JPH05131759A - Thermal transfer image receiving paper and production thereof - Google Patents

Abstract

PURPOSE:To provide the title image receiving paper excellent in blocking resistance and having good image reproducibility generating no image blur or missing dots. CONSTITUTION:In thermal transfer image receiving paper characterized in that an intermediate layer based on a radical polymerizable composition and an image receiving layer having dyeing properties to a heat-sublimable dye are provided on a support, the center line average roughness (Ra) of the support is 1.0mum or less. By this constitution, the thermal transfer image receiving paper excellent in blocking resistance and having good image reproducibility generating no image blur or missing dots in the printing evaluation, due to a thermal head is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimation-type thermal transfer image-receiving paper which is coated on a highly smooth support and has excellent blocking resistance, image blurring and white spots, and good image reproducibility. The present invention relates to a manufacturing method.

[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, particularly for reproducing multicolor gradation images. The principle of such a sublimation type thermal transfer printer is to convert an image into an electric signal,
Furthermore, this electric signal is converted into a heat signal by a thermal head to heat a sheet (ink donor sheet) coated with sublimation ink, and the sublimated ink is fixed on an image receiving paper that is in close contact with the ink donor sheet to reproduce an image. To do. The surface of such an image receiving paper is generally provided with an image receiving layer for fixing the ink with a polymer such as saturated copolyester, polyacetate and the like.

[0003]

In recent years, in sublimation type thermal transfer type printers, it has been required to increase the printing speed and the quality of transferred images. When a porous base material such as plain paper is used as the support for the image-receiving paper for heat-sensitive transfer, the smoothness is low and the image quality is poor. For the purpose of improving the transfer image quality, art paper, coated paper, etc. Coated paper, synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc., or laminated paper or synthetic paper laminated with these synthetic resins on one side or both sides, it is unavoidable to use these. Since it is inferior in heat resistance, it causes shrinkage due to heat on the support surface and blocking with an ink donor sheet in combination with the high smoothness, which rather deteriorates the image quality. In addition, since increasing the printing speed inevitably leads to an increase in the thermal printing temperature, the above situation tends to be exacerbated. As one means for solving such a problem, a sublimation-type thermal transfer image-receiving paper in which a radical-polymerizable oligomer is coated on a substrate and radiation-crosslinked is known (JP-A-62-173295). However, there are the following problems in actually using such a sublimation type thermal transfer image receiving sheet. That is, it is desirable that the sheet used as the substrate has an appropriate cushioning property from the viewpoint of promoting adhesion with the ink donor sheet at the time of printing, but when the radical polymerizable composition is cured, this cushioning property is Since the radical polymerizable composition is scarce, the dyeing property to the sublimation dye is generally weak and the blocking is excellent, but 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 sublimation dye as an image-receiving layer for heat-sensitive transfer and, at the same time, between the thermoplastic resin and the support of the image-receiving paper for heat-sensitive transfer. It has already been proposed that by providing a radical polymerization composition layer in (1), a thermal transfer image receiving paper without blocking can be obtained at the same time as obtaining a high transferred image density (Japanese Patent Application No. 2-138959). Regarding the improvement.

That is, in the case of the ordinary printing method, the ink is transferred from the printing plate to the paper by applying a large pressure, so that good printing is possible except for the paper having an extremely rough surface, but the sublimation heat transfer sheet. In the sublimation thermal transfer recording method using the thermal head, the pressure of the thermal head is much smaller than that in the printing method, and thus a high smooth surface is required to obtain a good printed surface.

[0006]

The present inventor has found the following method as a result of earnest research on means for solving the above-mentioned problems. That is, when obtaining an image-receiving paper for heat-sensitive transfer characterized in that an intermediate layer containing a radically polymerizable composition as a main component and an image-receiving layer having a dyeability to a heat sublimable dye are provided on a support, the center line average Roughness (Ra) is 1.0
It was found that by using a support having a thickness of μ or less, a high-resolution image-receiving paper for thermal transfer having no image blur can be obtained.

The present invention will be described in detail below. Substrates that can be used for sublimation heat transfer image receiving paper are usually art paper,
Coated paper such as paper, synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, and polyamide, or laminated paper in which these synthetic resins are laminated on one side or both sides, synthetic paper, composite material by laminating the above materials, etc. The center line average roughness (Ra) is 1.0 as shown in the present invention.
When a support larger than μ is used, high-resolution printing is possible even if an intermediate layer containing a radically polymerizable composition as a main component or an image-receiving layer having a dyeability to a heat sublimable dye is provided on the support. It was difficult to provide a sufficiently smooth and uniform layer to obtain.

Examples of the thermoplastic resin of the image-receiving layer having dyeability to a heat sublimable dye include those having an ester bond such as polyester resin, polyacrylic ester resin, polycarbonate resin, polyvinyl acetate resin. , Styrene acrylate resin, etc. In addition, polyurethane resin having urethane bond, polyamide resin (nylon) having amide bond, urea resin having urea bond, and other highly polar compounds. As the one having a bond, polycaprolactone resin, polystyrene resin, polyvinyl chloride, polyacrylonitrile resin or the like can be used, or a copolymer containing at least one of the constitutional units of the above resin as a main component, for example, vinyl chloride-acetic acid. It can also be used as a vinyl copolymer, styrene-butadiene copolymer, etc., The resin alone or a mixture of two or more thereof can be used to.

Any of the above-mentioned thermoplastic resins can be preferably used for the purpose of the present invention, but a polyester resin or the like is preferable for the purpose of improving the dyeing property of the sublimation dye and improving the transfer density. Further, the above resin can be dissolved in water or an organic solvent and applied on the substrate, or can be emulsified in an aqueous solution and applied on the substrate as an emulsion. Further, if necessary, an additive such as a dye, a pigment, a wetting agent, a defoaming agent, a dispersant, an antistatic agent, a release agent and a fluorescent brightening agent can be contained.

With respect to pigments, in particular, inorganic particles typified by silica, calcium carbonate, kaolin, clay, zinc oxide, barium sulfate and titanium oxide are contained in the thermoplastic resin layer or the radically polymerizable composition layer for blocking. The objective of improvement can be achieved. Further, a releasing agent can be used for the same purpose, but specifically, solid waxes such as polyethylene wax, amide wax, Teflon powder, fluorine-based and phosphoric ester-based surfactants, and silicon compounds. Etc., but a curable silicone compound is preferably used because it is difficult for blurring of transferred dye and transfer or reduction in image density to occur.

Examples of the curable silicon compound include a reaction curable type, an ionizing radiation curable type, and a catalyst curable type. In the present invention, ultraviolet rays or electron beams are irradiated after the image receiving layer is formed. And ionizing radiation-curable silicon compounds are conveniently used. Further, the radical polymerizable composition is mainly composed of the following ultraviolet-ray-polymerizable or electron-beam-polymerizable resins, and these resins may be used without a solvent or diluted with a solvent, if necessary. A reaction initiator is mixed and used.

The ultraviolet ray or electron beam polymerizable resin used in the present invention is a compound having a reactive group such as an acryloyl group, a methacryloyl group, or an epoxy group at a molecular end or a molecular side chain, and is an unsaturated polyester or modified. Unsaturated polyesters, acrylic polymers, acrylic monomers, methacrylic polymers, methacrylic onomers, monomers or oligomers having a vinyl type unsaturated bond, epoxy compounds and the like can be used alone or together with other solvents. The following is a typical example.

(A) Polyester acrylate, polyester methacrylate For example, Aronix M-530
0, Aronix M-5400, Aronix M-55
00, Aronix M-5600, Aronix M-5
700, 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, Toa Gosei 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 such as 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 and urethane methacrylate such as 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 acrylates, monofunctional methacrylates such as 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 acrylates, polyfunctional methacrylates such as 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 compounds such as glycidyl methacrylate, 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane and 1,3-bis (N, N-diepoxypropylaminomethyl) benzene ..
The product name of Mitsubishi Gas Chemical Co., Ltd. is GE-510,
Examples include TETRAD-X and TETRAD-C.

The photoinitiator used in the present invention includes acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthones, azo. There are compounds, etc., and they are selected from the viewpoints of the type of polymerization reaction of the radically polymerizable resin and the radically polymerizable silicone resin, stability, and compatibility with a radical irradiation device. 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.

The method of applying the thermoplastic resin or the radically polymerizable composition onto the substrate includes, for example, blade coating, air doctor coating, squeeze coating, air knife coating, reverse roll coating, gravure roll and transfer roll coating, and bar coating. A method such as coating or curtain coating is used. Also, if necessary,
After applying the radically polymerizable composition on the support, a highly smooth film or the like is laminated and irradiated with radiation from the film side to cure the film, and then the film may be peeled off to provide the thermoplastic resin layer. Further, after coating the radically polymerizable composition on the support, when contacting with a metal roller or the like having high smoothness, the support is irradiated with radiation to cure and then peeled off to form a thermoplastic resin layer. May

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 , and more preferably 5 to 30 g / m ² . As the ionizing radiation for curing the radically polymerizable composition, generally, ultraviolet rays, α
Ray, β ray, γ ray, X ray, electron ray, etc.
Rays, β rays, γ rays, and X rays are accompanied by the problem of danger to the human body, so ultraviolet rays and electron rays, which are easy to handle and are 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. If it is 0.1 Mrad or less, a sufficient irradiation effect cannot be obtained, and if it is 10 Mrad or more, the paper or film substrate is deteriorated, which is not preferable. As an electron beam irradiation method, a scanning method, a curtain beam method, or the like is adopted, and an accelerating voltage for irradiating the electron beam is preferably about 100 to 300 KV. Further, when ultraviolet rays are used, 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, etc. are preferably used.

[0023]

The present invention is a heat-sensitive transfer image-receiving paper having a cured radically polymerizable composition intermediate layer and a thermoplastic resin layer on a highly smooth support in the production of a heat-sensitive transfer image-receiving paper. Since the radically polymerizable composition layer is present between the body and the ink donor sheet or the thermoplastic resin layer, heat shrinkage or blocking of the support is prevented, and image reproducibility without image blurring or blank areas A good image-receiving paper for thermal transfer was obtained.

[0024]

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.

[0025]

EXAMPLE 1 lamination with polyethylene - you encountered a photographic support the (Ra = O.58μ) the following formulation as a radical polymerization composition over coating so as to 10.0 g / m ^2, UV irradiation After curing with (80W: 3 pieces), apply a polyester resin emulsion (Vylonal MD-1330: Toyobo) with an air knife coater so that the dry solid content becomes 3.0 g / m ² , and dry. An image receiving paper for post thermal transfer was obtained. [Radical Polymerizable Composition] Acrylic Monomer M-220 97 parts (Toagosei Kagaku Kogyo Co., Ltd.) Benzyl dimethyl ketate IRGACURE 951 3 parts (Ciba-gaigi)

[0026]

Example 2 A radically polymerized composition having the following composition was coated on a cast coated paper (Ra = 0.25 μm) using a gravure offset coater so as to be 15.0 g / m ^2. Then, after curing by electron beam irradiation (accelerating voltage: 175 KV, irradiation dose 1 Mrad), a polyester solid emulsion (Vylonal MD-1330: Toyobo) and silica with an air-knife coater each have a dry solid content of 5 After coating and drying so as to be 0.0 g / m ² and 0.5 g / m ² , an image-receiving paper for heat-sensitive transfer was obtained. [Radical polymerizable composition] Acrylic monomer M-210 70 parts (Toagosei Chemical Industry Co., Ltd.) Titanium oxide 30 parts

[0027]

Example 3 The following composition as a radical polymerization composition was coated on a coat paper (Ra = 0.89μ) by using a gravure offset coater so as to be 12.5 g / m ^2. After curing by electron beam irradiation (accelerating voltage: 150 KV, irradiation dose of 1.5 Mrad), polyester resin emulsion (Vylonalal MD-1930: Toyobo) and silica were dried to a solid content of 2.5 g / m ² , respectively. 0.
An image was coated with an air knife coater so as to have a concentration of 3 g / m ² and dried to obtain an image-receiving paper for heat-sensitive transfer. [Radical polymerizable composition] 80 parts of acrylic oligomer M-210 (Toagosei Chemical Industry Co., Ltd.) 20 parts of barium sulfate

[0028]

Comparative Example 1 A high-smooth plain paper (Ra = 1.23μ) was coated with the following radical polymerization composition using a gravure offset coater at a rate of 18.0 g / m ^2. Then, electron beam irradiation (accelerating voltage: 200K
V, irradiation dose of 1.5 Mrad), and then a polyester resin emulsion (Vylonalal MD-1330: Toyobo) and silica were dried with an air knife coater to a dry solid content of 3.0 g / m ² and 0. An image-receiving paper for heat-sensitive transfer was obtained after coating and drying at 5 g / m ² . [Radical Polymerizable Composition] Acrylic Oligomer TC-120S 50 parts (Nippon Kayaku) Acrylic Monomer M-210 35 parts (Toa Gosei Kagaku Kogyo) Syloid 161 15 parts (Fuji Davison)

[0029]

[Comparative Example 2] A radical polymerization composition having the following composition was coated on a plain paper base paper (Ra = 2.53 μm) using a gravure offset coater so as to have a content of 20.0 g / m ^2. After curing by electron beam irradiation (accelerating voltage: 200 KV, irradiation dose 1.5 Mrad), air-knife co-
Polyester resin emulsion (Byronal M
D-1330: manufactured by Toyobo) and silica coating so that the dry solid content of each 3.0 g / m ² and 0.5 g / m ^2, to obtain a Te thermal transfer-receiving sheet after drying. [Radical Polymerizable Composition] Acrylic Oligomer TC-120S 50 parts (Nippon Kayaku) Acrylic Monomer M-210 35 parts (Toa Gosei Kagaku Kogyo) Syloid 161 15 parts (Fuji Davison)

[0030]

Comparative Example 3 Polyester resin emulsion (Vylonal MD-1930: on synthetic paper (Ra = 1.12μ))
(Toyobo) and silica have a dry solid content of 2.5 g / m ² each.
And air-knife coater so that it becomes 0.3 g / m ²
Was coated and dried to obtain an image-receiving paper for thermal transfer. In addition, an ink donor sheet for evaluation was prepared as follows. Kaya Set Bull-906 10 parts (Nippon Kayaku sublimation dye) Ethyl semeroses 10 parts Syloid 244 10 parts (Fuji Devison silica gel) Isopropyl alcohol 30 parts Sublimation dye solution is crushed with a ball mill for 2 days. Then, a wire bar was applied on the heat-resistant polyester film for about 1.
5 g / m ^{2 was} applied to make a donor sheet. The ink donor sheet thus obtained and the image-receiving paper for heat-sensitive transfer were placed on top of each other, and dot-shaped heating according to the image information was carried out by a thermal head to form an image. Regarding blocking, the state in which no blocking was observed was evaluated as ◯, and the state in which blocking was completely observed was evaluated as x, and at the same time, the dot reproducibility of the intermediate layer is shown in Table 1.

[Table 1]

[0031]

[Effect] In the production of the image-receiving paper for heat-sensitive transfer as in the present invention, it has dyeability to the intermediate layer of the radically polymerizable composition cured on the highly smooth support having Ra of 1.0 μ or less and the heat sublimable dye. By providing the image-receiving layer, since the radically polymerizable composition layer is present between the highly smooth support and the ink donor sheet or the thermoplastic resin layer, heat shrinkage and blocking of the support are prevented, and An image receiving paper for thermal transfer having good image reproducibility was obtained.

Claims (4)

[Claims] 1. An image-receiving paper for heat-sensitive transfer characterized in that an intermediate layer containing a radically polymerizable composition as a main component and an image-receiving layer having a dyeability to a heat sublimable dye are provided on the support. A thermal transfer image-receiving paper having a center line average roughness (Ra) of 1.0 μ or less. 2. The image-receiving paper for thermal transfer according to claim 1, wherein the radical-polymerizable composition comprises a compound having an acryloyl group, a methacryloyl group or an epoxy group. 3. An intermediate layer containing a radically polymerizable composition as a main component is provided on a support, and the radically polymerizable composition is cured by ultraviolet irradiation or electron beam irradiation, and then the intermediate layer is thermally sublimable. A method for producing an image-receiving paper for heat-sensitive transfer, which comprises providing an image-receiving layer having a dyeing property. 4. An intermediate layer containing a radically polymerizable composition as a main component and an image receiving layer having dyeability to a heat sublimable dye are provided on the support, and then the radical polymerization is performed by irradiation with ultraviolet rays or electron beams. A method for producing an image-receiving paper for heat-sensitive transfer, which comprises curing the composition.