JP3280730B2 - Thermal transfer image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates has a vivid hue, thermal transfer dye-providing material containing excellent thermal transferable dye transferability
The present invention relates to an image forming method using a material.

[0002]

2. Description of the Related Art As a technique relating to a color hard copy, a thermal transfer method, an electrophotographic method, an ink jet method, and the like are currently 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 involves heating a thermal transfer material having a heat-meltable ink layer formed on a base film with a thermal head to melt the ink and recording the resultant on a thermal transfer image-receiving material, and a thermal transfer dye on the base film. There is a method in which a thermal transfer dye-providing material having a formed color material layer formed thereon is heated by a thermal head to thermally transfer and transfer the dye onto the thermal transfer image-receiving material.The latter thermal transfer transfer method uses energy applied to the thermal head. By changing the amount, the transfer amount of the dye can be changed, so that gradation recording becomes easy, 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. It is difficult to retransfer, and it is easy to prepare a thermal transfer dye-providing material. In particular, it has been desired to develop a dye that satisfies these requirements.

[0003] Japanese Patent Application Laid-Open No. 4-89291 discloses that
A thermal transfer material using an azomethine dye derived from a β, γ unsaturated nitrile coupler is disclosed.

However, a phenomenon in which an image formed by transfer is blurred or blurred with time is observed. JP-A-3-
No. 83,885 and JP-A-61-64492 disclose a method in which a mordant is contained in an image receiving layer to thermally transfer a dye having a mordant group such as a phenolic hydroxyl group.

[0005]

A conventionally known azomethine dye derived from a β, γ-unsaturated nitrile coupler has a high pKa of the dye, and is used together with a basic compound to dissociate the dye. Could not be used. Therefore, the disadvantage that the sharpness of the transferred image decreases with time cannot be solved.

[0006] The purpose of the present invention, the image-receiving layer contain a mordant or a basic substance, in an image forming method for transferring a dye having a dissociative group (mordant group), transferring property, concentration, hue excellent image It is to get. Another object of the present invention is to solve various problems desired in an image forming method using a thermal transfer dye-providing material.

[0007]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
In the thermal transfer dye donating material comprising a dye-donor layer containing a heat migrating dye, <br/> thermal transfer dye-donating layer is formed by at least one containing a thermally migrating dye represented by formula (I) The dye donating material and the thermal transfer dye receiving material
And heat it in accordance with the image information to cause thermal diffusion transfer of the dye.
Image forming method, wherein the thermal transfer dye receiving material is basic
An image characterized by containing a substance and / or a mordant
Achieved by the imaging method . General formula (I)

[0008]

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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]

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In the formula (II), R ¹ , R ² , R ³ and R
⁴ is 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, 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), sulfonic acid group (salt)
Represents

[0012]

In the formula (III), Ar is an optionally substituted aryl group or heteroaromatic group derived from a diazo component .

The general formula (I) will be described below in detail. 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 1 to 30 carbon atoms, for example, methyl, cyclopropyl, vinyl, allyl, octyl, methoxyethyl, cyanoethyl, ethyl, propyl, butyl), an alkoxy group (preferably having 1 to 30 carbon atoms) 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 (eg, 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), carbamoyl group [preferably an alkylcarbamoyl group having 2 to 30 carbon atoms (eg, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butyi) Rucarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcar 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-tolylcarbamoyl, m-methoxyphenylcarbamoyl, 4, 5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), preferably 4 carbon atoms To 30 phthalylcarbamoyl groups (for example, 2-pyridylcarbamoyl, 3
-Pyridylcarbamoyl, 4-pyridylcarbamoyl,
2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2
-(4-methylphenyl) 1,3,4-thiadiazolylcarbamoyl)], a sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl and dimethylsulfamoyl), an aminocarbonylamino group (preferably C1-30, for example, methylaminocarbonylamino, dimethylaminocarbonylamino), alkoxycarbonylamino group (preferably, C2-30, for example, methoxycarbonylamino, ethoxycarbonylamino), hydroxy group, amino group (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), a nitro group, an aryloxy group (preferably having 6 to 30 carbon atoms, for example, phenoxy, p-methoxyphenoxy, o-chlorophenoxy), a sulfamoylamino group ( It preferably has 0 to 30 carbon atoms such as methylsulfamoylamino and dimethylsulfamoylamino), an alkylthio group (preferably 1 to 30 carbon atoms such as methylthio and ethylthio), and an 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, for example, methanesulfonyl, p-
Toluenesulfonyl), acyl group (preferably having 1 carbon atom)
-30, for example, formyl, acetyl, benzoyl, p-
Toluyl), a heterocyclic oxy group (preferably having 3 to 3 carbon atoms)
30), an azo group (preferably having 3 to 30 carbon atoms, for example, p
-Nitrophenylazo), an acyloxy group (preferably having 1 to 30 carbon atoms, for example, acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms)
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), and an imide group (preferably having 4 carbon atoms). To 30, for example, phthalimide), a heterocyclic thio group (preferably having 3 to 30 carbon atoms),
A sulfinyl group (preferably having 1 to 30 carbon atoms, for example, diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 30 carbon atoms, for example, diaminophosphoryl), a carboxylic acid group (including a sodium salt and a potassium salt thereof), a sulfonic acid group (Including its sodium and potassium salts).

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

When V represents = CZ-, less of Y and Z
One of them is preferably an electron-withdrawing group. Electronic
As the attractive group, Hammett substituent constant σ_pValue is 0.1
It is preferably 0 or more, more preferably 0.35 or more. σ
_pThe value is most preferably 0.60 or more. σ _pThe value is 2.
0 or less is preferable. At that time, the electron-withdrawing groups of Y and Z
Those not present are the substituents already mentioned for X above.
You. More preferably, X is an alkyl group (carbon number
1-8), alkoxy group (1-6 carbon atoms), acylamido
No. group (C2-6), aryl group (C6-1)
3) a heterocyclic group (3 to 10 carbon atoms).

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

As used herein, Hammett's substituent constant σ _p
Values are reported by Hansch, C. Leo et al. (Eg, J. Med.
Chem. 16, 1207 (1973); ibid. 20, 30,
4 (1977)).

Examples of the substituent or atom having a value of σ _p 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, trifluoromethyl). Methanesulfonylmethyl, 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-benzimidazolyl) , 1-tetrazolyl), nitro group, azo group (eg, phenylazo), substituted amino group (eg, ditrifluoromethylamino), substituted alkoxy group (eg, trifluoromethoxy), alkylsulfonyloxy group (eg, methanesulfonyloxy), acyloxy Groups (eg, acetyloxy, benzoyloxy), arylsulfonyloxy groups (eg, benzenesulfonyloxy), phosphoryl groups (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups, sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) And the like.

The substituent having a value of σ _p of 0.35 or more includes a substituted alkyl group (eg, trifluoromethyl, perfluorobutyl), a nitrile group, an acyl group (eg, acetyl, benzoyl, formyl), a carboxyl group, a carbamoyl group (Eg, carbamoyl, methylcarbamoyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted aromatic group (eg, pentafluorophenyl), heterocyclic residue (eg, 1-tetrazolyl), nitro group, azo group Groups (eg, phenylazo), substituted amino groups (eg, ditrifluoromethylamino), substituted alkoxy groups (eg, trifluoromethoxy), alkylsulfonyloxy groups (eg, methanesulfonyloxy), phosphoryl groups (eg, dimethoxyphospho) Ryl, diphenylphosphoryl), a sulfamoyl group, a 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 (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, and benzenesulfonyl).

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

In the formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a nonmetallic substituent, and the nonmetallic substituent may be an alkyl group (having a carbon number of 1 to 12, for example, methyl, ethyl, n-propyl, iso-propyl, t-butyl, trifluoromethyl), an alkoxy group (1 to 12 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy), an aryl group ( Carbon number 6
To 20, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), a nitro group, an acyl group (1 to 20, for example, formyl, acetyl, benzoyl, p-methoxybenzoyl), an alkylthio group (1 to carbon atoms) To 20, for example, methylthio, ethylthio),
An arylthio group (C6 to C20, for example, phenylthio, p-chlorophenylthio), a sulfonyl group (C1 to C20, for example, methanesulfonyl, ethanesulfonyl, toluenesulfonyl), an amino group (C0 to C20, 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 atom Number 7-1
5 arylcarbonylamino groups (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (2 to 13 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cyano group, A sulfonylamino group (1 to 10 carbon atoms, for example, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), a carbamoyl group [an alkylcarbamoyl group having 2 to 12 carbon atoms (for example, 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 group 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)], a sulfamoyl group (0 to 12 carbon atoms, for example, methylsulfamoyl and dimethylsulfamoyl), an aminocarbonylamino group (1 to 10 carbon atoms, for example, methylaminocarbonylamino, dimethyl Aminocarbonylamino) and an alkoxycarbonylamino group (2 to 10 carbon atoms, for example, methoxycarbonylamino, 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 the present invention. And the pKa of the hydroxyl group is 7
It is preferable to select the substituents as follows. Preferred substituents from the above viewpoint include a chlorine atom, a cyano group, an acyl group, a nitro group, an alkoxycarbonyl group,
Examples include an aryloxycarbonyl group and an aminocarbonyl group. Among them, it is most preferred that R ¹ and R ⁴ are hydrogen atoms and R ² and R ³ are both chloro atoms.

In the formula (III), Ar is an aryl group or a heterocyclic group derived from a diazo component. The aryl group derived from the diazo component represented by Ar is an optionally substituted aryl group having 6 to 30 carbon atoms. Examples of the substituent for substituting the aryl group include an alkyl group (methyl, ethyl), an alkoxy group (methoxy, ethoxy, isopropoxy), an aryloxy group (phenoxy), an acyloxy (acetyloxy, pivaloyloxy), an aryl group (phenyl), Halogen atoms (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).

Further, a heterocyclic group (having 2 to 30 carbon atoms) is also preferred. Preferred heterocycles include imidazolyl, pyridyl, pyrazolyl, thiazolyl, benzoimidazolyl, quinolyl, benzopyrazolyl, benzothiazolyl, isothiazolyl, benzoisothiazolyl, pyridoisothiazolyl, and thiadiazolyl. No.

A preferred specific example of Ar is C 6
To 30 aryl groups such as 2-cyano-4-nitrophenyl, 2-chloro-4-nitrophenyl , 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) and a heterocyclic group having 2 to 30 carbon atoms, for example, the following groups.

[0029]

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

[0031]

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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
(II) or (III).

[0033]

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[0034]

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In the formula (II), R ¹ , R ² , R ³ and R
⁴ are each independently R ¹ , R ² , R ³ and R of formula (I)
It is synonymous with what ⁴ represents. However, R ¹ , R ² , R ³
And at least one of 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 a 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), or an alkyl group (having 1 to 8 carbon atoms). Equations 6 to 13). The aryl group may be unsubstituted or have a substituent. The substituent is preferably an electron-withdrawing group having a Hammett substituent constant σ _p value of 0 or more. More preferably, 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, wherein the sum of σ _p values of Y and Z is 0.7 or more. Is preferably, more preferably 1.0 or more, and most preferably 1.2 or more.

[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 or a heteroaromatic group derived from a diazo component, and specific examples and preferred examples thereof include those described for Ar in the formula (I).

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

[0040]

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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, at least one of which is a methine group having an electron-withdrawing group. It is. n represents an integer of 0 to 2. Q
Represents a non-metallic atomic group necessary for forming a heterocyclic ring or an aromatic ring together with-(-) C = S- (T = U) n- residue. A represents the following general formula (II) or (III)
Represents a group represented by

[0042]

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[0043]

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

The general formula (V) will be described in detail.
When S, T and U each represent a methine group, each represents —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 ones of 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- or 6-membered condensed ring, for example, a benzo condensed ring, a pyrido condensed ring or the like.
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 described in the description of Y and Z in the formula (I).

In the general formula (II), Q is a 5- or more-membered ring, preferably a 5- or 5- membered ring, together with a bonding carbon atom or nitrogen atom.
Represents an atom or an atomic group necessary for forming an 8-membered ring, more preferably a 5- or 6-membered ring, and the divalent group forming the ring includes a divalent amino group, an ether bond, a thioether bond, It represents an alkylene group, an alkenylene group, an imino group, a sulfonyl group, a carbonyl group, or the like, and these may have a substituent. Here, as a substituent,
The substituents exemplified for the aforementioned R ¹ can be mentioned. Particularly preferably, Q is a thioether bond, an imino group or a sulfonyl group.

The following are specific examples of the dye used in the present invention. The present invention is not limited to these.

[0048]

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[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

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[0053]

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[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

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The present invention will be described in further detail with reference to synthesis examples of dyes used in the present invention.

Synthesis Example 1 Synthesis of Compound (28) 0.5 g (2.6 mmol) of 3- (2,2-dicyanovinylidene) -3-phenylpropionitrile, methanol 4
A solution consisting of 0 ml was cooled on ice and stirred. Add 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 as to keep the internal temperature at 5 ° C. or lower. After reacting at 5 ° C or less 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 0.7 g Yield 64.1%
λ _{max (DMF)} 565.4 nm

The dye used in the present invention is a so-called dissociable dye, which is used when the proton of the hydroxy group represented by the formula (II) of the dye is dissociated or when the -NH- group of the formula (III) is dissociated.
When the rotons are dissociated, they provide excellent sharp absorption for image formation. In order to sufficiently dissociate in the image receiving layer, the pKa of the dye at 25 ° C. needs to be 7.0 or less. And pKa is preferably 5.0 or less. Furthermore, the pKa of the dye is 3.0
The following is preferred.

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

Further, Japanese Patent Application Laid-Open No. 3-205189 describes
A group that suppresses fading ¹, R^Two, R^Three, R
^Four, X, Y
It is preferable for improving the performance.

The heat transferable dye of the present invention is contained in a colorant layer on a support, is used as a thermal transfer dye-providing material, and is used for image formation by a thermal transfer system. Next, the case where the heat transferable dye of the present invention is used for image formation of a thermal transfer system will be described in detail below. Usually, in order to form a full-color image, dyes of three colors, yellow, magenta and cyan, are required. 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 kinds of the dyes of the present invention may be mixed and used as the same color.

Next, the 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, a continuous roll, or a ribbon. The yellow, magenta, and cyan dyes of the present invention are usually disposed 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 dye of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or can be printed on the 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 dry film thickness.
It is preferably set to a range of from 5 to 5 μm, particularly from 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 used together with the above-mentioned dye, any of the binder resins conventionally known for such a purpose can be used, and those having high heat resistance and which do not hinder the transfer of the dye when heated are usually used. Selected. For example, vinyl resins such as polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (for example, polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), polyvinylpyrrolidone, and polychlorinated resins 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-based 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, for example, about 20 to 600 per 100 parts by weight of the dye.
It is preferred to use it in parts by weight. In the present invention, any of conventionally known ink solvents 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 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; The thickness of the support of the thermal transfer dye-providing material is generally from 2 to
30 μm. 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. 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.

In order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve the slip, the dye donating material is preferably subjected to anti-sticking treatment on the side of the support on which the dye donating layer is not provided. . 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. Polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80
To 110 ° C., and from the viewpoint that there are many reaction sites with the isocyanate, the weight% of the vinyl butyral portion is 1%.
5% to 40% is preferred. As an alkali metal salt or alkaline earth metal salt of a phosphate ester, Gaffa RD720 manufactured by Toho Chemical Co., Ltd. is used, and 1 to 50% by weight, preferably 10 to 4% by weight based on polyvinyl butyral resin.
It is preferable to use about 0% by weight. The heat-resistant slip layer is desirably accompanied by 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. Excellent results are generally achieved with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate-grafted gelatin,
Ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly (vinyl alcohol),
Poly (ethylene imine), poly (acrylic acid), mixture of poly (vinyl alcohol) and poly (vinyl acetate), mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) )). 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 undercoating layer may be used as long as it has a desired effect. Preferred specific examples include (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate) -2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester such as Bostick 7650 (Emhart Corp., Bostick 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 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 from either side, preferably from the back side of the thermal transfer dye-providing material, heat is applied according to image information by a 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 in accordance with the magnitude of the heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be transferred in the same manner. The heating means is not limited to a thermal head, and a known means such as a laser beam (for example, a semiconductor laser), an infrared flash, and a hot pen can be used. In systems using a laser, the dye-donor material contains a material that strongly absorbs the laser beam. When the dye-donor material is irradiated with a laser beam,
The absorbing material converts the light energy to thermal energy and immediately transfers the heat to nearby dyes, which heats them up to their heat transfer temperature for transfer to the image receiving material. The absorbent material is present in a layer below the dye and / or is mixed with the dye. The laser beam is modulated with electrical signals representing the shape and color of the original image, and only those areas of the dye that need to be present on the dye-donor to reconstruct the original color of interest are heated and thermally transferred. A more detailed description of the process is described in British Patent 2,083,726A.
The absorbing material disclosed in GB 2,083,726A for its laser system is carbon. In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to perform printing using various thermal printing printers, facsimile or magnetic recording, optical recording, etc., image printing, television, C
It can be used for creating prints from the RT screen. For details of the thermal transfer recording method, reference can be made to JP-A-60-34895.

In a preferred embodiment of the present invention, the dye-providing material comprises a polyethylene terephthalate support coated on a cyan dye, a magenta dye and a yellow dye in successively repeated areas. A color transfer image is formed. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
Ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA for thermal transfer of dye from dye-donor to image-receiving material.
Several types of lasers can be used, such as a solid state laser such as G, or a semiconductor laser such as gallium-arsenic that emits in the infrared region of 750-870 nm. However, in practice,
Semiconductor lasers are 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 accepts a heat transfer dye which has a function of dyeing the heat transfer dye transferred from the heat transfer dye donating material at the time of printing, and a substance capable of receiving the heat transfer dye having a function of dyeing the heat transfer dye alone. Or a film containing about 0.5 to 50 μm in thickness together with other binder substances. In the present invention, a dye fixing agent is used as a substance capable of accepting a heat transferable dye.

In the above case, the dye fixing agent can be arbitrarily selected from commonly used dye fixing agents, and among them, a 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).

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In the formula (VI) , 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 the carbon atom to D ² . D ² represents a tertiary amino group, a nitrogen-containing heterocyclic group, or a quaternary cation group.

A¹Specifically, a hydrogen atom, a halogen
Atoms (for example, chlorine atom, bromine atom, etc.)
Or an alkyl group having 1 to 4 carbon atoms (for example, methyl,
Propyl, butyl, etc.). a¹Is preferably
Represents a hydrogen atom or a methyl group. D¹Specifically,
-OCO-, -COO-,-(CH_Two)_V-, -SO _Two
-, -COO- (CH_Two)_V-, -OCO- (CH_Two)
_V-(V represents an integer of 1 to 3), -O-, -CON
H-, -CON (R¹)-, -SO_TwoN (R¹)-,-
CONHCONH-, -CONHCOOO- or -C₆H
_Four− (Where R¹Is synonymous with that of formula (I))
Represents a group composed of one or a combination of these.
D¹Is -C₆H_FourIn the case of-, the benzene ring is a substituent
May be provided. As a substituent, a halogen atom (eg,
Chlorine atom, bromine atom, etc.), alkyl group (for example, methyl
, Ethyl, propyl, butyl, chloromethyl, methoxy
An alkoxy group (eg, methoxy, ethoxy, etc.)
, Propoxy, butoxy, etc.). D¹
Is preferably -OCO-, -OCO- (CH_Two)
_V-, -COO- (CH_Two)_V-, -CH_Two-Or -C
₆H_Four-CH_TwoRepresents-.

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, the ring structure represents oxygen, nitrogen or may also be a 5-6 membered ring which contains 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, and these may be substituted. Examples of the substituent include R ¹ described above. When D ² represents a quaternary cation group, the quaternary cation group preferably includes a quaternary ammonium group and a quaternary imidazole group. The quaternary ammonium group is represented by the following general formula (VII).

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In the formula (VII) , D ⁶ , D ⁷ and D ⁸ each independently have the same meaning as R ¹ . D ⁶ and D ⁷ or D ⁷ and D ⁸ or D ⁶ and D ⁸ may form a ring structure, and the ring structure is D ⁴
And D ⁵ are synonymous. M represents an anion that neutralizes the cation charge in the substituent. The anion may be any of an inorganic anion or an organic anion, and is preferably a perchlorate ion, an iodine ion, a bromine ion, or a substituted arylsulfonate ion (for example, p-toluenesulfonate ion). is there. D ⁶ ,
D ⁷ and D ⁸ each preferably independently represent an alkyl group having 1 to 6 carbon atoms or a benzyl group. Examples of the quaternary imidazole group include the following general formula (VIII).

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In the formula (VIII) , D ⁹ has the same meaning as R ¹ . M has the same meaning as described above. R ⁹ is preferably a substituted or unsubstituted alkyl group. The repeating unit represented by the formula (VI) 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 (VI) , the formula (V
Any monomer may be used as long as it corresponds to another repeating unit copolymerizable with the polymer component of I) . Preferably, it is a vinyl compound, and more specifically, methacrylates, acrylates, styrenes, heterocyclic vinyls, and the like. These other monomers are used in an amount not exceeding 90 mol% in the total polymer component of the polymer dye fixing agent. The repeating unit represented by the formula (VI) and other polymer components may be present in the polymer in a random form or a block form. Hereinafter, specific representative examples of the dye fixing agent used in the present invention will be described, but the present invention is not limited thereto. (The 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.
No. 5,124, No. 3,148,061, JP-A-60
-118834, 60-122941, JP-A-6
Dye fixing agents described in JP-A-2-244043 and JP-A-62-244036 are exemplified. 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
No. 853, No. 4,450,224, JP-A-48-2
8325 and the like. Other preferred examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Patent Nos. 3,709,690, 3,898,088, and 3,958,995. And JP-A-60-57836, JP-A-60-60643, and JP-A-60-60643.
0-122940, 60-122942, 60
-235134 and the like.

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

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[0084]

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[0085]

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[0086]

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[0087]

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The polymer dye fixing agent of the present invention has a molecular weight of 1
× 10 ³ to 1 × 10 ⁶ is suitable, and especially 1 × 10 ⁴ to
2 × 10 ⁵ is preferred. The above-mentioned polymer dye fixing agent may form a receptor layer alone. Further, it can be used by mixing with a synthetic resin described below. The coating amount of the dye fixing agent is suitably from 0.2 to 30 g / m ² , preferably from 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 as a pendant. The polymer dye fixing agent is preferably easily soluble in an organic solvent containing substantially no water. Examples of the organic solvent include toluene, xylene, methylene chloride, chloroform dichloroethane, hexane, pentane, acetone, cyclohexane, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylacetamide, dimethylformamide, methanol, ethanol, isopropanol, acetonitrile, propionitrile, and terola. 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 a mixture with a synthetic resin, those skilled in the art can easily determine the type and composition of the dye fixing agent and the image forming process to be used. Is 10
It is preferably used at a ratio of / 90 to 100/0.

As the synthetic resin, an ordinary synthetic resin can be used as long as it can receive the dye transferred from the transfer sheet. Specifically, it is the following synthetic resin. (A) those having an ester bond: terephthalic acid, isophthalic acid, dicarboxylic acid components such as succinic acid (these dicarboxylic acid components may be substituted with a sulfo 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, 6
No. 3-7971, No. 63-7972, No. 63-797
No. 3 and No. 60-294862. Also, commercially available products include Byron 290, Byron 200, Byron 280, and Byron 3 manufactured by Toyobo.
00, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009, ATR-
2010 or 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, such as polysulfone resin. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride 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 substance capable of accepting a heat transferable dye or as a dye diffusing agent. Specific examples of the high boiling organic solvent and the hot solvent are described in JP-A Nos. 62-174754 and 62-245253.
Nos. 61-209444 and 61-200538
Nos. 62-8145, 62-9348, 62
-30247 and 62-136646.

Further, a mordant and a basic substance for mordanting the dye can be contained. As mordants and basic substances, those described in JP-A-61-64492, JP-A-1-188391, and JP-A-3-83885 can be used. A basic polymer may be used instead of the mordant to dissociate the dye. Examples of the basic polymer include AEA (manufactured by Sankyo Co., Ltd.). Further, 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. Tertiary amines are 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 accepting a heat transferable dye is dispersed in a water-soluble binder and carried. 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. The image receiving layer may be composed of two or more layers. In this case, the layer closer to the support is made of a synthetic resin with a low glass transition point, or a high boiling point organic solvent or a hot solvent is used to enhance the dyeing properties of the dye.The outermost layer has a glass transition point Use a synthetic resin with a higher point, minimize the amount of high-boiling organic solvent or thermal solvent used or minimize the amount of stickiness on the surface, adhesion with other substances, and transfer to other substances. It is desirable to adopt a configuration that prevents failures such as retransfer and blocking with the thermal transfer dye donating material. The thickness of the image receiving layer is 0.5 to 50 μm in total.
m, particularly preferably in the range of 3 to 30 μm. 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 a layer having one or more functions of any of a cushion layer, a porous layer, and a dye diffusion preventing layer, 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 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, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, and the like constituting the thermal transfer image receiving material of the present invention include silica,
Fine powders such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobon, titanium oxide, and alumina may be contained. 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 property, dent after transfer, and the like. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based synthetic paper), high-quality 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 paper backing, 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. And a film or sheet treated to give white reflectivity to this plastic or a laminate of any combination of the above.

The thermal transfer image-receiving material may use a fluorescent whitening agent. For example, K. Vevnkataraman ed., “The Chem
istry of Synthetic Dyes ", Vol. 5, Chapter 8, JP-A-61
Compounds described in -143752 and the like can be mentioned. More specifically, a stilbene compound,
Coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyril-based compounds, 2,5-dibenzoxazole-thiophene-based compounds, and the like can be given. The fluorescent whitening agent can be used in combination with the anti-fading agent. 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 preferable to include a releasability 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 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 isocyanate) is emulsified and dispersed in a water-soluble binder. Is effective to use a carboxy-modified silicone oil (for example, product name: X-22-3710 manufactured by Shin-Etsu Silicone Co., Ltd.).

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. In the case of curing an organic solvent-based polymer, JP-A-61-199997 and JP-A-58-21439.
Hardening agents described in No. 8, etc. can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin. For curing of a water-soluble polymer, see U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
No. 55, No. 62-245261, No. 61-18942
The hardeners described in the above items are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (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. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Further, Japanese Patent Application Laid-Open No. 61-159644
The compounds described in (1) are also effective. As an ultraviolet absorber,
Benzotriazole-based compounds (US Pat. No. 3,533,533)
794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), benzophenone-based compounds (such as JP-A-56-2784), and others.
-48535, 62-136641, 61-8
No. 8256 and the like. In addition, Japanese Unexamined Patent Publication
The UV-absorbing polymer described in -260152 is also effective. As the metal complex, US Pat. No. 4,241,15
No. 5, No. 4,245,018, columns 3-36, No. 4,254,195, columns 3-8, JP-A-62-174.
Nos. 741, 61-88256 (27)-(29)
Page, Japanese Patent Application No. 62-234103, 62-31109
No. 6, Japanese Patent Application No. 62-230596 and the like. Examples of useful anti-fading agents are described in JP-A-62-2.
No. 15272, pages (125) to (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 supplied from the outside to the image receiving material by a method such as transferring from a dye donating material. You may. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

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, promoting development, and the like. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicones) Polyethylene oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like, nonionic surfactants: alkyl carboxylate, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, and other carboxy, sulfo, phospho, sulfate, sulfate, and phosphate groups Anionic surfactants containing an acidic group such as: amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides and other double-sided surfactants: alkylamine salts, aliphatic or aromatic Heterocyclic quaternary salts such as quaternary ammonium salts, viridinium and imidazolium
Cationic surfactants such as secondary ammonium salts and aliphatic or heterocyclic containing phosphonium or sulfonium salts can be used. Specific examples thereof are described in JP-A-62-173463 and JP-A-62-183457.
No. etc. Further, when dispersing a substance capable of accepting a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent whitening agent and other hydrophobic compounds in a water-soluble binder, an interface is used as a dispersing aid. Preferably, an activator is used. For this purpose, besides the above-mentioned surfactants,
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-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, JP-A-61-20944 and JP-A-62-13.
No. 5,826, 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 ethylene tetrafluoride resin. A matting agent can be used for the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 29, benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 952.

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DESCRIPTION OF THE PREFERRED EMBODIMENTS Detailed embodiments of the present invention will be described below. 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 provided with a heat-resistant lubricating layer on one side was used as a support.
On the side opposite to the side provided with the heat-resistant lubricating layer, a dye-donating layer coating composition (1) having the following composition was applied using a gravure coater so that the thickness after drying was 0.6 μm. ,
A thermal transfer dye-providing material (1) (hereinafter also simply referred to as a dye-providing material) was obtained. Dye-donating 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: Takeda Pharmaceutical) 0 0.5 g methyl ethyl ketone 100 ml toluene 80 ml

Preparation of Thermal Transfer Image-Receiving Material (1) A laminated synthetic paper having a thickness of 150 μm was used as a support.
A receiving layer coating composition (1) having the following composition is applied to the surface using a wire bar coater so that the thickness when dried becomes 5 μm, and the thermal transfer image-receiving material (1) (hereinafter simply referred to as the image-receiving material) ) Was produced. Drying was carried out in an oven at 80 ° C. for 1 hour after temporary drying with a dryer. Receptive 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 (Shin-Etsu Silicone KP-857) 0.5 g Methyl ethyl ketone 100 ml Toluene 50 ml Cyclohexanone Preparation of 10 ml of dye-donating materials (2) to (10) The dye-donating materials (2) to (10) were prepared in the same manner except that the dye 28 and the binder resin of the dye-donating material (1) were changed to those shown in Table 7 below. A dye-donating material (A) for comparison with (10) was prepared.

[0103]

[Table 7]

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[0105] transcription experiments obtained as described above, thermal transfer dye-providing material (1) to
A transfer experiment was performed using (10) and (A) and the thermal transfer dye receiving material (1). The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are overlapped so that the dye-providing layer and the receiving layer are in contact with each other. Output of 0.25 W / dot, pulse width of 0.1 to 10 msec,
Heating was performed under the condition of a dot density of 6 dots / mm, and a 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 for reflection density of the image using a reflection densitometer (manufactured by X Rite Inc., built-in status A filter). The recorded image receiving material was allowed to stand in a 60 ° C. oven for 2 weeks, and the degree of image bleeding was observed. The criterion was indicated by ○ when the image hardly changed from that before storage, Δ when the image slightly blurred, and × when the image blurred very much. The results are shown in Table 8 below.

[0106]

[Table 8]

Example2  Preparation of Thermal Transfer Dye Image Receiving Materials (2) to (10)
Polyvinyl acetal resin AEA (manufactured by Sankyo)
Instead, a dye fixing agent and a binder resin shown in Table 9 below are used.
In place of the above, the thermal transfer dye image-receiving materials (2) to
(8) and a comparative image-receiving material (B) without using a dye fixing agent
Produced.

[0108]

[Table 9]

Transfer Experiment Using the dye receiving materials (2) to (10) and (B) thus prepared and the dye donating materials (1) to (6) prepared in Example 1, the method of Example 2 was used. Transfer, density measurement, and bleeding tests were performed. Table 10 shows the results.

[0110]

[Table 10]

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

[0112]

According to the image forming method of the present invention, the transfer density is high, it is possible to obtain a good color, excellent single lifting robustness, good image blurring without storage stability over time.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-89291 (JP, A) JP-A-4-226393 (JP, A) JP-A-6-227163 (JP, A) 30993 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A color containing a heat transferable dye on a support.
A thermal transfer dye-providing material having an element donating layer,
The dye donating layer contains a heat transferable dye represented by the general formula (I).
An image forming method of superimposing a thermal transfer dye-providing material containing at least one kind and a thermal transfer dye image-receiving material, heating according to image information, and thermally diffusing and transferring the dye,
An image forming method, wherein the thermal transfer dye image-receiving material contains a basic substance and / or a mordant. The general formula (I) ## STR1 ## In the formula (I), V represents a nitrogen atom or -CZ =
You. X, Y and Z each independently represent a monovalent substituent. A is a group represented by the following formula (II). Embedded image In the formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent water
Element atom or halogen atom, alkyl group, aryl group,
Terrorist ring, cyano, hydroxy, nitro, amino
Group, alkoxy group, aryloxy group, acylamino
Group, aminocarbonylamino group, sulfamoylamino
Group, alkylthio group, arylthio group, alkoxycal
Bonylamino group, sulfonylamino group, carbamoyl
Group, sulfamoyl group, sulfonyl group, alkoxycal
Bonyl group, heterocyclic oxy group, azo group, acyloxy
Group, carbamoyloxy group, silyloxy group, aryl
Oxycarbonyl group, imide group, heterocyclic thio group, sulf
Finyl group, phosphoryl group, acyl group, carboxylic acid group
(Salt) and a sulfonic acid group (salt). 2. A color containing a heat transferable dye on a support.
In the thermal transfer dye providing material ing a hydrogen donor layer, the
The dye donating layer contains a heat transferable dye represented by the general formula (I).
An image forming method of superimposing a thermal transfer dye-providing material containing at least one kind and a thermal transfer dye image-receiving material, heating according to image information, and thermally diffusing and transferring the dye,
An image forming method, wherein the thermal transfer dye image-receiving material contains a basic substance and / or a mordant. The general formula (I) ## STR3 ## In the formula (I), V represents a nitrogen atom or -CZ =
You. X, Y and Z each independently represent a monovalent substituent. A is a group represented by the following formula (III). Embedded image In the formula (III), Ar is each derived from a diazo component
Optionally substituted aryl or heteroaromatic group
It is.