JP2003320758A - Sublimation ribbon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sublimation ribbon with a protective layer in which the protective layer having good adhesive properties on all kinds of bodies to be transferred, being easily releasable from a substrate without providing a release layer, having a good transparency influencing no effect on visibility of an image, and in addition, excellent in protection of the image, can be formed. <P>SOLUTION: In the sublimation ribbon with the protective layer which has a region for the protective layer for forming the protective layer by transferring it on the image formed on an image receiving body, this region for the protective layer is provided with a transparent protective layer comprising a styrene/ acrylic copolymer resin on the substrate and in addition, provided with a heat- sensitive adhesive layer comprising an acrylic resin and a wax on this transparent protective layer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimation ribbon, and more particularly to a protection having a protective layer for protecting characters and images sublimated and transferred onto an image receptor by a sublimation type thermal recording system using a thermal head or the like. Regarding sublimation ribbons with layers.

[0002]

2. Description of the Related Art In a sublimation type thermal recording system, a ribbon-shaped or sheet-shaped thermal transfer recording medium to which a sublimable dye is applied is heated by a thermal head or the like, and the sublimable dye is placed on an image receptor which is in contact with the thermal transfer recording medium. It is a method of transferring characters and images.

As the thermal head, one having a large number of dot-shaped heating elements which are pulse-driven according to image information is used. For example, color printing of an image is also possible by transferring three colors of yellow, magenta, and cyan in an overlapping manner according to each chromaticity signal. In such a sublimation type thermal recording system, since the density of one dot can be changed by temperature modulation of the thermal head, analog gradation recording becomes possible and it is suitable for use in a full color printer.

The sublimation type thermal recording system is applied to various purposes because it can easily form high quality images.
Image storability is insufficient when the dye transferred onto the image receptor is exposed to the surface. For this reason, it has been conventionally practiced to provide a protective layer made of a transparent resin on the image receptor to which the image has been transferred.

[0005]

When the protective layer is composed of one layer, the resin conventionally used for the protective layer is acrylic resin, acrylic ester resin, vinyl chloride / vinyl acetate copolymer / polyester. Resin, etc. However, since only these resins have poor releasability from the base material when the protective layer is transferred, it is general that waxes such as polyethylene wax are contained in the resin in an amount of about 10% (special characteristics). Kaihei 5-8555, JP-A 5-1
No. 55149).

In a sublimation ribbon, an easy adhesion layer is generally provided between the sublimation ink layer (sublimation dye region) and the substrate in order to facilitate the adhesion between the two.
However, in the case where this easy-adhesion layer was provided, it was not possible to reliably peel off the protective layer from the substrate by adding about 10% of the wax as described above. On the other hand, when the wax is excessively added, problems such as deterioration of scratch resistance of the protective layer, deterioration of adhesion of the protective layer to a vinyl chloride card, image bleeding, and deterioration of transparency occur.

Japanese Unexamined Patent Publication (Kokai) No. 4-35988 discloses that a heat-sensitive adhesive layer is provided on the protective layer, and a release layer is provided below the protective layer. However, even if the heat-sensitive adhesive layer is provided, the transfer of the protective layer may not be sufficient if the release layer is not provided. On the other hand, if the release layer is provided, a three-layer structure is formed and the number of manufacturing steps increases and productivity decreases. . In addition, the multilayer structure is disadvantageous in terms of breaking of the protective layer.

The present inventor has filed Japanese Patent Application No. 2001-227067
In the above, by providing a protective layer containing a specific styrene acrylic copolymer as a main component, without adding a wax, and without providing a heat-sensitive adhesive layer or a release layer, the releasability of the protective layer, We have proposed a one-layer sublimation ribbon with a protective layer, which has excellent functions such as adhesion to adherends and image protection performance. However, there is still room for improvement in the adhesiveness of the receptive layer to cards such as polyester resin, polycarbonate resin, and acrylonitrile styrene copolymer resin.

The present invention has been made in order to solve the above-mentioned problems, and has good adhesiveness even to a certain transfer target, and even if a peeling layer is not provided, even if it is an easily adhesive layer. It is an object of the present invention to provide a sublimation ribbon with a protective layer, which is easily peeled from a base material even when the above is provided, and which has excellent image protection properties and transparency.

[0010]

Means for Solving the Problems As a result of intensive studies by the present inventors, the protective layer has a two-layer structure in which a transparent protective layer and a heat-sensitive adhesive layer are provided on the transparent protective layer, and a specific component is blended in each layer. The inventors have found that the above-mentioned object can be achieved, and have achieved the present invention.

That is, the sublimation ribbon with a protective layer of the present invention is a sublimation ribbon having a protective layer region for forming a protective layer by transferring it onto an image formed on an image receptor. It is characterized in that a transparent protective layer containing a styrene-acrylic copolymer resin is provided thereon, and a heat-sensitive adhesive layer containing an acrylic resin and a wax is provided on the transparent protective layer.

Further, in the sublimation ribbon with the protective layer of the present invention, the content of the acrylic resin and the wax in the heat-sensitive adhesive layer is
The weight ratio is 99: 1 to 90:10.

Further, the sublimation ribbon with a protective layer of the present invention is characterized in that the wax in the heat-sensitive adhesive layer is polyethylene wax.

The sublimation ribbon with a protective layer of the present invention is characterized in that the transparent protective layer contains silica.

Further, the sublimation ribbon with a protective layer of the present invention comprises
It is characterized in that an easy adhesion layer is provided between the base material and the transparent protective layer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below. The sublimation ribbon with a protective layer of the present invention is formed of a protective layer region and a sublimation dye region containing a sublimation dye. Figure 1
Shows an outline of a cross section of each region, using a frame-sequential ribbon as an example. That is, sublimation dye regions such as a yellow ink region Y, a magenta ink region M, and a cyan ink region C are provided on the base material 1, and a protective layer region OP is further provided. A black ink area K is also provided if necessary. A sublimation ribbon with a protective layer of the present invention is obtained by repeating a unit composed of these regions. FIG. 2 is a schematic sectional view showing only the structure of the protective layer region of FIG.
The transparent protective layer 2 and the heat-sensitive adhesive layer 3 are provided on one surface of the substrate 1 which is common to the sublimation dye region.

As the substrate 1, a commonly used paper or plastic film can be used.
Particularly, a polyester film is preferably used. Also,
The thickness of the base material is about 1 to 10 μm, preferably 4 to 6 μm
It is a degree.

On the surface opposite to the surface of the base material 1 on which the transparent protective layer 2 is laminated, in order to protect the base material from heat and ensure slipperiness, a heat-resistant protective layer (made of a silicone resin) is used. (Illustration) may be provided.

A styrene-acrylic copolymer resin is used as a main component in the transparent protective layer. Since styrene-acrylic copolymer resin has excellent transparency, it has no effect on the visibility of images, and when used as a protective layer on the surface of an image receptor, it has surface protection properties such as scratch resistance and plasticizer resistance. And excellent in surface gloss. Further, even when an easily adhesive layer described later is provided between the base material and the transparent protective layer, it is excellent in releasability from the base material at the time of transfer.

For the transparent protective layer, an ink is prepared by stirring, dissolving and dispersing a material containing a styrene-acrylic copolymer resin as a main component in a suitable solvent, and the ink is prepared by a known method such as gravure coating. It can be formed by coating and drying on top. The coating amount of the transparent protective layer when dried is 0.4 to 3.0.
It is preferably g / m ² . Coating amount is 3.0g / m
^{When it is} larger than ² , the energy necessary for sufficiently transferring the transparent protective layer is insufficient, so-called sensitivity is insufficient, the sharpness of the transparent protective layer is deteriorated, and the transparency is lowered.
Problems such as higher costs arise. On the other hand, when the coating amount is less than 0.4 g / m ² , the image is not sufficiently protected and the protective layer does not function. Further, the transparent protective layer is required to have releasability, but if the heat-sensitive adhesive layer penetrates into the transparent protective layer, the adhesive component enters the transparent protective layer and the releasability is impaired.

It is preferable that silica is contained in the transparent protective layer. This is because peelability and scratch resistance are improved.
The content of silica is preferably 1 to 10% by weight with respect to the entire transparent protective layer. If it is less than 1% by weight, the effect of improving the releasability is small, and if it is more than 10% by weight, the protective layer becomes matte and the gloss is lost. Silica has a particle size of 0.8 μm
Or less, preferably 0.6 μm or less, and a specific surface area of 20 m ² /
It is preferably g or less, and more preferably 10 m ² / g or less. Such a silica has a small particle size and a small surface area, and therefore has sufficient transparency. In addition, after transfer, it is hard without impairing the gloss, and thus has an effect of enhancing scratch resistance as a protective layer. On the other hand, when the silica is out of the above range, the particle size is large and the surface area is large, so that diffuse reflection occurs and the transparency is deteriorated. In addition, since the porosity is high, the porosity becomes soft and the scratch resistance is poor.

As shown in FIG. 3, the substrate 1 and the transparent protective layer 2
An easy-adhesion layer 4 made of polyurethane, polyester, or the like may be provided in order to improve the adhesiveness between both. In addition,
In the following drawings, the same members as in FIG.
The same reference numerals are used and the description thereof is omitted. As the easy-adhesion layer, one having good adhesion to the substrate can be used, but a polyurethane resin or a polyester resin is particularly preferable. The easy-adhesion layer 4 can be formed by dissolving or dispersing these materials in an appropriate solvent, applying the material on the substrate 1 by a known method, and drying the material. The coating amount of the easy-adhesion layer is about 0.01 to 0.10 g / m ² when dried.

On the transparent protective layer 2, a heat-sensitive adhesive layer 3 (FIGS. 2 and 3) containing an acrylic resin and wax is provided. By providing the heat-sensitive adhesive layer 3, the wax in the heat-sensitive adhesive layer is melted by heat at the time of heat-sensitive transfer, and the wettability to the transfer target, so-called "sticking" is improved.
Further, since the original adhesiveness of the acrylic resin is further utilized, good adhesiveness can be obtained without selecting the transfer target. In the present invention, the heat-sensitive adhesive layer contains wax, but since the transparent protective layer does not contain wax, the protective function of the transparent protective layer itself such as scratch resistance is adversely affected. There is no fear.

Acrylic resin is compounded in the heat-sensitive adhesive layer of the present invention because of the transparency of the entire protective layer, the adhesiveness to all transfer targets, the resistance to plasticizer, and the transparency containing styrene-acrylic copolymer resin. This is because it has excellent adhesion to the protective layer.

The weight ratio of acrylic resin to wax in the heat-sensitive adhesive layer is preferably 99: 1 to 90:10. Within this range, as described above, the wax in the layer is melted by heat during heat-sensitive transfer, the wettability to the transfer target, so-called "cling", is improved, and the original adhesiveness of the acrylic resin is further utilized. Be done. Further, the transparency of the image can be maintained without impairing the transparency of the acrylic due to the dust of the wax. If the weight ratio of the wax to the acrylic resin is less than 99: 1, the effect of wetting the wax becomes small. On the other hand, when the weight ratio of the wax is more than 90:10, the adhesion to the transfer target becomes weak and the transparency also deteriorates.

Examples of the wax in the heat-sensitive adhesive layer include carnauba wax, paraffin wax, candelilla wax, microcrystalline wax, sazol wax, polyethylene wax and the like. Polyethylene wax is particularly preferable. Among the above waxes, polyethylene wax has a good wettability and a large cohesive force, so that the abrasion resistance can be improved without impairing the durability as a protective layer.

The polyethylene wax preferably has a melting point of 80 to 140 ° C. If the temperature is lower than 80 ° C, there is a risk of stickiness, so-called blocking, and 140 ° C.
This is because if it is higher, it becomes difficult to melt with heat and the sensitivity to heat decreases. The molecular weight is 500 to 3,000.
Is preferred. If it is less than 500, stickiness, that is, so-called blocking may occur, and if it is more than 3,000, solubility may be deteriorated and an ink may not be prepared.

For the heat-sensitive adhesive layer 3, an ink is prepared by stirring, dissolving, and dispersing a material such as acrylic resin or wax in a suitable solvent, and the ink is applied onto the transparent protective layer 2 by a known method such as gravure coating. It can be formed by drying.
The dry coating amount of the heat-sensitive adhesive layer is 0.5 to 1.0 g / m.
It is preferably ² . If the amount is less than 0.5 g / m ² , the adhesiveness is poor, and if the amount is more than 1.0 g / m ² , the image may be muddy and the visibility may be inferior.

Between the transparent protective layer 2 and the heat-sensitive adhesive layer 3,
An ultraviolet absorbing layer (not shown) may be provided to improve light resistance. The ultraviolet absorbing layer is composed of an ultraviolet absorbent and an acrylic resin or the like. If necessary, a filler such as silica that does not impair the transparency may be added. As a particularly preferred embodiment, a reactive ultraviolet absorber such as benzophenone or benzotriazole and an acrylic monomer,
A copolymer composed of an oligomer is preferable for suppressing bleeding and maintaining the strength of the layer. The coating amount is 0.2-2.0
g / m ² is preferred. When it is less than 0.2 g / m ² , the effect of light resistance is small. On the other hand, if the coating amount is more than 2.0 g / m ² , the sharpness will deteriorate.

Instead of separately providing an ultraviolet absorbing layer as described above, an ultraviolet absorbent may be added to the transparent protective layer. In this case, the content in the entire transparent protective layer is 5 to
50% by weight is preferred. If it is less than 5% by weight, the effect cannot be obtained, and if it is more than 50% by weight, the transparent protective layer itself becomes brittle.

In the sublimation dye area, yellow, magenta, and cyan inks containing sublimation dyes are prepared by a known method,
It can be formed by coating and drying with a gravure coater or the like.

For convenience of explanation, the sublimation ribbon having the frame-sequential structure has been described.
Needless to say, for example, a ribbon having a line-sequential structure or a monocolor ribbon may be used.

The image receptor for transferring an image and forming the protective layer by using the sublimation ribbon with the protective layer of the present invention is not particularly limited as long as it has dyeability of sublimation dye of each color. As the image-receiving layer, a layer made of polyvinyl chloride resin, polyester resin, polycarbonate resin, acrylonitrile styrene resin, or the like can be used.

[0034]

【Example】

Example 1 [Sublimation Ribbon with Protective Layer] First, three color inks of yellow, magenta and cyan containing a sublimable dye having the following composition were prepared.

[0035] (Yellow ink)   Yellow disperse dye 5.5 parts by weight   (Macrolex Yellow 6G, manufactured by Bayer)   Polyvinyl butyral resin (S-REC BX-1, manufactured by Sekisui Chemical) 4.5 parts by weight   Methyl ethyl ketone / toluene (weight ratio 1/1) 89.0 parts by weight

(Magenta Ink) Instead of the yellow disperse dye, a magenta disperse dye (Disperse Red6) is used.
It is the same as the yellow ink except that 0) is used.

(Cyan ink) Cyan disperse dye (Solvent Blue 63) instead of the yellow disperse dye.
The same as the yellow ink except that was used.

(Black Ink) The black ink used had the following composition. Carbon black (MA-8, manufactured by Mitsubishi Chemical) 15.0 parts by weight Polyester resin 15.0 parts by weight (Diaclone ER1002, manufactured by Mitsubishi Rayon) Methyl ethyl ketone 35.0 parts by weight Toluene 35.0 parts by weight Total 100.0 parts by weight

(Ink for transparent protective layer) The following formulation was dissolved and stirred to prepare an ink for transparent protective layer. Styrene / acrylic copolymer resin (Hymer SB102, manufactured by Sanyo Kasei Co., Ltd., styrene: acrylic = 50: 50, Mw = 290,000) 30 parts by weight Methyl ethyl ketone 35 parts by weight Toluene 35 parts by weight Total 100.0 parts by weight

(Ink for heat-sensitive adhesive layer) The composition of the ink for heat-sensitive adhesive layer is as follows. Acrylic resin (Dianal BR-75, manufactured by Mitsubishi Rayon) 24.9 parts by weight Polyethylene wax (Varico wax POLYWAX1000, manufactured by Toyo Ink, melting point 112.8 ° C, molecular weight 1,000) 0.1 parts by weight Methyl ethyl ketone 37.5 parts by weight Parts Toluene 37.5 parts by weight Total 100.0 parts by weight Diinal BR-75 was dissolved in a mixed solvent of methyl ethyl ketone and toluene. Varico wax POLYWAX1000 was added to toluene separately and dissolved by stirring at 80 ° C. for 2 hours. After cooling this solution, it was added to the solution of Dianal BR-75 with stirring to prepare an ink for a heat-sensitive adhesive layer.

(Preparation of Sublimation Ribbon with Protective Layer) FIG. 4 shows the structure of the sublimation ribbon with a protective layer to be prepared. Base material is a polyethylene terephthalate film KM65 (manufactured by Toyobo Co., Ltd.) having a thickness of 5 μm, which is prepared by in-line coating a polyurethane-based resin with a coating amount of 0.08 g / m ² on one surface in advance to form the easy adhesion layer 4. Used as 1. A silicone resin was applied on the other surface of the base material 1 at a coating amount of 0.9 g / m ² and dried to form a heat resistant protective layer 5.

On the easy-adhesion layer 4, a yellow ink, a magenta ink, a cyan ink, and a black ink are applied in a gravure coater at a coating amount of 0.8 g / m ² , and a transparent protective layer ink is applied at a coating amount of 1.
At 5 g / m ² , the heat-sensitive adhesive layer ink was applied onto the transparent protective layer at a coating amount of 0.8 g / m ² in a frame-sequential manner and dried. As a result, the sublimable dye regions Y, M and C, the black ink region K and the protective layer region O are formed.
A sublimation ribbon with a protective layer of the present invention having P was produced. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 99.5: 0.
It is 5.

[0043]

Example 2 A sublimation ribbon with a protective layer was prepared in the same manner as in Example 1 except that 24.8 parts by weight of DIALAL BR-75 and 0.2 parts by weight of POLYWAX1000 were used as the heat-sensitive adhesive layer. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 99: 1.

[0044]

Example 3 A sublimation ribbon with a protective layer was produced in the same manner as in Example 1 except that 23.8 parts by weight of DIALAL BR-75 and 1.2 parts by weight of POLYWAX 1000 were used as the heat-sensitive adhesive layer. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 95: 5.

[0045]

Example 4 A sublimation ribbon with a protective layer was produced in the same manner as in Example 1 except that 22.5 parts by weight of DIALAL BR-75 and 2.5 parts by weight of POLYWAX1000 were used as the heat-sensitive adhesive layer. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example is 90:10.

[0046]

Example 5 A sublimation ribbon with a protective layer was produced in the same manner as in Example 1 except that 21.2 parts by weight of DIALAL BR-75 and 3.8 parts by weight of POLYWAX1000 were used as the heat-sensitive adhesive layer. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 85:15.

[0047]

Example 6 A sublimation ribbon with a protective layer was produced in the same manner as in Example 3 except that the transparent protective layer contained silica and the procedure was as follows. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 95: 5. Styrene / acrylic copolymer resin (Hymer SB102, manufactured by Sanyo Kasei Co., Ltd., styrene: acrylic = 50: 50, Mw = 290,000) 30 parts by weight Silica (SO-E2, manufactured by Admafine, particle size 0.4 to 0) .6 μm, specific surface area 5 to 10 m ² / g) 1.5 parts by weight Methyl ethyl ketone 35 parts by weight Toluene 33.5 parts by weight Total 100.0 parts by weight

[0048]

[Example 7] A modified acrylic resin containing 5% polyethylene wax (Plus Coat STA-5 clear, manufactured by Wakoshin Chemical Industry Co., Ltd., solid content 18%) was used as it was as a heat-sensitive adhesive layer, in the same manner as in Example 6. A sublimation ribbon with a protective layer was prepared. The weight content ratio of acrylic resin and polyethylene wax in the heat-sensitive adhesive layer in this example was 95: 5.

[0049]

Example 8 A sublimation ribbon with a protective layer was produced in the same manner as in Example 3 except that the composition of the heat-sensitive adhesive layer was changed as follows. The difference between this example and Example 3 is only that the wax was changed from polyethylene wax to microcrystalline wax. The weight content ratio of the acrylic resin and the microcrystalline wax in the heat-sensitive adhesive layer in this example was 95: 5. Acrylic resin (Dianal BR-75, manufactured by Mitsubishi Rayon) 23.8 parts by weight Microcrystalline wax (Varico wax MEKON WHITE, manufactured by Toyo Ink, melting point 92.8 ° C) 1.2 parts by weight Methyl ethyl ketone 37.5 parts by weight Toluene 37 .5 parts by weight 100.0 parts by weight

[0050]

Comparative Example 1 A sublimation ribbon with a protective layer was produced in the same manner as in Example 1 except that the composition of the heat-sensitive adhesive layer ink did not contain wax and the composition was as follows. Acrylic resin (Dianal BR-75, made by Mitsubishi Rayon) 25.0 parts by weight Methyl ethyl ketone 37.5 parts by weight Toluene 37.5 parts by weight Total 100.0 parts by weight

[0051]

Comparative Example 2 A sublimation ribbon with a protective layer was produced in the same manner as in Example 1 except that the transparent protective layer was formed as a single layer without forming the heat-sensitive adhesive layer.

[0052]

Comparative Example 3 The transparent protective layer ink was coated with the ink of Example 6 at a coating amount of 1.5 g / m ² to form a transparent protective layer, and a heat-sensitive adhesive layer having the following composition was formed on the surface of the transparent protective layer. A sublimation ribbon with a protective layer was produced in the same manner as in Example 6 except that the heat-sensitive adhesive layer was formed by applying the coating ink at a coating amount of 0.8 g / m ² .

[0053] (Ink for heat-sensitive adhesive layer)   Vinyl chloride / vinyl acetate copolymer   (VYLF, made by UCC, Tg = 68 ° C., degree of polymerization 220) 30 parts by weight   Micro silica 0.4 part by weight   Methyl ethyl ketone 35 parts by weight   35 parts by weight of toluene

[0054]

Comparative Example 4 An ink having the following composition was applied as a transparent protective layer ink at a coating amount of 1.5 g / m ² to form a transparent protective layer, and the heat-sensitive adhesive of Example 6 was formed on the surface of the transparent protective layer. A sublimation ribbon with a protective layer was produced in the same manner as in Example 6 except that the layer-forming ink was applied at a coating amount of 0.8 g / m ² to form the heat-sensitive adhesive layer.

[0055] (Ink for transparent protective layer)   Acrylic silicone graft resin   (Cymac US-350, manufactured by Toagosei, solid content 30%) 60 parts by weight   Methyl ethyl ketone 20 parts by weight   20 parts by weight of toluene                                                       100 parts by weight

[0056]

[Evaluation test] (Print) Card printer (PERSON
A sublimation-type cybernet size PET card (base material: polyethylene terephthalate, receiving layer) of the sublimation-type PET card obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was set in AC11, manufactured by FARGO. Material: Polyester resin, made by Tomoegawa Paper Co., Ltd.).

(Evaluation of Scratch Resistance and Adhesion) A scratch resistance test using an eraser was conducted on the printed surface covered with the protective layer under the following conditions. This test prints with black ink area
It is a face evaluation. The inks in the yellow, magenta, and cyan color areas have penetrated into the transferred material, so that the influence of rubbing is small, whereas the black ink is on the transferred material, and therefore the influence of rubbing is large. Because. Scratch tester: Rub Testing Machine
(Manufactured by Yasuda Seiki Seisakusho) Eraser: Dragonfly MONO Eraser load: 523gf / cm ² Rubbing frequency: 20 times Evaluation criteria: ◎: No problem with 20 reciprocating scratches ○: No problem with 10 reciprocating abrasions △: 5 reciprocating cycles No problem with rubbing. ×: Failure occurred due to reciprocating rubbing within 3 times. XX: Card with protective layer could not be prepared.

(Evaluation of Transparency) Gloss Meter (Re made by DR. LANGE
The glossiness of the printed matter at 60 ° irradiation was evaluated using a flekto meter). In this evaluation, the glossiness of the printed surface is checked, but as a result, the transparency of the protective layer is evaluated. Evaluation criteria: ◎: Glossiness of 80% or more O: Glossiness of 60% or more and less than 80% Δ: Glossiness of 40% or more, less than 60% ×: Glossiness of less than 40% XX: Cannot create a card with a protective layer Was

(Peelability Test) The peeling noise when the protective layer was transferred during printing was evaluated. The larger the peeling sound, the poorer the peeling property. Evaluation criteria: ◎: No peeling noise ○: Slight peeling noise △: Large peeling noise ×: No transfer × ×: Card with protective layer could not be prepared

(Plasticizer resistance test) TAG TYPE NA
The printed card was put in ME PLATE Nafu-55 (made by KOKUYO, made by soft vinyl chloride) and stored at 25 ° C for 1 year. In this test, the state in which the dye in the color region in the formed image is transferred to NAME PLATE through the protective layer is evaluated. Evaluation criteria: ◎: No transfer of sublimation dye to NAME PLATE ○: Slightly △: Transfer of sublimation dye to NAME PLATE Large ×: Protective layer melted XX: Card with protective layer could not be prepared

(Comprehensive Evaluation) Evaluation Criteria: ⊚: 4 or more ⊚ in each evaluation test are excellent, and ○: All evaluation tests are evaluated as ○ or ◎, and there is no problem in practical use Δ: Even if one has a rating of △, it is a practical level ×: There is a rating of even one, and there is a problem in practical use XX: a level of impracticality

[0062]

[Evaluation Results] The evaluation results of the sublimation ribbons with protective layers obtained in Examples 1 to 8 and Comparative Examples 1 to 4 are shown below.

[Table 1]

[Table 2]

[Table 3]

The wax content in the heat-sensitive adhesive layer was gradually increased from Examples 1 to 5, but the ratio of acrylic resin to wax from the above table to Examples 2 to 4 was 99: 1 to 1: 1. It can be seen that in the case of 90:10, the adhesiveness is good because of the wetting effect with respect to the transferred material, and the other characteristics are well balanced and good results are obtained. .

In Example 6, the transparent protective layer contains silica as compared with Example 3, but it is understood that the peelability and the scratch resistance are improved. In Example 7, the acrylic resin and polyethylene wax in the heat-sensitive adhesive layer of Example 6 were changed to a modified acrylic resin alone containing 5% polyethylene wax, but the same performance was obtained as a whole. .

From a comparison between Example 8 and Example 3, it can be seen that the adhesiveness is improved as compared with Example 8 in which microcrystalline wax was used in the heat-sensitive adhesive layer. It is considered that this is because the cohesive force was stronger in Example 3 in which polyethylene wax was used.

In Comparative Example 1, since no wax was blended in the heat-sensitive adhesive layer, the wetting effect on the transferred material was lost and the adhesiveness was deteriorated. In Comparative Example 2, the heat-sensitive adhesive layer was eliminated and the transparent protective layer alone was formed, but the heat-sensitive adhesive layer was not present, resulting in poor adhesion.

Comparative Example 3 is a sublimation ribbon with a protective layer in which the transparent protective layer of the present invention (Example 6) is used as the transparent protective layer and the conventional heat-sensitive adhesive layer is used as the heat-sensitive adhesive layer. . Printing was performed on a card using this sublimation ribbon, but the protective layer could not be transferred, and the intended card with a protective layer could not be prepared. Therefore, it was impossible to evaluate. Comparison between Example 6 and Comparative Example 3 shows that the heat-sensitive adhesive layer of the present invention containing an acrylic resin and wax is excellent in all evaluations.

Comparative Example 4 is a sublimation ribbon with a protective layer in which a conventional transparent protective layer is used as the transparent protective layer and the heat-sensitive adhesive layer uses the heat-sensitive adhesive layer of the present invention (Example 6). When printing was performed on a card using this sublimation ribbon, the heat-sensitive adhesive layer adheres to the card, but the transparent protective layer underneath does not peel off from the substrate, so after all, transfer the protective layer. It was not possible to produce the intended card with protective layer. Therefore, it was impossible to evaluate. Comparison between Example 6 and Comparative Example 4 shows that the transparent protective layer of the present invention containing a styrene-acrylic copolymer resin is excellent in all evaluations.

Further, these Example 6 and Comparative Example 3
By comparison with Examples 4 and 4, the sublimation ribbon with a protective layer of the present invention having a combination of two layers of a transparent protective layer containing a styrene-acrylic copolymer resin and a heat-sensitive adhesive layer containing an acrylic resin and a wax was excellent. It can be seen that it has characteristics.

[0070]

According to the sublimation ribbon with a protective layer of the present invention,
The following remarkable effects peculiar to the present invention can be obtained. Good adhesion of the protective layer to the transferred material. Unlike a conventional sublimation ribbon with a protective layer, it is possible to satisfactorily peel and transfer from a substrate without providing a peeling layer in the protective layer region. Even in the case where the easy-adhesion layer is provided on the base material, the protective layer can be favorably peeled from the base material and transferred. Since the protective layer has excellent transparency, a clear image can be obtained without affecting the visibility of the image formed under the protective layer. Since the protective layer has excellent scratch resistance and plasticizer resistance, the image can be reliably protected.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing one unit of a sublimation ribbon with a protective layer of the present invention, which comprises a sublimation dye region and a protective layer region.

FIG. 2 is a cross-sectional view showing a configuration of a protective layer region of a sublimation ribbon with a protective layer of the present invention.

FIG. 3 is a cross-sectional view showing a configuration of a protective layer region of a sublimation ribbon with a protective layer of the present invention when an easily adhesive layer is provided.

FIG. 4 is a schematic cross-sectional view showing the structure of a sublimation ribbon with a protective layer used in an example of the present invention.

[Explanation of symbols]

1 base material 2 Transparent protective layer 3 Thermal adhesive layer 4 Easy adhesive layer 5 Heat-resistant protective layer Y Yellow ink area M magenta ink area C cyan ink area K black ink area OP protective layer area

Claims (5)

[Claims] 1. A sublimation ribbon with a protective layer having a protective layer region for transferring onto an image formed on an image receptor to form a protective layer, wherein the protective layer region is a styrene-acrylic copolymer on a substrate. A sublimation ribbon with a protective layer, comprising a transparent protective layer containing a resin, and a heat-sensitive adhesive layer containing an acrylic resin and a wax provided on the transparent protective layer. 2. The sublimation ribbon with a protective layer according to claim 1, wherein the weight ratio of the acrylic resin and the wax in the heat-sensitive adhesive layer is 99: 1 to 90:10. 3. The sublimation ribbon with a protective layer according to claim 1, wherein the wax in the heat-sensitive adhesive layer is polyethylene wax. 4. The sublimation ribbon with a protective layer according to claim 1, wherein the transparent protective layer contains silica. 5. The sublimation ribbon with a protective layer according to claim 1, further comprising an easy-adhesion layer between the substrate and the transparent protective layer.