JPH05221151A - Thermal transfer material - Google Patents

Abstract

PURPOSE:To increase transfer density and to prevent blurring of image by adding a coloring matter having a desorption group to be substituted for an active hydrogen compound in an image receiving layer through thermal transition into a coloring matter layer and adding an active hydrogen compound into an image receiving layer. CONSTITUTION:The thermal transfer material is composed of a coloring matter donative material having a coloring matter layer on a support and an image receiving material having an image receiving layer on the support. The coloring matter layer in the thermal transfer material contains a coloring matter having a desorption group to be substituted for an active hydrogen compound in the image receiving layer through thermal transition while the image receiving layer contains the active hydrogen compound. According to the composition, a thermal transfer material having high transfer density and causing no blurring of image can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer material comprising a dye-donor element and an image-receiving element.

[0002]

2. Description of the Related Art At present, a thermal transfer method, an electrophotographic method, an ink jet method and the like are being studied vigorously as a technology relating to a color hard copy. The thermal transfer method has many advantages over other methods because the apparatus is easy to maintain and operate and the apparatus and consumables are inexpensive. In the thermal transfer system, a thermal transfer dye-donating material having a heat-meltable ink layer formed on a base film is heated by a thermal head to melt the ink and record on the thermal transfer image-receiving material, and heat transfer to the base film. There is a method of heating a thermal transfer dye-donating material having a dye-donating layer containing a functional dye with a thermal head to transfer the dye to a thermal transfer image-receiving material by thermal transfer. The amount of dye transfer can be changed by changing the applied energy, which facilitates gradation recording and is particularly advantageous for high-quality full-color recording.

The dye used in the above heat transfer transfer system is preferably a dye that is easily transferred to heat in order to reduce the load on the thermal head and to increase the recording speed. Or, in a high temperature and high humidity environment, there is a problem in the storage stability of the record after transfer because it moves in the image receiving layer to reduce the sharpness of the image, or moves to a contact object to be contaminated. There has been a long-awaited method of satisfying them.

In order to solve these problems, an application has been made for the purpose of stabilizing the storage of the dye in the image receiving layer by a thermal reaction, and among them, JP-A-60-26006.
0, 60-260381 and 60-2603.
No. 91 is excellent. However, even in these cases, there are defects that the storage stability of the dye in the image-receiving layer is insufficient, the transfer density is difficult to obtain, and the storage stability in the dye-donor layer is insufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermal transfer material composed of a dye-donor element and an image-receiving element that overcomes the above-mentioned deficiencies.

[0006]

The above objects of the present invention are as follows.
A thermal transfer material comprising a dye-donor material having a dye layer on a support and an image-receiving material having an image-receiving layer on the support,
A thermal transfer material characterized in that the dye layer contains a dye having a leaving group that can be thermally transferred to replace the active hydrogen compound in the image receiving layer, and the image receiving layer contains the active hydrogen compound.

The dye used in the present invention is represented by the following general formula (I). A- (B-X _n0 ) _n (I)

In the formula, 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 (II), the general formula (II)

[0009]

[Chemical 1]

(In the formula, R ¹ represents a hydrogen atom or a nonmetallic atomic group, R ² represents an aryl group or a heteryl group,
R ³ represents a hydrogen atom, an alkyl group or an aryl group, or a heteryl group, and R ⁴ represents an alkyl-substituted amino group or a hydroxyl group. Specific examples of these are disclosed in JP-A 1-22
Nos. 5592, 2-24191 and JP-A-63-111.
094, 63-122594, 63-1821
91, 63-182190 and the like.
The bond with B may be any of R ^{1 to} R ⁴ . ) Those represented by the general formula (III), the general formula (III)

[0011]

[Chemical 2]

(Where R is^FiveIs a heteryl group or an aryl group
And R⁶Represents a non-metal atomic group, R⁷, R⁸Is
Represents a hydrogen atom, an alkyl group or an aryl group, n₁Is
It represents an integer of 1 to 4. Specific examples of these are disclosed in JP-A-62-1
55194, 62-211190, and JP-A-3-2.
No. 05189. The bond with B is R ^Five
~ R⁸Which may be any) represented by the general formula (IV)
And the like. General formula (IV)

[0013]

[Chemical 3]

(Wherein R ⁹ represents an aryl group or a heteryl group, R ¹⁰ represents an alkyl group, R ¹¹ represents a cyano group, a carbamoyl group or an acyl group, and R ¹² 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 ^{9 to} R ¹² . )

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

[0016]

[Chemical 4]

(Wherein R ¹³ and R ¹⁴ represent a hydrogen atom or a non-metal atomic group, R ¹⁵ 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 ₂ 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 ¹³ , R ¹⁴ , R ¹⁵ , Y
Any of these), those represented by general formula (VI), general formula (VI)

[0018]

[Chemical 5]

(Wherein R ¹⁶ , R ¹⁷ and R ¹⁹ represent a hydrogen atom or a non-metal atomic group, R ¹⁸ 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 ₃ represents an integer of 1 to 4. Specific examples of these are described in Japanese Patent Application Nos. 2-330774 and 3-162325. The bond with B may be any of R ^{16 to} R ¹⁹ and Z. ), Those represented by general formula (VII), general formula (VII)

[0020]

[Chemical 6]

(In the formula, R ²⁰ and R ²¹ represent a nonmetallic atomic group, R ²² represents a hydrogen atom or a nonmetallic atomic group, and R ²³ represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group. And n ₄ represents an integer of 1 to _4. Specific examples thereof are described in 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 ^{20 to} R ²³ . ), Those represented by general formula (VIII), general formula (VIII)

[0022]

[Chemical 7]

(In the formula, R ²⁴ , R ²⁵ and R ²⁶ represent a hydrogen atom or a non-metal atomic group, R ²⁷ represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group,
n ₅ 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 ^{24 to} R ²⁷ . ), General formula (VIII)
Or those represented by (IX), general formula (VIII), general formula (IX)

[0024]

[Chemical 8]

(Wherein R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R
³⁴ , R ³⁵ and R ³⁶ represent a hydrogen atom or a non-metal atomic group,
R ³³ and R ³⁷ represent an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group, Q represents a group of non-metal atoms necessary for forming a carbocycle or a heterocyclic ring, and n ₆ , n ₇ represents an integer of 1 to 4. Specific examples of these are disclosed in JP-A-61-22993 and 61-31292.
No. 61-35994, No. 61-57651, No. 62-191191, No. 64-20194, and JP-A-2-98492. The bond with B may be any of R ^{28 to} R ³⁷ and Q. ), Those represented by general formula (X), general formula (X)

[0026]

[Chemical 9]

(Wherein R ³⁸ represents an acyl group or a carbamoyl group, R ³⁹ and R ⁴⁰ represent a hydrogen atom or an alkyl group or an aryl group, R ⁴¹ represents a hydrogen atom or a non-metal atomic group, and R ⁴² represents Represents an amino group or a hydroxyl group which may be substituted with an alkyl group or an aryl group, and n ₈ is 1 to 4
Represents the integer. Specific examples of these are disclosed in JP-A-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 ^{38 to} R ⁴² . ),

Examples of the anthraquinone dye represented by A include those represented by the general formula (XI), the general formula (XI)

[0029]

[Chemical 10]

(In the formula, R ⁴³ represents a hydrogen atom or a non-metal atomic group, and n ₉ represents an integer of 1 to 6. Specific examples thereof are JP-A-59-227948 and 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
Any of ⁴³ may be used. )

Examples of the naphthoquinone dye represented by A include those represented by the general formula (XII) and the general formula (XII)

[0032]

[Chemical 11]

(In the formula, R ⁴⁴ represents a hydrogen atom or a non-metal atomic group, and n ₁₀ 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 ⁴⁴ . )

Examples of the methine dye represented by A include those represented by the general formula (VIII), the general formula (VIII)

[0035]

[Chemical 12]

(In the formula, R ⁴⁵ represents an aryl group or a heterocyclic group, and R ⁴⁶ 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 and 3-
230994, JP-A-61-163895, JP-A-3-197185 and the like. The bond with B is R ⁴⁵ . ), Those represented by general formula (XIV), general formula (XIV)

[0037]

[Chemical 13]

(Wherein R ⁴⁷ represents a hydrogen atom or a non-metal atomic group, R ⁴⁸ represents a cyano group, an aryl group, a heterocyclic group or a substituted vinyl group, and G represents a non-necessary group for forming a heterocycle. Represents a group of metal atoms.
-6559, 2-34450, 2-208093
No. 2-215595, No. 2-215594, JP-A Nos. 63-74685, 63-74688, No. 2-258298, No. 64-42286, 60-156760, and No. 60-156760. 64-42286, 62
No. 273265, No. 62-220557, JP-A No. 2
-175294, 3-49999, 1-196
396 and 1-196395. The bond with B may be any of R ⁴⁷ , R ⁴⁸ and G),

Examples of the quinophthalone dye represented by A include those represented by the general formula (XV), and the general formula (XV)

[0040]

[Chemical 14]

(In the formula, R ⁴⁸ represents a hydrogen atom or a halogen atom, and R ⁴⁹ represents a hydrogen atom or a non-metal atomic group. Specific examples thereof are JP-A-60-53565 and 63-189289. , No. 63-182193, etc. The bond with B is R ⁴⁹ ) and the like.

As -B- in the general formula (I),
Is mentioned. -CO- [CR⁴⁹(R^Fifty)] N₁₁− (However
And R⁴⁹, R^FiftyIs a hydrogen atom or substituted with 1 to 7 carbon atoms
Optionally an alkyl group, which may be substituted with 6 to 10 carbon atoms
Represents an aryl group or X, and n₁₁Represents an integer from 0 to 4
Forget ), -O-CO- [CR⁵¹(R⁵²)] N₁₂− (However
And R⁵¹, R⁵²Is R⁴⁹, R^FiftyAnd n₁₂Is n₁₁
I agree. ), -NR⁵³-CO- [CR
⁵⁴(R⁵⁵)] N₁₃-(However, R⁵³, R⁵⁴, R⁵⁵Is R⁴⁹,
R^FiftyAnd n₁₃Is n₁₁I agree. ),-
[CR⁵⁶(R⁵⁷)] N₁₄-(However, R⁵⁶, R⁵⁷Is R⁴⁹,
R^FiftyAnd n₁₄Is n₁₁I agree. ), -N
R⁵⁸SO₂-[CR⁵⁹(R⁶⁰)] N₁₅-(However, R⁵⁸,
R⁵⁹, R⁶⁰Is R⁴⁹, R ^FiftyAnd n₁₅Is n₁₁Same as
It means ), -O-SO₂-[CR⁶¹(R⁶²)] N₁₆
(However, R⁶¹, R⁶²Is R⁴⁹, R^FiftyAnd n₁₆Is
n₁₁I agree. ),-CR⁶³= CR⁶⁴-CR⁶⁵(R
⁶⁶)-(However, R⁶³, R⁶⁴, R⁶⁵, R⁶⁶Is R⁴⁹, R^FiftyWhen
I agree. ), -Ph-CR⁶⁷(R⁶⁸)-(However, P
h represents a phenylene group, R⁶⁷, R⁶⁸Is a hydrogen atom or
It represents an alkyl group having 1 to 3 carbon atoms. ), -Het-
(However, Het is a pentagonal compound having at least one nitrogen atom.
Represents a 6-membered heterocycle. Examples for these specific examples
For example, the groups described in Chemical formula 15 can be mentioned. ).

[0043]

[Chemical 15]

Examples of X in the general formula (I) include the following. Halogen atom, -OR ⁶⁹ (wherein R ⁶⁹ is an optionally substituted alkyl group having 1 to 7 carbon atoms, and 6 to 1 carbon atoms)
It represents an aryl group of 0 or a heteryl group of 2 to 10 carbon atoms. ), -SR ⁷⁰ (however, R ⁷⁰ is synonymous with R ⁶⁹ ), -OSO ₂ -R ⁷¹ (however, R ⁷¹ is synonymous with R ⁶⁹ ), -O-CO-R ⁷² (however. , R ⁷² is synonymous with R ⁶⁹ ), —S—CO—NR ⁷³ (R ⁷⁴ ) (provided that R ⁷³ ,
R ⁷⁴ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 10 carbon atoms. ), -NR ⁷⁵ (R ⁷⁶ ) (however, R ⁷⁵ , R ⁷⁶
Represents an optionally substituted alkyl group having 1 to 7 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or R ⁷⁵ , R ⁷⁶ and a nitrogen atom together form, for example, pyrrolidine, piperidine. A 5- or 6-membered heterocycle such as morpholine, piperazine, imidazole or pyrazole may be formed. ), - O-CO-NR 77 (R 78) ( where, R ^77,
R ⁷⁸ is synonymous with R ⁷³ and R ⁷⁴ . ). -SO-R ^79, (where, R ⁷⁹ is synonymous with ^{R 69.) - NR 80 (} SO 2 -
R ⁸¹ ) (provided that R ⁸⁰ is synonymous with R ⁷³ and R ⁸¹ is synonymous with R ⁶⁹ ), —O—CO—NR ⁸² (R ⁸³ ) (provided that
R ⁸² is synonymous with R ⁷³ and R ⁸³ is synonymous with R ⁶⁹ . ), -O-CO-CO- ^R84 ( ^R84 is synonymous with ^R69 ), -O-CO-O- ^R85 ( ^R85 is synonymous with ^R69 ), -S-CO. -R ⁸⁶ (R ⁸⁶ is synonymous with R ^69.)

In the general formula (I), n ₀ is an integer of 1 to 3, and n is an integer of 1 to 3.

Specific examples of the dye represented by formula (I) used in the present invention are shown below, but the dyes are not limited to these.

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

The synthesis examples of the dye of the present invention are shown below.

Synthesis example. Synthesis of dye No. 1 6-amino-2,4-dichloro-3-methylphenol monohydrochloride 6.9 g and dimethylacetamide 40 ml
Was stirred under an ice bath. To this, 2.4 ml of chloroacetyl chloride was added dropwise over 10 minutes. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 30 minutes. Ice water to reaction liquid 1
Add 50 ml and stir for 30 minutes. By suction filtration, washing with water and air-drying, 7.6 g of 2,4-dichloro-6-chloroacetylamino-3-methyl-phenol (intermediate A) was obtained. 7.0 g of the intermediate thus obtained, 400 ethyl acetate
ml, ethanol 200 ml, aqueous solution 340 ml containing sodium carbonate 38.7 g, and p-N, N-diethylaminoaniline monosulfate 7.5 g were stirred at room temperature, and ammonium persulfate 6.6 g was added thereto over 10 minutes. .. Two
The crystals precipitated by stirring for 0 minute were filtered. Methanol wash once, water wash once, air dry mp 182-3 ℃ dye
6.1 g of No. 1 was obtained.

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

The usage of the heat transferable dye of the present invention will be described. The thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. The yellow, magenta and cyan dyes are usually arranged on the support so as to form independent areas. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. In addition, three kinds of thermal transfer dye-donor materials in which the above yellow dye, magenta dye, and cyan dye are provided on separate supports, respectively,
From these, it is also possible to sequentially perform thermal transfer of dyes to one thermal transfer image receiving material. 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 as a dry film thickness.
It is preferable to set m, particularly 0.4 to 2 μm. The coating amount of the dye is 0.03 to 1 g / m ² , preferably 0.1 to 0.6 g / m ² .

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

As the support of the thermal transfer dye-providing material, any conventionally known one can be used. 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-providing material is generally 2 to
It is 30 μm. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer. As a result, the transfer density is further improved. Also, a slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof. In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to perform anti-sticking treatment on the side of the support on which the dye-donor layer is not provided. For example, it is preferable to provide a heat resistant slip layer mainly containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or an alkaline earth metal salt of a 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 the phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, and the content is 1 to 50% by weight, preferably 1% by weight based on the polyvinyl butyral resin.
It is preferable 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 dye-donor element may be provided with a hydrophilic barrier layer for preventing the diffusion of the dye toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. Generally good results are gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate grafted gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired effect, but preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate). / 2-aminoethyl methacrylate / -2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example, Bostic 7650 (M Heart Company, Bostic Chemical Group) Alternatively, a chlorinated high density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the undercoat layer is not particularly limited, but it is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material and heat is applied in accordance with the image information from either side, preferably the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and known ones such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In laser-based systems, the thermal transfer dye-donor material preferably contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into heat energy, transfers the heat to the dye in the immediate vicinity, and the dye is transferred to the heat transfer image-receiving material at a temperature (heat transfer temperature). ) Is heated up to. The absorbent material is layered below the dye and / or is mixed with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstitute the original target color and heat transfer. For a more detailed description of this process, see British Patent 2,
083,726A. British Patent 2,0
The absorbing material disclosed in the 83,726A for its laser system is carbon.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system, etc. It can be used to make prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to. In a preferred embodiment of the invention, the thermal transfer dye-donor element comprises a polyethylene terephthalate support coated with cyan dye, magenta dye and yellow dye in successive repeating regions, wherein the thermal transfer step is performed sequentially for each dye. A transfer image of three colors is formed. Of course, when the thermal transfer process is performed in a single color, a monochrome transfer image is obtained. Thermal transfer of dyes from a thermal transfer dye-donor material to a thermal transfer image-receiving material includes ion gas lasers such as argon or krypton, metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby or YAG, or 7
Several lasers can be used, such as semiconductor lasers such as gallium-arsenide, which emit in the infrared range from 50 to 870 nm. However, in practice, semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention comprises a support having an image-receiving layer for receiving the dye transferred from the dye-providing material. This image-receiving layer contains a substance capable of receiving the heat-transferable dye, which has a function of dyeing the heat-transferable dye, which receives the heat-transferable dye transferred from the heat-transfer dye-providing material during printing. Or with other binder substances, it is preferable that the coating has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive a heat transferable dye.

(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 or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 may be mentioned. As commercially available products, Toyon 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 synthetic resin as described above, a mixture or copolymer of these may be used. In addition, JP-A 1-188
The basic compounds and / or mordants described in No. 391 and No. 3-83685 can also be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in No. -30247 and No. 62-136646 can be mentioned. The image receiving layer of the thermal transfer image receiving material is
A substance capable of receiving the heat transferable dye may be dispersed in a water-soluble binder and carried. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a crosslinking reaction by a hardening agent is preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having a higher dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used as the outermost layer. Using a synthetic resin with a higher point, or sticking the surface to other substances, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents failures such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to 50.
μm, particularly preferably in the range of 3 to 30 μm. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

Examples of the active hydrogen compound contained in the image-receiving layer include a hydroxyl group (or its salt), a mercapto group, a carboxyl group (or its salt), a sulfonic acid group (or its salt), a sulfinic acid group (or its salt), Known low molecular weight compounds or high molecular weight compounds having an amino group, an amide group, a hydrazino group or a hydrazide group, preferably a hydroxyl group, a carboxyl group or an amino group can be mentioned. Of these, preferred are compounds having a secondary amino group. Specific examples thereof are listed below.

[0069]

[Chemical formula 24]

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer depends on the material
It is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, and also serves as an adhesive in some cases. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat. The image receiving layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, and the like, which constitute the thermal transfer image receiving material, include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, and synthetic zeolite. Fine powder of zinc oxide, lithopone, titanium oxide, alumina or the like may be contained. The support used for the thermal transfer image receiving material can withstand the transfer temperature, and has smoothness, whiteness, slipperiness,
Any material can be used as long as it satisfies the requirements in terms of frictional property, antistatic property, and dent after transfer.
For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), 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 that have been treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. For example, see “The Chem” edited by K. Veenkataraman.
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyryl-based compounds, and 2,5-dibenzoxazolethiophene-based compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent. In the present invention, in order to improve the releasability of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably the outermost layer corresponding to the contact surface of both materials. It is preferable to include a release agent in the. Solid release agents such as polyethylene wax, amide wax, and Teflon powder: Wax-like substances: Fluorine-based or phosphate-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. Although any of the above releasing agents can be used, silicone oil is particularly preferable. As non-denatured silicone oil, carboxy-modified, amino-modified,
Modified silicone oil such as epoxy modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data issued by Shin-Etsu Silicone Co., Ltd.
When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is emulsified and dispersed in a water-soluble binder. Is effectively a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710).

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

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. Examples of the antioxidant include chroman compounds, coumarans 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, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681
No., etc.), benzophenone compounds (JP-A-56-27)
No. 84, etc., and JP-A-54-48535 and 6
There are compounds described in Nos. 2-136641 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 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-7556
8 and the compounds described in JP-A-63-199248. Examples of useful anti-fading agents are disclosed in JP-A-62-2
15272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image receiving material may be contained in the image receiving material in advance, or may be supplied to the image receiving material from the outside by a method of transferring from the dye providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, 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, silicones Polyethylene oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc., nonionic surfactants: alkyl carboxylates, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, and other carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups Anionic surfactants containing acidic groups such as:
Amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Heterocyclic fourth such as
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used. Specific examples of these are disclosed in JP-A Nos. 62-173463 and 62-18345.
No. 7 etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

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

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EXAMPLES In the following Examples and Comparative Examples, production of a thermal transfer dye-donor material and a thermal transfer image-receiving material, printing using both materials, and a test of the thermal transfer image-receiving material will be described. (Example 1) (Preparation of thermal transfer dye-donating material) A 6 μm-thick polyester film (manufactured by Teijin) having a heat-resistant slip layer made of a thermosetting acrylic resin on one side was used as a support, and the heat-resistant slip property of this support An ink for forming a dye-donor layer having the following composition was coated on the surface opposite to the layer-provided side with a wire bar and dried by heating in a hot oven to obtain Sample I-101. Cyan dye donating ink Dye (Compound A below) 3 parts

[0082]

[Chemical 30]

Polyvinyl butyral resin (Denka Butyral 5000A: manufactured by Denka Kagaku) 3 parts Silicon oil (KF96: manufactured by Shin-Etsu Silicone) 0.1 part Polyisocyanate (Takenate D-11DN: manufactured by Takeda Pharmaceutical Co., Ltd.) 0.1 part Methyl ethyl ketone 50 parts Toluene 50 parts Dry coating amount 1.0 g / m ² The dye of Sample I-101 was changed to the compound shown in the table below,
Samples I-102 to I-111 were prepared. Samples Compound No. I-102 1 I-103 2 I-104 3 I-105 4 I-106 5 I-107 6 I-108 7 I-109 8 I-110 9 I-111 10

(Preparation of thermal transfer image-receiving material) As a support, low-density polyethylene in which ultramarine blue was kneaded was laminated on one surface of high-quality paper having a thickness of 175 μm to a thickness of 33 μm, and high density polyethylene was applied on the opposite surface. Using a polyethylene-coated paper laminated to a thickness of 32 μm, the composition for hydrophilic binder layer (1) was coated and dried on the side of the low-density polyethylene laminate so that the coating amount of gelatin was 1 g / m ² .

Composition for hydrophilic binder layer (1) Gelatin 60 parts Water 3000 parts Surfactant (compound represented by the following chemical formula B) 2.3 parts Thickener (potassium polystyrene sulfonate) 1.4 parts

[0086]

[Chemical 31]

Further, the composition (2) for image receiving layer having the following composition was coated on the hydrophilic binder layer by Giesser coating so that the coating amount of the polyester resin was 10 g / m ² .
An image receiving material for thermal transfer R-101 was prepared by drying. Drying was carried out for 30 minutes in a 100 ° C. oven after natural drying in a draft.

Image-Receiving Layer Composition (2) Polyester Resin (Vylon 200: Toyobo) 20 Parts Silicon Oil (Ether Modified Silicon Oil: Shin-Etsu Silicone) 0.5 Parts Methyl Ethyl Ketone 100 Parts Toluene 100 Parts For this sample R-101 1.0 parts each of the following compounds was added to prepare samples R-102 to R-110.

Sample Compound No. R-102 H-1 R-103 H-2 R-104 H-3 R-105 H-4 R-106 H-15 R-107 H-16 R-108 H-27 R-109 H-28 R-110 H-29

1) Measurement of transfer density Using a Fujifilm video printer VP8000,
Created cyan ink sheets I-101 to I-11
1 was transferred to R-sheets R-101 to 110, the transfer density was measured by Xrite, and the transferability was evaluated by the R density. For the transferred image, the maximum density of cyan color was transferred using a pattern generator.

2) Image blur Using an impulse sealer, the formed ink sheet and image receiving sheet were superposed and heated to a rod shape having a width of about 2 mm to 10 cm to perform transfer. The heating was performed at about 180 ° C. and the heating time was 2 seconds. The obtained image was placed in a constant temperature bath at 60 ° C. and 70% relative humidity, and bleeding of the image after 3 weeks was visually determined. Almost no change from the initial stage ○ Slightly bleeding △ Very bleeding was evaluated as bokeh ×. The results, as shown in Table 1, show that the present invention has both high transfer density and no blurring of the image, and shows excellent performance.

[0092]

[Table 1]

[0093]

According to the present invention, a thermal transfer material having a high transfer density and no image blur can be obtained.

Claims (1)

[Claims] 1. A thermal transfer material comprising a dye-donor material having a dye layer on a support and an image-receiving material having an image-receiving layer on the support, wherein the dye layer undergoes thermal transfer to activate active hydrogen in the image-receiving layer. A thermal transfer material comprising a dye having a leaving group capable of substituting with a compound, and the image-receiving layer containing an active hydrogen compound.