type aluminum powder is provided on the gloss preventing layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording medium, and more particularly to a thermal transfer recording medium intended to clearly express a color print rich in hue.

[0002]

2. Description of the Related Art In recent years, a thermal transfer recording system using a thermal head has been rapidly spread, and has been used for various purposes. In the past, many monochrome thermal transfer recording media were handled and were the mainstream. However, with the expansion of applications in recent years, a color thermal transfer recording medium having a rich hue has been required.

Conventionally, there has been a color thermal transfer recording medium having a transparent colored ink layer provided on a substrate, but since the ink layer to be transferred has transparency and does not have concealing property, the transfer paper is When color mixing occurs due to the influence of hue, or when a medium of a different color is overlaid and printed again on a transfer medium that has been printed once,
At the intersection of the respective colors, the desired hue could not be faithfully expressed due to the influence of the coloring material of the first transfer.

As a color thermal transfer recording medium having a concealing property, a heat-meltable transparent ink layer and a heat-meltable ink layer containing a metal powder are sequentially formed on a base material in JP-A-62-90288. Japanese Patent Application Laid-Open No. Sho 63-63
No. 30288 gazette discloses that a metal vapor deposition layer is provided. Although such a color thermal transfer medium has a hiding property, the hue of the transparent colored layer becomes a metallic luster tone due to the adhesion of the metal powder-containing layer or the metal deposition layer and the transparent colored layer after transfer, Due to the hue of the color, a color mixture with the hue of the transparent colored layer was generated, and the desired hue could not be obtained.

Some white pigment layers use a white pigment layer to provide hiding power, but the white pigment layer does not have a metallic luster tone as compared with the metal powder containing layer or the metal vapor deposition layer.
Printed matter with good hue when the white pigment itself has poor hiding power and when a dye or pigment with a weak hiding property such as green is used in the colored ink layer or when printing on black or dark transfer materials. Was difficult to get. When a white pigment layer is used, in order to obtain a good hiding property, it is necessary to increase the layer thickness to about 20 μm or increase the blending ratio of the white pigment in the white pigment layer. When the layer thickness is too thick, the transferability becomes poor, and when the blending ratio is increased, the flexibility becomes poor and the ink peels off. No one using the white pigment layer could satisfy the concealing property and the transfer property which were the objectives of the present inventor.

Further, JP-A-60-36184 discloses a heat-sensitive transfer type correction member in which a white layer and a leafing type aluminum powder-containing concealing layer are sequentially provided on a base material.
When the leafing type aluminum powder is used as the metal powder in the concealing layer of the thermal transfer recording medium, when the layer is coated with the leafing characteristics as shown in FIG. 6, the leaves are arranged on the surface of the coating film so that the leaves float on the water surface. Therefore, during thermal transfer printing, the aluminum powder-containing concealing layer is arranged on the transfer medium side, that is, the surface side of the transfer medium, and the adhesiveness with the transfer medium is poor, and satisfactory printing cannot be obtained. Further, as shown in FIG. 8, since the aluminum powder-containing concealing layer contains finer aluminum fine particles than necessary, the light rays incident from the printing surface and the light rays reflected by the aluminum powder are irregularly reflected by the fine particles, resulting in whiteness. However, the hue of the aluminum powder-containing concealing layer became turbid, and a satisfactory hue could not be obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above problems in a color thermal transfer recording medium and allows the original hue of the thermal transfer recording medium to be overprinted or printed on a transfer paper of any hue. It is intended to provide an excellent color thermal transfer recording medium capable of clearly expressing a desired color.

[0008]

In order to solve the above-mentioned problems, the present invention provides "1. A thermal transfer ink comprising a base material, a heat-meltable transparent colored ink layer, an antiglare layer and a hiding layer, which are sequentially provided. 2. A thermal transfer recording medium, characterized in that a non-leafing type aluminum powder is used as a hiding metal powder in the hiding layer in a layer 2. The hiding metal powder is a high white non-leafing aluminum powder. 3. The thermal transfer recording medium according to claim 3. 3. The thermal transfer recording medium according to any one of claims 1 and 2, wherein the absolute amount of the concealing metal powder is 0.2 to 1.5 g per 1 m ² of the thermal transfer recording medium. The average water surface coverage area of the metal powder is 10,000
4. A hiding metal powder having a cm ² / g or more content.
A thermal transfer recording medium according to any one of 1. 5. Transparent colored ink layer is 1.0 to 3.0 μm, anti-glare layer is 1.0 to 4.0 μm, and hiding layer is 0.5 to 3.0 μm.
5. The thermal transfer recording medium according to claim 1, wherein the entire thermal melt transfer layer has a thickness of 2.5 to 8.0 μm. 6. 6. The thermal transfer recording medium according to claim 1, wherein the anti-gloss layer is a heat-fusible layer containing a white hiding color material. Is a color thermal transfer recording medium.

The transparent colored ink layer is a layer formed by mixing a colorant, a heat-melting resin, wax, various activators, lubricants, etc., and the colorant is selected from general dyes and pigments having various hues. As a heat-meltable resin,
Vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyester resin, epoxy resin, polycarbonate resin, phenol resin, polyimide resin, cellulose resin, polyamide resin, acrylic resin,
Examples include petroleum resins. Examples of the waxes include natural waxes such as beeswax, carnauba wax, gallow wax, wax, candelilla wax, nuka wax and montan wax, paraffin wax, microcrystalline wax, oxidized wax, polyethylene wax, ozokerite, ceresin and ester wax.
In addition, various commonly used activators, lubricants and the like may be added. The various components may be used alone or as a mixture, and the colorant is preferably 10 to 35% by weight, the hot-melt resin is 20 to 90% by weight, and the wax is preferably 0 to 20% by weight. Various activators, lubricants and the like can be appropriately mixed as long as the performance as a thermal transfer recording medium is not deteriorated. The layer thickness is preferably 1.0 to 3.0 μm.

The gloss preventive layer is a layer formed by blending a masking colorant, a heat-melting resin, a wax, various activators, a lubricant, etc., and has a masking power for covering the gloss and the metallic color of the masking layer. It is a layer to have. As its means, the effect is obtained by mixing a coloring agent having a hiding power.

Since the anti-gloss layer is located between the hiding layer and the transparent colored ink layer and has a hiding power, it is possible to obtain an effect of preventing color mixing between the two.

As the color material to be used, a color material having a concealing property can be appropriately used. For example, titanium oxide, magnesium oxide, zinc oxide, antimony oxide, boron nitride, lithopone, lead white, zinc sulfide, other white pigments such as lead sulfate, hiding dyes and pigments, calcium carbonate, magnesium carbonate, barium carbonate, Examples include extenders such as talc, clay, gypsum, silica, alumina, barium sulfate, mica such as mica, serisainite and muscovite, montmorillonite, kaolinite, halloysite, wax stone, clay lime, crustonite, bentonite and other clays. To be These coloring materials may be used alone or in combination.

Further, in consideration of the influence on the hue of the transparent colored ink layer, a light color is preferable, and titanium oxide, magnesium oxide, zinc oxide, antimony oxide, boron nitride,
In addition to white pigments such as lithopone, white lead, zinc sulfide, and lead sulfate,
Transparent coloring ink layer of any hue as long as it is a white coloring material such as a pigment or pigment having a hiding power, calcium carbonate, magnesium carbonate, barium carbonate, talc, clay, gypsum, silica, alumina, barium sulfate and other extender pigments. It is more suitable because it can be used in a unified manner, especially when using white pigments such as titanium oxide, magnesium oxide, zinc oxide, antimony oxide, boron nitride, lithopone, lead white, zinc sulfide, and lead sulfate. It is possible to obtain good results with high frequency.

The amount of the color material blended in the gloss preventive layer is 10
˜70 wt% is preferred, and 40-60 wt% is more preferred. When it is lower than this range, the effect of hiding the gloss and metallic color of the hiding layer tends to be lowered, while when it is higher than this range, the flexibility tends to be poor and the ink tends to peel off, which is not preferable. The heat-meltable resin, wax, various activators, lubricants and the like may be any ones by using the components described in the colorant-containing ink layer. At that time, the same component may be used, or two or more different components may be selected.

In the present invention, since the material to be transferred is concealed by the concealing layer, the antiglare layer should have a concealing power enough to cover the luster and the metallic color of the concealing layer, and to reduce the layer thickness of the layer. It is possible to select the colorant compounding ratio relatively freely, and the thermal melt transfer property is also improved. The thickness of the gloss preventive layer is preferably 1.0 to 4.0 μm. When the thickness is smaller than this range, the effect of hiding the gloss and the metallic color of the hiding layer tends to decrease, while when the thickness becomes thicker, the total thickness becomes thicker, and the transferability at the time of heat-melt transfer tends to be deteriorated. Absent.

The hiding layer is a layer formed by blending non-leafing type aluminum powder, heat-meltable resin, wax, various activators, lubricants and the like. Since the non-leafing type aluminum powder in the hiding layer increases the opacity of the ink, it has the effect of hiding the hue of the transfer paper and the underlying hue during overprinting to prevent color mixing, and the original hue of the thermal transfer recording medium. Can be expressed.

When a leafing type aluminum powder having a leafing characteristic imparted by a surface treatment or the like is used in the concealing layer, as described above, when the layer is coated with the leafing characteristic as shown in FIG. 6, Since the leaves are arranged on the surface of the coating so that they float on the water surface,
At the time of thermal transfer printing, the hiding layer is arranged on the transfer medium side, that is, on the surface side of the transfer medium, and the adhesiveness to the transfer medium is poor, and satisfactory printing cannot be obtained.

Further, since the aluminum powder is unevenly distributed on the transfer medium side of the hiding layer, that is, on the surface side of the transfer medium, the aluminum powder is in excess in the ratio of the aluminum powder and the binder in the vicinity of the surface, and the sheet-like thermal transfer recording is performed. When the medium is wound into a roll and stored for a long time, the aluminum powder is likely to migrate to the opposite surface of the ink, the stability over time is poor and blocking occurs, and the transferred aluminum powder causes damage to the thermal head and cannot be used. . Further, during printing, the friction between the transfer medium and the medium to be transferred causes background stains on portions other than the thermal transfer portion, which is not preferable.

The non-leafing type aluminum powder, which is the masking metal powder in the masking layer, is spread very thin, and its average particle size is preferably 5.0 to 25.0 μm.
If it is finer or larger than this range, the hiding property tends to be inferior.

When the aluminum powder is added, the one having the above-mentioned average particle diameter is used, but it is unavoidable in the production that a minute amount of fine-particle powder having a particle diameter smaller than the average particle diameter is mixed. Such fine particles are difficult to be arranged in parallel in the coating film, and the light receiving area of each particle is small, so that the whiteness of the coated surface is reduced and the hue becomes cloudy.

As shown in FIG. 8, in the concealing layer containing the leafing type aluminum powder, the light rays incident from the printing surface and the light rays reflected by the aluminum powder are irregularly reflected by the fine particles, and the whiteness is impaired. The hue of the layer becomes cloudy, and a satisfactory hue cannot be obtained.

In order to solve this drawback, the present invention uses a non-leafing type aluminum powder.

The non-leafing type aluminum powder is
Unlike leafing type aluminum powder, aluminum flakes are a type in which aluminum flakes are uniformly dispersed or settled in the coating film, and have the property of being arranged in parallel with the coating film as the solvent evaporates during coating film formation after coating. Is. Due to this property, the non-leafing type aluminum powder is arranged or evenly dispersed on the antiglare layer side of the concealment layer as shown mainly in FIGS. 4 to 5 in the entire thermal transfer recording medium. In other words, in other words, after thermal transfer printing, they are arranged on the printing surface side of the hiding layer or dispersed uniformly.

As a result, as shown in FIGS. 7 and 8, the light rays incident from the printed surface through the transparent colored ink layer and the gloss preventive layer are not irregularly reflected by the aluminum fine particles unlike the leafing type aluminum,
Whiteness is maintained and the hue does not become cloudy.

The present invention can be achieved by using a non-leafing type aluminum powder for the hiding metal powder in the hiding layer, and further, a high white non-leafing aluminum is used for the hiding metal powder in the hiding layer. This will give you better results. As shown in FIG. 9, this high-white non-leafing type aluminum powder was obtained by polishing the rough surface and edges of the non-leafing type aluminum powder and adjusting the particle size distribution. Light incident through the transparent colored ink layer and anti-glare layer is reflected without diffuse reflection, it is easy to arrange in parallel, good concealment is obtained, and whiteness of the coating surface is improved, resulting in color reproduction. It improves the sex. Also, there is little influence on the anti-glare layer, and the layer thickness of the anti-glare layer can be reduced,
It becomes possible to limit the content of the hiding colorant, and the effects such as improvement in heat sensitivity can be obtained.

Such high white aluminum powder is
As described above, the rough surface and the end of the powder are polished, and the particle size distribution is adjusted, but the whiteness is high white non-leafing in a highly transparent resin binder such as an acrylic resin. -Type aluminum powder is dispersed and prepared in a suitable solvent so that high white aluminum powder: binder = 30: 70, and dried on a white medium such as YUPO paper, peach coated paper or white polyester film to a dry thickness of about It is applied so as to have a thickness of 20 μm, and indicates, for example, one having an L value of the Hunter color difference of 57 or more in a spectrocolorimeter such as MSC-1 manufactured by Suga Test Instruments Co., Ltd.

The thermal transfer recording medium 1 m ² per 0 as the absolute amount of the non-leafing type aluminum powder concealing layer.
2-1.5g is required, preferably 0.3-1.0g
Is. The content of the hiding layer is preferably 10 to 50% by weight. If it is less than this range, it tends to be difficult to obtain the desired hiding property, while if it is more than this range, the coating film is more likely to peel off from the substrate, and the stability as a coating ink is poor, and the blending amount is When the absolute amount when the value is near the lower limit increases, the layer thickness increases,
The thermal sensitivity tends to be poor, which is not preferable. Further, the heat-melting resin, wax, various activators, lubricants, etc. may be prepared by using the components described in the above transparent colored ink layer. At that time, the same component may be used, or two or more different components may be selected. The layer thickness is preferably 0.5 to 3.0 μ.

The non-leafing type aluminum powder in the hiding layer has an average water surface coverage area of 10,000.
It is preferable to use aluminum powder of cm ² / g or more. The average water surface covered area is the maximum area where 1 g of aluminum powder can be arranged in a line to cover the surface of water, but the average water surface covered area is 10,000 even with the same absolute amount.
Those having a surface area of 0 cm ² / g or more have a large effect of coating the surface by themselves and tend to improve the hiding property.

Each of the layers used in the present invention has the layer thickness as described above, but the total thickness of the hot melt transfer layer is 2.5 to 8.
It is necessary to have a layer thickness of 0 μm. If the thickness is smaller than this range, the thickness of each layer becomes thin for the reason explained in the description of each layer, and the effect thereof is hindered. On the other hand, when it becomes thicker, the thermal sensitivity at the time of thermal fusion transfer is lowered, and good printing cannot be obtained.
The heat-melt transfer layer is easily peeled off from the substrate, which is not preferable.

If necessary, a heat-melting substance such as carnauba wax, rice wax, candelilla wax, montan wax, paraffin wax, polyethylene wax, or heat-melting resin may be provided between the substrate and the transparent colored ink layer. A heat-meltable release layer containing the main component can be provided for controlling thermal sensitivity.

In addition, polyamide resin, petroleum resin, terpene resin, alkyd resin,
A hot melt adhesive layer containing a polyester resin, a polyvinyl chloride resin, a polyvinyl alcohol resin or the like as a main component may be provided for the purpose of improving the adhesion to the heat transfer medium and the transfer property.

As the substrate, any film or sheet generally used as a support for a thermal transfer recording medium can be arbitrarily used, and examples thereof include plastic films such as polyester, polyimide, polycarbonate, triacetyl cellulose and nylon, cellophane and sulfuric acid. Examples include paper and condenser paper.

If necessary, a heat resistant slipping layer for preventing sticking can be provided on the surface of the substrate opposite to the ink layer.

In the thermal transfer recording medium of the present invention, as a technique suitable for coating each layer on a substrate, a technique known in the art can be applied. For example, each layer except the metal hiding layer is formed by hot-melt coating the composition, or solvent-coating a coating solution obtained by dispersing or dissolving the composition in an appropriate solvent, and the non-hiding layer is a non-coating layer. Due to the performance of leafing aluminum powder, hot melt coating is not suitable, but solvent coating is suitable. As the coating method, a wire bar coating method, a gravure coating method,
Any technique such as the reverse roll coater method can be adopted.

[0035]

In the color thermal transfer recording medium of the present invention, the non-leafing type aluminum powder in the metal hiding layer enhances the opacity of the ink, and the hiding colorant in the antiglare layer prevents the hue from mixing with the hue of the hiding layer. In addition, since it does not have a metallic luster tone and the total layer thickness is relatively thin, thermal fusion transfer is facilitated, and the hue of the transparent colored ink layer can be vividly expressed.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples.

Example 1 On a surface of a 6-micron-thick polyester film provided with a heat-resistant slip layer on one surface, the components of the following layers were added to the opposite surface in a resin-soluble solvent to give a solid content of 30% by weight. Was prepared, and each layer was sequentially coated and dried to obtain a thermal transfer recording medium. The thickness of each layer, the type of aluminum powder in the concealing layer, the absolute amount, and the average water surface coverage are shown in Table 1. (Transparent colored ink layer) Blue pigment 20% by weight (Dainichiseika Co., Ltd., Cyanine Blue 4920G) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc., Plenact Al) -M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Gloss prevention layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipaque CR-50) Polyester resin 35 % By weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (AC-629 manufactured by Allied Signal Co., Ltd.) (concealment) Layer) High white non-leafing aluminum powder 20% by weight (Showa Aluminum Powder Co., Ltd. SAP2172, flat Particle size 9 μm) Polyester resin 65% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd.) , AC-629)

Thereafter, each layer of Examples 2 to 12 was sequentially coated in the same manner as in Example 1 to obtain a thermal transfer recording medium. In addition,
Table 1 shows the thickness of each layer, the type of aluminum powder in the hiding layer, the absolute amount, and the average water surface coverage area.

Example 2 (Transparent Colored Ink Layer) Blue pigment 20% by weight (Dainichi Seika Co., Ltd., cyanine blue 4920G) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Ltd., Plenact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Anti-gloss layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipek CR) -50) Polyester resin 35% by weight (Byron 220 manufactured by Toyobo Co., Ltd.) Dispersant (manufactured by Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (manufactured by Allied Signal Co., Ltd.) AC-629) (Hiding layer) High white non-leafing aluminum powder 40% by weight (Showa Aluminum Powder Co., Ltd.) SAP2171N, average particle size 11 μm) Polyester resin 50% by weight (Toyobo Co., Ltd. Byron 220) Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629)

Example 3 (Transparent Colored Ink Layer) Blue pigment 20% by weight (Dainichi Seika Co., Ltd., cyanine blue 4920G) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Ltd., Plenact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Anti-gloss layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipek CR) -50) Polyester resin 35% by weight (Byron 220 manufactured by Toyobo Co., Ltd.) Dispersant (manufactured by Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (manufactured by Allied Signal Co., Ltd.) AC-629) (Hiding layer) High white non-leafing aluminum powder 10% by weight (Showa Aluminum Powder Co., Ltd.) SAP2173, average particle size 6 μm) Polyester resin 75% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (Allied signal) AC-629 manufactured by Co., Ltd.)

Example 4 (Transparent Colored Ink Layer) Red pigment 20% by weight (Daika Seika Co., Ltd., Seika Fast Red 1547) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto) Plenact Al-M manufactured by Co., Ltd. 5% by weight Polyethylene wax 10% by weight (AC-629 manufactured by Allied Signal Co., Ltd.) (Anti-gloss layer) Titanium oxide 50% by weight (Taipaque manufactured by Ishihara Sangyo Co., Ltd.) CR-50) Polyester resin 35% by weight (TOYOBO Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd.) , AC-629) (Hiding layer) Non-leafing type aluminum powder 20% by weight (Stap manufactured by Ecart Co., Ltd.) a 10 nl, average particle size 7 μm) Polyester resin 65% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (Allied signal ( Co., Ltd., AC-629)

Example 5 (Transparent Colored Ink Layer) Red pigment 20% by weight (Daika Seika Co., Ltd., Seika Fast Red 1547) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto) Plenact Al-M manufactured by Co., Ltd. 5% by weight Polyethylene wax 10% by weight (AC-629 manufactured by Allied Signal Co., Ltd.) (Anti-gloss layer) Titanium oxide 50% by weight (Taipaque manufactured by Ishihara Sangyo Co., Ltd.) CR-50) Polyester resin 35% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (manufactured by Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (manufactured by Allied Signal Co., Ltd.) , AC-629) (Hiding layer) Non-leafing type aluminum powder 40% by weight (Stap manufactured by Ecart Co., Ltd.) a888 nl, average particle size 9 μm) Polyester resin 50% by weight (Toyobo Co., Ltd. Byron 220) Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629)

Example 6 (Transparent Colored Ink Layer) Yellow pigment 20% by weight (Dainichi Seika Co., Ltd., Yellow AP77) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc.) ), Preneact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Anti-gloss layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipek CR- 50) Polyester resin 35% by weight (Toyon Boseki Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC -629) (Hiding layer) Non-leafing type aluminum powder 30% by weight (Stapa15nl manufactured by Ecart Co., Ltd., flat Particle size 5 μm) Polyester resin 55% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd.) , AC-629)

Example 7 (Transparent Colored Ink Layer) Yellow pigment 20 wt% (Dainichi Seika Co., Ltd., Yellow AP77) Polyester resin 65 wt% (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc.) ), Preneact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Anti-gloss layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipek CR- 50) Polyester resin 35% by weight (Toyon Boseki Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc., Planeact Al-M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC -629) (Hiding layer) High white non-leafing aluminum powder 30% by weight (MC-77 manufactured by Asahi Kasei Metals Co., Ltd. , Average particle size 18 μm) Polyester resin 55% by weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd. ), AC-629)

Example 8 (Transparent Colored Ink Layer) Green pigment 30% by weight (Cyanine Green 2G-550D, manufactured by Dainichiseika Co., Ltd.) Vinyl chloride-vinyl acetate copolymer 65% by weight (Denki Kagaku Kogyo KK) DENKALAC TF300K) Dispersant 5% by weight (Kao Atlas Co., homogenol L18) (Anti-gloss layer) Titanium oxide 60% by weight (Ishihara Sangyo Co., Ltd., Taipaque CR-50) Vinyl chloride-vinyl acetate Polymer 35 wt% (Denkarac TF300K manufactured by Denki Kagaku Kogyo Co., Ltd.) Dispersant 5 wt% (Kao Atlas Co., Homogenol L18) (Hiding layer) High white non-leafing aluminum powder 30 wt% (Asahi Kasei Metals) AM-1501 manufactured by Co., Ltd., average particle diameter 8 μm) Vinyl chloride-vinyl acetate copolymer 65% by weight (electrochemical Gaku Kogyo Co., Ltd. Dencarac TF300K) Dispersant 5 wt% (Kao Atlas Co., Homogenol L18)

Example 9 (Transparent colored ink layer) Green pigment 10% by weight (Cyanine Green 2G-550D, manufactured by Dainichiseika Co., Ltd.) Vinyl chloride-vinyl acetate copolymer 65% by weight (Denki Kagaku Kogyo KK) DENKALAC TF300K) Dispersant 5% by weight (Kao Atlas Co., Homogenol L18) Carnauba wax 20% by weight (Anti-gloss layer) Titanium oxide 20% by weight (Ishihara Sangyo Co., Ltd., Taipaque CR-50) Chloride Vinyl-vinyl acetate copolymer 55% by weight (Denkalac TF300K manufactured by Denki Kagaku Kogyo Co., Ltd.) Dispersant 5% by weight (Homogenol L18 manufactured by Kao Atlas Co., Ltd.) Carnauba wax 20% by weight (hiding layer) High white non Leafing type aluminum powder 50% by weight (MB-500 manufactured by Asahi Kasei Metals Corporation, average particle size 21 m) vinyl chloride - vinyl acetate copolymer 40 wt% (manufactured by Denki Kagaku Kogyo Co., Ltd. Denka rack TF300K) Carnauba wax 10 wt%

Example 10 A heat-meltable release layer having the following composition was provided between the transparent colored ink layer and the substrate, and the heat-meltable release layer, the transparent colored ink layer, and
An anti-gloss layer and a concealing layer were sequentially applied to obtain a thermal transfer recording medium. (Hot-melt release layer) Ethylene-vinyl acetate resin 30% by weight (Mitsui DuPont Polychemical Co., Ltd. Evaflex 150) Candelilla wax 70% by weight (Transparent colored ink layer) Green pigment 25% by weight (Dainichi Seika Co., Ltd. ), Cyanine green 2G-550D) Vinyl chloride-vinyl acetate copolymer 70 wt% (Denkarac TF300K manufactured by Denki Kagaku Kogyo Co., Ltd.) Dispersant 5 wt% (Kao Atlas Co., homogenol L18) (Gloss) Prevention layer) Titanium oxide 30% by weight (Taipaque CR-50, manufactured by Ishihara Sangyo Co., Ltd.) 65% by weight vinyl chloride-vinyl acetate copolymer (DENKALAC TF300K, manufactured by Denki Kagaku Co., Ltd.) Dispersant 5% by weight ( Homogenol L18 manufactured by Kao Atlas Co., Ltd. (Hiding layer) High white non-leafing aluminum powder 0% by weight (MR-7000 manufactured by Asahi Kasei Metals Co., Ltd., average particle diameter 15 μm) Vinyl chloride-vinyl acetate copolymer 65% by weight (Denkarac TF300K manufactured by Denki Kagaku Kogyo Co., Ltd.) Dispersant 5% by weight (Kao) Atlas Co., Ltd., Homogenol L18)

Example 11 A heat-melting adhesive layer having the following composition was provided on the outer side of the hiding layer as viewed from the base material, and a transparent colored ink layer, an anti-gloss layer, a hiding layer and a heat-melting adhesive layer were sequentially coated on the base material. A thermal transfer recording medium was obtained. (Transparent Colored Ink Layer) Green Pigment 25% by Weight (Dainichiseika Co., Ltd., Cyanine Green 2G-550D) Vinyl Chloride-Vinyl Acetate Copolymer 70% by Weight (Denkalac TF300K, Denki Kagaku Co., Ltd.) Dispersion Agent 5% by weight (Kao Atlas Co., homogenol L18) (Gloss prevention layer) Titanium oxide 30% by weight (Ishihara Sangyo Co., Ltd., Taipaque CR-50) Vinyl chloride-vinyl acetate copolymer 65% by weight ( Denkaraku TF300K manufactured by Denki Kagaku Kogyo Co., Ltd. Dispersant 5% by weight (Kao Atlas Co., Ltd., homogenol L18) (Hiding layer) High white non-leafing aluminum powder 30% by weight (Made by Asahi Kasei Metals KK MR -7000, average particle diameter 15 μm) Vinyl chloride-vinyl acetate copolymer 65% by weight (Denki Denki Co., Ltd.) Rack TF300K) Dispersant 5% by weight (Kao Atlas Co., Homogenol L18) (Hot melt adhesive layer) Polyamide resin 80% by weight (Sanwaide # 550D, Sanwa Chemical Industry Co., Ltd.) Polyethylene wax 20% by weight (Allied. Signal Co., Ltd., AC-629)

The thickness of each layer, the type of aluminum powder in the concealing layer, the absolute amount, the average water surface coverage, and each example in the above examples were printers manufactured by Autonics Co., BC-
Table 1 shows the results of evaluation by printing on peach coated paper with 8MK-2.

(Test Method) (1) Vividness of hue (reproducibility): visually determined after printing. ◎: Vivid ○: Slightly dull color tone but no problem level X: Dull color tone and problematic (2) Color mixture in overprinting: After printing with a red thermal transfer recording medium in advance, Visually judge the transfer when overprinting on it. ⊚: No color mixture is observed ○: Slight color mixture is observed but there is no problem x: Color mixture is conspicuous problem (3) Influence of transfer medium: Visual after printing on black print medium Determined by. ⊚: Not affected by the transfer medium at all ◯: Slightly affected by the transfer medium but at a level without a problem ×: Sufficiently affected by the transfer medium (4) Gloss of printing surface: After printing, judge visually. A: No gloss X: Gloss (5) Printability (transferability): Visually determined after printing. ◎: Good transferability ○: Good transferability was not obtained on some transfer target media ×: Good transferability was not obtained (6) Ink peeling off: During thermal transfer printing Visually judge ink peeling. ⊚: No peeling of ink ○: Surface peeling occurs in some print patterns but there is no problem ×: Surface peeling occurs and there is a problem (7) Background stain: Coverage during thermal transfer printing The transfer medium is soiled and visually determined. ◎: No background stain ×: There is background stain

[0051]

[Table 1]

Comparative Example 1 A thermal transfer recording medium was obtained in the same manner as in Example 1, except that only the transparent colored ink layer and the heat resistant slipping layer were applied, and the antiglare layer and the hiding layer were not applied.

Comparative Example 2 In Example 1, except that the transparent colored ink layer, the hiding layer and the heat resistant slipping layer were each coated, and the antiglare layer was not coated,
A thermal transfer recording medium was obtained in the same manner.

Comparative Example 3 In Example 1, except that the transparent colored ink layer, the gloss preventive layer and the heat resistant slipping layer were each coated, and the concealing layer was not coated,
A thermal transfer recording medium was obtained in the same manner.

Comparative Example 4 The following layer compositions were sequentially applied in the same manner as in Example 1 to obtain a thermal transfer recording medium. Table 2 shows the thickness of each layer of Comparative Examples 1 to 4, the type of aluminum powder in the hiding layer, the absolute amount, and the average water surface coverage area. (Transparent colored ink layer) Blue pigment 20% by weight (Dainichiseika Co., Ltd., cyanine blue 4920G) Polyester resin 65% by weight (Toyobo Co., Ltd. Byron 220) Dispersant (Ajinomoto Co., Inc., Plenact Al) -M) 5% by weight Polyethylene wax 10% by weight (Allied Signal Co., Ltd., AC-629) (Gloss prevention layer) Titanium oxide 50% by weight (Ishihara Sangyo Co., Ltd., Taipaque CR-50) Polyester resin 35 % By weight (Vylon 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (AC-629 manufactured by Allied Signal Co., Ltd.) (concealment) Layer) Leafing type aluminum powder 20% by weight (Stapa15 manufactured by Ecart Co., Ltd., average particle size 5 μm) Polyene Tell resin 65% by weight (Byron 220 manufactured by Toyobo Co., Ltd.) Dispersant (Plainact Al-M manufactured by Ajinomoto Co., Inc.) 5% by weight Polyethylene wax 10% by weight (AC-629 manufactured by Allied Signal Co., Ltd.) )

The thickness of each layer, the kind of aluminum powder in the concealing layer, the absolute amount, the average water surface coverage, and each comparative example in the above Comparative Examples and a printer manufactured by Autonics Co., Ltd., BC-
Table 2 shows the results of evaluation by printing on peach coated paper with 8MK-2. The test method used was the same as in the example.

[0057]

[Table 2]

[0058]

The thermal transfer recording medium of the present invention comprises a transparent colored ink layer provided on a substrate, an antiglare layer provided on the transparent colored ink layer, and a non-leafing type aluminum powder on the antiglare layer. With a concealment layer, transfer paper of any hue is not affected by the transfer paper, no color mixture occurs in overprinting, and the hue originally possessed by the thermal transfer recording medium is vividly expressed. be able to.

[0059]

[Brief description of drawings]

1 to 3 are cross-sectional views showing a typical example of the thermal transfer recording medium of the present invention, and FIGS. 4 and 5 are non-leafing type aluminum powders in the metal powder in the concealing layer of the thermal transfer recording medium of the present invention. FIG. 6 is a cross-sectional view showing an embodiment of aluminum powder when used, FIG. 6 is a cross-sectional view when similarly using a leafing type aluminum powder, and FIG. 7 is a concealment after thermal transfer when a non-leafing type aluminum powder is used. FIG. 9 is an enlarged cross-sectional view showing a mode of concealment after thermal transfer when a high-white non-leafing aluminum powder is used, and FIG. 10 shows a non-leafing aluminum powder not subjected to high-white treatment. It is an expanded sectional view showing the mode of concealment after thermal transfer when used.

[0060]

[Fig. 1]

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[0065]

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[Fig. 10]

[0070]

[Description of References] 1 ... Substrate 2 ... Transparent colored ink layer 3 ... Gloss prevention layer 4 ... Concealment layer 5 ... Heat-meltable release layer 6 ... Heat-meltable adhesion Layer 7 ... Non-leafing aluminum powder 8 ... Aluminum fine powder 9 ... Arranged aluminum powder 10 ... Leafing aluminum powder 11 ... Transfer medium 12 ... High white non-leafing aluminum Powder 13: Non-leafing type aluminum powder that is not treated with high whiteness

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 26, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a sectional view showing a typical example of a thermal transfer recording medium of the present invention.

FIG. 2 is a sectional view showing a typical example of a thermal transfer recording medium of the present invention.

FIG. 3 is a sectional view showing a typical example of a thermal transfer recording medium of the present invention.

FIG. 4 is a cross-sectional view showing an aspect of aluminum powder when non-leafing type aluminum powder is used as the metal powder in the hiding layer of the thermal transfer recording medium of the present invention.

FIG. 5 is a cross-sectional view showing an embodiment of aluminum powder when non-leafing type aluminum powder is used as the metal powder in the hiding layer of the thermal transfer recording medium of the present invention.

FIG. 6 is a cross-sectional view showing an embodiment of aluminum powder when a leafing type aluminum powder is used as the metal powder in the hiding layer of the thermal transfer recording medium of the present invention.

FIG. 7 is a cross-sectional view showing a mode of hiding after thermal transfer when a non-leafing type aluminum powder is used as the metal powder in the hiding layer of the thermal transfer recording medium of the present invention.

FIG. 8 is a cross-sectional view showing a mode of concealment after thermal transfer when a leafing type aluminum powder is used as the metal powder in the concealing layer of the thermal transfer recording medium of the present invention.

FIG. 9 is an enlarged cross-sectional view showing a mode of concealment after thermal transfer when a high white non-leafing type aluminum powder is used as the metal powder in the concealing layer of the thermal transfer recording medium of the present invention.

FIG. 10 is an enlarged cross-sectional view showing a mode of concealment after thermal transfer when non-leafing type aluminum powder which is not subjected to high-white treatment is used as the metal powder in the concealing layer of the thermal transfer recording medium of the present invention.

[Description of References] 1 ... Substrate 2 ... Transparent colored ink layer 3 ... Gloss prevention layer 4 ... Concealment layer 5 ... Heat-meltable release layer 6 ... Heat-meltable adhesion Layer 7 ... Non-leafing aluminum powder 8 ... Aluminum fine powder 9 ... Arranged aluminum powder 10 ... Leafing aluminum powder 11 ... Transfer medium 12 ... High white non-leafing aluminum Powder 13: Non-leafing type aluminum powder that is not treated with high whiteness

[Procedure amendment]

[Submission date] November 26, 1994

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

[Fig. 2]

[Figure 3]

[Figure 4]

[Figure 5]

[Figure 6]

[Figure 7]

[Figure 8]

[Figure 9]

[Figure 10]

Claims (6)

[Claims] 1. A heat-meltable transparent colored ink layer on a substrate,
A thermal transfer recording medium, comprising a non-leafing type aluminum powder as the masking metal powder in the masking layer in a thermal transfer ink layer comprising a gloss preventive layer and a masking layer successively provided. 2. The thermal transfer recording medium according to claim 1, wherein the concealing metal powder is a high-white non-leafing type aluminum powder. 3. The thermal transfer recording medium according to claim 1, wherein the absolute amount of the concealing metal powder is 0.2 to 1.5 g per 1 m ² of the thermal transfer recording medium. 4. The average water surface coverage area of the concealing metal powder is 1
The thermal transfer recording medium according to any one of claims 1 to 3, wherein the thermal transfer recording medium is a metal powder having a hiding power of 20,000 cm ² / g or more. 5. The transparent colored ink layer has a thickness of 1.0 to 3.0 μm.
m, the antiglare layer is 1.0 to 4.0 μm, and the hiding layer is 0.5
.About.3.0 .mu.m, and the entire heat-melt transfer layer is 2.5-8.
The thermal transfer recording medium according to claim 1, which has a thickness of 0 μm. 6. The thermal transfer recording medium according to claim 1, wherein the antiglare layer is a heat-meltable layer containing a white hiding color material.