JPH05278350A - Image receiving sheet for thermal transfer - Google Patents

Abstract

PURPOSE:To provide an image receiving sheet for thermal transfer which is excellent in abrasion resistance and of high image quality. CONSTITUTION:An image receiving sheet for thermal transfer is obtained wherein an intermediate layer having a radical polymeric composition which is excellent in heat resistance as a main component is provided on a base material and an image receiving layer is provided on the intermediate layer processed to be made easily adhesive. Therefore, the image receiving sheet for thermal transfer which is excellent in abrasion resistance by printing evaluation with a hot head and besides of high image quality, is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image receiving sheet for heat-sensitive transfer which has excellent abrasion resistance and high image quality.

[0002]

2. Description of the Related Art In recent years, a sublimation-type thermal transfer printer has been used as a means for color hard copy, especially for reproducing multicolor gradation images. The principle of such a sublimation-type thermal transfer type printer is that an image is converted into an electric signal, and the electric signal is further converted into a heat signal by a thermal head so that a sheet (ink donor sheet) coated with a sublimation type ink The heated and sublimated ink is fixed by an image-receiving sheet closely attached to an ink donor sheet to reproduce an image. In particular, in recent years, there has been a demand for higher printing speed and higher quality of transferred images, which inevitably leads to an increase in applied heat energy. Therefore, coated paper such as art paper or coated paper generally used as a support is required. When paper, polyethylene, polypropylene, polyethylene terephthalate, synthetic resin film such as polyamide, or laminated paper in which these synthetic resins are laminated on paper on one side or both sides, synthetic paper, etc. are used, these are inferior in heat resistance, The heat generated during printing causes the support to shrink,
Since it has drawbacks such as lack of dot reproducibility of images, a heat resistant support has been required.

In response to such a demand, a sublimation type thermal transfer image-receiving sheet in which a radically polymerizable composition is coated on a support and radiation-crosslinked is known (Japanese Patent Laid-Open No. 173295/1987). However, in general, such a radically polymerizable composition has poor dyeing property to a dye and is excellent in heat resistance,
As a result, it is difficult to obtain high transfer density and high image quality.

On the other hand, the present inventors have used a thermoplastic resin having an excellent dyeing property for a dye as an image-receiving layer for heat-sensitive transfer and, at the same time, using the thermoplastic resin and a support for the image-receiving paper for heat-sensitive transfer. It has already been proposed that by providing a radical polymerization composition layer between them, a high transfer image density can be obtained, and at the same time, a high quality image transfer paper for thermal transfer can be obtained which is not adversely affected by thermal softening of the support (Japanese Patent Application Flat 2-13895
9) The present invention relates to the improvement.

That is, a radically polymerizable composition is generally coated without a solvent and crosslinked by irradiation with ultraviolet rays or electron beams. When an image receiving layer is provided on an intermediate layer containing the polymerizable composition as a main component, Peeling occurs between the image receiving layer and the intermediate layer. In particular, this is remarkable when the water-soluble or water-dispersible thermosoftening resin composition is used for the image receiving layer, since the intermediate layer containing the radically polymerizable composition as a main component is generally lipophilic.

[0006]

SUMMARY OF THE INVENTION Under the circumstances, the present invention provides an image-receiving sheet for heat-sensitive transfer which has an improved adhesive force between an intermediate layer containing a radical-polymerizable resin composition as a main component and an image-receiving layer.
The purpose is to provide

[0007]

Means for Solving the Problems The inventors of the present invention have earnestly studied means for solving the above problems, and as a result, surface treatment of an intermediate layer containing a radically polymerizable composition as a main component with easy adhesion. The present invention has been accomplished by finding that doing so is effective.
As a method of making the intermediate layer easily adhesive, a method of modifying the intermediate layer surface by corona treatment, plasma treatment, or the like,
There are a method in which the surface of the intermediate layer is roughened by a solvent treatment, and a method in which a resin having good adhesiveness is applied to both the intermediate layer and the image receiving layer. As such a resin, any resin having good adhesiveness to both layers can be preferably used. For example, an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a urethane resin, a styrene butadiene resin or a copolymer thereof. Examples include coalescing. Also, the coating amount is 0.5 to 10.0 g as a dry solid content.
The range of / m ² is preferable.

The present invention will be described in detail below. The support that can be used for the thermal transfer image-receiving sheet is usually art paper,
Coated paper such as coated paper, plain paper base paper, polyethylene, polypropylene, polyethylene terephthalate,
Synthetic resin films such as polyamide, or laminated paper in which these synthetic resins are laminated on one side or both sides, synthetic paper, composite materials by laminating the above materials, etc. are considered, but radically polymerizable composition on the support. The surface roughness of the intermediate layer after applying the product is the center line average roughness (R
As long as it is 0.5 μm or less in a), particularly preferably 0.2 μm or less, the material is not particularly limited, but a highly smooth support is preferable.

The resin constituting the image-receiving layer which has dyeability to a dye which is melted or sublimated by heat and migrates,
Any one can be preferably used as long as it has a strong interaction with the dye and the dye can be stably diffused in the resin. For example, as a resin having an ester bond, a polyester resin, a polyacrylic ester resin , A polycarbonate resin, a polyvinyl acetate resin, a styrene acrylate resin, etc .; a urethane resin having a urethane bond; a polyamide resin (nylon) having an amide bond; a urea bond As having
Urea resin; In addition, as the other one having a highly polar bond, polycaprolactone resin, polystyrene resin, polyvinyl chloride, polyacrylonitrile resin, etc. can be used, or at least one of the structural units of the above resin is used. It can also be used as a copolymer having a main component, for example, a vinyl chloride-vinyl acetate copolymer, a styrene-butadiene copolymer, and the like, and the above resins can be used alone or in combination of two or more. I can. Further, the above resin can be dissolved in water or an organic solvent and applied on the intermediate layer, or can be emulsified in an aqueous solution and applied as an emulsion.
The adhesiveness between the image-receiving layer coated using an intermediate layer containing a radically polymerizable resin composition as a main component and an organic solvent as a solvent is
Since the intermediate layer itself generally has an affinity for an organic solvent, many of them have relatively good correlated adhesiveness, but in the case of an aqueous system, the adhesiveness is generally poor, and the effect of the easy adhesion treatment of the present invention is great. The effect is recognized even in the organic solvent system,
It is not particularly limited.

In the present invention, the release agent added to the image-receiving layer is used for the purpose of preventing blocking. That is, the radical-polymerizable composition used for the intermediate layer has high heat resistance and excellent heat resistance, and has the purpose of preventing blocking due to thermal softening of the support. A blocking measure is also required for the image-receiving layer in contact with the ink layer. For example, waxes such as higher fatty acid or its ester, amide or its metal salt, shellac wax, montan wax, carnauba wax, polyethylene wax and Teflon powder; And phosphoric acid ester type surfactants; silicone oil and the like. As the silicone oil, modified silicone oils such as amino-modified silicone, epoxy-modified silicone, alkyd-modified silicone and the like can be used. If necessary, a curable silicon compound can also be used as the silicon compound. Examples of the curable silicon compound include a reaction curable type, an ionizing radiation curable type, and a catalyst curable type.

Further, if necessary, dyes, pigments, wetting agents,
It is also possible to contain additives such as a defoaming agent, a dispersant, an antistatic agent, a fluorescent brightening agent, an ultraviolet absorber and a light stabilizer. Particularly with regard to pigments, blocking is improved by including inorganic particles typified by silica, calcium carbonate, kaolin, clay, zinc oxide, barium sulfate, titanium oxide in the thermoplastic resin layer or the radical polymerizable composition layer. The purpose of can be achieved.

The ultraviolet ray or electron beam polymerizable resin used in the intermediate layer of the present invention is a compound having a reactive group such as an acryloyl group, a methacryloyl group or an epoxy group at the molecular end or in the molecular side chain, and is unsaturated. A polyester, a modified unsaturated polyester, an acrylic polymer, an acrylic monomer, a methacrylic polymer, a methacrylic monomer, a monomer or oligomer having a vinyl unsaturated bond, an epoxy compound, etc. can be used alone or together with other solvents. The following is a typical example.

(A) Polyester acrylate, polyester methacrylate; for example, Aronix M-53
00, Aronix M-5400, Aronix M-5
500, Aronix M-5600, Aronix M-
5700, Aronix M-6100, Aronix M
-6200, Aronix M-6300, Aronix M-6500, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100 (above, Toagosei Chemical Industry Co., Ltd. trade name), Viscoat 700, Viscoat 3700 (above,
Product name of Osaka Organic Chemical Industry Co., Ltd., Kayarad HX-2
20, Kayarad HX-620 (above, Nippon Kayaku Co., Ltd.)
Product name)

(B) Epoxy acrylate, epoxy methacrylate; for example, NK ester, EA-800,
NK Ester, EPM-800 (above, trade name of Shin-Nakamura Chemical Co., Ltd.), Viscoat 600, Viscoat 540
(Above, product name of Osaka Organic Chemical Industry Co., Ltd.), Photomer 3016, Photomer 3082 (above, product name of San Nopco Co., Ltd.)

(C) Urethane acrylate, urethane methacrylate; for example, Aronix M-1100, Aronix M-1200, Aronix M-1210,
Aronix M-1250, Aronix M-126
0, Aronix M-1300, Aronix M-13
10 (above, product name of Toagosei Chemical Industry Co., Ltd.), viscoat 812, viscoat 823, biscoat 823 (above, product name of Osaka Organic Chemical Industry Co., Ltd.), NK ester,
U-108-A, NK ester, U-4HA (above, Shin Nakamura Chemical Co., Ltd. trade name)

(D) Monofunctional acrylate, monofunctional methacrylate; for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofur. Furyl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, glycidyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, butoxyethyl acrylate and the like. Ethylene oxide-modified phenoxyphosphoric acid acrylate Ethylene oxide-modified butoxylated phosphoric acid acrylate, and other trade names of Toa Gosei Chemical Industry Co., Ltd. are Aronix M-101, Aronix M-102, Aronix M-111, Aronix M-113. , Aronix M-114, Aronix M-117, Aronix M-152, Aronix M-154 and the like.

(E) Polyfunctional acrylate, polyfunctional methacrylate; for example, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene. Glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, isocyanuric acid diacrylate, pentaerythritol triacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate Methacrylate, ethylene oxide modified polyethylene Examples thereof include ethylene erythritol tetraacrylate, propylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified dipentaerythritol polyacrylate, and ethylene oxide-modified dipentaerythritol polyacrylate. The product names of Toagosei Kagaku Kogyo Co., Ltd. are Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-230, Aronix M-233, Aronix M-240, Aronix M-245, Aronix M. -305, Aronix M-309, Aronix M-310, Aronix M
-315, Aronix M-320, Aronix M-
325, Aronix M-330, Aronix M-4
00, TO-458, TO-747, TO-755, T
HIC. TA2 etc. are mentioned.

(F) Epoxy compound; examples include glycidyl methacrylate, 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, 1,3-bis (N, N-diepoxypropylaminomethyl) benzene and the like. ..
The product name of Mitsubishi Gas Chemical Co., Ltd. is GE-510,
Examples include TETRAD-X and TETRAD-C.

As the photoinitiator used in the present invention, acetophenones such as di- or trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethyl thiuram monosulfide,
There are thioxanthones, azo compounds and the like, and they are selected from the viewpoints of the type of polymerization reaction of the radical-polymerizable resin and the radical-polymerizable silicone resin, stability, compatibility with a radical irradiation device, and the like. The amount of the photoinitiator used is usually in the range of 1 to 5% with respect to the radical polymerizable resin or the radical polymerizable silicone resin. In addition, a storage stabilizer such as hydroquinone may be used in combination with the photoinitiator.

When the intermediate layer of the present invention is provided, if necessary, the radically polymerizable composition is foamed or after containing hollow fine particles, it is applied to a support and cured by irradiation with a fine void. Pores may be included.

The method of coating the image-receiving layer or the intermediate layer of the radically polymerizable composition on the substrate is, for example, blade coating, air doctor coating, squeeze coating, air knife coating, reverse roll coating, gravure roll or transfer roll coating, A method such as bar coating or curtain coating is used. Also, if necessary,
After coating the support on the support with a radically polymerizable composition, a film having high smoothness may be laminated and irradiated with radiation from the film side to cure the film, and then the film may be peeled off to provide the image receiving layer. In addition, after the radically polymerizable composition is applied to the support, it is contacted with a metal roller or the like having a high smoothness, the support is irradiated with radiation to be cured, and then the surface is peeled off, followed by surface treatment.
An image receiving layer can be provided thereon.

The amount of the radically polymerizable composition coated on the substrate varies depending on the type of the substrate, but is about ^{2 to} 50 g / m ² ,
More preferably, it is 5 to 30 g / m ² . The ionizing radiation for curing the radically polymerizable composition generally includes ultraviolet rays, α rays, β rays, γ rays, X rays, electron rays and the like, but α rays, β rays, γ rays or X rays are Since the problem of danger to the human body is accompanied, ultraviolet rays and electron beams, which are easy to handle and widely used industrially, are effective.

When an electron beam is used, it is desirable to adjust the amount of the electron beam to be irradiated within the range of 0.1 to 10 Mrad. When it is 0.1 Mrad or less, a sufficient irradiation effect cannot be obtained, and when it is 10 Mrad or more, the paper or film substrate is deteriorated, which is not preferable. As the electron beam irradiation method, a scanning method, a curtain beam method or the like is adopted, and the acceleration voltage for irradiating the electron beam is 100 to 300K.
V is suitable. Also, when using ultraviolet rays,
It is necessary to add a sensitizer to the radical polymerization composition, and the sensitizer described above can be appropriately used. As the light source, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a tungsten lamp and the like are preferably used.

[0024]

According to the present invention, an intermediate layer containing a radically polymerizable composition having excellent heat resistance as a main component is provided on a support, and the intermediate layer is subjected to easy adhesion treatment and then melted or sublimated by heat. By providing an image-receiving layer having excellent dyeing property to the dye that migrates with time, the image-receiving layer for thermal transfer has excellent abrasion resistance and high image quality.
I got it.

[0025]

The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples. In addition, "part" in an Example is a weight part.

Example 1 The following intermediate layer composition was coated on a photographic support laminated with polyethylene at a rate of 10.0 g / m ² and cured by ultraviolet irradiation (80 W: 3 lines). After providing an intermediate layer (Ra = 0.45), corona treatment is performed, and then an image receiving layer having the following composition is applied by a gravure roll coater so that the dry solid content is 3.0 g / m ^2. Thus, an image-receiving sheet for thermal transfer was obtained. 1. Intermediate layer composition Acrylic monomer M-220 (Toagosei Kagaku Kogyo Co., Ltd.) 97 parts IRGACURE 951 (Ciba-Geigy) 3 parts 1. Image-Receiving Layer Bayronal MD-1330 (Toyobo) 80 parts Polyethylene wax 20 parts

Example 2 The following composition was used as an intermediate layer composition on a polyester film by using a gravure offset coater.
It was applied so that it would be 5.0 g / m ² , and cast-coated paper was superposed, and then cured by electron beam irradiation (accelerating voltage: 175 KV, irradiation dose 1 Mrad) from the film surface, and then the film was peeled off. After providing a highly smooth intermediate layer on the cast coated paper, a vinyl acetate acrylic resin dissolved in an organic solvent was applied at a dry solid content of 2.0 g / m ^{2 and then the} following gravure roll coater was used. The blended image-receiving layer was coated so as to have a dry solid content of 5.0 g / m ² , to obtain an image-receiving sheet for thermal transfer. 1. Intermediate layer composition Acrylic monomer M-210 (Toagosei Chemical Industry Co., Ltd.) 70 parts Titanium oxide 30 parts 2. Image-receiving layer Vinyl chloride / vinyl acetate copolymer 75 parts Silicon oil 5 parts Synthetic silica 20 parts

Example 3 Coat paper was coated with the following composition as an intermediate layer composition using a gravure offset coater at 15.5 g / m ² and electron beam irradiation (accelerating voltage). : 150K
V, irradiation dose of 1.5 Mrad) to provide an intermediate layer, and then the surface of the intermediate layer is surface-roughened with an organic solvent (toluene), and then the image receiving layer is dissolved in an organic solvent to obtain a dry solid content of the following formulation. Was set to be 3.5 g / m ² to obtain an image-receiving sheet for thermal transfer. 1. Intermediate layer composition Acrylic oligomer M-210 (Toagosei Chemical Industry Co., Ltd.) 70 parts Barium sulfate 30 parts 2. Image-receiving layer Byron 200 (Toyobo) 95 parts SF-8417 (Amino-modified silicone oil, Toray silicone) 5 parts

Comparative Examples 1, 2 and 3 In the same manner as in Examples 1, 2, and 3 except that the intermediate layer was not subjected to the easy-adhesion treatment, thermal transfer image-receiving sheets were prepared. Obtained.

Comparative Example 4 An image receiving sheet for thermal transfer was obtained in the same manner as in Example 1 except that the intermediate layer containing the radically polymerizable composition as a main component was not provided.

Further, the ink donor sheet for evaluation was prepared as follows. Kaya Set Bull-906 (Nippon Kayaku, sublimation dye) 10 parts Ethyl semeroses 10 parts Syloid 244 (Fuji Devison silica gel) 10 parts Isopropyl alcohol 30 parts A sublimation dye solution with a ball mill for 2 days. After crushing, about 1.
5 g / m ^{2 was} applied to give a donor sheet.

Thus, the obtained ink donor sheet and the image-receiving sheet for heat-sensitive transfer are overlaid relative to each other, and dot heating according to image information is carried out by a thermal head (Hitachi Video Printer VY-50). To form an image. Regarding the evaluation, the image quality is determined by whether or not there are white spots in the dot area in the dot reproducibility, and the adhesiveness is determined by sticking a sero tape to the image receiving layer and peeling the image receiving layer when peeled. It was judged.

[0033]

[Table 1]

[0034]

INDUSTRIAL APPLICABILITY As in the present invention, in a heat-sensitive transfer image-receiving sheet, an intermediate layer of a radically polymerizable composition having good heat resistance which is cured by ultraviolet rays or electron beams is provided on a support, and an image-receiving layer is provided on the intermediate layer. At this time, an easy-adhesion treatment made it possible to obtain an image-receiving sheet for heat-sensitive transfer which has high abrasion resistance and high image quality.

Claims (2)

[Claims] 1. An intermediate layer containing a radically polymerizable composition as a main component, which is used in combination with a thermal transfer medium having a dye layer containing a dye that migrates by heat melting or sublimation, and said dye. A heat-sensitive transfer image-receiving sheet comprising a dye-receiving image-receiving layer sequentially coated, wherein the intermediate layer is an easily-adhesive surface-treated intermediate layer. -G. 2. The image-receiving sheet for heat-sensitive transfer according to claim 1, wherein the image-receiving layer is mainly composed of a water-soluble or water-dispersible thermosoftening resin having dyeability to the dye.