JPH07125462A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To obtain an image excellent in transfer properties, hue and fastness, in a thermal transfer recording material wherein a thermal transfer dye donating material and a thermal transfer image receiving material are provide on a support, by using a specific dye as a thermal transfer dye and using a basic substance and/or a mordant as a dye receiving compd. CONSTITUTION:In a thermal transfer system for obtaining a print from an image electronically formed by a color video camera, a thermal transfer recording material for recording an image by the heating corresponding to image data is obtained by providing a thermal transfer dye donating layer provided with a dye donating layer containing a thermal transfer dye and a thermal transfer provided with a receiving layer containing a dye acceptive compd. on a support. In this case, as the thermal transfer dye, a dye represented by general formula (R<1> and R<2> are a hydrogen atom or a substituent group and R<3> is a substituted or non-substituted aromatic group or a heterocyclic group) is used and the dye acceptive compd. is a basic substance and/or mordant. not lowered in sharpness can be formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material for recording an image by heating corresponding to image information.

[0002]

BACKGROUND OF THE INVENTION In recent years, thermal transfer systems have been developed for obtaining prints from electronically formed images on color video cameras. According to the method for obtaining such a print, the color-separated image is converted into an electric signal, and this signal is transmitted to the printer. To obtain a print, the dye-donor element is placed face-to-face with the image-receiving element and inserted between the thermal head and the platen roller. The thermal head is energized and heated according to the transmitted signal.
The dye-donor element is heated from the back side by a thermal head, and the dye in the dye-donor element is transferred to the image-receiving element and recorded as an image. In the case of a color image, this operation is followed by heating with yellow, magenta, cyan, and optionally black dye-donor elements to record an image. An alternative method of obtaining a thermal print using the aforementioned electrical signal is to use a laser instead of a thermal head. In this method, the dye-donor element contains a substance that strongly absorbs laser light. When the dye-donor material is irradiated with laser light, the light-absorbing substance converts light energy into heat energy, heats the dye-donor material, and the dye transfers to the image-receiving material. This light absorbing substance is contained in the dye-donor layer or in contact therewith. The laser light is modulated with an electrical signal to heat the dye-donor element.

It is desirable that the dye-donor material used in the above thermal transfer recording system uses a dye that is apt to transfer heat as much as possible in order to reduce the load on the thermal head and increase the recording speed. However, for that reason, during storage or under high temperature and high humidity environment, the pigment may precipitate,
There is a problem that the dye moves in the recorded image-receiving material to reduce the sharpness of the image, or it transfers to a contact object to cause contamination.

In order to solve this problem, Japanese Patent Publication No. 4-1
5760, JP-A-1-188391, and 3-
No. 83685 discloses a method in which a mordant is contained in the image receiving layer and a dye having a mordant group such as a phenolic hydroxyl group is thermally transferred. As a yellow dye used in this method, a pyrazolone azo dye is described in JP-B-4-15760, and an acetoacetanilide azomethine dye is described in JP-A-3-92386.

[0005]

However, in the case of the combination of the above yellow dye with the basic substance and / or the mordant, the dissociation of the dye is insufficient and the mordant is incomplete, resulting in the sharpness of the image with the passage of time. , Or there is a problem in color reproduction because the hue is broad, a sufficient transfer density cannot be obtained due to reasons such as a small molecular extinction coefficient of the dye and a low heat transfer property, and image stability, In particular, a combination of a yellow dye and a basic substance and / or a mordant which are poor in light fastness or which satisfy all the properties have not been found yet, and improvement thereof has been desired.

Therefore, an object of the present invention is to provide a dissociative yellow dye and a basic substance which have a high heat transfer property, exhibit excellent spectral characteristics when dissociated, have a high spectral absorption coefficient, and are excellent in light and wet heat fastness. It is an object of the present invention to provide a thermal transfer recording material which, when combined with a mordant and / or a mordant, is excellent in transferability, hue and fastness, and which gives an image with no reduction in sharpness.

[0007]

These objects of the present invention have been achieved by the following constitutions. (1) A thermal transfer recording material comprising a thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a receiving layer containing a dye-receiving compound on the support. Wherein the heat transferable dye is a dye represented by the general formula (1), and the dye receiving compound is a basic substance and / or a mordant.

[0008]

[Chemical 3]

In the formula, R ¹ represents a hydrogen atom or a substituent, R ³ represents a substituted or unsubstituted aromatic group or a heterocyclic group, and X is necessary for forming a nitrogen-containing 5-membered ring. Represents a group of atoms. (2) In the thermal transfer recording material of (1), the general formula (1)
The heat transferable dye represented by the following general formula (2) or (3)
The thermal transfer recording material characterized by

[0010]

[Chemical 4]

In the formula, R ¹ and R ² represent a hydrogen atom or a substituent, and R ³ represents a substituted or unsubstituted aromatic group or a heterocyclic group.

The present invention will be described in detail below. In the general formula (1), R ¹ represents a hydrogen atom or a substituent, and as the substituent, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, an anilino group, Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy Represents a group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may further have a substituent.

More specifically, R ¹ is a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms, a substituent linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group, or an aryl group, an alkenyl group, an alkynyl group, a hydroxy group). It may be substituted with a group, amino group, nitro group, carboxy group, cyano group, or halogen atom, for example, methyl group, isopropyl group, t-butyl group, trifluoromethyl group, methoxyethoxy group, 2-methane. Sulfonylethyl group, 2-methanesulfonamidoethyl group, cyclohexyl group, adamantyl group, etc.); aryl group (having 6 to 6 carbon atoms)
12, for example, phenyl group, 4-t-butylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, etc .; cyano group; alkoxy group (having 1 to 12 carbon atoms, for example, methoxy group, ethoxy group, 2 -Phenoxyethoxy group, 2-methoxyethoxy group, 2-methanesulfonylethoxy group, etc.); aryloxy group (eg, phenoxy group, 2-methoxyphenoxy group, etc.); acylamino group (eg, acetamide group, benzamide group, etc.); Anilino group (eg, phenylamino group, 2-chloroanilino group, etc.); Ureido group (eg, phenylureido group,
Methylureido group, etc.); Sulfamoylamino group (eg, N, N-dipropylsulfamoylamino group, etc.);
Alkylthio group (eg, methylthio group, 2-phenoxythio group, etc.); Arylthio group (eg, phenylthio group, etc.); Alkoxycarbonylamino group (eg, methoxycarbonylamino group, etc.); Sulfonamide group (eg, methanesulfonamide group) , Benzenesulfonamide group and the like); carbamoyl group (for example, N-ethylcarbamoyl group, N-phenylcarbamoyl group and the like); sulfamoyl group (for example, N-ethylsulfamoyl group, N, N
-Diethylsulfamoyl group, etc.); sulfonyl group (eg, methanesulfonyl group, toluenesulfonyl group, etc.);
Alkoxycarbonyl group (eg, methoxycarbonyl group, butoxycarbonyl group, etc.); Heterocyclic oxy group (eg, 2-tetrahydropyranyloxy group, etc.); Acyloxy group (eg, acetoxy group, etc.); Carbamoyloxy group (eg, N -Methylcarbamoyloxy group etc.); Silyloxy group (eg trimethylsilyloxy group etc.); Aryloxycarbonylamino group (eg phenoxycarbonylamino group etc.); Imido group (eg N-phthalimido group, N-succinimido group etc.) A heterocyclic thio group (eg, 2-pyridylthio group); a phosphonyl group (eg, phenoxyphosphonyl group, phenylphosphonyl group, etc.); an acyl group (eg, acetyl group, benzoyl group, etc.).

Of these, preferred is an alkyl group,
It is a phenyl group, a phenoxy group, or an alkoxy group, and these groups may have a substituent. Also, carbon number is 8
The following are particularly preferred. R ³ represents a phenyl group or a naphthyl group as the aromatic group, and O, N,
Represents a 3-8 membered ring having at least one atom of S,
It may have a condensed ring. For example, 2-thiazolyl, 2
-Benzothiazolyl, 3-benzothiazolyl, 1,3
4-thiadiazol-2-yl, 1,2,4-thiadiazol-5-yl, 3-pyrazolyl, 5-pyrazolyl,
2-thienyl, 2-imidazolyl, 2-benzimidazolyl, 3-isoxazolyl, 5-isothiazolyl, 2
-Pyridyl, 4-pyridyl, 2-quinolyl, 4-quinolyl and the like, which may have the substituent described in R ¹ as a substituent. X represents an atomic group necessary for forming a nitrogen-containing 5-membered ring, preferably a 5-membered ring having 1 to 3 nitrogen atoms, and particularly preferably the following general formula (2) or (3). expressed.

[0015]

[Chemical 5]

R ¹ and R ³ have the same meanings as the substituents described in formula (1), and R ² represents the same substituent as R ¹ . The above dye needs to have a low pKa in order to be dissociated and mordanted in the image receiving layer described later, and preferably the pKa is 1 or less.
It is preferable to select the substituents R ¹ , R ² and R ³ so as to be 8 or less, and more preferably 7 or less. Specific examples of the dye used in the present invention are shown below, but the present invention is not limited thereto.

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

The dye represented by the general formula (2) or (3) is obtained by diazotizing the coupler component represented by the general formula (4) or (5) and the amine compound represented by the general formula (6). Obtained by coupling.

[0025]

[Chemical 13]

R ¹ , R ² and R ³ have the same meanings as described in the general formula (2) or (3). Next, synthesis examples of the dye of the present invention will be shown. (Synthesis Example 1) Dye; Synthesis of D-5 13 g of p-cyanoaniline was added with 36 ml of hydrochloric acid / 100 m of water.
l solution, and under ice cooling sodium nitrite 7.6 g /
A solution of 50 ml of water was slowly added dropwise and stirred for 1 hour to prepare a diazo solution. Then, 6-t-butyl-2-methyl-1H-pyrazolo [1,5-b] [1,2,4] triazole 18 g / sodium acetate 40 g / methanol 30
Slowly add the adjusted diazo solution to 0 ml of the mixture,
After continuing stirring for 1 hour, water was added and the precipitated crystals were collected by filtration to obtain 26 g of dye; D-5. mp. 202-3 ° C
λmax = 462 nm (acetone + 1% triethylamine)

Synthesis Example 2 Dye; Synthesis of D-27 0.85 g of sodium nitrite was added to 6 ml of concentrated sulfuric acid to prepare 6
After heating and dissolving at 0 ° C., 20 ml of a mixed solution of acetic acid / propionic acid (3: 2) was added while cooling. To this solution, 1.85 g of 2-amino-5-ethylthio-1,3,4-thiadiazole was added under ice cooling and stirred for 1 hour to prepare a diazo solution. Then 6-t-butyl-2-methyl-
1H-pyrazolo [1,5-b] [1,2,4] triazole 1.8 g / sodium acetate 7 g / methanol 50 m
The adjusted diazo solution was slowly added to the mixture of 1 and the mixture was stirred for 1 hour, water was added, and the precipitated crystals were collected by filtration.
2.8 g of Dye-D-27 was obtained. mp. 237-8 ° C
λmax = 458 nm (ethyl acetate + 1% triethylamine) The heat transferable dye of the present invention is contained in the color material layer on the support and used as a thermal transfer dye-donating material for image formation by a thermal transfer system. Next, the case where the heat transferable dye of the present invention is used for image formation of a thermal transfer system will be described in detail below.

Usually, in order to form a full-color image, dyes of three colors of yellow, magenta and cyan are required. Therefore, the compound of the present invention can be used as a yellow dye, and the other two colors can be selected from conventionally known dyes to form a full-color image. Similarly to the yellow dye used in the present invention, the other two colors are preferably dissociative dyes. 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 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 regions. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a frame-sequential or line-sequential manner. In addition, the above yellow dye,
It is also possible to prepare three kinds of thermal transfer dye-providing materials in which a magenta dye and a cyan dye are respectively provided on different supports, and from these, the dyes are thermally transferred to one thermal transfer image-receiving material in sequence. Each of the dyes 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 a 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, particularly 0.4 to 2 in terms of dry film thickness.
It is preferable to set in the range of μm. The amount of dye applied is 0.
03 to 1 g / m ² , more preferably 0.1 to 0.6 g / m ^2.
Is.

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

Any conventionally known support can be used as the support of the thermal transfer dye-providing material. For example, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin. Examples thereof include polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm.
Is. 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. This further improves the transfer density. As the hydrophilic polymer, the water-soluble polymer described above can be used. A slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof.

In order to prevent sticking due to heat of the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to perform sticking prevention 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 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 and a glass transition point of 80.
From about 110 ° C. and from the viewpoint of many reaction sites with isocyanate, the weight percentage of vinyl butyral portion is 1
5 to 40% is preferable. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafak RD720 manufactured by Toho Chemical Co., Ltd. is used, and 1 to 50% by weight, preferably 10 to 4% by weight based on the polyvinyl butyral resin.
It is recommended to use about 0% 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 dye from diffusing 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 graft 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). -Methacrylic acid-2-aminoethyl-methacrylic acid-2-hydroxyethyl) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example Bostic 7650 (Mhart Inc., 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 means of a heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material 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 a known one such as a laser beam (for example, a semiconductor laser) infrared flash, a hot pen, or the like can be used. In laser-based systems, the dye-donor material contains a material that strongly absorbs the laser beam. When the dye-providing material is irradiated with a laser beam,
The absorptive material converts light energy into heat energy which immediately transfers the heat to nearby dyes and heats them to their heat transfer temperature for transfer to the image receiving material. The absorbent material is present in layers under 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 dye-donor material to reconstitute the original target color and heat transfer. A more detailed description of this process can be found in British Patent 2,083,726A.
The absorbing material disclosed for that laser system in British Patent 2,083,726A is carbon. In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to print by using various printers of thermal printing system, facsimile, or print production of image by magnetic recording system, optical recording system, television, C
It can be used to create prints from the RT screen. For details of the thermal transfer recording method, reference can be made to the recording of JP-A-60-34895.

In a preferred embodiment of the invention, the dye-donor element comprises a polyethylene terephthalate support coated in successive repeating regions of a cyan dye, a magenta dye and a yellow dye, the steps being carried out sequentially for each color to give a three-part dye. Form a color transfer image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
For the thermal transfer of dyes from dye-donor materials to image-receiving materials, ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA.
Several types of lasers can be used, such as solid state lasers such as G, or semiconductor lasers such as gallium-arsenide that emit in the infrared region of 750 to 870 nm. However, in practice,
A semiconductor laser is 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 contains a basic substance having a function of receiving the dye transferred from the dye-donating material on the support and dissociating the received dye. And / or an image receiving layer containing a mordant is provided. (Hereinafter, the basic substance and the mordant will be referred to as a dye fixing agent.) The dye fixing agent has a compound having a primary to tertiary, more preferably a tertiary amino group, and a nitrogen-containing heterocyclic group. A compound and a compound having these quaternary cation groups. Among them, polymer dye fixing agents are particularly preferable. Examples of the polymer dye fixing agent include polymers containing a repeating unit represented by the following general formula (7).

[0037]

[Chemical 14]

In the formula (7), a ¹ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 4 carbon atoms. D ¹ represents a divalent group connecting a carbon atom and D ² . D ² represents a tertiary amino group, a nitrogen-containing heterocyclic group or a quaternary cation group.

A¹Specifically, hydrogen atom, halogen
Group atom (for example, chlorine atom, bromine atom, etc.), cyano group
Or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl
, Propyl, butyl, etc.). a¹Is preferably
Represents a hydrogen atom and a methyl group. D¹Specifically,
-OCO-, -COO-,-(CH₂)_v-, -SO ₂
-, -COO- (CH₂)_v-, -OCO- (CH₂)
_v-(V represents an integer of 1 to 3), -O-, -CON
H-, -CON (R¹)-,-SO₂N (R¹)-,-
CONHCONH-, -CONHCOO- or -C₆H
_Four-(Where R¹Is synonymous with that of formula (I))
Represents a group formed alone or in combination thereof.
D¹Is -C₆H_FourWhen-is represented, the benzene ring is a substituent
May have. As a substituent, a halogen atom (for example,
For example, chlorine atom, bromine atom, etc.), alkyl group (eg methyl
Ru, ethyl, propyl, butyl, chloromethyl, methoki
Cimethyl, etc.), alkoxy groups (eg methoxy, etoxy)
Ci, propioxy, butoxy, etc.) and the like. D¹
Is preferably -OCO-, -OCO- (CH₂)
_V-, -COO- (CH₂)_V-, -CH₂-Or-C
₆H_Four-CH₂Represents-.

When D ² represents a tertiary amino group, the tertiary amino group is represented by —N (D ⁴ ) D ⁵ , and D ⁴ and D ⁵ each independently have the same meaning as R ¹ . D ⁴ and D ⁵ may form a ring structure, and the ring structure represents a 5- or 6-membered ring which may contain oxygen, nitrogen or sulfur. D ⁴ and D
⁵ preferably independently represents an alkyl group having 1 to 6 carbon atoms or a benzyl group. When D ² represents a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group is preferably an imidazole group or a pyridyl group, which may be substituted. Examples of the substituent include the above R ¹ . When D ² represents a quaternary cation group, the quaternary cation group is preferably a quaternary ammonium group or a quaternary imidazole group. The quaternary ammonium group is represented by the following general formula (8).

[0041]

[Chemical 15]

In equation (8), D⁶, D⁷, D⁸Each is independent
Is synonymous with R1. D⁶And D⁷Or D⁷And D⁸Or
D⁶And D⁸May form a ring structure, and the ring structure is D^Four
And D ^FiveIs synonymous with that formed by. M is a positive in the substituent
Represents an anion that neutralizes ionic charge. As anion
Is an inorganic or organic anion.
May be used, preferably perchlorate ion, iodine ion
Ion, bromine ion, substituted aryl sulfonate ion (eg
For example, p-toluenesulfonate ion). D⁶,
D⁷, D⁸It is preferable that each independently has 1 to 6 carbon atoms.
It represents a rukyl group or a benzyl group. Quaternary imidazole
Examples of the group include the following general formula (9).

[0043]

[Chemical 16]

In the formula (9), D ⁹ has the same meaning as R ¹ . M has the same meaning as above. R ⁹ is preferably a substituted or unsubstituted alkyl group. Ra, Rb and Rc each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The repeating unit represented by the formula (7) is contained in the polymer in an amount of 10 mol% to 100 mol%. Furthermore, as a polymer component which can be contained in the polymer together with the polymer component represented by the formula (7),
Any monomer may be used as long as it is a monomer corresponding to another repeating unit copolymerizable with the polymer component of the formula (7). Preferred are vinyl compounds, and more specifically, methacrylic acid esters, acrylic acid esters, styrenes,
Heterocyclic vinyls and the like can be mentioned. These other monomers are used within the range of not more than 90 mol% in the total polymer components of the polymer dye fixing agent. The repeating unit represented by the formula (7) and the other polymer component may be present in the polymer in a random form or a block form.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
5,124, 3,148,061, JP-A-60.
-118834, 60-122941, JP-A-6-6
The dye fixing agents described in JP-A No. 2-244043, JP-A No. 62-244036 and the like can be mentioned. Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101 and 2,093,041,
No. 1,594,961, U.S. Pat. No. 4,124,3
No. 86, No. 4,115,124, No. 4,273,
853, 4,450,224, JP-A-48-2
Examples thereof include dye fixing agents described in No. 8325. Other preferable specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. Nos. 3,709,690, 3,898,088 and 3,958,995. Nos. 60-57836, 60-60643 and 6
0-122940, 60-122942, 60
-235134 and the like are mentioned. Specific representative examples of the dye fixing agent used in the present invention are shown below, but the present invention is not limited to these. (Numbers represent mol%)

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

The molecular weight of the polymeric dye fixing agent of the present invention is 1
X10 ³ to 1x10 ⁶ are suitable, and especially 1x10 ⁴ to
2 × 10 ⁵ is preferable. The above-mentioned polymer dye fixing agent can also form the receiving layer by itself. It can also be used as a mixture with the synthetic resin described below. The amount of the dye fixing agent applied is suitably 0.2 to 30 g / m ² , and preferably 0.5 to 15 g / m ² . The Tg of the polymer dye fixing agent is 0 to 120 ° C. Among them, Tg is preferably 30 to 70 ° C. The polymer dye fixing agent is preferably a polymer having a tertiary amino group, and more preferably a polymer having a tertiary amino group in a pendant. The polymer dye fixing agent is preferably easily soluble in an organic solvent containing substantially no water. As the organic solvent, toluene, xylene, methylene chloride, chloroform dichloroethane, hexane, pentane, acetone, cyclohexane, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylacetamide, dimethylformamide, methanol, ethanol, isopropanol, acetonitrile, propionitrile, terrara Hydrofuran, diethyl ether and the like can be mentioned.

When used in combination with a synthetic resin, it can be easily determined by those skilled in the art depending on the kind and composition of the dye fixing agent and the image forming process used.
The fixative / synthetic resin ratio is preferably 10/90 to 100
It is preferably used at / 0. Any synthetic resin may be used as long as it can accept the dye transferred from the transfer sheet, and specifically, the following synthetic resins (a) to (f) are used.

(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 sulfo group or a carboxyl group) and ethylene glycol, Polyester resin obtained by condensation of 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, 63-7971 and 63
-7972, 63-7973, 60-2948.
Examples thereof include those described in No. 62. As commercially available products, Toyon Byron 290, Byron 200,
Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009, 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, polyacrylonitrile resin, etc.

In addition to the above synthetic resins, mixtures or copolymers of these can also be used. In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling point organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat transferable dye or as a dye diffusing agent. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A-62-1747.
54, 62-245253, 61-20944.
No. 4, No. 61-200538, No. 62-8145,
No. 62-9348, No. 62-30247, No. 62-
The compound described in No. 136646 can be mentioned.
The image receiving layer of the thermal transfer image receiving material of the present invention may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a crosslinking reaction by a hardening agent is preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having 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 image receiving layer is 0.5 to 50 μm, especially 3 to 50 μm.
The range of 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer. The intermediate layer is either a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more functions depending on the constituent material,
In some cases, it also serves as an adhesive. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but 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, cushion layer, porous layer, diffusion-preventing layer, adhesive layer, etc. constituting the thermal transfer image-receiving material of the present invention includes silica,
Fine powders such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobone, titanium oxide and alumina may be contained. If the support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic 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 added 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. A film or sheet that has 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. An example is K. Vevnkataraman's "The Chem.
istry of Synthetic Dyes ", Volume 5, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples thereof 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 releasability between the thermal transfer dye-donor material and the thermal transfer image-receiving material, the outermost layer, which is a layer constituting the dye-donating material and / or the image-receiving material, particularly preferably a surface contacting both materials, is used. It is preferable to include releasability. As release agents, solid or wax-like substances such as polyethylene wax, amide wax, Teflon powder: Surfactants such as fluorine-based and phosphoric ester-based: 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 an isocyanate) is also 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-providing 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. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61-159644
The compounds described in No. 1 are also effective. As an ultraviolet absorber,
Benzotriazole compounds (US Pat. No. 3,533,
No. 794), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (JP 56-2784 etc.) and others JP 54.
-48535, 62-136641, 61-8.
8256 and the like. In addition, JP-A-62
The ultraviolet absorbing polymer described in JP-A-260152 is also effective. Examples of the metal complex include U.S. Pat. No. 4,241,15.
5, No. 4,245,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A-62-174.
741 and 61-88256 (27) to (29).
Page, Japanese Patent Application Nos. 62-234103 and 62-31109.
6 and Japanese Patent Application No. 62-230596. 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 such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

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 (for example, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol,
Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agent: alkyl carboxylate, alkyl sulfonate,
Alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactant containing an acidic group such as a carboxy group, a sulfo group, a phosphor group, a sulfuric acid ester group and a phosphoric acid ester group:
Double-sided surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, viridinium, 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-62-173463 and JP-A-62-183457.
No. 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 surfactants mentioned above,
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-donating material and the thermal transfer image-receiving material 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-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, polyolefins and polymethacrylates 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.

[0061]

EXAMPLES Examples of the present invention will be shown below. However, the thermal transfer recording method of the present invention is not limited to the following examples.

Example 1 Preparation of Thermal Transfer Dye-donor Material (1) A 5 μm thick polyethylene terephthalate film having a heat resistant slipping layer provided on one side was used as a support.
A composition (1) for coating a dye-donor layer having the following composition was applied to the side opposite to the side provided with the heat resistant slipping layer using a gravure coater so that the thickness after drying would be 0.6 μm. ,
A thermal transfer dye-providing material (1) (hereinafter, also simply referred to as a dye-donating material) was obtained. Dye Donor Layer Coating Composition (1) Dye; D-3 10 Polyvinyl butyral (Denka Butyral 5000A: manufactured by Electrochemical) 10 g Silicone oil (KF-96: manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N: Takeda Yakuhin) 0.5g Methyl ethyl ketone 100ml Toluene 80ml

Preparation of Thermal Transfer Image Receiving Material (1) A laminated type synthetic paper having a thickness of 150 μm was used as a support.
The composition (1) for applying a receptive layer having the following composition was applied to the surface using a wire bar coater so that the thickness when dried was 5 μm, and the thermal transfer image receiving material (1) (hereinafter, also simply referred to as an image receiving material) was used. Produced). Drying was performed temporarily with a dryer and then in an oven at 80 ° C. for 1 hour. Receptor layer coating composition (1) Dye fixing agent; P-19 (manufactured by Sankyo Co., Ltd., AEA) 26 g Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KP- manufactured by Shin-Etsu Silicone) 857) 0.5 g Methyl ethyl ketone 100 ml Toluene 50 ml Cyclohexanone 10 ml Preparation of dye-donor materials (2) to (10) and (A) Dye of dye-donor material (1); D-3 and binder resin are shown in Table 1. Instead, in the same manner as above, dye-donor elements (2) to (10) and a dye-donor element for comparison (A) were produced.

[0064]

[Table 1]

Transfer Experiment Thermal transfer dye-donor materials (1) to (1) obtained as described above.
Transfer experiments were conducted using (10) and (A) and the thermal transfer dye image-receiving material (1). The thermal transfer dye-donor material and the thermal transfer image-receiving material are superposed so that the dye-donor layer and the receptor layer are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donor material, and the output of the thermal head is 0.25 W /
By heating under the conditions of dots, pulse width 0.1 to 10 msec, and dot density 6 dots / mm, and dye was dyed imagewise on the receiving layer of the image receiving material, clear image recording without transfer unevenness was obtained. Was given. The portion (Dmax) where the density of the recorded image-receiving material obtained at this time was saturated was measured by a reflection densitometer (X
Rite Inc., built-in status A filter) was used to measure the maximum transfer density of the image. Next, the recorded image receiving material was irradiated with a fluorescent lamp of 17,000 lux for 7 days, and the light fastness of the image was examined. Further, the image was stored in an oven at 60 ° C. for 2 weeks and the thermal stability of the image was examined. The reflection density after the test of the portion showing the reflection density of 1.0 was measured, and the stability was evaluated by the residual ratio (%) with respect to the reflection density of 1.0 before the test. Further, the degree of image bleeding was observed after the recorded image receiving material was stored in an oven at 60 ° C. for 2 weeks.
The criteria for judgment are indicated by ◯ when the image has hardly changed from that before storage, Δ when slightly blurred, and × when extremely blurred. The results are shown in Table 2. It can be seen that when the dye of the present invention is used, a clear image having high transfer density and excellent light and heat fastness can be obtained, and that there is no image blur with time. On the other hand, when the dye-providing material for comparison was used, the transferability was low, and further, the dissociation of the dye after transfer was insufficient, so that the transfer density was low and a clear hue image could not be obtained.

[0066]

[Table 2]

Example 2 Preparation of Thermal Transfer Image Receiving Materials (2) to (7), and (B) Dye Fixing Agent of Receptor Layer Coating Composition (1) of Thermal Transfer Image Receiving Material (1) of Example 1; P- Instead of 19 (manufactured by Sankyo Co., Ltd., amino group-containing polyvinyl acetal resin), the dye fixing agents and binder resins shown in Table 3 were used, and other image receiving materials (2) to (7) were prepared in the same manner. Further, a comparative image-receiving material (B) containing no dye fixing agent was prepared.

[0068]

[Table 3]

Transfer Experiment A transfer experiment was conducted in accordance with the method of Example 1 using the thermal transfer dye-donor material obtained in Example 1 and the above-mentioned thermal transfer dye image-receiving materials (2) to (7) and (C). The transfer density was measured. Further, the degree of image bleeding was observed after the recorded image receiving material was stored in an oven at 60 ° C. for 2 weeks. The criteria for judgment are indicated by ◯ when the image has hardly changed from that before storage, Δ when slightly blurred, and × when extremely blurred. The results are shown in Table 4.

[0070]

[Table 4]

When the dye used in the present invention and the polymer dye fixing agent were used together (No. 1 to No. 16), blurring of the image by the bleeding test was not observed. The transfer density was also high. On the other hand, when the dye-providing material for comparison was used (No. 17), the transferability was low, and further, the dissociation of the dye after transfer was insufficient, resulting in a low transfer density and a clear hue image. I couldn't get it. Further, in a transfer experiment (No. 18) in which a polymer dye fixing agent was not used in the image receiving layer, the dye was present in a non-dissociated state, so that the dissociative dye did not exhibit the original color tone and the transfer density was low. Also, some blurring of the image due to the bleeding test was observed.

[0072]

When the thermal transfer recording material of the present invention is used, it is possible to obtain an image having a high transfer density, an excellent hue, an excellent fastness and no deterioration in sharpness with the passage of time.

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[Procedure amendment]

[Submission date] December 7, 1993

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[Chemical 10]

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[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

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Example 1 Preparation of Thermal Transfer Dye-donor Material (1) A 5 μm thick polyethylene terephthalate film having a heat resistant slipping layer provided on one side was used as a support.
A composition (1) for coating a dye-donor layer having the following composition was applied to the side opposite to the side provided with the heat resistant slipping layer using a gravure coater so that the thickness after drying would be 0.6 μm. ,
A thermal transfer dye-providing material (1) (hereinafter, also simply referred to as a dye-donating material) was obtained. Dye Donor Layer Coating Composition (1) Dye; D-3 10 g Polyvinyl butyral (Denka Butyral 5000A: manufactured by Denki Kagaku) 10 g Silicone oil (KF-96: manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N: Takeda Yakuhin) 0.5g Methyl ethyl ketone 100ml Toluene 80ml

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0064

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[0064]

[Table 1]

Claims (2)

[Claims] 1. A thermal transfer comprising a thermal transfer dye-donating material having a dye-donating layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a receiving layer containing a dye-receiving compound on the support. A thermal transfer recording material, wherein the heat transferable dye is a dye represented by the general formula (1), and the dye-receptive compound is a basic substance and / or a mordant. [Chemical 1] In the formula, R ¹ represents a hydrogen atom or a substituent, R ³ represents a substituted or unsubstituted aromatic group or a heterocyclic group, and X is an atomic group necessary for forming a nitrogen-containing 5-membered ring. Represents 2. The thermal transfer recording material according to claim 1, wherein the heat transferable dye represented by the general formula (1) is represented by the following general formula (2) or (3). Recording material [Chemical formula 2] In the formula, R ¹ and R ² represent a hydrogen atom or a substituent, and R ³
Represents a substituted or unsubstituted aromatic group or heterocyclic group.