JPH07112583A - Thermal transfer dye donating material - Google Patents

Abstract

PURPOSE:To provide a thermal transfer dye donating material capable of being used many times and obtaining recording not causing the blur or color transfer of an image during preservation. CONSTITUTION:A thermal transfer dye donating material is used in combination with an image receiving material wherein a receiving layer containing a diene compd. (or dienophile compd.) is provided on a support and formed by successively laminating a thermal transfer dye donating layer containing a dye having dienophile (or diene) and a dye transfer coatributing layer on the support.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer dye-donor element, and more particularly to a thermal transfer dye-donor element for multiple recording.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer systems have been known. Among them, a thermal transfer dye is used as a recording agent, and a thermal transfer dye is supported on a support such as paper or plastic film to obtain a thermal transfer dye-donating material. A method of forming various full-color images on a thermal transfer image-receiving material such as paper or a plastic film provided with a dye receiving layer has been proposed. In this case,
A thermal head or a laser beam is used as a heating means, a large number of three-color or four-color dots are transferred to an image receiving material by heating for an extremely short time, and a full-color image of an original is reproduced by the multi-color dots. Is. However, in this method, one yellow, magenta, and cyan (and black) dye-donor elements are used to obtain one full-color image, and each dye-donor element is heated according to the image signal. To get a recorded image, after use,
Even if an unused portion remains, each dye-providing material is discarded, so that the running cost is high.
Therefore, in order to improve this drawback, a so-called multiple recording method has recently been proposed in JP-A-5-64981 in which the same dye-donor material is repeatedly used for recording an image. Specifically, the dye-donor material and the image-receiving material are superposed and run at a constant speed on the thermal head to perform thermal transfer recording, and the method is repeated and the speed of the image-receiving material to the thermal head is set to the thermal speed of the dye-donor material. The speed is greater than the speed for the head and n times (n>
There is an n-times mode method of traveling at the speed of 1). However, these constant velocity and n-fold mode multiple recording methods cause clear transfer due to reverse transfer of dye from the receiving layer to the dye-donor layer, resulting in color turbidity during the next transfer and ghost of previous recorded information. There are times when you cannot obtain a good image. Therefore, the above-mentioned deterioration in image quality can be improved by adopting a two-layer structure of a dye supplying layer having a high dye concentration and a dye transfer contributing layer having a low dye concentration. That is, the dye corresponding to the amount consumed from the dye transfer contributing layer for image formation is replenished from the dye supply layer, and the image quality of multiple transfer is improved. In order to facilitate the supply of the dye from the dye supplying layer to the dye transfer contributing layer, the dye concentration should be set to the dye supplying layer> the dye transfer contributing layer, and the dye supplying layer with respect to the thermal diffusion coefficient representing the heat transfer property of the dye> It is effective to establish the relationship of the dye transfer contributing layer. A low molecular weight dye is effective for increasing the concentration of the dye in each layer and increasing the thermal diffusion coefficient. However, simply lowering the molecular weight of the dye may cause the dye in the receptor layer to re-diffuse in a state where the image-receiving material on which the image is recorded is stored, and the image may be blurred. Further, when the recorded receiving layer is stored by being overlapped with another substance, for example, an untransferred image-receiving sheet, the dye in the image may be transferred to the other substance and may be contaminated.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to provide a thermal transfer recording material which can be transferred and recorded many times, is clear without color turbidity or ghost, and is free from bleeding or contamination during storage of image records. Is.

[0004]

The above-mentioned object is a thermal transfer dye-donating material which is used in combination with a thermal transfer image-receiving material having a dye-receiving layer for receiving a heat-transferable dye on a support. The material is formed by laminating a dye supply layer and a dye transfer contributing layer each containing a heat transferable dye in a binder in order from the support side, and the heat transferable dye has a diene. Either a dye and a dienophile compound is contained in the receiving layer, or the heat transferable dye is a dye having a dienophile and the diene compound is contained in the receiving layer. Was achieved with a thermal transfer dye-donor element. The configuration and the like of the present invention will be described in detail.

The diene-containing dye used in the thermal transfer dye-donor element of the invention is represented by formula (I). The dienophile compound used in combination with the dye having a diene is represented by the general formula (II) or (III). General formula (I) A- (B-X ) n , where A represents a dye main portion, B represents a single bond or a divalent linking group, X is ^{CR 1 (R 2) = CR} 3 -CR 4
Represents CR ⁵ (R ⁶ ). Here, R ^{1 to} R ⁶ represent a hydrogen atom or a nonmetallic atomic group. R ¹ and R ⁵ and / or R ³ and R ⁴ and / or R ¹ and R ² and / or R ³ and R ⁴ and / or R ¹ and R ² and / or R ⁵ and R ⁶ and / or R ¹ And R ³ and / or R ⁴ and R ⁵ may together form a carbocycle or a heterocycle. B is R ¹
It may be bonded even with any to R ^6, or R ¹ to R ⁶
Instead of either of them, the diene skeleton may be directly bonded.
Among them, the bond between B and R ¹ or R ² is particularly preferable.
n represents an integer of 1 to 3. Formula ^{(II) CR 7 (R 8} ) = CR 9 (R 10) where R ⁷ to R ¹⁰ represents a hydrogen atom or a nonmetallic atom group. However, not all of R ^{7 to} R ¹⁰ are hydrogen atoms. R ⁷ and R ⁹ and / or R ⁷ and R ⁸ and / or R ⁹ and R ¹⁰ and / or R ⁸ and R ⁹ may be taken together to form a carbocycle or a heterocycle. General formula (III) CR ¹¹ ≡CR ¹² Here, R ¹¹ and R ¹² represent a hydrogen atom or a nonmetallic atomic group. However, neither R ¹¹ nor R ¹² is a hydrogen atom. R ¹¹ and R ¹² may be joined together to form a carbocycle or a heterocycle.

Another one of the combinations of the present invention is a dye having a dienophile represented by the general formula (IV) and a diene compound represented by the general formula (V). General formula (IV) A- (BY) n Here, A, B, and n are synonymous with those of general formula (I). Y is CR ¹³ (R ¹⁴ ) = CR ¹⁵ (R ¹⁶ ) or CR ¹⁷ ≡
Represents CR ¹⁸ . R ^{13 to} R ¹⁸ represent a hydrogen atom or a non-metal atomic group. R ¹³ and R ¹⁵ and / or R ¹³ and R ¹⁴ and / or R ¹⁵ and R ¹⁶ and / or R ¹⁴ and R ¹⁶ or R ¹⁷ and R ¹⁸
May together form a carbocycle or a heterocycle.
B may be bonded to any of R ^{13 to} R ¹⁸ , or may be bonded directly to the dienophile skeleton in place of any of R ^{13 to} R ¹⁸ . Formula ^{(V) CR 19 (R 20} ) = CR 21 -CR 22 = CR 23 (R 24) wherein R ¹⁹ to R ²⁴ represents a hydrogen atom or a nonmetallic atom group. However, not all of R ^{19 to} R ²⁴ are hydrogen atoms. R ¹⁹ and R ²³ and / or R ²¹ and R ²² and / or R
¹⁹ and R ²⁰ and / or R ²³ and R ²⁴ and / or R ²⁰ and R
²⁴ may together form a carbocycle or a heterocycle.

The general formula (I) will be described in detail. A represents a dye main body, and any known dye may be used. Examples thereof include azo type, azomethine type, anthraquinone type, naphthoquinone type, methine type and quinophthalone type. Examples of the azo dye represented by A include those represented by the general formula (VI), the general formula (VI)

[0008]

[Chemical 1]

(In the formula, R ²⁵ represents a hydrogen atom or a nonmetallic atomic group, R ²⁶ represents an aryl group or a heteryl group,
R ²⁷ represents a hydrogen atom, an alkyl group, an aryl group or a heteryl group, and R ²⁸ represents an amino group or a hydroxyl group which may be alkyl-substituted. Specific examples of these are disclosed in JP-A 1-22
5592, 2-24191, JP-A-63-111.
094, 63-122594, 63-1821
91, 63-182190 and the like.
In the formula, * represents a site where the dye main body A and the linking group B can be bonded, and the linking group B is bonded to any one of the sites marked with *. And the general formula (VII), which is represented by the general formula (VII)

[0010]

[Chemical 2]

(Wherein R ²⁹ represents a heteryl group or an aryl group, R ³⁰ represents a hydrogen atom or a non-metal atomic group,
R ³¹ and R ³² represent a hydrogen atom, an alkyl group or an aryl group, and n ₂ represents an integer of 1 to 4. Specific examples of these are disclosed in JP-A Nos. 62-55194 and 62-212190.
It is described in JP-A-3-205189. The bond with B may be any of R ^{29 to} R ^32, but especially R ²⁹ and R ³¹
And are preferred. ) Examples thereof include those represented by the general formula (VIII). General formula (VIII)

[0012]

[Chemical 3]

(Wherein R ³³ represents an aryl group or a heteryl group, R ³⁴ represents an alkyl group, R ³⁵ represents a cyano group, a carbamoyl group or an acyl group, and R ³⁶ represents an alkyl group. A specific example is JP-A-61-2445.
95, 62-290583, and JP-A-3-8885.
No. 1 and the like. The bond with B may be any of R ^{33 to} R ^36, but R ³³ is particularly preferable. )

Examples of the azomethine dye represented by A include those represented by the general formula (IX) and the general formula (IX)

[0015]

[Chemical 4]

(Wherein R ³⁷ and R ³⁸ represent a hydrogen atom or a non-metal atomic group, R ³⁹ represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group, and Y represents a nitrogen-containing heterocycle. Represents the group of non-metal atoms required to form,
n ₃ represents an integer of 1 to 4. Specific examples of these are described in JP-A-64-63194, JP-A-2-208094, JP-A-3-205189, JP-A-2-265791, JP-A-2310087, JP-A-2-53866 and the like. Has been done. The bond with B is R ³⁷ , R ³⁸ , R ³⁹ , Y
It may be either, but especially, an alkylamino group of R ³⁹ or Y
And are preferred. ) Those represented by the general formula (X), the general formula (X)

[0017]

[Chemical 5]

(Wherein R ⁴⁰ , R ⁴¹ and R ⁴³ represent a hydrogen atom or a non-metal atomic group, R ⁴² represents an amino group or a hydroxyl group which may be substituted by an alkyl group or an aryl group,
Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and n ₄ represents an integer of 1 to 4. Specific examples thereof are described in Japanese Patent Application Nos. 2-330774 and 3-162325. The bond with B may be any of R ^{40 to} R ⁴³ and Z, but an alkylamino group of R ⁴² , R ⁴¹ or Z is particularly preferable. ) Represented by general formula (XI), general formula (XI)

[0019]

[Chemical 6]

(Wherein R ⁴⁴ and R ⁴⁵ represent a nonmetallic atomic group, R ⁴⁶ represents a hydrogen atom or a nonmetallic atomic group, and R ⁴⁷ represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group. And n ₅ represents an integer of 1 to 4. Specific examples thereof are JP-A-2-155693, 1
-110565, 2-668, 2-28264
No. 2, No. 2-53865, No. 2-53866, EP4
36736A1 and the like. The bond with B may be any of R ^{44 to} R ⁴⁷ , but the alkylamino group of R ⁴⁷ is particularly preferable. Those represented by the general formula (XII), the general formula (XII)

[0021]

[Chemical 7]

(Wherein R ⁴⁸ , R ⁴⁹ and R ⁵⁰ represent a hydrogen atom or a non-metal atomic group, R ⁵¹ represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group,
n ₆ represents an integer of 1 to 4. Specific examples of these are described in JP-A-63-205288. The bond with B may be any of R ^{48 to} R ^51, but the alkylamino group of R ⁵¹ or R ⁴⁸ is particularly preferable. ) Represented by the general formula (XIII) (or XIV), the general formula (XIII), the general formula (XIV)

[0023]

[Chemical 8]

(Wherein R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R
⁵⁸ , R ⁵⁹ and R ⁶⁰ represent a hydrogen atom or a non-metal atomic group,
R ⁵⁷ and R ⁶¹ represent an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group, Q represents a non-metal atom group necessary for forming a carbocycle or a heterocyclic ring, and n ₇ , n ₈ represents an integer of 1 to 4. Specific examples of these are described in JP-A-61-22993 and 61-31292.
No. 61-35994, No. 61-57651, No. 62-191191, No. 64-20194, and JP-A No. 2-98492. The bond to B may be any of R ^{52 to} R ⁶¹ and Q, but R ⁵⁷ , an alkylamino group of R ⁶¹ , or R ⁵⁴ or R ⁵⁸ is particularly preferable. ) Represented by general formula (XV), general formula (XV)

[0025]

[Chemical 9]

(Wherein R ⁶² represents an acyl group or a carbamoyl group, R ⁶³ and R ⁶⁴ represent a hydrogen atom or an alkyl group or an aryl group, R ⁶⁵ represents a hydrogen atom or a non-metal atomic group, and R ⁶⁶ represents Represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group, and n ₉ is 1 to 4
Represents the integer. Specific examples of these are disclosed in JP-A No. 1-1765.
No. 90, No. 1-176589, No. 1-176591.
No. 3-92386, Japanese Patent Application No. 3-170310, and the like. The bond with B may be any of R ^{62 to} R ^66, but the alkylamino group of R ⁶⁶ or R ⁶³ is particularly preferable. ) Examples of the anthraquinone dye represented by A include those represented by the general formula (XVI), the general formula (XVI)

[0027]

[Chemical 10]

(In the formula, R ⁶⁷ represents a hydrogen atom or a non-metal atomic group, and n ₁₀ represents an integer of 1 to 6. Specific examples thereof are JP-A-59-227948 and JP-A-63-249694.
No. 63-15790, No. 61-255897,
60-151097, EP-365392, JP-A-3-1290096, 1-135690, 1-.
183584 and the like. The bond with B is R
^It may be any of ⁶⁷ , but R ^{67 at the} 1st or 4th position is particularly preferable. ) Examples of the naphthoquinone dye represented by A include those represented by the general formula (XVII), the general formula (XVII)

[0029]

[Chemical 11]

(In the formula, R ⁶⁸ represents a hydrogen atom or a non-metal atomic group, and n ₁₁ represents an integer of 1 to 4. Specific examples thereof are described in JP-A-60-151098.
The bond to B may be any of R ⁶⁸ , but especially R ^{68 at the} 5-position
And are preferred. ) Examples of the methine dye represented by A include those represented by the general formula (XVIII), those represented by the general formula (XVIII)

[0031]

[Chemical 12]

(In the formula, R ⁶⁹ represents an aryl group or a heterocyclic group, and R ⁷⁰ represents a hydrogen atom or a cyano group. Specific examples thereof are JP-A 64-47587 and 60-239.
No. 290, No. 60-28451, No. 62-19618.
No. 6, No. 60-53564, No. 60-31563,
63-141799, JP-A-2-579, 3-
230994, JP-A-61-163895, JP-A-3-197185 and the like. The bond with B is with R ⁶⁹ . ) Represented by general formula (XIX), general formula (XIX)

[0033]

[Chemical 13]

(Wherein R ⁷¹ represents a hydrogen atom or a non-metal atomic group, R ⁷² represents a cyano group, an aryl group, a heterocyclic group or a substituted vinyl group, and G represents a group necessary for forming a heterocyclic group. Represents a group of non-metal atoms, specific examples of which are disclosed in JP-A Nos. 2-6559, 2-3450, and 2-20809.
No. 3, No. 2-215595, No. 2-215594,
JP-A-63-74685, JP-A-63-74688, JP-A-2-258298, JP-A-64-42286,
No. 60-156760, No. 64-42286, No. 6
2-273265, 62-220557, JP-A-2-175294, 3-49999, 1-19.
Nos. 6396 and 1-196395. The bond with B may be any of R ⁷¹ , R ⁷² and G, but G is particularly preferable. ) Examples of the quinophthalone dye represented by A include those represented by the general formula (XX), the general formula (XX)

[0035]

[Chemical 14]

(Wherein R ⁷³ represents a hydrogen atom or a halogen atom, R ⁷⁴ represents a hydrogen atom or a non-metal atomic group, and n
₁₂ represents an integer of 1 to 4. Specific examples thereof include JP-A-60-53565 and 63-189289.
No. 63-182193 and the like. B
The bond with and is R ⁷⁴ ) and the like. The dyes represented by A other than the above are described below. General formula (XXI)

[0037]

[Chemical 15]

(In the formula, R ⁷⁵ represents a heteryl group or an aryl group, R ⁷⁶ represents a hydrogen atom or a non-metal atomic group,
n ₁₃ represents an integer of 1 to 4. ) General formula (XXII)

[0039]

[Chemical 16]

(In the formula, R ⁷⁷ represents a hydrogen atom or a non-metal atomic group, R ⁷⁸ and R ⁷⁹ represent a hydrogen atom, an alkyl group or an aryl group, and n ₁₄ represents an integer of 1 to 4.) Formula (XXIII)

[0041]

[Chemical 17]

(In the formula, R ⁸⁰ represents a heteryl group or an aryl group, and R ⁸¹ and R ⁸² represent a hydrogen atom or a nonmetallic atomic group.) General formula (XXIV)

[0043]

[Chemical 18]

(In the formula, R ⁸³ represents a hydrogen atom or a non-metal atomic group, and R ⁸⁴ represents a heteryl group or an aryl group.)

General formula (XXV)

[0046]

[Chemical 19]

(Wherein R ⁸⁵ and R ⁸⁶ represent a hydrogen atom or a non-metal atomic group, R ⁸⁷ represents a heteryl group or an aryl group, and n ₁₅ represents an integer of 1 to 4). )

[0048]

[Chemical 20]

(In the formula, R ^{88 to} R ⁹¹ represent a hydrogen atom or a nonmetallic atomic group, and n _{17 to} n ₂₀ represent an integer of 1 to 4.
B in the general formula (I) or (IV) is a single bond or a divalent linking group which connects the dye body A and X or Y, and is preferably represented by the general formula (XXVII). *-(Z ¹ -L-) _r -Z ² -** (XXVII) In the general formula (XXVII), * represents the position at which A is bonded,
* Represents a position bonded to X or Y, Z ¹ and Z ² are each independently a single bond, —NH—, —O—, —S—, —CO—,
_{-SO 2 -, - OCO -,} - COO -, - NHCO-,
_{-CONH -, - SO 2 NH -} , - NHSO 2 -, - S
_{O 2 O -, - OSO 2} -, - OCOO -, - OCONH
-, - NHCOO -, - NHCONH -, - NHSO 2
NH -, - OCOS -, - SCOO -, - OSO 2 NH
-, or represents a -NHSO ₂ O-. L is a single bond, an alkylene group (having 1 to 6 carbon atoms), an arylene group (for example, o-
Phenylene, p-phenylene), cycloalkylene group (for example, 1,4-cyclohexylene), divalent heterocyclic group (for example, pyrrolidine, piperidine, morpholine, piperazine, pyrrole, pyrazole, imidazole, 1,
2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, 1,2,4-triazolidine-3,5dione, pyridine, thiophene)
And may be a linking group formed by combining these groups. r represents 0 or an integer of 1 to 3.

B is more preferably a single bond or
A linking group is mentioned as a specific example. * -CH₂-**, * -C₂H_Four-**, *-(C
H₂)₃-** * -C₂H_FourOC₂H_Four-**, * -NHCONH- *
*, * -NHCO-** * -CONH-**, * -CO-**, * -CONHC
H₂-**, * -SO₂-**, * -C₂H_FourNHCO-**, *-
CH₂CONH **-*-NHCH₂CH₂OCO-**, * -NH-**,
* -O-**, * -S-**, * -OCO-**, * -COO-**,
* -SO₂NH-**, * -NHSO₂-**, * -OCONH-**, * -N
HCOO-**, * -C ₂H_Four-CO-**

CR ¹ (R ² ) = CR ³ -CR ⁴ = CR ⁵
In (R ⁶ ), R ^{1 to} R ⁶ are hydrogen atoms, alkyl groups (having 1 to 10 carbon atoms, including those having a substituent, such as methyl, ethyl, propyl, and isopropyl); alkoxy groups (having 1 to 10 carbon atoms). Including those having a substituent, for example, methoxy, ethoxy, propoxy, isopropoxy); halogen atom; acylamino group [C 1-10
Alkylcarbonylamino groups (including those having a substituent. For example, formylamino, acetylamino, propionylamino, isobutylamino, hexahydrobenzoylamino, pivaloylamino, trifluoroacetylamino, heptafluorobutyrylamino, chloropropionylamino, cyano. Acetylamino, phenoxyacetylamino), arylcarbonylamino groups having 7 to 15 carbon atoms (including those having a substituent. For example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, o-fluorobenzoylamino, m-methoxy. Benzoylamino, p-trifluoromethylbenzoylamino, 2,4-dichlorobenzoylamino, p-
Methoxycarbonylbenzoylamino, 1-naphthoylamino), and C2-C15 hetarylcarbonylamino groups (including those having a substituent, for example, picolinoylamino, nicotinoylamino, pyrrole-2-carbonylamino, thiophene-). 2-carbonylamino, furoylamino, piperidine-4-carbonylamino)]; alkoxycarbonyl group (having 2 to 10 carbon atoms, including those having a substituent, for example, methoxycarbonyl, ethoxycarbonyl); cyano group; alkoxycarbonylamino group ( C2-C10, including those having a substituent, such as methoxycarbonylamino, ethoxycarbonylamino, isopropoxycarbonylamino, methoxyethoxycarbonylamino, N-methylmethoxycarbonylamino); Arylamino group (having 1 to 10 carbon atoms.
Including those having a substituent. For example, methylaminocarbonylamino, dimethylaminocarbonylamino, butylaminocarbonylamino); sulfonylamino group (having 1 to 10 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino, benzenesulfonylamino); carbamoyl group [ 1 to 1 carbon atoms
An alkylcarbamoyl group of 0 (including those having a substituent. For example, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl,
t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl), carbon number 7 to 15 arylcarbamoyl groups (including those having a substituent, for example, phenylcarbamoyl, p-toluylcarbamoyl, m-methoxyphenylcarbamoyl,
4,5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o
-Fluorophenylcarbamoyl, 1-naphthylcarbamoyl), and a heterylcarbamoyl group having 3 to 15 carbon atoms (including those having a substituent. For example, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2-thiazolyl Lucarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methyl) pyridylcarbamoyl, 2- (5-methyl) 1,3,4-thiadiazolylcarbamoyl)]; sulfamoyl group (carbon number 0-10.
For example, methylsulfamoyl, dimethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl); acyl group [including an alkylcarbonyl group having 1 to 10 carbon atoms (including those having a substituent. For example, formyl, acetyl, propionyl, Hexahydrobenzoyl, pivaloyl, trifluoroacetyl, heptafluorobutyryl, chloropropionyl, cyanoacetyl, phenoxyacetyl), and arylcarbonyl groups having 7 to 15 carbon atoms (including those having a substituent. For example, benzoyl, p-
Toluyl, pentafluorobenzoyl, o-fluorobenzoyl, m-methoxybenzoyl, p-trifluoromethylbenzoyl, 2,4-dichlorobenzoyl, p-
Methoxycarbonylbenzoyl, 1-naphthoyl], an alkylthio group having 1 to 10 carbon atoms (including those having a substituent, for example, methylthio, ethylthio), 6 to 1 carbon atoms
5 represents an arylthio group having 5 substituents (including those having a substituent, such as phenylthio), or a dialkylamino group having 2 to 15 carbon atoms (eg, dimethylamino, diethylamino). Preferred among R ^{1 to} R ⁶ is a hydrogen atom,
It is a C1-C3 alkyl group or a C1-C3 alkoxy group. It is also preferable that R ¹ and R ⁵ together form a carbocycle or a heterocycle. Particularly preferred is represented by the general formula (XXVIII).

[0052]

[Chemical 21]

Here, R ^{2 to} R ⁶ are as defined above. Q
¹ is -CR ⁹² (R ⁹³ )-, -O-, -S-, or -NR
^94- indicates. R ⁹² and R ⁹³ are synonymous with R ¹ , and R ⁹⁴ represents a hydrogen atom, an alkyl group (having 1 to 5 carbon atoms), an aryl group (having 6 to 10 carbon atoms), or an acyl group (having 1 to 5 carbon atoms). . The bond with B is preferably R ² . n is preferably 1. The general formula (II) will be described in detail. R ^{7 to} R ¹⁰ are synonymous with R ¹ . R ^{7 to} R ¹⁰ are preferably hydrogen atoms or electron withdrawing groups (preferably having a Hammett σ _p value of 0.
2 or more). Examples thereof include a halogen atom and an ester group (having 2 to 40 carbon atoms. Those having a substituent are included.
For example, methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl, hexadecyloxycarbonyl, phenoxycarbonyl, p-octadecyloxyphenoxycarbonyl), cyano group, carbamoyl group (having 1 to 40 carbon atoms, including those having a substituent, for example, methylcarbamoyl). , Dimethylcarbamoyl, butylcarbamoyl, cyclohexylcarbamoyl, octadecylcarbamoyl, benzylcarbamoyl, phenylcarbamoyl, p-toluylcarbamoyl, 4,5-dichlorophenylcarbamoyl), sulfamoyl group (having 0 to 0 carbon atoms).
40. For example, methylsulfamoyl, phenylsulfamoyl), an acyl group (having 1 to 40 carbon atoms, such as acetyl, phenoxyacetyl, benzoyl), a sulfonyl group (having 1 to 40 carbon atoms, such as methylsulfonyl, octylsulfonyl, phenylsulfonyl) or A nitro group is mentioned. It is also preferred that R ⁷ and R ⁹ together form a carbocycle or a heterocycle. Particularly preferred are those represented by the general formula (X
XIX).

[0054]

[Chemical formula 22]

Here, R ⁸ and R ¹⁰ are as defined above. Q
² -O -, - S- or -NR ⁹⁵ - represent. R ⁹⁵ represents a hydrogen atom, an alkyl group (having 1 to 40 carbon atoms) or an aryl group (having 6 to 50 carbon atoms). The compounds of general formula (XXIX) may be linked to each other by a suitable linking group (represented by B above) to form a bis type or tris type.
It is also used as a polymer type containing the general formula (XXIX) in the side chain and / or main chain. In that case, either a homopolymer type or a copolymer type may be used. The general formula (III) will be described in detail. R ¹¹ and R ¹² are synonymous with R ¹ . R ¹¹ , R ¹²
Of these, a hydrogen atom or an electron-withdrawing group (preferably having a Hammett σ _p value of 0.2 or more) is preferable. Of these, preferred are ester groups (having 2 to 4 carbon atoms).
0. Including those having a substituent. For example, methoxycarbonyl, hexadecyloxycarbonyl, phenoxycarbonyl, p-octadecyloxyphenoxycarbonyl), a carbamoyl group (having 1 to 40 carbon atoms, including those having a substituent, such as methylcarbamoyl, butylcarbamoyl, octadecylcarbamoyl, phenylcarbamoyl). Is mentioned.

As the dienophile compound, the compound represented by the general formula (II) is more preferable than the compound represented by the general formula (III). It is more preferable to incorporate an atomic group having a fading-suppressing effect described in JP-A-3-205189 into the compounds represented by the general formulas (II) and (III). Among the dyes represented by the general formula (I), particularly preferable ones are represented by the general formula (XXX).

[0057]

[Chemical formula 23]

Here, A is synonymous with the above, and W is -NH.
-Or-O-.

Among the compounds represented by the general formula (II), particularly preferred compounds are represented by the general formula (XXXI).

[0060]

[Chemical formula 24]

R ⁹⁶ is an alkyl group (having 1 to 4 carbon atoms).
0. And an aryl group (having 6 to 50 carbon atoms, including those having a substituent). The general formula (IV) will be described in detail. A, B and n have the same meaning as above. R ^{13 to} R ¹⁶ are synonymous with R ^{7 to} R ¹⁰ , and preferred examples are also synonymous with R ^{7 to} R ¹⁰ . R ¹⁷ , R ¹⁸ are R ¹¹ ,
It is synonymous with R ¹² , and preferred examples are synonymous with R ¹¹ and R ¹² . The general formula (V) will be described in detail. R ¹⁹ ~ R ²⁴
Is synonymous with R ^{1 to} R ⁶ , and preferred examples are synonymous with R ^{1 to} R ⁶ . The compounds of general formula (V) may be linked to each other by a suitable linking group (represented by B above) to form a bis type or tris type. It is also used as a polymer type containing the compound of the general formula (V) in the side chain or main chain. In that case, either a homopolymer type or a copolymer type may be used. Among the dyes represented by the general formula (IV), particularly preferable ones are represented by the general formula (XXXII).

[0062]

[Chemical 25]

Here, A and B are synonymous with the above. In the compound represented by the general formula (V), JP-A-3-205189 is known.
It is more preferable to incorporate an atomic group having the fading-suppressing effect described in No. Among the compounds represented by the general formula (V), particularly preferred compounds are represented by the general formula (XXXIII).

[0064]

[Chemical formula 26]

Where W is --NH-- or --O-- and R is
³⁰ is an alkyl group (having 1 to 40 carbon atoms, including those having a substituent), an aryl group (having 1 to 40 carbon atoms, including those having a substituent), and a heteryl group (having 2 to 40 carbon atoms. (Including those having a group), an amino group (having 0 to 4 carbon atoms)
0. Including those having a substituent. ), An alkoxy group (having 1 to 40 carbon atoms, including those having a substituent), and an aryloxy group (having 6 to 40 carbon atoms, including those having a substituent). Specific examples of the dye represented by formula (I) used in the present invention are shown below.

[0066]

[Chemical 27]

[0067]

[Chemical 28]

[0068]

[Chemical 29]

[0069]

[Chemical 30]

[0070]

[Chemical 31]

[0071]

[Chemical 32]

[0072]

[Chemical 33]

Specific examples of the compound represented by the general formula (II) used in the present invention are shown below.

[0074]

[Chemical 34]

[0075]

[Chemical 35]

[0076]

[Chemical 36]

[0077]

[Chemical 37]

[0078]

[Chemical 38]

Specific examples of the compound represented by the general formula (III) used in the present invention are shown below.

[0080]

[Chemical Formula 39]

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

[0082]

[Chemical 40]

[0083]

[Chemical 41]

[0084]

[Chemical 42]

[0085]

[Chemical 43]

[0086]

[Chemical 44]

[0087]

[Chemical formula 45]

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

[0089]

[Chemical formula 46]

[0090]

[Chemical 47]

[0091]

[Chemical 48]

Although only examples of carbon skeletons have been given for the diene part or the dienophile part, a diene part or a dienophile part containing a hetero atom (preferably N, S, O) for carrying out a so-called hetero Diels-Alder reaction can be used. You may use the dye or compound which has. Specific examples thereof will be shown.

[0093]

[Chemical 49]

[0094]

[Chemical 50]

The synthesis examples of the dye of the present invention are shown below. Synthesis example 1. Synthesis of Dye I-1 1-1. Intermediate 2- (N
Synthesis of -furfurylcarbamoyl) -1-naphthol 2-phenoxycarbonyl-1-naphthol 5.3 g,
Furfurylamine 6.0 g and acetonitrile 25 ml
Was heated to reflux for 2 hours. After cooling to room temperature, 20 ml of water was gradually added while stirring. The precipitated crystals are collected by filtration,
4.0 g of the target product was obtained. 1-2. Synthesis of Dye I-1 2.0 g of the intermediate obtained above, 120 ml of ethyl acetate, 60 ml of isopropanol, 10% aqueous sodium carbonate solution, and p- (N, N-diethyl) aniline sulfate 2.2
4. Stir g at room temperature and add ammonium persulfate to it.
7g was added over 5 minutes. After reacting for 20 minutes, the ethyl acetate layer was separated. The ethyl acetate solution was concentrated under reduced pressure to about 20 ml on a rotary evaporator. To this, 100 ml of methanol was added and stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration to obtain 2.6 g of the desired product, mp 134-5 ° C.

Synthesis Example 2. Synthesis of Dye IV-1 2-1. Synthesis of intermediate N-ethyl-N- [2- (1-maleimido) ethyl] -m-toluidine 14.7 g of N-ethyl-N- (2-aminoethyl) -m-toluidine and 300-90 ml of toluene 80-90. The mixture was heated and stirred so that the temperature was kept at 0 ° C. To this, a solution of maleic anhydride and 60 ml of toluene was added dropwise over 1 hour. The bath temperature was raised and toluene was gradually distilled off over 2 hours. The resulting crude product was purified by silica gel chromatography (developing solvent hexane, ethyl acetate 1: 1) to give 3
0.5 g of the desired product was obtained. 2-2. Synthesis of Dye IV-1 0.93 g of aniline, 10 ml of water and 2.5 ml of hydrochloric acid were stirred and cooled in an ice bath, 0.69 g of sodium sulfite was gradually added thereto, and the mixture was reacted for 20 minutes to synthesize a diazonium salt solution. . 2-1 Intermediate obtained in 2-1
g, methanol 150 ml and sodium acetate 4.91
While stirring g, the mixture was cooled to 10 ° C. or lower in an ice bath, and the whole amount of the diazonium salt solution was added thereto. After reacting for 10 minutes, the precipitated crystals were collected by filtration. This is recrystallized from acetonitrile to give the desired product (mp: 134-5 ° C, 2.3 g).
Got The dye of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and applied on a support, or can be printed on the support by a printing method such as a gravure method. The thickness of the dye-donor layer containing these dyes is usually about 0.2 to 5 μm, preferably 0.4 to 2 μm as a dry film thickness. The coating amount of the dye is 0.03 to 5 g / m ² , preferably 0.1 to 1.
It is 0 g / m ² .

As the binder resin used together with the above dyes in the dye supplying layer and the dye transfer contributing layer of the present invention, any binder resin known in the related art for such purpose can be used, and it is usually heat resistant. Those that are high and do not interfere with dye transfer when heated are selected.
For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-vinyl acetate copolymer),
Polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin (for example, Polyvinyl alcohol, partially saponified polyvinyl alcohol such as polyvinyl acetal, polyvinyl butyral), petroleum-based resin, rosin derivative, coumarone-indene resin, terpene-based resin, polyolefin-based resin (for example, polyethylene, polypropylene) and the like are used. When different binder resins are used for the dye supplying layer and the dye transfer contributing layer, resins having different glass transition temperatures (Tg), preferably Tg
It is preferable to use a resin having a difference of 10 ° C. or more. In the present invention, such a binder resin is preferably used in a ratio of about 20 to 900 parts by weight in the dye transfer contributing layer per 100 parts by weight of the dye. The dye supply layer preferably has a higher dye concentration than the transfer contribution layer, and is preferably 1.5 to 3 times. 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. The thickness of the dye supply layer is 0.1 to 20 μm, preferably 0.5 to 10 μm
The thickness of the dye transfer contributing layer is 0.05 to 5 μm, preferably 0.1 to 2 μm.

Any conventionally known support can be used as the support of the thermal transfer dye-donor element. Examples thereof include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-donor element is generally 2 to
It is 30 μm. An undercoat layer may be provided if necessary.

A slipping layer may be provided in order to prevent the thermal head from sticking to the thermal transfer dye-providing material. 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 of the thermal head and improve slippage when printing from the back side of the thermal transfer dye-donor material, it is preferable to perform anti-sticking treatment on the side of the support on which the dye-containing layer is not provided. . For example, it is preferable to provide a heat resistant slip layer mainly containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or an alkaline earth metal salt of phosphoric acid ester, and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110 ° C., and a vinyl butyral portion having a weight percentage of 15 to 40% from the viewpoint of many reaction sites with isocyanate. Is good. As the alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, which is 1 to 50% by weight, preferably 1% by weight based on the polyvinyl butyral resin.
It is recommended to use about 0 to 40% by weight. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The thermal transfer 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. In general, excellent results have been obtained with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate graft gelatin, ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol), poly (ethyleneimine), poly ( Acrylic acid),
Mixtures of poly (vinyl alcohol) and poly (vinyl acetate), poly (vinyl alcohol) and poly (acrylic acid)
And a mixture of cellulose monoacetate and poly (acrylic acid). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol). The thermal transfer dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired effect, but a preferable specific example is a (acrylonitrile / vinylidene chloride / acrylic acid) copolymer (weight ratio 14: 80: 6),
(Butyl acrylate / 2-aminoethyl methacrylate / -2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example, Bostik 7650 (Mhart, Bostik. Chemical Group) or chlorinated high density poly (ethylene-trichloroethylene) resins. The coating amount of the undercoat layer is not particularly limited, but is usually 0.1 to 2.
Used in an amount of 0 g / m ² .

The thermal transfer image receiving material used in the present invention will be described. The image receiving material is formed by providing a dye receiving layer on a support. The dye receiving layer is a layer containing the above-mentioned diene compound or dienophile compound. It is preferred to include a binder material with the above compounds. Various polymers are used as the binder substance. Examples of the polymer include the following resins.

(A) those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group) and ethylene. Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate or polymethacrylic acid ester resin : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 may be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used. (B) Those having a urethane bond, such as polyurethane resin. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used.

The dye-receiving layer may contain a high-boiling organic solvent or a thermal solvent as a substance for promoting the acceptance of the heat-transferable dye or as a diffusion aid of the dye. As specific examples of the high boiling point organic solvent and the heat solvent, there is disclosed in JP-A-62-62.
-174754, 62-245253, 61-
209444, 61-200538, 62-8
No. 145, No. 62-9348, No. 62-30247.
And the compounds described in JP-A Nos. 62-136646. The dye receiving layer may have a structure in which the above various substances are 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 dye receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having enhanced dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used for the outermost layer. Using a synthetic resin with a higher point, sticking to the surface, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents troubles such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the dye receiving layer is preferably 0.5 to 50 μm, particularly preferably 3 to 30 μm. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm. In the present invention, if 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 properties, dents after transfer, etc. Anything can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. Films or sheets treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

An intermediate layer may be provided between the support and the dye receiving layer. The intermediate layer is a cushion layer,
It is either a porous layer or a dye diffusion preventing layer, or a layer having two or more of these functions, and in some cases also serves as an adhesive. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat. The dye receiving layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, etc. are silica,
Fine powders of clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained.

A fluorescent whitening agent may be used in the dye receiving layer. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. 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 dye-providing layer and the dye-transfer-contributing layer (hereinafter referred to as the dye-donor layer) and the dye-receiving layer, in the dye-donor layer and / or the dye-receiving layer,
It is particularly preferable to incorporate a release agent in the outermost layer that is in contact with the surface where both materials come into contact. As a release agent,
Solid or wax-like substances such as polyethylene wax, amide wax, and Teflon powder: Fluorine-based or phosphate-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. Can be used, but silicone oil is particularly preferable. As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data issued by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name KF-100).
T) is effective.

The dye-donor layer and dye-receiving layer used in the present invention may be hardened with a hardener. When curing an organic solvent-based polymer, JP-A-61-11999
Nos. 97 and 58-215398 can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water soluble polymers, US Pat. No. 4,678,739, 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
The hardeners described in No. 61 and No. 61-18942 are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardener (such as dimethylol urea), or polymer hardener (JP-A-62-23415).
Compounds described in No. 7 and the like).

An anti-fading agent may be used in the dye donating layer and the dye receiving layer. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (Japanese Patent Laid-Open No. 56-2784, etc.), Other Japanese Patent Laid-Open Nos. 54-48535, 62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,245,018.
No. 3 to 36 columns, No. 4,254,195 No. 3 to 8
Column, JP-A-62-174741, JP-A-61-88256.
(27) to (29), JP-A-1-75568, JP-A-63-199248, and the like. Examples of useful anti-fading agents are disclosed in JP-A-62-21527.
2 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the dye-receiving layer may be contained in the dye-receiving layer in advance, or supplied to the image-receiving material from the outside by a method such as transferring from the dye-donating layer. You may do it. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

Various surfactants can be used in the dye-donor layer and the dye-receptive layer for the purposes of coating aid, improvement of releasability, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. For example,
Saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene Non-ionic surfactants such as oxide adducts), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars: alkyl carboxylates, alkyl sulfones Acid salt, alkylnaphthalene sulfonate, alkyl sulfate ester, alkyl phosphate ester, N-a Such as carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group and the like such as le-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphoric acid esters Anionic surfactant containing an acidic group: amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides: alkylamine salts,
Aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. . Specific examples of these are disclosed in JP-A-6
Nos. 2-173463 and 62-183457. Also, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder,
It is preferable to use a surfactant as the dispersion aid. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-59
The surfactants described on pages 37 to 38 of No. 157636 are particularly preferably used.

The dye-donor layer and the dye-receptive layer may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-Sho 6 can be used.
1-20944, 62-135826 and the like, fluorine-based surfactants, or oily fluorine-based compounds such as fluorine oil or hydrophobic fluorine such as solid fluorine compound resins such as tetrafluoroethylene resin Compounds. A matting agent can be used in the dye-donating layer and the dye-receiving layer. Silicon dioxide as a matting agent,
In addition to the compounds described on page (29) of JP-A-61-88256, such as polyolefin or polymethacrylate, JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 63-274952. The dye-donor layer and the dye-receiving layer of the present invention are formed on a support by a conventionally known method. For example, it is formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate.

[0110]

EXAMPLES The following are detailed examples of the present invention. However, the thermal transfer material of the present invention is not limited to the examples shown below. Example 1 A 6 μm-thick polyamide film having a heat resistant slipping layer formed on the back surface was used as a support, and the coating solution (1) for dye supply layer having the following composition was first applied to the side on which the heat resistant slipping layer was not formed. ,
It was applied by a gravure coater so that the thickness after drying was 5 μm, and dried. Dye supply layer coating solution (1) Dye I-1 15 g Polyvinyl butyral (Denka Butyral 5000A: manufactured by Denki Kagaku) 4 g Polyisocyanate (Takenate D110N: manufactured by Takeda Pharmaceutical Co., Ltd.) 1 g Methyl ethyl ketone 50 ml Toluene 50 ml Coating liquid (1) for the dye transfer contributing layer having the following composition
Was applied by a gravure coater so that the thickness after drying was 1 μm, and dried to prepare a thermal transfer dye-donor material (1).

Dye Transfer Contribution Layer Coating Liquid (1) Dye I-1 4 g Ethylcellulose (N100G, manufactured by Shin-Etsu Chemical) 4 g Amino-modified silicone oil (KF857, Shin-Etsu Chemical) 0.5 g Methyl ethyl ketone 30 ml Toluene 20 ml In addition, Other dye-donor materials (2) to (10) and (a) to (f) were prepared by changing the dyes shown in Table 1.

[0112]

[Table 1]

[0113]

[Chemical 51]

Next, on both sides of a high-quality paper having a thickness of 140 μm,
A resin-coated paper laminated with polyethylene to a thickness of 30 μm was used as a support, and the receiving layer coating solution (1) having the following composition was used to apply a dry thickness of 10 μm with a wire bar coater. Then, it was dried to prepare a thermal transfer image receiving material (1).

Receptor Layer Coating Liquid (1) Dienophile compound II-5 20 g Polyester resin (Vylon 200: manufactured by Toyobo) 80 g Silicone oil (KF857: manufactured by Shin-Etsu Chemical) 4 g Isocyanate (KP-90: Dainippon Ink and Chemicals) 4 g Methyl ethyl ketone 400 g Toluene 50 g Further, the dienophile compounds were changed to the compounds shown in Table 2 to prepare other image receiving materials (2) to (5) and (a) to (c).

[0116]

[Table 2]

The surface of the dye-providing material containing the dye and the receiving layer of the image-receiving material were superposed, and the output was 0.3 w / dot, the dot density was 12 dots / mm, and the current pulse width was 0.2-using a thermal head. 7msec 2 material feed rate 8mm /
Thermal transfer was performed under the condition of sec to obtain a dye image record.
Next, the previously used dye-donor element and the new image-receiving element were overlaid, and thermal transfer was again performed under the above conditions.
The same dye image recording as at the beginning was obtained. The highest density portion of the obtained image was measured with a reflection densitometer (Model 310, manufactured by XRite). Further, the obtained image was stored in an oven at 60 ° C. for 3 weeks, and the bleeding of the image after storage was visually determined. The criteria for evaluation were as follows: ○: little change from before storage, Δ: slightly bleeding, ×: very bleeding.
Further, the obtained image and the dye-receiving layer of a postcard to which only the dye-receiving layer was transferred were overlapped, and a weight of 1 kg was applied, and the image was stored in an oven at 60 ° C. for 1 week. The transfer of the image after storage was visually determined. The criteria for judgment were as follows: O when the image dye hardly transferred to the dye receiving layer, Δ when slightly transferred, and X when very transferred. The results are shown in Table 3.

[0118]

[Table 3]

Example 2 Using the dye-donor material (1) and the image-receiving material (1) of Example 1, the feeding speed of the material was set to 1 mm / sec for the dye-donating material and 8 mm / sec for the image-receiving material among the printing conditions. Instead, thermal transfer was performed. A clear dye image record was obtained. Further, the dye-donor material was changed to (2), and thermal transfer of a different color was performed on the image-receiving material subjected to the thermal transfer under the same conditions. An image having no color turbidity due to reverse transfer was recorded.

[0120]

The effects of the present invention described above are summarized as follows. 1) By using the material of the present invention, clear image recording can be obtained by n-times mode transfer and multiple-times transfer in the same-times mode. 2) By using the dyes and compounds of the present invention, image recording can be obtained without color bleeding during storage and contamination due to transfer of dyes to other substances.

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[Procedure amendment]

[Submission date] February 28, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

[0072]

[Chemical 33]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

[0091]

[Chemical 48]

Claims (1)

[Claims] 1. A thermal transfer dye-donating material which is used in combination with a thermal transfer image-receiving material having a dye-receiving layer for receiving a heat-transferable dye on a support, wherein the thermal transfer dye-donating material is provided on a support. It is formed by laminating a dye supply layer and a dye transfer contributing layer each containing a heat transferable dye in a binder resin in order from the support side, and the heat transferable dye is a dye having a diene, and A thermal transfer dye-providing material, wherein the layer contains a dienophile compound, or the heat-transferable dye is a dye having a dienophile and the receiving layer contains a diene compound.