JP2893131B2 - Thermal transfer dye donating material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermal transfer dye donating material. More specifically, the present invention relates to a thermal transfer dye donating material containing a novel dye having a clear hue.

(Prior Art) At present, as a technique relating to a color hard copy, a thermal transfer method, an electrophotographic method, an ink jet method and the like are being vigorously studied. The thermal transfer method has many advantages over other methods because the maintenance and operation of the apparatus are easy and the apparatus and consumables are inexpensive.

The thermal transfer method is a method in which a thermal transfer dye-providing material having a heat-meltable ink layer formed on a base film is heated by a thermal head to melt the ink and is recorded on the thermal transfer image-receiving material. There is a method in which a thermal transfer dye-providing material having a coloring material layer containing a conductive dye formed thereon is heated by a thermal head to thermally transfer the dye onto a thermal transfer image-receiving material.The latter thermal transfer transfer method uses a thermal head. By changing the applied energy, the transfer amount of the dye 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 dye used in this method, and very few satisfy all the required performances.

The required performance includes, for example, having favorable spectral characteristics in terms of color reproduction, being easily transferred to heat, being resistant to light and heat, being resistant to various chemicals, being hardly degraded in sharpness, and reducing image sharpness. Retransfer is difficult, and thermal transfer dye-providing materials are easily produced.

(Problems to be Solved by the Present Invention) Among them, a cyan dye having an excellent hue is hardly known, and its development has been strongly desired.

Various dyes for thermal transfer have been proposed, and among them, JP-A-64-53893, JP-A-64-20194, and JP-A-64-2479.
No. 2, No. 64-24795, No. 63-290793, No. 63-308072
No. 63-308072, JP-A-1-176593, 1-1309
90, the indoaniline dye has relatively excellent performance. However, these dyes have a broad absorption and have a problem in color reproduction of an image.

Also, among the above dyes, those having relatively good absorption are
Indoaniline dyes derived from disubstituted and trisubstituted phenol couplers are expensive due to the large number of synthesis steps.

Also, conventionally known magenta dyes have various disadvantages. For example, pyrazolone azomethine dyes are disclosed in
No. 205288 and the like. However, this dye had unnecessary side absorption in the yellow region.

Further, pyrazolobenzimidazole azomethine dyes are disclosed in JP-A-1-176592 and the like. However, this dye had low fastness.

JP-A-64-63194 discloses a pyrazoloazole azomethine dye. However, this dye was difficult to synthesize and expensive.

As described above, conventionally known azomethine dyes have various drawbacks, and development of dyes that are easy to synthesize, have low cost, and have excellent absorption has been desired.

(Object of the Present Invention) An object of the present invention is to provide a thermal transfer dye-providing material having a dye having excellent spectral characteristics and high heat transferability. Another object of the present invention is to provide a thermal transfer dye-providing material having a dye which is easy to synthesize and has low cost.

Other objects of the present invention are apparent from the description of the specification.

(Means for Solving the Problems) The above object of the present invention has been attained by the following constitutions.

A thermal transfer dye-providing material comprising a support having thereon a dye-donating layer containing a heat-transferable dye, wherein the heat-transferable dye is a dye represented by formula (I): .

In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent.

R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

V is a nitrogen atom or Represents

 X, Y, and Z represent non-metallic substituents.

At least one of Y and Z represents an electron-withdrawing substituent.

X and Y and / or Y and Z and / or R ¹ and R ² and / or R ² and R ⁵ and / or R ⁵ and R ⁶ and / or R ³ and R ⁶ and / or R ³ and R ⁴ are May be combined with each other to form a ring structure.

X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be further substituted.

Where: Is a notation indicating that Y and X may be either cis or trans to the double bond.

However, it does not form a heterocyclic ring by combining with Y X except that the atom of X bonded to the carbon atom of is a nitrogen atom is excluded.

Among the dyes represented by the general formula (I), a dye represented by the following general formula (II) or (III) is preferable.

In the formula, S, T and U each represent a nitrogen atom, a methine group or a methine group having an electron-withdrawing group, at least one of which represents a methine group having an electron-withdrawing group; And Q is Together with a group of nonmetallic atoms necessary to form a heterocyclic or aromatic ring.

R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent.

R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic group.

R ¹ and R ² and / or R ² and R ⁵ and / or R ⁵ and R ⁶ and / or R ³ and R ⁶ and / or R ³ and R ⁴ are bonded to each other to form a ring structure; Is also good.

S, T, U, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be further substituted.

In the formula, at least one of R ⁷ and R ⁸ represents an electron-withdrawing substituent, and the other represents a substituent.

R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent.

R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic group.

R ¹ and R ² and / or R ² and R ⁵ and / or R ⁵ and R ⁶ and / or R ³ and R ⁶ and / or R ³ and R ⁴ are bonded to each other to form a ring structure; Is also good.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be further substituted.

However, it does not combine with R ⁸ to form a heterocyclic ring. R ⁷ atoms R ⁷ is a nitrogen atom attached to the carbon atom of excluding.

 Hereinafter, the general formula (I) will be described in detail.

R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a non-metallic atomic group, among which a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an acylamino group, an alkoxycarbonyl group , Cyano group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminocarbonylamino group, sulfonylamino group,
Preferred are a carbamoyl group, a sulfamoyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, and an amino group.

Specific examples thereof include a hydrogen atom, an alkyl group (including those having a substituent. C 1 to C 12, for example, methyl, ethyl,
Isopropyl, butyl, methoxyethyl, cyclohexyl, phenethyl), alkoxy group (including those having a substituent; having 1 to 12 carbon atoms, for example, methoxy, ethoxy, isopropoxy, methoxyethoxy), and aryloxy group (having a substituent) C6 to C12, for example, phenoxy, p-methoxyphenoxy, p-chlorophenoxy, p-methylphenoxy), a halogen atom (for example, fluorine, chlorine, bromine), an acylamino group [having 1 carbon atom
To 10 alkylcarbonylamino groups (including those having a substituent; for example, formylamino, acetylamino, propionylamino, isobutyrylamino, hexahydrobenzoylamino, pivaloylamino, trifluoroacetylamino, heptafluorobutyrylamino, chloro Propionylamino, cyanoacetylamino, phenoxyacetylamino), a vinylcarbonylamino group having 3 to 10 carbon atoms (including those having a substituent; for example, acryloylamino, methacryloylamino, crotonoylamino), and a carbon atom having 7 to 10 carbon atoms 15 arylcarbonylamino groups (including those having a substituent; for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, o-fluorobenzoylamino, m-methoxybenzoylamino, p- Trifluoromethylbenzoylamino, 2,4-dichlorobenzoylamino, p-methoxycarbonylbenzoylamino, 1-naphthoylamino), a hetenylcarbonylamino group having 5 to 13 carbon atoms (including those having a substituent. Noylamino,
Nicotinoylamino, pyrrole-2-carbonylamino, thiophene-2-carbonylamino, furoylamino, piperidine-4-carbonylamino)], cyano group, alkoxycarbonyl group (including those having a substituent. For example, methoxycarbonyl, ethoxycarbonyl), alkoxycarbonylamino group (including those having a substituent. C2-10, for example, methoxycarbonylamino, ethoxycarbonylamino, isopropoxycarbonylamino, methoxyethoxycarbonylamino, N-methylmethoxy Carbonylamino, t-
Butoxycarbonylamino, hexyloxycarbonylamino), aryloxycarbonylamino group (including those having a substituent, having 7 to 15 carbon atoms such as phenoxycarbonylamino, orthochlorophenoxycarbonylamino), aminocarbonylamino group (Including those having a substituent; having 1 to 10 carbon atoms, such as methylaminocarbonylamino, dimethylaminocarbonylamino, and butylaminocarbonylamino); and a sulfonylamino group (1 to 10 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino, phenylsulfonylamino), a carbamoyl group [having 1 to 12 carbon atoms
Alkyl carbamoyl group having a substituent. For example, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl,
t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, allylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl,
Tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl), an arylcarbamoyl group having 7 to 15 carbon atoms (including those having a substituent. For example, phenylcarbamoyl, p-tolylcarbamoyl, m-methoxyphenylcarbamoyl, 4,5- Dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl,
1-naphthylcarbamoyl), a hetenylcarbamoyl group having 4 to 12 carbon atoms (including those having a substituent.
2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methyl) pyridylcarbamoyl, 2- (5-methyl ) 1,3,4-thiadiazolylcarbamoyl)]), a sulfamoyl group (carbon 0)
To 12, for example, methylsulfamoyl, dimethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl), and aryl group (including those having a substituent; for example, phenyl, p-tolyl, p-methoxyf) Enil, p
-Chlorophenyl), an alkylthio group (including those having a substituent, for example, methylthio and butylthio), an arylthio group (including those having a substituent, for example, phenylthio, p-tolylthio), a sulfonyl group (for example,
Methanesulfonyl, butanesulfonyl, phenylsulfonyl), acyl groups (eg, acetyl, butyroyl),
And amino groups (eg, methylamino, dimethylamino, anilino).

Preferred among R ² , R ³ and R ⁴ is a hydrogen atom.

Among R ₁ , more preferred are an electron donating group and a hydrogen bonding group. For example, an alkyl group (C1-14; for example, methyl, ethyl, isopropyl, methoxyethyl, p-methoxyphenoxymethyl), an alkoxy group (C1-14; for example, methoxy, ethoxy, isopropoxy), Acylamino group (C2-14; for example, acetylamino group, pivaloylamino group), alkoxycarbonylamino group (C2-14)
14. For example, methoxycarbonylamino, ethoxycarbonylamino, isopropoxycarbonylamino, Aminocarbonylamino group (1-14 carbon atoms, methylaminocarbonylamino, ethylaminocarbonylamino,
Dimethylaminocarbonylamino), a sulfonylamino group (1-14 carbon atoms, methanesulfonylamino, p-toluenesulfonylamino) and the like.

Among these, an acylamino group, an alkoxycarbonylamino group, and an aminocarbonylamino group are most preferred.

R ⁵ and R ^{6 each} represent a hydrogen atom, an alkyl group (including those having a substituent. C 1 to C 12, for example, methyl, ethyl, isopropyl, butyl, cyclopentyl, cyclohexyl,
2-methoxyethyl, 2-chloroethyl, 2-hydroxyethyl, 2-cyanoethyl, cyanomethyl, 2-methylsulfamoylethyl, 2-methylsulfonylaminoethyl, 2-methoxycarbonylethyl, 2-acetoxyethyl, methoxycarbonylmethyl, Benzyl, allyl) or aryl group (including those having a substituent; 6 to 12 carbon atoms such as phenyl, p-tolyl, m-chlorophenyl) or heterocyclic group (including those having a substituent; 12, for example Represents

Preferred among R ₄ and R ₅ are alkyl groups having 1 to 6 carbon atoms.

Examples of the ring which may be formed by combining R ⁵ and R ⁶ include, for example, And a ring that may be formed by combining R ² and R ⁵ or R ³ and R ⁶ is, for example, And a preferable example.

In the general formula (I), X is a hydrogen atom, a halogen atom, preferably an aliphatic group having 1 to 12 carbon atoms, preferably an aromatic group having 6 to 12 carbon atoms (for example, phenyl and naphthyl);
Heterocyclic group (eg, 3-pyridyl, 2-furyl), alkoxy group (eg, methoxy, 2-methoxyethoxy), aryloxy group (eg, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy) ), Alkenyloxy groups (eg, 2-propenyloxy), acyl groups (eg, acetyl, benzoyl), ester groups (eg, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), aliphatic or An aromatic sulfonyl group (eg, methanesulfonyl, phenylsulfonyl), an aliphatic or aromatic thio group (eg, ethylthio, phenylthio), a cyano group, a carboxy group,
Represents a nitro group, a sulfo group and the like.

As used herein, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon, and is meant to include saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. Representative examples include methyl, ethyl, butyl, iso-propyl, tert-butyl, ter
There are t-octyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, propargyl group and the like.

In the general formula (I), V is In the formula, at least one of Y and Z represents an electron-withdrawing substituent, preferably a substituent having a Hammett's substituent constant σp of 0.10 or more, more preferably a substituent of 0.35 or more. Represents, more preferably,
The value of σp represents a substituent of 0.60 or more. This σp value is preferably 2 or less. Hammett's substituent constant σ
As the value of p, a report by Hansch, C. Leo et al. (for example, J. Med.
Chem. 16 , 1207 (1973); ibid. 20 , 304 (1977)).

Examples of the substituent or atom having a value of σp of 0.10 or more include a chlorine atom, a bromine atom, an iodine atom, and a substituted alkyl group (for example, trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluoro Butyl), a nitrile group, an acyl group (eg, formyl, acetyl, benzoyl), a carboxyl group, a substituted or unsubstituted carbamoyl group (eg, carbamoyl, methylcarbamoyl), an alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), Substituted aromatic groups (eg, pentachlorophenyl, pentafluorophenyl), heterocyclic residues (eg, 2-benzoxazolyl,
2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), nitro group, azo group (eg, phenylazo), substituted amino group (eg, ditrifluoromethylamino), substituted alkoxy group (eg, trifluoromethoxy), alkyl Sulfonyloxy group (eg, methanesulfonyloxy), acyloxy group (eg, acetyloxy, benzoyloxy), arylsulfonyloxy group (eg, benzenesulfonyloxy), phosphoryl group (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group, sulfonyl group (For example, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like.

As the substituent having a value of σp of 0.35 or more, a substituted alkyl group (eg, trifluoromethyl, perfluorobutyl),
Nitrile group, acyl group (for example, acetyl, benzoyl,
Formyl), carboxyl group, carbamoyl group (eg, carbamoyl, methylcarbamoyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted aromatic group (eg, pentafluorophenyl), heterocyclic residue ( For example, 1-tetrazolyl), nitro group, azo group (eg, phenylazo), substituted amino group (eg, ditrifluoromethylamino), substituted alkoxy group (eg, trifluoromethoxy), alkylsulfonyloxy group (eg, methanesulfonyloxy), phosphoryl group (Eg, dimethoxyphosphoryl, diphenylphosphoryl), a sulfamoyl group, a sulfonyl group (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like.

As the substituent having a value of σp of 0.60 or more, a nitrile group,
Examples include a nitro group and a sulfonyl group (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like.

When Y or Z is not an electron-withdrawing group, examples of the substituent include an aliphatic group (eg, methyl, ethyl or isopropyl), an alkoxy group (eg, methoxy, ethoxy, isopropoxy), or an amide group (eg, acetylamino, pivalylamino). Or isopropionylamino), an aromatic group (eg, phenyl, 4-alkoxyphenyl), and a heterocyclic group (eg, 2-furyl, 2-thienyl, 2-thiazolyl).

 Next, general formula (II) will be described.

Among the formula (II), those represented by R ^1, R ^2, R ³ and R ⁴ of the general formula (I) in the R ^1, R ^2, R ³ and same as those represented by the R ⁴ is there. Specific examples and preferable examples thereof include those described in the formula (I).

In the general formula (II), S, T and U each represent a nitrogen atom, a methine group or a methine group having an electron-withdrawing group, at least one of which represents a methine group having an electron-withdrawing group; When representing a methine group as described above, And when T represents a methine group as described above, And when U represents a methine group as described above, Represents When S and T each represent a methine group as described above, R ⁹ and R ¹⁰ may be the same or different and may combine with each other to form a ring. Similarly, when T and U each represent a methine group as described above, R ¹⁰ and R ¹¹ may be the same or different and may combine with each other to form a ring.

In that case, it is preferably a condensed ring, for example, a benzene condensed ring or a pyridine condensed ring.

As the substituents R ⁹ , R ¹⁰ and R ¹¹ , for example, the substituents listed in the aforementioned X can be mentioned. At least one of the substituents R ⁹ , R ¹⁰ and R ¹¹ is an electron-withdrawing group, preferably represents a substituent having a Hammett's substituent constant σp of 0.10 or more, more preferably 0.35 or more. And more preferably a substituent having a value of σp of 0.60 or more. Examples of the substituent include the substituents listed for Y or Z above.

In the general formula (II), Q represents an atom or an atomic group necessary for forming a 5- or more-membered ring, preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring, together with a bonding carbon atom or nitrogen atom. And the divalent group forming a ring represents a divalent amino group, an ether bond, a thioether bond, an alkylene group, an alkenylene group, an imino group, a sulfonyl group, a carbonyl group, etc., which have a substituent. You may. Here, as the substituent include the substituents listed in the R _1.

Particularly preferably, Q is a thioether bond, an imino group,
It is a sulfonyl group.

 Next, the general formula (III) will be described.

Among the formula (III), those represented by R ^1, R ^2, R ³ and R ⁴ of the general formula (I) in the R ^1, R ^2, R ³ and same as those represented by the R ⁴ is there. Specific examples and preferable examples thereof include those described in the formula (I).

In the general formula (III), at least one of R ⁷ and R ⁸ represents an electron-withdrawing substituent, preferably a substituent having a Hammett's substituent constant σp value of 0.10 or more, more preferably It represents a substituent having a value of 0.35 or more, more preferably a substituent having a value of σp of 0.60 or more. Examples of the substituent include the substituents enumerated above in Y or Z.

When R ⁷ or R ⁸ represents a substituent, for example, preferably an aliphatic group having 1 to 16 carbon atoms (eg, methyl, ^n- propyl, t-butyl, isopropyl, 3-phenoxypropyl, cyclopentyl, benzyl, Allyl, propargyl), preferably an aromatic group having 6 to 16 carbon atoms (eg, phenyl, naphthyl), a heterocyclic group (eg, 2-furyl, 2
-Thienyl, 2-pyrimidyl, 2-thiazolyl) and the like.

The dye of the present invention may have an atomic group having an effect of suppressing fading in the dye molecule. It is particularly preferable when high image fastness is required.

The atom group having the effect of suppressing fading is bonded to any of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R _{6 in} the formula (I) of the dye; Is also good.

For an atomic group that has the effect of suppressing fading,
All those described in -27078 can be used.

Specific examples of the atomic group having the effect of suppressing fading are given below, but the present invention is not limited thereto.

The azomethine dye used in the transfer material of the present invention can give various color tones such as magenta, blue, cyan, and biolett, but the dye represented by the formula (II) generally has a magenta color tone. The dye represented by the formula (IV) generally has blue and cyan tones.

Hereinafter, specific compound examples of the dye of the present invention are shown, but the present invention is not limited thereto.

The dye used in the present invention is synthesized by oxidative coupling of the coupler compound (A) and the color developing agent (B).

In the formula (A), L represents a hydrogen atom or a group which leaves during the oxidative coupling reaction.

Alternatively, the dye used in the present invention is synthesized by dehydrating and condensing a coupler compound (A) and a nitroso compound (C). However, in this case, L in the coupler compound is a hydrogen atom.

Step 1 40 g of sodium hydride (60%), tetrahydrofuran 1
To the place where 80 ml is stirred at room temperature, A solution of 51.5 g and 41 g of acetonitrile dissolved in 30 ml of tetrahydrofuran was added dropwise. After stirring at 30 ° C for 10 hours, 50
The reaction was carried out at 6 ° C. for 6 hours. After cooling, the reaction solution was poured into 500 ml of water, and extracted with ethyl acetate. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The crude product was treated with ethyl acetate, n-
Recrystallize using hexane, 17.5 g was obtained. (Yield 24.3%).

Step 2 After refluxing 2.4 g, malonitrile 1.2 g, and ethanol 10 ml for 3 hours, the reaction solution was poured into ice water. Then, when concentrated hydrochloric acid was added to adjust the pH of the solution to 1, a brown colored oil was separated. When the stirring was further continued, the oily substance crystallized, so that filtration was performed. The crystals are washed with water, dried, 2.5 g was obtained. (Yield 77.5%).

Step 3 While stirring 200 ml of ethanol at an internal temperature of 200 ° C., 6.2 g of acetic anhydride was added dropwise. After stirring for 10 minutes, crystals were precipitated and were collected by filtration. The crystals were washed with ethanol and dried to obtain 12.0 g of Compound-1. (Yield 75.3%
mp 170-171 ° C).

Usually, in order to form a full-color image, dyes of three colors, yellow, magenta and cyan, are required.

Therefore, magenta and cyan dyes are selected from the heat transferable dyes of the present invention, and yellow dyes are selected from conventionally known dyes, whereby a full-color image can be formed.

Alternatively, the heat transfer dye of the present invention may be used as one of magenta and cyan, and a conventionally known dye may be used as the other two colors.

For the same color, the dye of the present invention and a conventionally known dye may be mixed and used.

Further, two or more kinds of the heat transferable dyes of the present invention may be mixed and used as the same color.

The thermal transfer dye-providing material can be used in the form of a sheet, a continuous roll, or a ribbon. Yellow of the present invention,
The magenta and cyan dyes are usually arranged on a support so as to form independent regions. 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, three types of thermal transfer dye-providing materials in which the above-described yellow dye, magenta dye, and cyan dye are respectively provided on separate supports are prepared, and thermal transfer of the dye to one thermal transfer image-receiving material can be sequentially performed from these materials. .

The yellow dye, magenta dye and cyan dye of the present invention can each be dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or can be printed on a support by a printing method such as a gravure method. .
It is preferable that the thickness of the dye-donating layer containing these dyes is set in the range of usually about 0.2 to 5 μm, particularly 0.4 to 2 μm in terms of dry film thickness.

As the binder resin used together with the heat transferable dye of the present invention, any of conventionally known binder resins for such a purpose can be used, and usually has high heat resistance,
In addition, one that does not hinder the transfer of the dye when heated is selected. For example, polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (for example, polymethyl methacrylate, polyacrylamide, polystyrene-acrylonitrile), vinyl resins such as polyvinylpyrrolidone, polyvinyl chloride resins Resins (eg, vinyl chloride-vinyl acetate copolymer), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (eg, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol polyvinyl acetal resin (for example, polyvinyl alcohol) Le, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g. polyethylene,
Polypropylene) is used.

In the present invention, such a binder resin is a dye 10
It is used at a rate of about 30 to 600 parts by weight per 0 parts by weight.

As the ink solvent for dissolving or dispersing the above dye and binder resin, conventionally known ink solvents can be used freely. Specifically, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutanol, ketones, etc. As a system, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
Toluene, xylene, etc. as aromatics, dichloromethane, trichloroethane, etc. as halogens, dioxane,
Examples include tetrahydrofuran and the like and mixtures thereof. It is important that these solvents are used by selecting the dye to be used at a predetermined concentration or more and dissolving or dispersing the binder sufficiently. For example, it is preferable to use the solvent in an amount of about 5 to 20 times the total weight of the dye and the binder.

As the support of the thermal transfer dye-providing material, any of conventionally known supports can be used. For example, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; condenser paper; cellulose ester; fluoropolymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene;
Polysulfone; cellophane and the like.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30.
μ. An undercoat layer may be provided as needed. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer. This further improves the transfer density. As the hydrophilic polymer, the above-mentioned water-soluble polymer can be used.

Also, a slipping layer may be provided to prevent the thermal head from sticking to the dye-providing material. The slipping layer is composed of a lubricating material with or without a polymer binder, such as a surfactant, a solid or liquid lubricant or a mixture thereof.

The dye-donor material is preferably subjected to anti-stinging treatment on the side of the support on which the dye-donor layer is not provided, in order to prevent the sticking due to the heat of the thermal head when printing from the back surface and to improve the slip.

For example, it is preferable to provide a heat-resistant slip layer mainly composed of a reaction product of a polyvinyl butyral resin and an isocyanate, an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and a filler. A polyvinyl butyral resin having a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 110 ° C, and a vinyl butyral portion having a weight percentage of 15 to 40% from the viewpoint of a large number of reaction sites with isocyanate Is good. As an alkali metal salt or an alkaline earth metal salt of a phosphate ester, Gafack RD720 manufactured by Toho Chemical Co., Ltd. is used, and 1 to 50% by weight, preferably 10 to 40% by weight based on polyvinyl butyral resin.
It is good to use about.

The heat-resistant slip layer desirably has heat resistance in the lower layer, and a combination of a synthetic resin curable by heating and a curing agent thereof, for example, polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The dye-providing material may be provided with a hydrophilic barrier layer for preventing the diffusion of the dye toward the support. The hydrophilic dye barrier layer contains a hydrophilic substance useful for the intended purpose. In general, excellent results were obtained from seratin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly (vinyl alcohol), poly (ethyleneimine), poly (ethyleneimine) Acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid), or a mixture of cellulose monoacetate and poly (acrylic acid) Can be obtained. Particularly preferred are:
Poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

An undercoat layer may be provided on the dye-providing material. In the present invention, any undercoat layer may be used as long as the desired action is obtained.
Preferred specific examples are (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14: 80: 6),
(Butyl acrylate-methacrylic acid-2-aminoethyl-methacrylic acid-2-hydroxyethyl) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example, Bostek 7650 (Emhart Co., Bostics Chemical Co.)
Group) or chlorinated high density poly (ethylene-trichloroethylene) resins. The coating amount of the undercoat layer is not particularly limited, but is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superimposed on the thermal transfer image-receiving material, and heat energy is applied from any surface, preferably from the back surface of the thermal transfer dye-providing material, according to image information by a heating means such as a thermal head. Thereby, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material in accordance with the magnitude of the heating energy, and a color image having excellent clarity and resolution can be obtained. Further, the anti-fading agent can be transferred in the same manner.

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

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

For details of the thermal transfer recording method, see JP-A-60-34895.
See the description of the issue.

The thermal transfer image-receiving material used together with the thermal transfer dye-providing material of the present invention in carrying out the thermal transfer recording method will be described. This thermal transfer image-receiving material has a support provided with at least one image-receiving layer capable of receiving a heat transferable dye.

Whatever the support used for the thermal transfer image-receiving material can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, dent after transfer, etc. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based synthetic paper, etc.),
Fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially polyethylene on both sides) Paper support such as polyolefin, polyvinyl chloride, polyethylene terephthalate,
Various plastic films or sheets such as polystyrene, methacrylate, and polycarbonate, and films or sheets treated to give white reflectivity to the plastic, or a laminate of any combination of the above can also be used.

Among these, polyolefin-coated paper is preferable because it has features such as not causing concave deformation due to heating during thermal transfer, being excellent in whiteness, and having little curl.

The thermal transfer image receiving material is provided with a dye image receiving layer. This image receiving layer accepts a heat transfer dye which is transferred from the heat transfer dye providing material at the time of printing, and a dye receiving substance having a function of dyeing the heat transfer dye alone, or other dye-receiving substance. 0.5 ~ 50μ thickness included with binder material
It is preferable that the film has a thickness of about m.

Examples of the dye-receiving polymer which is a typical example of the dye-receiving substance include the following resins.

(A) Those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with a sulfone group, a carboxyl group, etc.), ethylene glycol, diethylene glycol, Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc .: Polyacrylate resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate or polymethacrylate resin: Polycarbonate resin : Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395, 63
-7971, 63-7972, 63-7973, 60-294862
And those described in (1). In addition, as commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140,
Byron GK-130, Kao ATR-2009, ATR-2010 and the like can be used.

(B) Those having a urethane bond Polyurethane resin and the like.

(C) Those having an amide bond, such as polyamide resin.

(D) Those having a urea bond, such as a urea resin.

(E) Those having a sulfone bond.

 Polysulfone resin and the like.

(F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin and the like.

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

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a dye-receiving substance or as a dye diffusion aid.

Specific examples of high boiling organic solvents and thermal solvents are disclosed in
62-174754, 62-245253, 61-209444, 61
-200538, 62-8145, 62-9348, 62-3024
No. 7, 62-136646.

The image receiving layer of the thermal transfer image receiving material may have a configuration in which a dye-receiving substance is dispersed and supported in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener is preferable, and gelatin is particularly preferable.

As a method for dispersing the dye-receiving substance in the water-soluble binder, any of the known dispersion methods for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typically,
A method in which a solution in which a dye-receiving substance is dissolved in an organic solvent immiscible with water is mixed with an aqueous solution of a water-soluble binder to emulsify and disperse. The latex of the dye-receiving substance (polymer) is mixed with an aqueous solution of a water-soluble binder. There are methods.

The image receiving layer may be a single layer or may be composed of two or more layers. When two or more layers are provided, the layer closer to the support may be made of a synthetic resin having a low glass transition point, or may have a structure in which a high boiling point organic solvent or a heat solvent is used to enhance the dyeing property of the dye. Use a synthetic resin with a higher glass transition point, minimize the amount of high-boiling organic solvent or hot solvent used or minimize the amount of stickiness on the surface, adhesion with other substances, and transfer of the dye after transfer. It is desirable to adopt a configuration that prevents troubles such as retransfer to another substance and blocking with a thermal transfer dye donating material.

The total thickness of the image receiving layer is 0.5 to 50 μm, particularly 3 to 30 μm.
m, in the case of a two-layer structure, the outermost layer is 0.1 to 2 μm, especially 0.2 to 2 μm.
It is preferable that the thickness be in the range of 1 μm.

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

The intermediate layer is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, depending on the constituent material. In some cases, the intermediate layer also functions as an adhesive. .

The dye diffusion preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but is preferably a water-soluble binder, and examples thereof include the water-soluble binder described above as the binder for the image receiving layer, particularly gelatin.

The porous layer is a layer that prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support, and plays a role of effectively using the applied heat.

The image receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer, etc. constituting the thermal transfer image receiving material include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate,
Barium sulfate, aluminum silicate, synthetic zeolite,
Fine powders such as zinc oxide, lithon, titanium oxide, and alumina may be contained.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. For example, K. Veenkataraman ed., “The Chemistry of Sy
nthetic Dyes ", Vol. 5, Chapter 8, JP-A-61-143752, and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, 2,5-dibenzooxazole thiophene compounds, etc. Is mentioned.

The optical brightener can be used in combination with a fading inhibitor.

In the present invention, in order to improve the releasability between the thermal transfer dye-providing material and the thermal transfer image-receiving material, the outermost layer which contacts the surface of the dye-providing material and / or the image-receiving material, particularly preferably the surface where both materials are in contact with each other It is preferred that a release agent be contained in the resin.

Examples of the release agent include solid or wax-like substances such as polyethylene wax, amide wax, and Teflon powder: surfactants such as fluorine-based and phosphate-based agents: paraffin-based, silicone-based, and fluorine-based oils. Any release agent can be used, but silicone oil is particularly preferred.

As the silicone oil, a modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used in addition to the unmodified silicone oil. Examples thereof include various modified silicone oils described on pages 6 to 18B of Technical Data of "Modified Silicone Oil" issued by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd .: trade name X-22)
−3710) is effective.

In order to further enhance the fastness of the dye, an anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. When an anti-fading agent is used in the thermal transfer dye-providing material, it may be included in the dye-providing layer, or may be provided on a support in a region other than the region where the dye-providing layer is provided.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of ultraviolet absorbers include benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681, etc.), benzophenone-based compounds (JP-A-56-2784, etc.), and others. Showa 54
And compounds described in JP-A-48535, JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741 and JP-A-61-88256, pages (27) to (29),
JP-A-62-234103, JP-A-62-31096, Japanese Patent Application No. 62-23059
There are compounds described in No. 6, etc.

Examples of useful anti-fading agents are described in JP-A-62-215272 (125).
~ (137).

An anti-fading agent for preventing fading of the dye transferred to the image receiving material may be previously contained in the image receiving material,
The image may be supplied to the image receiving material from the outside by a method such as transferring from a dye donating material.

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

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be cured by a hardener.

When curing organic solvent-based polymers, see
Hardening agents described in JP-A-199997 and JP-A-58-215398 can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin.

For curing of the water-soluble polymer, U.S. Pat.No. 4,678,739, column 41, JP-A-59-116655, JP-A-62-245261, and JP-A-61-265261 can be used.
Hardening agents described in 18942 are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners ), Vinyl sulfone hardener (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

The thermal transfer image-receiving material may contain an anti-fading agent as described above in advance.

In the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development.

Nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants can be used.
Specific examples thereof are described in JP-A Nos. 62-173463 and 62-183457.

Further, when dispersing a substance capable of accepting a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightener and other hydrophobic compounds in a water-soluble binder, as a dispersing aid. Preferably, a surfactant is used. For this purpose, besides the above-mentioned surfactants, JP-A-59-157636 discloses
The surfactants described on pages 37 to 38 are particularly preferably used.

In the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material,
An organic fluoro compound may be included for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds are described in JP-B-57-9053, columns 8 to 17;
Nos. 61-20944, 62-135826 and the like, fluorine-based surfactants, or oily fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the thermal transfer dye donating material and the thermal transfer image receiving material. As a matting agent, silicon dioxide,
Japanese Patent Application Laid-Open (JP-A) such as polyolefin or polymethacrylate
In addition to the compounds described on pages 61-88256 (29), there are compounds described in Japanese Patent Application Nos. 62-110064 and 62-110065, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.

Example 1 FIG. 1 shows the absorption characteristics of the dye represented by the formula (I) of the present invention in ethyl acetate.

In FIG. 1, the solid line represents Compound 1 of the present invention, and the dashed line represents (As described in JP-A-2-98492) As described above, the dye of compound 1 of the present invention In comparison with the above, it is apparent that there is no side absorption at 400 nm to 450 nm, and that the absorption form is a sharp one, which is similar to a so-called blocking dye which is advantageous in color reproduction. Also,
It can be seen that the compound of the present invention also has a larger ε, and it is easy to obtain a high maximum density of an image.

Example 2 (Preparation of Thermal Transfer Dye Donor Material (A)) Thickness 6 μm of which heat-resistant lubrication treatment was applied to the back surface as a support
m of a polyethylene terephthalate film (manufactured by Teijin), and the coating composition (A-1) for a thermal transfer dye-donor layer having the following composition was dried on a film surface with a wire bar coating to a thickness of 1.5 μm. To form a thermal transfer dye-providing material (A).

Coating composition for thermal transfer dye donating layer (A-1) Dye (No.-1) 10 mmol Polyvinyl butyral resin (Denka butyral 5000-A manufactured by Denki Kagaku 3 g Toluene 40 ml Methyl ethyl ketone 40 ml Polyisocyanate (Takenate D110N manufactured by Takeda Pharmaceutical)
0.2 ml dye And a comparative material (B) was prepared.

(Preparation of Thermal Transfer Image Receiving Material (1)) Synthetic paper with a thickness of 150 μm (Oji Yuka, YUPO
-FPG-150), and applying the coating composition (1-1) for an image receiving layer having the following composition to the surface thereof by wire bar coating so that the thickness when dried becomes 8 μm to obtain a thermal transfer image receiving material (1). Formed. After drying with a dryer,
Performed in oven at 100 ° C. for 30 minutes.

Coating composition for image receiving layer (1-1) Polyester resin (Vylon-280 manufactured by Toyobo) 22 g Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF- manufactured by Shin-Etsu Silicone)
857) 0.5 g methyl ethyl ketone 85 ml toluene 85 ml cyclohexanone 15 ml Thermal transfer dye-providing material (A) obtained as above
And (B) and the thermal transfer image-receiving material (1) are superposed such that the thermal transfer dye-donor layer and the image-receiving layer are in contact with each other, and a thermal head output of 0.25 W / Dot, pulse width 0.15 ~ 15mS
Printing was performed under the conditions of ec and a dot density of 6 dots / mm, and a cyan dye was image-dyed on the image receiving layer of the heat transfer material. As a result, a clear image recording material without transfer unevenness was obtained.

The obtained recorded image-receiving material was dried at 60 ° C for 10
A one-day forced thermal fade test was performed.

 The residual ratio was measured at a concentration of 1.0.

As described above, it is clear that the color image using the compound 1 of the present invention has excellent thermal stability.

Example-3 The heat-migrating dye-donor layer coating composition (A-
Using dyes shown in Table 2 instead of dye 1 of 1),
Heat transfer dye-donating materials (C) to (K) were prepared.

When printing was performed using the image receiving material (1) produced in Example 2, clear image recording without transfer unevenness was obtained with any of the dyes, and the density was high. Also, the heat fastness was excellent.

Example-4 Thermal transfer dye-donor layer coating composition (A-1) of Example-2
Thermal transfer dye-providing materials (L) (M) using the resins and dyes shown in Table 3 in place of the polyvinyl butyral resin
(N) was prepared.

When printing was performed using the same image receiving material (1) as in Example 2, clear image recording without transfer unevenness was obtained. The heat fastness was also excellent.

Example-5 (Production of Thermal Transfer Image-Receiving Material) Synthetic paper having a thickness of 150 μm as a support (manufactured by Oji Yuka: YUPO
-FPG-150) and the thickness of the coating composition for an image receiving layer having the following composition on the surface when dried by wire bar coating.
It was applied so as to have a thickness of 10 μm to prepare a thermal transfer image-receiving material (2). Drying was carried out in a oven at a temperature of 100 ° C. for 30 minutes after preliminary drying with a drier.

Coating composition for image receiving layer (2-1) Polyester resin No. 1 20 g Amino-modified silicone oil (KF-857: Shin-Etsu Silicone) 0.5 g Epoxy-modified silicone oil (KF-100T: Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 85 ml Toluene 85ml cyclohexanone 30ml When printing was performed in combination with the dye-providing materials of Examples 2 and 3, clear image recording was obtained. Also,
The heat fastness was also excellent.

Example-6 (Preparation of thermal transfer image-receiving material (3)) Resin-coated paper in which polyethylene was laminated to a thickness of 15μ and 25μ respectively on both sides of 200μ paper was prepared.
A coating composition for an image receiving layer having the following composition was applied to the laminated surface having a thickness of μ by a wire bar coating so as to have a dry thickness of 10 μm, and dried to prepare a thermal transfer image receiving material (3).

Coating composition for image receiving layer (3-1) Polyester resin No. 1 25 g Amino-modified silicone oil (KF857: manufactured by Shin-Etsu Silicone) 0.8 g Polyisocyanate (KP-90: manufactured by Dainippon Ink) 4 g methyl ethyl ketone 100 ml toluene 100 ml When printing was performed in the same manner as in Example 5, clear and high-density image recording was obtained.

Example -7 (Preparation of Thermal Transfer Image-Receiving Material (4)) An organic solvent solution of a dye-receiving polymer having the composition (B ') was emulsified and dispersed in a gelatin aqueous solution having the composition (A') below with a homogenizer. A gelatin dispersion of the material was prepared.

(A ') Gelatin aqueous solution Gelatin 2.3 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 ml Water 80 ml (B') Dye receptive polymer solution Polyester resin 7.0 g (Toyobo: Byron 300) Carboxy-modified silicone oil 0.7 g (Shin-Etsu Made of silicone: X-22-3710) Methyl ethyl ketone 20 ml Toluene 10 ml Triphenylphenyl phosphate 1.5 g Fluorosurfactant (a) Was dissolved in 10 ml of a mixed solvent of water / methanol (1: 1) to obtain a coating composition for a receiving layer. This coating composition was applied to a 150 μm-thick synthetic paper (YUPO-SGG-150 manufactured by Oji Oil Chemical Co., Ltd.) whose surface was corona-discharged to a wet film thickness of 75 μm by a wire bar coating method, and dried.

Thermal transfer dye-providing material (A) obtained in Examples 2 and 3
To (N) and the thermal transfer image-receiving material (4), an image was recorded in the same manner as in Example 2. The obtained image was high in density and sharp, and high in light fastness.

Example-8 (Production of heat transferable dye image-receiving material (5)) A thermal transfer image-receiving material (5) was produced in the same manner as in Example 1 using the coating composition (5-1) for the image-receiving layer.

Coating composition for image receiving layer (5-1) The same composition as the coating composition for image receiving layer (1-1) of Example 1 except that 7 g of the following ultraviolet absorber is added.

Example Using Thermal Transfer Dye Donor Materials (A) to (K)
When printing was performed in the same manner as in Example 1, a clear and high-density image was obtained. The light fastness was also higher than when the thermal transfer image-receiving material (1) was used.

[Brief description of the drawings]

 FIG. 1 is a graph showing the absorption characteristics of a dye.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-226393 (JP, A) JP-A-4-265798 (JP, A) JP-A-4-267197 (JP, A) 89869 (JP, A) JP-A-3-218342 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/38-5/40 CA (STN) REG (STN)

Claims (3)

(57) [Claims] 1. A thermal transfer dye-providing material comprising a support having thereon a dye-donating layer containing a heat-migrating dye, wherein the heat-migrating dye is a dye represented by the general formula (I). Thermal transfer dye-providing material. In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent. R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. V is a nitrogen atom or Represents X, Y and Z each represent a nonmetallic substituent. Y
And at least one of Z represents an electron withdrawing substituent. X and Y and / or T and Z and / or R ¹ and R ² and / or
Alternatively, R ² and R ⁵ and / or R ⁵ and R ⁶ and / or R ³ and R ⁶ and / or R ³ and R ⁴ may be bonded to each other to form a ring structure. ^{X, Y, Z, R 1} , R 2, R 3, R 4, R 5, R 6 may be further substituted. (Where Is a notation indicating that Y and X may be either cis or trans to the double bond. However, it does not combine with Y to form a heterocyclic ring. X except that the atom of X bonded to the carbon atom of is a nitrogen atom is excluded. 2. The thermal transfer dye-providing material according to claim 1, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (II). In the formula, S, T and U are each a nitrogen atom, a methine group or a methine group having an electron-withdrawing group, at least one of which represents a methine group having an electron-withdrawing group;
Represents an integer of ２2, and Q is Together with a group of nonmetallic atoms necessary to form a heterocyclic or aromatic ring. R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent. R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² and / or R ² and R ⁵ and / or R ⁵ and R ⁶ and / or R ³ R ⁶ and / or R ³ and R ⁴ may combine with each other to form a ring structure . S, T, U, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be further substituted. 3. The thermal transfer dye-providing material according to claim 1, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (III). In the formula, at least one of R ⁷ and R ⁸ represents an electron-withdrawing substituent, and the other represents a substituent. R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a nonmetallic substituent. R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² and / or R ² and R ⁵ and / or R ⁵ and R ⁶ and / or
Alternatively, R ³ and R ⁶ and / or R ³ and R ⁴ may be bonded to each other to form a ring structure. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be further substituted. However, it does not combine with R ⁸ to form a heterocyclic ring. R ⁷ atoms R ⁷ is a nitrogen atom attached to the carbon atom of excluding.