JPH02273293A - Image receiving medium for sublimation type thermal transfer - Google Patents

Abstract

PURPOSE:To improve the releasability between an image receiving medium (dye receiving layer) and a transfer recording medium (dye transfer layer) while the adhesive strength between a substrate and the dye receiving layer is held by providing an intermediate layer based on a specific vinyl chloride resin between the substrate and the dye receiving layer based on a vinyl chloride resin and a release agent. CONSTITUTION:An intermediate layer C mainly composed of a vinyl chloride resin containing a COOH-group and a dye receiving layer B mainly consisting of a vinyl chloride resin and a release agent are laminated to an image receiving substrate A in this order. A heat-sublimable dye is sublimed and diffused from the dye receiving layer 4 of a sublimable transfer recording medium by the heat from a thermal head 1 and the sublimed dye is transferred to the dye receiving layer B of an image receiving medium. The sublimed dye transferred to the image receiving medium is diffused through the dyeable resin forming the dye receiving layer B to be fixed to said resin. The vinyl chloride resin having the COOH-group used in the intermediate layer C is a copolymer wherein vinyl chloride and a polymerizable unsaturated carboxylic acid are main monomers and vinyl chloride is contained as a main component quantitatively and polymerizable unsaturated carboxylic acid is an auxiliary component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image receiving medium for sublimation type thermal transfer, which is used in combination with a thermal transfer recording medium having a transfer layer containing a heat sublimable dye.

[Conventional technology]

The sublimation thermal transfer recording method, which uses a thermal transfer recording medium having a transfer layer containing a heat sublimable dye and an image receiving medium that receives the dye sublimated by thermal printing from the back side of the recording medium, has excellent halftone recording. In recent years, it has attracted attention as a device that can provide full-color hard copies that are close to color photographs.

Conventionally, the image-receiving medium used in this recording method consists of a dye-receiving layer made of a thermoplastic polyester resin, etc., which exhibits strong dyeability against heat-sublimable dyes, and a release agent, on a substrate (synthetic paper, etc.). The formed one is used. but,
Since polyester resin has low heat resistance, it has the drawback that it fuses with the transfer recording medium (color sheet) during recording and the color fades after storage.

In order to solve these problems, it has been proposed to use vinyl chloride resin alone or in combination with the polyester resin as the resin constituting the dye-receiving layer (Japanese Patent Application Laid-Open No. 1983-1992). -24996, 61-283
No. 595, No. 62-294595, No. 63-511.
No. 81), this vinyl chloride resin can be said to be superior to polyester resins in terms of post-recording releasability, light resistance, storage stability, and the like.

[Problem to be solved by the invention]

However, even when vinyl chloride resin is used as the resin constituting the dye-receiving layer, if the content of the release agent in the dye-receiving layer is low, the adhesion between the transfer substrate and the dye transfer layer may be extremely poor when used as a transfer recording medium. Unless a strong material is used, the transfer layer will be peeled off toward the image-receiving medium after recording.Conversely, the separation in the dye-receiving layer may be sufficiently improved to sufficiently improve the releasability between the transfer recording medium and the image-receiving medium. If the amount of molding agent is increased, the adhesion between the dye-receiving layer and the substrate in the image-receiving medium will be reduced, resulting in the drawback that the receptor layer will be peeled off toward the transfer recording medium after recording.

The present invention solves the above-mentioned problems, has good heat resistance, has high adhesive strength between the substrate and the dye-receiving layer, and has a high adhesive strength between the image-receiving medium (dye-receiving layer) and the transfer recording medium (dye-receiving layer) after recording. It is an object of the present invention to provide an image receiving medium that has good releasability from a transfer layer).

[Means for Solving the Problems] According to the present invention, an intermediate layer mainly composed of a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units, a vinyl chloride resin, and a mold release agent are provided on a substrate. An image-receiving medium for sublimation thermal transfer is provided, characterized in that it is formed by laminating dye-receiving layers mainly consisting of .

That is, the image receiving medium for sublimation thermal transfer of the present invention contains vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units between the substrate and the dye-receiving layer whose main components are a vinyl chloride resin and a release agent. Since the structure includes an intermediate layer mainly composed of a copolymer (hereinafter simply referred to as vinyl chloride resin containing a C0OH group), the substrate is not affected by the release agent in the dye-receiving layer, and therefore While maintaining the adhesive strength between the substrate and the dye-receiving layer, the releasability between the image-receiving medium (dye-receiving layer) and the transfer recording medium (dye-transfer layer) becomes good.

Next, the present invention will be explained with reference to the drawings.The specific structure and operation of the present invention are as follows.

In FIG. 1, the image-receiving medium of the present invention is comprised of an image-receiving substrate A, a dye-receiving layer B, and an intermediate layer C. That is, 1 the image receiving medium of the present invention has an intermediate layer C mainly made of a vinyl chloride resin containing a C0OH group and a dye receiving/WB mainly made of a vinyl chloride resin and a mold release agent on an image receiving substrate A.
It has a structure in which these are laminated in that order. Further, 1 indicates a thermal head, and the sublimation transfer recording medium is composed of a heat-resistant layer 2, a transfer substrate 3, and a dye transfer layer 4.

Heat from the thermal head 1 causes the heat sublimable dye to sublimate and diffuse from the dye transfer layer 4 of the sublimation transfer recording medium, and the sublimated dye is transferred to the dye receiving layer B of the image receiving medium. The sublimation dye transferred to the image-receiving medium diffuses into the dye-staining resin forming the dye-receiving layer B and dyes the medium.

As mentioned above, in conventional image-receiving media, it is known to include a flying agent such as silicone oil in the dye-receiving layer B in order to prevent heat fusion during recording and improve releasability after recording. However, when the H-type agent content is low,
The peelability improvement effect was insufficient, as shown in Figure 2.
After recording, the dye transfer layer 4 is peeled off to the dye receiving layer B side.

However, when the content of the release agent is increased in order to improve the releasability, the adhesive force between the image-receiving substrate A and the dye-receiving layer B becomes weaker, and as shown in FIG. However, the image receiving medium of the present invention has a phenomenon in which the dye receiving layer B is peeled off to the dye transfer layer 4 side.
The dye-receiving layer B is mainly composed of a vinyl chloride resin with excellent mold release properties and a mold release agent, and the intermediate r is mainly composed of a vinyl chloride resin containing a COOH group.
Since the nc is provided between the receiving substrate A and the dye-receiving layer 8, the image-receiving substrate ^ is not affected by the release agent in the dye-receiving layer B, and the relationship between the image-receiving substrate A and the dye-receiving layer NB is The adhesive strength is maintained high, and the adhesive strength is further improved because the intermediate layer C contains a COOH group, and peeling between the image receiving substrate A and the dye receiving layer 8 after recording is prevented, and it is heat resistant. It has excellent properties such as durability, light resistance, and storage stability.

The vinyl chloride resin containing a C0OH group used in the intermediate NC of the present invention is a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as main monomers, and quantitatively, vinyl chloride is the main monomer. component and a polymerizable unsaturated carboxylic acid as a subcomponent. In this case, examples of the polymerizable unsaturated carboxylic acid include acrylic acid, methacrylic acid, and maleic acid.

In addition to vinyl chloride and a polymerizable unsaturated carboxylic acid, this copolymer also contains other comonomers such as vinyl acetate,
Vinyl alcohol derivatives such as vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.
It may contain meth)acrylic acid derivatives; maleic acid derivatives such as diethyl maleate and dibutyl maleate; vinyl ether derivatives such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; and olefins such as ethylene and propylene.

The monomer ratio in the copolymer is 60 to 90 for vinyl chloride.
ft% by weight, 0.5-5% by weight of polymerizable unsaturated carboxylic acid
.

The content of components other than vinyl chloride and polymerizable unsaturated carboxylic acid is preferably about 5 to 39.5% by weight.

Preferred specific examples of this copolymer include the following.

Vinyl chloride/maleic acid copolymer.

Vinyl chloride/acrylic acid copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/acrylic acid copolymer, ethylene/vinyl chloride/maleic acid copolymer, ethylene/vinyl chloride/acrylic Acid copolymer, vinyl chloride/vinyl propionate/acrylic acid copolymer.

Vinyl chloride/vinyl propionate/maleic acid copolymer, etc.

Among these, vinyl chloride/vinyl acetate/maleic acid copolymer is preferably used, and its commercially available products include, for example, VMCH and VMCC manufactured by Union Carbide.
Denkabinir 1oooc, 10 manufactured by Denki Kagaku Kogyo Co., Ltd.
Examples include 0OC3, 100OCK.

Moreover, in the present invention, an incyanate compound can also be added to the intermediate layer C. When an incyanate compound is added, C00)I in the vinyl chloride copolymer
The hardening reaction between the group and the isocyanate compound has the effect of improving the hardness and the abrasion resistance of the surface of the dye-receiving layer B.

In this case, the isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate,
, 4-diphenylmethane diisocyanate, triphenylmethane triisocyanate, and the like, and adducts of these with hexanetriol and the like can also be used. In addition, the usage ratio of the vinyl chloride resin containing the C00I+ group and the incyanate compound is 0.2 to 2.0 in molar ratio of NCO/C00)1.
A range of is preferred.

Examples of the vinyl chloride resin used in the dye receiving date of the present invention include polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, etc., and the vinyl chloride component is 80%
Those with a weight of at least 100% are preferable.

Commercially available products include 1, such as Union Carbide's VY.
) Ill, VYNS, VYHD, VYLF, etc. and Denkabinyl 10100O, 100OA manufactured by Denki Kagaku Kogyo Co., Ltd.
LoooL, 10000, MHEloo, ME120
etc. In addition, as the mold release agent, for example, amino-modified silicone, epoxy-modified silicone, alkyd-modified silicone, etc. are used, and commercially available products include XF393, KF857, KFlooT, and KF1 manufactured by Shin-Etsu Chemical Co., Ltd.
03, KNS305, KS705, PL3, KM740
etc. The ratio of the mold release agent to the vinyl chloride resin is preferably in the range of 1.0 to 20% by weight.

Incidentally, the dye-receiving layer B and the intermediate layer C may also contain a filler. Examples of fillers include white pigments such as silica, titanium oxide, and calcium carbonate, and the amount added is 5 to 6 times the amount of resin in the receiving layer or intermediate Ja.
0% by weight is preferred. others.

These layers can also contain surfactants, ultraviolet absorbers, antioxidants, etc. as appropriate.

In addition, as the substrate A in the image receiving medium of the present invention, synthetic paper, art paper, high quality paper, coated paper, gravure paper, baryta paper, cellulose fiber paper, plastic film, etc. are preferably used alone or in a laminate thereof. used. In particular, the image-receiving medium of the present invention has improved adhesion because the intermediate layer contains C0OH groups, so it maintains sufficient adhesion even with baryta paper, plastic films, etc., where conventional dye-receiving layers had low adhesion. The amount of the dye-receiving layer and intermediate layer coated on the substrate is preferably 0.1 to 20 g/rrr in terms of solid content.

〔Effect of the invention〕

The image receiving medium for sublimation thermal transfer of the present invention has cooy
Since the intermediate layer mainly made of a vinyl chloride resin containing a + group and the dye receiving layer mainly made of a vinyl chloride resin and a release agent are laminated in that order, the dye transfer layer is placed on the dye receiving layer side after recording. There is no peeling off and the dye receiving layer is not peeled off to the dye transfer layer side.
The releasability between the dye-receiving layer and the dye-transfer layer (ie, between the image-receiving medium and the transfer recording medium) is good, and the heat resistance, light resistance, and storage stability are also excellent. In addition, since the intermediate layer contains C0OH groups, its adhesion is improved, so it maintains sufficient adhesion even when the substrate is made of baryta paper, plastic film, etc., which had low adhesion with conventional dye-receiving layers. The dye-receiving layer is not peeled off to the dye-transfer layer side.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts shown below are based on weight.

Example 1 A mixture having the following composition was sufficiently mixed and dispersed to prepare a coating liquid for an intermediate layer [liquid A] and a coating liquid for a receptor layer [liquid B].

[Liquid A]

40 parts of toluene methyl ethyl ketone 40 parts [Liquid B] 80 parts of tetrahydrofuran Next [
[Liquid A] using a wire bar, synthetic paper (trade name: Yubo FPG-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.) with a thickness of approximately 150
After coating on top and drying for 1 minute at a drying temperature of 75°C,
Liquid] was applied onto the intermediate layer using a wire bar and dried for 1 minute at a drying temperature of 75°C. A pm intermediate layer and a receptor layer were formed. Thereafter, the obtained image receptor was heated at 100° C. for 1 hour to prepare an image receiving medium of the present invention.

On the other hand, as a sublimation transfer recording medium, a 6-pa-thick P film with a silicone cured resin film (approximately 1 piece thick) as a back layer was used.
A coating liquid for an ink layer (ie, dye transfer layer) [Liquid C] having the following formulation was coated on the ET film to a thickness of about 2 mm to obtain a transfer recording medium.

[Liquid C]

Images were recorded by changing the heating energy using a single head. The recording density of the thermal head is 6 dots/
Example 2 In Example 1, the following [Liquid D] and [Liquid E] were used instead of [Liquid A] and [Liquid B], respectively. Other than that, Example 1
In the same manner as above, nine image-receiving media of the present invention were prepared.

[Liquid D]

Toluene Methyl ethyl ketone 40 parts 40 parts [Liquid E] Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer recording medium and image receiving medium are overlapped so that the ink layer of the transfer medium and the dye receiving layer of the image receiving medium face each other, and transfer is performed. From the back side of the recording medium, 40 parts of saddleluene and 40 parts of methyl ethyl ketone were then used to record an image in the same manner as in Example 1.Comparative Example] [2 liquid] was used as the coating liquid for the receptor layer. Establish a middle class! Images were recorded on L2 and H images on comparative image receiving media in the same manner as in Example 1, except that there was no error.

[Liquid F] 1-Lueno 40 parts Methyl ethyl ketone 40 parts Comparative Example 3 In Comparative Example 1, F (Liquid II) was used instead of [Liquid 1]. An image receiving medium for comparison was prepared in the same manner as above, and images were recorded.

[Liquid H] 1-Luene 40 parts Methyl ethyl ketone 40 parts Comparative example S
In Comparative Example 1, the following [G liquid] was used instead of [rF liquid].
of.

A comparative image receiving medium was prepared in the same manner as in Comparative Example 1, except that 1.5 IJ images were recorded.

r(liquid) i-Luene 40 parts Methyl ethylene ketone 40 parts The surfaces of the transfer recording medium and the image receiving medium after the image recording were observed at one glance. The results are shown in Table 1.

From Table 1 onwards, it can be seen that by using the image receiving medium for sublimation type thermal transfer of the present invention, there is no possibility that a drop of peeled material will be deposited from the ink sheet to the image receiving medium, and there will be no possibility that the peeled material will be transferred from the image receiving medium to the ink sheet. It can be seen that no fusion of peeled materials occurs.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view showing the image receiving mechanism of the sublimation type thermal transfer image receiving medium according to the present invention, and also includes a schematic sectional view of the sublimation transfer recording medium. A... Image receiving substrate, B... Dye receiving layer, C... Intermediate layer, l... Thermal head, 2... Heat resistant layer of transfer recording medium, 3... Transfer substrate of transfer recording medium , 4...Dye transfer layer of transfer recording medium. FIG. 2 is a schematic cross-sectional view of the image receiving medium and the recording medium when the dye-receiving layer contains less release agent and the dye-receiving layer peels off due to thermal adhesion. Furthermore, FIG. 3 shows that in the conventional image receiving medium, !a
FIG. 3 is a schematic cross-sectional view of an image-receiving medium and a transfer recording medium in which there is a large amount of release agent in the material-receiving layer, resulting in poor peeling due to heat fusion.

Claims (1)

[Claims] (1) An intermediate layer mainly made of a copolymer containing vinyl chloride and a polymerizable unsaturated carboxylic acid as monomer units, and a dye-receiving layer mainly made of a vinyl chloride resin and a mold release agent are laminated on the substrate in that order. An image receiving medium for sublimation type thermal transfer, characterized in that: