JP2572769B2 - Sublimation type thermal transfer recording image receiver - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an image receiving body for thermal transfer recording using a sublimable dye.

[Conventional technology]

Facsimile printers that are rapidly spreading in recent years,
Various methods such as electrophotography, ink jet, and thermal transfer recording have been studied for color recording such as color recording of an OA terminal such as a copying machine and color recording of a television image. In terms of maintainability, ease of operation, and inexpensive equipment and consumables,
This is advantageous as compared with other methods.

The thermal transfer recording method, the dye on the sheet-like substrate,
Superimposing an image receiver on the ink-coated surface of a color sheet coated with ink containing a binder, etc., and heating the back of the color sheet with a thermal head to transfer the dye in the color sheet to the image receiver The recording is performed.

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, the sublimation transfer amount of the dye can be easily controlled by adjusting the energy applied to the thermal head, so that the gradation expression is easy and it is particularly advantageous for color recording.

Since the image receiving body in the sublimation type thermal transfer method needs to dye the dye sublimated from the color sheet onto the image receiving body, the surface of the image receiving body is mainly composed of a resin having a high affinity for the dye to be used. (Hereinafter simply referred to as "image receiving layer"). For this purpose, polyvinylpyrrolidone (Japanese Patent Application Laid-Open No. 57-91296), polyester (Japanese Patent Application Laid-Open No. 57-107885), and hydroxyethyl cellulose (particularly, 57-137191), amino alkyd resin (JP-A-5
8-209596), PVC (JP-A-59-223425), styrene-butadiene copolymer (JP-A-59-229391), phenolic resin (JP-A-59-184339), polycarbonate (JP-A-59-184339)
19138), and the use of resins such as butyral resin (JP-A-61-11293) is described in the above patents.

By the way, the image receiving body not only dyes the sublimed dye and obtains a high-density record, but also ensures that the color of the obtained transfer record does not fade or discolor, It is necessary that the storage stability of the recorded matter such that the image of the matter is not blurred is also good.

Further, when producing an image receiving body, it is necessary to dissolve or disperse the resin for forming the image receiving layer in an appropriate solvent and apply it on the surface of the substrate. Therefore, the resin used for forming the image receiving layer is a solvent. It is necessary that the solubility or dispersibility of the compound be good.

However, the image receiver using the resin described in any of the above patents does not necessarily satisfy all the requirements of the above image receiver.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image receiving body for sublimation-type thermal transfer recording that is easy to manufacture, enables high-density transfer recording, and has excellent storage stability of recorded matter.

[Means for solving the problem]

The present inventors have studied the resin forming the image receiving layer.As a result, it is easy to manufacture by using a copolymer resin formed with acrylonitrile and styrene as essential components, and high density transfer recording is possible. In addition, it has been found that an image receiver having good storage stability of a recorded matter can be obtained.

That is, the present invention provides at least one copolymer selected from the group consisting of acrylonitrile-acryl rubber-styrene copolymer resin, acrylonitrile-ethylene propylene rubber-styrene copolymer resin, and acrylonitrile-chlorinated polyethylene-styrene copolymer resin. The present invention provides a sublimation type thermal transfer recording image receiving body having an image receiving layer mainly composed of a resin and a release agent on the surface of a substrate.

The copolymer resin used in the present invention includes acrylonitrile-special acrylic rubber-styrene copolymer resin (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer resin (AES resin), and acrylonitrile-chlorinated polyethylene-styrene copolymer. It is a resin selected from resins (ACS resin).

As a method for producing these resins, when producing this type of copolymer, it is selected from generally employed methods,
For example, a solution polymerization method in which each resin material component is dissolved and polymerized in a hydrocarbon or aromatic solvent, a suspension polymerization method in which polymerization is performed in an aqueous dispersion system, and a method in which copolymerization or graft polymerization is performed by an emulsion polymerization method. No. As a catalyst for these polymerizations, an ordinary radical polymerization catalyst is used. The properties of the resins vary depending on the ratio of the raw material components, the polymerization method, etc., but the copolymer used in the present invention preferably has a heat distortion temperature (ASTMD-648 method) in the range of 60 to 120 ° C. It is. If resins having a heat distortion temperature in these ranges are used, these resins are appropriately softened by heat during transfer recording, and the dye sublimated and transferred can be diffused inside. In addition, since these resins have good affinity for the dye, the dye is strongly dyed, and the dyed dye does not migrate under normal conditions, and a recorded matter having good fixability can be obtained. Can be. Furthermore, in these resins, since the stability of the dye is good, a good recorded matter without fading can be obtained, and a recorded matter with particularly good light fastness can be obtained.

Specific examples of these resins include the following products that are generally commercially available for molding materials.

AS resins include, for example, Tyryl-767, 769, 78
9, 783, Styracure 709, 703, 727 (trade name, manufactured by Asahi Kasei Corporation), Estyrene AS-20, AS-3
0, AS-41, AS-61 (all trade names, manufactured by Nippon Steel Chemical Co., Ltd.), Sebian-N-020, 020F, 020SF, 010, 050, 050
F, 050SF, NF-1, 080SF, NF012A (trade name, manufactured by Daicel Chemical Industries, Ltd.), Denka AS-S, H (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.), Lightac 330PC, 200
PC, 100PC, 120PC (trade names, manufactured by Mitsui Toatsu Chemicals, Inc.), Sunlex SAN-C, SAN-H, Collimate S-325, S
-320, S-315 (trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) and Kibisan PN-117, PN-127, PN-127H (trade name, manufactured by Baoli Chemical Co., Ltd.).

As AAS resins, for example, Vitax V6100A, V61
01AH, V6101A, V6000, V6001, V6001A, V6700, V6701,
V6702, V6101AK, V8000, V9000, V6810, V6815, V682
0, Vaifunen VN201E, VN301, VN303, VN100E (all trade names, manufactured by Hitachi Chemical Co., Ltd.).

As AES resin, for example, Unibright # 701, # 60
1, # 500, # 500K, # 801, # 300, # 401, # 901 (trade name, manufactured by Sumitomo Nogatack Co., Ltd.), JSR AES110,
115, 145, 117, 147, 550 (trade names, manufactured by Nippon Synthetic Rubber Co., Ltd.).

As the ACS resin, for example, ACS resin NF-920, NF-960,
NF-1060 and NF-760 (trade names, manufactured by Showa Denko KK).

The above resins may be used alone or in a mixture in the image receiving layer of the present invention. The image-receiving layer of the present invention contains the above resin as a main component. In some cases, the resin further contains a saturated polyester resin, an acrylic resin, a methacrylic resin, a styrene resin, a polycarbonate resin, a cellulose acetate,
Polyvinyl butyral, vinyl chloride resin, vinyl chloride,
It may contain a vinyl acetate copolymer resin, a polyarylate resin, or the like.

The image receiving layer needs to contain a release agent in order to prevent heat fusion with the color sheet image receiving body at the time of transfer recording and to improve releasability of both after transfer, and for this purpose. Particularly preferably, a silicone compound is used, but other various waxes, fluorine compounds, fine particles and the like are also effectively used. Further, in order to obtain releasability, a layer containing these release agents may be formed on the image receiving layer.

The image receiving layer or the layer containing a release agent formed on the image receiving layer contains an ultraviolet absorber, a light stabilizer, an antioxidant, an optical brightener, an antistatic agent, and the like. Is also good.

Examples of the base of the image receiving body include various papers formed from cellulose fibers, various synthetic papers synthesized from synthetic resins, and plastic films.

As a method for forming the image receiving layer of the present invention, the copolymer resin containing acrylonitrile and styrene as essential components is dissolved in a suitable solvent, a suitable release agent is added, and if necessary, other resins and What is necessary is just to add the above-mentioned various additives, prepare a coating solution, apply it on a substrate, and dry it.

As a solvent for preparing the coating liquid, various organic solvents can be used because the resin containing acrylonitrile and styrene as essential components used in the present invention has good solubility in organic solvents, but toluene and xylene can be used. Aromatic solvents such as methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexane, ester solvents such as ethyl acetate and butyl acetate, halogen solvents such as methylene chloride, trichloroethylene and chlorobenzene, and ether solvents such as tetrahydrofuran and dioxane Solvents and amide solvents such as dimethylformamide and N-methylpyrrolidone are used.

The coating method can be arbitrarily selected from commonly used methods, for example, a method using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, etc. Maki Shoten 1977). The thickness of the image receiving layer formed on the substrate is usually 0.1
2020 μm, preferably 1-10 μm.

The sublimable dye used in the color sheet for thermal transfer recording used together with the image receptor of the present invention includes azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone, azomethine, coumarin, Various nonionic sublimable dyes such as a condensed polycyclic system are used.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples, but the examples do not limit the present invention.

Example 1 (a) Preparation of Image Receiver 10 parts by weight of AS resin (trade name: Sanlex SAN-C: manufactured by Mitsubishi Monsanto Kasei Co., Ltd., heat deformation temperature: 91 ° C.) was dissolved in 15 parts by weight of methyl ethyl ketone and 15 parts by weight of toluene. The coating solution for the image receiving layer prepared by adding 0.5 parts by weight of amino-modified silicone KF393 (trade name: Shin-Etsu Chemical Co., Ltd.) to the solution is applied to a 150 μm-thick polypropylene synthetic paper with a wire bar and dried. Then, an image receiving layer having a dry film thickness of about 5 μm was formed to prepare an image receiving body.

(B) Preparation of Color Sheet A biaxially stretched polyethylene terephthalate film (6 μm thick) whose back surface of the ink-coated surface was heat-treated with a polyimide resin was used. Apply 10 parts by weight of resin, 85 parts by weight of toluene ink, dry,
A color material layer having a dry film thickness of about 1 μm was formed to produce a color sheet.

(C) Transfer recording test and storage stability test of recorded matter (i) Transfer recording test The ink-coated surface of the above color sheet is superimposed on the image receiving layer surface of the image receiving body prepared in (a) above, and a heating resistance of 8 dots / mm. Using a thin-film type line thermal head having a body density, recording was performed under the following conditions to obtain a recorded matter having a color density shown in Table 1 below.

Recording line density 8 lines / mm Applied power of thermal head 0.3 W / dot Applied pulse width of thermal head 6 ms (ii) Storage stability test of recorded matter The above recorded matter was exposed with a xenon fade meter for 20 hours and exposed. The degree of subsequent discoloration was measured with a color difference meter, and the results are shown in Table 1 below.

Table 1 shows the results of observing the above recorded matter under a condition of 60 ° C. × 60% RH for 5 days, and then observing the degree of color bleeding of the recorded matter with a microscope.

Example 2 Instead of the dye used in Example 1 (b), the following structural formula (I
An image receiving body and a color sheet were prepared in the same manner as in Example 1 except that a color sheet was prepared using the yellow dye represented by I), and a test was conducted to obtain the results shown in Table 1 below.

Example 3 Instead of the dye used in Example 1 (b), the following structural formula (II)
An image receiver and a color sheet were prepared and tested in the same manner as in Example 1 except that a color sheet was prepared using the cyan dye represented by I). The results are shown in Table 1.

Examples 4 to 6 Except for using an AAS resin (trade name: Vitax V6700: manufactured by Hitachi Chemical Co., Ltd., heat deformation temperature 95 ° C.) in place of the AS resin used in Examples 1 to 3, except that a receiver was prepared. Is Example 1
An image receiving member and a color sheet were prepared in the same manner as in Examples 1 to 3, and tests were conducted. The results are shown in Table 1 below.

Examples 7 to 9 Instead of the AS resin used in Examples 1 to 3, an AES resin (trade name: Unibright UV-500: manufactured by Sumitomo Nogatack Co., Ltd., heat deformation temperature 90 ° C.) Except for the preparation, an image receiving member and a color sheet were prepared in the same manner as in Examples 1 to 3, and tests were performed. The results are shown in Table 1 below.

Examples 10 to 12 Except for using the ACS resin (trade name: NF-920: manufactured by Showa Denko KK, heat deformation temperature of 82 ° C.) instead of the AS resin used in Examples 1 to 3, except that an image receiving body was prepared. An image receiving member and a color sheet were prepared in the same manner as in Examples 1 to 3, and tests were conducted. The results are shown in Table 1 below.

Comparative Examples 1-3 Polyvinyl chloride (degree of polymerization 1,100, Wako Pure Chemical Industries, Ltd.)
10 parts by weight) was dissolved in 100 parts by weight of tetrahydrofuran, and a coating solution prepared by adding 0.5 parts by weight of amino-modified silicone KF393 to the solution was applied to a 150 μm-thick polypropylene synthetic paper with a wire bar and dried. Dry film thickness about 5
An image receiving layer was formed by forming a μm image receiving layer. Each color sheet was prepared in the same manner as in Examples 1 to 3, and was tested using the above-mentioned image receptor in the same manner as in Examples 1, 2, and 3, respectively. The results shown were obtained.

Comparative Examples 4 to 6 The same as Examples 1 to 3 except that an image receptor was prepared using a polyester resin (trade name: Byron 200: manufactured by Toyobo Co., Ltd.) instead of the AS resin used in Examples 1 to 3. An image receptor and a color sheet were prepared by the method, and a test was conducted. The results are shown in Table 1 below.

[Effects of the Invention] The image receiving body for sublimation type thermal transfer recording of the present invention is easy to manufacture, and when the image receiving body for sublimation type thermal transfer recording of the present invention is used, high density recording can be performed and light resistance Thus, a recorded matter having good storage stability such as fixability can be obtained.

Therefore, it can be advantageously used for color recording in an OA terminal such as a facsimile, a printer, a copying machine, etc., which is rapidly spreading in recent years, and for color recording of a television image.

Claims (1)

(57) [Claims] An at least one copolymer selected from the group consisting of acrylonitrile-acryl rubber-styrene copolymer resin, acrylonitrile-ethylene propylene rubber-styrene copolymer resin, and acrylonitrile-chlorinated polyethylene-styrene copolymer resin. A sublimation type thermal transfer recording image receiving body, comprising an image receiving layer mainly containing a resin and a release agent on the surface of a substrate.