JP3280523B2 - Thermal transfer recording medium - Google Patents

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 for use in a thermal transfer recording apparatus such as a thermal transfer printer or a facsimile equipped with a print head such as a thermal head, and more particularly to an image (character, image, etc.) exhibiting metallic luster. )
The present invention relates to a thermal transfer recording medium for forming a recording medium.

[0002]

2. Description of the Related Art Conventionally, a thermal transfer recording medium in which a heat-fusible ink layer is provided on a substrate has been known.

Since the thermal transfer recording medium is generally provided in the form of a roll, a large load is applied to the center portion of the roll of the thermal transfer recording medium. There were problems that the coating film adhered to the substrate (blocking), making unwinding difficult, and even if unwinding was possible, the ink layer was transferred to the substrate.

As a method for preventing the blocking,
JP-A-6-15971 discloses that the uppermost layer of the thermal transfer recording medium contains fine particles having an average particle diameter larger than the average value of the thickness of the uppermost layer, and a part of the fine particles is removed from the uppermost layer. A method is disclosed in which the area of contact with a substrate is reduced when the film is wound on a roll by being exposed.

[0005]

The present inventors applied the above-described blocking prevention method to a thermal transfer recording medium provided with a metal deposition layer, but could not obtain a high-luminance metallic glossy image.

[0006] When the present inventors examined the reason,
In order to prevent blocking, the fine particles contained in the adhesive layer, which is the uppermost layer of the thermal transfer recording medium provided with the metal deposition layer , have an average particle diameter larger than the average value of the layer thickness of the adhesive layer. It has been found that the surface of the metal vapor deposited layer becomes uneven, and a high-luminance metallic gloss image cannot be obtained.

SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide a thermal transfer recording medium capable of preventing blocking and obtaining a high-luminance metallic glossy image.

[0008]

The present invention provides a thermal transfer recording medium comprising at least one heat-fusible layer, a metal deposition layer and an adhesive layer provided on one surface of a substrate in this order, The heat transfer recording medium for forming a metallic glossy image, wherein the adhesive layer contains 30 to 75% by weight of non-melting particles having an average particle diameter of 0.2 μm or less (first invention).
About.

Further, the present invention provides the above-mentioned first invention, wherein:
A metallic luster mark, wherein a protective resin coating layer and a colored layer are provided from the substrate side as the heat-fusible layer.
The present invention relates to a thermal transfer recording medium for image formation (second invention).

Further, the present invention is the first or second invention, wherein the non-meltable particles are at least one selected from the group consisting of calcium carbonate, silica, titanium oxide, carbon black, magnesium carbonate and zirconia. Metallic glossy image formation characterized by the following:
The present invention relates to a thermal transfer recording medium for use (third invention).

Here, the non-meltable particles are particles that are not melted by thermal energy at the time of thermal transfer.

[0012]

According to the first invention, the average particle diameter of the non-melting particles contained in the adhesive layer of the thermal transfer recording medium is as small as 0.2 μm or less. Even when the particles are exposed to the surface, the surface of the adhesive layer does not become uneven enough to cause irregular reflection of light, so that the metal deposited layer after transfer becomes smooth, and an image (character, image, Etc.) and the content of the particles is 3
When the amount is as large as 0 to 75% by weight, a sufficient amount of the non-melting particles is exposed on the surface of the adhesive layer, so that the blocking of the thermal transfer recording medium can be prevented.

According to the second aspect of the present invention, by providing a protective resin coating layer and a colored layer as the heat-fusible layer, an image (character) having excellent fastness and exhibiting high-luminance metallic luster of various hues is provided. , Images, etc.).

According to the third invention, by using calcium carbonate, silica, titanium oxide, carbon black, magnesium carbonate or zirconia as the non-melting particles, the blocking of the thermal transfer recording medium can be more effectively prevented, and It is possible to form an imprint (character, image, etc.) exhibiting a high-brightness metallic luster.

Hereinafter, the thermal transfer recording medium of the present invention will be described in detail.

FIG. 1 is a schematic sectional view of a preferred embodiment of the thermal transfer recording medium of the present invention.

In FIG. 1, a protective resin coating layer 2, a coloring layer 3, a metal deposition layer 4, and an adhesive layer 5
Are provided in this order, and a release layer 6 is provided between the base material 1 and the colored layer 2.

As the substrate 1, any film or sheet generally used as a support for a thermal transfer recording medium can be used as long as it can withstand heat during thermal transfer. For example, a polyester film, a polyamide film, Examples include plastic films such as polycarbonate films and thin papers such as condenser paper. The thickness of the substrate 1 is suitably about 2 to 9 μm.

Further, a heat-resistant stick preventing layer may be provided on the surface of the substrate 1 opposite to the above-mentioned layers.

The protective resin coating layer 2 is provided to maintain the robustness of an image after thermal transfer, and is a layer mainly composed of a thermoplastic resin.

Examples of the thermoplastic resin (here, the resin includes an elastomer, the same applies hereinafter) include polyester resins, cellulose resins, acrylic resins, polyamide resins, polyurethane resins, polystyrene resins, and phenol resins. , Petroleum resin, ketone resin, ethylene-
One or more of vinyl acetate copolymer resin, epoxy resin, polypropylene resin, rosin resin and the like are used. Further, additives such as a lubricant, an antistatic agent, an antioxidant, and a surface modifier may be appropriately mixed with the resin.

The above resin is dissolved in an appropriate solvent (the above additives may be dissolved in a solvent together), applied to a substrate, and dried to form a protective resin coating layer.

The coating amount of the protective resin coating layer (the coating amount after drying,
Hereinafter the same) is preferably from 0.2 to 1.0 g / m ² . If the coating amount of the protective resin coating layer is less than 0.2 g / m ² , the robustness of the image after thermal transfer tends to be unable to be maintained. In addition, the coating amount of the protective resin coating layer was 1.0 g.
If it exceeds / m ² , the thermal transferability and the cutting property will be poor, and it will be difficult to form a printed image exhibiting high-brightness metallic luster.

The coloring layer 3 is provided for obtaining metallic luster of various hues, and is mainly composed of a binder resin (the resin includes an elastomer, the same applies hereinafter) and a pigment.

The coloring layer usually comprises 5 to 50% by weight of a pigment, 20 to 95% by weight of a binder resin, 0.1 to 10% by weight of a dispersant and 0 to 10% by weight of a wax.

Examples of the binder resin include polyester resins, cellulose resins, polyamide resins, polyurethane resins, polystyrene resins, ethylene-vinyl acetate copolymer resins, hydrocarbon resins, ketone resins, phenol resins, One or more thermoplastic resins such as an epoxy resin, a polypropylene resin, a rosin resin, and a terpene resin are used.

As the pigment, either an organic pigment or an inorganic pigment can be used. A dye may be used in combination for adjusting the hue. As the pigment, for example, a yellow pigment, a magenta pigment, a cyan pigment, and one or a mixture of two or more of them can be appropriately used. These color pigments are preferably transparent.

Examples of the yellow pigment include disazo yellow HR, naphthol yellow S, Hanza yellow 5G, Hanza yellow 3G, Hanza yellow G, Hanza yellow GR, Hanza yellow A, Hanza yellow RN, Hanza yellow R, benzidine yellow, and benzidine. One or more of yellow G, benzidine yellow GR, permanent yellow NCG, quinoline yellow lake and the like are used.

Examples of the magenta pigment include quinacridone red, permanent carmine F5B, permanent red 4R, brilliant fast scarlet, brilliant carmine BS, permanent carmine FB, lithol red, permanent red F5R, brilliant carmine 6B, and pigment scarlet 3.
B, rhodamine lake B, rhodamine lake Y, alizarin lake, or one or more of these are used.

Examples of the cyan pigment include one such as Victoria Blue Lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue and the like.
Species or two or more species are used.

Examples of the wax include natural waxes such as wood wax, beeswax, lanolin, carnauba wax, candelilla wax, montan wax and ceresin wax; petroleum waxes such as paraffin wax and microcrystalline wax; oxidized wax, ester wax, Synthetic waxes such as low molecular weight polyethylene wax, Fischer-Tropsch wax, α-olefin-maleic anhydride copolymerized wax; lauric acid,
Higher fatty acids such as myristic acid, palmitic acid, stearic acid, and behenic acid; higher fatty alcohols such as stearyl alcohol and docosanol; higher fatty acid monoglycerides, fatty acid esters of sucrose, fatty acid esters of sorbitan, and the like; esters such as oleylamide One or more of amides and bisamides can be used.

The binder resin is dissolved in an appropriate solvent (the wax may be dissolved in the solvent as well), and the pigment is mixed with a dispersant and dispersed therein, and then coated on a substrate, dried and colored. Form a layer.

The coating amount of the colored layer is 0.2 to 1.0 g / m
Preferably it is ² . The coating amount of the colored layer is 0.2 g / m
^If it is less than ² , the color of the colored layer is light and a desired hue cannot be obtained. If it exceeds 1.0 g / m ² , the transferability becomes poor and a clear metallic glossy color image cannot be obtained.

The metal of the metal deposition layer 4 includes aluminum, zinc, tin, nickel, chromium, titanium, copper, silver,
A simple substance, a mixture, an alloy, or the like of gold, platinum, or the like can be used, but aluminum is usually preferably used. The metal deposition layer can be formed by a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method.

The thickness of the metal deposition layer is preferably 100 to 800 angstroms from the viewpoint of obtaining a high-brightness metallic luster.

The adhesive layer 5 is provided for bonding the printed image to the image receiving body by hot-melt bonding during transfer, and is made of a resin containing non-melting fine particles.

As the non-melting fine particles, inorganic material particles are preferably used, but organic material particles may be used as long as they do not melt during thermal transfer. As the inorganic material, calcium carbonate, silica, titanium oxide, carbon black, magnesium carbonate, zirconia, and the like are used, and calcium carbonate, silica, carbon black, and magnesium carbonate are preferably used in terms of ink stability. As the organic material, organic pigments such as Fanar Pink, Fanar Blue, Heliogen Blue, and Paliogen Yellow are used. As the non-melting fine particles, two or more kinds of the inorganic materials and / or the organic materials may be mixed and used.

The non-melting fine particles preferably have an average particle diameter of 0.2 μm or less. If the average particle diameter is larger than the above range, the surface of the metal deposition layer after thermal transfer becomes uneven, so that a high-luminance metallic gloss image tends not to be obtained. Further, the particle size of the non-fusible fine particles,
The average particle diameter is preferably at least 0.01 μm.
If the average particle diameter is smaller than the above range, a sufficient blocking effect tends to be not obtained.

The non-melting fine particles are contained in the adhesive layer.
It is preferably contained in an amount of about 75% by weight. When the content is lower than the above range, the effect of preventing blocking tends to be insufficient with the non-melting fine particles having a small particle size, and when the content is higher than the above range, a high-luminance metallic gloss image is formed. There is a tendency not to be obtained.

Examples of the resin (herein, the resin includes an elastomer, the same applies hereinafter) include polyester resins, cellulose resins, polyamide resins, polyurethane resins, polystyrene resins, ethylene-vinyl acetate copolymer resins, One or more thermoplastic resins such as hydrocarbon resins, ketone resins, phenol resins, epoxy resins, polypropylene resins, rosin resins, and terpene resins are used.

The resin is dissolved in an appropriate solvent, and the fine particles are further dispersed. The resultant is coated on a metal vapor and dried to form an adhesive layer.

The coating amount of the adhesive layer is 0.1 to 1.0 g / m
Preferably it is ² .

A release layer 6 is provided between the substrate 1 and the colored layer 2.
Is preferably formed.

The release layer 6 is melted by a heat signal from a thermal head or the like at the time of thermal transfer, and is transferred to the transfer layer (colored layer 2, vapor deposition anchor layer 3, metal vapor deposition layer 4 and adhesive layer 5) of the heating section.
) From the base material 1 easily.
The release layer contains wax as a main component, and may optionally contain a thermoplastic resin (including an elastomer, the same applies hereinafter).

As the wax, for example, wood wax,
Natural waxes such as beeswax, lanolin, carnauba wax, candelilla wax, montan wax and ceresin wax; petroleum waxes such as paraffin wax and microcrystalline wax; oxidized wax, ester wax, low molecular weight polyethylene wax, Fischer-Tropsch wax, α- Synthetic waxes such as olefin-maleic anhydride copolymer wax; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid; higher aliphatic alcohols such as stearyl alcohol and docosanol; higher fatty acid monoglycerides and sucrose Esters such as fatty acid esters and fatty acid esters of sorbitan; one or more of amides such as oleylamide and bisamides can be used.

Examples of the thermoplastic resin include polyester resin, polyamide resin, polyurethane resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl acetate-maleic acid terpolymer. , Polyvinyl butyral, α-olefin-maleic anhydride copolymer, ethylene- (meth) acrylate copolymer, low molecular weight styrene resin, ethylene-styrene copolymer, styrene-butadiene copolymer, petroleum resin, rosin One or more of a series resin, a terpene resin, a polypropylene resin, an ionomer resin and the like can be used.

When a resin is blended in the release layer, the content of the resin in the release layer is preferably 50% by weight or less.

The coating amount of the release layer is 0.1 to 1.5 g / m
Preferably it is ² .

In the above, the embodiment in which the protective resin coating layer and the colored layer are provided between the base material and the metal deposition layer from the base material side has been described, but the present invention is limited to such an embodiment. Instead, the following aspects can be adopted.

(1) Only a protective resin coating layer (deposition anchor layer) is provided between a base material (a release layer when a release layer is provided on the base material, the same applies hereinafter) and a metal deposition layer. Provide.

(2) Only a coloring layer is provided between the substrate and the metal deposition layer.

(3) A colored layer and a protective resin coating layer (deposition anchor layer) are provided between the substrate and the metal vapor deposition layer from the substrate side.

Next, the present invention will be described with reference to examples.

Examples 1 to 4 A heat-resistant stick layer was provided on one side, and the thickness was 4.5 μm.
Using a polyethylene terephthalate film of m as a base material, a coating solution having the following formulation was applied to the surface opposite to the stick layer and dried to form a release layer having an application amount of 0.4 g / m ² .

Component Weight% Paraffin wax (melting point: 76 ° C.) 0.5 Polyethylene wax (melting point: 90 ° C.) 3.0 Ethylene-vinyl acetate copolymer (softening point: 70 ° C.) 2.5 Toluene 64 Isopropyl alcohol 30 Apply the coating liquid of the following formulation on the stick layer,
Drying was performed to form a protective resin coating layer having a coating amount of 0.3 g / m ² .

Ingredient Weight% Elitel UE3380 7.0 (Polyester resin manufactured by Unitika Ltd.) Toluene 30 Methyl ethyl ketone 63 A coating solution having the following formulation is applied on the protective resin coating layer and dried to obtain a coating amount of 0.3 g. / M ² of a colored layer was formed.

Component weight% Elitel UE3380 3.5 (polyester resin manufactured by Unitika Ltd.) Pigment Yellow IRC 1.2 (yellow pigment manufactured by Sanyo Dyeing Co., Ltd.) Pigment Carmine F5B 0.3 (manufactured by Sanyo Dyeing Co., Ltd.) (Red pigment) Toluene 30 Methyl ethyl ketone 65 An aluminum vapor-deposited layer having a thickness of 200 Å was provided on the colored layer by a vacuum vapor deposition method.

A coating solution having the formulation shown in Table 1 was applied on the aluminum vapor-deposited layer and dried to obtain a coating amount of 0.4 g / m ^2.
Was formed.

The following items were evaluated for each of the obtained thermal transfer recording media. Table 1 shows the results.

(1) Metallic glossy tape printer (NAME LAND manufactured by Casio Co., Ltd.)
KL-1000) under the following printing conditions, and the printed metallic luster was visually evaluated.

<Printing conditions> Printing speed: 20 mm / sec. Printing energy: 3 Printing pattern: Test (demo) pattern built into the printer Image receiver: Polyethylene terephthalate film provided with a black-colored polyester resin layer <Evaluation criteria> 3: High-brightness metallic luster. 2: There is a slight metallic luster. 1: No metallic luster.

(2) Blocking Resistance Each thermal transfer recording medium is slit into a ribbon having a width of 8 mm.
This is rolled into a pancake and rolled,
After storing for 96 hours under the conditions of a temperature of 50 ° C. and a humidity of 85% RH, the blocking resistance was evaluated by printing property and ribbon sticking property.

[Printability] Using the rolled ribbon after storage, printing was performed under the same conditions as in (1) above, and the transferability was visually checked.
The cutting properties and the like were evaluated and collectively expressed as printability.

<Evaluation Criteria> 2: Printability equivalent to that of a thermal transfer recording medium stored at room temperature. 1: Printing is faint.

[Ribbon sticking property] After holding the roll-shaped ribbon at one end, drop the roll under its own weight, and after the roll has reached the floor, pull one end of the ribbon to unwind the ribbon and determine whether the entire length of the ribbon is unwound. Was evaluated.

2: The entire length of the ribbon is unwound. 1: Stopping on the way, everything cannot be unraveled.

Comparative Examples 1 to 3 As the adhesive layer, a coating liquid having the formulation shown in Table 1 was applied in an amount of 0.4.
A thermal transfer recording medium was prepared in the same manner as in Examples 1 to 3 except that the coating was performed so as to give g / m ^2, and the evaluation was performed by the same method and conditions. Table 1 shows the results.

[0068]

[Table 1]

[0069]

According to the first invention, the diameter of the non-melting particles contained in the adhesive layer of the thermal transfer recording medium is 0.2 μm.
Because of the small, even if the particles are exposed on the surface of the adhesive layer, the surface of the adhesive layer does not become uneven enough to cause irregular reflection of light,
Therefore, the deposited metal layer after transfer becomes smooth, and it is possible to form an image (character, image, etc.) exhibiting high-brightness metallic luster, and the content of the particles is as large as 30 to 75% by weight. Thereby, since a sufficient amount of non-fusible particles are exposed on the surface of the adhesive layer, blocking of the thermal transfer recording medium can be prevented.

According to the second aspect of the present invention, by providing a protective resin coating layer and a colored layer as the heat-fusible layer, an image (character) having excellent fastness and exhibiting a high-luminance metallic luster of various hues is provided. , Images, etc.).

According to the third aspect of the present invention, by using calcium carbonate, silica, titanium oxide, carbon black, magnesium carbonate or zirconia as the non-melting particles, the blocking of the thermal transfer recording medium can be prevented more favorably. It is possible to form an imprint (character, image, etc.) exhibiting a high-brightness metallic luster.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing one embodiment of a thermal transfer recording medium of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Protective resin coating layer 3 Colored layer 4 Metal deposition layer 5 Adhesive layer 6 Release layer

Continuation of the front page (56) References JP-A-2-162095 (JP, A) JP-A-62-183386 (JP, A) JP-A-2-196693 (JP, A) JP-A-60-253587 (JP, A) JP-A-3-151282 (JP, A) JP-A-61-51388 (JP, A) JP-A-62-21592 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) B41M 5/38-5/40

Claims (3)

(57) [Claims] 1. A thermal transfer recording medium comprising at least one heat-meltable layer, a metal deposition layer and an adhesive layer provided on one surface of a substrate in this order, wherein the adhesive layer has an average particle diameter of A heat transfer recording medium for forming a metallic glossy image , comprising 30 to 75% by weight of non-melting particles having a particle size of 0.2 [mu] m or less. 2. The thermal transfer recording medium for forming a metallic glossy image according to claim 1, wherein a protective resin coating layer and a colored layer are provided from the substrate side as the heat-fusible layer. 3. The non-fusible particle is at least one selected from the group consisting of calcium carbonate, silica, titanium oxide, carbon black, magnesium carbonate, and zirconia. Thermal transfer recording medium for forming images with metallic luster .