JP3061318B2 - Thermal dye transfer image forming method - Google Patents

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 with a sharp decrease in sharpness over time.

[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 each information processing system have been developed and adopted. As one of such recording methods, a thermal transfer recording method has been widely used in recent years because a device to be used is lightweight, compact, has no noise, is excellent in operability and maintainability, is easy to colorize, and is easy to use. . The thermal transfer recording method includes a method in which a thermal transfer dye-providing material having a heat-fusible ink layer supported on a support is heated by a thermal head to melt the ink and transfer the image onto an image receiving material (fusion transfer method). A method in which a thermal transfer dye-providing material having a dye-donating layer containing a dye and a binder is heated by a thermal head to thermally transfer only the dye to the image-receiving layer of the image-receiving material to perform recording (thermal transfer method; Thermal transfer method). The present invention relates to a thermal transfer dye-providing material used in the latter thermal transfer method.
Here, the heat transferable dye refers to a dye which can be transferred from a thermal transfer dye-providing material to a thermal transfer image-receiving material by sublimation or diffusion in a medium.

[0003]

However, there are various restrictions on the heat transfer dyes conventionally used in this method, and very few heat transfer dyes have the required performance without insufficiency. The required properties include, for example, having favorable spectral characteristics for color reproduction, being easily transferred to heat, not discoloring or fading to light or heat, being less deteriorated by various chemicals, and being sharp after image formation. Are difficult to lower, the image is hardly retransferred, and the thermal transfer dye-providing material is easily prepared. Among them, the fact that the sharpness is hardly reduced particularly with time is a particularly important performance in image recording. However, conventionally used heat-migrating dyes do not have sufficient performance, and the sharpness is reduced in a short period of time. Therefore, improvement has been desired from the viewpoint of preservation of images. This decrease in sharpness is considered to be due to the fact that the heat transfer dye transferred onto the image receiving paper cannot be fixed sufficiently strongly. In the first place, a heat transferable dye is a dye that exhibits a sufficiently large diffusing ability when heated, and therefore is easily diffused even at room temperature. Therefore, increase the molecular weight of the dye,
If the diffusion at room temperature is suppressed to improve the storability of the image, there is a dilemma that the diffusion at the time of thermal transfer is reduced and an image having a practical density cannot be formed. In order to solve this dilemma, it is considered that the heat transfer dye may be fixed by any method when the heat transfer dye is transferred to the image receiving paper. Several techniques based on this concept have been disclosed. Techniques for forming and fixing a chelate dye from a compound capable of forming a chelate and a polyvalent metal ion in an image receiving paper are disclosed in JP-A-60-22997, JP-A-60-2398 and JP-A-60-2398.
Nos. 3-140884, 61-219691, 61
No. 31289, No. 59-48189, No. 63-29
No. 254, No. 59-171687, No. 59-7889
No. 3, JP-A-1-105789, JP-B-2-4143
No. 1. This technique has a major drawback in that the polyvalent metal ion compound contained in the image receiving paper has low temporal stability and the image receiving paper is colored with time. Japanese Patent Application Laid-Open Nos. 60-46296 and 61-154995 disclose a technique in which a basic dye and an electron accepting substance are reacted in an image receiving layer to fix the basic dye to a positive charge.
Nos. 58-220788 and 63-173,692. This technology includes light, heat,
It had a major drawback of low robustness to the atmosphere. In the first place, basic dyes are generally less fast than disperse dyes and the like used in ordinary sublimation transfer systems. Therefore, the low fastness of the image according to the above method is due to the fastness of the basic dye, and is a serious problem. Japanese Patent Application Laid-Open Nos. 61-14994 and 61-18574 disclose a technique in which a leuco dye and an electron acceptor are reacted in an image receiving paper to form a dye and immobilize the dye.
No. 2, JP-B-63-32635. This technique also has a drawback that the formed image has low robustness to light, heat, air, and the like. This disadvantage is also a major problem due to the low fastness of the dye derived from the leuco 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 same is disclosed in Japanese Patent Publication No. 62-14763. If this technique is applied to thermal transfer as it is, there is a problem in the temporal stability of the thermal transfer dye-providing material because the reactive dye is unstable. Techniques for generating and fixing a dye by a chemical reaction in an image receiving paper are disclosed in JP-A-61-31293 and U.S. Pat. No. 5,011,811. This technique has problems in the absorption characteristics and fastness of the produced dye. Further, there is a disadvantage that it is difficult to satisfy other important performances required for the dye because the structure of the dye to be formed is restricted due to the necessity of forming the dye in a short time by a chemical reaction.

Accordingly, the present inventor has proposed that the dye having excellent absorption as a dye for image formation and having high fastness to light, heat, air, moisture, chemicals, and the like, has absorption and fastness of the dye within the molecule. It was considered that if the dye in which a basic atomic group was introduced via a linking group so as not to affect it was transferred to an image-receiving paper containing an acidic substance, the dye would be immobilized by electrostatic interaction. As a result, according to the above method, the dye is sufficiently strongly immobilized, and, unlike the conventionally known immobilization method, a dye having high robustness can be selected and used, so that the robustness of the formed image is improved. The present invention was found to be high, and the present invention was completed.

Here, the prior art will be described. JP-A-3-205189 describes a dye in which an amino group is bonded to a dye molecule via a linking group, and specific compound examples are also exemplified. (Dye numbers 63, 64,
65, 70, 94, 105, 106). Further, Example 10 of the above specification describes an experiment in which a dye is transferred 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 at all. This is because, in the examples of the above specification, transfer to an image receiving layer to which a substituted phenol is added is not performed using a dye having an amino group bonded to the molecule via a linking group. Further, in the specification, there is no description about a peculiar phenomenon (dye is fixed) due to a combination of a dye having an amino group and an image receiving layer containing a phenol. That is, it is impossible to predict the specific effects of the present invention from the description in the above specification. Also, JP-A-3-30993 and JP-A-3-262689.
Nos. 3-7386 and 3-88851 also exemplify dyes having an amino group bonded to the molecule via a linking group. However, also in these, there is no description of Examples in combination with an image receiving material containing an acidic substance, and there is no description on the effects thereof.

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal dye capable of improving the sharpness of an image over time without impairing the properties required for a heat transferable dye such as hue, fastness to light and heat, and transferability. An object of the present invention is to provide a transfer image forming method.

The present invention has been achieved by the following method. A thermal transfer dye-providing material having a dye-providing layer containing a heat-migrating dye on a support is heated in accordance with image information or uniformly, and a dye image is formed on a thermal transfer dye-receiving material superimposed on the thermal transfer dye-providing material. 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): .

Embedded image A- (LB) _q (I)

[0008]

In the formula, A represents a dye residue having absorption in the visible region and / or infrared region, L represents a divalent linking group, B represents a basic atomic group, and q represents 1 Represents an integer of 1 to 3. When q is 2 or more, LB may be the same or different. Two or more LBs may be bonded to each other. However, the acidic substance contained in the image receiving material is as follows:
A compound containing an acidic group represented by the general formula (P) or an acidic compound
If it is a polymer or copolymer of the compound containing a group
Excludes General formula (P)

Embedded image (In the formula, X represents a leaving group, and Y represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring together with -C = N-.)

Hereinafter, the present invention will be described in more detail. A in the general formula (I) represents a dye residue having absorption in a visible region and / or an infrared region. The dye residue of the present invention can be used in principle with any structure as long as it has absorption in the visible region and / or the infrared region. In view of the nature of the present invention in which thermal transfer is performed, a dye residue having excellent thermal transferability is preferred. As the dye residue having excellent thermal transferability, a dye residue having a relatively low molecular weight and a high molar extinction coefficient and hardly causing association and crystallization of dyes is preferable. Dyes used for sublimation transfer hard copy and dye residues used for sublimation dyeing are suitable for these. As dyes for sublimation transfer hard copy and dyes 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 preferred.

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In the formula (III), R ¹ , R ² and R ³ represent an atomic group required for the dye residue represented by the formula (III) to complete an azomethine dye having visible and / or infrared absorption. Express. R ¹ and R ² may combine 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 or p-aminophenols. Examples of the coupler compound include phenols, naphthols, or 5-pyrazolones, 1H-pyrazolo [1,5-a] benzimidazoles, and 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; and active methylene compounds such as acylacetonitrile, acylacetanilide, diacylmethane, and malondianilide. No. R ³ is derived from p-phenylenediamines or p-aminophenols which 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 below.

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

[0018]

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In the formula (V), R ⁶ and R ⁹ are each 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 that can be substituted on a benzene ring. R
²⁴ and R ²⁵ each independently represent a hydrogen atom, 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 an alkyl group (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),
A halogen atom (eg, bromine, fluorine, chlorine), an acylamino group [preferably an 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
-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) Alkylcarbamoyl groups such as 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 having 4 carbon atoms
To 20 hetenylcarbamoyl 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 0 to 20, for example, methylsulfamoyl, dimethylsulfamoyl), an aminocarbonylamino group (preferably having 1 to 20, for example, methylaminocarbonylamino, Dimethylaminocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino), hydroxy group, amino group (preferably having 0 to 20 carbon atoms such as 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 or 2-pyridyl) Frills, 2
-Tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 20 carbon atoms, for example, phenoxy, p-
Methoxyphenoxy, o-chlorophenoxy), a sulfamoylamino group (preferably having 0 to 20, for example, methylsulfamoylamino, dimethylsulfamoylamino), an 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),
A sulfonyl group (preferably having 1 to 20 carbon atoms, for example, methanesulfonyl, p-toluenesulfonyl), an acyl group (preferably having 1 to 20 carbon atoms, for example, formyl, acetyl, benzoyl, p-toluyl), a heterocyclic oxy group (preferably Represents 3 to 20 carbon atoms, an azo group (preferably 3 to 20 carbon atoms, for example, p-nitrophenylazo), an acyloxy group (preferably 1 to 20 carbon atoms, for example, acetyloxy, benzoyloxy), and a carbamoyloxy group ( It preferably has 1 to 20 carbon atoms, for example, methylcarbamoyloxy), and 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), and 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 a hydrogen atom. R ⁷ and R ^{8 each} represent an alkyl group (1 to 30 carbon atoms), an alkoxy group (1 to 30 carbon atoms), an aryloxy group (6 to 30 carbon atoms), a cyano group, an acyloxy group (1 to 30 carbon atoms), Alkoxycarbonyl group (C1-30), aryloxycarbonyl group (C6-30), aminocarbonyl group (C1-3)
0) is preferred. R ⁶ is preferably —NR ²⁴ R ²⁵ .
R ²⁴ and R ²⁵ each independently represent an alkyl group (C 1
To 30) and an aryl group (6 to 30) are preferred. R
^9, -OH or ^-NR 24 ^{R 25} are preferred.
R ²⁴ and R ²⁵ are preferably each independently a hydrogen atom, an alkyl group (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 , or —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 each independently represent
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 combine with each other to form a ring structure. More preferably, R ¹⁴ is a cyano group or a hydrogen atom. R ^{16, R 17} are each independently a cyano group, -COOR ²⁶ (carbon number 2 to 30), - C
ONR is ²⁶ R ²⁷ (1 to 30 carbon atoms). R ⁵ is p
Position is an aryl group substituted with ^{-NR 28, R 29 (6~30} carbon atoms). 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.

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 that can be substituted on a benzene ring. Specific examples of the substituent that can be substituted on the benzene ring include:
R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R in the formula (V)
¹³ can be mentioned.

Among the dye residues represented by A, general formula (II)
Those represented by I) and (IV) are most preferred.

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 (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 -or -NR ³⁰ SO ₂ NR ^31- alone or in combination. R ³⁰ , R ³¹
Each independently represents a hydrogen atom, an alkyl group, or an aryl group. However, the residue showing basicity represented by B in 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 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 sterically twisted, and the π electron system of the A portion and the B portion is substantially changed. Must be insulated.

Specific examples of -L- include an alkylene group (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. −
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. Conversely, when it is required to immobilize the dye sufficiently strongly, q is preferably 2 or 3.

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

The atomic group showing basicity is more preferably selected in combination with the constituents of the image-receiving paper, the constituents of the dye-providing material, and the structure of the dye residue used in the present invention. As a viewpoint for this selection, for example, basicity and nucleophilicity can be mentioned. For example, when the nucleophilicity or basicity is high, a nucleophilic reaction is performed on the dye residue to reduce the preservability of the dye or a hardening agent of isocyanates used when preparing a thermal transfer dye-providing material. Adverse effects such as reacting with On the other hand, when the basicity is low, sufficient interaction with the acidic substance in the image receiving paper does not occur, and the dye is not sufficiently fixed.

As a measure of the basicity of a basic substance, the pKa value of the conjugate acid of the basic substance is generally widely known. Preferable dyes having an atomic group showing basicity according to the present invention are those having a pKa value of the conjugate acid in the range of 3.0 to 14.0 as measured in water at 25 ° C.

The conjugate acid has a pKa value of 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. The pKa of the conjugate acid is 3 to 1.
Examples of the basic organic compound in the range of 4.0 include the following. Aniline derivatives Conjugated 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 heterocycle Quinoline 4.9 Piperazine 9.8 Morpholine 8.3 Isoquinoline 5.4

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

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

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

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Hereinafter, specific examples of the dye represented by formula (I) used in the present invention will be shown.

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The acidic substance contained in the thermal transfer dye image-receiving material used in the present invention is an acidic substance defined by Bronsted and Lewis. Among acidic substances,
Carboxylic acid group, sulfonic acid group, phenolic hydroxyl group, enol hydroxyl group, active methylene group, -CO-NH-CO
_{-, - SO 2 -NH-CO} -, - SO 2 -NH-SO 2
Organic compounds having at least one group such as —, as a substituent are preferred.

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

The pKa value is widely known as a scale representing the acidity of an acidic substance. The preferred acidic substance of the present invention has a pKa value of 25 ° C. and a value measured in water of 3.
It is in the range of 0 to 14.0. Among them, those having a pKa value in the range of 6.0 to 11.0 are more preferable. The most preferred 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 has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group,
Enol hydroxyl group, active methylene group, -CO-NH-C
_{O -, - SO 2 -NH-} CO -, - SO 2 -NH-SO
_It may be a polymer having a ₂ -group or the like. The above-mentioned polymer may be used as a main component for constructing the image receiving layer, or may be used by adding to the polymer of the main component.

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 preferred when image robustness is required. Examples of the atomic group having the effect of suppressing fading include the atomic groups described in JP-A-3-205189.

Preferred among the above atomic groups are those represented by the formula (V)
III), (IX), (X) and (XI).

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In the formula (VIII), X represents —O— or
-NR ⁴⁶ -is represented. R ⁴⁶ is a hydrogen atom or an optionally substituted alkyl group. R ³² represents an alkyl group which may be substituted. R ³³ , R ³⁴ , R ³⁵ , R
³⁶ and R ³⁷ each independently represent a hydrogen atom or a nonmetallic substituent. However, at least one 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.

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 each} represent a hydrogen atom, an optionally substituted alkyl group (1 to 30 carbon atoms), an optionally substituted alkoxy group (1 to 30 carbon atoms),
It is an acylamino group (1-30 carbon atoms). R ³⁵ is -O
Is -R ^32. R ³² is an optionally substituted alkyl group (having 1 to 30 carbon atoms).

In the 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 nonmetallic substituent.

More preferably, R ³⁸ is an optionally substituted arylcarbonyl group (C 7-30) or an optionally substituted benzotriazole ring group.
R ³⁹ , R ⁴⁰ , R ⁴¹ and R ^{42 each} represent a hydrogen atom, an alkyl group (1 to 30 carbon atoms), an alkoxy group (1 to 30 carbon atoms), an acylamino group (1 to 30 carbon atoms), an alkoxycarbonyl group ( Carbon number 1-30).

In the formula (X), R ⁴³ , R ⁴⁴ and R ⁴⁵ are
Represents a hydrogen atom, an optionally substituted alkyl group, or an aryl group. In the formula (XI), R ^{38 ′} , R ^{39 ′} , R
^{40 ′} , R ^{41 ′} and R ^{42 ′} represent a hydrogen atom or a substituent that can be substituted on a benzene ring. R ^{38 '} , R ^42'
Is preferably an alkyl group. R ^{39 ′} and R ^{41 ′} are preferably a hydrogen atom. R ^{40 ′} represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group,
Aminocarbonyl, acyloxy and acylamino groups are preferred. More preferably, R ⁴³ , R ⁴⁴ , R ⁴⁵
Is an optionally substituted alkyl group (1 to 30 carbon atoms)
It is. The atomic group having the effect of suppressing fading and the acidic substance include 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 , or R ⁴⁵ . The following are specific examples.

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It is preferable to select and use an atomic group that effectively suppresses fading of the dye used from these atomic groups. 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.

Preferred examples of the combination of an atomic group having the effect of suppressing fading and the dye residue represented by A in the general formula (I) will be described. When the dye residue of A has a structure represented by the formula (III), it is preferable to select an atom group represented by the formula (VIII) as an atomic group having an effect of suppressing fading. In particular, when A has a structure derived from a pyrazolotriazole coupler, the effect of suppressing fading is particularly large and is preferred. The above combination mainly suppresses light fading of the dye.

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

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

When the dye residue A has a structure derived from a phenol or naphthol coupler, selecting (IX) as an 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 per unit area. Preferably.

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

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A preferred combination of the basic 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 group represented by B and pK value 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 the combination are described below.

Basic Substance Acidic Substance Contained in Image Receiving Layer of Conjugated Acid pKa Value pKa Value 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 5.0. Morpholine 8.3 p-nitrophenol 7.2 6. Benzylamine 9.3 phthalimide 8.3 7. Benzylamine 9.3 m-nitrophenol 9.3 8. 8. Ethylenediamine 10.0 Phenol 10.0 Triethylamine 11.0 Phenol 10.0 10. Pyrrolidine 13.0 CH ₃ COCH ₂ COOEt 11.0 However, the basic substance is 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
Combinations in the range of 7.0-11.0 are most preferred.

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

The heat transferable dye is contained in a dye-donor layer on a support to form a thermal transfer dye-donor material, which is used for image formation by a thermal 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, a full-color image can be formed by using the dye represented by the general formula (I) as one of the three primary colors and selecting the other two colors from known dyes. Further, two kinds of three primary colors of the dye represented by the general formula (I) may be used, and the other color may be selected from known dyes. For the same color, a 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 as the same color.

The method of using 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, a continuous roll, or a ribbon. The heat-migrating dyes are usually arranged on a support so as to form independent regions. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. Alternatively, three types of thermal transfer dye-providing materials each having the above-mentioned yellow dye, magenta dye, and cyan dye separately provided on a support may be prepared, and thermal transfer of the dye to one thermal transfer image-receiving material may be sequentially performed from these materials. . The dye of the present invention and the dye used in combination with the dye may be dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or may be printed on the support by a printing method such as a gravure method. it can.
It is preferable that the thickness of the dye-donating layer containing these dyes is set to a range of usually about 0.2 to 5 μm, particularly 0.4 to 2 μm in dry film thickness. The coating amount of the dye is 0.03 to 1.0
g / m ² are preferred. Among them, 0.1 to 0.6 g / m ²
Is more preferred.

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.
In addition, one that does not hinder the transfer of the dye when heated is 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 resins (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resins, polystyrene-polyphenylene oxide, cellulose resins (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 preferably used, for example, at a ratio of 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 an ink solvent for dissolving or dispersing the above-mentioned dye and 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,
Examples include polyphenylene sulfide, polypropylene, polysulfone, cellophane and the like. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm.

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 a sticking preventing treatment on the side of the support on which the dye donating layer is not provided.

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.

The dye-providing material may be provided with an undercoat layer.

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 having excellent sharpness and resolution gradation 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 the case of using a laser as the heat source, the thermal transfer dye-providing material preferably contains a material that strongly absorbs laser light. When the thermal transfer dye-providing material is irradiated with laser light, the absorbing material converts the light energy into thermal energy, transfers that heat to the nearby dye, and is heated to a temperature at which the dye transfers to the thermal transfer image-receiving material. The absorbent material is present in a layer below the dye and / or is mixed with the dye. A more detailed description of this process can be found in UK Patent 2,083,7.
No. 26A. As the above laser,
Several lasers are available, but small, low cost,
Semiconductor lasers are preferred in terms of stability, reliability, durability, and ease of modulation.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material, so that printing using various thermal printing printers, facsimile, or magnetic recording, magneto-optical recording, optical recording, etc. Can be used to create prints from television, television, and CRT screens. For details of the thermal transfer recording method, reference can be made to JP-A-60-34895.

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

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

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: polyester resins and the like. (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. (D) Other materials having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin and the like. In addition to the above synthetic resins, mixtures or copolymers thereof can also be used.

In the thermal transfer image-receiving material, especially in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a diffusion aid for 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 accepting a heat transferable dye is dispersed and supported in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener is preferable. The image receiving layer may be composed of two or more layers. In this case, use a synthetic resin with a low glass transition point for the layer closer to the support, or use a high-boiling organic solvent or a heat solvent to enhance the dyeing properties of the dye. 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, transfer to other substances after transfer. It is desirable to adopt a configuration that prevents failures such as retransfer and blocking with the thermal transfer dye donating material. The total thickness of the image receiving layer is 0.5 to
A range of 50 μm, especially 3 to 30 μm is preferred. In the case of a two-layer structure, the outermost layer is 0.1 to 2 μm, particularly 0.2 to 1 μm
It is preferable to set it in the range. The image receiving layer may optionally contain another type of dye fixing agent. As the dye fixing agent, any of mordants described in JP-A-3-83885 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 constituent material,
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 in some cases also serves as an adhesive.

If the support used in the thermal transfer image-receiving material can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, and dents after transfer, etc. Anything can be used.

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

In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the surface of the layer constituting 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 release agent in the outermost layer corresponding to the above.

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

A vinyl sulfone hardener (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (such as 62-23415
No. 7, etc.).

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. 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 with each other.

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

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.

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

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. Example 1 (Preparation of Thermal Transfer Dye Donating Material (1-1)) A 6 μm thick polyethylene terephthalate film (manufactured by Teijin) having a heat-resistant lubricating treatment applied to the back surface was used as a support. The thickness of the coating composition for a thermal transfer dye-providing layer having a dry composition of 1.
It was applied and formed so as to have a thickness of 5 μm to prepare a thermal transfer dye-providing material (1-1). Coating composition for thermal transfer dye donating layer: Dye 1 10 mmol Polyvinyl butyral resin (Denka Butyral 5000-A manufactured by Denki Kagaku) 3 g Toluene 40 cc Methyl ethyl ketone 40 cc Polyisocyanate (Takenate D1 10N manufactured by Takeda Pharmaceutical) 0.2 cc The thermal transfer dye-providing material of the present invention and the comparative thermal transfer dye-providing materials (1-2) to (1-18) were prepared in the same manner as described above except that the other dyes described 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 Oil Chemical Co., Ltd.)
-150), a thermal transfer image-receiving material was prepared by applying a coating composition for an image-receiving layer having the following composition to the surface thereof by wire bar coating so that the thickness when dried was 8 μm. Drying was carried out in a oven at a temperature of 100 ° C. for 30 minutes after preliminary drying with a drier. Coating composition for image receiving layer: 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-providing materials (1-1) to (1-18) thus obtained and the thermal transfer image-receiving material were
The thermal transfer dye-donor layer and the image receiving layer are superposed so as to be 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 ms, Printing was performed under the conditions of a dot density of 6 dots / mm, and a dye was dyed on the image receiving layer of the image receiving material in an image-like manner. 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 color images (decrease in sharpness) was examined. Further, the recorded image receiving material was irradiated with a fluorescent lamp of 17,000 lux for 7 days, and the light fastness of the color image was examined. Status A reflection densities before and after irradiation were measured, and the ratio was used to evaluate stability. (Measured in the region where the concentration is 1.0.) The results are shown in Table 1.
Shown in No. for comparison. 19, JP-A-3-92385.
The results for the sample prepared and transcribed in Example 1 of No. 1 are shown. (Page 12 of the specification, the first row of Table 2).
Thermal recording material No. 1 (using Dye-2) and image receiving material A).

(Table 1) No. Thermal transfer dye Color density Maximum density Image fastness Remarks Light fastness (%) Sharpness 1 1-1 1 2.0 69 ○ The present invention 2 1-2 2 2.4 89 ○ ３ 3 1-3 4 2.591 ○ 〃 4 1-4 92.889 ○ ５ 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 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 ○

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The fastness of the image was evaluated as follows. ：: No reduction in sharpness is visually observed. Δ: わ ず か Slightly observed visually. X: The image is blurred and the sharpness is easily reduced visually. As described above, it can be seen 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 apparent that the image transfer sharpness of the thermal transfer dye-providing material 1-19 using the comparative dye a having no basic moiety via a linking group in the dye molecule is significantly reduced. Furthermore, in the comparative sample by the known fixing method, although the sharpness did not decrease, 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 in place of the acidic substance I-12 of the coating composition for the image receiving layer in Example 1. ) Was prepared. When transfer was performed using the thermal transfer dye-providing materials (1-1) to (1-18) prepared in Example 1, clear images without transfer unevenness were obtained. In addition, as a result of the forced test, light fastness was excellent, and sharpness did not decrease. On the other hand, in the image of the sample subjected to thermal transfer using (2-10) containing no acidic substance, the blur was remarkable in the test made by heat and heat.
Table 3 shows the results. (Table 2) No. Thermal transfer dye image-receiving material Acidic substance Remarks 1 2-1 I-1 Present invention 22-2 I-2 〃3 2-3 I-3 ２4 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 Remarks 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 31- 3 4 2-3 I-3 ○ △ 4 1-4 9 2-4 I-5 ○ △ 5 1-5 12 2-5 I-11 ○ △ 61-6 13 2-6 I-13 ○ △ 7 1-7 17 2-7 I-16 ○ 〃 8 1-8 19 2-8 I-17 ○ ９ 9 1-9 22 2-9 I-36 ○ 〃 10 1-5 12 2-10 None × Compare An example

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

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-141092 (JP, A) JP-A-4-110193 (JP, A) JP-A-5-58060 (JP, A) JP-A-5-58060 212976 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (4)

(57) [Claims] 1. A support comprising a dye donating layer containing a heat transferable dye.
The thermal transfer dye-providing material having the above, according to the image information,
Or uniformly heated in the heat dye transfer image forming method for forming a dye image to a thermal transfer dye providing material and superimposed on the thermal transfer dye image-receiving material, the thermal transfer dye image-receiving material has an acidic substance, and the An image forming method, wherein the heat transferable dye is represented by the following general formula (I). A- (LB) _q (I) In the formula, A represents a dye residue having absorption in a visible region and / or an infrared region, L represents a divalent linking group, and B represents basicity Represents an atomic group, and q represents an integer of 1 to 3.
When q is 2 or more, LB may be the same or different. Two or more LBs may be bonded to each other. However
And the acidic substance contained in the image receiving material is represented by the following general formula:
A compound containing an acidic group represented by (P) or a compound containing an acidic group
Except when the compound is a polymer or copolymer of the compound.
Good. General formula (P) (In the formula, X represents a leaving group, and Y represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring together with -C = N-.) 2. The method according to claim 1, wherein the acidic substance is an organic compound having a carboxylic acid group and / or a sulfonic acid group and / or a phenolic hydroxyl group and / or an enol hydroxyl group and / or an active methylene group. 2. The image forming method according to 1., 3. The image forming method according to claim 2, wherein in the general formula (I), the basic group B showing the basicity is represented by an amine residue. A- (LB) _q (I) In the formula, A represents a dye residue having absorption in a visible region and / or an infrared region, L represents a divalent linking group, and B represents basicity Represents an atomic group, and q represents an integer of 1 to 3.
When q is 2 or more, LB may be the same or different. Two or more LBs may be bonded to each other. 4. The image forming method according to claim 3, wherein the acidic substance has an atomic group having an effect of suppressing fading of the dye in the molecule.