JPH06227162A - Heat transfer coloring matter donating material - Google Patents

Abstract

PURPOSE:To obtain heat transfer coloring matter donating material, which realizes transferred image having high density, excellent hue and maintainability, by a method wherein thermally migrating coloring matter represented by the specified general formula is included in coloring matter accepting layer, which is provided on the support made of heat transfer coloring matter donating material. CONSTITUTION:The heat transfer coloring matter donating material concerned is produced by providing thermally migrating coloring matter-containing coloring matter donating layer on support. In this case, the coloring matter donating layer contains at least one coloring matter among the thermally migrating coloring matters represented by the general formula noted elsewhere, in which V represents nitrogen atom or-CZ= and X, Y and Z respectively represent univalent substituent groups independently. Further, A is phenolic residue or azo dyestuff having the substituent group of aryl group. Thus, heat transfer coloring matter donating material, which realizes transferred image having high density, excellent hue and maintainability, can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer dye-donor element using a heat transferable dye. More specifically, it relates to a thermal transfer dye-donating material containing a novel dye having a clear hue and excellent in transferability, and an image forming method using the same.

[0002]

2. Description of the Related Art At present, a thermal transfer method, an electrophotographic method, an ink jet method and the like are vigorously studied as a technology relating to a color hard copy. The thermal transfer method has many advantages over other methods because the apparatus is easy to maintain and operate and the apparatus and consumables are inexpensive. In the thermal transfer system, a thermal transfer material having a heat-fusible ink layer formed on a base film is heated by a thermal head to melt the ink, and the thermal transfer image-receiving material is recorded, and a heat transfer dye is applied on the base film. There is a method in which the thermal transfer dye-donor material containing the contained color material layer is heated by a thermal head to transfer the dye to the thermal transfer image-receiving material by thermal transfer, but the latter thermal transfer transfer method uses the energy applied to the thermal head. By changing the amount, the transfer amount of the dye can be changed, which facilitates gradation recording and is particularly advantageous for high-quality full-color recording. However, the heat transferable dye used in this system has various restrictions, and very few satisfy all the required performances. Required performances include, for example, having favorable spectral characteristics for color reproduction, easy heat transfer, strong resistance to light and heat, strong resistance to various chemical agents, sharpness not easily deteriorated, and image It is difficult to retransfer, and it is easy to prepare a thermal transfer dye-donor material. Therefore, it has been desired to develop a dye satisfying these requirements.

By the way, in Japanese Patent Laid-Open No. 4-89291,
Thermal transfer materials using azomethine dyes derived from β, γ unsaturated nitrile couplers are shown.

However, a phenomenon in which an image formed by transfer is blurred or blurred over time is recognized. JP-A-3-
No. 83,685 and JP-A-61-64492 disclose a method of thermally transferring a dye having a mordant group such as a phenolic hydroxyl group by incorporating a mordant in the image receiving layer.

[0005]

The conventionally known β, γ-unsaturated nitrile coupler-derived azomethine dye has a high pKa of the dye and is used as a dissociative dye which is used together with a basic compound to dissociate the dye. It was not possible to use it. Therefore, it has not been possible to solve the drawback that the sharpness of the transferred image decreases with time.

The object of the present invention is to have excellent spectral characteristics,
It is an object of the present invention to provide a thermal transfer dye-donor element that has a high molecular extinction coefficient, a high thermal transfer property, and various dyes having high fastness, and that gives a high density image. Another object of the present invention is to obtain an image excellent in transferability, density and hue in a method of transferring a dye having a dissociative group (mordanting group) by incorporating a mordant or a basic substance in the image receiving layer. is there. Another object of the present invention is to solve various problems desired for thermal transfer dye-donor elements.

[0007]

SUMMARY OF THE INVENTION The present invention comprises:
A thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye, wherein the dye-donating layer contains at least one heat-transferable dye represented by formula (I). Achieved by donor material.
General formula (I)

[0008]

[Chemical 4]

In the formula (I), V is a nitrogen atom or -C
Represents Z =. X, Y and Z each independently represent a monovalent substituent. A is a group represented by the following general formulas (II) and (III).

[0010]

[Chemical 5]

In the formula (II), R ¹ , R ² , R ³ and R
⁴ are each independently a hydrogen atom or a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an aminocarbonylamino group, a sulfur group. Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group , Aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, carboxylic acid group (salt thereof), sulfonic acid group (salt thereof)
Represents

[0012]

[Chemical 6]

In the formula (III), Ar is an aryl group derived from a diazo component or a heteroaromatic group. Further, the present invention is an image forming method in which the thermal transfer dye-donor material and the thermal transfer dye image-receiving material are superposed, heated according to image information, and the dye is thermally diffused and transferred, wherein the thermal transfer dye-image receiving material is a base. It was achieved by including a volatile substance and / or a mordant.

The general formula (I) will be described in detail below. V represents a nitrogen atom or -CZ =. X,
Y and Z each independently represent a monovalent substituent. As the monovalent substituent,

A hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 30, for example, methyl, cyclopropyl, vinyl, allyl, octyl, methoxyethyl, cyanoethyl, ethyl, propyl, butyl), an alkoxy group (preferably having a carbon number of 1 to 1). 30, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy), a halogen atom (for example, bromine, fluorine, chlorine), an acylamino group [preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (for example, formylamino, acetylamino, propionylamino). , Cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (for example, benzoylamino,
p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cyano group, a sulfonylamino group (preferably having 1 carbon atom). -30, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), a carbamoyl group [preferably an alkylcarbamoyl group having 2 to 30 carbon atoms (for example, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butyl). Rucarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbyl Moil, benzylcarbamoyl,
Ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-
Dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl), preferably an arylcarbamoyl group having 7 to 30 carbon atoms (for example, phenylcarbamoyl, p-toluylcarbamoyl, m-methoxyphenylcarbamoyl, 4, 5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), preferably 4 carbon atoms ˜30 phthalylcarbamoyl groups (eg 2-pyridylcarbamoyl, 3
-Pyridylcarbamoyl, 4-pyridylcarbamoyl,
2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2
-(4-methylphenyl) 1,3,4-thiadiazolylcarbamoyl)], sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl), aminocarbonylamino group (preferably 1 to 30 carbon atoms, such as methylaminocarbonylamino, dimethylaminocarbonylamino), alkoxycarbonylamino groups (preferably 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino), hydroxy groups, amino groups (preferably carbon) Number 0
30, for example amino, methylamino, dimethylamino,
Anilino), an aryl group (preferably having 6 to 30 carbon atoms,
For example, phenyl, m-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 30 carbon atoms,
For example, 2-pyridyl, 2-furyl, 2-tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 30 carbon atoms such as phenoxy, p-methoxyphenoxy, o-chlorophenoxy), sulfamoylamino group ( Preferably, it has 0 to 30 carbon atoms, for example, methylsulfamoylamino, dimethylsulfamoylamino), alkylthio group (preferably 1 to 30 carbon atoms, for example, methylthio, ethylthio), arylthio group (preferably 6 to 30 carbon atoms, For example, phenylthio, p-methoxyphenylthio, o-chlorophenylthio), a sulfonyl group (preferably having 1 to 30 carbon atoms, such as methanesulfonyl, p-
Toluenesulfonyl), acyl group (preferably having 1 carbon atom)
~ 30, for example formyl, acetyl, benzoyl, p-
Toluyl), heterocyclic oxy group (preferably having 3 to 7 carbon atoms)
30), an azo group (preferably having a carbon number of 3 to 30, for example p
-Nitrophenylazo), an acyloxy group (preferably having a carbon number of 1 to 30, such as acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having a carbon number of 1 to 30).
30, for example, methylcarbamoyloxy), a silyloxy group (preferably having 3 to 30 carbon atoms, for example, trimethylsiloxy), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, for example, phenoxycarbonyl), an imide group (preferably having 4 carbon atoms). To 30, for example, phthalimido), a heterocyclic thio group (preferably having 3 to 30 carbon atoms),
Sulfinyl group (preferably having 1 to 30 carbon atoms, such as diethylaminosulfinyl), phosphoryl group (preferably having 0 to 30 carbon atoms, such as diaminophosphoryl), carboxylic acid group (including its sodium salt, potassium salt, etc.), sulfonic acid group (The sodium salt, the potassium salt, etc. are also included.) Etc. are mentioned.

X is an aryl group (having 6 to 13 carbon atoms) or a heterocyclic group (having 3 to 1 carbon atoms) among those listed above.
0), an alkyl group (having 1 to 8 carbon atoms), and a cyano group are preferable. The heterocyclic group is preferably a heterocyclic group in which the bonding position is a carbon atom. Of these, a heteroaromatic group is preferable. X
When is an aryl group or a heteroaromatic group, it is preferably unsubstituted or substituted with an electron-withdrawing group. As the electron-withdrawing group, the Hammett substituent constant σ _p
The value is preferably 0 or more, more preferably 0.1 or more described later.

When V represents = CZ-, less Y and Z
At the same time, one of them is preferably an electron-withdrawing group. Electronic
As the attracting group, the Hammett substituent constant σ_pValue is 0.1
It is preferably 0 or more, and more preferably 0.35 or more. σ
_pMost preferably, the value is 0.60 or more. σ _pThe value is 2.
It is preferably 0 or less. At that time, with Y and Z electron-withdrawing groups
The ones not present are the substituents mentioned above for X.
It At that time, more preferably, X is an alkyl group (carbon number
1-8), alkoxy group (C1-6), acylami
No group (having 2 to 6 carbon atoms), aryl group (having 6 to 1 carbon atoms)
3) and a heterocyclic group (having 3 to 10 carbon atoms).

It is more preferable that both Y and Z are electron withdrawing groups. At that time, the sum of the Hammett substituent constant σ _p values of Y and Z is preferably 0.7 or more, and 1.0
More preferably, it is more preferably 1.2 or more, most preferably 1.2 or more.

Hammett's substituent constant σ _{p as used} herein
The values are reported by Hansch, C. Leo et al. (Eg J. Med.
Chem. 16, 1207 (1973); ibid. 20, 30
4 (1977)).

The substituent or atom having a value of σ _p of 0.10 or more includes a chlorine atom, a bromine atom, an iodine atom, and a substituted alkyl group (eg, trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoro). Rmethanesulfonylmethyl, perfluorobutyl), nitrile group, acyl group (eg formyl, acetyl, benzoyl), carboxyl group, substituted or unsubstituted carbamoyl group (eg carbamoyl, methylcarbamoyl), alkoxycarbonyl (eg methoxycarbonyl, ethoxycarbonyl) , Isopropoxycarbonyl), substituted aromatic groups (eg pentachlorophenyl, pentafluorophenyl), heterocyclic residues (eg 2-benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazole) Group, 1-tetrazolyl), nitro group, azo group (eg phenylazo), substituted amino group (eg ditrifluoromethylamino), substituted alkoxy group (eg trifluoromethoxy), alkylsulfonyloxy group (eg methanesulfonyloxy), acyloxy Group (eg acetyloxy, benzoyloxy), arylsulfonyloxy group (eg benzenesulfonyloxy), phosphoryl group (eg dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group, sulfonyl group (eg trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) And so on.

Substituents having a σ _p value of 0.35 or more include substituted alkyl groups (eg trifluoromethyl, perfluorobutyl), nitrile groups, acyl groups (eg acetyl, benzoyl, formyl), carboxyl groups, carbamoyl groups. (Eg carbamoyl, methylcarbamoyl), alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted aromatic group (eg pentafluorophenyl), heterocyclic residue (eg 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 dimethoxyphospho) Examples thereof include ril, diphenylphosphoryl), sulfamoyl group, sulfonyl group (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like.

Examples of the substituent having a value of σ _p of 0.60 or more include a nitrile group, a nitro group and a sulfonyl group (eg trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like.

A represents a group represented by the formula (II) or the formula (III).

In the formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a non-metal substituent, and the non-metal substituent is an alkyl group (carbon number). 1 to 12, for example, methyl, ethyl, n-propyl, iso-propyl, t-butyl, trifluoromethyl), alkoxy group (having 1 to 12 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy), aryl group ( Carbon number 6
To 20, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), nitro group, acyl group (having 1 to 20 carbon atoms, for example, formyl, acetyl, benzoyl, p-methoxybenzoyl), alkylthio group (having 1 carbon atom). To 20, eg, methylthio, ethylthio),
Arylthio group (6 to 20 carbon atoms, for example, phenylthio, p-chlorophenylthio), sulfonyl group (1 to 20 carbon atoms, for example, methanesulfonyl, ethanesulfonyl, toluenesulfonyl), amino group (0 to 20 carbon atoms, for example, Methylamino, ethylamino, dimethylamino), halogen atom (bromine, fluorine, chlorine), acylamino group [alkylcarbonylamino group having 1 to 12 carbon atoms (eg formylamino, acetylamino, propionylamino, cyanoacetylamino), carbon Number 7 to 1
5 arylcarbonylamino group (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (having 2 to 13 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cyano group, Sulfonylamino group (1 to 10 carbon atoms, such as methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), carbamoyl group [alkylcarbamoyl group having 2 to 12 carbon atoms (eg, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, Isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl,
Cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl,
Prenylcarbamoyl, 2,3-dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl), an arylcarbamoyl group having 7 to 15 carbon atoms (for example, phenylcarbamoyl, p-toluylcarbamoyl, m-methoxy). Phenylcarbamoyl, 4,5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), Heterylcarbamoyl groups having 4 to 12 carbon atoms (for example, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-benz Azo Li carbamoyl, 2-benzimidazolylthio carbamoyl, 2- (4-methyl) 1,
3,4-thiadiazolylcarbamoyl)], sulfamoyl group (having 0 to 12 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl), aminocarbonylamino group (having 1 to 10 carbon atoms, for example, methylaminocarbonylamino, dimethyl) And aminocarbonylamino) and alkoxycarbonylamino groups (having 2 to 10 carbon atoms, such as methoxycarbonylamino and ethoxycarbonylamino).

Preferred among R ¹ , R ² , R ³ and R ⁴ are electron withdrawing substituents. R ¹ , R ² , R ³ ,
R ⁴ is selected to lower the pKa of the phenolic hydroxyl groups of the dyes of this invention. And the pKa of the hydroxyl group is 7
It is preferred to select the substituents so that Preferred substituents from the above viewpoint are a chloro atom, a cyano group, an acyl group, a nitro group, an alkoxycarbonyl group,
An aryloxy carbonyl group and an amino carbonyl group are mentioned. Among them, it is most preferable that R ¹ and R ⁴ are hydrogen atoms and both R ² and R ³ are chloro atoms.

In the formula (III), Ar is an aryl group derived from a diazo component or a heterocyclic group. The aryl group derived from the diazo component represented by Ar is an optionally substituted aryl group having 6 to 30 carbon atoms. As a substituent for substituting the aryl group, an alkyl group (methyl, ethyl), an alkoxy group (methoxy, ethoxy, isopropoxy), an aryloxy group (phenoxy), an acyloxy (acetyloxy, pivaloyloxy), an aryl group (phenyl), Halogen atom (chlorine, fluorine, bromine),
Aryloxycarbonyl group (phenoxycarbonyl), alkyloxycarbonyl group (methoxycarbonyl, ethoxycarbonyl), cyano group, nitro group, carbamoyl group (methylcarbamoyl, ethylcarbamoyl), acyl group (acetyl group, pivaloyl group), acylamino group ( Acetylamino, propionylamino), alkoxycarbonylamino group (methoxycarbonylamino, ethoxycarbonylamino), aryloxycarbonylamino group (phenoxycarbonylamino), aminocarbonylamino group (dimethylaminocarbonylamino, diethylaminocarbonylamino), sulfonyl group ( Methanesulfonyl, ethanesulfonyl, toluenesulfonyl), sulfamoyl group (methylsulfamoyl,
Dimethylsulfamoyl), a sulfonylamino group (methanesulfonylamino, ethanesulfonylamino), an amino group, a hydroxy group, and a heterocyclic group (benzotriazolyl, benzotetrazolyl).

A heterocyclic group (having 2 to 30 carbon atoms) is also preferable. Preferred heterocycles include imidazolyl group, pyridyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, quinolyl group, benzopyrazolyl group, benzothiazolyl group, isothiazolyl group, benzoisothiazolyl group, pyridoisothiazolyl group, and thiadiazolyl group. Can be mentioned.

A preferred example of Ar is 6 carbon atoms.
~ 30 aryl groups, 2-cyano-4-nitrophenyl, 2-chloro-4-nitrophenyl, such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, p-chlorophenyl, m-chlorophenyl,
o-chlorophenyl, p-nitrophenyl, p-cyanophenyl, p- (N, N-diethyl) phenyl, 2,4
-Dichlorophenyl, m-fluorophenyl, p-tolyl, p-mesylphenyl, 3,4-dicyanophenyl,
4-methoxycarbonylphenyl, 2,4,6-trichlorophenyl), a heterocyclic group having 2 to 30 carbon atoms, for example, the groups shown below.

[0029]

[Chemical 7]

Among the dyes represented by the general formula (I),
Those represented by the following general formula (IV) are preferable.

[0031]

[Chemical 8]

In the formula, X represents an aryl group, a heterocyclic group having a carbon atom at the bonding position, a cyano group or an alkyl group.
Y and Z each independently represent an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.1 or more. A is the following general formula
Represents (II) or (III).

[0033]

[Chemical 9]

[0034]

[Chemical 10]

In the formula (II), R ¹ , R ² , R ³ and R
⁴ is each independently R ¹ , R ² , R ³ and R in formula (I)
It is synonymous with what ⁴ represents. However, R ¹ , R ² , R ³
At least one of R ⁴ and R ⁴ is a halogen atom, a cyano group, an acyl group, a nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an aminocarbonyl group. Ar in the formula (III) represents an aryl group or a heteroaromatic group derived from the diazo component.

The general formula (IV) will be described in detail. X
Represents an aryl group (having 6 to 13 carbon atoms), a heterocyclic group having a carbon atom at the bonding position (having 3 to 10 carbon atoms), and an alkyl group (having 1 to 8 carbon atoms). 6 to 13). The aryl group may be unsubstituted or may have a substituent. The substituent is preferably an electron-withdrawing group having a Hammett substituent constant σ _p value of 0 or more. It is more preferable that the σ _p value is 0.1 or more.

Y and Z each independently represent an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.1 or more. At that time, the sum of the σ _p values of Y and Z is 0.7 or more. Is preferable, 1.0 or more is more preferable, and 1.2 or more is most preferable.

[0038] Specific examples of R ^1, R ^2, R ³ and R ^4, and preferred examples thereof include those described in R ^1, R ^2, R ³ and R ⁴ of formula (I). Ar represents an aryl group derived from a diazo component or a heteroaromatic group, and specific examples and preferable examples thereof include those mentioned for Ar in the formula (I).

Another preferred structure of the dye represented by the general formula (II) is represented by the following general formula (V).

[0040]

[Chemical 11]

In the formula (V), S, T and U are each a nitrogen atom, a methine group or a methine group having an electron-withdrawing group, and at least one of them is a methine group having an electron-withdrawing group. Is. n represents an integer of 0 to 2. Q
Represents a non-metallic atomic group necessary for forming a hetero ring or an aromatic ring together with a-(-) C = S- (T = U) n-residue. A is the following general formula (II) or (III)
Represents a group represented by.

[0042]

[Chemical 12]

[0043]

[Chemical 13]

In the formula (II), R ¹ , R ² , R ³ and R
⁴ has the same meaning as represented by R ¹ , R ² , R ³ and R ⁴ in formula (IV). In formula (III), Ar has the same meaning as Ar in formula (III) described in the explanation of formula (I).

The general formula (V) will be described in detail.
When S, T, U represents a methine group, respectively, -C (R ^{5)
=, - C (R 6)} =, - C (R 7) = represented by. R
⁵ , R ⁶ and R ⁷ each independently have the same meaning as that represented by X in formula (I). Two adjacent R ⁵ , R ⁶ and R ⁷ may combine with each other to form a ring structure.
At this time, it is preferably a 5-membered or 6-membered condensed ring, and represents, for example, a benzo condensed ring or a pyrido condensed ring.
At least one of R ⁵ , R ⁶ and R ⁷ is preferably a substituent having a Hammett substituent constant σ _p value of 0.10 or more, more preferably a substituent of 0.35 or more,
More preferably, it represents a substituent having a σ _p value of 0.60 or more. The σ _p value is 0.8 or less. Specific examples thereof include those mentioned in the description of Y and Z in formula (I).

In the general formula (II), Q is a 5-membered ring or more, preferably 5 to 8 together with a carbon atom or a nitrogen atom to be bonded.
Represents an atom or atomic group necessary for forming a member ring, more preferably a 5-membered ring or a 6-membered ring, and the divalent group forming the ring is a divalent amino group, an ether bond, a thioether bond or an alkylene. Represents a group, an alkenylene group, an imino group, a sulfonyl group, a carbonyl group, etc., which may have a substituent. Here, as the substituent,
The substituents enumerated above for R ¹ may be mentioned. Particularly preferably, Q is a thioether bond, imino group or sulfonyl group.

Specific examples of the dye used in the present invention are shown below. The present invention is not limited to these.

[0048]

[Chemical 14]

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Chemical 17]

The present invention will be described in more detail by showing synthesis examples of dyes used in the present invention.

Synthesis Example-1 Synthesis of Compound (28) 3- (2,2-dicyanovinylidene) -3-phenylpropionitrile 0.5 g (2.6 mmol), methanol 4
The solution consisting of 0 ml was ice-cooled and stirred. To this, 0.6g
A diazo solution containing a diazonium salt synthesized by the nitrosylsulfuric acid method was added from (2.9 mmol) of 2-methylsulfonyl-4-nitroaniline so that the internal temperature was kept at 5 ° C or lower. After reacting at 5 ° C or lower for 1 hour and at room temperature for 1 hour,
The precipitated crystals were collected by filtration and washed with methanol. The crystals collected by filtration were recrystallized from 5 ml of acetone / 30 ml of methanol without drying. Yield 0.7g Yield 64.1%
λ _{max (DMF)} 565.4nm

The dye used in the present invention is a so-called dissociative dye, which gives excellent sharp absorption for image formation when the proton of the hydroxy group of the dye is dissociated. In order to dissociate sufficiently in the image receiving layer, the dye p
Ka must be 7.0 or less at 25 ° C. The pKa is preferably 5.0 or less. Furthermore, the pKa of the dye is preferably 3.0 or less.

The dye used in the present invention cannot obtain a sufficient transfer density at the time of thermal transfer unless it has a large diffusion ability. Therefore, the dye molecular weight is preferably small. Specifically, the molecular weight is preferably 500 or less, more preferably 400 or less. Most preferably, it is 350 or less.

Further, it is described in JP-A-3-205189.
R is the atomic group that suppresses fading ¹, R², R³, R
^Four, X, Y can also be attached to the image for lightfastness
It is preferable for improving the property.

The heat transferable dye of the present invention is contained in a color material layer on a support to form a heat transfer dye-providing material, which is used for image formation by a heat transfer system. Next, the case where the heat transferable dye of the present invention is used for image formation in a thermal transfer system will be described in detail below. Usually, three color dyes of yellow, magenta, and cyan are required to form a full-color image. Therefore, the compound of the present invention can be used as a magenta dye or a cyan dye, and the other two colors can be selected from conventionally known dyes to form a full-color image. For the same color, the dye of the present invention and a conventionally known dye may be mixed and used. Further, two or more of the dyes of the present invention may be mixed and used in the same color.

Next, a method of using the thermal transfer dye of the present invention will be described. The thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. The yellow, magenta and cyan dyes of the present invention 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 frame-sequential or line-sequential manner. Further, it is also possible to prepare three types of thermal transfer dye-donor materials in which the above-mentioned yellow dye, magenta dye, and cyan dye are provided on separate supports, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be carried out sequentially. . Each of the dyes of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and applied on a support, or can be printed on a support by a printing method such as a gravure method. The thickness of the dye-donor layer containing these dyes is usually about 0.2 in terms of dry film thickness.
It is preferable to set in the range of ˜5 μm, especially 0.4 to 2 μm.

The coating amount of the dye is 0.03 to 1 g / m ² , more preferably 0.1 to 0.6 g / m ² . As the binder resin to be used together with the above-mentioned dye, any of the conventionally known binder resins for such purpose can be used, and usually those having high heat resistance, and those which do not hinder the transfer of the dye when heated To be selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin (eg polyvinyl alcohol, polyvinyl Acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene) and the like. In the present invention, such a binder resin is used in an amount of about 20 to 600 per 100 parts by weight of the dye.
It is preferably used in a proportion of parts by weight. In the present invention, any conventionally known ink solvent can be used as the ink solvent for dissolving or dispersing the dye and the binder resin.

As the support of the thermal transfer dye-providing material, any conventionally known one 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-donor element is generally 2 to
It is 30 μm. 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 further improves the transfer density. As the hydrophilic polymer, the water-soluble polymer described above can be used. A slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof.

In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to perform sticking prevention treatment on the side of the support on which the dye-donor layer is not provided. . For example,
It is preferable to provide a heat-resistant slip layer mainly containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or alkaline earth metal salt of phosphoric acid ester, and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80.
From about 110 ° C. and from the viewpoint of many reaction sites with isocyanate, the weight percentage of vinyl butyral portion is 1
5 to 40% is preferable. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafak RD720 manufactured by Toho Chemical Co., Ltd. is used, and 1 to 50% by weight, preferably 10 to 4% by weight based on the polyvinyl butyral resin.
It is recommended to use about 0% by weight. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as 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-donor element may be provided with a hydrophilic barrier layer for preventing the dye from diffusing toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. Generally good results are gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired effect, but preferred specific examples include (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 Bostic 7650 (Mhart Inc., Bostic Chemical Group) Alternatively, a chlorinated high density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the undercoat layer is not particularly limited, but it 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 superposed on the thermal transfer image-receiving material, and heat is applied according to the image information from either side, preferably from the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and a known one such as a laser beam (for example, semiconductor laser) infrared flash, a hot pen, or the like can be used. In laser-based systems, the dye-donor material contains a material that strongly absorbs the laser beam. When the dye-providing material is irradiated with a laser beam,
The absorptive material converts light energy into heat energy which immediately transfers the heat to nearby dyes and heats them to their heat transfer temperature for transfer to the image receiving material. The absorbent material is present in layers under the dye and / or is mixed with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the dye-donor material to reconstitute the original target color and heat transfer. A more detailed description of this process can be found in British Patent 2,083,726A.
The absorbing material disclosed for that laser system in British Patent 2,083,726A is carbon. In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to print by using various printers of thermal printing system, facsimile, or print production of image by magnetic recording system, optical recording system, television, C
It can be used to create prints from the RT screen. For details of the thermal transfer recording method, reference can be made to the recording of JP-A-60-34895.

In a preferred embodiment of the invention, the dye-donor element comprises a polyethylene terephthalate support coated in successive repeating regions of a cyan dye, a magenta dye and a yellow dye, the steps being carried out sequentially for each color to give a triple dye. Form a color transfer image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
For the thermal transfer of dyes from dye-donor materials to image-receiving materials, ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA.
Several types of lasers can be used, such as solid state lasers such as G, or semiconductor lasers such as gallium-arsenide that emit in the infrared region of 750 to 870 nm. However, in practice,
A semiconductor laser is advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

The thermal transfer image receiving material is provided with a dye receiving layer. This receiving layer contains a substance capable of receiving the heat transferable dye which has a function of receiving the heat transferable dye transferred from the heat transfer dye-providing material during printing and dyeing the heat transferable dye. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. In the present invention, a dye fixing agent is used as the substance capable of receiving the heat transferable dye.

In the above case, the dye fixing agent can be arbitrarily selected from the commonly used dye fixing agents, and among them, the polymer dye fixing agent is particularly preferable. Here, the polymer dye fixing agent includes a polymer containing a repeating unit represented by the following general formula (VI).

[0074]

[Chemical 18]

In the formula (XX), a ¹ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 4 carbon atoms. D ¹ represents a divalent group connecting a carbon atom and D ² . D ² represents a tertiary amino group, a nitrogen-containing heterocyclic group or a quaternary cation group.

A¹Specifically, hydrogen atom, halogen
Group atom (for example, chlorine atom, bromine atom, etc.), cyano group
Or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl
, Propyl, butyl, etc.). a¹Is preferably
Represents a hydrogen atom and a methyl group. D¹Specifically,
-OCO-, -COO-,-(CH₂)_V-, -SO ₂
-, -COO- (CH₂)_V-, -OCO- (CH₂)
_V-(V represents an integer of 1 to 3), -O-, -CON
H-, -CON (R¹)-,-SO₂N (R¹)-,-
CONHCONH-, -CONHCOO- or -C₆H
_Four-(Where R¹Is synonymous with that of formula (I))
Represents a group constituted by one or a combination thereof.
D¹Is -C₆H_FourWhen-is represented, the benzene ring is a substituent
May have. As a substituent, a halogen atom (for example,
For example, chlorine atom, bromine atom, etc.), alkyl group (eg methyl
Ru, ethyl, propyl, butyl, chloromethyl, methoki
Cimethyl, etc.), alkoxy groups (eg methoxy, etoxy)
Ci, propioxy, butoxy, etc.) and the like. D¹
Is preferably -OCO-, -OCO- (CH₂)
_V-, -COO- (CH₂)_V-, -CH₂-Or-C
₆H_Four-CH₂Represents-.

When D ² represents a tertiary amino group, the tertiary amino group is represented by —N (D ⁴ ) D ⁵ , and D ⁴ and D ⁵ each independently have the same meaning as R ¹ . D ⁴ and D ⁵ may form a ring structure, and the ring structure represents a 5- or 6-membered ring which may contain oxygen, nitrogen or sulfur. D ⁴ and D
⁵ preferably independently represents an alkyl group having 1 to 6 carbon atoms or a benzyl group. When D ² represents a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group is preferably an imidazole group or a pyridyl group, which may be substituted. Examples of the substituent include the above R ¹ . When D ² represents a quaternary cation group, the quaternary cation group is preferably a quaternary ammonium group or a quaternary imidazole group. The quaternary ammonium group is represented by the following general formula (VII).

[0078]

[Chemical 19]

In the formula (XXI), D⁶, D⁷, D⁸Each is independent
To R¹Is synonymous with. D⁶And D⁷Or D⁷And D⁸Or
D⁶And D⁸May form a ring structure, and the ring structure is D^Four
And D ^FiveIs synonymous with that formed by. M is a positive in the substituent
Represents an anion that neutralizes ionic charge. As anion
Is an inorganic or organic anion.
May be used, preferably perchlorate ion, iodine ion
Ion, bromine ion, substituted aryl sulfonate ion (eg
For example, p-toluenesulfonate ion). D⁶,
D⁷, D⁸It is preferable that each independently has 1 to 6 carbon atoms.
It represents a rukyl group or a benzyl group. Quaternary imidazole
Examples of the group include the following general formula (VIII).

[0080]

[Chemical 20]

In the formula (XXII), D ⁹ has the same meaning as R ¹ above. M has the same meaning as above. R ⁹ is preferably a substituted or unsubstituted alkyl group. The repeating unit represented by the formula (XX) is contained in the polymer in an amount of 10 mol% to 100 mol%. Further, as a polymer component that can be contained in the polymer together with the polymer component represented by the formula (XX), the formula (X
Any monomer may be used as long as it is a monomer corresponding to another repeating unit copolymerizable with the polymer component of X). Preferred are vinyl compounds, and more specifically, methacrylic acid esters, acrylic acid esters, styrenes, heterocyclic vinyls and the like can be mentioned. These other monomers are used within the range of not more than 90 mol% in the total polymer components of the polymer dye fixing agent. The repeating unit represented by the formula (XX) and the other polymer component may be present in the polymer in a random form or a block form. Specific representative examples of the dye fixing agent used in the present invention are shown below, but the present invention is not limited to these. (Numbers represent mol%) As the nitrogen-containing heterocyclic group, an imidazole group and a pyridyl group are preferable. Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include U.S. Pat. Nos. 4,282,305 and 4,11.
5,124, 3,148,061, JP-A-60.
-118834, 60-122941, JP-A-6-6
The dye fixing agents described in JP-A No. 2-244043, JP-A No. 62-244036 and the like can be mentioned. Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101 and 2,093,041,
No. 1,594,961, U.S. Pat. No. 4,124,3
No. 86, No. 4,115,124, No. 4,273,
853, 4,450,224, JP-A-48-2
Examples thereof include dye fixing agents described in No. 8325. Other preferable specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. Nos. 3,709,690, 3,898,088 and 3,958,995. Nos. 60-57836, 60-60643 and 6
0-122940, 60-122942, 60
-235134 and the like are mentioned.

Specific examples of the polymer dye fixing agent are shown below.

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

The molecular weight of the polymer dye fixing agent of the present invention is 1
X10 ³ to 1x10 ⁶ are suitable, and especially 1x10 ⁴ to
2 × 10 ⁵ is preferable. The above-mentioned polymer dye fixing agent can also form the receiving layer by itself. It can also be used as a mixture with the synthetic resin described below. The amount of the dye fixing agent applied is suitably 0.2 to 30 g / m ² , and preferably 0.5 to 15 g / m ² . The Tg of the polymer dye fixing agent is 0 to 120 ° C. Among them, Tg is preferably 30 to 70 ° C. The polymer dye fixing agent is preferably a polymer having a tertiary amino group, and more preferably a polymer having a tertiary amino group in a pendant. The polymer dye fixing agent is preferably easily soluble in an organic solvent containing substantially no water. As the organic solvent, toluene, xylene, methylene chloride, chloroform dichloroethane, hexane, pentane, acetone, cyclohexane, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylacetamide, dimethylformamide, methanol, ethanol, isopropanol, acetonitrile, propionitrile, terrara Hydrofuran, diethyl ether and the like can be mentioned.

The most preferable polymer dye fixing agent is a derivative of polyvinyl alcohol having a tertiary amino group as a pendant. When used in combination with a synthetic resin, it can be easily determined by those skilled in the art according to the type and composition of the dye fixing agent and the image forming process used, but the fixing agent / synthetic resin ratio is preferable. Is 10
It is preferably used at / 90 to 100/0.

As the synthetic resin, an ordinary synthetic resin can be used as long as it can accept the dye transferred from the transfer sheet. Specifically, the following synthetic resins are used. (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 sulfo group or a carboxyl group), ethylene glycol, diethylene glycol, Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate: polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395 and 6
3-7971, 63-7792, 63-797.
No. 3 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 3
00, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009, ATR-
2010 etc. can be used. (B) Those having a urethane bond, such as polyurethane resin. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling point organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat-transferable dye or as a dye diffusing agent. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-245253.
No. 61-209444 and 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned.

Further, a mordant and a basic substance for mordanting the dye can be contained. As the mordant and the basic substance, those described in JP-A-61-64492, JP-A-1-188391 and JP-A-3-83685 can be used. A basic polymer may be used in place of the mordant to dissociate the dye. Examples of the basic polymer include AEA (manufactured by Sankyo Co., Ltd.) and the like. Also, a basic compound may be used instead of the mordant. At this time, the basic compound preferably has a ballast group (diffusion resistant group) in the molecule. A tertiary amine is preferred as the basic compound.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried 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 crosslinking reaction by a hardening agent is preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having enhanced dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used for the outermost layer. Using a synthetic resin with a higher point, sticking to the surface, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents troubles such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to 50 μm.
m, particularly 3 to 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 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 is either a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more functions depending on the constituent material,
In some cases, it also serves 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 a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is a layer which prevents 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-preventing layer, adhesive layer, etc. constituting the thermal transfer image-receiving material of the present invention includes silica,
Fine powders such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobone, titanium oxide and alumina may be contained. If the support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer, etc. Anything can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), 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 Paper support such as added paper, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc. A film or sheet that has been treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. An example is K. Vevnkataraman's "The Chem.
istry of Synthetic Dyes ", Volume 5, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples thereof include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyryl-based compounds, and 2,5-dibenzoxazolethiophene-based compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent. In the present invention, in order to improve releasability between the thermal transfer dye-donor material and the thermal transfer image-receiving material, the outermost layer, which is a layer constituting the dye-donating material and / or the image-receiving material, particularly preferably a surface contacting both materials, is preferred. It is preferable to include releasability. As release agents, solid or wax-like substances such as polyethylene wax, amide wax, Teflon powder: Surfactants such as fluorine-based and phosphoric ester-based: paraffin-based, silicone-based, fluorine-based oils, etc. Although any of the above releasing agents can be used, silicone oil is particularly preferable. As non-denatured silicone oil, carboxy-modified, amino-modified,
Modified silicone oil such as epoxy modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data 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 an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is effectively a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710).

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in the publications are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61-159644
The compounds described in No. 1 are also effective. As an ultraviolet absorber,
Benzotriazole compounds (US Pat. No. 3,533,
No. 794), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (JP 56-2784 etc.) and others JP 54.
-48535, 62-136641, 61-8.
8256 and the like. In addition, JP-A-62
The ultraviolet absorbing polymer described in JP-A-260152 is also effective. Examples of the metal complex include U.S. Pat. No. 4,241,15.
5, No. 4,245,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A-62-174.
741 and 61-88256 (27) to (29).
Page, Japanese Patent Application Nos. 62-234103 and 62-31109.
6 and Japanese Patent Application No. 62-230596. Examples of useful anti-fading agents are disclosed in JP-A-62-2.
15272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be contained in the image-receiving material in advance, or may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of releasability, improvement of sliding property, antistatic property, acceleration of development and the like. For example, saponin (steroidal), alkylene oxide derivative (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone Polyethylene oxide adducts), glycidol derivatives (for example, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like: alkylcarboxylic acid salts, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphoric acid esters and other carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups Anionic surfactants containing acidic groups such as: Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides, etc. double-sided surfactants: alkyl amine salts, aliphatic or aromatic Group 4 quaternary ammonium salts, heterocycles such as viridinium and imidazolium
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used. Specific examples of these are disclosed in JP-A-62-173463 and JP-A-62-183457.
No. etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. For this purpose, in addition to the surfactants mentioned above,
The surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin. A matting agent can be used in the thermal transfer dye-donating material and the thermal transfer image-receiving material. Matting agents such as silicon dioxide, polyolefins and polymethacrylates are disclosed in JP-A-61-88256.
JP-A-63-274944 and JP-A-63-274, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page (29).
There are compounds described in No. 952.

[0100]

EXAMPLES The following are detailed examples of the present invention. However, the thermal transfer recording method of the present invention is not limited to the following examples.

Example 1 Preparation of Thermal Transfer Dye-donor Material (1) A 5 μm thick polyethylene terephthalate film having a heat resistant slipping layer provided on one side was used as a support.
A composition (1) for coating a dye-donor layer having the following composition was applied to the side opposite to the side provided with the heat resistant slipping layer using a gravure coater so that the thickness after drying would be 0.6 μm. ,
A thermal transfer dye-providing material (1) (hereinafter, also simply referred to as a dye-donating material) was obtained. Dye Donor Layer Coating Composition (1) Dye 28 10 g Polyvinyl butyral (Denka Butyral 5000A: manufactured by Denki Kagaku) 10 g Silicone oil (KF-96: manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N: manufactured by Takeda Yakuhin) 0 0.5g Methyl ethyl ketone 100ml Toluene 80ml

Preparation of Thermal Transfer Image Receiving Material (1) A laminated type synthetic paper having a thickness of 150 μm was used as a support,
The composition (1) for applying a receptive layer having the following composition was applied to the surface using a wire bar coater so that the thickness when dried was 5 μm, and the thermal transfer image receiving material (1) (hereinafter, also simply referred to as an image receiving material) was used. Produced). Drying was performed temporarily with a dryer and then in an oven at 80 ° C. for 1 hour. Receptor layer coating composition (1) Dye fixing agent P-19 26 g Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KP-857 manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 100 ml Toluene 50 ml Cyclohexanone 10 ml Preparation of dye-donor materials (2) to (10) Dye-donor material (2) was replaced with those shown in Table 1 below for dye 7 and binder resin of dye-donor material (1), but otherwise in the same manner. ~ (10) and a dye-donor element (A) for comparison were prepared.

[0103]

[Table 7]

[0104]

[Chemical formula 26]

Example 2 Transfer Experiment Thermal transfer dye-donor elements (1) to (1) obtained as described above.
A transfer experiment was conducted using (10) and (A) and the thermal transfer dye image receiving material (1). The thermal transfer dye-donor material and the thermal transfer image-receiving material obtained as described above are overlaid so that the dye-donor layer and the receptor layer are in contact, and a thermal head is used from the support side of the thermal-transfer dye-donor material. Output 0.25W / dot, pulse width 0.1-10msec,
Heating was performed under the condition that the dot density was 6 dots / mm, and the dye was dyed imagewise on the receiving layer of the image receiving material. The portion where the density of the recorded image-receiving material obtained at this time is saturated (Dmax
) Was measured using a reflection densitometer (manufactured by X Rite Inc., status A filter built-in). Further, the degree of image bleeding was observed after the recorded image receiving material was left in an oven at 60 ° C. for 2 weeks. The judgment criteria are shown by ◯ when the image hardly changes from before storage, Δ when slightly bleeding, and x when extremely blurred. The results are shown in Table 2 below.

[0106]

[Table 8]

Example 3 Preparation of Thermal Transfer Dye Image Receiving Materials (2) to (10) Instead of the dye fixing agent amino group-containing polyvinyl acetal resin AEA (manufactured by Sankyo Co., Ltd.) of the composition for coating the receiving layer of Example 1. In place of the dye fixing agent and the binder resin shown in Table 9 below, other thermal transfer dye image receiving materials (2) to
A comparative image-receiving material (B) was prepared without using (8) and a dye fixing agent.

[0108]

[Table 9]

Transfer Experiment Using the dye image-receiving materials (2) to (10) and (B) prepared and the dye-donor materials (1) to (6) prepared in Example 1, according to the method of Example 2, Transfer and density measurements and bleed tests were performed. The results are shown in Table-4.

[0110]

[Table 10]

When the dye used in the present invention and the polymer dye fixing agent were used together (No. 1 to No. 8), blurring of the image by the bleeding test was not observed. The transfer density was also high. On the other hand, in a transfer experiment (No. 9, 10) in which the polymer dye fixing agent was not used in the image receiving layer, the dye did not exhibit the original color tone of the dissociative dye and the transfer density was low. Also, some blurring of the image due to the bleeding test was observed.

[0112]

By using the thermal transfer dye-providing material of the present invention, an image having a high transfer density, an excellent hue and an excellent fastness can be obtained. Further, when transfer is performed on an image receiving paper containing a basic substance and / or a mordant in the image receiving layer, an image having good storage stability without blurring with time can be obtained.

Claims (2)

[Claims] 1. A thermal transfer dye-donating material comprising a support and a dye-donor layer containing a heat-transferable dye, wherein the dye-donor layer contains at least the heat-transferable dye represented by formula (I). A thermal transfer dye-providing material containing one kind. General formula (I) In formula (I), V represents a nitrogen atom or -CZ =. X, Y and Z each independently represent a monovalent substituent.
A is a group represented by the following formulas (II) and (III). [Chemical 2] In formula (II), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkoxy group, aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino Group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl Represents a group, an acyl group, a carboxylic acid group (salt thereof), and a sulfonic acid group (salt thereof). [Chemical 3] In formula (III), Ar is an aryl group or heteroaromatic group derived from a diazo component. 2. An image forming method comprising superposing the thermal transfer dye-donor material according to claim 1 and a thermal transfer dye-image receiving material, heating the dye according to image information, and thermally diffusing and transferring the dye. An image forming method, wherein the material contains a basic substance and / or a mordant.