JPH03210368A - New quinoxalone dye - Google Patents

Abstract

PURPOSE:To obtain a yellow quinoxalone dye having a very vivid color by forming a compound having a specified structural formula. CONSTITUTION:A quinoxalone dye shown by formula I, wherein R1, R2, and R3 are each H, halogen, alkyl, alkoxy or acylamino; R4 is H, alkyl, aryl or a heterocyclic group; m is an integer of 0 to 4: R5 is halogen, nitro or a monovalent organic group and may represent two or more different groups when m is 2 or greater; A is hydroxyl or a group shown by -NR6R7 (wherein R6 and R7 are each H or alkyl, which may be combined together to form a heterocyclic ring); B is a substituent capable of forming a hydrogen 1 bond. This quinoxalone dye is useful for various pictures and recordings including photograph, as a dye for various filters, and as a dye for plastics and clothing.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to quinoxalone dyes, specifically for use in various images and recordings including photography, various filter dyes,
The invention further relates to quinoxalone yellow dyes useful for dyeing plastics and clothing.

[Background of the invention]

Various dyes including azo dyes have been used as yellow dyes. For example, for use in photography, azomethine dyes obtained by coupling an oxidized product of an aromatic primary amine developing agent such as p-phenylenediamine or p-aminophenol with an acylacetanilide compound are known.

However, even with azomethine dyes for photography, unnecessary absorption due to poor absorption tails hinders improvements in color reproduction. Dyes are desired.

Furthermore, a yellow dye with a clearer color tone is desired for thermal transfer recording, hard copying such as inkjet L tinting, etc., and this is a dye used for other purposes such as plastics, ink, and clothing. - The same applies to pigments.

[Purpose of the invention]

It is therefore an object of the present invention to provide a new yellow dye having a very vivid color tone.

Another purpose is to sharply cut the long wavelength absorption edge,
The objective is to provide a yellow dye with low side absorption.

Still another object is to provide a yellow dye having heat resistance and light resistance that is also useful for photography.

[Structure of the invention]

The above object of the present invention is represented by the following general formula, where R2 and R1 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an acylamino group, and R4 represents a hydrogen atom, Represents an alkyl group, an aryl group, or a heterocyclic group. R3 represents a halogen atom, a nitro group, or a monovalent organic group, and m represents an integer of 0 to 4. When m is 2 or more, R6 may represent two or more different groups.

A represents a hydroxyl group or a group represented by -NR6R. Here, R6 and R2 each represent a hydrogen atom or an alkyl group. Furthermore, R6 and R7 may be combined with each other to form a heterocycle.

B represents a hydrogen bonding substituent.

The compound represented by the general formula will be described in detail below.

The halogen atom represented by R2 and R1 is a fluorine, chlorine, bromine or iodine atom, preferably a fluorine or chlorine atom.

The alkyl group represented by R2 and R8 is preferably a substituted or unsubstituted alkyl group having 1 to 35 carbon atoms,
Among these, unsubstituted alkyl groups having 8 or less carbon atoms, such as methyl, ethyl, i-propyl, and butyl, and substituted alkyl groups, such as methanesulfonamidoethyl and methoxyethyl, are preferred.

Examples of the alkoxy group represented by R2 and R5 include substituted or unsubstituted alkoxy groups having 1 to 35 carbon atoms, such as unsubstituted alkoxy groups having 8 or less carbon atoms such as methoxy, ethoxy, and i-propoxy; Alkoxy-substituted alkoxy groups such as ethoxy are preferred.

The acylamino group represented by R□, R2, and R1 includes unsubstituted alkanamide groups having 1 to 22 carbon atoms such as acetamide, propionamide, lauroylamide, chloroacetamide, trichloroacetamide, trifluoroacetamide, and pentafluoropropionamide. Among these, substituted or unsubstituted alkanamide groups having 8 or less carbon atoms are preferred.

Examples of the acylamino group include arylamide groups such as benzamide, na7+-amide, and substituted benzamide groups such as m-nitrobenzamide, p-chlorobenzamide, p-methoxybenzamide, and m-propionbenzamide. .

As the sulfonamide group, unsubstituted alkanesulfonamides having 1 to 22 carbon atoms are preferred, such as methylsulfonamide, ethylsulfonamide, butylsulfonamide, hexadecylsulfonamide, etc., and hensensulfonamide, naphthalenesulfonamide, p -Toluenesulfonamide, p-dodecylbenzenesulfonamide group, p
Substituted or unsubstituted arylsulfonamide groups such as -chlorobenzenesulfonamide, p-dodecyloxybenzenesulfonamide, and 2-octyloxy-5octylbenzenesulfonamide are preferred.

The alkyl group represented by R2 includes methyl, ethyl,
1-2 carbon atoms such as i-propyl, t-butyl, dodecyl, etc.
2 unsubstituted alkyl groups, alkoxy-substituted alkyl groups such as dodecyloxyethyl, methoxyethyl, and octyloxyethyl, hydroxy-substituted alkyl groups such as hydroxyethyl groups and hydroxypropyl groups, and further carboxyl groups, carboethoxy groups, and sulfo groups. Various alkyl groups substituted with, etc. are mentioned.

The aryl group represented by R4 includes unsubstituted aryl groups such as phenyl and naphthyl, as well as aryl groups substituted with various substituents including nitro group, cyano group, hydroxyl group, carboxyl group, and sulfo group. Representative examples include an aryl group (preferably a phenyl group) substituted with a halogen atom such as fluorine or chlorine, and an alkyl group substituted with the same alkyl group as mentioned above for the alkyl group represented by R4. Examples include phenyl groups, and phenyl groups substituted with alkoxy groups having 1 to 22 carbon atoms (preferably unsubstituted alkoxy groups) such as methoxy, ethoxy, i-propoxy, and dodecyloxy. Also, unsubstituted alkanamide groups having 1 to 22 carbon atoms represented by acetamide, lauroylamide, etc., 2,4-di-t-amylphenoxypropionamide, 3-valmitoylphenoxyacetamide, p-C lauroylamide) Phenylbutanamide, l
An aryl group (among which a phenyl group is preferred) substituted with a substituted alkanamide group such as -methyl-2-dodecylsulfonylglopionamide is also preferred. or,
A sulfonamide group is also a preferred substituent, and the above-mentioned R1, R
An aryl group (particularly a 7-enyl group) substituted with an unsubstituted alkanesulfonamide group or a substituted or unsubstituted arylsulfonamide group listed as the substituent represented by 2.R is also preferable. Furthermore, it may be an aryl group substituted with an alkoxycarbonyl group having 1 to 22 carbon atoms such as ethoxycarbonyl or dodecyloxycarbonyl, or a substituted alkoxycarbonyl group such as dodecyloxycarbonyl ethoxycarbonyl,
Other examples include aryl groups (preferably phenyl groups) substituted with various substituents, such as phenoxy, phenoxycarbonyl, dimethylamino, diethylamino, anilino, alkylthio, acetyloxy, and lauroyloxy.

The heterocyclic group represented by R4 includes 2-pyridyl, 2-
Pyrimidyl, 4-pyrimidyl, 2-thiazolyl, benzothiazolyl, benzimidazolyl, 2-oxasilyl,
Examples include multiple groups such as benzoxasilyl, oxadiazolyl, thiadiazolyl, triazolyl, etc., and these groups may be further substituted with various substituents such as those listed for the above-mentioned aryl group.

The halogen atom represented by R6 is preferably a fluorine or chlorine atom, and the monovalent organic group is not particularly limited as long as it does not essentially impair the properties of the dye of the present invention, but preferably methyl, Alkyl groups such as ethyl, alkoxy groups such as methoxy, ethoxy, hexadecyloxy, cyano groups, amine groups, dialkylamino groups such as dimethylamino, acylamino groups represented by acetamide, lauroylamide, benzamide, etc., methanesulfonamide, Sulfonamide groups represented by butanesulfonamide, benzenesulfonamide, etc. are preferred.

When A represents -NR, R, R5 and R7 may be the same or different and represent a hydrogen atom or an alkyl group,
Examples of alkyl groups include unsubstituted alkyl groups such as methyl, ethyl, butyl, β-hydroxyethyl, β-methoxyethyl, acetyloxyethyl, cyanethyl, β-methanesulfonamidoethyl, carboxyethyl, γ-sulfopropyl, and carboethoxy. Examples include substituted alkyl groups such as methyl.

It is preferable that each group has 1 to 22 carbon atoms.

Examples of the heterocyclic group that R6 and R7 may combine with each other include pyrrolidino, piperidino, piperazino,
Examples include multiple groups such as morpholino. Furthermore, R6 and R7 may each be combined with R2 or R1 to form a similar heterocyclic group.

The hydrogen-bonding group represented by B is preferably a hydroxyl group, anilino group (anilino, p-methylanilino, p-methoxyanilino, p-chloroanilino, p-
Substituted and unsubstituted anilino groups such as nitroanilino and m-chloroanilino), -NHCOR, group, NtlSO2Rs
group, where R8 represents an alkyl group, an aryl group, an alkylamino group, a dialkylamino group, or an arylamino group.

The alkyl group represented by R1 includes methyl, ethyl,
5aIC-butyl, t-butyl, hexyl, decyl,
Examples include straight-chain or branched alkyl groups having 22 or less carbon atoms, such as dodecyl, and cyclic alkyl groups (eg, cyclopentyl, cyclohexyl, adamantyl, etc.). Further, these alkyl groups may have a substituent, and preferable substituents include halogen atoms such as fluorine and chlorine, phenyl,
Examples include aryl groups such as p-butanamidophenyl.

The aryl group represented by R3 is preferably a phenyl group or a naphthyl group, and these phenyl groups or naphthyl groups may have a substituent. Examples of the substituent include a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an alkylamide group, an alkylsulfonamide group, an arylamide group, an arylsulfonamide group, an alkylcarbamoyl group, an arylcarbamoyl group, and an alkoxycarbonyl group. , an aryl group, an oxycarbonyl group, an alkanoyloxy group, an arylcarbonyloxy group, and the like. Specifically, poo phenyl, pentafluorophenyl, p-nitrophenyl, m-hydroxyphenyl, tolyl, p~methoxyphenyl, p-
Dodecyloxyphenyl, 2-butoxy-5-octylphenyl, p-pivaloylamidophenyl, pentanamidophenyl, pentafluoropropionamidophenyl, p-methanesulfonamidophenyl, m-butanesulfonamidophenyl, p-benzamidophenyl, p
-1□Rylamidophenyl, benzenesulfonamidophenyl, p-dodecylbenzenesulfonamidophenyl, 2-year-old ctyloxy-5-octylbenzenesulfonamidophenyl, o-7' thylcarbamoyl phenyl,
p-(phenylcarbamoyl)phenyl, p-(p-methoxyphenylcarbamoyl)phenyl, 0-ethoxycarbonylphenyl, p-butoxycarbonylphenyl, acetoxyphenyl, hexanoyloxyphenyl,
Six groups include benzoyloxyphenyl.

Examples of the alkylamino group and dialkylamino group include ethylamino group, dimethylamino group, butylamino group, dipropylamino group, etc., and examples of the arylamino group include anilino, p-methoxyanilino, m-nitroanilino, etc. Examples include substituted and unsubstituted anilino groups.

Typical specific examples of the quinoxalone dye of the present invention are shown below, but the present invention is not limited thereto.

■ 1O OCH.

C,H.

*CsHw(L) These compounds are obtained by converting the coupler compound described in Japanese Patent Application No. 1-262791 filed on October 7, 1999 by the present inventors into N,N-dialkyl-p-fuynylenecyamine. can be easily obtained by oxidative coupling with

Typical synthesis examples are shown below.

Synthesis Example (Synthesis of Compound Example 1) Synthesis of 0-butanamidobenzoylacetic acid ethyl ester 9.40 g of diethyl carbonate was dissolved in 30 mQ of toluene,
2.08 g of sodium hydride (60% content) was added thereto and heated to 70°C. While stirring, 4.10 g of 2-butanamide acetophenone was added little by little over 20 minutes.

The reaction was further continued at 80°C for 2 hours. After cooling, add glacial acetic acid 3.
After adding 2 g, 100 mQ of ice water was added and extracted with ethyl acetate. After thoroughly washing the ethyl acetate layer with water, it was dehydrated with anhydrous magnesium sulfate, and the ethyl acetate was concentrated. A light brown oil remained. The yield was 5.45 g, which was used as it was in the next reaction without any particular purification.

5.45 g of crude 0-butanamidobenzoylacetic acid ethyl ester and 8.04 g of 2-chloro-5-dodecyloxycarbonylaniline were mixed with 100 ml of xylene and boiled for 3 hours. After xylene was distilled off under reduced pressure, acetonitrile was added for crystallization. After filtering, it was further recrystallized with acetonitrile.

Yield: 4.35g Melting point: 99-100°C Identified by NMR and Mass spectrum.

Synthesis of Compound Example 1 2.86g of compound example (1) of Synthesis Example 1 was added to 1 part of ethyl acetate.
Dissolved in 00ml12, N-chlorosuccinimide 0.6
Add 6 g and stir at room temperature for 24 hours.

Next, water was added and the ethyl acetate layer was washed three times with water, and the dityl acetate layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure.

The residual oil was recrystallized from n-hexane to obtain white crystals.

Yield 2.38g Melting point 100-103°C0 Exemplary compound l
Synthesis of 1.21 g of a-(0-butanamidobenzoyl)-α-chloro-2-chloro-5-dodecyloxycarbonylacetanilide in ethyl acetate,
Separately, dissolve 20.0 g of sodium carbonate and 0.9 g of Kodak CD-3 (developing agent) in 200 m of water. The reaction was carried out until there was no remaining coupler by layer chromatography.

The ethyl acetate layer was thoroughly washed with water, dehydrated with anhydrous sodium sulfate, and then concentrated under reduced pressure. Next, this was purified by column chromatography to obtain 85 g of yellow dye (Exemplary Compound 1) as an amorphous solid. This substance was confirmed by NMR and Mass spectrum.

The absorption characteristics of this obtained yellow dye are shown below in comparison with a separately synthesized comparative dye Y-1.

Incidentally, comparative dye Y-1 is a typical azomethine dye commonly used in the photographic industry.

Comparative dye (Y-1) Note that Δλ,. 2 is a number that represents the break on the long wavelength side, and is a measurement of the difference between the wavelength that gives the maximum absorbance and the wavelength where the absorbance decreases on the long wavelength side and falls on the sail 2. The smaller this number is, the sharper it is. Indicates that it has been cut. Furthermore, since ε is also quite high, it can be seen that it is very preferable as a yellow dye.

The absorption curve in methanol is shown in FIG.

Furthermore, the dye of the present invention is excited in a wide range from ultraviolet to visible light and emits G fluorescence (emission maximum: 532 nm).

This property is also more preferable as a yellow dye because it has the effect of correcting unnecessary 0 part tails.

The dye of the present invention is a benzoylacedoanilide having the following structure represented by the above general formula, which the present inventors have already filed, and p
-Produced with very good efficiency by oxidative coupling reaction with fluorinatediamine-based or p-aminophenol-based compounds.

The details of the formation mechanism are unknown, but the benzoyl group
Due to the hydrogen-bonding group in the position, the p-phenylenediamine moiety in ordinary coloring dyes becomes electron deficient, resulting in nucleophilic attack 1. It is presumed that the quinoxalone dye is oxidized to form a ring after receiving a nucleophilic addition attack from the amide moiety, and is further oxidized to form a quinoxalone dye.

Therefore, by using the above-mentioned coupler, the quinoxalone dye of the present invention can be efficiently obtained in a photographic developer. may have been done.

The present invention is useful for photographic processes, and also for other uses, such as 7414904, taking advantage of its excellent light absorption properties.
8, No. 58-18169, No. 58-205798, No. 58-219086, No. 61-22993, No. 62-191191, No. 62-225564, etc., or an inkjet process. method,
It is also useful as a yellow dye for images in color electrophotography, printing, etc. It is also used for dyeing plastics, and as a pigment in ink. It is also suitable for various purposes.

Further, in order to improve the stability of the dye of the present invention against light or heat, a known stabilizer may be used in combination.

When applying the dye of the present invention to, for example, a thermal transfer method, an ink is prepared by dispersing or dissolving the dye in the form of fine particles in a medium together with a clarifying agent, and the ink is applied onto a base film and dried. to create a transfer sheet.

Binders for ink preparation include water-soluble resins such as starch, cellulose, and acrylic resins; polystyrene,
Examples include resins soluble in organic solvents such as polycarbonate, polysulfone, lyle resin, and methacrylic resin. In the case of organic solvent-soluble resins, they can be used not only as an organic solvent solution but also in the form of an aqueous dispersion.

In addition to water, media for ink preparation include alcohols such as methanol, incubanol, and isobutyl alcohol; cellosolves such as methyl cellosolve and ethyl cellosolve; aromatics such as toluene, xylene, and chlorobenzene; acetic acid. Esters such as ethyl and butyl acetate; Ketones such as acetone methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Chlorinated solvents such as dichloromethane, chloroform, and trichloroethylene; Ethers such as dioxane and tetrahydrofuran; N, N-dimethylformamide, N- Organic solvents such as methylpyrrolidone may be mentioned.

Suitable base films for applying ink for creating transfer sheets include thin paper such as condenser paper and glassine paper, and plastic films with good heat resistance such as polyester, polyamide, and polyimide. Further, the thickness of the base film is preferably in the range of 3 to 50 μm.

A gravure coater, reverse roll coater, rod coater, air doctor coater, etc. can be used to apply the ink to the base film. The thickness of the ink coating layer after drying is preferably in the range of 0.1 to 5 μm. (Yuji Harasaki,
"Coating Method J (1979)" The dye of the present invention has sharp spectral absorption and a clear yellow color, so by combining it with appropriate magenta and cyan colors, full-color recording with good color reproducibility can be obtained. In addition, because the molecular extinction coefficient is large, it is possible to obtain high-speed recording with high color density without placing a large burden on the thermal head.Furthermore, it is stable against heat, light, moisture, chemicals, etc., so transfer It does not thermally decompose during recording, and the resulting records have excellent storage stability.

Since the dye of the present invention has good solubility in organic solvents and good dispersibility in water, it is easy to prepare a uniformly dissolved or dispersed ink with high concentration. It is possible to obtain a transfer sheet coated uniformly and at a high concentration. Therefore, by using these transfer sheets, recordings with good uniformity and color density can be obtained.

As an example, the case where the dye is used in a thermal transfer method has been described here, but the vivid color tone of the dye of the present invention can be utilized in various other uses by using various methods suitable for the use.

〔Effect of the invention〕

The dye of the present invention is useful as a yellow dye for color image formation by the subtractive color method, and can also be mixed with cyan or magenta dye to produce yellow or blue dyes, for example, as a filter dye for solid-state image pickup tubes and color LCD televisions. It can also be used as a filter.

The dye of the present invention has an extremely good hue as a yellow dye, has a high molar extinction coefficient (1), and has high fastness to heat, at least in the above-mentioned applications.

Compared to known azomethine-based or azo-based yellow dyes, the dye of the present invention has a sharply cut tail on the long wavelength side of the spectral transmittance curve in hue, and therefore sub-absorption in the edge region is greatly reduced, resulting in irregularities. Absorption is low, and the molar extinction coefficient in the blue region is about 1.5 to 2 times as large. It also has good light resistance and heat resistance, and has extremely favorable properties in terms of color reproduction for color photography based on the subtractive color method.

〔Example〕

Next, as an example of a preferred method of using the dye of the present invention, a case where the dye is used in a thermal transfer process will be illustrated, but the present invention is not limited thereby.

Example 1 Transfer sheets 1 to 3 were prepared by applying ink having the following composition using a wire bar to a 9 μm thick polyethylene terephthalate film base whose back surface was heat-resistant treated and drying. Next, using the compounds (1), (4), (6), (14) of the present invention in place of the comparative dye (Y-2),
Samples 4 to 6 were created.

Ink (A) Comparative dye (Y-2) Log, polysulfone resin 1
An ink was prepared by mixing 0 g and 80 g of chlorobenzene and treating with a paint conditioner for 10 minutes.

The dye and resin were completely dissolved to obtain a uniform ink (A).

Ink (B) Comparative dye (Y-2) 3g, polyvinyl butyral It
4.5 g of fat, 45 g of methyl ethyl ketone, and 45 g of toluene were mixed and prepared in the same manner as in (1).

Ink (C) 2 g of comparative dye (Y-2), 8 g of ethyl cellulose, and 90 g of Improper Tool were mixed and treated with a paint conditioner using glass beads for 30 minutes.

Each of the obtained samples was thermally transferred to the following image receiving layer using a thermal head.

Image-receiving layer (1) 10 g of an aqueous dispersion of 34% by weight of saturated polyester (Pyronal MC-1200 manufactured by Toyobo Co., Ltd.) and silica gel (N1psil E22 manufactured by Nippon Silikani Gyo Co., Ltd.)
A paint prepared by mixing 5 g of OA) was applied to high-quality paper using a wire bar.

Image-receiving layer (2) Polyester resin (Vylon10 manufactured by Toyobo Co., Ltd.
3) 8g EVA polymer plasticizer (Elvaloy 74
1P Mitsui Polychemical) 2g, amino-modified silicone (KF-857, Shin-Etsu Chemical Department) 0.4g, epoxy-modified silicone (KF-103, Shin-Etsu Chemical Department)
0-4g5 methylated methyl ketone 36g, toluene 3
A paint prepared by mixing 6 g of cyclohexane and 18 g of cyclohexane was applied to synthetic paper (Yubo FPG #150, manufactured by Tamago Yuka Co., Ltd.).

Image-receiving layer (3) Polycarbonate resin (Makrolon manufactured by Bayer)
5705) in a mixture of methylene chloride and trichloroethyl 1/N, ICI Melinex 990 (Melin
ex 990) coated on a white polyester support.

The transfer sheet of the present invention and the image-receiving layer are stacked with their respective dye-carrying layers and dye-receiving surfaces facing each other,
Head applied voltage 10v1 printing time 4-0 from the back side of the sample
Recording was performed with a thermal head under conditions of m5ec, and the results shown in Table 1 were obtained.

*l: Color density is measured using an optical densitometer (Konica Corporation PCA-
65 type).

Book 2: For robustness, test samples at 50'C! After saving the image, it is marked ◎ if the sharpness of the image does not change and the color does not transfer even if you rub the surface with white paper, and if the sharpness decreases slightly and the color transfers to some extent, it is marked ○. , The blank paper was colored with △.

Comparative dye (Y-2) Shi21'Is Shin2uli3Nrl:>U2urls Example 3 Instead of the polyethylene terephthalate film base used in Example 1, the dye used in Example 1 was applied to a 15 μm polyimide film base. Transfer sheets 8 and 9 were prepared by applying the ink (dye used was Y3) using a wire bar and drying, respectively. Next, samples 10 and 11 were prepared using the compound (2) of the present invention in place of the comparative dye (Y-3). Transfer was performed using the same thermal head as in Example 1, and the results shown in Table 2 were obtained.

Comparative dye (Y-3)

[Brief explanation of drawings]

FIG. 1 shows absorption curves of the dye of the present invention and a comparative dye in methanol, where the vertical axis shows the absorbance and the horizontal axis shows the wavelength (nm).

Claims (1)

[Claims] A quinoxalone dye represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2 and R_3 are each a hydrogen atom,
It represents a halogen atom, an alkyl group, an alkoxy group, or an acylamino group, and R_4 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R_5 represents a halogen atom, a nitro group, or a monovalent organic group, and m represents an integer of 0 to 4. When m is 2 or more, R_5 may represent two or more different groups. A represents a hydroxyl group or a group represented by -NR_6R_7. Here, R_6 and R_7 each represent a hydrogen atom or an alkyl group. Furthermore, R_6 and R_7 may be combined with each other to form a heterocycle. B represents a hydrogen bonding substituent. ]