JPH06320875A - Perforation transfer type recording material and recording method capable of forming multicolor image - Google Patents

Abstract

PURPOSE:To transfer an image of high resolving power to an image receiving layer by exposing a recording material wherein colorant layers and barrier layers are laminated on a support in this order to perforate the same and superposing the perforated recording material on an image receiving material and heating both materials to transfer colorants only to perforation parts. CONSTITUTION:A cyan color layer 6, a colorant barrier layer 5, a magenta color layer 4, a colorant barrier layer 3, an yellow color layer 2 and a colorant barrier layer 1 are laminated on a support 7 to form a recording material. The outermost colorant barrier layer 1 of this recording material is subjected to intensive exposure to be perforated to perform imagewise exposure of cyan + magenta + yellow and, thereafter, exposure is successively performed to successively perforate the barrier layers 3, 5 and the necessary colorant layers are exposed to perform imagewise recording. The surfaces of the colorant layers of the recording material subjected to imagewise recording are superposed on the image receiving layer 8 laminated on the support 10 of an image receiving material through a cushion layer 9 and the whole is passed through a heating and pressing device to transfer a necessary full-color image on the image receiving layer 8.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a perforation transfer image recording material capable of obtaining a multicolor image with high resolution, and a perforation transfer recording method using the same.

[0002]

2. Description of the Related Art Conventionally, as a thermal transfer recording method, a thermal transfer recording material having a heat-fusible coloring material layer or a coloring material layer containing a heat sublimable dye provided on a substrate and an image receiving material are opposed to each other, and a thermal head is used. There is a method of transferring and recording an image by pressing a heat source controlled by an electric signal such as an energizing head from the ink sheet (recording material) side. The thermal transfer recording has features such as noiseless, maintenance-free, low cost, easy colorization, and digital recording, and is used in various fields such as various printers, recorders, facsimiles, computer terminals and the like.

On the other hand, in recent years, in the medical and printing fields, there has been a demand for a recording method having a high resolution, capable of high-speed recording, and capable of image processing, so-called digital recording. However, in the conventional thermal transfer recording method using a thermal head or a current-carrying head as a heat source, it is difficult to increase the density of the heating elements in terms of the life of the head heating element, and it is difficult to obtain a high-resolution image. .

To solve this problem, thermal transfer recording using a laser as a heat source is disclosed in JP-A-49-15437, 49-17743 and 57.
-87399, 59-143659, etc. In thermal transfer recording using a laser as a heat source, the resolution can be increased by narrowing the laser spot. But,
When recording with a laser, it is common to perform recording by scanning a minute spot, and unless the spot is scanned on the recording medium at high speed, the recording time cannot be shortened and the recording speed is improved. This is generally disadvantageous as compared with the case of using batch exposure or a line thermal head.
In addition, since the amount of heat given by light is generally smaller than the amount of heat given by a heating element such as a thermal head, in this respect also, photothermal conversion type heat mode recording using light from a laser or the like improves the recording speed. It is in a disadvantageous situation to make it happen.

On the other hand, in JP-A-63-35383 and 63-35387, a sublimable ink layer and a protective layer containing a thermoplastic resin as a main component are provided on a support, and the protective layer is a laser beam. After perforating the protective layer by melting it by making it adhere, the protective layer and the image receiving paper are brought into close contact with each other, and heating by a laser or a thermal head is applied from the side of the support having the sublimable ink layer, so that image information is thermally transferred to the image receiving layer. The technique to do is described. According to the present technology, the laser output is reduced as much as possible, the protective layer containing a thermoplastic resin as a main component is melted, and the surface tension of the melted thermoplastic resin pulls the melted portion to the peripheral portion to form a hole. It is said to be the point.

Further, Japanese Patent Laid-Open No. 4-201486 discloses a technique of using a metal vapor deposition film for the dye barrier layer (corresponding to the above-mentioned protective layer).

In these techniques, the amount of heat required for the transfer is not limited because the transfer of the color material itself is performed by another means as compared with the method of transferring the color material by the heat of the laser light described above.
However, the above patent does not show a clear recognition of the intensity of the exposure to be irradiated, nor a clear recognition of whether the light absorbing layer is an ink layer or a protective layer. .

On the other hand, US Pat. Nos. 5,156,938 and 5,171,650
As another technique, No. 1 discloses that an ink layer or a layer between the support and the ink layer is irradiated with a laser beam having an extremely high power density to cause an explosion, and this force blows the ink layer to the image receptor. There is a description of transfer technology.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and provides a multicolor image recording method and recording material capable of recording a high resolution image and having a relatively simple process. The purpose is to provide.

[0010]

SUMMARY OF THE INVENTION The inventors of the present invention irradiate a coloring material barrier layer with high power density exposure,
We have found a technique in which the color material barrier layer is perforated by exploding and the color material can be transferred to the image receiving layer by heating or pressurizing from the minute holes. Also, by making the layer structure a multilayer structure,
The present invention has been completed by finding an effective method capable of recording multiple colors. That is, the above object of the present invention is achieved by the following configurations.

(1) A color material layer and a color material barrier layer are layered on a support, and the color material barrier layer is sequentially imaged by high-energy light from the uppermost layer side of the recording material laminated in this order. After perforating, superimposing with image receiving material, heating and / or
Alternatively, a perforation transfer recording method in which the color material of the color material layer is transferred to the image receiving layer only by perforation by pressure.

(2) A perforation transfer type recording material in which a color material layer and a color material barrier layer are laminated on a support a plurality of times in this order.

(3) The color material layers are layers of different colors
The perforation transfer recording material according to (1).

(4) The color material layer has three colors of yellow, magenta and cyan, or four colors of yellow, magenta, cyan and black.
The perforation transfer recording material according to (1), which is a color layer.

First, the perforation transfer recording method (image formation) of the present invention will be described.

In the image forming process, first, as shown in FIG. 1, the uppermost layer of the coloring material barrier layer formed on the support is subjected to high intensity exposure, and the uppermost layer of the coloring material barrier layer is perforated. You can get started.

For the sake of convenience, the process for forming a full-color image using the perforated transfer type recording material (hereinafter also referred to as "recording material") having the following 6-layer structure will be described below.
Aspects of the invention are not so limited.

Support / Cyan colorant layer / Colorant barrier layer /
Magenta color material layer / color material barrier layer / yellow color material layer / color material barrier layer.

First, in a full-color image, cyan,
High intensity exposure (for example, 100mW, semiconductor laser light with an emission wavelength of 830nm is used with a half-value width narrowed to 6μm) is used to expose any part that requires magenta or yellow, and the uppermost layer of the colorant barrier layer is punched. Glow. For convenience, this exposure pattern is referred to as cyan + magenta + yellow image exposure. Next, by performing cyan + magenta exposure and then cyan exposure, the barrier layer is sequentially punched from the top for each exposure, and the color material layer of the required color is exposed. At this time, scattered color material layer, particles of the color material barrier layer,
Since the powder may pollute the optical system, it is preferable to provide a transparent protective material between the optical system and the recording material, which is easy to clean or attach / detach.

The color material layer surface of the recording material on which the image is recorded in this manner is superposed so as to face the image receiving surface of the image receiving material.
The required full-color image can be obtained on the image-receiving layer by passing it through a heating / pressurizing device such as a laminator.

As the light source for high intensity exposure, xenon light, halogen light, semiconductor laser, He-Ne laser, Ar
A laser, a YAG laser, a carbon dioxide laser, etc. are mentioned. A semiconductor laser is preferable in terms of handling, but is not limited thereto.

The exposure power density is preferably 100,000 W / cm ² or more at the focal plane, more preferably 200, W / cm ² .
It is 000 W / cm ² or more. At power densities below this range, it may not be possible to effectively explode or perforate the colorant barrier layer, depending on the thickness and absorbance of the colorant barrier layer. The exposure speed is preferably 1 m / sec or more, more preferably 2 m / sec or more.

The holes formed by the high-intensity exposure may be halftone dots or continuous holes.

The heating energy can be applied from the image receiving material side, the recording material side, or both when the recording material and the image receiving material are superposed and heated over the entire surface. By this heating, the heat diffusible dye in the color material layer diffuses and transfers from the color material layer to the image receiving layer of the image receiving material only in the portion where the color material barrier layer does not exist, and an image is formed. The heating temperature is not particularly limited, but usually 60 to 200 ° C
Is preferable, and 80 to 150 ° C. is more preferable. It is also preferable to apply pressure with heating, and it is preferable to apply a pressure of 0.5 kg / cm ² or more.

Further, in the present invention, by using the pressure transferable ink layer as the color material layer, the ink can be transferred to the image receiving sheet only by the pressure. Further, by using the melted thermal transfer ink for the color material layer, the melted ink can be transferred as the color material.

The image once transferred to the image receiving material can be transferred to another substrate together with the image receiving layer.

The recording material of the present invention has a color material barrier layer formed on the color material layer, and therefore has excellent storability.

Further, in the perforation transfer recording method of the present invention, since laser light can be used for perforating the color material barrier layer, high resolution recording is possible. Further, it is possible to control the thermal energy to express the gradation of light and shade of the image, and to promote the diffusion of the dye into the image receiving material to more reliably express the continuous gradation of the image. If a dot generator is used, it is possible to give heat energy according to the size of the halftone dot.

The recording material of the present invention basically comprises a support 7 on which a color material layer 6 (4, 2) and a color material barrier layer 5 (3, 1) are laminated a plurality of times in this order. (See FIG. 1) The support is not particularly limited as long as it has good dimensional stability and can withstand a heat source such as a laser during image recording. For example, thin paper such as condenser paper or glassine paper; polyethylene terephthalate, polyamide A heat resistant plastic film such as polycarbonate, polysulfone, polyvinyl alcohol, cellophane, or polystyrene can be used.

The thickness of the support is usually preferably in the range of 2 to 200 μm, more preferably 25 to 100 μm.

The color material layer contains a binder as an essential component in addition to the color material, and further contains optional components such as additives as necessary.

In the present invention, the color material transferred to the image receiving layer is preferably a heat diffusing dye, but not limited to this, other dyes or pigments may be used. Alternatively, a so-called hot-melt type may be adopted.

The heat diffusible dye is not particularly limited as long as it has a heat diffusibility or a sublimation property. As the heat-diffusible cyan dye, there are JP-A-59-78895, JP-A-59-227948, and JP-A-60-2496.
No. 6, No. 60-53563, No. 60-130735, No. 60-131292, No. 61-1
No. 9936, No. 61-22993, No. 61-31292, No. 61-31467,
61-35994, 61-49893, 61-148269, 62-19
Examples thereof include naphthoquinone-based, anthraquinone-based and azomethine-based dyes described in 1191, 63-91287, 63-91288, 63-290793 and the like.

As the heat diffusible magenta dye, there is disclosed in JP-A-59
-78896, 60-30392, 60-30394, 60-253595
Issue 61-262190, Issue 63-5992, Issue 63-205288, Issue 6
4-159, anthraquinone series described in 64-63194, etc.,
Examples thereof include azo type and azomethine type dyes.

As the heat-diffusible yellow dye, JP-A-59 is used.
-78896, 60-27594, 60-31560, 60-53565
No. 61-12394, No. 63-122594, etc., and methine-based, azo-based, quinophthalone-based, anthrythothiazole-based dyes and the like.

For the black layer, a mixture of yellow, magenta and cyan dyes or a black dye can be used.

The heat diffusible dye is obtained by a coupling reaction between a compound having an open-chain or closed active methylene group and an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. An azomethine dye, and a phenol derivative or a naphthol derivative,
An indoaniline dye obtained by a coupling reaction with an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative can also be preferably used. Further, the dye used in the present invention does not necessarily have to have a color finally required in the color material layer of the perforation transfer recording material, and may be discolored or developed after being transferred to the image receiving material. It may have a desired color.

The amount of these heat diffusible dyes to be used is usually 0.1 to 20 g, preferably 0.2 to 5 g per 1 m ² . The content of the heat diffusible dye in the color material layer is usually in the range of 5 to 70% by weight, preferably 30 to 70% by weight.

As the binder used in the color material layer, resins known in the thermal transfer recording field can be used. The polyvinyl acetal-based resin and the cellulose-based resin described below are preferable, but not limited thereto.

As the polyvinyl acetal resin, there are various compounds depending on the degree of acetalization and the content of acetyl groups, residual hydroxyl groups and the like, and representative examples thereof include polyvinyl acetoacetal and polyvinyl butyral.

Examples of the cellulosic resin include nitrocellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose butyrate, and the like. Among them, nitrocellulose is particularly preferable.

Resins known in the field of thermal transfer recording other than the above include acrylic resin, methacrylic resin, polycarbonate, polyvinyl alcohol, polyvinyl formal,
Examples thereof include polyvinyl ether, polyvinylpyrrolidone, polystyrene, polystyrene copolymers and ionomer resins.

One or more of these binders can be appropriately selected and used. The binder is
Usually, it is preferable to add 30 to 70% by weight to the entire coloring material layer. Further, the weight ratio of the binder and the heat diffusible dye in the color material layer is preferably in the range of 1:10 to 10: 1, and 2: 8 to
8: 2 is particularly preferred.

The thickness of the color material layer may be adjusted so that the dye can be moved by the application of heat energy, and is usually in the range of 0.2 to 10 μm, preferably 0.4 to 5 μm.

The additives to be added to the color material layer in the present invention include modified silicone resins, fluororesins, surfactants, waxes, higher fatty acids, higher aliphatic alcohols, higher aliphatic ethers and fine metal powders. , Silica gel, carbon black, organic fillers, inorganic fillers, curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylic acid, and epoxies). Further, in order to promote transfer, a heat-melting substance such as higher fatty acid ester described in JP-A-59-106997 can be used. The amount of the additive to be added cannot be uniformly determined depending on the kind of the additive and the purpose of the addition, but the amount of the additive as a whole is preferably 50% by weight or less with respect to the binder.

Specific examples of the modified silicone resin include polyester-modified silicone resin, acrylic-modified silicone resin, urethane-modified silicone resin, cellulose-modified silicone resin, alkyd-modified silicone resin, epoxy-modified silicone resin, and the like. They may be used alone or in combination of two or more.

The content of the modified silicone resin in the color material layer is usually 0.01 to 10% by weight, preferably 0.01 to 2.0% by weight.

The color material layer is formed by dissolving or dispersing the above-mentioned heat diffusible dye, binder and optional additives in a solvent to prepare a coating solution, and coating and drying it on a support. be able to.

The binder may be used not only in one kind or in two or more kinds dissolved in a solvent, but also in a latex dispersion.

As the solvent, water, alcohols (eg ethanol, propanol, butanol), cellosolves, esters (eg ethyl acetate, butyl acetate), aromatics (eg toluene, xylene, chlorobenzene), ketones (eg Acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, dioxane), chlorine-based solvents (eg chloroform, trichloroethylene) and the like can be mentioned. The solvent may be used alone or in combination of two or more.

For coating, generally known surface sequential coating with a gravure roll, extrusion coating, wire bar coating,
Roll coating, slide hopper coating, etc. can be used.

The colorant barrier layer must have at least the property that the colorant (heat diffusible dye) of the colorant layer does not pass through under heat or pressure and that it absorbs high-intensity exposure.
For this purpose, the colorant barrier layer has (1) a water-soluble resin, (2) a resin having an ionic bond, or (3) a Tg (glass transition point) of 8 or less.
0 ° C or higher, preferably 100 ° C or higher, more preferably 120 ° C
It is preferable to contain the above resin as a main component.

As the water-soluble resin, gelatin, polyvinyl alcohol, water-soluble polyvinyl formal, water-soluble polyvinyl acetal, water-soluble polyvinyl butyral, polyvinyl pyrrolidone, water-soluble polyester, water-soluble nylon, polyacrylic acid, water-soluble polyurethane, methyl cellulose, Examples thereof include hydroxypropyl cellulose. Further, copolymers of monomer components constituting these resins can also be used.

Examples of the resin having an ionic bond include ionomer resins and the like, styrene substituted with a sulfo group,
Resins containing acrylic acid, methacrylic acid, phthalic anhydride, etc. as copolymer components, and Na ⁺ , K as counter ions
^Examples include those to which ⁺ , Ca ²⁺ , Zn ²⁺ , NH ₄ ^+, etc. have been added. Further, gelatin, casein and the like are also preferably used.

Examples of the resin having Tg of 80 ° C. or higher include polyvinyl chloride, polystyrene, polyaryl methacrylate, polybenzyl methacrylate, polycarbonate, nylon, polyphenylene oxide, gelatin, polyparabanic acid and the like. Among them, polymethylmethacrylate, polybenzylmethacrylate, polycarbonate,
Examples include nylon, polyester and polyparabanic acid. Further, it is a copolymer of monomer components such as styrene, vinyl chloride, methyl methacrylate, aryl methacrylate, acrylonitrile, ethylene oxide, benzyl methacrylate, cyclohexyl methacrylate, etc., and has a Tg of 80.
A resin having a temperature of ℃ or higher is also preferably used. Further, a thermosetting resin having no glass transition point is also included in the resins having a Tg of 80 ° C. or higher and is preferable as a resin component of the colorant barrier layer of the present invention.

The ratio of the resin component to the color material barrier layer is
30 to 99% by weight is preferred. The proportion of the resin component of the present invention in the resin component is preferably 50% by weight or more, more preferably 70% by weight or more, and most preferably 90% by weight or more.

The colorant barrier layer also preferably contains a light absorbing substance for absorbing high intensity exposure. This light-absorbing substance may be the above resin component itself when the wavelength of high-intensity exposure is in the visible light region from ultraviolet light to 500 nm or less.

When the wavelength of the high-intensity exposure is in the visible light region, various pigments and dyes that absorb the exposure wavelength can be contained in the colorant barrier layer. When the wavelength is in the red to near-infrared region, the dyes and carbon black described in Japanese Patent Application No. 4-334584, page 7, can be used. For example, from the near-infrared absorbing dyes described in the functional materials June 1990, pp. 64-68, and the functional dyes for optical recording described in coloring materials 61 (1988) 218-223, cyanine-based dyes, squarylium System, croconium system, azurenium system, phthalocyanine system, naphthalocyanine system, anthraquinone system, dithiol metal complex salt system, indoaniline metal complex system, intermolecular CT
Complex dyes, transition metal chelate dyes, and aluminum diimmonium dyes can be selected and used. (Specifically, IR-6 to 8) When a water-soluble resin is used for the colorant barrier layer, it is preferable that the light absorbing substance is also water-soluble, and especially tricarbohydrate having a water-soluble substituent such as a sulfo group. Cyanine dyes are preferred. (Specifically, IR-1 to 5) Representative specific examples of preferable light absorbing substances are shown below.

[0059]

[Chemical 1]

[0060]

[Chemical 2]

The light-absorbing substance may be added if necessary, but when the exposure wavelength is in the infrared region, it is preferable to contain 1 to 50% by weight of the above-mentioned near-infrared absorbing dye. The near-infrared absorbing dye can be added in a larger amount if it does not deteriorate the barrier function of the coloring material barrier layer. In the image recording of the present invention, it is preferable to use a semiconductor laser from the viewpoint of handleability of the exposure system, but the emission wavelength in this case is usually in the infrared region, and in response to this, the colorant barrier is used. The layer preferably has absorption in the infrared region.

In addition to the above, the colorant barrier layer also contains additives such as surfactants, conductive compounds for antistatic agents, release agents for preventing blocking, and mats as additives for improving coating properties. Agents and the like can be contained if necessary.

The film thickness of the colorant barrier layer is preferably as thin as possible, as long as it does not impair the barrier function, specifically in the range of 0.1 to 2.0 μm, preferably 0.1 to 1.0.
μm. However, if the exposure intensity is high enough,
Since it is possible to perforate even with a thicker film thickness, it is not limited to this range.

Exposure wavelength used for image formation of the colorant barrier layer (for example, 780,810,830 nm for semiconductor lasers)
The transmission density is preferably 0.3 to 3.0, and more preferably 0.5 to 2.0.

The color material barrier layer may be formed of a plurality of layers having separated functions as required. The functions to be separated include, for example, colorant barrier property, conductivity, light absorption,
Blocking resistance and the like can be mentioned, and these functions can be provided in different layers.

The perforated transfer type recording material of the present invention is prepared as follows.

First, the above-mentioned coloring material layer is applied onto the above-mentioned support, and further the coloring material barrier layer is applied. The recording material of the present invention can be obtained by further alternately coating a color material layer and a color material barrier layer on this.

Regarding the color material barrier layer, basically the same composition can be applied a plurality of times, but a plurality of colors can be recorded by using different color materials in the color material layer. Recording material can be created. or,
Regarding the colorant barrier layer, the addition of various additives to the uppermost layer, in particular, prevents blocking, imparts slipperiness, and imparts electrical conductivity, and has a different function from that inside. Can also be held.

The thickness, composition and the like of the color material layer can be changed according to image recording by exposure. For example, since the coloring material layer closest to the support does not need to be perforated by exposure, the film thickness may be large. Specifically 1-10
It can be μm. When a black layer is used as the color material layer, the amount of the color material for obtaining the black color tends to increase, and thus the layer thickness may need to be increased. It may be preferable that the color material layer is a black layer.

Further, the color material layer disposed in the middle portion needs to be scattered at the same time due to the explosion of the color material barrier layer located thereunder during exposure as shown in FIG. preferable. Specifically, it is 0.2 to 2 μm, more preferably 0.2 to 1 μm.

The binders used in the color material layer and the color material barrier layer can be selected from those mentioned above. For example, when multiple layers are simultaneously coated, it is preferable to use a water-soluble or water-dispersible binder. By using a water-based coating solution for each layer, multi-layer coating can be performed and the productivity is greatly improved.

The layer farthest from the support of the colorant barrier layer may be relatively thick because only that layer needs to be perforated during exposure. Although the film thickness is not particularly limited, it can be 0.5 to 2.0 μm in combination with obtaining sufficient colorant barrier property. On the other hand, the coloring material barrier layer located in the middle portion must simultaneously scatter the coloring material layer located thereabove during exposure, so the layer itself is thin and the exposure wavelength used for image formation (for example, 780 nm , 830 nm) is effectively absorbed. To this end, for example, the film thickness of the colorant barrier layer is 0.1 to 0.5 μm, and the content of the colorant that absorbs the exposure wavelength used for image formation of the colorant barrier layer is 30 to
It can be 50% by weight.

When a plurality of color material layers are used, the color material used in the layer farthest from the support in the color material layers should pass through the color material barrier layer, such as yellow. Even in this case, it is preferable that the color is inconspicuous after being transferred to the image receiving material.

As the layer structure of the recording material of the present invention, in addition to this, an intermediate layer (for example, for improving adhesiveness and imparting cushioning properties) may be provided between the lowermost color material layer and the support, or the support may be provided. A back coat layer (for imparting slipperiness, antistatic properties, antiblocking properties, etc.) may be provided on the back surface.

Further, the recording material may be provided with perforations or provided with a detection mark or the like for the convenience of use.

Next, the image receiving material used together with the recording material of the present invention will be described.

The image-receiving material is composed of a support and an image-receiving layer, but the image-receiving material may be formed by the self-supporting image-receiving layer itself. With respect to the image receiving material, generally used image receiving sheets for sublimation transfer can be used other than those described below.

As the support, for example, paper, coated paper, synthetic paper (polypropylene, polystyrene or a composite material obtained by laminating them on paper or a plastic film),
White or transparent polyethylene terephthalate film,
Examples thereof include white or transparent polyvinyl chloride and polyolefin-coated paper. The thickness of the support is usually 20 to 300 μm, preferably 30 to 200 μm.

The image receiving layer is formed of a binder for the image receiving layer and various additives. As the binder for the image receiving layer,
Polyvinyl chloride resin, copolymer resin of vinyl chloride and other monomers (eg alkyl vinyl ether, vinyl acetate, etc.), polyester resin, acrylic ester, polyvinylpyrrolidone, polycarbonate, cellulose triacetate, styrene acrylate resin, vinyl toluene acrylate Resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin and the like can be mentioned.

The above resin may be newly synthesized and used, or a commercially available product may be used. In any case,
From the viewpoint of physical properties, Tg is -20 as a binder for the image receiving layer.
A resin in the range of to 150 ° C is preferable, and a resin in the range of 30 to 120 ° C is particularly preferable. Also, the average weight molecular weight is 2,000 to 100,000.
Resins in the range are preferred.

In the formation of the image-receiving layer, the above-mentioned various resins may be crosslinked or cured by utilizing radiation active points (if there are no reactive active points), they are crosslinked or cured by radiation, heat, moisture, catalyst or the like. Well, in this case, a radiation-active monomer such as epoxy or acrylic, or a cross-linking agent such as isocyanate can be used.

A peeling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler (filler), and a pigment can be added to the image receiving layer. Moreover, you may add a plasticizer, a thermal solvent, etc. as a sensitizer.

The release agent can improve the releasability between the recording material and the image receiving material, and includes, for example, silicone oil (including what is called a silicone resin); polyethylene wax, achidwax, Teflon powder and the like. Mold waxes: fluorine-based or phosphoric acid ester-based surfactants and the like can be mentioned, and among them, silicone oil is preferable.

The addition amount of the simple addition type silicone oil is
Since it may vary depending on the type, it cannot be uniformly decided, but generally it is 0 for the binder for the image receiving layer.
It is 5 to 50% by weight, preferably 1 to 20% by weight.

Examples of the reaction-curable silicone oil include those obtained by reaction-curing an amino-modified silicone oil and an epoxy-modified silicone oil. For catalyst-curable or photocurable silicone oil, use KS-705F-P.
S, KS-705F-PS-1, KS-770-PL-3 (Catalyst-curable silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.), KS-720, KS-774-PL-3
(Photocurable silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The amount of these photocurable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image receiving layer.

The release layer may be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the release agent in an appropriate solvent, coating and drying the solution.

As the antioxidant, JP-A-59-182785 can be used.
No. 60-130735, JP-A No. 1-127387 and the like, and compounds known to improve image durability in photographs and other image recording materials.

Examples of the UV absorber and the light stabilizer include JP-A-59-158287, 59-196292, 61-283595, and 62-.
229594, 63-74686, 63-145089, 63-122596
And compounds known in the art for improving image durability in photographs and other image recording materials.

Examples of the filler include inorganic fine particles and organic fine particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina and the like, and organic fine particles include fluorine resin particles and guanamine resin particles. Resin particles such as acrylic resin particles and silicone resin particles can be used.

These inorganic / organic fine particles differ depending on the specific gravity, but it is preferable to add 0.1 to 70% by weight.

Examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

As the plasticizer, phthalic acid esters, trimellitic acid esters, pyromellitic acid esters,
Adipic acid esters, other oleic acid esters,
Succinic acid esters, maleic acid esters, sebacic acid esters, oxalic acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxystearic acid, orthophosphoric acid esters, phosphite esters, glycol esters, etc. Can be mentioned.

Further, the image receiving layer may contain an additive for reacting with the coloring material transferred from the coloring material layer to cause discoloration, color development or fixation.

The total amount of the additives to be added is usually in the range of 0.1 to 50% by weight based on the binder for the image receiving layer.

The image-receiving layer is prepared by dispersing or dissolving the components for forming the image-receiving layer in a solvent to prepare a coating solution, coating on the surface of a support and drying the mixture, or a mixture containing the components for forming the image-receiving layer. It can be formed by a laminating method in which the surface of the melt-extruded support is laminated.

As the solvent used in the coating method, tetrahydrofuran, methyl ethyl ketone, toluene, xylene,
Examples thereof include chloroform, dioxane, acetone, cyclohexane, butyl acetate and the like.

When the laminating method is adopted, the coextrusion method can also be adopted when the support is a synthetic resin.

The image receiving layer may be formed over the entire surface of the support or may be formed on a part of the surface.

The thickness of the image receiving layer is generally 1 to 50 μm, preferably about 2 to 10 μm. On the other hand, when the self-supporting image-receiving layer itself forms the image-receiving material, the thickness of the image-receiving layer is usually 60 to 200 μm, preferably about 90 to 150 μm.

An overcoat layer may be laminated on the surface of the image receiving material for the purpose of preventing fusion and improving image storability. The overcoat layer can be formed by gravure coating, wire bar coating, roll coating, or any other known coating method or laminating method. The thickness of this layer is usually 0.05 to 3 μm.

When the image receiving material comprises a support and an image receiving layer, a cushion layer is provided between the support and the image receiving layer in order to reduce noise and transfer and record an image corresponding to image information with good reproducibility. Can be provided.

As a material for forming the cushion layer, a material having Tg of 20 ° C. or less is generally preferable. For example, SBR, E
VA, SIS, SEBS, polybutadiene, etc. may be mentioned. Further, it is also possible to use a material having a low elastic modulus, a material having rubber elasticity, or a thermoplastic material which is easily softened by heating and has improved adhesiveness, specifically, natural rubber, acrylate rubber, butyl rubber, nitrile rubber, Butadiene rubber, isoprene rubber, styrene-butadiene rubber,
Chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, fluorine rubber, neoprene rubber, chlorosulfonated polyethylene, epichlorohydrin, EPDM (ethylene / propylene / diene rubber), elastomers such as urethane elastomer, polyethylene, polypropylene, polybutadiene, polybutene, impact resistance ABS resin, polyurethane, ABS resin, acetate, cellulose acetate, amide resin, polytetrafluoroethylene, nitrocellulose, polystyrene, phenol-formaldehyde resin, polyester, impact-resistant acrylic resin, styrene-butadiene copolymer, ethylene-acetic acid Vinyl copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, vinyl chloride resin with plasticizer Vinylidene chloride resin,
Among polyvinyl chloride, polyvinylidene chloride and the like, resins having a small elastic modulus can be mentioned.

The thickness of the cushion layer is preferably 5 to 100 μm, more preferably 10 to 50 μm.

[0105]

EXAMPLES The present invention will be described in more detail based on the following examples, but the embodiments of the present invention are not limited thereto.
In the following, "part" means "part by weight".

Example 1 (Production of Recording Material) The following compositions were mixed and dispersed to prepare a coating liquid for a color material layer containing a heat diffusible dye.

Cyan colorant layer coating liquid Thermal diffusible dye [Nippon Kayaku Co., Ltd .: Kayaset Blue 714] 4 parts Polyvinyl butyral resin 4 parts [Sekisui Chemical Co., Ltd .: Eslec BX-1] Methyl ethyl ketone 82 parts Cyclohexanone 10 parts Magenta color material layer coating liquid Thermal diffusion dye [Kayaset Red TD-FB manufactured by Nippon Kayaku Co., Ltd.] 4 parts Polyvinyl butyral resin 4 parts [Eslec BX-1: above] Methyl ethyl ketone 82 parts Cyclohexanone 10 parts Yellow color material Layer coating liquid Thermal diffusible dye [Nippon Kayaku Co., Ltd .: Kayaset Yellow AG] 4 parts Polyvinyl butyral resin 4 parts [ESREC BX-1: above] Methyl ethyl ketone 82 parts Cyclohexanone 10 parts Next, mix the following compositions Then, a coating liquid for a colorant barrier layer containing an infrared absorbing dye was prepared.

[0108] colorant barrier layer composition -1 Gelatin 3.5 parts near infrared absorbing dye (IR-1) 1.5 parts of pure water 95 parts colorant barrier layer composition -2 Gelatin 3.5 parts near infrared absorbing dye (IR-1) 1.5 Part Matting agent (silicon resin particles with a particle size of 2.0 μm) 0.1 part [Toshiba Silicone Co., Ltd .: Tospearl T-120] Pure water 94.9 parts First of all, the cyan color material layer coating liquid is prepared as described above. 100 μm thick polyethylene terephthalate (PE
T) Apply and dry on a film using a wire bar,
A cyan color material layer having a thickness of 1 μm was formed. Next, a coating liquid of coloring material barrier layer composition-1 was applied and dried using a wire bar to form a coloring material barrier layer having a thickness of 0.5 μm.

Similarly, the magenta color material layer 0.8 μm,
Color material barrier layer-1 0.5 μm, Yellow color material layer 0.8 μm,
Color material barrier layer-2 0.7 μm was sequentially formed to prepare a recording material.

(Production of Image Receiving Material) A cushion layer coating solution and an image receiving layer coating solution having the following compositions were prepared.

Cushion layer coating liquid Eva Flex EV-47X [Mitsui DuPont Chemical Co., Ltd .: ethylene vinyl acetate resin] 30 parts Toluene 70 parts Image receiving layer coating liquid Vinyl chloride-vinyl isobutyl ether copolymer 9 parts [BASF Corporation Made: Laroflex MP25] Polyester modified silicone resin 1 part [Shin-Etsu Silicone Co., Ltd .: X-24-8300] Methyl ethyl ketone 40 parts Cyclohexanone 10 parts First of all, by applying a wire bar to a 25 μm thick PET base with a silicon resin undercoat. An image receiving layer having a thickness of μm was formed.

Next, the kneaded thickness of titanium white
Cushion layer coating liquid is applied to a 100 μm white PET base with a blade coater to a dry film thickness of 30 μm,
Immediately after that, the sheet was pasted with the sheet coated with the image-receiving layer, and the 25-μm-thick PET base on the image-receiving layer side was peeled off to form a 30-μm cushion layer and a 2-μm image-receiving layer on a 100-μm-thick support. An image receiving material having the above was obtained.

(Formation of Image) << Perforation of Color Material Barrier Layer >> A laser beam of a semiconductor laser LTO90MD / MF (manufactured by Sharp Corporation: wavelength 830 nm, maximum optical output 100 mW) is applied to the color material barrier layer which is the uppermost layer of the recording material. The uppermost coloring material barrier layer was perforated by converging it into a beam having a diameter of about 6 μm and irradiating it at a scanning speed of 2 m / sec (optical efficiency was 60%). The dot diameter of the point-pierced portion was 8 μm.

This first exposure pattern was done with the finally required pattern of the sum of all the yellow, magenta and cyan images.

Next, similarly, exposure was performed with an image pattern of the sum of magenta and cyan. At this time, as the exposure condition, only the scanning speed was changed to 1.8 m / sec.

Further, similarly, exposure was performed with a cyan image pattern. The scanning speed was 1.8 m / sec.

<< Transfer of Coloring Material >> The recording material having the colorant barrier layer perforated as described above and the image receiving material are superposed so that the colorant barrier layer and the image receiving layer are in contact with each other, and 2 kg / cm ² at 120 ° C.
The coloring material (diffusible dye) was transferred to the image receiving layer only on the perforated portion through a hot roll capable of heating and pressing. The transferred image was a full color image formed of yellow, magenta and cyan. When the reflection densities (solid densities) of the portions of the image pattern in which only yellow, only magenta, and only cyan were transferred as solid were measured, they were 2.5, 2.3, and 2.4 for blue, green, and red densities, respectively.

The reflection density (white background density) of the unperforated portion was 0.08, which was the same as the reflection density of the image receiving material before passing through the heat roll.

Example 2 A recording material similar to that of Example 1 was prepared, except that a black color material layer having the following composition was provided as the lower layer. Black colorant layer coating liquid Thermal diffusible dye [Kayaset Blue 714: As mentioned above] 4 parts Thermal diffusible dye [Mitsui Toatsu Dye KK: MS Magenta] 4 parts Thermal diffusible dye [Mitsui Toatsu Dye KK] : MS yellow] 4 parts Polyvinyl acetal [KS-52 manufactured by Sekisui Chemical Co., Ltd.] 10 parts Methyl ethyl ketone 200 parts Cyclohexanone 78 parts The above black color material layer coating solution is applied to a PET film having a thickness of 100 μm and a wire bar of 2 μm. A thick black colorant layer was applied. Then, cyan, magenta, and yellow color material layers and color material barrier layers were provided in exactly the same manner as in Example 1.

(Formation of Image) The above recording material was used in the same manner as in Example 1.
In the same manner as above, the image signal of the sum of yellow, magenta, cyan, and black, the image signal of the sum of magenta, cyan, and black, the image signal of the sum of cyan, black, and the image signal of black is exposed four times, and heating and application are performed. A color material was transferred to the image receiving layer under pressure to obtain a full color image.

The black reflection density of the solid transfer portion is orange density.
It was 2.1.

[0122]

According to the perforation transfer type recording material and recording method of the present invention, a high resolution multicolor image can be recorded by a relatively simple process.

[Brief description of drawings]

FIG. 1 is a time-series schematic view of a recording method using a perforation transfer recording material of the present invention.

[Explanation of symbols]

1, 3, 5 Color material barrier layer 2, 4, 6 Color material layer of each color (for example, yellow, magenta, cyan) 7 Recording material support 8 Image receiving layer 9 Cushion layer 10 Image receiving material support

Claims (4)

[Claims] 1. A color material layer and a color material barrier layer are layered on a support, and the color material barrier layer is imagewise punched by high-energy light from the uppermost layer side of a recording material laminated in this order a plurality of times. After that, the perforation transfer recording method is characterized in that the color material of the color material layer is transferred to the image receiving layer only by overlapping with the image receiving material and heating and / or pressing. 2. A perforation transfer type recording material comprising a support and a color material layer and a color material barrier layer laminated on the support a plurality of times in this order. 3. The perforation transfer recording material according to claim 1, wherein the color material layers are layers having different colors. 4. The perforation transfer recording material according to claim 1, wherein the color material layer is a layer of three colors of yellow, magenta and cyan or a layer of four colors of yellow, magenta, cyan and black.