JPH0516545A - Thermal transfer recording material and recording method - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer recording material containing coloring matter having good inking properties and exhibiting excellent absorbing characteristics as a magenta image through chelation by providing an ink layer containing coloring matter represented by a specified formula on a support. CONSTITUTION:In a thermal transfer recording material, an ink layer containing coloring matter represented by formula I is provided on a support. In the formula, A represents an atom group forming a five-membered or six-membered aromatic heterocycle together with two carbon atoms and X, X represents -O-, -S-, -N- or-N-(R)-,(R is a hydrogen atom or an alkyl group), Y and Z represent a hydrogen atom or a monovalent group, respectively, and u, w represent integers of 1-5, respectively. Consequently, a thermal transfer recording material containing-coloring matter having excellent inking properties and diffusivity and exhibiting excellent absorption characteristics as a magenta image through chelation and forming an image with high density, high durability and good color tone of magenta can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording material and a heat-sensitive transfer recording method using this recording material. More specifically, it has excellent thermal diffusivity and gives excellent absorption characteristics as a magenta image by forming a chelate. The present invention relates to a heat-sensitive transfer recording material containing a dye and a heat-sensitive transfer recording method using the heat-sensitive transfer recording material to form a magenta image with a chelate dye having excellent image durability such as light resistance and fixing property on an image receiving material.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a color hard copy, a color recording technique by ink jet, electrophotography, thermal transfer, etc. has been studied.

Of these, the thermal transfer system has the advantages that it is easy to operate and maintain, that the device can be made smaller and the cost can be reduced, and that the running cost is low. .

In this heat-sensitive transfer system, a transfer sheet (heat-sensitive transfer recording material) in which a meltable ink layer is provided on a support
Of a transfer sheet having an ink layer containing a heat diffusible dye (sublimable dye) on a support, and a method of heating the ink by a heat sensitive head to melt transfer the ink onto a transfer target sheet (image receiving material). There are two types of thermal diffusion transfer method (sublimation transfer method) in which the above thermal diffusion dye is transferred to a transfer target sheet by heating by the above, and the latter thermal diffusion transfer method changes the thermal energy of the thermal head. It is advantageous for full-color recording because the gradation of the image can be controlled by changing the transfer amount of the dye according to the above.

By the way, in the thermal transfer recording of the thermal diffusion transfer system, the dye used in the thermal transfer recording material is important, and the stability of the obtained image, that is, the light fastness and the fixing property is not good in the conventional ones. It has the drawback of

In order to improve that point, JP-A-59-7 is used.
8893, 59-109394, 60-239.
Each publication of No. 8 discloses an image forming method in which a chelating heat-diffusible dye is used and an image is formed on the image-receiving material by the chelated dye.

Although these image forming methods are excellent methods for improving light resistance and fixing property, the magenta dyes disclosed in these publications are applied to the ink layer of the thermal transfer recording material. At this time, it is said that sufficient density cannot be obtained due to low solubility (ink suitability) in a solvent used or low transferability, or an image having a color tone that is sufficiently satisfactory as magenta cannot be obtained. I have a problem.

The present invention has been made to improve the above circumstances.

That is, the object of the present invention is to provide a thermal transfer recording material containing a dye which has good suitability for ink formation, good diffusibility, and gives excellent absorption properties as a magenta image by forming a chelate, and high density, high durability. It is an object of the present invention to provide a heat-sensitive transfer recording method capable of forming an image having good properties and good color tone as magenta.

[0010]

The present invention for achieving the above object has a thermal transfer recording characterized by having an ink layer containing a dye represented by the following general formula [I] on a support. Which is a material and has an ink layer containing a dye represented by the following general formula [I] on a support, an ink layer of a heat-sensitive transfer recording material and an image receiving material are superposed, and the heat-sensitive transfer recording material is used in accordance with image information. It is a heat-sensitive transfer recording method, which comprises heating and forming an image by a chelate dye formed by a reaction between the dye and a metal ion on an image receiving material.

[0011]

[Chemical 1]

In the formula, A represents an atomic group forming a 5-membered or 6-membered heteroaromatic ring with two carbon atoms and X, and X represents -O-, -S-, -N = or-. N (R)
-(Wherein R represents a hydrogen atom or an alkyl group), Y and Z each represent a hydrogen atom or a monovalent group, and u and w each represent an integer of 1 to 5.

The general formula [I] will be described in more detail.
Y and Z represent a hydrogen atom or a monovalent group.

Examples of the monovalent group include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group (eg, a linear or branched alkyl group having 1 to 12 carbon atoms), an aryl group. (For example, a phenyl group,
Naphthyl group), alkoxy group (for example, having 1 carbon atom)
~ 12 linear or branched alkyloxy groups), amino groups (e.g., alkylamino groups, dialkylamino groups), acylamino groups (e.g., 1 to 12 carbon atoms).
A linear or branched alkylcarbonylamino group, phenylcarbonylamino group) or a sulfonyl group (for example,
A linear or branched alkylsulfonyl group having 1 to 12 carbon atoms, a phenylsulfonyl group), an alkoxycarbonyl group (for example, a linear or branched alkyloxycarbonyl group having 1 to 12 carbon atoms), an aryloxycarbonyl group ( For example, a phenyloxycarbonyl group),
Carbamoyl group (for example, linear or branched alkylaminocarbonyl group having 1 to 12 carbon atoms, dialkylaminocarbonyl group), urethane group (for example, linear or branched alkyloxycarbonylamino group having 1 to 12 carbon atoms) ), A cyano group, a nitro group, and the like.

The alkyl group or phenyl group may further have a substituent, and examples of the substituent include the monovalent groups described above.

Preferable examples of Z include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and the like, and a hydrogen atom or a methyl group is particularly preferable.

Examples of preferable Y include a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonyl group, an alkyl group, a carbamoyl group, and the like, and a hydrogen atom or a branched alkylcarbonylamino group having 1 to 8 carbon atoms and a carbon atom are particularly preferable. Examples thereof include branched alkylaminocarbonyl groups of number 1 to 8 and diethylaminocarbonyl group.

Preferred u is an integer of 1 to 3, particularly 1 or 2.

The preferable w is an integer of 1 to 3, particularly 1 or 2.

A represents a group of atoms forming a 5-membered or 6-membered heteroaromatic ring with two carbon atoms and X, and examples of the heteroaromatic ring include pyridine, pyrimidine, pyrrole, thiophene, furan and pyrazole. Examples thereof include rings such as triazole, thiazole and oxazole. Preferred are pyridine, pyrazole and triazole rings.

X is --O--, --S--, --N = or --N
(R)-, preferably -N = or -N (R)
− R represents a hydrogen atom or an alkyl group, and examples of the alkyl group include a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. A group, particularly preferably a methyl group.

1 to 8 show specific examples of the compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention).

The thermal transfer recording material of the present invention comprises an ink layer containing a dye represented by the above general formula [I] provided on a support.

The content of the dye in the ink layer is preferably 0.1 to ²⁰ g per 1 m ² of the support.

For the ink layer, a coating material for forming a heat-sensitive layer is prepared by dissolving one or more of the above-mentioned dyes in a solvent together with a binder, or by dispersing the dye in the solvent in the form of fine particles. It can be formed by applying a coating composition for formation on a support and drying it appropriately.

The dry thickness of the ink layer is 0.1-5 μm.
m is preferred.

The binder is a cellulosic material,
Water-soluble polymers such as polyacrylic acid type, polyvinyl alcohol type, polyvinylpyrrolidone type, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, ethyl cellulose and the like can be mentioned. .

These binders may be used not only in the form of one or two or more dissolved in an organic solvent, but also in the form of latex dispersion.

The amount of binder used is 1 m of support.
0.1 to 50 g per ² is preferable. As the solvent,
Water, alcohols (eg ethanol, propanol), cellosolves (eg ethyl cellosolve),
Esters (eg ethyl acetate), aromatics (eg toluene, xylene, chlorobenzene), ketones (eg acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, dioxane), chlorinated solvents (eg chloroform) , Trichlorethylene) and the like.

The support has good dimensional stability,
Any material can be used as long as it can withstand the heat of the thermal head during recording, but thin paper such as condenser paper and glassine paper, and heat resistant plastic film such as polyethylene terephthalate, polyamide and polycarbonate are preferably used.

The thickness of the support is preferably from 2 to 30 μm, and the support has an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the dye from transferring to the support and dyeing. May be.

Further, the back surface of the support (the side opposite to the ink layer)
May have a sticking prevention layer for the purpose of preventing the head from sticking to the support.

The heat-sensitive transfer recording material of the present invention is described in JP-A-59-106997 on an ink layer using an image-receiving material described later such as plain paper which is not particularly provided with an image-receiving layer. It may have a heat fusible layer containing such a heat fusible compound. As the heat-melting compound, a colorless or white compound having a melting point of 65 to 130 ° C. is preferably used, and examples thereof include waxes such as carnauba wax, beeswax, candeli wax, and higher fatty acids such as stearic acid and behenic acid. Examples thereof include alcohols such as xylitol, amides such as acetamide and benzamide, and ureas such as phenylurea and diethylurea.

The heat-melting layer may contain a polymer such as polyvinylpyrrolidone, polyvinyl butyral, and saturated polyester in order to improve the retention of the hot solvent.

The heat-sensitive transfer recording material of the present invention can obtain a magenta dye image from one kind of dye, but in order to obtain a heat-sensitive transfer recording material capable of full-color image recording, the magenta dye containing the magenta dye of the present invention can be used. It is preferable that a total of three layers, that is, the ink layer, the cyan ink layer containing the heat diffusing cyan dye, and the yellow ink layer containing the heat diffusing yellow dye, are sequentially and repeatedly coated on the same surface of the support.

If necessary, a yellow ink layer,
In addition to the cyan ink layer, the magenta ink layer containing the dye according to the present invention, and a heat-sensitive layer containing a black image-forming substance, a total of 4 layers may be sequentially and repeatedly coated on the same surface of the support.

In the heat-sensitive transfer recording method of the present invention, after the ink layer of the heat-sensitive transfer recording material and the image-receiving material are superposed, heat corresponding to image information is applied to the heat-sensitive transfer recording material so that the metal ion and the heat-sensitive layer are formed. An image is formed on the receiving material by the chelating dye formed by reaction with the dye therein.

In this case, since the compound represented by the general formula [I] is used as the dye in the present invention, it is possible to efficiently obtain an image which is highly stable at high density and which is preferable in color reproduction.

The metal ions may be present in the image receiving material or may be present in the heat fusible layer provided on the surface of the ink layer.

The above-mentioned thermal transfer recording method will be described with reference to the drawings. In FIG. 9, when the metal ions are present in the image-receiving layer 2 of the image-receiving material 3 composed of the support 1 and the image-receiving layer 2, the support 4 is formed. The dye in the ink layer 5 of the thermal transfer recording material 6 including the ink layer 5 is diffused and transferred to the image receiving material 3 by the heat from the heating resistor 8 of the thermal head 7, and the metal ions in the image receiving layer 2 are transferred. Reacts with to form chelate dyes.

Further, in FIG. 10, when the metal ions are present in the heat fusible layer 9 provided on the surface of the ink layer 5, a feeling of the support 4, the ink layer 5, and the heat fusible layer 9 is obtained. The dye in the ink layer 5 of the thermal transfer recording material 10 is diffused and transferred to the heat fusible layer 9 by heat from the heating resistor 8 of the thermal head 7, where it reacts with the metal ions to form a chelate dye. The heat-fusible substance 9a containing the chelate dye is transferred to the image-receiving material such as plain paper by cohesive failure or interfacial peeling, or the heat-melting layer is transferred to the image-receiving material 11 and then transferred to the image-receiving material. The dye diffuses and migrates to the functional layer, where it reacts with the metal ions to form a chelate dye.

As the metal ion, the first of the periodic table is used.
There are divalent and polyvalent metals belonging to Group 8 to Group 8, among which Al, Co, Cr, Cu, Fe, Mg, M.
n, Mo, Ni, Sn, Ti and Zn are preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable.

These metal ions are added as a metal ion supply compound (hereinafter sometimes referred to as a metal source) into the image receiving layer or the heat fusible layer. Examples of these metal sources include inorganic or organic salts of the metal ions and complexes of the metal ions, of which salts and complexes of organic acids are preferable.

Specific examples are Ni ²⁺ , Cu ²⁺ and Cr.
A salt of a lower fatty acid such as acetic acid or the like with ²⁺ , Co ²⁺ and Zn ²⁺ ,
Examples thereof include salts of higher fatty acids such as stearic acid and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid.

Further, a complex represented by the following general formula can also be preferably used.

[M (Q ₁ ) _l (Q ₂ ) _m (Q ₃ ) _n ] ^{p +} (Y ⁻ ) _{p where} M is a metal ion, preferably Ni ²⁺ , C
It represents u ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ²⁺ .

Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of forming a coordination bond with the metal ion represented by M, and may be the same or different from each other.

These coordination compounds can be selected, for example, from the coordination compounds described in Chelate Chemistry (5) (Nankodo).

Y represents an organic anion, and specific examples thereof include tetraphenylboron anion and alkylbenzene sulfonate anion.

L represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0,
In these, the complex represented by the above general formula is tetradentate or 6
Is determined by the conformation, or Q ¹ , Q ² ,
Determined by the number of ligands on Q ³ .

P represents 1 or 2, preferably 2
Is.

When p is 2, the coordinating group of the coordinating compound represented by Q ¹ , Q ² and Q ³ is not anionized.

[0053] The addition amount of the metal source is usually provided to the image-receiving material or thermofusible layer, preferably ^{0.2~20g / m 2, 1~10g / m} 2 is more preferable.

The image-receiving material used in the present invention is generally made of paper, a plastic film, or a paper-plastic film composite as a support, and a polyester resin, polyvinyl chloride resin, vinyl chloride and other materials as an image-receiving layer thereon. One or more polymer layers of a copolymer resin with a monomer (for example, vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, etc. are formed. Further, the support itself may be used as an image receiving material.

[0055]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

(Example 1) -Preparation of paint-The following raw materials were mixed to obtain a paint of a uniform solution containing the heat-diffusible dye according to the present invention.

[0057]       Compound 2 of the present invention (see FIG. 1) ... 10 g       Nitrocellulose resin: 10g       Methyl ethyl ketone: 400 ml.

—Preparation of Thermal Transfer Recording Material— The above coating composition was applied onto a polyethylene terephthalate film having a thickness of 4.5 μm using a wire bar so that the coating amount of the dye after drying was 0.4 g / m ^2. Then, a thermal transfer recording material 1 was prepared by drying and forming an ink layer on the polyethylene terephthalate film.

A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichiseika) is provided as a sticking prevention layer on the back surface of the polyethylene terephthalate film.

—Preparation of Image Receiving Material— Polyethylene is laminated on both sides of paper, and a polyethylene layer on one side thereof [white pigment (TiO ₂ ) and a bluing agent are contained. ], And 0.15 g / m ² of silicone oil as an image receiving layer and the following metal source (applied amount 5 g / m ² )
A vinyl chloride resin containing the above was applied at a coating amount of 10 g / m ² to obtain an image receiving material.

[0061] Metal _{Source: [Ni (NH 2 CH 2} CONH 2) 3] 2+ [(C 6 H 5) 4 B] 2 - - thermal transfer recording method - sensitive and image receiving material and the thermal transfer recording material 1 The ink layer surface of the thermal transfer recording material 1 and the image receiving surface of the image receiving material were superposed so as to face each other, a thermal head was applied from the back surface of the thermal transfer recording material 1, and image recording was performed under the following recording conditions. As a result, magenta image 1 having excellent gradation was obtained.

Table 1 shows the results of evaluation of the maximum density (D _max ), fixing property, color tone and light resistance of this image 1 in the following manner.

[0063]   Main scanning and sub scanning linear density: 8 dots / mm   Recording power: 0.6W / dot   Heating time of thermal head: Add stepwise from 20msec to 0.2msec                           The heat time was adjusted.   Evaluation of maximum density: The maximum of the transferred image (usually by X-rit310TR)                           , The part where the application time was the maximum) The reflection density was measured.

[0064]   Evaluation of fixability: Image 1 was sandwiched between laminated pouch films and laminated.                           LAC1702 "PRO" (Fuji Plastic Co., Ltd.)                           Product) was used for lamination. The resulting laminate                           Allow the image to stand at 77 ° C for 24 hours, and                           It was visually evaluated.

Next, the image 1 prepared separately was superposed on the image receiving material, a load of 20 kg / m ² was applied, and the mixture was left at 60 ° C. for 48 hours, and the degree of retransfer to the image receiving material was visually evaluated.

Image bleeding: No bleeding is observed. B: Bleeding is slightly observed. X: Severe bleeding. Retransfer ◯: Retransfer is hardly observed. Δ: Retransfer is not observed. X: Retransfer is severe. (Examples 2 to 7, Comparative Examples 1 to 3) Instead of the compound 2 of the present invention used in Example 1, the dye compound 3 of the present invention (see FIG. 1), 6 (see FIG. 2), 7 (see FIG. 2). (See FIG. 2), 8 (see FIG. 2), 17 (see FIG. 5), 19 (see FIG. 5) and the comparative dye compounds A, B and C described below and having substantially the same composition as the thermal transfer recording material 1. Thermal transfer recording materials 2 to 10 were prepared.

Comparative dye compound A:

[0068]

[Chemical 2]

Comparative dye compound B:

[0070]

[Chemical 3]

Comparative dye compound C:

[0072]

[Chemical 4]

Images were recorded using these thermal transfer recording materials in the same manner as in Example 1 to form images 2 to 10.

The images 2 to 10 thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 1. Also, images obtained using Dye Compound 8 and Comparative Dye Compound B
The absorbance of the image obtained by using is shown in FIG.

[0075]

[Table 1]

As can be seen from Table 1, in the examples of the present invention, the suitability of the dye as an ink is good, the fixability of the image and the light resistance are good, and a high-density image can be obtained.

(Example 8) On the polyethylene terephthalate film used as the support in Example 1, an ink layer containing the yellow dye having the following structure, an ink layer containing the magenta dye 2 according to the present invention, and a cyan dye having the following structure. Ink layers containing the above were sequentially applied to prepare a heat-sensitive transfer material.

Yellow dye:

[0079]

[Chemical 5]

Cyan dye:

[0081]

[Chemical 6]

The same binder as in Example 1 was used for each heat-sensitive layer. Further, the amounts of the dye and the binder attached are the same as in Example 1.

Next, a full color image was prepared by using a video printer (VY-100, manufactured by Hitachi, Ltd.) using the heat-sensitive transfer material and the same image receiving material as in Example 1, and good color reproducibility was obtained. The full color image shown was obtained.

Further, both the fixability and the image stability of this image were good.

(Example 9) 5 g of a ball mill dispersion of P-toluamide as an intermediate layer on the heat-sensitive transfer material of Example 8;
100 ml of an aqueous solution containing 7 g of polyvinylpyrrolidone, 3 g of gelatin and 0.3 g of the following hardener was applied so that the amount of P-toluamide attached would be 0.5 g / m ² .

Hardener

[0087]

[Chemical 7]

Further, on the intermediate layer, the above-mentioned metal source (coating amount: 1.0 g / m ² ) as a heat-melting layer, the following ultraviolet inhibitor (coating amount: 0.1 g / m ² ) and the following antioxidant (coating amount: 0.1 g / m ² ) and ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, coating amount 0.2 g / m ² ).
Carnauba wax containing (m ² ) (coating amount: 2.0 g / m ² ) was applied by hot melt coating to obtain a heat-sensitive transfer material.

Using this heat-sensitive transfer material and image-receiving material, full-color image recording was carried out by a video printer in the same manner as in Example 8. As the image receiving material, white plain paper was used. The obtained image had good color reproducibility, gradation, and image stability.

UV protection agent;

[0091]

[Chemical 8]

Antioxidants;

[0093]

[Chemical 9]

[0094]

EFFECTS OF THE INVENTION According to the present invention, a magenta dye having excellent heat resistance, thermal diffusivity and chelate reactivity can give a dye image with high stability and high stability, and also has a good storability of ink sheet. It is possible to provide a thermal transfer recording material and a thermal transfer recording method capable of efficiently recording using the material.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 2 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 3 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 4 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 5 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 6 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 7 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 8 is an explanatory diagram showing a structural formula of a typical magenta dye according to the present invention.

FIG. 9 is an explanatory diagram of a thermal transfer recording method of the present invention.

FIG. 10 is an explanatory diagram of a thermal transfer recording method of the present invention.

11 is a graph showing the absorbance of an image obtained using Magenta Dye Compound 8 and an image obtained using Comparative Dye Compound B. FIG.

[Explanation of symbols]

1 support 3 Image receiving material 4 support 5 ink layer 6 Thermal transfer recording material 10 Thermal transfer recording material 11 Image receiving material (plain paper)

Claims (2)

[Claims] 1. A heat-sensitive transfer recording material having an ink layer containing a dye represented by the following general formula [I] on a support. [Chemical 1] [Wherein A represents an atomic group forming a 5-membered or 6-membered heteroaromatic ring together with two carbon atoms and X, and X represents
Is -O-, -S-, -N = or -N (R)-(wherein R represents a hydrogen atom or an alkyl group), Y and Z each represent a hydrogen atom or a monovalent group, and u and w represents an integer of 1 to 5, respectively. ] 2. A heat-sensitive transfer recording material comprising an ink layer containing a dye represented by the general formula [I] according to claim 1 on a support and an ink layer of the heat-sensitive transfer recording material and an image receiving material. Is heated according to image information, and an image is formed on the image receiving material by a chelate dye formed by the reaction of the dye and a metal ion.