JP2003073580A - Dye composition, ink composition and ink sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye composition having high fastness to light and active oxygen and to provide an ink composition or an ink sheet by which high image fastness can be obtained when image is formed therefrom. SOLUTION: This dye composition comprises an organic dye and one or more kinds of barbituric acid derivatives represented by the general formula (1) [wherein R<1> and R<2> are each independently cyano group, an acyl group, an alkoxycarbonyl group or a dialkylaminocarbonyl group; Y is oxygen atom or sulfur atom]. This ink composition comprises an organic dye in which an anion part develops color, one or more kinds of the water-soluble barbituric acid derivatives, a water-soluble cationic polymer compound and water. This ink sheet has an ink layer comprising an organic dye, one or more kinds of the barbituric acid derivatives and a binder resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dye composition having improved light fastness, and an ink composition and an ink sheet having improved light fastness of an image forming portion.

[0002]

[Employee's Technology] The image forming method using the ink jet recording method or the thermal transfer recording method can easily form a full-color image, and the apparatus used for the method is small. However, if the formed image is left for a long time in the vicinity of light or an air purifier, for example, fading due to light or ozone is likely to occur, and the image has sufficient fastness to light and active oxygen. However, further improvement is desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. That is, the present invention provides a dye composition having high fastness to light and active oxygen, and also provides an ink composition or an ink sheet capable of obtaining high image fastness when an image is formed from them. The purpose is to provide.

[0004]

The present inventors have found that by combining an organic dye with a specific barbituric acid derivative, a dye composition having high fastness to light and active oxygen can be obtained. The present invention has been completed.

Means for solving the above problems are as follows. That is, it is a dye composition containing <1> an organic dye and at least one barbituric acid derivative represented by the following general formula (1).

[0006]

[Chemical 2]

(In the general formula (1), R ¹ and R ² are each independently a cyano group, an acyl group, an alkoxycarbonyl group,
Alternatively, it represents a dialkylaminocarbonyl group, and Y represents an oxygen atom or a sulfur atom. ) <2> The dye composition according to <1>, wherein the organic dye is an organic dye in which an anion portion is colored, and the barbituric acid derivative is a water-soluble barbituric acid derivative. . <3> An organic dye whose anion portion is colored and a water-soluble barbituric acid derivative represented by the above general formula (1)
An ink composition comprising at least one species, a water-soluble cationic polymer compound, and water. <4> An ink sheet having an ink layer containing an organic dye, at least one barbituric acid derivative represented by the general formula (1), and a binder resin.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The dye composition of the present invention will be described in detail below. The dye composition of the present invention comprises an organic dye and a specific barbituric acid derivative.

The barbituric acid derivative of the present invention, which constitutes the above-mentioned organic dye and dye composition, is represented by the following general formula (1).

[0010]

[Chemical 3]

In the general formula (1), R ¹ and R ² each independently represent a cyano group, an acyl group, an alkoxycarbonyl group or a dialkylaminocarbonyl group, and Y represents an oxygen atom or a sulfur atom. In general formula (1), the acyl groups represented by R ¹ and R ² preferably have 2 to 20 total carbon atoms. Examples of the acyl group include acetyl group, propanoyl group, butanoyl group, hexanoyl group, octanoyl group, 2-ethylhexanoyl group, decanoyl group, benzoyl group, 2-methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group. Group, 2-methoxybenzoyl group, 3-methoxybenzoyl group, 4-methoxybenzoyl group, 2-fluorobenzoyl group, 3-fluorobenzoyl group, 4-
Fluorobenzoyl group, 2-chlorobenzoyl group, 3-
Examples thereof include chlorobenzoyl group and 4-chlorobenzoyl group, but are not limited thereto. Further, the acyl group may have a substituent, and these substituents include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms in total,
And a dialkylamino group having a total of 2 to 20 carbon atoms,
As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include a 2-methoxyethoxy group and a 2- (2-methoxy) ethoxyethoxy group, and examples of the dialkylamino group include a dimethylamino group, a diethylamino group and a dibutylamino group.

In the general formula (1), the alkoxycarbonyl groups of R ¹ and R ² preferably have 2 to 20 carbon atoms in total. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octylcarbonyl group, 2
-Ethylhexyloxycarbonyl group, decyloxycarbonyl group, 1-phenylethoxycarbonyl group, 2-
Examples include phenylethoxycarbonyl group, 2-phenoxyethoxycarbonyl group, 2- (2-methyl) phenoxyethoxycarbonyl group, 2- (3-methyl) phenoxyethoxycarbonyl group, 2-phenoxypropoxycarbonyl group, and the like. It is not limited. The alkoxycarbonyl group may have a substituent, and examples of the substituent include a hydroxyl group, the aforementioned alkoxy group having 1 to 10 carbon atoms and a dialkylamino group.

In the general formula (1), the dialkylaminocarbonyl group of R ¹ and R ² preferably has 2 to 20 total carbon atoms. Examples of the dialkylaminocarbonyl group include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, a dibutylaminocarbonyl group, a dihexylaminocarbonyl group, and a dioctylaminocarbonyl group, but are not limited thereto. Absent.

Specific examples of the barbituric acid derivative represented by the general formula (1) are shown below, but the compounds used in the present invention are not limited thereto.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

The water-soluble barbituric acid derivative used in the ink composition of the present invention has a hydroxyl group, an ethyleneoxy group, a cyanomethyl group or a carbon atom in R ¹ and / or R ² in the general formula (1). When it has an alkyl group of 8 or less, the water solubility tends to increase, and, for example, (A-1) to (A-3) among the above-mentioned specifically mentioned barbituric acid derivatives, (A-6), (A-
9)-(A-19), (A-22), (A-26)-
(A-28), (A-32) to (A-42), (A-4
7) to (A-49) are water-soluble barbituric acid derivatives used in the ink composition of the present invention.

The content of the barbituric acid derivative in the dye composition is 0.1 with respect to the organic dye described below.
˜100 times molar amount is preferable, and 1 to 50 times molar amount is more preferable. If the amount used is less than 1 times the molar amount, the fading prevention effect becomes insufficient, and if it exceeds 100 times the molar amount, the color of the dye composition may deteriorate.

As the organic dye, known disperse dyes, oil-soluble dyes, photographic dyes and the like can be used. For example,
As the quinophthalone yellow dye, there is disclosed in JP-A-60-5.
No. 3565, No. 63-182193, No. 63-189.
No. 289 and the like, dicyanostyryl yellow dyes are disclosed in JP-A-59-78895 and the like, and pyridoneazo yellow dyes are disclosed in JP-A-60-27954. Id 61-262
No. 191 and the like. Further, as a tricyanostyryl magenta dye, there is disclosed in JP-A-59-788.
The azo-based magenta dyes are disclosed in JP-A No. 96-30391 and JP-A No. 61-227.
092, 61-227091, 60-3039.
No. 4, JP-A No. 62-294593 and the like, and as an azomethine-based magenta dye, JP-A-63-
Nos. 203388 and 64-63194 are disclosed, and examples of anthraquinone-based magenta dyes include:
JP-A-60-131293, 64-77584,
No. 60-159091, No. 61-268495, and the like. Further, as indoaniline-based cyan dyes, JP-A-61-22993 and 60-2
No. 39289, No. 61-19396, No. 64-201
The anthraquinone-based cyan dyes disclosed in JP-A No. 60-151097 and JP-A No.
0-53563, 61-284489, 63-
JP-A Nos. 60-239291 and 62-1 disclose azo cyan dyes disclosed in Japanese Patent Publication No. 5993 and the like.
32688, 62-87393, 64-585.
The naphthoquinone-based cyan dyes disclosed in JP-A No. 91-78894 and JP-A 59-78894.
It is disclosed in gazettes such as 227490.

As the organic dye having the anion moiety colored, those which are classified as an acid dye, a direct dye or a food dye in the color index can be used. Further, dyes classified as oil-soluble dyes that are soluble in the alkaline region can be used. Examples of organic dyes whose anion moiety is colored are shown below, but the invention is not limited thereto.

C. I. Acid Yellow 1, 3, 11,
17, 19, 23, 25, 29, 36, 38, 40, 4
2,44,49,59,61,70,72,75,7
6,78,79,98,99,110,111,12
7, 131, 135, 142, 162, 164, 16
5, C.I. I. Direct Yellow 1,8,11,12,
24, 26, 27, 33, 39, 44, 50, 58, 8
5,86,87,88,89,98,110,142,
144, C.I. I. Food Yellow 3,4, C.I. I. Acid Red 1,6,8,9,13,14,18,26,
27, 32, 35, 37, 42, 51, 52, 57, 7
5,77,80,82,85,87,88,89,9
2,94,97,106,111,114,115,1
17, 118, 119, 129, 130, 131, 13
3,134,138,143,145,154,15
5,158,168,180,183,184,18
6,194,198,209,211,215,21
9,249,252,254,262,265,27
4,282,289,303,317,320,32
1,322, C.I. I. Direct Red 1, 2, 4,
9, 11, 13, 17, 20, 23, 24, 28, 3
1, 33, 37, 39, 44, 46, 62, 63, 7
5, 79, 80, 81, 83, 84, 89, 95, 9
9,113,197,201,218,220,22
4,225,226,227228,229,230,
231, C.I. I. Hood Red 7, 9, 14,

C. I. Acid Blue 1,7,9,1
5,22,23,25,27,29,40,41,4
3,45,54,59,60,62,72,74,7
8,80,82,83,90,92,93,100,1
02, 103, 104, 112, 113, 117, 12
0,126,127,129,130,131,13
8,140,142,143,151,154,15
8, 161, 166, 167, 168, 170, 17
1,182,183,184,187,192,19
9,203,204,205,229,234,23
6,249, C.I. I. Direct Blue 1,2,6,1
5,22,25,41,71,76,77,78,8
0,86,87,90,98,106,108,12
0,123,158,160,163,165,16
8,192,193,194,195,196,19
9,200,201,202,203,207,22
5,226,236,237,246,248,24
9, C.I. I. Food Blue 1, 2, C.I. I. Acid Black 1,2,7,24,26,29,31,48,5
0,51,52,58,60,62,63,64,6
7, 72, 76, 77, 94, 107, 108, 09,
110, 112, 115, 118, 119, 121, 1
22, 131, 132, 139, 140, 155, 15
6,157,158,159,191, C.I. I. Direct Black 17, 19, 22, 32, 38, 51, 5
6,62,71,74,75,77,94,105,1
06,107,108,112,113,117,11
8, 132, 133, 146, 154, 168, C.I.
I. Hood Black 2.

Any oil-soluble dye can be used as long as it is soluble in an alkaline aqueous solution. As a preferable oil-soluble dye, oil yellow 105 (trade name,
Orient Chemical Co., Ltd.), Oil Yellow 10
7 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I.
I. Solvent Yellow 29, C.I. I. Solvent Yellow 29 (trade name, manufactured by Orient Chemical Industry Co., Ltd.),
C. I. Solvent Yellow 16, C.I. I. Solvent Yellow 56, Varifast Yellow 1105 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 77,
C. I. Solvent Yellow 33, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 150,
C. I. Solvent Yellow 21, C.I. I. Solvent Yellow 151, C.I. I. Solvent Yellow 56,
C. I. Solvent Yellow 16, C.I. I. Solvent Yellow 33, Aizenspiron Yellow GRLH (trade name, Hodogaya Chemical Co., Ltd.), Aizenspiron Yellow 3RH (trade name, Hodogaya Chemical Co., Ltd.), Aizenspiron Yellow C-2GH (trade name) ,
Hodogaya Chemical Co., Ltd.), Eisenspiron Yellow C-GNH (trade name, Hodogaya Chemical Co., Ltd.),
C. I. Solvent Yellow 88, C.I. I. Solvent Yellow 89, C.I. I. Solvent Yellow 25, C.I.
I. Solvent Yellow 163, C.I. I. Solvent Yellow 21), Oil Yellow 185 (trade name, manufactured by Chuo Synthetic Chemical Co., Ltd., CI Solvent Red 18 similar product), Alcohol Yellow Y-10 (trade name, manufactured by Chuo Synthetic Chemical Co., Ltd.), C.I. I. Solvent Yellow 93,
C. I. Solvent Yellow 98, C.I. I. Solvent Yellow 104, C.I. I. Solvent yellow 11
4), C.I. I. Solvent Yellow 112, C.I. I. Solvent Yellow 105, C.I. I. Solvent Yellow 113 and the like can be mentioned.

As the red color system, C.I. I. Solvent Red 27, C.I. I. Solvent Red 24, C.I. I. Solvent Red 109, Varifast Red 2303 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Red 8, Varifast Red 3306 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Red 132, Oil Pink 312 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Red 218, C.I. I. Solvent Red 179, C.I. I.
Solvent Red 135, C.I. I. Solvent Red 1
11, C.I. I. Solvent Red 132, C.I. I. Solvent Red 122, C.I. I. Solvent Red 13
2, Oleosol Red 2G (trade name, manufactured by Taoka Chemical Industry Co., Ltd.), C.I. I. Solvent Red 218, C.I. I.
Solvent Red 24, C.I. I. Solvent red 2
7, C.I. I. Solvent Red 18, Eisenspiron Red BEH (trade name, Hodogaya Chemical Co., Ltd.),
C. I. Solvent Red 81, Aizen spirone red GEH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), Aizen spirone red C-GH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), Aizen spirone red C-BH ( (Trade name, manufactured by Hodogaya Chemical Co., Ltd.), C.I. I. Solvent Red 49, C.I. I. Solvent Red 130, C.I.
I. Solvent Red 132, C.I. I. Solvent Red 125, C.I. I. Solvent Red 7, C.I. I. Solvent Red 225, C.I. I. Solvent Red 13
5, C.I. I. Solvent Red 230, C.I. I. Solvent Red 127, C.I. I. Solvent Red 49, Alcohol Pink P-30 (trade name, manufactured by Chuo Synthetic Chemical Industry Co., Ltd.), C.I. I. Solvent Red 155, C.I. I. Solvent Red 52 and the like can be mentioned.

As the blue color, oil blue 613 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Blue 35), Oil Blue BOS (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Blue 1
603 (trade name, manufactured by Orient Chemical Industry Co., Ltd.),
C. I. Solvent Blue 38, Varifast Blue 1
607 (trade name, manufactured by Orient Chemical Industry Co., Ltd.),
C. I. Solvent Blue 70, Varifast Blue 2
610 (trade name, manufactured by Orient Chemical Industry Co., Ltd.),
C. I. Solvent Blue 70), C.I. I. Solvent Blue 70, Oleosol Blue G (trade name, manufactured by Taoka Chemical Industry Co., Ltd.), C.I. I. Solvent Blue 25, C.I.
I. Solvent Blue 14, Eisenspiron Blue G
NH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue 2BNH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue BPNH (trade name,
Hodogaya Chemical Co., Ltd.), Eisenspiron Blue C-RH (trade name, Hodogaya Chemical Co., Ltd.), C.I.
I. Solvent Blue 73, C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 48, C.I. I. Solvent Blue 68, C.I. I. Solvent Blue 25, C.I.
I. Solvent Blue 132), C.I. I. Solvent Blue 67, Kayaset Blue K-FL (trade name, manufactured by Nippon Kayaku Co., Ltd.), Alcohol Blue B-10 (trade name,
Chuo Synthetic Chemical Industry Co., Ltd.), C.I. I. Solvent Blue 94, C.I. I. Solvent Blue 78), C.I. I. Solvent Blue 95, C.I. I. Solvent Blue 35, Dialesin Blue H3G (trade name, manufactured by Mitsubishi Kasei Co., Ltd.) and the like can be mentioned.

As the black system, C.I. I. Solvent Black 3, C.I. I. Solvent Black 3, C.I. I. Solvent Black 7, Oil Black BY (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Black 1
802 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Black 1807 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Black 34,
C. I. Solvent Black 29, C.I. I. Solvent Black 27, Varifast Black 3830 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Black 5, Spirit Black SSBB, C.I.
I. Solvent Black 5, C.I. I. Solvent Black 5, C.I. I. Solvent Black 7, Oplas Black 836 (trade name, manufactured by Orient Chemical Industry Co., Ltd.),
Oplas Black 838 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Solvent Black 3, C.I.
I. Solvent Black 27, Oleosol Black AR
(Trade name, manufactured by Taoka Chemical Co., Ltd.), C.I. I. Solvent Black 3, C.I. I. Solvent Black 7, Aizenspiron Black MH (trade name, Hodogaya Chemical Co., Ltd.), Aizenspirone Black GMH Special (trade name, Hodogaya Chemical Co., Ltd.), Aizenspiron Black RLH Special (trade name) , Hodogaya Chemical Co., Ltd.), C.I. I. Solvent Black 28,
C. I. Solvent Black 29, C.I. I. Solvent Black 7 and the like can be mentioned. The oil-soluble dye having a low solubility in the alkaline region can be used by using it in combination with a water-soluble organic solvent capable of dissolving the oil-soluble dye.

The dye composition of the present invention may contain an organic solvent, water and the like, if necessary, and the organic dye may be dissolved or dispersed in these.

Next, the ink composition of the present invention will be described. The ink composition of the present invention contains at least the above-mentioned organic dye capable of forming a color, the water-soluble barbituric acid derivative, the water-soluble cationic polymer compound, and water. The ink composition of the present invention is preferably used for inkjet recording, water-soluble paints and the like. The content of the organic dye is 0.5 to 20% by mass, preferably 1 to 10% by mass, based on the ink composition. If it is less than 0.5% by mass, sufficient optical density cannot be obtained, and if it exceeds 20% by mass, it becomes difficult to adjust the viscosity suitable for ink ejection. The content of the water-soluble barbituric acid derivative in the ink composition is
The molar amount of the organic dye is preferably 0.1 to 100 times, more preferably 1 to 50 times. When the amount used is less than 1 times the molar amount, the effect of preventing discoloration of an image when an image is formed using the ink composition becomes insufficient, and
If it exceeds a molar amount of 00 times, the color of the image may deteriorate.

As the water-soluble cationic polymer compound, known compounds can be used. For example, as the polyethyleneimine-based polymer, there are JP-A-62-119280, JP-A-2-255876, JP-A-2-296876, and JP-A-3-296876.
No. 188174 and the like. Further, as another polymer such as an amino acid type, Japanese Patent Application Laid-Open No. 7-30501
No. 1, No. 8-113743, No. 10-88053, and the like. The content of the water-soluble cationic polymer compound is 0.5 to 20% by mass, preferably 1 to 10% by mass based on the ink composition. If it is less than 0.5% by mass, it is not possible to impart sufficient water resistance to the printed matter, and if it exceeds 20% by mass, it becomes difficult to adjust the viscosity suitable for ink ejection.

Further, the ink composition of the present invention may contain an acid. The acid that can be used is not particularly limited, but an acid having a dissociation constant and water solubility capable of adjusting the pH of the entire ink composition to an appropriate range is preferable, and an inorganic acid such as hydrochloric acid, Hydrobromic acid, sulfuric acid, or phosphoric acid, organic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso
-Valeric acid, caproic acid, glycolic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Alternatively, carboxylic acids such as tartaric acid, their substitution products, or sulfonic acids corresponding thereto can be used. The above-mentioned acids can be used alone or as a mixture of two or more, and by containing such an acid, an ink bleed preventing effect can be obtained.

The pH of the ink composition of the present invention is generally 5 to 11.5, preferably 6 to 11, depending on the acid.
More preferably, it is preferably adjusted to 7 to 10.5 before use. When the pH is less than 5, the solubility in the ink composition liquid becomes low depending on the dye species, and it may be difficult to secure the print density as the inkjet ink composition.
On the other hand, when the pH exceeds 11.5, not only a safety problem occurs but also bleeding is difficult to stop.

When an acid is added to the dye-containing aqueous ink composition according to the present invention, the water-soluble cationic polymer compound and the acid can be mixed as they are, but the polymer compound is produced. It is also possible to prepare a water-soluble cationic polymer compound by using a quaternized salt monomer of the above-mentioned acid and an acid, and adjust the pH appropriately from this polymer compound by adding a salt or a base. it can.

The aqueous ink composition for ink jet of the present invention uses water as a solvent. As this water, pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water can be used. Further, it is preferable to use water that has been sterilized by irradiation with ultraviolet rays, addition of hydrogen peroxide, or the like, because it is possible to prevent the generation of mold and bacteria when the ink composition is stored for a long period of time.

The ink composition of the present invention prevents the ink composition from drying at the tip of the print head nozzle, improves the permeation rate of the ink composition into the recording paper, and / or dissolves the dye in the ink composition liquid. It is also possible to contain a water-soluble organic solvent for the purpose of improving the properties. The water-soluble organic solvent is not particularly limited as long as it is an organic solvent compatible with water, and any water-soluble organic solvent can be used. A solvent having a vapor pressure smaller than that of water is preferable. Examples of such water-soluble organic solvents include ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
2-butene-1,4-diol, 2-methyl-2,4-
Polyhydric alcohols such as pentanediol, glycerin and 1,2,6-hexanetriol, especially dihydric or trihydric alcohols, diethylene glycol dimethyl ether,
Or ethers such as diethylene glycol diethyl ether, particularly di-lower alkyl ethers of diethylene glycol, ketones such as acetonylacetone, γ-butyrolactone, diacetin, ethylene carbonate, esters such as triethyl phosphate, formamide, dimethylformamide, diethylformamide. , Or nitrogen compounds such as dimethylacetamide, sulfur compounds such as dimethyl sulfoxide, sulfolane, or 1,3-propane sultone, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, or 2-iso. Propoxy ethanol, 2-butoxy ethanol, 2
-Lower alkoxy lower alcohols such as isopentyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl Ether, tetraethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol,
Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diacetone alcohol,
Examples thereof include polyfunctional compounds such as thiodiglycol, 2-methoxyethyl acetate, diethylene glycol monoethyl ether acetate, and hexamethylphosphoramide.

Since each of the above-mentioned organic solvents may have various effects, it is preferable to use them taking these effects into consideration. For example, as a solvent which also has an effect of improving the prevention of drying of the ink composition liquid, polyhydric alcohols such as glycerin, diethylene glycol, or thiodiglycol are used as a solvent which also has an effect of promoting penetration of the ink composition into paper. Polyhydric alcohol ethers such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl ether can be preferably used. Further, these water-soluble organic solvents can be used alone or in combination of two or more.

The total content of the water-soluble organic solvent is not particularly limited, but is preferably 60% by mass or less, more preferably 40 to 10% by mass based on the total mass of the composition.

The dye-containing ink composition of the present invention may further contain a water-soluble base. Examples of this base include alkali metal hydroxides (for example, potassium hydroxide,
Or sodium hydroxide), or an inorganic base such as ammonia, mono-, di- or tri-lower alkylamine (for example, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, diisopropylamine, tert-butylamine, dibutylamine, Diisobutylamine, isopropylamine, sec
-Butylamine, or pentylamine), mono-, di-
Alternatively, tri-lower alkenylamine (eg, allylamine, diallylamine), lower alkoxy lower alkylamine (eg, 3-ethoxypropylamine, 3-
Methoxypropylamine), mono-, di- or tri-lower hydroxyalkylamines (eg 2-aminoethanol, 2-((dimethylamino) ethanol, 2
-(Diethylamino) ethanol, diethanolamine, N-butyldiethanolamine, triethanolamine, or triisopropanolamine), iminobispropylamine, 3-diethylaminopropylamine,
It is preferable to use organic amines such as dibutylaminopropylamine, methylaminopropylamine, dimethylaminopropylamine and methyliminobispropylamine. These bases have the effect of assisting the dissolution of the dye in the ink composition.

The content of the water-soluble base is not particularly limited, but with an inorganic base, it is preferably 2% by mass or less, more preferably 0.01 to 1 based on the total amount of the composition.
% By mass, preferably 2 with respect to the total amount of the organic base.
It is 0 mass% or less, more preferably 1 to 10 mass%.

Further, the dye-containing water-based ink composition according to the present invention has a surface of an additive generally used in a conventional water-based ink composition for ink jet recording, such as ethyl alcohol or isopropyl alcohol. Tension adjusting agent, viscosity adjusting agent such as polyvinyl alcohol or carboxymethyl cellulose, anionic surfactant such as fatty acid salt, sulfate ester salt, sulfonate salt or phosphate ester salt, amine salt, quaternary ammonium salt, or pyridinium salt Cationic surfactants such as, polyethylene glycol or polypropylene glycol derivatives, nonionic surfactants such as polyhydric alcohol fatty acid ester,
Amino acid derivatives, betaine derivatives, amphoteric surfactants such as polyethylene glycol or polypropylene glycol amine derivatives, cationic polymer stabilizers such as urea, tetramethylurea and thiourea, optical brighteners, methyl p-oxybenzoate, Or a bactericidal agent such as 1,2-benzisothiazolin-3-one, a rust preventive agent such as benzotriazole,
Preservatives and the like can be contained if necessary.

Next, the ink sheet of the present invention will be described. The ink sheet of the present invention has an ink layer containing the organic dye, the barbituric acid derivative, the binder resin, and a support. The ink sheet of the present invention is preferably used as a thermal transfer sheet, a sublimation transfer sheet or the like used for thermal transfer recording. The content of the organic dye is 0.
It is 03 to 5 g / m ² , preferably 0.1 to 1 g / m ² .
If it is less than 0.03 g / m ² , sufficient density cannot be obtained in the ink transfer portion, and if it exceeds 5 g / m ² , it becomes difficult to adjust the density of the ink transfer portion. The content of the barbituric acid derivative is 0.1 to the above organic dye.
A 100-fold molar amount is preferable, and a 1- to 50-fold molar amount is more preferable. If the amount used is less than 1 times the molar amount, the effect of preventing fading of the image becomes insufficient when the image is formed using the ink sheet, and if the amount exceeds 100 times the molar amount, the color of the image may deteriorate. .

As the binder resin used in the ink layer, any of the binder resins known in the prior art for such purposes can be used, and generally has high heat resistance and does not hinder the migration of the dye when heated. Things are selected. For example, polyamide resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic resin (for example, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile),
Vinyl-based resins such as polyvinylpyrrolidone, polyvinyl chloride-based resins (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate-based resins, polystyrene, polyphenylene oxide, cellulose-based resins (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 partially saponified polyvinyl alcohol such as polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral), petroleum resin, rosin derivative , Coumarone-indene resin, terpene resin, polyolefin resin (for example, polyethylene, polypropylene Emissions) and the like can be used. In the present invention, such a binder resin is preferably used in a ratio of about 20 to 300 parts by mass in the dye layer per 100 parts by mass of the dye. In the transfer agent layer, the transfer agent (organic dye) 1
It is preferably used in a ratio of about 20 to 300 parts by mass per 00 parts by mass. In the present invention, any conventionally known ink solvent can be used as the ink solvent for dissolving or dispersing the organic dye transfer agent and the binder resin. The thickness of the dye layer is 0.1 to 5 μm, preferably 0.5 to 2 μm, and the thickness of the transfer agent layer is 0.05 to 5 μm.
μm, preferably 0.1 to 2 μm.

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

Further, the ink sheet may be provided with a hydrophilic barrier layer in order to prevent the diffusion of the organic dye toward the support. The hydrophilic organic dye barrier layer is
It contains hydrophilic substances that are useful for the intended purpose. Generally good results have been obtained with gelatin, polyacrylamide, polyisopropylacrylamide, butyl methacrylate graft gelatin, ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, polyvinyl alcohol, polyethyleneimine, polyacrylic acid, polyvinyl alcohol and polyvinyl acetate. Obtained by using a mixture, a mixture of polyvinyl alcohol and polyacrylic acid or a mixture of cellulose monoacetate and polyacrylic acid. Especially preferred are polyacrylic acid, cellulose monoacetate or polyvinyl alcohol. Further, the ink sheet may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired function, but a preferred specific example is an acrylonitrile / vinylidene chloride / acrylic acid copolymer (mass ratio 1
4: 80: 6), butyl acrylate / methacrylic acid-2
-Aminoethyl / 2-hydroxyethyl methacrylate copolymer (mass ratio 30:20:50), linear / saturated polyester such as BOSTIC 7650 (Mhart Inc.,
Bostic Chemical Group) or chlorinated high density poly (ethylene-trichloroethylene) resins. 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 .

The ink layer of the present invention is formed on the support by a conventionally known method. For example, it can be formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate. The dry thickness of the ink layer is 0.2 to 5 μm, preferably 0.4 to 2 μm.

[0050]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, "%" is used unless otherwise specified.
Means "mass%", and "part" means "part by mass".

Example 1 (ink sheet) (a) Preparation of ink 2 g of dye represented by the following structural formula (D): barbituric acid derivative represented by specific example (A-48) of the present invention 0.5 g ethyl cellulose 2 g toluene 45 g A mixture having the above composition was treated with an ink conditioner for 1 hour to prepare an ink.

[0052]

[Chemical 11]

(B) Preparation of Ink Sheet The above ink was applied onto a polyethylene terephthalate film (7 μm thick) using a wire bar # 40 and then naturally dried to prepare a transfer sheet. (C) Transfer recording The ink-coated surface of the ink sheet is superposed on a high-quality paper coated with a polyester resin, and recording is performed by heating the ink sheet on the side opposite to the ink-coated surface under the following conditions using a thermal head. Then, it was possible to obtain a uniform and high color density record of 1.02 in clear yellow color. [Recording conditions] Main scanning and sub-scanning linear density: 4 dots / mm Recording power: 1 w / dot head heating time: 5 msec

Comparative Example 1 In Example 1, (A-4
Transfer recording was performed in the same manner as in Example 1 except that the barbituric acid derivative represented by 8) was not used, and recording with a yellow density of 1.03 was obtained.

<Evaluation of Light Resistance> The transferred sheets of Example 1 and Comparative Example 1 were irradiated with light for 48 hours using a xenon lamp weatherometer (manufactured by Atlas, USA). The residual concentration ratio is shown in Table 1.

[0056]

[Table 1]

Example 2 (Ink Composition) (a) Preparation of Water-Soluble Cationic Polymer Compound To 550 g of 35 mass% hydrochloric acid, 286 g (5 mol) of monoallylamine was added dropwise with stirring at 5 to 10 ° C. under ice cooling. did. After the dropping, water and hydrogen chloride were removed at 60 ° C. under reduced pressure by a rotary evaporator to obtain white crystals. The crystals were dried under reduced pressure at 80 ° C. to obtain 485 g of monoallylamine-hydrochloride. A monoallylamine-hydrochloride was prepared in a 70% by mass aqueous solution, and 50 g of this aqueous solution was charged with 2,2′-azobis (2-aminopropane) dihydrochloride as a radical initiator in an amount of 2 to the monoallylamine-hydrochloride.
It was dissolved in an amount of mol%, and 25 g of 35 mass% hydrochloric acid was added. Then, static polymerization was carried out at 60 ° C. for 40 hours. After the polymerization was completed, the system was charged with acetone (1900 g) / methanol (1
It was poured into a mixed solution of 00g), and the formed precipitate was filtered. The filter cake is desalted to a molecular weight of 1500, pH 11.
9 polyallylamine was obtained.

(B) Preparation of Ink Composition 1 of polyallylamine (MW 1500) prepared above
C. in a 0 mass% aqueous solution. I. Acid Yellow 23 (2
g), the barbituric acid derivative (0.2 g) shown in the specific example (A-30) of the present invention was dissolved to prepare 100 g of an aqueous solution. 1N hydrochloric acid aqueous solution was added dropwise to this aqueous solution to adjust pH.
Was adjusted to 10.0 to prepare an ink composition. (C) Image recording The above ink composition was filtered with a 5 μm filter. The ink composition supply portion of an ink jet printer (PM-770C, manufactured by Seiko Epson Corporation) was improved so that the ink composition was filled, and Y was printed on plain paper Xerox-P.
A solid image of (yellow) was printed.

Comparative Example 2 An ink composition was prepared in the same manner as in Example 2 except that the barbituric acid derivative represented by (A-30) in Example 2 was not used, and a Y (yellow) solid image was prepared. Was printed.

<Evaluation of Light Resistance> The image recording portions of Example 2 and Comparative Example 2 were irradiated with light for 24 hours using a xenon lamp weatherometer (manufactured by Atlas, USA), and the degree of fading in the image was visually observed as follows. It was evaluated according to the standard. [Standard] A: Almost no fading was observed. ◯: Fading was slightly observed. Δ: A considerable amount of fading was observed. X: The degree of fading was remarkable.

<Ozone Resistance Evaluation> After the image recording portions of Example 2 and Comparative Example 2 were left in an ozone atmosphere of 3 ppm for 8 hours, the degree of fading of the image (coloring and density) was visually observed according to the following criteria. evaluated. [Standard] A: Almost no fading was observed. ◯: Fading was slightly observed. Δ: A considerable amount of fading was observed. X: The degree of fading was remarkable.

From the results shown in Table 2, it was found that the image recording portion using the ink composition of the example was superior in light resistance and ozone resistance to the comparative example.

[0063]

[Table 2]

[0064]

The dye composition of the present invention is excellent in light resistance and ozone resistance, and the ink composition or ink sheet of the present invention has light resistance and ozone resistance when an image is formed from them. High and excellent image fastness is obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 11/00 B41J 3/04 101Y

Claims (4)

[Claims] 1. A dye composition comprising an organic dye and at least one barbituric acid derivative represented by the following general formula (1). [Chemical 1] (In the general formula (1), R ¹ and R ² each independently represent a cyano group, an acyl group, an alkoxycarbonyl group or a dialkylaminocarbonyl group, and Y represents an oxygen atom or a sulfur atom.) 2. The organic dye is an organic dye in which an anion portion is colored, and the barbituric acid derivative is a water-soluble barbituric acid derivative.
The dye composition according to. 3. An ink containing an organic dye having an anion moiety colored, one or more water-soluble barbituric acid derivative represented by the general formula (1), a water-soluble cationic polymer compound, and water. Composition. 4. An ink sheet having an ink layer containing an organic dye, one or more kinds of barbituric acid derivatives represented by the general formula (1), and a binder resin.