JPH05238174A - Thermal dye-transfer image forming method - Google Patents

Abstract

PURPOSE:To prevent the lowering of the sharpness angle of an image formed by thermal transfer with the elapse of time and to prevent the lowering of the fastness of the image against light and heat at the same time by thermally transferring a thermal transfer dye expressed by a specific general formula to a thermal transfer image substance from a thermal transfer dye donating material. CONSTITUTION:A thermal transfer dye donating material wherein a dye donating layer containing a thermal transfer dye is provided on a support is heated corresponding to image data or uniformly to form a dye image on the thermal transfer dye image receiving material superposed on the thermal transfer dye donating material. The thermal transfer dye image receiving material contains an acidic substance and the thermal transfer dye is expressed by formula I (wherein L is a divalent connection group, B is an atom group showing basicity, q is an integer of 1-3 and L and B may be the same or different when q is 2 or more). As a result, the lowering of the sharpness angle of an image formed by thermal transfer with the elapse of time can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal dye transfer image forming method capable of forming an image in which the sharpness of an image is less likely to decrease.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is light and compact, noise-free, excellent in operability and maintainability, and easy to colorize. . The thermal transfer recording method is a method in which a thermal transfer dye-donating material carrying a heat-fusible ink layer on a support is heated by a thermal head to melt the ink and transfer it to the image receiving material (melt transfer method), and thermal transferability. A thermal transfer dye-donor material having a dye-donor layer containing the dye and a binder is heated by a thermal head to transfer only the dye to the image-receiving layer of the image-receiving material for recording (heat transfer method. It is also called a thermal transfer method). The present invention relates to a thermal transfer dye-donor element used in the latter thermal transfer system having this content.
Here, the heat transferable dye means a dye which can be transferred from the thermal transfer dye-donating material to the thermal transfer image-receiving material by sublimation or diffusion in a medium.

[0003]

However, there are various restrictions on the heat transferable dyes conventionally used in this system, and there are very few heat transferable dyes that have the required performances. Required properties include, for example, having preferable spectral characteristics for color reproduction, easy heat transfer, no discoloration or fading due to light or heat, little deterioration by various chemicals, and sharpness after image formation. Is less likely to decrease, image retransfer is less likely to occur, and a thermal transfer dye-donor material is easier to prepare. Among these, it is a particularly important performance in image recording that the sharpness is not likely to decrease with time. However, the heat transferable dyes that have been used conventionally do not have sufficient performance, and the sharpness is lowered in a short period of time, and improvement from the viewpoint of image preservation has been desired. It is considered that this decrease in sharpness is due to the fact that the heat transferable dye transferred onto the image receiving paper cannot be fixed sufficiently strongly. In the first place, the heat transferable dye is a dye showing a sufficiently large diffusivity by being heated, and therefore, it is fairly easy to diffuse even at room temperature. Therefore, increase the molecular weight of the dye,
If it is attempted to suppress the diffusion at room temperature to improve the storability of the image, therefore, there is a dilemma that the diffusivity at the time of thermal transfer is also reduced and an image having a practical density cannot be formed. In order to solve this dilemma, it is considered that the heat transferable dye may be fixed by some method when the heat transferable dye is transferred to the image receiving paper. Some technologies based on this idea are disclosed. A technique of forming a chelate dye from a compound capable of forming a chelate and a polyvalent metal ion in an image-receiving paper and immobilizing the chelate dye is disclosed in JP-A-60-22997, JP-A-60-2398, and JP-A-60-2398.
No. 3-144084, No. 61-219691, No. 61
-31289, 59-48189, 63-29.
No. 254, No. 59-171687, No. 59-7889.
No. 3, JP-A-1-105789, Japanese Patent Publication No. 2-4143
No. 1 is disclosed. This technique has a major drawback in that the polyvalent metal ion compound contained in the image receiving paper has low stability over time and the image receiving paper is colored over time. Further, a technique of reacting a basic dye with an electron accepting substance in the image-receiving layer to immobilize the basic dye by positively charging it is disclosed in JP-A-60-46296 and 61-154995.
Nos. 58-220788 and 63-173692. This technology includes light, heat, and
It had a major drawback of low fastness to the atmosphere. In the first place, basic dyes are generally less fast than disperse dyes used in ordinary sublimation transfer systems. Therefore, the low image fastness of the above method is due to the basic fastness of the dye, which is a big problem. Then, a technique of reacting a leuco dye with an electron accepting substance in an image receiving paper to form a dye and immobilize it is disclosed in JP-A-61-14994 and 61-18574.
No. 2 and Japanese Examined Patent Publication No. 63-32635. This technique also has a drawback that the formed image has low fastness to light, heat, air and the like. This drawback is also a big problem due to the low fastness of the leuco dye-derived dye. Further, in the field of transfer dyeing, a technique of forming a covalent bond with a dyeing substance by using a reactive dye and immobilizing the dye is disclosed in Japanese Patent Publication No. 62-14673. If this technique is applied to thermal transfer as it is, the reactive dye is unstable, so that there is a problem in stability over time of the thermal transfer dye-providing material. Then, a technique of forming a dye by a chemical reaction in an image receiving paper and immobilizing the dye is disclosed in JP-A-61-31293 and US Pat. No. 5,011,811. This technique has a problem in absorption characteristics and fastness of the produced dye. Furthermore, since it is necessary to generate a dye in a short time by a chemical reaction, the structure of the dye formed is limited, and it is difficult to satisfy other important performances required for the dye.

Therefore, the inventor of the present invention has excellent absorption as a dye for image formation and has high fastness to light, heat, air, moisture, chemicals, etc. in the molecule of the dye. It was thought that the dye would be immobilized by electrostatic interaction if the dye having a basic atomic group introduced through a linking group so as not to affect it was transferred onto an image-receiving paper containing an acidic substance, and the inventors conducted diligent studies. As a result, according to the above method, the dye is sufficiently strongly immobilized, and unlike the conventionally known immobilization method, since a dye having high fastness can be selected and used, the fastness of the formed image can be improved. The inventors have found that it is high and completed the present invention.

Here, the conventional technique will be described. JP-A-3-205189 describes a dye in which an amino group is bonded to a dye molecule through a linking group, and specific compound examples are also illustrated. (Dye numbers 63, 64,
65, 70, 94, 105, 106). Further, Example 10 in the above specification describes an experiment for transferring a dye using an image receiving layer to which a substituted phenol which is an acidic substance is added. However, even if the above is known,
The present invention is not limited in any way. This is because, in the examples of the above-mentioned specification, transfer to the image receiving layer to which the substituted phenol is added is not carried out by using the dye in which the amino group is bonded to the molecule through the linking group. Further, in the specification, there is no description about a peculiar phenomenon (the dye is fixed) due to the combination of the dye having an amino group and the image receiving layer containing a phenol. That is, it is impossible to predict the unique effects of the present invention from the description in the above specification. Also, JP-A-3-30993 and 3-262689.
Nos. 3,7,386, and 3,88,851 also exemplify dyes having an amino group bonded to the molecule through a linking group. However, also regarding these, there is no description of Examples in combination with an image receiving material containing an acidic substance, and no description of their effects.

The object of the present invention is to improve the deterioration of the sharpness of an image with the passage of time without impairing the performance required for a heat transferable dye such as hue, fastness to light and heat, and transferability. A transfer image forming method is provided.

The present invention has been achieved by the following method.
A thermal transfer dye-donor material having a dye-donating layer containing a heat-transferable dye is heated on a support in accordance with image information or uniformly, and a dye image is formed on the thermal transfer dye-receiving material superposed with the thermal transfer dye-donating material. A method of forming a thermal dye transfer image, wherein the thermal transfer dye image-receiving material contains an acidic substance, and the heat transferable dye is represented by the following general formula (I).

[0008]

[Chemical 3]

In the formula, A represents a dye residue having absorption in the visible region and / or infrared region, L represents a divalent linking group, and B represents an atomic group exhibiting basicity. q
Represents an integer of 1 to 3. When q is 2 or more, L
-B may be the same or different. 2 or more LB
May be combined.

The present invention will be described in more detail below. A in the general formula (I) represents a dye residue having absorption in the visible region and / or infrared region. The dye residue of the present invention can be used in principle having any structure as long as it has absorption in the visible region and / or the infrared region. Due to the nature of the present invention of thermal transfer, a dye residue having excellent thermal transfer properties is preferred. As the dye residue having excellent thermal transfer properties, those having a relatively low molecular weight and a high molar extinction coefficient, and those in which dyes are less likely to associate or crystallize are preferable. Suitable for these are dyes used for sublimation transfer hard copy and residues of dyes used for sublimation dyeing. As a dye for sublimation transfer hard copy and a dye for sublimation dyeing,
Examples thereof include dye residues such as azo dyes, azomethine dyes (including indoaniline dyes), anthraquinone dyes, naphthoquinone dyes, styryl dyes, quinophthalone dyes, bisazo dyes, merocyanine dyes and methine dyes. Among them, the following general formulas (III), (IV), (V),
Those represented by (VI) and (VII) are preferable.

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

In the formula (III), R ¹ , R ² and R ³ are the atomic groups necessary for completing the azomethine dye in which the dye residue represented by the formula (III) has visible and / or infrared absorption. Represent. R ¹ and R ² may combine with each other to form a ring structure. More specifically, R ¹ and R ² are derived from a coupler compound that forms an azomethine dye by an oxidative coupling reaction with p-phenylenediamines and p-aminophenols. Examples of the coupler compound include phenols, naphthols, 5-pyrazolones, 1H-pyrazolo [1,5-a] benzimidazoles, 1H-pyrazolo [5,1-c] -1,2,4. -Triazoles, 1H-pyrazolo [2,3-b] -1,
Heterocycles having active hydrogen such as 2,4-triazoles and 2,4-diphenylimidazoles, as well as active methylene compounds such as acylacetonitriles, acylacetanilides, diacylmethanes and malondianilides. Can be mentioned. R ³ is derived from p-phenylenediamines and p-aminophenols that form an azomethine dye by an oxidative coupling reaction with a coupler compound. R ³ is preferably a substituted or unsubstituted aryl group substituted at the p-position with a substituted amino group or an —OH group. Specific examples of the substituent in the case of being substituted include those described for R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the formula (V) described later.

In the formula (IV), R ⁴ represents an optionally substituted aryl group or heteroaryl group, or an active methylene residue. R ⁵ represents an aryl group or a heteroaryl group. R ⁴ and R ⁵ are selected so that the formula (IV) is an azo dye having absorption in the visible or near infrared. R ⁴ is a phenyl group in which the p-position is substituted with a substituted amino group (4-diethylaminophenyl, 2-acetylamino-4-diethylaminophenyl, N-ethyl-N-benzyl-4-aminophenyl), pyridone residue, amino Examples include pyrazole residue, pyrazolone residue, imidazole residue, aminothiophene residue, β-naphthol residue, phenol residue, aminoisothiazole residue, pyrazolotriazole residue, dimedone residue, acylacetanilide residue, etc. As. R ⁵ is derived from an azo component that reacts with a coupler to form an azo dye. R ⁵ represents a phenyl group which may be substituted, (having 6 to 30 carbon atoms, for example, phenyl, m-chlorophenyl, p-nitrophenyl, m
-Methoxyphenyl), optionally substituted isothiazole residue, thiazole residue, thiophene residue, triazole residue, thiadiazole residue and the like. A specific example is shown below.

[0018]

[Chemical 9]

In the formula (V), R ⁶ and R ⁹ are independently-
Represents NR ²⁴ R ²⁵ or OH. R ⁷ , R ⁸ , R ¹⁰ ,
R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring. R ²⁴ and R ²⁵ each independently represent an optionally substituted alkyl group or an optionally substituted aryl group.

Specific examples of R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include alkyl groups (preferably having 1 to 2 carbon atoms).
0, for example, methyl, ethyl, propyl, butyl), an alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy),
Halogen atom (eg bromine, fluorine, chlorine), acylamino group [preferably alkylcarbonylamino group having 1 to 20 carbon atoms (eg formylamino, acetylamino,
Propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 20 carbon atoms (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (preferably carbon). Number 2
To 20, for example, methoxycarbonyl, ethoxycarbonyl), cyano group, sulfonylamino group (preferably having 1 to 20 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), carbamoyl group [preferably having 2 carbon atoms]. 20 alkylcarbamoyl groups (eg methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxy) Carbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl Phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl), preferably an arylcarbamoyl group having 7 to 20 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
To 20 heterylcarbamoyl groups (eg 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methylphenyl)) 1, 3, 4
-Thiadiazolylcarbamoyl)], a sulfamoyl group (preferably having a carbon number of 0 to 20, such as methylsulfamoyl, dimethylsulfamoyl), an aminocarbonylamino group (preferably having a carbon number of 1 to 20, such as methylaminocarbonylamino, Dimethylaminocarbonylamino), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino), a hydroxy group, an amino group (preferably having 0 to 20 carbon atoms, for example, amino, methylamino,
Dimethylamino, anilino), an aryl group (preferably having 6 to 20 carbon atoms such as phenyl, m-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 20 carbon atoms such as 2-pyridyl, 2- Frills, 2
-Tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 20 carbon atoms, for example, phenoxy, p-
Methoxyphenoxy, o-chlorophenoxy), sulfamoylamino group (preferably having 0 to 20 carbon atoms, for example, methylsulfamoylamino, dimethylsulfamoylamino), alkylthio group (preferably having 1 to 2 carbon atoms).
0, for example, methylthio, ethylthio), an arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio, p
-Methoxyphenylthio, o-chlorophenylthio),
Sulfonyl group (preferably having 1 to 20 carbon atoms, for example, methanesulfonyl, p-toluenesulfonyl), acyl group (preferably having 1 to 20 carbon atoms, for example, formyl, acetyl, benzoyl, p-toluyl), heterocyclic oxy group (preferably Is C3-20), an azo group (preferably C3-20, for example p-nitrophenylazo), an acyloxy group (preferably C1-20, for example, acetyloxy, benzoyloxy), a carbamoyloxy group ( Preferably, it has 1 to 20 carbon atoms, for example, methylcarbamoyloxy), a silyloxy group (preferably 3 to 2 carbon atoms).
0, for example, trimethylsiloxy), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, for example, phenoxycarbonyl), an imide group (preferably having 4 to 2 carbon atoms).
0, for example, phthalimide, a heterocyclic thio group (preferably having 3 to 20 carbon atoms), a sulfinyl group (preferably having 1 to 20 carbon atoms, for example, diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 20 carbon atoms, for example, diaminophosphoryl). ), An azolyl group (preferably having 2 to 2 carbon atoms)
0, for example 2-pyrazolyl).

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are preferably
It is a hydrogen atom. R ⁷ and R ⁸ are alkyl groups (having 1 to 1 carbon atoms)
30), alkoxy groups (C1 to C30), aryloxy groups (C6 to C30), cyano groups, acyloxy groups (C1 to C30), alkoxycarbonyl groups (C1 to C30), aryloxy. Carbonyl group (6 to 6 carbon atoms
30) and an aminocarbonyl group (having 1 to 30 carbon atoms) are preferable. R ⁶ is preferably —NR ²⁴ R ²⁵ . R ²⁴ and R ²⁵ are preferably each independently an alkyl group (having 1 to 30 carbon atoms) or an aryl group (6 to 30). R ⁹ is —OH or —NR ²⁴
R ²⁵ is preferred. R ²⁴ and R ²⁵ are preferably each independently an alkyl group (having 1 to 30 carbon atoms) or an aryl group (6 to 30).

In the formula (VI), R ¹⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or a cyano group. R ¹⁶ and R ¹⁷ each independently represent a cyano group, —COOR ²⁶ , —CONR ²⁶ R ²⁷ , an optionally substituted aryl group, or an optionally substituted alkyl group. R ¹⁵ is, p--position -OR ^26, -NR ²⁸ R ²⁹
Represents an aryl group substituted with. R ²⁶ , R ²⁷ , R ²⁸ ,
R ^29's each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R ¹⁴ and R ²⁶ and / or R ¹⁴ and R ²⁸ may combine with each other to form a ring structure. More preferably, R
¹⁴ is a cyano group or a hydrogen atom. R ¹⁶ and R ¹⁷ are each independently a cyano group, —COOR ²⁶ (having 2 to 30 carbon atoms), and —C.
ONR ²⁶ R ²⁷ (having 1 to 30 carbon atoms). R ⁵ is an aryl group (having 6 to 3 carbon atoms) substituted at the p-position with —NR ²⁸ and R ^29.
0). R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.

In the formula (VII), R ¹⁸ represents a hydroxyl group. R
¹⁹ , R ²⁰ , R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring.

Among the dye residues represented by A, one represented by the general formula (II
Most preferred are those represented by I) and (IV).

In the general formula (I), L represents a divalent linking group. As the divalent linking group, an arylene group (having 6 carbon atoms
To 30), an alkylene group (having 1 to 30 carbon atoms), -S-,
^{-O -, - NR 30 -,} - SO -, - SO 2 -, - NR 30
_{^{CO -, - NR 30 SO 2}} -, - NR 30 COO -, - NR
It is preferable to use ³⁰ CONR ³¹ −, —NR ³⁰ SO ₂ NR ³¹ − alone or in combination. R ³⁰ , R ³¹
Each independently represent a hydrogen atom, an alkyl group or an aryl group. However, the basic residue represented by B of the formula (I) and the dye residue represented by A are combined so as not to be conjugated by π electrons. Therefore, in the case of other than the alkylene group, the plane of the dye and the plane of the linking group and / or the plane of the linking group and the π electron of the B residue are twisted three-dimensionally, so that the A part and the B part π electron system are substantially separated. I have to insulate.

Specific examples of -L- include alkylene groups (having 1 to 30 carbon atoms, for example, methylene, ethylene, n-
_{Butylene, -CH (CH 3) -CH 2} -, n- octylene), an arylene group (4 to 30 carbon atoms, such as phenylene, naphthylene), - NHCO -, - N (CH 3) CO
_{-, - NHSO 2 -, -} N (CH 3) SO 2 -, - NHC
ONH-, -NHSO ₂ NH-, and the like. −
The most preferred of L- is an alkylene group.

Q represents an integer of 1 to 3. When high transferability of the dye is required, q is preferably 1 from the viewpoint of reducing the molecular weight of the dye. On the contrary, when the dye is required to be immobilized sufficiently strongly, q is preferably 2 or 3.

B in the general formula (I) represents an atomic group showing basicity. Basicity is according to Bronsted's definition and Lewis's definition.

The basic atomic group is more preferably selected in combination with the constituents of the image receiving paper used in the present invention, the constituents of the dye-donor material, and the structure of the dye residue. Examples of viewpoints for selection include basicity and nucleophilicity. For example, when the nucleophilicity or basicity is high, a nucleophilic reaction is performed on a dye residue to reduce the storage stability of the dye, or a hardener for isocyanates used when preparing a thermal transfer dye-donating material. The adverse effect such as reacting with occurs. On the other hand, when the basicity is low, sufficient interaction does not occur with the acidic substance in the image receiving paper, and the dye is not sufficiently immobilized.

As a measure of the basicity of a basic substance, the pKa value of the conjugate acid of the basic substance is generally known. The dye having a basic atomic group of the present invention is preferably one in which the pKa value of this conjugate acid is in the range of 3.0 to 14.0 as measured in water at 25 ° C.

The pKa value of this conjugate acid is 3.0 to 14.0.
Examples of the compound in the range include an organic compound having an amino group (including a substituted amino group and a substituted anilino group) and a nitrogen-containing heterocyclic group. PKa of conjugate acid is 3-1
The following are mentioned as an example of the basic organic compound in the range of 4.0. Aniline derivative Conjugate acid pKa o-toluidine 4.7 m-toluidine 5.1 p-toluidine 5.1 N-methylaniline 4.8 aniline 4.6 alkylamine derivative methylamine 10.7 ethylenediamine 10.0 n-butylamine 10.8 Benzylamine 9.3 Nitrogen-containing heterocycles Quinoline 4.9 Piperazine 9.8 Morpholine 8.3 Isoquinoline 5.4

Among them, the conjugate acid pK is more preferable.
The a value is in the range of 6.0 to 11.0.

The basic atomic group represented by B is most preferably a tertiary amino group having a conjugate acid pKa value in the range of 8.0 to 11.0.

Specific examples of the amine residue and the nitrogen-containing heterocyclic residue are shown below.

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

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

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

The acidic substance contained in the thermal transfer dye image-receiving material used in the present invention is an acidic substance according to Bronsted's definition and Lewis's definition. Among the acidic substances,
Carboxylic acid group, sulfonic acid group, phenolic hydroxyl group, enolic hydroxyl group, active methylene group, -CO-NH-CO
_{-, - SO 2 -NH-CO} -, - SO 2 -NH-SO 2
An organic compound having at least one group such as-and the like as a substituent is preferable.

From the above-mentioned acidic substances, it is preferable to select and use a preferable acidic substance depending on the combination with the constituent substance of the image-receiving paper used in the present invention and the dye. As a point of view when selecting this, for example, acidity can be mentioned. When the acidity is high, the interaction between acid and base becomes strong, but on the other hand, adverse effects such as accelerated fading of the dye under acidic conditions occur. On the contrary, when the acidity is low, sufficient interaction between acid and base does not occur, and the dye is not sufficiently immobilized.

The pKa value is widely known as a measure of the acidity of an acidic substance. The preferable acidic substance of the present invention has a pKa value of 25 ° C. and a measured value in water of 3.
It is in the range of 0 to 14.0. Among them, the pKa value is more preferably in the range of 6.0 to 11.0. The most preferable acidic substance contained in the image-receiving layer of the present invention is a substituted phenol having a pKa value in the range of 9.0 to 11.0.

The acidic substance used in the present invention includes a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group as a partial structure,
Enolic hydroxyl group, active methylene group, -CO-NH-C
_{O -, - SO 2 -NH-} CO -, - SO 2 -NH-SO
_It may be a polymer having ₂ -groups. The above-mentioned polymer may be used as a main component for constructing the image receiving layer, or may be added to the main component polymer and used.

The acidic substance contained in the image receiving layer is preferably an organic compound having an atomic group having an effect of suppressing fading. It is particularly preferable when image fastness is required. Examples of atomic groups having an effect of suppressing fading include the atomic groups described in JP-A-3-205189.

Preferred among the above atomic groups are those of the formula (VII
I), (IX), and (X).

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

[0056]

[Chemical formula 24]

In the formula (III), X is --O-- or --NR.
⁴⁶ - represents a. R ⁴⁶ is a hydrogen atom or an optionally substituted alkyl group. R ³² represents an optionally substituted alkyl group. R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each independently represent a hydrogen atom or a non-metal substituent. However,
At least one of R ³³ and R ³⁵ is —O— or —NR ⁴⁶
− R ⁴⁶ is a hydrogen atom or an optionally substituted alkyl group.

More preferably, X is --O--. R ³²
Is an optionally substituted alkyl group (having 1 to 3 carbon atoms).
0). R ³³ , R ³⁴ , R ³⁶ , and R ³⁷ are each a hydrogen atom, an optionally substituted alkyl group (having 1 to 30 carbon atoms), an optionally substituted alkoxy group (having 1 to 30 carbon atoms),
It is an acylamino group (having 1 to 30 carbon atoms). R ³⁵ is -O
-R ³² . R ³² is an optionally substituted alkyl group (having 1 to 30 carbon atoms).

In formula (IX), R ³⁸ represents an optionally substituted arylcarbonyl group, an optionally substituted heterocyclic group, or an optionally substituted alkylcarbonyl group. R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² represent a hydrogen atom or a non-metal substituent.

More preferably, R ³⁸ is an optionally substituted arylcarbonyl group (having 7 to 30 carbon atoms) or an optionally substituted benzotriazole ring group.
R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are each a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms), an alkoxy group (having 1 to 30 carbon atoms), an acylamino group (having 1 to 30 carbon atoms), an alkoxycarbonyl group ( It has 1 to 30 carbon atoms.

In the formula (X), R ⁴³ , R ⁴⁴ and R ⁴⁵ represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. More preferably, R ⁴³ , R ⁴⁴ and R ⁴⁵ are an optionally substituted alkyl group (having 1 to 30 carbon atoms). Specific examples will be given below.

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

[Chemical 30]

From these atomic groups, it is preferable to select and use an atomic group that suppresses fading of the dye used particularly effectively. When a plurality of dyes are used, it is preferable to select and use an atomic group that is particularly effective for the dye having the lowest fastness.

Examples of preferable combinations of an atomic group having an effect of suppressing fading and a dye residue represented by A of the general formula (I) will be given. When the dye residue of A has a structure represented by the formula (III), it is preferable to select an atomic group represented by the formula (VIII) as an atomic group having an effect of suppressing fading. Among them, when A has a structure derived from a pyrazolotriazole coupler, the effect of suppressing fading is particularly large and preferable. The above combination mainly suppresses photobleaching of the dye.

When the dye residue of A has a structure represented by the formula (IV), an atomic group having an effect of suppressing fading is
It is preferable to select those of formula (VIII) and formula (X). These mainly suppress the photobleaching of the dye.

(I of an atomic group having an effect of suppressing fading is
The structure of formula (X) suppresses photobleaching of almost any dye regardless of the structure of the dye residue.

When the dye residue of A has a structure derived from a phenol and a naphthol coupler, selecting (IX) as the atomic group having an effect of suppressing fading can suppress the thermal fading of the dye.

The coating amount of the acidic substance in the image-receiving layer is selected so as to be equal to or more than the number of moles of the dye per unit area in the maximum density region of the transferred image. Preferably.

Specific examples of the acidic substance used in the present invention are shown below.

[0075]

[Chemical 31]

[0076]

[Chemical 32]

[0077]

[Chemical 33]

[0078]

[Chemical 34]

Preferred combinations of the basic atomic group represented by B and the acidic substance contained in the image receiving paper will be described below. PKa value of the conjugate acid of the basic atomic group represented by B and pK of the acidic substance contained in the image receiving paper
It is preferable that the a values are substantially equal or the pKa value of the acidic substance is smaller. Specific examples of combinations will be described below.

Basic substance Conjugate acid contained in image-receiving layer pKa value pKa acidic substance 1. Aniline 4.6 2,4-dinitrophenol 4.0 2. Aniline 4.6 Benzoic acid 4.2 3. Pyridine 5.2 HCOCH ₂ COH 5.0 4. Isoquinoline 5.4 CH ₃ COOH 5.0 5. Morpholine 8.3 p-nitrophenol 7.2 6. Benzylamine 9.3 Phthalimide 8.3 7. Benzylamine 9.3 m-nitrophenol 9.3 8. Ethylenediamine 10.0 Phenol 10.0 9. Triethylamine 11.0 Phenol 10.0 10. Pyrrolidine 13.0 CH ₃ COCH ₂ COOEt 11.0 However, the basic substance was described using a model compound having no dye residue.

Among these combinations, both the pKa value of the conjugate acid of the basic substance and the pKa value of the acidic substance are
Most preferably, the combination is in the range of 7.0 to 11.0.

A preferable combination of the dye residue and the acidic substance is a combination of the dyes represented by the formulas (III) and (IX) and the substituted phenol (pKa value 7.0 to 11.0).

The heat transferable dye is contained in the dye-donor layer on the support to form a heat-transfer dye-donor material, which is used for image formation in the heat transfer system. Next, the image forming method of the present invention will be described in detail below. Usually, in order to form a full-color image, dyes of three primary colors of yellow, magenta and cyan are required. Therefore, the dye represented by the general formula (I) can be used as one of the three primary colors, and the other two colors can be selected from known dyes to form a full-color image. Also, two kinds of dyes of three primary colors represented by the general formula (I) may be used, and the other one color may be selected from known dyes and used. For the same color, the dye represented by the general formula (I) and a conventionally known dye may be mixed and used. Further, two or more kinds of the dyes represented by the general formula (I) may be mixed and used in the same color.

The usage of the heat transferable 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 heat transfer dye is usually arranged on the support so as to form independent areas. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. 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 separately provided on a support, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be performed sequentially. .. The dye of the present invention and the dye used in combination with it may be dissolved or dispersed in a suitable solvent together with a binder resin and applied on a support, or printed on a support by a printing method such as a gravure method. it can.
The thickness of the dye-donor layer containing these dyes is usually about 0.2 to 5 μm, preferably 0.4 to 2 μm, as a dry film thickness. The amount of dye applied is 0.03 to 1.0
g / m ² is preferred. Among them, 0.1 to 0.6 g / m ²
Is more preferable.

As the binder resin used together with the above-mentioned dye, any of the binder resins known in the related art for such purpose can be used, and usually has high heat resistance,
Moreover, one that does not interfere with the migration of the dye when heated is 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 resins (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 preferably used in a proportion of, for example, about 20 to 600 parts by weight per 100 parts by weight of the dye.

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. Any conventionally known support can be used as the support of the thermal transfer dye-providing material. For example polyethylene terephthalate,
Polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide,
Examples thereof include polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm.

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 heat from the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to carry out anti-sticking treatment on the side of the support on which the dye-donor layer is not provided.

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.

The dye-donor element may be provided with an undercoat layer.

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 the back side of the thermal transfer dye-providing material, by means of heating means such as a thermal head. By applying energy, the dye of 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 having excellent sharpness and resolution gradation can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and known means such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In the case of using a laser as the heat source, it is preferable that the thermal transfer dye-providing material contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into thermal energy, transfers the heat to the dye in the immediate vicinity, and is heated to a temperature at which the dye transfers to the thermal transfer image-receiving material. The absorbent material is layered below the dye and / or is mixed with the dye. For a more detailed description of this process, see British Patent 2,083,7.
26A. As the above laser,
Several lasers are available, but small, low cost,
A semiconductor laser is preferable in terms of stability, reliability, durability and ease of modulation.

In the present invention, the thermal transfer dye-donating material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system, etc. It can be used to make prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to.

The image-receiving paper receives the dye that has transferred heat,
A constitution in which an image receiving layer having a function of forming an image is formed on one surface of the support is preferable.

The image-receiving layer is a film containing an acidic substance, which forms an ion pair with the dye and consequently has the effect of fixing the dye, alone or together with other binder substances.

The thickness of the image receiving layer is preferably 0.5 to 50 μm. Among them, 3 to 30 μm is particularly preferable.

As the binder substance used in the image receiving layer,
The following polymers are preferred.

(A) Those having an ester bond, such as polyester resin. (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. (D) Others having a highly polar bond Polycaprocraton resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the synthetic resin as described above, a mixture or copolymer of these may be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling point organic solvent or a thermal solvent as a diffusion aid of the heat transferable dye. The image receiving layer of the thermal transfer image receiving material 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 a higher dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used as the outermost layer. Using a synthetic resin with a higher point, or sticking the surface to other substances, 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 failures such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to
A range of 50 μm, particularly 3 to 30 μm is preferable. In the case of a two-layer structure, the outermost layer is 0.1-2 μm, especially 0.2-1 μm
It is preferable that it is within the range. The image-receiving layer may optionally contain other types of dye fixing agents. As the dye fixing agent, any of the mordants described in JP-A-3-83685 and those described in JP-A-1-188391 can be used.

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer depends on the material
It is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, and also serves as an adhesive in some cases.

The support used for the thermal transfer image-receiving material can withstand the transfer temperature, and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, and dent after transfer. Anything can be used.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the present invention, in order to improve the releasability between the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably, the surfaces of both materials contacting each other. It is preferable to add a release agent to the outermost layer corresponding to the above.

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.

Vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane etc.), N-methylol type hardeners (dimethylol urea etc.) or polymer hardeners (special Kaisho 62-23415
Compounds described in No. 7).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. 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 of transferring from the dye providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

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 peeling property, improvement of sliding property, antistatic property, acceleration of development and the like.

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 static charge, improving releasability and the like.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material.

[0108]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following specific examples as long as the gist of the invention is not exceeded. Example 1 (Preparation of Thermal Transfer Dye-donating Material (1-1)) A polyethylene terephthalate film (manufactured by Teijin) having a thickness of 6 μm and having a heat resistant slip treatment on the back surface was used as a support, and the following was formed on the surface of the film. The coating composition for the thermal transfer dye-donating layer having the composition is dried by wire bar coating to have a thickness of 1.
A thermal transfer dye-donor material (1-1) was prepared by coating so as to have a thickness of 5 μm. Coating composition for thermal transfer dye-donating layer: Dye 1 10 mmol Polyvinyl butyral resin (Denkabu Chirar 5000-A manufactured by Denki Kagaku) 3 g Toluene 40 cc Methyl ethyl ketone 40 cc Polyisocyanate (Takenate D1 10N manufactured by Takeda Pharmaceutical Co., Ltd.) 0.2 cc Thermal transfer dye-donor materials of the present invention and comparative thermal transfer dye-donor materials (1-2) to (1-18) were prepared in the same manner as above except that the other dyes shown in Table 1 were used.

(Preparation of thermal transfer image-receiving material) Synthetic paper having a thickness of 150 μm (YUPO-FPG manufactured by Oji Yuka Co., Ltd.) as a support.
-150) was used to apply a coating composition for an image receiving layer having the following composition to the surface by wire bar coating so that the thickness when dried was 8 μm to prepare a thermal transfer image receiving material. Drying was carried out for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition for image-receiving layer: Acidic substance I-12 2.2 g Polyester resin (Vylon-280 manufactured by Toyobo) 22 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 2.0 g Methyl ethyl ketone 85 cc Toluene 85 cc Cyclohexanone 15 cc

The thermal transfer dye-donor materials (1-1) to (1-18) obtained as described above and the thermal transfer image-receiving material were
The thermal transfer dye-donor layer and the image-receiving layer are superposed so that they are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donor material, the output of the thermal head is 0.25 W / dot, the pulse width is 0.15 to 15 milliseconds, Printing was performed under the condition of a dot density of 6 dots / mm, and a dye was dyed imagewise on the image-receiving layer of the image-receiving material. As a result, clear image recording without transfer unevenness was obtained. Next, each of the recorded thermal transfer image-receiving materials obtained as described above was stored for 14 days at 80 ° C. under dry conditions, and the stability of the color image (decrease in sharpness) was examined. Further, the recorded image receiving material was irradiated to a fluorescent lamp of 17,000 lux for 7 days, and the light fastness of the color image was examined. The Status A reflection density before and after irradiation was measured, and the stability was evaluated by the ratio. (Measurement was carried out in the region where the density was 1.0.) The results are shown in Table 1.
Shown in. For comparison, No. Japanese Patent Laid-Open No. 3-92385
The results for the samples prepared and transferred in Example 1 of the publication are shown. (Specification, page 12, second row of table.
Thermal recording material No. 1 (using Dye-2) and the image receiving material A).

(Table 1) No. Thermal transfer dye Maximum color density Image fastness Remarks Donor No. Light fastness (%) Sharpness 1 1-1 1 2.0 69 ○ The present invention 2 1-2 2 2.4 89 ○ 〃 3 1-3-3 4 2.5 91 ○ 〃 4 1-4 2.8 89 89 ○ 〃 5 1-5 12 3.0 71 ○ 〃 6 1-6 13 2.9 69 ○ 〃 7 1-7 17 2.6 72 ○ 〃 8 1-8 19 2.5 65 ○ ○ 〃 9 1-9 22 2.4 82 ○ 〃 10 1-10 26 2.0 85 ○ 〃 11 1-11 33 2.2 91 ○ 〃 12 1-12 35 2.5 90 ○ 〃 13 1-13 37 2.1 91 ○ 〃 14 1-14 46 2.1 90 ○ 〃 15 1-15 50 1.9 72 ○ 〃 16 1-16 52 1.9 85 ○ 〃 17 1-17 56 2.2 86 ○ 〃 18 1-18 a 2.9 36 × Comparative example 19 1.0 34 ○ 〃

[0112]

[Chemical 35]

The image fastness was evaluated as follows. ◯: No decrease in sharpness is visually observed. △: 〃 slightly visible. X: The image is blurred and the sharpness is easily deteriorated by visual observation. As described above, it is understood that the sharpness of the image formed by the image forming method of the present invention does not decrease even under the forced condition. On the other hand, it is clear that the sharpness of the image is remarkably lowered in the thermal transfer dye-donor material 1-19 using the comparative dye a having no basic portion through the linking group in the dye molecule. Further, in the comparative sample obtained by the known fixing method, the sharpness was not lowered, but the light fastness of the image was extremely low because the fastness of the dye was low.

Example 2 The thermal transfer dye image-receiving materials (2-1) to (2-9) were prepared by using the acidic substances shown in Table 2 instead of the acidic substance I-12 of the image-receiving layer coating composition of Example 1. ) Was produced. When transfer was performed using the thermal transfer dye-donor materials (1-1) to (1-18) produced in Example 1, a clear image having no transfer unevenness was obtained. As a result of the forced test, the light fastness was excellent and the sharpness was not lowered. On the other hand, the image of the sample subjected to the thermal transfer using (2-10) containing no acidic substance was markedly blurred in the heat strength test.
The results are shown in Table 3. (Table 2) No. Thermal transfer dye image receiving material Acidic substance Remarks 1 2-1 I-1 Present invention 2 2-2 I-2 〃 3 2-3 I-3 〃 4 2-4 I-5 〃 5 2-5 I-11 〃 6 2-6 I-13 〃 7 2-7 I-16 〃 8 2-8 I-17 〃 9 2-9 I-36 〃 10 2-10 None Comparative example (Table 3) No. Thermal transfer dye Dye Thermal transfer dye Acidic substance Image fastness Remark Donor material Image receiving material (sharpness) 1 1-1 1 2-1 I-1 ○ Present invention 2 1-2 2 2-2 I-2 ○ 〃 3 1- 3 4 2-3 I-3 ○ 〃 4 1-4 9 2-4 I-5 ○ 〃 5 1-5 12 2-5 I-11 ○ 〃 6 1-6 13 2-6 I-13 ○ 〃 7 1-7 17 2-7 I-16 ○ 〃 8 1-8 19 2-8 I-17 ○ 〃 9 1-9 22 2-9 I-36 ○ 〃 10 1-5 12 2-10 None × Comparison An example

As described above, according to the thermal transfer method of the present invention, a high density and vivid image can be obtained. In addition, the sharpness of the image does not deteriorate over time, and the light fastness of the image is high.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 23, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

In the formula (V), R ⁶ and R ⁹ are independently-
Represents NR ²⁴ R ²⁵ or OH. R ⁷ , R ⁸ ,
R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring. R
²⁴ and R ²⁵ each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are preferably hydrogen atoms. R ⁷ and R ⁸ are an alkyl group (having 1 to 30 carbon atoms), an alkoxy group (having 1 to 30 carbon atoms), an aryloxy group (having 6 to 30 carbon atoms), a cyano group, an acyloxy group (having 1 to 30 carbon atoms), Alkoxycarbonyl group (C1 to C30), aryloxycarbonyl group (C6 to C30), aminocarbonyl group (C1 to C3)
0) is preferred. R ⁶ is preferably —NR ²⁴ R ²⁵ .
R ²⁴ and R ²⁵ are each independently an alkyl group (having 1 carbon atom).
.About.30) and aryl groups (6 to 30) are preferred. R
⁹ is preferably -OH or -NR ²⁴ R ²⁵ .
R ²⁴ and R ²⁵ are preferably each independently a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms), or an aryl group (6 to 30).

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

In the formula (VI), R ¹⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or a cyano group. R ^{16, R 17} are each independently a cyano ^group, -COOR 26, -CONR ²⁶ R
²⁷ represents an optionally substituted aryl group or an optionally substituted alkyl group. R ¹⁵ is —O at the p-position
R ^26, represents an aryl group substituted with ^-NR 28 ^{R 29.} R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are each independently
It represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R ¹⁴ and R
²⁶ and / or R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring structure. More preferably, R ¹⁴ is a cyano group or a hydrogen atom. R ¹⁶ and R ¹⁷ are each independently a cyano group, —COOR ²⁶ (having 2 to 30 carbon atoms), and —C.
ONR ²⁶ R ²⁷ (having 1 to 30 carbon atoms). R ⁵ is p
The position is an aryl group (having 6 to 30 carbon atoms) substituted with -NR ²⁸ and R ²⁹ . R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹
Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

In the formula (VII), R ¹⁸ represents a hydroxyl group. R ¹⁹ , R ²⁰ , R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring. Specific examples of the substituent capable of substituting on the benzene ring are:
R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , and R in formula (V)
^The ones mentioned in ¹³ can be mentioned.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Chemical 15]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

[Chemical 16]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

[Chemical 19]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Of the above atomic groups, preferred are those of formula (V
III), (IX), (X), and (XI).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

[Chemical formula 24]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction content]

In the formula (VIII), X is --O-- or
-NR ⁴⁶ - represents a. R ⁴⁶ is a hydrogen atom or an optionally substituted alkyl group. R ³² represents an optionally substituted alkyl group. R ³³ , R ³⁴ , R ³⁵ , R
³⁶ and R ³⁷ each independently represent a hydrogen atom or a non-metal substituent. However, at least 1 of R ³³ and R ³⁵
One may, -O- or ^{-NR 46} - it is. R ⁴⁶ is a hydrogen atom or an optionally substituted alkyl group.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

In the formula (X), R ⁴³ , R ⁴⁴ and R ⁴⁵ are
It represents a hydrogen atom, an optionally substituted alkyl group or an aryl group. In formula (XI), R ^{38 ′} , R ^{39 ′} , R
^{40 ′} , R ^{41 ′} and R ^{42 ′} represent a hydrogen atom or a substituent capable of substituting on the benzene ring. R ^{38 '} , R ^42'
Is preferably an alkyl group. R ^{39 ′} and R ^{41 ′} are preferably hydrogen atoms. R ^{40 ′} represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group,
An aminocarbonyl group, an acyloxy group and an acylamino group are preferred. More preferably, R ⁴³ , R ⁴⁴ , R ⁴⁵
Is an optionally substituted alkyl group (having 1 to 30 carbon atoms)
Is. The atomic group having an effect of suppressing fading and the acidic substance are R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R.
³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R
⁴³ , R ⁴⁴ , and R ⁴⁵ are bonded to each other. Specific examples will be given below.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

[0063]

[Chemical formula 26]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

From these atomic groups, it is preferable to select and use an atomic group that suppresses fading of the dye used particularly effectively. When a plurality of dyes are used, it is preferable to select and use an atomic group that is particularly effective for the dye having the lowest fastness.

Claims (4)

[Claims] 1. A thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye on a support according to image information.
Alternatively, in the thermal dye transfer image-forming method of forming a dye image on the thermal transfer dye image receiving material which is heated uniformly and superposed with the thermal transfer dye image providing material, the thermal transfer dye image receiving material contains an acidic substance, and A migrating dye is represented by the following general formula (I). [Chemical 1] In the formula, A represents a dye residue having absorption in the visible region and / or infrared region, L represents a divalent linking group, and B represents an atomic group exhibiting basicity. q represents an integer of 1 to 3. When q is 2 or more, L-B may be the same or different. Two or more LBs may be bonded to each other. 2. The thermal dye transfer image forming method according to claim 1, wherein the acidic substance contained in the thermal transfer dye image receiving material is a carboxylic acid group and / or a sulfonic acid group and / or a phenolic hydroxyl group and / or an enolic hydroxyl group and / or
Alternatively, an organic compound having active methylene. 3. The thermal transfer dye in the thermal dye transfer image forming method according to claim 2, which is represented by the following general formula (II). [Chemical 2] In the formula, A represents a dye residue having absorption in the visible region and / or infrared region, L represents a divalent linking group, and B represents
Represents an amine residue. q represents an integer of 1 to 3. When q is 2 or more, L-B may be the same or different. 4. The thermal dye transfer image forming method according to claim 3, wherein the acidic substance contained in the thermal transfer dye image receiving material has an atomic group in the molecule which has an effect of suppressing fading of the dye. What to do.