JPH089272B2 - Transfer recording medium and transfer recording method - Google Patents

Description

The present invention relates to a transfer recording medium suitable for recording high-resolution characters or images, particularly to a transfer recording medium suitable for color recording and a transfer recording method.

<Prior Art> Recently, various terminals have been required due to the development of office automation. Among them, there is a great demand for a recording device for converting an electric signal into a visible image, a so-called printer. There are few things to go. For example, generally used recording methods include an ink jet method, an electrophotographic method, and a thermal transfer method, and the maintenance of the apparatus by using a powder such as a liquid or toner, the complexity of operability, Alternatively, since a thermal head is used, there are problems such as a short head life and a low printing speed.

Therefore, a discharge transfer method is known as one of high-speed and relatively good-resolution characters or image forming means. For example, a thermographic copying method disclosed in Japanese Patent Publication No. No. 22030 discloses a transfer medium.

 Hereinafter, a conventional discharge transfer method will be described with reference to the drawings.

FIG. 1 is a cross-sectional view of a discharge transfer medium used in the method, in which a light reflection layer 2 is on the upper surface of a support 1, a photothermal conversion layer 3 is on the lower surface,
A heat transferable solid ink layer 4 is provided on the lower surface of the photothermal conversion layer 3. Although not shown, if a roughening layer is provided between the support 1 and the light reflecting layer 2, the light-reflecting layer can be more easily destroyed by discharge and stabilized.

2 to 4 show a conventional recording process using the recording medium, and the same parts as those in the first embodiment are designated by the same reference numerals. Reference numeral 5 denotes an image receiving sheet, 6 denotes a xenon lamp, and 7 denotes a flash. In the recording process, as shown in FIG. 2, the light reflection layer 2 is removed according to a pattern of information by a known discharge breakdown recording means, and as shown in FIG. The paper 5 is brought into close contact with the light reflection layer 2, and a flash light including ultraviolet rays, visible rays and infrared rays is emitted from the xenon flash lamp 6.

Then, the flash light applied to the part where the light reflection layer 2 remains is reflected, and the flash light applied to the part where the light reflection layer is removed passes through the support 1 and reaches the photothermal conversion layer. The light-to-heat conversion layer absorbs flash energy and effectively converts it into heat energy. At this time, the thermal transferable solid ink laminated on the photothermal conversion layer is thermally melted or sublimated by thermal energy, and as a result, transferred and fixed on the image-receiving sheet which is in close contact, and as shown in FIG. Can be obtained.

On the other hand, "IBM Technical Disclosure B" published in May 1976.
ulletin "(Vol. 18, No. 12, p. 4142) discloses a thermal laser transfer printing process in which an image is formed on an ink sheet provided with a heat transferable solid ink layer on a support. By converging the laser light based on the information and converting the light energy of the laser into heat energy by the ink, the ink is transferred and fixed imagewise on the image-receiving sheet that is adhered as in the case of the discharge transfer method. To obtain a transferred image.

<Problems to be Solved by the Invention> However, in the conventional discharge transfer method as described above, when an image receiving paper having a high surface smoothness is used, it is relatively clear and
Moreover, although it has a desired density and can transfer the pattern by discharge breakdown recording almost faithfully, it has a surface smoothness such as plain paper such as copy paper and bond paper used as business paper in Europe and America. When a low image-receiving sheet is used, the transfer of ink is limited only to the contact point between the ink layer and the image-receiving paper, and in the vicinity thereof, so "white spots" occur when transferring a solid image, and fine line images are also generated. There is a problem that untransferred parts called “chip” and “hanuke” appear when transferring, and thin lines “togile” and “scratch” are likely to occur.

Further, in order to improve the transfer recording quality, it is conceivable to lower the melting point or melt viscosity of the heat-fusible binder or to lower the sublimation start temperature of the heat-sublimable paint. As a result, unresolved image transfer occurs, and the image is easily transferred even at a relatively low temperature.
The phenomenon appears as another problem.

Further, the greatest feature of the discharge transfer method is that it faithfully and sharply transfers high-resolution characters and images by electric discharge recording, but in the conventional configuration described above, the edge portion of the transferred image is There is a problem in that the print thickening due to "blurring" or "blurring" is often seen, and thus the so-called "crisp" quality, which lacks contrast and sharpness, tends to be a problem.

Furthermore, regarding the gradation expression of each primary color required to obtain a full-color transferred image by the discharge transfer method, in the conventional configuration, the gradation expression obtained by discharge breakdown recording is faithful. There is a problem that it is difficult to transfer to.
That is, in the discharge breakdown recording pattern of the area gradation expression by the dither method or the like, the flash light energy irradiation area absorbed by the ink layer or the photothermal conversion layer can be controlled in accordance with the recording dot density, but the gradation is sufficient. In order to obtain good performance, the resolution at the time of transfer becomes unreasonable, the transfer recording density tends to be saturated to a constant value, and gradation expression at high dot density is difficult.

On the other hand, also in the case of the thermal transfer method using a laser beam, the transferability of the ink to the image receiving sheet having a close surface smoothness is remarkably poor as in the case of the discharge transfer method. However, there is a problem that the printing cost is increased because the printer has to be used. In this case, in order to improve the transferability of the ink to the low smoothness image receiving sheet, it is possible to increase the energy of the laser beam or increase the contact pressure between the ink sheet and the image receiving sheet, but the recording device is large. There was a problem that it became expensive.

<Means for Solving Problems> The present invention has been made as a result of intensive studies in order to solve the problems in view of the above circumstances, and its outline is that a binder is provided on a light-transmitting support. , At least one photodecomposable compound selected from a double salt of a chloride of a diazo compound and a metal halide, a complex salt of a diazo compound with an acid of a fluoride, a complex salt of a diazo compound with an organic boron salt, and a diad compound And a transfer recording medium, characterized in that a thermal transferable solid ink layer is provided via an intermediate layer containing a photothermal conversion substance, and a binder on the light transmissive support,
Double salt of diazo compound and metal halide, complex salt of diazo compound and acid of fluoride, complex salt of diazo compound and organic boron salt, and at least one photodegradable compound and photothermal conversion substance selected from azide compound Of a transfer recording medium having a heat-transferable solid ink layer provided via an intermediate layer containing an image-receiving sheet adhered to the surface of the heat-transferable solid ink layer, and a light based on image information is provided on the back surface of the transfer recording medium. By radiating energy, the heat transferable solid ink layer is selectively heat-melted and transferred to the image receiving sheet, and then the transfer recording medium and the image receiving sheet are separated and separated to form a transfer recorded image on the image receiving sheet. And a transfer recording method.

First, the structure of the transfer recording medium according to the present invention will be described. FIG. 5 shows a typical constitution of the transfer recording medium according to the present invention. One surface of the light transmissive support 1 is a double salt of a chloride of a diazo compound and a metal halide, a diazo compound and a fluoride. The thermal transferable solid ink layer 4 is provided via the intermediate layer 9 containing at least one photodecomposable compound selected from the complex salt of an acid, the complex salt of a diazo compound and an organic boron salt, and a diad compound. Has been.

[Light-Transmissive Support] Various heat-resistant resin films such as polyethylene terephthalate, polyimide, polycarbonate, cellophane and aromatic amide are used for the light-transmissive support used in the present invention, and the thickness of the film is 1 to 100 μm. , Preferably 4
A range of up to 30 μm is suitable.

[Intermediate Layer] The intermediate layer in the present invention is a double salt of a chloride of a diazo compound and a metal halide in a binder, a complex salt of a diazo compound and an acid of a fluoride, a complex salt of a diazo compound and an organic boron salt, and a diad compound. At least one photodegradable compound selected from the above and a photothermal conversion substance are dissolved or dispersed to form a layer. In this case, as the material system of the binder suitable for the intermediate layer, at least one selected from thermoplastic resins, waxes and rubbers can be used.

As the thermoplastic resin, a thermoplastic elastomer is desirable, and specific examples thereof include olefin resins such as polyethylene, polypropylene, polybutylene and polybudadiene, acrylic resins such as polymethylmethacrylate and ethylene-ethyl acrylate copolymer. , Polystyrene, AS
Styrene resin such as resin, BS resin, ABS resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl butyral, vinylidene chloride / acrylonitrile copolymer, vinyl chloride /
Vinyl-based copolymers such as vinyl acetate copolymers, vinyl chloride / vinylidene chloride copolymers, propylene / vinyl chloride copolymers, polyamide resins such as nylon 6, nylon 66 and nylon 12, saturated polyester resins, polycarbonate resins, polyacetal resins, Polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyurethane resin, tetrafluoroethylene resin,
Fluororesin such as trifluoroethylene resin and polyvinylidene fluoride, fibrin resin such as ethylene cellulose, cellulose acetate and nitrocellulose, epoxy resin, ionomer resin, rosin derivative resin, etc., organic solvent soluble resin system, gelatin, glue, hydroxy Ethyl cellulose, carboxymethyl cellulose, methyl cellulose,
Carboxymethyl hydroxyethyl cellulose, hydroxyethyl starch, gum arabic, saccharose octaacetate, ammonium alginate, sodium alginate, polyvinyl alcohol, polyvinyl butyral,
Examples thereof include water-soluble resin systems such as polyvinylpyrrolidone, polyvinylamine, polyethylene oxide, polystyrenesulfonic acid, polyacrylic acid, polyamide, and isobutylene / maleic anhydride copolymers, and emulsion systems of the organic solvent-soluble resin systems described above. .

Specific examples of waxes include candelilla wax, carnauba wax, rice wax, wood wax, plant wax such as jojoba oil, beeswax, lanolin, animal wax such as whale wax, montan wax, ozokerite, ceresin and the like. Mineral wax, paraffin wax,
Microcrystalline wax, petroleum wax such as petrolactam, synthetic hydrocarbon such as Fischer-Tropsch wax, polyethylene wax, modified wax such as montan wax derivative, paraffin wax derivative, microcrystalline wax derivative, hardened castor oil,
Examples thereof include hydrogenated waxes such as hydrogenated castor oil derivatives, 12-hydroxystearic acid, stearic acid amides, higher alcohols and the like, and mixtures of these waxes with organic substances or inorganic substances.

Specific examples of rubbers include natural rubber, isoprene rubber, styrene-butadiene rubber (SBR), butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber,
Examples include ethylene / propylene rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, hydrin rubber, urethane rubber, polysulfide rubber, silicone rubber, fluororubber, and these rubbers, as well as blends of rubbers with organic or inorganic substances. be able to.

The binder for these intermediate layers may be a single poison or a mixture of two or more types, but the binder is not limited to these.

Next, the photodegradable compound to be added to the intermediate layer is ultraviolet light,
Prompt photolysis by light including visible light and infrared rays is an essential condition, and examples thereof include a double salt containing a salt of the diazo compound, a complex salt, and an azide compound. The following items can be mentioned as characteristics required for the diazo compound and the diad compound.

1) Capable of being uniformly dissolved or dispersed in the intermediate layer.

2) High photolysis rate and effective generation of nitrogen gas.

3) Must be resistant to thermal or mechanical shock.

As the diazo compound having these properties, those conventionally used in the field of diazo copying materials can be mentioned as they are. That is, specific examples thereof include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, and 4diazo. -1-dibenzylaminobenzene,
4-diazo-1-ethylhydroxyaminobenzene, 4,
-Diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-2,5-diethoxybenzene, 4-diazo-1-morpholino Benzene, 4-diazo-1-morpholino-2,5-dimethoxybenzene, 4-diazo-1-morpholino-2,5-diethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4 -Diazo-1-formolino-2,5-
Diisopropoxybenzene, 4-diazo-1-anilinobenzene, 4-diazo-1-dimethylamino-3-carboxybenzene, 4-diazo-1-toluylmercapto-2,5-diethoxybenzene, 4-diazo- 1,4-Methoxybenzoylamino 2,5-diethoxybenzene, 4-diazo-1-pyrrolidino-3-methylbenzene, 4-diazo-1-pyrrolidino-2-methylbenzene, 4-diazo-1-dimethylamino- 2- (4'chlorophenoxy)
-5-chlorobenzene etc. can be mentioned.

The photodecomposable compound in the present invention is a double salt of the chloride of the diazo compound described above and a metal halide such as zinc chloride, cadmium chloride or tin chloride, which is stabilized against heat or a solvent. Is. Further, by forming a complex salt of the diazo compound with an acid of a fluoride such as tetrafluoroboric acid, hexafluorophosphoric acid, fluorosulfuric acid or an organic boron salt such as sodium tetraphenylboron, it is stable against heat and dissolution. It was done.

On the other hand, an aromatic azide compound is particularly effective as the azide compound. That is, as a specific example, Other than the above 4,4'-diazido-diphenyl sulfone, 4,
4'-diazidobenzsulfone, 4,4'-diazidostilbene, 4,4'-diazidobenzalacetone, 2-6-di- (4-azidobenzal) -4-methylcyclohexanone, 4,4'- Diazido diphenyl sulfide, 1,2-
(4,4'-diazidodiphenyl) ethane, 4,4'-diazidodiphenyl ether, azidobenzoxazoles,
Examples thereof include 4'-diazido-diphenylmethane, 4,4'-diazidostilbene-2,2'-disulfonic acid sodium salt, azidobenzoic acid and azidobenzenesulfonic acid. Since these azide compounds can be optically sensitized, a practical photosensitivity can be improved by adding a sensitizer as needed.

The photodegradable compounds used in the present invention may be used alone or in combination of two or more. The amount of these photodegradable compounds used is appropriately in the range of 0.1 to 80 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total solid content in the intermediate layer.

Next, the photothermal conversion substance to be simultaneously blended in the intermediate layer is an essential condition that it absorbs light including ultraviolet rays, visible rays and infrared rays over a wider wavelength range, and more effectively converts it into heat energy. Suitable material systems include inorganic and organic pigments or dyes, UV absorbers, infrared absorbers and the like. That is, as specific examples thereof, carbon black, graphite, iron powder, copper powder, chromium powder, metal powder such as aluminum powder, metal oxides, sulfides, selenides, ferrocyanides, chromates, silicic acid. Inorganic pigments such as salts, azo pigments, dyed lake pigments, nitro pigments,
Organic pigments such as nitroso pigments, phthalocyanine pigments, metal complex pigments, perylene pigments, isoindolinone pigments, quinacridone pigments, nitrone dyes, nitro dyes, azo dyes, stilbene azo dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, Dyes such as thiazole dyes, azine dyes, oxazine dyes, sulfur dyes, anthraquinone dyes, indigoid dyes and phthalocyanine dyes,
Salicylic acid-based, benzophenone-based benzotriazole-based, cyanoacrylate-based, nickel-dibutyldithiocarbamate, benzoate-based quenchers, and UV absorbers such as hindered amines, commercially available infrared series agents (Mitsui Toatsu Inc. IR absorber PA-1001, PA-1005, PA
1006, IRF-905, IRF-700 manufactured by Fuji Film Co., Ltd.) and the like.

These photothermal conversion substances may be used alone or in combination of two or more. The amount of the photothermal conversion substance used is appropriately in the range of 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total solid content in the intermediate layer.

In addition, a heat-dominant substance may be added to the intermediate layer, if necessary, in order to effectively amplify the pressure and pressure hardening by the nitrogen gas during the photolysis of the photodecomposable compound in the binder. In this case, the heat-fusible substance may be any substance as long as it is compatible with the binder and the photodecomposable compound and is melted or softened by the heat energy to promote the thermal expansion of the nitrogen gas generated by the photolysis.

Specific examples thereof include higher fatty acid amides such as lauric acid amide, stearic acid amide, and N-behenylbenzamide, aromatic carboxylic acid amides, higher fatty acids such as lauric acid, stearic acid, and oleic acid, or esters thereof.
Examples thereof include polyethylene glycol, polyethylene oxide, polyethylene oxide / polypropylene oxide graph copolymer and the like.

Furthermore, a plasticizer such as a phthalate ester type, a glycol ester type, an epoxy type, a polyester type, or a vinyl polymer may be added as needed for the purpose of imparting plasticity to the intermediate layer. Further, a dispersant, a pigment, a surfactant or the like may be added, if necessary, for the purpose of improving the dispersion state and the coating film formation state.

The above-mentioned binder, photodecomposable compound, photothermal conversion substance and, if necessary, various additives are added and dissolved or dispersed in an appropriate solvent to form an intermediate layer paint. Dissolution or dispersion at the time of producing the coating material of the intermediate layer can be performed by a conventionally used planetary mixer, butterfly mixer, sand mill, tank mixer, attritor, three-roll mill, vibrator mill, jet mill, or the like. . The intermediate layer paint is formed on the surface of the light transmissive support by a solvent coating method. The coating can be carried out using an air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, or the like. The thickness of the intermediate layer is 0.01 to 20 μm, preferably
The range of 0.1 to 10 μm is suitable.

[Heat transferable solid ink layer]

The heat transferable solid ink layer is made of a heat fusible or heat sublimable material, and any of those conventionally used in the field of heat transfer ink sheets can be applied as they are. That is, in the case of the heat-fusible ink layer, the constituent substances are mainly composed of a binder having a low melting point substance, a colorant, and a softening agent. The low-melting-point binder is a solid or semi-solid substance having a melting point in the range of 40 to 120 ° C., and specific examples thereof include carnauba wax, paraffin wax, microcrystalline wax ester wax, oxide wax, montan wax, etc. Wax, stearic acid, higher fatty acid such as behenic acid, higher alcohol such as palmityl alcohol, stearyl alcohol, higher fatty acid ester such as cetyl palmitate and cetyl stearate, amide such as acetamide, stearic acid amide, ester gum, Examples thereof include rosin derivatives such as rosin phenol resin, polymer compounds such as terpene resin and cyclopentadiene resin, higher amines such as stearylamine and palmitinamine, polyethylene glycol, polyethylene oxide and the like. These low melting point substances may be used alone or in combination of two or more. The colorant can be selected from conventionally known dyes or pigments. Specific examples of the cyan colorant include magenta colorant such as diaceriton fast brilliant blue R (manufactured by Mitsubishi Kasei Co., Ltd., trade name), Kayaron polyester blue B-SF conc (manufactured by Nippon Kayaku Co., Ltd., trade name). As for Diacerington Fast Red R (manufactured by Mitsubishi Kasei), Kayaron Polyester Pink RCL-E
(Nippon Kayaku Co., Ltd., trade name) and other yellow dyes include Kayaron Polyester Light Yellow 5G-S (Nippon Kayaku Co., Ltd. trade name), Aizenspiron Yellow GRH
(Trade name, manufactured by Hodogaya Chemical Co., Ltd.) and the like.
Further, as cyan pigments, cerulean blue, phthalocyanine blue, etc., as magenta pigments, brilliant carmine, alizarin lake, etc., as yellow pigments, Hansa Yellow, bisazo yellow, etc., as black pigments, carbon black, graphite, oil. Black etc. can be mentioned.

In the ink layer, etc., if necessary, a thermoplastic resin such as ethylene-vinyl acetate copolymer, butyral resin, polyamide resin, or an oil agent such as a plasticizer, mineral oil, or vegetable oil may be added and used. .

On the other hand, in the case of the thermal sublimation ink layer, the constituent materials mainly consist of a binder and a colorant. It is desirable that the binder has a relatively high melting point or softening point in order to avoid melt transfer during transfer. Specific examples thereof include polysulfone, polycarbonate, polyester, polyphenylene oxide, organic solvent-soluble resin systems such as cellulose derivatives, polyvinyl alcohol, polyvinyl butyral, hydroxyethyl cellulose, carboxymethyl cellulose, water-soluble or water-dispersible polyester, water-soluble or Examples thereof include water-soluble or water-dispersible resin systems such as water-dispersible acrylic resins, and organic solvent-soluble resin system emulsion systems described above.

The heat sublimation or heat vaporization colorant is generally used in transfer printing or thermal transfer ink of fibers, from disperse dyes, oil-soluble dyes, acid dyes, mordant dyes, vat dyes, basic dyes, etc. You can choose. Specific examples thereof include azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone, azomethine, coumarin, and condensed polycyclic dyes.

 The starting temperature of these dyes is preferably 150 ° C or lower.

If necessary, an antiblocking agent, an inorganic or organic pigment, an antioxidant, an ultraviolet absorber, an antistatic agent, a surfactant, etc. may be added to the ink layer for use. The heat transferable solid ink layer is formed on the above-mentioned intermediate layer by a hot melt coating method or a solvent coating method. The ink layer thickness is 0.1
A range of -10 μm, preferably 1-5 μm is suitable.

Next, the transfer recording method of the present invention, which is performed using the transfer recording medium having the above-mentioned structure, will be described.

That is, the process for carrying out the transfer recording method of the present invention is described as follows with reference to the drawings.

(1) As shown in FIGS. 6A and 6B, the surface of the image receiving sheet 5 is brought into close contact with the surface of the heat transferable solid ink layer 4 constituting the transfer recording medium. The image receiving sheet in this case is
For example, a sheet-like material such as paper or film capable of carrying and forming a final image is applied.

(2) The back surface of the transfer recording medium (the surface opposite to the heat transferable solid ink layer through the support) is irradiated with light energy based on image information. As means for irradiating light energy based on image information in this case, for example, as shown in FIG. 6 (a), a metal vapor deposition film 2 is provided on a transparent substrate 10, and the vapor deposition film is subjected to discharge breakdown or photopolymerization. Then, a so-called negative mask sheet 11 is produced by removing it in an image-like manner by a peeling phenomenon (peeling apart) or the like, and this is superposed on the back surface of the transfer recording medium, and a flash 7 is irradiated by xenon, an iodine lamp 6 or the like.

As shown in FIG. 6B, the laser light 13 which is image-wise controlled from the back surface of the transfer recording medium and focused by the focusing lens 12, that is, YAG laser, helium / cadmium laser, argon ion laser, krypton laser, Irradiation is performed while scanning with an excimer laser, a nitrogen laser, a metal deposition laser, a carbon dioxide gas laser, a dye laser, a semiconductor laser, or the like.

As a result, light energy is converted to heat energy based on the photothermal conversion substance forming the intermediate layer,
The heat-transferable solid ink layer becomes the heat-melting portion 14 in a state in which it can be permeated and transferred to the image receiving sheet 5.

(3) The transfer recording medium and the image receiving sheet are separated and separated, and the image 8 made of the heat transferable solid ink is transferred to the image receiving sheet.

The photodecomposable compound in the intermediate layer constituting the transfer recording medium of the present invention is photodecomposed by heat generation in the process (2) to generate gas, which causes volume expansion of the intermediate layer, As a result, the effect of pressing and pressing the image receiving sheet, particularly the surface of the sheet having low surface smoothness, is exerted, and the function of improving the ink transfer property is exhibited.

<Example> Hereinafter, the present invention will be described in detail with reference to examples, but the present examples do not limit the present invention. It should be noted that all compounding parts are parts by weight.

Example 1 [Formation of intermediate layer] Glass beads were added to the above mixed solution and dispersed for 100 minutes with a paint shaker to prepare a paint for the intermediate layer. Then, the coating material was applied onto a polyethylene terephthalate film having a thickness of 6 μm under a drying condition of 75 ° C. for 1 minute using a wire bar so that the coating thickness after drying was 1.5 μm to form an intermediate layer. .

[Formation of thermal transferable solid ink layer] (A) Yellow ink (Y) (B) Magenta ink (M) (C) Cyan ink (C) (D) Black ink (BK) Each mixture of the above (A), (B), (C) and (D) was melt-mixed at 95 ° C. and then stirred for 60 minutes with a homomixer to obtain a heat-meltable ink. The melting points of the Y, M, C and BK inks were 75, 74, 72 and 69 ° C, and the melt viscosities at 100 ° C were 126, 34, 22 and 120 cp. Each of the above inks was coated on the intermediate layer by a hot melt coating method so that the thickness of each layer was 3.5 μm to form a thermal transferable solid ink layer, and Y, M, C and BK of the present invention were formed.
Four types of transfer recording media having the ink layers of

Next, a roughened layer having a layer thickness of 6 μm containing silica (SiO ₂ ) having an average particle size of 5 μm is provided on a light-transmitting support made of a polyethylene terephthalate film having a thickness of 12 μm, and further on the roughened layer. A mask sheet provided with a light-reflecting layer that can be removed by discharge breakdown recording by providing an Al vapor-deposited layer of about 500 Å was obtained.

Image information was recorded on the mask sheet in a character pattern, a solid pattern, and a gradation pattern by a dither method with a head applied voltage of 45 V by using an ordinary electric discharge recording device to prepare a negative mask sheet. Then, the polyethylene terephthalate surface of the mask sheet and the back surface of the transfer recording medium, that is, the polyethylene terephthalate surface were overlapped with each other, and the image receiving paper was brought into close contact with the heat transferable solid ink surface of the transfer recording medium. Subsequently, a xenon flash device (FX-150 manufactured by Ideal Chemical Co., Ltd.) was used to irradiate the entire surface with flash light from the light reflecting layer side of the mask sheet. At this time, the contact pressure between the heat transferable solid ink layer surface and the image receiving paper surface is 50
The g / cm ² and 100 g / cm ² flash energy was adjusted to a constant value of 13 mJ / mm ² . Further, as the image receiving paper, three kinds of paper were used, that is, a bond paper having a Bekk smoothness of the surface of 4 to 6 seconds, a copy paper of 50 to 60 seconds and a thermal transfer paper of 300 to 320 seconds.

After the flash irradiation, the transfer recording medium of the present invention and the image receiving paper are
A transfer image was obtained on the image-receiving paper by peeling and separating by the .degree. Peeling method.

Examples 2 to 4 Transfer recording media of the present invention were obtained in the same manner as in Example 1 except that the binder in the intermediate layer was changed to the following. On this occasion,
The solid content plasticization ratios of the binder, the photodegradable compound and the photothermal conversion substance and the coating layer thickness were adjusted to be the same as in Example 1.

Binder of Example 2: 30% by weight methyl ethyl ketone / toluene solution of polyester resin (manufactured by Toyobo Co., Ltd., trade name Byron 30-S) Binder of Example 3: vinyl chloride vinyl acetate copolymer resin (manufactured by Denki Kogyo Kogyo KK, Product name Denka Vinyl 1000A
S) 20% by weight methyl ethyl ketone solution Binder of Example 4: 20% by weight toluene solution of microcrystalline wax (Nippon Seiwa Co., Ltd., trade name Hymic 1070) The transfer recording method was performed in the same manner as in Example 1. It was

Examples 5 to 6 Transfer recording media of the present invention were obtained in the same manner as in Example 1 except that the photodecomposable compound in the intermediate layer was changed to the following. At this time, the composition ratio of each solid component of the binder, the photodecomposable compound and the photothermal conversion substance and the coating layer thickness were adjusted to be the same as in Example 1.

Photodegradable compound of Example 5: 4-diazo-1-diethylamino-2- (4'-chlorophenoxy) -5-chlorobenzene-6-fluorophosphate Photodegradable compound of Example 6: 1-diadopyrene The transfer recording method was performed in the same manner as in Example 1.

Example 7 The present invention was carried out in the same manner as in Example 1 except that the composition and preparation of the heat transferable solid ink layer were as follows.

(A) Yellow ink (Y) (B) Magenta ink (M) (C) Cyan ink (C) Glass beads were added to the above mixed solution and dispersed for 120 minutes with a paint shaker to obtain a color heat sublimable ink paint. Each of these inks was applied on the intermediate layer obtained in Example 1,
Using a wire bar, the layer thickness after drying at 60 ℃ for 2 minutes is 3μ.
m to obtain a transfer recording medium of the present invention. The transfer recording method was the same as in Example 1.

Example 8 Polyethylene terephthalate constituting the transfer recording medium of the present invention was prepared by using a 25 watt argon ion laser after adhering the image receiving paper to the surface of the heat transferable solid ink layer of the transfer recording medium obtained in Example 1. Irradiation was performed while scanning an image line having a diameter of 10 μm from the support side at a speed of 10 m / sec. After that, the transfer recording medium and the image receiving paper were separated and separated to obtain a transferred image on the image receiving paper.

Comparative Example 1 A transfer recording medium for comparison and transfer recording were performed in the same manner as in Example 1 except that the intermediate layer was not provided.

Comparative Example 2 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 1 except that the photodecomposable compound was not contained in the intermediate layer.

Comparative Example 3 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 1 except that the photothermal conversion substance was not contained in the photothermal conversion layer.

Comparative Example 4 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 1 except that the binder of the intermediate layer was changed to the following thermosetting resin and prepared.

Of the transfer recording media obtained from each of the above Examples and Comparative Examples, for a sample having a magenta heat transferable solid ink layer, the image quality of each sample subjected to transfer recording at a predetermined contact pressure was evaluated. The results as shown in the table were obtained. The image quality in Table 1 is based on visual judgment by visual inspection and enlarged photographs (25 times, 50 times), and the evaluation criteria are as follows.

That is, the "printing debris" of the fine line transfer part, "togere", "scratch", "white clear" of the solid transfer part, observing the degree of gradation expression, "printing debris", "togere", "scratch", When there is no "white clear" or "fog", the Macbeth reflection density of the solid part is 1 or more, and the gradation expression is good, it is ◎, "printed mark", "togere", "kasure",
If at least one of “white spots” and “fogging” occurs and the degree is not significant ○, at least one of “printing bokeh”, “togire”, “scratch”, “white blank” and “fogging” The case where one was relatively conspicuous was marked with Δ, and the case where “printed mark”, “toggle”, “blurred”, “white clear” and “fog” were conspicuous, and the case where the solid transfer part had insufficient density was marked with x. As is clear from Table 1,
It was confirmed by the present invention that an excellent image can be obtained on the image receiving sheet. It was confirmed that the same effect can be obtained with a transfer recording medium having a color ink other than magenta and a black ink.

<Advantages of the Invention> Since the present invention is configured as described above, it is possible to significantly widen the selection range of the image receiving sheet even though it is a transfer recording method, and it has been possible to obtain the prospect of expanding the applications of a wide variety of recording systems. .

That is, by providing an intermediate layer containing a photodecomposable compound on the transfer recording medium, the compound in this layer undergoes photodecomposition and gas is generated to enhance the pressure contact effect to the surface of the image receiving sheet. This enables high-resolution and high-density transfer even with low-sensitivity image-receiving sheets, and the heat-insulating effect of this gas significantly suppresses heat dissipation to the light-transmissive support side, resulting in a heat-transferable solid ink layer. By further increasing the temperature, the effect of the ink layer is amplified, in the case of a fusible ink, the maintenance of the molten state is enhanced, and in the case of a thermally sublimable ink, the amount of sublimation is greatly increased. It has become possible to improve the property.

[Brief description of drawings]

FIG. 1 is a sectional view of a conventional transfer recording medium, and FIGS.
FIG. 5 is a sectional view showing a conventional transfer recording method, FIG. 5 is a sectional view of a transfer recording medium of the present invention, and FIGS. 6 to 7 are views showing a transfer recording method of the present invention. 1 ... Light transmissive support, 2 ... Light reflection layer, 3 ... Photothermal conversion layer, 4 ... Thermal transfer solid ink layer, 5 ... Image receiving sheet, 6 ... Xenon flash lamp, 7 ... Flash light, 8
...... Transfer image, 9 …… Intermediate layer, 10 …… Substrate, 11 …… Mask sheet, 12 …… Focusing lens, 13 …… Laser light, 14…
… Melting part

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Riki Murata 3-1, Soba-cho, Shizuoka-shi, Shizuoka City, Ltd., within the Technical Research Institute of Tomagawa Paper Mill Co., Ltd. (72) Katsuhide Tsukamoto, 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Denki Sangyo Co., Ltd. (72) Inventor Yutaka Nishimura 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Denki Sangyo Co., Ltd. (56) References JP-A-49-37643 (JP, A) JP-A-60-236791 (JP) , A) JP-A-60-225795 (JP, A) JP-A-58-18290 (JP, A) JP-B-55-12396 (JP, B2)

Claims (3)

[Claims] 1. A binder, a double salt of a chloride of a diazo compound and a metal halide, a complex salt of a diazo compound and an acid of a fluoride, and a complex salt of a diazo compound and an organic boron salt on a light-transmissive support. And a thermal transferable solid ink layer via an intermediate layer containing at least one photodegradable compound selected from the group consisting of an azide compound and a photothermal conversion substance. 2. The transfer recording medium according to claim 1, wherein the binder of the intermediate layer is at least one selected from thermoplastic resins, waxes and rubbers. 3. A binder, a double salt of a chloride of a diazo compound and a metal halide, a complex salt of a diazo compound and an acid of a fluoride, and a complex salt of a diazo compound and an organic boron salt on a light-transmissive support. And a surface of the heat transferable solid ink layer of a transfer recording medium provided with a heat transferable solid ink layer through an intermediate layer containing at least one photodecomposable compound selected from diad compounds and a photothermal conversion substance. By closely contacting the image receiving sheet and irradiating the back surface of the transfer recording medium with light energy based on image information, the heat transferable solid ink layer is selectively heated and melted and transferred to the image receiving sheet, and then transfer recording is performed. A transfer recording method, wherein a transfer recorded image is obtained by separating and separating a medium and an image receiving sheet.