JP2566133B2 - Receptor for thermal transfer recording using sublimable dye - Google Patents

Description

The present invention relates to an image receptor for thermal transfer recording using a sublimable dye.

[Field of Industrial Application] An image receptor for heat-sensitive transfer recording using a sublimable dye of the present invention is used for color recording and television image color recording in OA terminals such as facsimiles, printers and copiers, which are rapidly becoming popular in recent years. It can be advantageously used for recording.

[Conventional technology]

Various methods such as electrophotography, ink jet, and thermal transfer recording have been studied for color recording such as color recording in the OA terminal and color recording of television images.
The thermal transfer recording method is more advantageous than other methods in terms of maintainability of the apparatus, easiness of operation, and low cost of the apparatus and consumables.

In the thermal transfer recording method described above, the image receiving material is superposed on the ink application surface of the color sheet in which the ink containing the dye and the binder is applied on the sheet-shaped substrate, and the back surface of the color sheet is heated by the thermal head. Recording is performed by heating and transferring the dye in the color sheet to the image receptor.

Such thermal transfer recording methods include a melt transfer recording method using a color sheet coated with a heat-meltable ink and a sublimation transfer recording method using a color sheet coated with an ink containing a sublimable dye. In the method, since the sublimation transfer amount of the dye can be easily controlled by adjusting the energy applied to the thermal head, gradation expression is easy and it is particularly advantageous for color recording.

Since the image receptor in the sublimation transfer recording method needs to dye the dye sublimated from the color sheet on the image receptor, the surface of the image receptor is mainly composed of a thermoplastic resin having a high affinity with the dye used. However, since the temperature of the thermal head is generally 200 ° C. or higher, the ink binder of the color sheet and the thermoplastic resin of the image receiving layer are heated. Therefore, there is a problem in that the color sheet is softened or melted, the color sheet and the image receptor are welded, and it becomes difficult to separate the both after recording.

Further, the obtained record is required to have long-term stability such that the color tone of the record does not fade or discolor over a long period of time and the image of the record is not blurred.

Conventionally, as a method of preventing fusion between such a color sheet and an image receptor, a method of improving heat resistance by using a crosslinkable resin in the image receiving layer (JP-A-58-215398, JP-A-58398).
No. 212994), or a method of roughening the surface of the image receiving layer by adding a pigment to the resin of the image receiving layer (JP-A-57-107885). However, in the former method, the resin of the image-receiving layer is cured by crosslinking, so that dyeing during transfer is poor and the color density is low. Also,
In the latter method, due to the roughening of the surface, the adhesion between the color sheet and the image receptor during transfer becomes insufficient, and a decrease in color density or color unevenness easily occurs, and the dye attached to the surface of the pigment during transfer is There was a drawback that later it would contaminate other papers.

Further, as an attempt to prevent the fusion of the color sheet and the image receptor, a method of applying silicone grease on the image receiving layer (JP-A-59-165688), or an amino-modified silicone and epoxy in the image receiving layer. A method has been proposed in which a reaction-cured product with a modified silicone is contained (JP-A-60-34898). However, the method using these silicone compounds has a drawback that the dye transferred from the former elutes in the grease and the image oozes out, and the latter does not completely react with the amino group and the epoxy group, and the epoxy group does not react. In the case of remaining, the remaining epoxy group reacts with the dye sublimated and transferred, and the dye discolors, so that there is a problem that the storage stability and stability of the recording are reduced.

[Problems to be solved by the invention]

An object of the present invention is to provide an image receptor for thermal transfer recording using a sublimable dye, which is excellent in peeling from a color sheet after transfer recording and which is excellent in stability.

[Means for solving problems]

The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, have they decided to include a specific amino-modified silicone in the image-receiving layer mainly composed of a thermoplastic resin formed on the surface of a substrate? The inventors have found that the object can be easily achieved by providing a layer containing a specific amino-modified silicone on the image receiving layer, and have reached the present invention.

That is, the image receptor for thermal transfer recording using the sublimable dye of the present invention is an image receptor having an image receiving layer containing a thermoplastic resin as a main component on the surface of the substrate, and the surface of the image receiving layer has an amine equivalent of 1900 or less. And an amino-modified silicone-containing layer containing the above amino-modified silicone and containing no epoxy-modified silicone.

In the present invention, various means can be used as a means for forming the surface of the image-receiving layer into a layer containing an amino-modified silicone, but usually, the image-receiving layer itself may contain an amino-modified silicone, or a layer containing an amino-modified silicone may be added. Further, it is convenient and preferable to provide a layer containing an amino-modified silicone.

Examples of the substrate for the image receptor of the present invention include various papers made of cellulose fibers, various synthetic papers made of synthetic resin, and plastic films.

As the thermoplastic resin for forming the image receiving layer in the image receiving material of the present invention, a disperse dye is generally used as a sublimation dye, and therefore a resin having an excellent affinity with such a dye (color) is desirable. Examples of the thermoplastic resin include dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid, ethylene glycol, diethylene glycol,
Polyester resins obtained by condensation with glycol components such as propylene glycol and neopentyl glycol, acrylic resins such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, polystyrene, AS resins, polycarbonate, polysulfone, polyvinyl Prolidon,
Examples thereof include ethyl cellulose, acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, etc., but saturated linear polyester resin and acrylic resin are disperse dyes. It is particularly preferable because it has an excellent affinity with. Further, these resins may be used alone or in a mixture.

Examples of the amino-modified silicone used in the present invention include compounds having structures represented by the following formulas (A) and (B) (in each formula, R represents CH ₃ or OCH ₃ ).

Amino-modified silicones having the structures represented by these formulas include, for example, Shin-Etsu Silicone from Shin-Etsu Chemical Co., Ltd.
KF-393, KF-857, KF-858, KF-859, KF-860, KF-861, KF
-862, KF-864, KF-865, X-22-3680, X-22-380D, X-2
It is marketed under the trade names 2-380C and KF-867. Of these, those with an amine equivalent weight of 1900 or less, such as KF
Since -393, KF-857, KF-862, KF-867 and the like show particularly excellent performance, an amino-modified silicone having an amine equivalent of 1900 or less is selected and used in the present invention.

The amine equivalent is represented by a value obtained by dividing the molecular weight of the silicone by the number of amino groups contained in the amino-modified silicone molecule. The smaller the amine equivalent, the higher the content of amino groups. The amine equivalents of the products are shown in the table below.

If an amino-modified silicone having an amine equivalent of 1900 or less is selected and used, the fusion between the color sheet and the image receptor can be sufficiently prevented without using the epoxy-modified silicone together. When used in combination, as described above, the unreacted epoxy group causes modification of the dye, resulting in deterioration of storage stability and stability of recording (see Comparative Example 11).

As a method of forming an image receiving layer containing an amino modified silicone in the image receiving layer itself in the present invention, an amino modified silicone is added to and mixed with a stock solution for an image receiving layer in which a thermoplastic resin is dissolved or dispersed in a suitable solvent. The prepared coating solution may be applied onto a substrate and dried, but heat treatment under appropriate conditions after drying can improve the peelability from the color sheet after transfer. Appropriate heat treatment conditions are 50 to 120 ° C. and 10 to 60 minutes.

The amount of the amino-modified silicone added is preferably 1 to 20% by weight based on the thermoplastic resin.

Water and various organic solvents are used as the solvent. As the organic solvent, toluene, aromatic solvents such as xylene, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone,
Ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol, isopropanol, butanol and methyl cellosolve, halogenated hydrocarbon solvents such as methylene chloride, trichloroethylene and chlorobenzene, ether solvents such as dioxane and tetrahydrofuran. Amide solvents such as dimethylformamide and N-methylpyrrolidone are used.

In addition to the above components, the coating liquid may further contain an ultraviolet absorber, an antioxidant, a light stabilizer, a brightening agent, etc., if necessary.

As the coating method, for example, a method using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, etc. (For details of these, refer to Yuji Harasaki, a bookstore, "Coating method" issued in 1977), etc. Used. The thickness of the image-receiving layer formed on the substrate is 0.1 to 10 μm, preferably 1 to 5 μm, as a dry coating film.

In order to obtain an image receptor obtained by forming a layer containing an amino-modified silicone on the image-receiving layer, which is another embodiment of the present invention, the above-mentioned image-receiving layer is used except that a coating solution containing no amino-modified silicone is used. The image-receiving layer may be formed on the substrate by the same method as the method described in 1. above, and the layer containing the amino-modified silicone may be further formed thereon.

As a method for forming the layer containing the amino-modified silicone, the amino-modified silicone was prepared alone or diluted with an appropriate solvent, and in some cases, mixed with a resin having good permeability of a sublimable dye. The solution is coated on the image-receiving layer containing no amino-modified silicone,
Just dry it. The applied film thickness is 0.00 as a dry film thickness.
It is 1 to 5 μm, preferably 0.01 to 1 μm.

There are various sublimable dyes used in the color sheet for thermal transfer recording using the image receptor of the present invention. For example, various sublimable dyes such as azo-based, anthraquinone-based, nitro-based, styryl-based, naphthoquinone-based, quinophthalone-based, azomethine-based, coumarin-based, and condensed polycyclic dyes are used.

〔The invention's effect〕

The image receptor of the present invention has good peeling from the color sheet after transfer recording, can obtain recording with good gradation and resolution, and has good storage stability of recording.

[Examples, etc.]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these Examples do not limit the present invention.
All "parts" described in these examples mean "parts by weight".

Example 1 a) Production of image receptor Saturated polyester resin TP-220 (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts, methyl ethyl ketone 15 parts, xylene
15 parts of amino-modified silicone KF-393 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and dissolved to obtain a coating solution for the image-receiving layer, and a synthetic paper Peachcoat WP-110 (Nisshinbo Industries, Inc.) (Product name) applied with wire bar No. 3 (wet film thickness 24 μm), then dried with hot air with a dryer,
A dry coating film (image receiving layer) having a thickness of about 7 μm was formed. Further, an image receptor was manufactured by heating in an oven at 100 ° C. for 30 minutes.

b) Production of color sheet Using a biaxially stretched polyethylene terephthalate film (thickness: 6 μm) whose back surface on which an ink was applied was heat-treated with a polyimide resin as a base film, a color sheet was produced by the method described below.

That is, the chemical structural formula 2 g of anthraquinone-based sublimable dye having, cellulose acetate (trade name L-30 manufactured by Daicel Chemical Industries, Ltd.) 10
An ink prepared by treating a mixture of 100 g of methyl ethyl ketone and 100 g of methyl ethyl ketone with a paint conditioner using glass beads for about 30 minutes is applied on the above-mentioned polyethylene terephthalate film using a wire bar and dried to obtain a color sheet (dry film thickness). About 1 μm) was obtained.

c) Transfer recording Overlying the ink-coated surface of the color sheet with the image-receiving layer surface of the image-receiving body, a thermal head having a heating resistor density of 4 dots / mm was used, and a power of 0.6 W / dot was applied.
Recording was carried out by applying various times as shown in Table 1 below. The result was that the sheet and the image receptor did not fuse during recording. Also, the sheet and the image receptor could be easily separated after recording.

Further, the obtained record has good resolution of each dot and shows a clear magenta color, and its color density is
As shown in the table, it increased with the application time. In addition,
Color density is densitometer RD-51 manufactured by Macbeth, Inc.
It was measured using a 4 type (filter: Ratten No. 58) (the same applies to Example 2 and thereafter).

The recorded image receptor is 60 ° C and 80% relative humidity.
When the recording stability was tested by leaving it for 3 days, no bleeding occurred in the recording, and discoloration and fading did not occur.

Example 2 a) Production of image receptor Polyester resin aqueous dispersion Bayronal MD-1200 (trade name, manufactured by Toyobo Co., Ltd., solid content: 34%) was applied to synthetic paper Peachcoat WP-110 (trade name, manufactured by Nisshinbo Co., Ltd.). After coating with wire bar No. 3 (wet film thickness 24 μm), it was dried with hot air using a dryer to form an image receiving layer of about 8 μm. Furthermore, on its surface, 5 parts of amino-modified silicone KF-393,
Apply a mixed solution of 95 parts of toluene with wire bar No. 1 (wet film thickness 6 μm) and dry with hot air with a dryer.
Further, it was heated and dried in an oven at 100 ° C. for 30 minutes to produce an image receptor.

b) Production of color sheet The same procedure as in Example 1 was carried out.

c) Transfer recording When transfer recording was performed in the same manner as in Example 1, there was no fusion of the image receiver and the sheet during recording, and the image receiver and the color sheet could be easily separated after recording.

In addition, each of the obtained recordings has good resolution of each dot and shows a clear magenta color, and its color density is
As shown in the table, it increased with the application time.

Furthermore, each record was tested by leaving it at 60 ° C and 80% relative humidity for 3 days, and there was no color bleeding or discoloration.
It showed good stability.

Examples 3 and 4 KF-393 used in Example 1 in the coating liquid for the image receiving layer.
Various image receivers were produced in the same manner as in Example 1 except that KF-857 (Example 3) or KF-867 (Example 4) was used instead of the above. Transfer recording was carried out in the same manner as in Example 1 except that each of these image receivers was used. In all cases, there was no fusion between the image receiver and the sheet during recording,
After recording, the image receptor and the color sheet could be easily separated.

In addition, each of the obtained recordings had good resolution of each dot, and showed a clear magenta color, and its color density increased with application time as shown in Table 1.

Furthermore, each record was tested by leaving it at 60 ° C and 80% relative humidity for 3 days, and there was no color bleeding or discoloration.
It showed good stability.

Examples 5 and 6 Instead of KF-393 used in Example 2, KF-857
Various image receivers were produced in the same manner as in Example 1 except that (Example 5) or KF-867 (Example 6) was used, respectively. Example 1 using each of these image receivers
When transfer recording was carried out in the same manner as in (1), there was no fusion between the image receptor and the sheet during recording, and the image receptor and the color sheet could be easily separated after recording.

In addition, each of the obtained recordings had good resolution of each dot, and showed a clear magenta color, and its color density increased with application time as shown in Table 1.

Furthermore, each record was tested by leaving it at 60 ° C and 80% relative humidity for 3 days, and there was no color bleeding or discoloration.
It showed good stability.

Examples 7 to 9 As sublimable dyes, the dyes shown in Table 2 were used in place of the dyes used in Example 1, and the other examples were used.
A color sheet was manufactured in the same manner as in. Transfer recording was performed in the same manner as in Example 1 except that this color sheet and the same image receptor as in Example 1 were used.

As a result, the color sheet after recording and the image receptor could be easily peeled off, and the obtained recording was good in both gradation and resolution.

Further, when the obtained recording was subjected to a standing test at 60 ° C. and a relative humidity of 80% for 3 days, there was no color bleeding, discoloration or discoloration, and all showed good recording stability.

Comparative Example 1 Except that KF-393 was not included in the coating liquid for the image receiving layer,
An image receptor and a color sheet were manufactured in the same manner as in Example 1.

Example 1 using the obtained image receptor and color sheet
Transfer recording was carried out in the same manner as in. As a result, the color sheet and the image receptor were fused, and peeling was difficult.

Comparative Examples 2 to 7 In place of 0.5 part of KF-393 used in the image-receiving layer coating solution of Example 1, various amino-unmodified silicones shown in Table 3 were used in the respective amounts. An image receptor was manufactured by the same method as in Example 1, and transfer recording was performed by the same method. As a result, in both cases, the color sheet and the image receptor were fused, and peeling was difficult.

Comparative Examples 8 and 9 An image receptor was prepared in the same manner as in Example 2 except that the amino-modified silicone solution shown in Table 4 was used in place of the toluene solution of KF-393 in Example 2. As a result of recording in the same manner, the image receptor and the color sheet were not fused at the time of recording, and the image receptor and the color sheet could be easily separated after the recording. In addition, the obtained recording had a clear magenta color with good gradation and resolution. But this record 60
When stored for 3 days in air at 80 ° C and 80% relative humidity, the dye oozes out and the recorded image is blurred.

Comparative Example 10 KF-393 used in Example 1 in the image receiving layer coating solution
Instead of (amine equivalent 360), KF-859 (amine equivalent 2250
An image receptor was manufactured in the same manner as in Example 1 except that (0) was used. When transfer recording was performed in the same manner as in Example 1 except that this image receptor was used, the color sheet and the image receptor tended to be fused, and peeling was difficult.

Comparative Example 11 Instead of the mixed solution of 5 parts of KF-393 (amino-modified silicone) and 95 parts of toluene used in Example 2,
KF-393 1 part, KF-101 (epoxy modified silicone) 4
An image receptor was produced in the same manner as in Example 2 except that a mixed solution of 1 part and 95 parts of toluene was used. Using this image-receiving paper and the color sheet of Example 7, the transfer recording was performed in the same manner as in Example 1 except that the image-receiving member and the color sheet were not fused during recording, and the image-receiving member was formed after recording. The color sheet could be easily peeled off. However, when this record was stored in air at 60 ° C. and 80% relative humidity for 3 days, discoloration of the recorded image was observed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-165688 (JP, A) JP-A-61-102293 (JP, A) JP-A-60-212394 (JP, A) JP-A-61- 27290 (JP, A)

Claims (3)

(57) [Claims] 1. An image receptor having an image receiving layer containing a thermoplastic resin as a main component on the surface of a substrate, wherein the surface of the image receiving layer is
Contains amine-modified silicone with an amine equivalent of 1900 or less,
An image receptor for heat-sensitive transfer recording using a sublimable dye, characterized in that an amino-modified silicone-containing layer containing no epoxy-modified silicone is formed. 2. The image receptor according to claim 1, wherein the image-receiving layer itself contains an amino-modified silicone. 3. The image receptor according to claim 1, further comprising an amino-modified silicone-containing layer provided on the image-receiving layer.