JPH044189A - Thermal transfer dye donative material - Google Patents

Abstract

PURPOSE:To prevent deformation, an occurrence of wrinkle, and a fusion with a thermal transfer image receiving material by incorporating at least one of specific three color dyes and a silicone compound. CONSTITUTION:On a substrate, a coloring material layer is formed. The coloring material layer contains at least one of an Yellow dye shown by a formula (I), a Magenta dye shown by a formula (II), and a Cyan dye shown by a formula (III) or/and a formula (IV) and a silicone compound. These dyes have resistance to light and heat and a sufficient resistance to chemicals. A thermal transfer recording material containing a thermal transfer dye donative material containing these dyes has superior fastness to light and color reproducibility. However, because these dyes have relatively low thermal transfer properties, it is required that the dyes should be transferred at high temp. or a thermal head should be heated for a long time. Therefore, sometimes the dye donative material may produce wrinkle or thermally fuse with a dye receiving material. In this case, this phenomenon can be prevented by incorporating a silicone compound in a layer of the dye donative material abutting on the dye receiving material.

Description

Detailed Description of the Invention (Industrial Field of Application) When X and Y are -C- or when Y and Z are l2 -C-, they combine with each other to form a saturated or unsaturated carbocyclic ring. may be formed.

In the formula, Q represents an atomic group necessary to form a 5-membered or more carbocyclic ring or a 5-membered or more heterocycle containing at least one nitrogen atom, and R14 to R19 represent j16 to R11' I agree with you, Rho, RlI, R11, R+2.

In the formula, Rzz to Rt9 are R! , R+ 6, and R", R" are Rth and R" are in agreement.

3. Detailed description of the invention The present invention relates to thermal transfer dye-providing materials.

(Prior Art) Currently, thermal transfer methods, electrophotography methods, inkjet methods, and the like are being actively studied as technologies related to color hard copies. The thermal transfer method has many advantages over other methods because the equipment is easy to maintain and operate, and the equipment and consumables are inexpensive.

Thermal transfer methods include a method in which a thermal transfer dye-providing material in which a heat-melting ink layer is formed on a base film is heated by a thermal head to melt the ink and recorded on a thermal transfer image-receiving material; There is a method in which a thermal transfer dye-providing material on which a coloring material layer containing a colorant is formed is heated with a heat nozzle to transfer the dye onto a thermal transfer image-receiving material. By changing the energy applied to the image, the amount of dye transferred can be changed, which facilitates gradation recording, which is particularly advantageous for high-quality full-color recording.

However, there are various restrictions on the heat-transferable dyes used in this method, and there are very few that satisfy all the required performances.

Required performances include, for example, spectral characteristics favorable for color reproduction, ease of thermal transfer, resistance to light and heat, resistance to various chemicals, resistance to loss of sharpness, and image quality. It is difficult to retransfer, and it is easy to make a thermal transfer dye-providing material. In particular, a combination of yellow, magenta, and cyan dyes has been strongly desired in order to obtain full-color images with excellent color reproduction and light fastness.

Further, there is a strong desire for a thermal transfer dye-providing material that does not deform and wrinkle when heated by a thermal head, and does not cause the material to fuse with the thermal transfer image-receiving material.

(Problem B to be Solved by the Invention) No full-color image obtained from a combination of three color dyes known for thermal transfer, yellow, magenta, and cyan, satisfies both color reproducibility and light fastness. Also,
Deformation such as wrinkles caused by heat and fusion were also insufficient.

(Object of the invention) In order to overcome the above-mentioned drawbacks, it is an object of the present invention to provide a new thermal transfer dye-providing material containing at least one of yellow, magenta, and 7723 color dyes and a silicone compound. .

(Means for Solving the Problems) The above object of the present invention is to provide a yellow dye represented by the following general formula (+), a magenta dye represented by the general formula (II), and a general formula (III) or This was achieved by a thermal transfer dye-providing material having a coloring material layer containing at least one cyan dye represented by the general formula (rV) and a silicone compound.

In the formula, R1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, R2 represents a hydrogen atom, an alkyl group, or an aryl group, and R3 represents an alkyl group or It represents a heteryl group, and R4 and R5 represent a hydrogen atom or an alkyl group.

I3 X, Y and Z represent -C- or a nitrogen atom (R13
is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
represents an aryloxy group or an amino group), and when X and Y are -C-, or when Y and Z are
-171G is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an acylamino group, a sulfonylamino group, a ureido group,
It represents an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or an amino group, and R11 and RI2 represent a hydrogen atom, an alkyl group, or an aryl group. R11 and 1llffi may be combined with each other to form a ring, or P and R1 or/
And R9 and R12 may be combined to form a ring.

May form an elementary ring.

In the formula, Q represents an atomic group necessary to form a 5-membered or more carbocyclic ring or a 5-membered or more heterocycle containing at least one nitrogen atom, I? 1 to Qll are identical to R6 to RIO, R10 and R11 are identical, and RI2 are identical.

In the dye koji formula, R22~l? 2q is the same as Rh-R10,
R30 and R11 are in agreement with R+1.1712.

Specific examples of the dye represented by the general formula (I) used in the present invention are shown below. The present invention is not limited to these.

N′”NHz Dye N.

pigment floor R Dyestuff z Pigment ( N The general formula (II) used in the present invention is shown below. Preferred specific examples of dyes to be used are shown below.

N- CH3 CH.

Specific examples of the dye represented by the general formula (III) used in the present invention are shown below.

The general formula used in the present invention is shown below. (TV) expressed as Specific examples of dyes that can be used are shown below.

These dyes of the present invention are resistant to light and heat, and have sufficient resistance to chemicals, and can be used to easily produce thermal transfer dye-providing materials.

A thermal transfer recording material using a thermal transfer dye-providing material containing the dye of the present invention has excellent light fastness and is less likely to lose sharpness, compared to a case where a conventionally known dye is used. Furthermore, full-color thermal transfer recording materials using these yellow, magenta, and nyan dyes have excellent color reproducibility.

However, these dyes have slightly lower thermal transfer properties than conventional dyes, so they must be transferred at high temperatures or for long periods of time.
It is necessary to improve the transfer density by heating the thermal head.

In this case, since the applied energy is greater than in the past, there are problems such as wrinkles in the dye-providing material and thermal fusion with the dye-receiving material.

As a result of various studies to solve these problems, it has been found that it is effective to include a silicone compound in the layer of the dye-donating material containing the dye of the present invention that is in contact with the dye-receiving material.

The silicone-based compounds used in the present invention include unmodified or modified silicone oil, toluene alkyl/aralkyl, etc. The modified silicone oil (including solid silicone oil) may have the following skeleton structure, for example: Examples of compounds having such compounds are listed.

Epoxy modified silicone oil CH3 〇 to C for example Polyether modified silicone oil -C ゝ、1 OA robiren (Forward below) Alkyl modified silicone oil for example Alcohol-modified silico oil 1] R;CH.

or OCR.

[(I CH.

Carboxyl modified silicone oil Amino modified silicone oil OOH For example HK For example (7) Fluorine modified silicone oil 00) Alkyl polyether modified silicone oil (7-1) (8) Higher fatty acid modified silicone oil R: Aliphatic hydrocarbon group (9 ) Epoxy/polyether modified silicone oil ■) OA The silicone-based fine particles used in the present invention are amorphous or true spherical fine particles of three-dimensionally crosslinked silicone rubber or silicone resin, such as Torefil@R manufactured by Toray Silicone ■. -902, R925, R-930, E-
500, E-501, E-600, E-601, E-
602, E-603, and Tospar J20.130.145.240 manufactured by Toshiba Silicone Corporation.

The average particle size of the silicone-based fine particles used in the present invention is 0.01
-20tm, preferably 0.1-10β is used.

Two or more types of silicone compounds used in the present invention can also be used in combination. In particular, it is preferable to use unmodified or modified silicone oil and silicone solid fine particles in combination.

The amount of the unmodified or modified noricone oil and the soricone compound soluble in the solvent used in the present invention is 0.00% of the total weight of the binder in the layer to which the noricone compound is added.
001 to 20%, preferably 0.01 to 10%, particularly preferably 051 to 1%.

Further, the coating amount of the silicone-based fine particles used in the present invention is usually 0.001 to 3 g/rrf, preferably 0.005 g/rrf.
~Ig/m, particularly preferably 0.01 to 0.5 g/m.

The unmodified or modified noricone oil used in the present invention is added to the coating solution as follows.

■ Noricorn oil is diluted as is with an organic solvent,
Add to the binder and dye/8 solution.

(2) When emulsifying and dispersing a dye and binder solution in an organic solvent in a hydrophilic polymer, Noricon oil is diluted with an organic solvent, emulsified and dispersed together, and added.

Further, the noricorn polymer (solid) used in the present invention is dissolved in an organic solvent such as toluene and added to the coating solution in the same manner as the noricorne oil.

The silicone-based fine particles used in the present invention are dispersed and added to an organic solvent solution of a pigment and a binder using a homogenizer or the like.

The thermal transfer dye-providing material of the present invention uses a thermal transfer dye-providing material having a dye-providing layer containing the yellow dye, magenta dye and/or cyan dye and a silicone compound on a support.

Thermal transfer dye-providing materials can be used in notebook form or in continuous roll or ribbon form. The yellow, magenta and cyan dyes of the present invention are usually arranged on a support so as to form independent areas. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. Alternatively, it is also possible to prepare three types of thermal transfer dye-providing materials in which the yellow, magenta, and cyan dyes described above are each provided on separate supports, and thermally transfer the dyes from these to one thermal transfer image-receiving material in sequence. .

The yellow dye, magenta dye, cyan dye, and silicone compound of the present invention are each dissolved or dispersed in a suitable solvent together with a binder resin, and then applied onto a support.
Alternatively, it can be printed on the support by a printing method such as a gravure method.

The thickness of the dye-donating layer containing these dyes is usually about 0.2 to 5t in dry film thickness! m, particularly preferably in the range of 0.4 to 2 JM.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. Examples include polyethylene terephthalate; polyamide; polyaramid; polycarbonate; glassine; condenser paper; cellulose ester: fluorine polymer; polyether: polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; cellophane.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
I am a prisoner. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer. This S further improves the transfer density.

As the hydrophilic polymer, the water-soluble polymers described above can be used.

Furthermore, as the binder resin used with the dye of the present invention, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not prevent the transfer of the dye when heated. Those that do not exist are selected. For example, polyamide resins, -polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride. resins (e.g. vinyl chloride-vinyl acetate copolymer), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate) , cellulose acetate butyrate, cellulose triacetate),
Polyvinyl alcohol resins (for example, partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, and polyolefin resins (for example, polyethylene and polypropylene) are used.

Such a binder resin is preferably used in a proportion of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin. Specifically, alcohol-based ink solvents include methanol, ethanol, isopropyl alcohol, butanol, and Butanol, etc. Ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Aromatics include toluene, xylene, etc. Halogens include dichloromethane, trichloroethane, etc.
Dioxane, tetrahydrofuran, etc. and mixtures thereof may be mentioned. It is important to select and use these solvents in such a way that the dye used has a predetermined concentration or higher and the hainter resin is sufficiently dissolved or dispersed. For example, it is preferred to use an amount of solvent that is about 9 to 20 times the total weight of the dye and binder resin.

In addition to the noricone compounds used in the present invention,
In order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the dye-donating material! 2 and/or the image-receiving material, particularly preferably the outermost layer corresponding to the surface in contact with both materials may contain a mold release agent other than the silicone compound as described below.

As a mold release agent, any conventionally known mold release agent can be used, such as solid or waxy substances such as polyethylene wax, amide wax, and Teflon powder, surfactants such as phosphate esters, and paraffin oils. .

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent.

When curing organic solvent-based polymers, JP-A-61
Hardeners described in Japanese Patent No. 199997 and No. 58-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Pat.
No. 6655, No. 62245261, No. 61-1894
Hardeners such as those described in No. 2 are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde),
Aziridine hardeners, Evoquin hardeners, vinyl sulfone hardeners (N,N'-ethylene-bis(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.) ), or polymer hardeners (compounds described in JP-A No. 62-234157, etc.).

Antifading agents may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, low phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-56-2784, etc.), and other JP-A-54-48535, JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Pat. No. 4,241,155;
Same No. 4,245,018 No. 3-364! IN, 4th
．． No. 254,195, columns 3 to 8, JP-A-62-174
There are compounds described in Japanese Patent Application No. 741, No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234103, Japanese Patent Application No. 62-31096, and Japanese Patent Application No. 62-230596.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
It is described on pages I25) to (I37).

The anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be included in the image-receiving material in advance, or it may be supplied to the image-receiving material from the outside by a method such as transfer from a dye-donating material. It's okay.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Various surfactants can be used in the constituent layers of thermal transfer dye-providing materials and thermal transfer image-receiving materials, such as coating aids, improving peelability, improving shearability, preventing static electricity, and accelerating development.

Nonionic surfactants: anionic surfactants; bifacial surfactants: cationic surfactants can be used. Specific examples are JP-A-62-173463 and JP-A No. 6218345.
It is stated in No. 7 etc.

In addition, when dispersing substances that can accept heat-transferable dyes, mold release agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. Preferably, an activator is used. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described in No. 6, pages 37-3 are particularly preferably used.

A capping agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 62-110065.

When printing from the back side of the dye-donating material, it is preferable to apply an anti-sticking treatment to the side of the support on which the dye-donating layer is not provided, in order to prevent sticking due to the heat of the thermal helad and improve slippage.

For example, it is preferable to provide a heat-resistant slump layer mainly consisting of (1) a reaction product of polyvinyl butyral resin and an isocyanate, (2) an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and (2) a filler. Polyvinyl butyral resins have a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110°C, and have a vinyl butyral portion of 15 to 40% by weight from the viewpoint of having many reaction sites with isocyanate. As the alkali metal salt or alkaline earth metal salt of the phosphoric acid ester, Toho Chemical's Gafac RD720 or the like is used, and it is used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. Good.

It is desirable that the heat-resistant slip layer has heat resistance as the lower layer.
A combination of a synthetic resin that can be cured by heating and its hardening agent,
For example, a combination of polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and a titanium chelating agent, or polyester and organic titanium compound may be provided by coating.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye toward the support. The hydrophilic dye barrier layer contains a hydrophilic material useful for dyeing purposes. Generally excellent results are obtained with gelatin, poly(acrylamide), poly(isopropylacrylamide),
Butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), mixture of poly(vinyl alcohol) and poly(vinyl acetate) , by using a mixture of poly(vinyl alcohol) and poly(acrylic acid) or a mixture of cellulose monoacetate and poly(acrylic acid). Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with a subbing layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but a preferred specific example is (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14:80:6).
), (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyester such as Bostik 7650 (Emhart, Bostic) stick chemical group) or chlorinated high density poly(ethylene-trichloroethylene) resins.

There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1
/2.0 g/m”.

It is preferable to provide a mark for position detection at the same time as the formation of any dye-donor layer when shaping the dye-donor layer, since this eliminates the need for ink or a printing process separate from the formation of the dye-donor layer.

What kind of support should be used for thermal transfer image-receiving materials, as long as it can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, and denting after transfer? It can also be used for things. For example, synthetic paper (polyolefin-based, polystyrene-based, etc. synthetic paper), high-quality paper, art paper, coated paper, cast coat paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper supports such as paperboards, paperboards, cellulose fiber papers, polyolefin-coated papers (especially papers coated on both sides with polyethylene), polyolefins,
Laminated products of various plastic films or sheets such as polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, films or sorting treated to give the plastic white reflective properties, and any combination of the above may also be used.

The thermal transfer image-receiving material is provided with an image-receiving layer. This image-receiving layer receives the heat-transferable dye transferred from the thermal transfer dye-providing material during printing, and contains a dye-receiving substance that functions to dye the heat-transferable dye alone or Examples of the dye-receiving bomber, which is a representative example of the dye-receptive material, which preferably forms a film with a thickness of about 0.5 to 50 mm together with other binder materials, include the following resins.

(a) Those with an ester bond (b) Those with urethane bonds (c) Those with an amide bond (d) Those with urea bonds (e) Those with a sulfon bond.

(f) Others having highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a dye-receiving substance or as a dye diffusion aid.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which the dye-receiving substance is dispersed and supported in a water-soluble binder. In this case, various known water-soluble polymers may be used as the water-soluble binder. However, a water-soluble polymer having a group capable of crosslinking with a hardening agent (eg, gelatin) is preferred.

The image-receiving layer may be composed of two or more layers. In that case, the layer closer to the support may be made of a synthetic resin with a low glass transition point, or a high boiling point organic solvent or hot solvent may be used to remove the dye. The composition has a structure with improved dyeability, and the outermost layer is made of a synthetic resin with a higher glass transition point, and the amount of high-boiling organic solvents and hot solvents used is minimized or eliminated to prevent surface sagging. It is desirable to have a structure that prevents failures such as adhesion with other substances, re-transfer of the dye after transfer to other substances, and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 g, especially 3 to 30 g.
A range of is preferred. In the case of a two-layer structure, the outermost layer is 0.1 to 2.
m, preferably in the range of 0.2 to 1 μm.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer.

The intermediate layer can be a cushion layer, a porous layer, or a
This layer has one of the functions of a dye diffusion prevention layer or a layer having two or more of these functions, and in some cases also serves as an adhesive.

The dye diffusion-preventing layer plays a role, in particular, in preventing the heat-transferable dye from diffusing into the support. The binder constituting this diffusion prevention layer may be water-soluble or organic solvent-soluble, but preferably a water-soluble binder.
Preferred examples include the water-soluble binders mentioned above as binders for the image-receiving layer, particularly gelatin.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support and effectively utilizes the applied heat.

The image-receiving layer, cushion layer, porous layer, diffusion prevention layer, adhesive layer, etc. that constitute the thermal transfer image-receiving material of the present invention include limestone, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, Fine powders of synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may also be included.

A fluorescent brightener may be used in the thermal transfer image-receiving material.

Examples include Veenkatara+man
i rThe Chen+1stry of 5ynt
hetic DyesJ Volume 8 Chapter 8, JP-A-61-1
Examples include compounds described in No. 43752 and the like.

Optical brighteners can be used in combination with antifade agents.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy corresponding to image information is applied, preferably from the back side of the thermal transfer dye-providing material, using a heating means such as a thermal head, thereby forming a dye-providing layer. can be transferred to a thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent clarity and resolution and gradation can be obtained.

The heating means is not limited to a thermal head, and known means such as a laser beam (for example, a semiconductor laser), an infrared flash, a thermal pen, etc. can be used.

In the present invention, by combining the thermal transfer dye-providing material with the thermal transfer image-receiving material, images can be printed by printing using various thermal printing printers, by facsimile, or by magnetic recording, magneto-optical recording, optical recording, etc. It can be used to create prints from , television, and CRT screens.

For details on the thermal transfer recording method, see Japanese Patent Application Laid-open No. 603489.
You can refer to the record of No. 5.

(Example) In the following Examples and Comparative Examples, production of a thermal transfer dye-providing material and a thermal transfer image-receiving material, printing using both materials, and testing of the thermal transfer image-receiving material were conducted as follows.

Example 1 (Preparation of thermal transfer dye-providing material) A polyethylene terephthalate film (manufactured by Kijin Co., Ltd.) having a thickness of 6ρ with heat-resistant slipping treatment on the back side was used as a support, and the dyes listed in Table 1 were applied on the surface of the film. A thermal transfer dye-providing material was prepared by applying a coating composition for a thermal transfer dye-providing layer having the following composition using a silicone compound and a silicone compound by wire bar coating so as to have a dry thickness of 1.5-.

(I dye xg Soricone compound yg Polyvinyl butyral resin (electrochemical type Denka Butyral 5000-A) 3.5
g Toluene 40 m Methyl ethyl ketone 40 d Polyisocyanate (Takeda Pharmaceutical DIION) 0.05
- (Preparation of thermal transfer image-receiving material) Synthetic paper with a thickness of 150 - (made by Tamago Yuka Co., Ltd., YUP
A thermal transfer image-receiving material (I ) was formed. Drying was performed for 30 minutes in an open air condition at a temperature of 100°C after temporary drying with a hair dryer.

z(I) Polyester resin (Toyobo Byron-280) 22g
Polyisocyanate (KP 90: manufactured by Dainippon Ink Chemical) Amine-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) Methyl ethyl ketone toluene cyclohexanone g 0.5 g 5R1 5Jd Table 1 (Continued) Table 1 Yellow dye for comparison (a) Magenta for comparison Dye (b) i Cyan dye for comparison (c) The dye-providing material and image-receiving material obtained as described above were superimposed so that the dye-providing layer and the image-receiving layer were in contact with each other, and heat was applied from the support side of the dye-providing material. Using head, output 0.25
Thermal transfer was performed under the conditions of W/dot, pulse width of 0.1 to 10 Ilsec, and dot density of 6 dots/1111 to obtain a recorded image on the image-receiving material.

When the obtained recorded images were compared between the case of the present invention and the comparative example, the case of the present invention was superior in color vividness.

Further, in the case of the present invention, the dye-donating layer was not fused to the image-receiving material. Furthermore, recording failures due to wrinkles caused by deformation of the dye-donating material were not observed in the case of the present invention.

The recorded image-receiving material obtained is 10,0OOQux for 7 days.
The stability of the color image was examined using a fluorescent lamp light resistance tester. Reflection density was measured before and after the test using an optical densitometer using a Status A filter, and the light fastness was evaluated based on the ratio. The results are shown in Table 2.

Furthermore, the transfer was repeated three times to the same image-receiving material using dye-providing materials -2, -6, and -1O to obtain full-color image records. Clear records with excellent color reproducibility and no unevenness such as wrinkles were obtained.

Table 2 (Continued) ×: Large occurrence Example 2 A thermal transfer dye-donating material was created using the resin shown in Table 3 instead of the polyvinyl butyral resin in the thermal transfer dye-donating layer coating composition of Example-1. .

When thermal transfer was carried out using the same image-receiving material as in Example 1, clear image recording with no transfer unevenness was obtained, and the light resistance was also excellent.

Table Example-3 (Preparation of thermal transfer image-receiving material (2)) 15 on each side of 200- paper! Prepare a resin-coated paper laminated with polyethylene to a thickness of 25 cm, and coat the image-receiving layer coating composition of the following composition on the laminated surface with a wire bar to a dry thickness of lOI! A thermal transfer image-receiving material (2) was prepared by applying the coating to give In and drying it.

Coating composition for image-receiving layer Polyester resin No. 1 25g amino-modified silicone oil (KF857: manufactured by Shin-Etsu Silicone) 0.8
g Polyisocyanate (KP-90: manufactured by Dainippon Ink) 4g Methyl ethyl ketone 1-luene Epoxy modified silicone oil (KF400T: manufactured by Shin-Etsu Silicone) Methyl ethyl ketone Toluene Soclohexanone 00mR 00d 0.5g 5m 85m! 30tl! Mo-i~ When thermal transfer was carried out in the same manner as in Example-1, a clear and highly light-fast image recording without wrinkles or fusion was obtained.

Example 4 (Preparation of thermal transfer image-receiving material (4)) An organic cutting solution of a dye-receiving polymer having the composition (B) was emulsified and dispersed in an aqueous gelatin solution having the composition (A) below using a homogenizer to form a dye-receiving material. A gelatin dispersion was prepared.

(A) Gelatin in water 2.3 g Dodenruhenzenesulfonic acid 20 d Sodium (5% aqueous solution) 0 d water (B) Dye-receptive polymer solution Polyester resin (Toyobo: Hiron 300) Carboxy-modified silicone oil (Shin-Etsu) Made of silicone:
0.5g of SOzNCH2COOK in water/mek(C
A solution of al norl (I:1) dissolved in 10 ml of a mixed solvent was added to prepare a coating composition for a receptor layer. This coating composition was coated on a 150-thick synthetic paper (YUPO-3GG-150 manufactured by Tamago Yuka Co., Ltd.) with a corona discharge applied to the surface, and was coated with a wire bar coating method to achieve a wet film thickness of 75 tons. It was applied and dried to give a thickness of m.

When thermal transfer was carried out using the obtained image-receiving material and the dye-providing material of the present invention described in Examples 1 and 2, a clear record with no wrinkles or fusion and excellent light resistance was obtained.

In addition, in the same manner as in Example 1, using the dye-providing material of the present invention containing yellow, magenta, and cyan dyes, the image was transferred three times to the same image-receiving material. We were able to obtain full-color image records.

Claims (1)

[Scope of Claims] A thermal transfer dye-providing material having a dye-providing layer on one surface of a support, wherein the dye-providing layer contains a yellow dye represented by general formula (I), a magenta dye represented by general formula (II), and A thermal transfer dye-providing material comprising at least one of cyan dyes represented by general formula (III) and/or general formula (IV) and a silicone compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R^1 is a hydrogen atom, an alkyl group, an alkoxy group,
It represents an aryl group, an alkoxycarbonyl group, a cyano group or a carbamoyl group, R^2 represents a hydrogen atom, an alkyl group or an aryl group, R^3 represents an aryl group or a heteryl group, R^4 and R^5 represent Represents a hydrogen atom or an alkyl group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, R^6 to R^1^0 are hydrogen atoms, halogen atoms,
Alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkoxycarbonyl group,
Represents a carbamoyl group, sulfamoyl group, sulfonyl group, acyl group or amino group, R^1^1, R^1^2
represents a hydrogen atom, an alkyl group or an aryl group. R^
1^1^ and R^1^2 may be combined with each other to form a ring, and R^8 and R^1^1 are/and R^9 and R^
1^2 may be combined to form a ring. X, Y and Z represent ▲a numerical formula, chemical formula, table, etc.▼ or a nitrogen atom (R^1^3 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group). Also, when X and Y are ▲There is a mathematical formula, chemical formula, table, etc.▼, or when Y and Z are ▲There is a mathematical formula, chemical formula, table, etc.▼, they may combine with each other to form a saturated or unsaturated carbon ring. good. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) In the formula, Q is an atomic group necessary to form a 5-membered or more carbocyclic ring or a 5-membered or more heterocycle containing at least one nitrogen atom. represents. , R^1^4~R^1^9 is R^4~R^
I agree with 1^0, and R^2^0 and R^2^1^ are R^
I agree with 1^1 and R^1^2. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^2^2 to R^2^9 are the same as R^6 to R^1^0, and R^3^0, R^3^1 is R^1^1, R
I agree with ^1^2.