JP2003089278A - Thermal transfer recording medium and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a resin containing a plasticizer such as a polyvinyl chloride from generating a fusion-bonding phenomenon and an image deterioration from occurring. SOLUTION: An anti-plasticizer resin layer containing a phenoxy resin is formed on the surface of a printed matter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an image-receiving layer provided on a support and is capable of forming an image with a melt-type thermal transfer ink or a sublimation-type thermal transfer ink, and then the surface of a substrate such as paper or plastic. The present invention relates to a thermal transfer recording medium that can be heat-bonded to, and a printed matter obtained by using the thermal transfer recording medium.

[0002]

2. Description of the Related Art A sublimation type thermal transfer recording method is mainly used as a method of recording a face image on an image display body containing a face image for personal authentication such as a license, employee ID, membership card and credit card. Has become.

In this sublimation type thermal transfer recording method, a sublimation type ink transfer ribbon obtained by coating a support sheet with an ink containing a sublimation (or heat transferability) dye so that it can be thermally transferred, and a thermoplastic material capable of receiving the sublimation dye. A sublimation type thermal transfer recording of a desired image on a recording medium is performed by superimposing a recording medium having a resin image receiving layer and selectively heating a thermal transfer ribbon based on image data with a thermal head or the like. is there. According to this method, it is widely known that a color image with rich gradation can be easily recorded. However, in the sublimation thermal transfer recording method, the image is easily scratched because the image is formed in the vicinity of the surface of the thermoplastic resin layer, and the dye density is re-sublimated so that the image density is likely to decrease with time. There are problems related to the durability of the card, such as the dye being decomposed by ultraviolet rays to change the color tone of the image.

On the other hand, the melt-type thermal transfer recording method comprises a heat-meltable ink transfer ribbon formed by coating a support sheet with a heat-meltable ink in which a coloring pigment or dye is dispersed in a binder such as resin or wax, and A recording medium having an image receiving layer made of a thermoplastic resin capable of receiving the heat-meltable ink transfer ribbon is superposed, and the thermal transfer ribbon is selectively heated by a thermal head or the like based on the image data, and the binder is applied to the recording medium. The desired image is recorded by transferring the heat-meltable ink containing the ink. According to this method, inorganic and organic pigments, which are generally said to have good light resistance, can be selected and used as the coloring material, and by devising the resin or wax used for the binder, scratches are less likely to occur It is possible to provide an image having excellent solvent properties. Further, by mixing a functional material such as a fluorescent pigment or a magnetic material into the ink, it is possible to easily form a special ink having high security. The image receiving layer may be any recording medium having adhesiveness to the binder, and a wide range of recording media can be selected, which is advantageous for the sublimation type thermal transfer method.

An image is formed on the transparent transfer type image receiving layer provided on the film substrate by the above-mentioned sublimation type thermal transfer recording method or fusion type thermal transfer recording method, and the image is recorded on the final recording medium to which the image is to be applied. A method of thermally transferring a transfer type image receiving layer has been proposed. According to this method, since the transfer type image receiving layer itself becomes a surface protective film after transfer, the mechanical strength of the surface is high and the smoothness of the resin layer surface is further improved.
By adjusting so that the affinity with the ink layer is improved, it is possible to form an image with rich gradation even in the fusion type thermal transfer system.

However, when a film containing a plasticizer such as a vinyl chloride resin used for a transparent resin cover is brought into contact with a printed matter on which the transfer type image receiving layer of the above method is formed and stored for a long time, When the plasticizer moves to the transfer type image receiving layer, fuses with vinyl chloride resin, etc. and peels off, the transfer type image receiving layer peels off from the final recording medium,
In the case of recording a sublimation type ink image, the sublimation type dye is easily diffused, resulting in problems such as blurring of the outline of the image and fading of the color.

That is, in the transfer type image-receiving layer formed by the conventional method, it was not possible to store the resin film containing the plasticizer in a stacked state for a long period of time.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide good printing characteristics by a sublimation type thermal transfer recording method or a melting type thermal transfer recording method, and to store it in a state of being superposed with a resin containing a plasticizer. Another object of the present invention is to obtain a printed matter that can be stably stored for a long period of time without fusion with this resin and deterioration of an image.

[0009]

The present invention firstly comprises a support, a plasticizer-resistant resin layer mainly containing a phenoxy resin formed on the support, and a plasticizer-resistant resin layer formed on the support. A thermal transfer recording medium comprising the formed heat-meltable heat-meltable ink image-receiving layer.

Secondly, the present invention comprises a support, a plasticizer-resistant resin layer mainly containing a phenoxy resin formed on the support, and a heat-adhesive layer formed on the plasticizer-resistant resin layer. A sublimable ink image-receiving layer is provided, and a thermal transfer recording medium is provided.

Thirdly, the present invention relates to a plasticizer-resistant resin layer mainly containing a phenoxy resin, a heat-meltable ink image-receiving layer laminated on the plasticizer-resistant resin layer, and the heat-meltable ink. Heat-fusible ink image received on the heat-fusible ink image-receiving layer, and a substrate thermally bonded to the hot-melt ink image-receiving layer via the heat-fusible ink image. provide.

Fourthly, the present invention relates to a plasticizer-resistant resin layer mainly containing a phenoxy resin, a heat-bondable sublimable ink image-receiving layer laminated on the plasticizer-resistant resin layer, and the heat-melting property. Provided is a printed matter comprising a sublimable ink image received on an ink image receiving layer, and a substrate thermally bonded to the sublimable ink image receiving layer via the sublimable ink image.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the thermal transfer recording medium of the present invention, a plasticizer-resistant resin layer and an image-receiving layer capable of receiving heat-bondable heat-meltable ink and / or sublimable ink are laminated in this order on a support. It is characterized in that the plasticizer-resistant resin layer mainly contains a phenoxy resin.

The printed matter of the present invention is subjected to melt-type or sublimation-type thermal transfer recording on the image-receiving layer of the above-mentioned thermal transfer recording medium, and then the image-receiving layer is brought into contact with the base material to perform thermal transfer together with the plasticizer resin layer. And a printed article obtained by peeling and removing the support, and receiving a plasticizer-resistant resin layer and a heat-meltable ink and / or sublimable ink laminated on the plasticizer-resistant resin layer. Image-receiving layer, an image formed on the image-receiving layer with a heat-fusible ink and / or a sublimable ink, and a base material thermally bonded to the image-receiving layer via the image. Is characterized in that it mainly contains a phenoxy resin.

When a printed matter is formed using the thermal transfer recording medium of the present invention, the image and image receiving layer are present between the substrate and the plasticizer-resistant resin layer, and the plasticizer-resistant resin layer is exposed on the surface of the printed matter. And functions as a protective layer for the image and image receiving layer. According to the present invention, since the plasticizer-resistant resin layer mainly contains the phenoxy resin, it is possible to sufficiently preserve the printed matter for a long period of time without causing fusion and migration with the plasticizer such as vinyl chloride resin. it can.

The present invention will be described in more detail below with reference to the drawings.

FIG. 1 is a sectional view showing the structure of an example of a thermal transfer recording medium according to the present invention.

As shown, this thermal transfer recording medium is
For example, a sheet-shaped support 1 made of polyethylene terephthalate, a plasticizer resin layer 2 made of a phenoxy resin provided on the support 1, and a polyester resin and silicone provided on the plasticizer resin layer 2 And an image receiving layer 3 made of a resin or the like capable of receiving a sublimable ink made of a mixture of resins.

FIG. 2 is a diagram showing how an image is formed on the thermal transfer recording medium shown in FIG. 1 by sublimation type thermal transfer recording using sublimable ink.

First, an ink ribbon 8 having an ink ribbon support 6 and a sublimable ink layer 7 formed thereon is prepared, and as shown in the figure, the sublimable ink layer 7 is formed into a sublimable ink image receiving layer 3. When applied to the above, the sublimable ink image 4 can be formed on the image receiving layer 3 by performing thermal transfer recording from the support 6 side according to an image signal, for example, by the thermal head 9. After image formation, the ink ribbon 8 is removed from the surface of the sublimable ink image receiving layer 3.

FIG. 3 is a diagram showing a constitution of an example of a printed matter formed by using a thermal transfer recording medium having a heat-meltable ink image.

As shown in the figure, this printed matter 10 is printed with an image 4 on a substrate 5 made of polyethylene terephthalate, for example.
Of the phenoxy resin and the plasticizer-resistant resin layer 2 made of a phenoxy resin are laminated.

In such a printed matter 10, the image receiving layer 3 of the thermal transfer recording medium shown in FIG. 3 is placed on the substrate 5 and heated and pressed to thermally bond the image receiving layer 3 and the substrate 5, and then By peeling and removing the support 1 from the plasticizer-resistant resin layer 2, a printed matter 10 as illustrated is obtained.

FIG. 4 is a diagram showing a state in which an image is formed on a thermal transfer recording medium similar to the thermal transfer recording medium shown in FIG. 1 by thermal fusion type thermal transfer recording using a thermal fusion ink.

This thermal transfer recording medium has a plasticizer-resistant resin layer 2 made of a phenoxy resin on a support 1, and an image receiving layer 13 capable of receiving, for example, a heat-fusible ink layer, and further, an image receiving layer 13. A heat-meltable ink image 14 that has been thermally transferred and recorded using a heat-meltable ink ribbon and a thermal head (not shown) is formed on the upper surface.

FIG. 5 is a diagram showing a constitution of an example of a printed matter formed by using a thermal transfer recording medium having a heat-meltable ink image.

This printed matter 20 is provided with an image receiving layer 13 capable of receiving a heat-meltable ink layer in place of the image receiving layer 3 capable of receiving a sublimable ink, and a heat-meltable ink image 14 in place of the sublimable ink image 4. Except for the above, it has the same configuration as the printed matter 10 shown in FIG. Similarly, the heat-meltable ink image-receiving layer 13 of the thermal transfer recording medium is placed on the substrate 5 and heated and pressed to thermally bond the heat-meltable ink image-receiving layer 13 and the substrate 5, and then to the support. By peeling and removing 1 from the plasticizer-resistant resin layer 2, a printed matter 20 as shown is obtained.

It is desirable that the plasticizer-resistant resin layer has not only the performance of blocking the plasticizer but also the adhesive strength with the support is appropriately adjusted. If the adhesive strength is too high, after heat bonding,
It becomes difficult to peel off the support, and if force is applied with force, the plasticizer-resistant resin layer and the image-receiving layer may be peeled off together on the base material, making it impossible to leave them on the base material side. If the adhesive force is too small, the plasticizer-resistant resin layer and the image receiving layer in the undesired areas other than the heat-bonded areas also tend to be transferred onto the substrate.

In the present invention, a phenoxy resin is used as the resin having such an appropriate adhesive force.

Examples of suitable phenoxy resin include PKHH, PKHJ, PK manufactured by Union Carbide under the trade name.
HW-35, PKHW-35R, PXKS-6994,
PXKS-7000, Tohto Kasei Co., Ltd. YP-50, Y
P-50S, YP-40ASM40, YP-50EK3
5, YPB-40AM40 etc. are raised.

In addition to the phenoxy resin, a small amount of polyester resin, epoxy resin, tackifier, etc. can be added to the plasticizer-resistant resin layer.

For example, by adding a polyester resin, the adhesive force to the substrate can be increased, and the peeling force can be adjusted by the addition amount. Also,
By adding the epoxy resin, the adhesive force to the base material can be reduced.

The plasticizer resin layer may be applied alone or in combination with, for example, an ultraviolet absorbing layer or a solvent resistant layer. For example, by using it in combination with an ultraviolet absorbing layer, fading of a recorded image due to ultraviolet rays can be reduced. Further, by using it in combination with a solvent resistant layer, it can be protected from destruction by an organic solvent.

The resin used in the image-receiving layer is excellent in dye receptivity of sublimation type thermal transfer ink and / or in adhesiveness to melt type thermal transfer, and also in adhesiveness to a substrate such as paper or plastic. Those that are preferable.

Examples of resins satisfying these conditions include vinyl acetate resins, ethylene-vinyl acetate copolymer resins, acrylic resins, polyester resins, polyurethane resins and mixtures of these resins.

The sublimation type thermal transfer ink receiving layer is preferably acrylic resin, polyester resin or polyurethane resin.

The heat-meltable ink receiving layer is preferably vinyl acetate resin or ethylene-vinyl acetate copolymer resin.

Specific examples of the vinyl acetate resin include Denki Kagaku Kogyo Co., Ltd., trade name Sakunor SN-04, Sakunor SN-04S, Sakunor SN-04D, Sakunor SN-09A, Sakunor SN-09T, and Sakunor SN-. 10, Sakunol SN-10N, Sakunol SN
-17A, ASR CH-09, ASR CL-13,
Clariant Polymer Co., Ltd. Movinyl DC, Daicel Chemicals Co., Ltd. Sebian A530, Sebian A70
0, Severian A707, Severian A710, Severian A
712, and Sebian A800.

Specific examples of the ethylene-vinyl acetate copolymer resin include Mitsui, DuPont, Polychemical Co., Ltd.
Product name Evaflex 45X, Evaflex 4
0, Evaflex 150, Evaflex 210, Evaflex 220, Evaflex 250, Evaflex 260, Evaflex 310, Evaflex 360, Evaflex 410, Evaflex 42
0, Evaflex 450, Evaflex 460, Evaflex 550, Evaflex 560, Movinyl 081F manufactured by Clariant Polymer Co., Ltd., Evatate D3022, D3012, D40 manufactured by Sumitomo Chemical Co., Ltd.
32, CV8030, hirodyne 1800-5, hirodine 1800-6, hirodine 1800-8, hirodine 3706, hirodine 430 manufactured by Herodine Industry Co., Ltd.
9, Bond CZ250, Bond CV31 manufactured by Konishi Co., Ltd.
05 etc.

As the acrylic resin, specifically, SEBIAN A4500 manufactured by Daicel Chemicals Co., Ltd.
0, Cébian A45610, Cébian A46777, Cébian A4635, Mitsubishi Rayon Co., Ltd. DIANAR BR-80, DIANAL BR-83, DIANAL B
R-85, Dinal BR-87, Dinal BR
-101, Dialnal BR-1002, Dialard BR-105, Dialard BR-106, Dialard BR-50, Dialard BR-52, Dialard BR-60, Dialard BR-73, Dialard B
R-75, Dialnal BR-77, Dialard BR
-80, Dinal BR-82, Dinal BR-
83, Dinal BR-85, Dinal BR-8
7, Dynal BR-88, Dynar BR-9
5, DIALAL BR-100, DIALNAL BR-1
08, Dinal BR-113 and the like.

As the polyester resin, specifically,
Toyobo Co., Ltd. Byron 200, Byron 220, Byron 240, Byron 245, Byron 280, Byron 296, Byron 530, Byron 560, Byron 600, Byron 290, Byronal MD110.
0, Bayronal MD1200, Bayronal MD12
45, Bayronal MD1400, Bayronal GX-
W27, Elitel UE-3300 manufactured by Unitika Ltd.,
Elitel UE-3320, Elitel UE-335
0, Elitel UE-3370, Elitel UE-33
80, Elitel UE-3600, Elitel UE-9
600, Elitel UE-3690 and the like.

As the polyurethane resin, specifically,
Daicel Chemical Products Co., Ltd. Solucote 1051, S
olucote1051-1, Solucote105
4-1, Solucote 1059 and the like can be mentioned.

For the plasticizer-resistant resin layer and the image-receiving layer having excellent image-receiving properties, a coating solution containing the above-mentioned resin is prepared and prepared by a method such as gravure coating, reverse coating, die coating, wire bar coating, and hot melt coating. , Apply,
It can be formed by drying.

[0044]

EXAMPLES Examples 1 and 2 As a support, a transparent polyester film having a thickness of 25 μm (manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd., product number: Diafoil S100) was prepared. On one side of this transparent polyester film, a coating solution for a plasticizer resin layer having the following composition was applied using a gravure coater so that the coating film thickness after drying would be 1 μm. Then, at 120 ℃ 2
After heating and drying for a minute, a plasticizer-resistant resin layer was formed.

Plasticizer-resistant resin layer coating solution composition Methyl ethyl ketone 92 parts by weight Water 4 parts by weight Phenoxy resin 4 parts by weight In addition, as a phenoxy resin, Union Carbide P
The one using KHH was designated as Example 1, and the one using PKHC manufactured by Union Carbide was designated as Example 2.

Next, an image-receiving layer coating solution having the following composition was applied onto the obtained plasticizer-resistant resin layer using a gravure coater so that the coating film thickness after drying would be 6 μm. The obtained coating film was heated and dried at 120 ° C. for 2 minutes to form an image receiving layer, thus obtaining a thermal transfer recording medium.

Plasticizer-resistant resin layer coating liquid composition Methyl ethyl ketone 40 parts by weight Toluene 40 parts by weight Byron 240 manufactured by Toyobo Co., Ltd. 20 parts by weight Using a heat melting type ink ribbon on the image receiving layer of the obtained thermal transfer recording medium. A color image was recorded with a thermal head of 300 dpi. Further, a card substrate manufactured by Toray Industries, Inc. was brought into contact with the receiving layer on which the color image was formed, and heated and pressed by a laminator LPD2306City manufactured by Fuji Plastics Co., which was adjusted to a roller temperature of 180 ° and a roller rotation speed of 1 m / min. An ID card was obtained by heat-bonding and then peeling off the support.

Each of the ID cards thus obtained was tested and evaluated for reproducibility of image points and fusion property with a vinyl chloride sheet as follows.

Reproducibility test of image points The reproducibility of the image points was visually observed using a 25 × magnifying glass with respect to the shape of the image points of the color image of the obtained ID card. As a result, those with small variations in the shape of the image points were evaluated as ◯, and those with large variations in the shape of the image points were evaluated as x.

Fusion test with vinyl chloride The fusion property with vinyl chloride was determined by stacking the obtained ID card with PVC sheet Altron All Season # 3300 manufactured by Mitsubishi Chemical MKV Co., Ltd. and applying a load of 15 g / cm ² . Call
After storing for 24 hours in a constant temperature bath adjusted to 75 ° C., the degree of fusion with the vinyl chloride sheet was observed.

As a result, those in which the vinyl chloride sheet and the ID were fused were evaluated as ◯, and those not fused were evaluated as x.

The reproducibility test of the image points was good in both Examples 1 and 2.

Further, fusion with vinyl chloride did not occur at all, and there was no problem in fusion property.

The results of the above evaluations are shown in Table 1 below.

Comparative Examples 1 to 4 In the same manner as in Example 1 except that the resin layer coating liquid having the following composition was used in place of the plasticizer-resistant resin layer coating liquid, the coating film thickness after drying was 1 μm. Such a resin layer was formed.

Resin layer coating liquid composition Methyl ethyl ketone 48 parts by weight Toluene 48 parts by weight Various resins shown in Table 1 4 parts by weight Next, an image receiving layer was formed on the obtained resin layer in the same manner as in Example 1, A thermal transfer recording medium was obtained.

An ID card was obtained in the same manner as in Example 1 using the obtained thermal transfer recording medium.

The ID card thus obtained was tested and evaluated in the same manner as in Example 1.

The results are shown in Table 1 below.

[0060]

[Table 1]

As is apparent from Table 1 above, when the thermal melting type thermal transfer recording is carried out using the thermal transfer recording medium having the plasticizer-resistant resin layer containing the phenoxy resin according to the present invention, the reproducibility of the image points is good. It was found that fusion with vinyl chloride did not occur. However, when another resin layer is formed instead of the plasticizer-resistant resin layer containing the phenoxy resin as in Comparative Examples 1 to 4, fusion with vinyl chloride occurs, and long-term storage is impossible. Do you get it.

Examples 3 and 4 In the same manner as in Example 1, a plasticizer resin layer was formed on the transparent polyester film. On the obtained plasticizer-resistant resin layer, an image receiving layer was formed in the same manner as in Example 1 except that Byron 200 was used instead of Byron 240 manufactured by Toyobo Co., Ltd. to obtain a thermal transfer recording medium. It was

A color image was formed on the obtained thermal transfer recording medium in the same manner as in Example 1 except that a sublimable ink ribbon was used in place of the heat-meltable ink ribbon to obtain an ID card.

When the obtained ID card was subjected to the vinyl chloride fusion test in the same manner as in Example 1, no fusion occurred at all.

Regarding the image formed by the sublimable ink,
The dye diffusion test was conducted as follows.

Dye Diffusion Test of Sublimable Ink The dye diffusion of the sublimable ink was visually observed using a 25 × magnifying glass to see how the dye of the color image of the obtained ID card was diffused. As a result, the image having the same image as before the test was evaluated as ◯, and the image in which the dye was diffused and looked blurred was evaluated as x.

Comparative Examples 5 to 8 Instead of the coating liquid for the plasticizer-resistant resin layer, the above Comparative Example 1 was used.
A thermal transfer recording medium was obtained in the same manner as in Example 3 except that the same resin layer coating solution as in Nos. 4 to 4 was used.

An ID card was obtained in the same manner as in Example 1 using the obtained thermal transfer recording medium.

The ID card thus obtained was tested and evaluated in the same manner as in Example 3.

The results are shown in Table 2 below.

[0071]

[Table 2]

As is clear from Table 2, when sublimation type thermal transfer recording is carried out using the thermal transfer recording medium having the plasticizer-resistant resin layer containing the phenoxy resin according to the present invention, the dye diffusion does not occur. It was found that fusion with vinyl chloride did not occur. However, when another resin layer is formed instead of the plasticizer-resistant resin layer containing a phenoxy resin as in Comparative Examples 5 to 8, fusion with vinyl chloride and diffusion of dye occur, which makes long-term storage impossible. It turned out that

[0073]

EFFECTS OF THE INVENTION By using the thermal transfer recording medium of the present invention, even if it is stored by being piled up with a resin containing a plasticizer such as vinyl chloride, the fusion with the resin and the deterioration of the image do not occur, and it can be used for a long time A print that can be stably stored is obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing the configuration of an example of a thermal transfer recording medium according to the present invention.

FIG. 2 is a sectional view showing a manufacturing process of an example of a printed matter according to the present invention.

FIG. 3 is a sectional view showing a configuration of an example of a printed matter according to the present invention.

FIG. 4 is a sectional view showing a manufacturing process of another example of the printed matter according to the present invention.

FIG. 5 is a cross-sectional view showing the configuration of another example of the printed material according to the present invention.

[Explanation of symbols]

1 ... Support, 2 ... Plasticizer-resistant resin layer, 3, 13 ... Image receiving layer,
4, 14 ... Image, 5 ... Base material, 6 ... Ink ribbon support,
7 ... Sublimable ink layer, 8 ... Ink ribbon, 9 ... Thermal head, 10 ... Printed matter

Claims (4)

[Claims] 1. A support, a plasticizer-resistant resin layer mainly containing a phenoxy resin formed on the support, and a heat-bondable heat-meltable ink image formed on the plasticizer-resistant resin layer. A thermal transfer recording medium comprising a layer. 2. A support, a plasticizer-resistant resin layer mainly containing a phenoxy resin formed on the support, and a heat-bondable sublimable ink image-receiving layer formed on the plasticizer-resistant resin layer. A thermal transfer recording medium comprising: 3. A plasticizer-resistant resin layer containing mainly a phenoxy resin, a heat-bondable heat-meltable ink image-receiving layer laminated on the plasticizer-resistant resin layer, and a heat-meltable ink image-receiving layer on the heat-meltable ink image-receiving layer. A printed matter comprising: a heat-meltable ink image that has been image-received; and a base material that is thermally bonded to the heat-meltable ink image-receiving layer via the heat-meltable ink image. 4. A plasticizer-resistant resin layer mainly containing a phenoxy resin, a heat-bondable sublimable ink image-receiving layer laminated on the plasticizer-resistant resin layer, and an image-receiving layer on the heat-meltable ink image-receiving layer. A printed matter comprising the sublimable ink image formed as described above, and a substrate thermally bonded to the sublimable ink image-receiving layer via the sublimable ink image.