JP3235184B2 - Pyridoneazo dyes and thermal transfer sheets using the dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pyridoneazo dye and a heat-sensitive transfer sheet using the dye.

[0002]

2. Description of the Related Art As a yellow dye used in a heat-sensitive transfer sheet, the following general formula (II):

[0003]

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The use of a pyridoneazo compound represented by the following formulas is disclosed in JP-A-60-27594 and JP-A-60-15.
2563, JP-A-61-244595, JP-A-62
-290583 and the like. This product has low solubility, so there is a restriction in the production of ink, the transfer density when formed into a sheet is insufficient, and the absorption wavelength is short, so when used in combination with magenta and cyan dyes, the density of black is insufficient. There was a problem that is.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above problems.

[0006]

The present invention relates to a novel yellow pyridoneazo dye represented by formula (I) and a heat-sensitive transfer sheet using the dye according to the first aspect of the present invention. Further details will be described. The dye represented by the general formula (I) of the present invention will be specifically described. In the formula, as the unsubstituted alkyl group represented by R,
Examples thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, and examples of the substituted alkyl group include a hydroxy-substituted alkyl group such as a 2-hydroxyethyl group and a 3-hydroxypropyl group; A carboxy-substituted alkyl group such as -carboxypropyl group; a cyano-substituted alkyl group such as 2-cyanoethyl group; an amino-substituted alkyl group such as 2-aminoethyl group;
A halogen atom-substituted alkyl group such as a 2,2,2-trifluoroethyl group; a phenyl-substituted alkyl group which may have a halogen atom such as a benzyl group or a p-chlorobenzyl group;
2-methoxyethyl group, 2-ethoxyethyl group, 2-
(N) a propoxyethyl group, a 3-methoxypropyl group,
An alkoxy-substituted alkyl group such as a 4-methoxybutyl group;
2- (2-methoxyethoxy) ethyl group, 2- (2-
(N) alkoxyalkoxy-substituted alkyl group such as (butoxyethoxy) ethyl group; alkenyloxyalkyl group such as allyloxyethyl group; aryloxyalkyl group such as 2-phenoxyethyl group; aralkyloxy substitution such as 2-benzyloxyethyl group. Alkyl group; 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2
An acyloxy-substituted alkyl group which may be substituted with a halogen atom such as a trifluoroacetyloxyethyl group; a methoxycarbonylethyl group, a (n) butoxycarbonylmethyl group, a 2-benzyloxycarbonylethyl group, a 2-furfuryloxycarbonyl A substituted or unsubstituted alkoxycarbonyl-substituted alkyl group such as an ethyl group; a 2-methoxycarbonyloxyethyl group,
(N) a substituted or unsubstituted alkoxycarbonyloxy-substituted alkyl group such as a propoxycarbonyloxyethyl group or a 2-benzyloxycarbonyloxyethyl group;
Examples include a heterocyclic-substituted alkyl group such as a furfuryl group and a tetrahydrofurfuryl group.

[0007] Examples of the cycloalkyl group represented by R include a cyclopentyl group and a cyclohexyl group. Further, as the substituted phenyl group represented by R, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, And a phenyl group having a halogen atom such as an atom, a chlorine atom and a bromine atom, a nitro group, a cyano group and a trifluoromethyl group.

The ring A is a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, a straight-chain or branched-chain alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom. Halogen atom such as atom, cyano group, nitro group, alkoxycarbonyl group having 1 to 8 carbon atoms, 1 carbon atom
To 8 alkylcarbonyloxy groups, carbamoyl groups,
An alkylcarbonyl group having 1 to 8 carbon atoms, an alkylcarbonylamino group having 1 to 8 carbon atoms, a sulfonamide group, an alkylester group having 1 to 8 carbon atoms, a phenylsulfonic acid group, an aralkyloxycarbonyl group, N-alkylcarbamoyl group having 1 to 8 carbon atoms, N, N-dialkylcarbamoyl group having 1 to 8 carbon atoms, trifluoromethyl group , phenylcarbonyl group and phenylca
Represents a benzene ring which may have a substituent selected from the group consisting of a rubonyloxyalkyl group ;

Specific examples of the pyridone azo dye used in the present invention include those represented by R and ring A in the general formula (I).
And the groups represented by are shown in Table 1 below.

[0010]

[Table 1]

[0011]

[Table 2]

[0012]

[Table 3]

[0013]

[Table 4]

[0014]

[Table 5]

[0015]

[Table 6]

[0016]

[Table 7]

[0017]

[Table 8]

[0018]

[Table 9]

[0019]

[Table 10]

The compound of the present invention represented by the above general formula (I) is produced, for example, as follows. That is, the general formula (III)

[0021]

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(Wherein ring A has the same meaning as in the above general formula (I)) by diazotizing an aniline represented by the general formula (IV)

[0023]

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(Wherein, R has the same meaning as in the above formula (I)).

Here, (IV) is an amine represented by the following general formula (V) R-NH ₂ (V) (wherein R has the same meaning as in the above general formula (I)), and cyanoacetic acid It is obtained by reacting methyl ester and trifluoroacetoacetic acid ethyl ester at 60 to 90 ° C. In the reaction, a solvent need not be used but may be used. If you use
Water, methanol, ethanol, isopropyl alcohol, butanol, dimethylformamide, N-methylpyrrolidone and the like are desirable.

In the case of forming a coloring material layer containing the above-mentioned dye in the thermal transfer sheet of the present invention, the method is not particularly limited, but usually the dye is dissolved or dispersed in a medium together with a binder in a medium. Thus, an ink is prepared, and the ink is applied on a substrate and dried to form a color material layer on the substrate. As the binder for preparing the ink, a binder having good heat resistance is used in order to prevent thermal fusion with an image receiving body during transfer recording. Particularly, a binder having a softening point and / or a heat deformation temperature of 100 ° C. or higher is used. preferable.

Specifically, cellulose-based, acrylic acid-based,
Organic solvents such as starch-based water-soluble resins, acrylic resins, methacrylic resins, polystyrene, polycarbonate, polysulfone, AS resins, polyethersulfone, polyvinylbutyral, polyester, ethylcellulose, acetylcellulose, phenoxy resins, and water-soluble resins. Can be mentioned.

These resins may be appropriately selected depending on the solvent used as a medium for preparing the ink, and may be any resin that is dissolved or uniformly dispersed in the solvent. As the usage of these resins,
The range is 1 to 40% by weight, preferably 5 to 30% by weight based on the total weight of the ink composition. As a medium for the ink preparation, in addition to water, methyl alcohol, isopropyl alcohol, alcohols such as isobutyl alcohol, methyl cellosolve, cellosolves such as ethyl cellosolve, aromatics such as toluene, xylene, chlorobenzene, ethyl acetate, Esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; chlorinated solvents such as methylene chloride, chloroform and trichloroethylene; ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide; Organic solvents such as methylpyrrolidone can be mentioned, and these may be used alone or as a mixture.

In the above-mentioned ink, in addition to the above-mentioned components, if necessary, organic and inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an antiblocking agent, an antifoaming agent, an antioxidant, a viscosity modifier And a release agent. The base material to which the ink for preparing the transfer sheet is applied includes condenser paper, tissue paper such as glassine paper, polyester,
A plastic film having good heat resistance such as polycarbonate, polyamide, polyimide, and polyaramid is suitable, and the thickness thereof may be in the range of 1 to 50 μm.

Of the above substrates, polyethylene terephthalate film is particularly advantageous in consideration of mechanical strength, solvent resistance, economy and the like. However, in some cases, the polyethylene terephthalate film does not always have sufficient heat resistance, and the running properties of the thermal head are insufficient. By providing a conductive resin layer, a thermal head having improved running properties can be used.

As a method of applying the ink to the base film, a reverse roll coater, a gravure coater,
The coating can be carried out using a rod coater, an air doctor coater, or the like.
What is necessary is just to apply | coat so that it may be in the range of 1-5 micrometers (Yuji Harazaki, Maki Shoten 1979 "coating method"). On the other hand, an ink composition for a thermal transfer sheet, which is another object of the present invention, contains a pyridoneazo dye represented by the general formula (I), a resin as a binder, and an organic solvent and / or water. Is what it is.

The details of the pyridone azo dye are as described above. Specifically, the binder is appropriately selected from the above-mentioned water-soluble or organic solvent-soluble resins depending on the solvent and used. Among the aforementioned resins, those having a heat distortion temperature and / or softening point of 100 ° C. or more are particularly preferred. The above-mentioned solvent is used as the organic solvent. In addition, additives such as the above-mentioned non-sublimable fine particles, dispersant, antistatic agent, antiblocking agent, antifoaming agent, antioxidant, viscosity modifier, release agent and the like may be used.

In the ink composition of the present invention, the amount of the dye represented by the general formula (I) is 1 to 30% by weight, preferably 3 to 20% by weight, based on the total weight of the ink. As a method of adjusting the ink composition of the present invention, a mixed solution comprising a dye, a solvent and a resin is placed in an appropriate container equipped with a stirrer, and if necessary, heated, or an additive or the like is added, and the dye is added. The coloring matter can be adjusted by dissolving in a solvent, or by using a paint conditioner, a ball mill, a sand grind mill, or the like, adding an additive or the like as needed, and uniformly dispersing the dye in the solvent.

[0034]

As described above, the pyridone azo dye represented by the general formula (I) used in the thermal transfer sheet of the present invention has a vivid yellow color. Therefore, by combining an appropriate cyan color and magenta color, the color reproducibility can be improved. It is suitable for obtaining good full-color recording, and it is easy to sublimate and / or diffuse heat, and has a large molecular extinction coefficient. In addition, since the dye of the present invention has a long absorption wavelength, a great effect on the color density is obtained when a color is mixed with another color to obtain a black color. Further, since it is stable against heat, light, moisture, chemicals, and the like, it does not decompose during transfer recording, has excellent storage stability, and is particularly excellent in light resistance. Further, since the dye has good solubility in organic solvents and good dispersibility in water, it is easy to prepare a high-concentration ink that is uniformly dissolved or dispersed,
By using these inks, it is possible to obtain a heat-sensitive transfer sheet on which a dye is uniformly applied at a high concentration. Therefore, by using such a heat-sensitive transfer sheet, it is possible to obtain a record with good uniformity and color density.

Further, the heat-sensitive transfer sheet of the present invention can use not only a thermal head but also an infrared ray or a laser beam as a heating means. Further, the ink composition of the present invention can be applied to a current-carrying film that generates heat by current-carrying and used as a current-carrying thermal transfer sheet.

[0036]

EXAMPLES The present invention will be described below in detail with reference to examples, but the examples do not limit the present invention.

Example 1 a) Synthesis of a pyridone compound 24.9 g of ethyl trifluoroacetoacetate, 13.5 g of methyl cyanoacetate and butylamine 2
0.0 g, and heated to 80-90 ° C.
Stirred at C for 8 hours. After cooling the above reaction solution to room temperature,
Add to a mixture of 304 ml of water and 28 ml of concentrated hydrochloric acid and add
Stirred for hours. The precipitated crystals were collected by suction filtration and dried to obtain 27.4 g of a pyridone compound in which R in the formula (IV) is an n-butyl group.

B) Synthesis of pyridone azo dye 8.1 g of m-fluoroaniline was mixed with 190 ml of water and 9 ml of concentrated hydrochloric acid, and 5.6 g of sodium nitrite was added thereto at 0 to 5 ° C.
Was added and stirred at 0-5 ° C. for 1 hour. 1.1 g of sulfamic acid was added thereto, and the mixture was stirred.
A methanol solution of 20 g of the pyridone compound represented by the formula was added at 0 to 5 ° C, and the pH of the reaction solution was adjusted to 5 to 6 with an aqueous sodium hydroxide solution. After stirring at 0 to 5 ° C for 2 hours, the precipitated crystals were collected by suction filtration, dried and purified by column chromatography. 1
Thus, 14.5 g of a pyridone azo dye represented by Formula 2 was obtained.
The product was yellow crystals having a melting point of 120.5 to 121.3 ° C.

C) Preparation of ink

[Table 11] Pyridone azo dye (dye of No. 12 in Table 1) 0.8 g AS resin ^* 1.0 g Toluene 8.0 g Cyclohexanone 1.0 g Total 10.8 g * AS resin: acrylonitrile-styrene copolymer resin

The mixture having the above composition was treated with a paint conditioner for 10 minutes to prepare an ink.

D) Preparation of Transfer Sheet The above-mentioned ink was coated on a polyethylene terephthalate film (5 μm thick) having a heat-resistant lubricated back surface with a bar coater to form a color material layer (dry film thickness: about 1 μm).
Was formed to prepare a transfer sheet.

E) Preparation of Image Receiving Sheet An image receiving layer (dry film thickness: about 5 μm) was formed by applying a resin solution having the following composition to one surface of a cellulose paper (180 μm thickness) coated with polyethylene having a surface of 10 μm thickness. ) Was formed to produce an image receiving sheet.

[0043]

[Table 12] PVC resin 20.0 g Amino-modified silicone 0.3 g Methyl ethyl ketone 40.0 g Toluene 40.0 g Total 100.3 g

F) Transfer Recording The ink-coated surface of the transfer sheet is superimposed on the recording medium, and recording is performed using a thermal head under the following conditions, and a clear yellow color having a uniform color density shown in Table 2 below is recorded. I got it.

Recording conditions Main scanning and sub-scanning recording density: 6 dots / mm Recording power: 0.2 W / dot Energizing time: 14 ms Color density was measured by Densitometer TR manufactured by Macbeth, USA.
It was measured using a -927 model.

Examples 2 to 7 The dyes shown in Table 1 were used in place of the dyes used in Example 1, and ink preparation, transfer sheet preparation, and transfer recording were performed in the same manner as in Example 1. The results are shown in Table 2. As is evident from Table 2, in all cases, a clear yellow color record was obtained.

Comparative Examples 1-2 In place of the dye used in Example 1, A,
Preparation of ink, preparation of a transfer sheet, and transfer recording were performed in the same manner as in Example 1 using each of the B2 dyes, and the results shown in Table 2 were obtained.

[0048]

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[0049]

[Table 13]

Example 8 Instead of the dye used in Example 1, a magenta dye represented by the following formula:

[0051]

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And a cyan dye represented by the following formula:

[0053]

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The preparation of ink and the preparation of a transfer sheet were carried out in the same manner as in Example 1, respectively. Under the same conditions as in Example 1, the above magenta and cyan transfer sheets
Using a transfer sheet prepared using the dye shown in Table 1 No. 18 as a yellow dye, yellow, magenta,
Transfer recording was performed by sequentially superimposing cyan, and the density of black was measured. As a result, a recorded matter of black having a high color density of 2.20 could be obtained.

Comparative Example 3 Transfer recording was performed under the same conditions as in Example 8 except that the dye B of Comparative Example 2 was used as the yellow dye, and the color density of the black portion was measured. Met.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-166989 (JP, A) JP-A-62-290583 (JP, A) JP-A-61-244595 (JP, A) JP-A-60-1985 152563 (JP, A) JP-A-60-27594 (JP, A) JP-A-4-211477 (JP, A) JP-A-1-167373 (JP, A) JP-A-4-276491 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 29/42 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] A pyridone azo dye represented by the following general formula (1): (Wherein R is a hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a cycloalkyl group, an allyl group or a substituted or unsubstituted phenyl group, and ring A is selected from the following substituent groups.
Represents a benzene ring which may have a substituted substituent. Substituent group; C1-C8 linear or branched alkyl group C1- C8 linear or branched alkoxy group halogen atom cyano group nitro group C1-C8 alkoxycarbonyl alkylcarbonyloxy group carbamoyl group of the alkyl group having 1 to 8 carbon atoms having 1 to 8 carbon atoms alkylcarbonylamino group sulfonic acid amide group sulfonic acid alkyl ester group phenyl sulfonate having 1 to 8 carbon atoms in the group 1 to 8 carbon atoms ester group aralkyloxycarbonyl group having 1 to 8 carbon atoms of N- alkylcarbamoyl group having a carbon number of 1 to 8 N, N- dialkylcarbamoyl group trifluoromethyl group phenylcarbonyl group phenylcarbonyloxy alkyl group) 2. A ring A is a halogen atom having 1 to 8 carbon atoms.
Alkoxycarbonyl, nitro and trifluoromethyl
Benzee having a substituent selected from the group consisting of tyl groups
Wherein R is an alkyl group.
The pyridone azo dye according to claim 1. On wherein the substrate, the heat-sensitive transfer sheet and having a color material layer containing a pin Ridon'azo based dyes described binder and to claim 1 or 2.