JPH02178088A - Pyrazolopyrimidin-5-one dye for thermal transfer recording - Google Patents

Abstract

PURPOSE:To obtain novel pyrazolopyrimidin-5-one dye for thermal transfer recording excellent in spectral absorption characteristics and also excellent in heat resistance and humidity resistance by using a specific dye for thermal transfer recording. CONSTITUTION:Pyrazolopyrimidin-5-one dye represented by formula I(wherein R1-R6 are respectively a hydrogen atom, an alkyl group or a substituted alkyl group and R1 and R2 or R1 and R4, and R2 and R6 may be bonded mutually to form a 5-or 6-membered ring. R7, R8 and R9 are respectively a monovalent substituent) can be synthesized by the oxidative coupling reaction of a coupler represented by formula II and a p-phenylenediamine type color forming developing agent in the presence of an oxidizing agent. This dye is especially used in a thermal transfer recording material as a photographic dye obtaining a cyan image by coupling the developing agent, which is oxidized by silver halide developed by a color forming developer containing the coupler represented by the formula II being the cyan coupler, for example, used in a silver halide color photographic material and the phenylenediamine developing agent represented by the formula III and exposed, and the coupler.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new dye for thermal transfer recording produced from a pyrazolopyrimidine-5-one rust conductor, and more specifically, it relates to a new dye for thermal transfer recording that has excellent spectral absorption characteristics and The present invention relates to a novel pyrazolopyrimidine-5-one dye for thermal transfer recording that has excellent heat resistance and moisture resistance.

[Background of the Invention] Pyrazolopyrimidine-5-one rust conductor was previously found to have excellent properties that could be used as a cyan coupler for color photography, and an application was filed as Japanese Patent Application No. 1982-204126. discloses a cyan coupler using the above-mentioned pyrazolopyrimidin-5-one rust conductor.

As a result of further various studies, the present inventor discovered that the dye obtained from the above-mentioned pyrazolopyrimidine-5-one rust conductor satisfies the conditions as a dye for thermal transfer recording. The present invention has been accomplished.

[Object of the Invention] An object of the present invention is to provide a novel pyrazolopyrimidine-5-one dye for thermal transfer recording, which has excellent spectral absorption characteristics as well as excellent heat resistance and moisture resistance.

[Structure of the Invention] The above object of the present invention has been achieved by a dye for thermal transfer recording represented by formula [1].

- Formula [11% Formula% [In the formula, R and R2 each represent a hydrogen atom, an alkyl group, or a substituted alkyl group, and R1 and R2 may be bonded to each other to form a 5- or 6-membered ring. .

Il, R4, R6 and R6 each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group.

Further, R1 and R4, R7 and R8 may be combined with each other to form a 5- or 6-membered ring, and R2, R8 and R9 each represent a monovalent substituent.] Hereinafter, the present invention will be described in more detail. Explain in detail.

- The pyrazolopyrimidine-5-one dye represented by the formula [1F] has many uses, such as thermal transfer recording,
It is applied to dyes for forming color images suitable for image media such as inkjet and printing, dyes for filters, dyes for photography, antihalation dyes, dyes for textiles, etc.

-Math [! In C, the mouth and R2 are preferably hydrogen atoms, alkyl groups, and substituted alkyl groups such as hydroxyalkyl groups, alkoxyalkyl groups, alkoxyalkoxyalkyl groups, and alkylsulfonamidoalkyl groups. Examples of these groups include carbon-based groups such as methyl group, ethyl group, propyl group, isopropyl group, 5ec-butyl group, butyl group, isobutyl group, tart-butyl group, octyl group, dodecyl group, octadecyl group, cyclohexyl group, etc. Examples include an alkyl group having a number of 1 to 18, a hydroxyethyl group, a methoxyethyl group, a methoxyethyl group, a methoxybutyl group, an ethoxyethyl group, a methoxyethoxyethyl group, a β-methanesulfonamidoethyl group, and the like.

Examples of the 5- or 6-membered ring formed by bonding R1 and R2 to each other include a pyrrolidino group, a piperidino group, a piperazino group, and a sulfolino group.

R,, R4, RS and R6 may be the same or different, and are preferably a hydrogen atom, a halogen atom,
These include an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylsulfonamidoalkyl group, an alkoxy group, and the like. Examples of these include a chlorine atom, a bromine atom, a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a methoxyethyl group, a methanesulfonamidoethyl group, a methoxy group, an ethoxy group, and the like.

The 5- or 6-membered ring formed by bonding R1 and R4, R2 and R6 to each other is preferably exemplified by the following groups.

Preferred monovalent substituents represented by R7, Ra and R include, for example, a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom), a cyano group, a nitro group, a carboxy group, even if each is substituted. good alkyl group,
alkoxy group, alkylamide group, arylamide group,
Alkylsulfonamide group, arylsulfonamide group, carbamoyl group, sulfamoyl group, dialkylcarbamoylamino group, dialkylsulfamoylamino group, each optionally substituted arylcarbamoylamino group, alkyloxycarbonylamino group, imide group, alkyl Examples include groups such as carbamoyl group, alkylsulfamoyl group, arylcarbamoyl group, arylsulfamoyl group, alkoxycarbonyl group, alkoxysulfonyl group, and the like.

To explain in more detail the monovalent substituents represented by R7, R8 and R9, representative examples of unsubstituted alkyl groups include methyl group, ethyl group, 5ac-butyl group, t-octyl group, dodecyl group, etc. A straight chain or branched group having 1 to 22 carbon atoms is preferable, and the substituted alkyl group is preferably a hydroxy-substituted alkyl group represented by hydroxyethyl, an alkoxy group represented by a methoxyethyl group, a methoxyethoxyethyl group, etc. Substituted alkyl groups are preferred.

Examples of unsubstituted alkoxy groups include straight-chain or branched alkoxy groups having 1 to 22 carbon atoms, such as methoxy, ethoxy, n-butoxy, 5ee-butoxy, dodecyloxy, and octadecyloxy groups. An alkoxy group is preferred, and the substituted alkoxy group is preferably an alkoxy-substituted alkyl group such as a methoxyethoxy group.

Examples of unsubstituted alkylamide groups include acetamido groups,
1 carbon atom represented by propionamide group, pentanamide group, laurylamide group, stearylamide group, etc.
-22 alkane amide groups are preferred, and substituted alkylamido groups include 2,4-di-t-amylphenoxyacetamide group, 2-(m-pentadecylphenoxy)
Preferred are phenoxy-substituted alkylamide groups represented by butanamide groups, chloroacetamide groups, trifluoroacetamide groups, perfluorobutanamide groups, and other halogen-substituted alkylamide groups.

Examples of the arylamide group include arylamide groups such as benzamide and naphthamide, alkoxy-substituted benzamide groups represented by 〇-tetradecaoxybenzamide group, M-laurylamide benzamide group, and m-laurylamide benzamide group.
(2-(2,4-di-7-amylphenoxy)hexaneamide)benzamide group, O-hexanedecanesulfonamide benzamide group, etc.; A halogen-substituted benzamide group represented by a benzamide group is preferred.

As the alkylsulfonamide group, a sulfonamide group of an alkane having 1 to 22 carbon atoms is preferred, such as a methanesulfonamide group, an ethanesulfonamide group, a butanesulfonamide group, a hexadecanesulfonamide group, and the like.

Examples of arylsulfonamides include unsubstituted arylamide groups such as benzenesulfonamide groups and naphthalenesulfonamide groups, as well as p-toluenesulfonamide groups, xylene sulfonamide groups, dodecylbenzenesulfonamide groups, and p-dodecyloxybenzene. Preferred as the substituted benzenesulfonamide group are an alkyl-substituted benzenesulfonamide group and an alkoxy-substituted benzenesulfonamide group represented by a sulfonamide group.

Furthermore, the alkyl group of the dialkylcarbamoylamino group and dialkylsulfamoylamino group is preferably an alkyl group having 1 to 8 carbon atoms, and methyl, ethyl, propyl, and butyl groups having 1 to 4 carbon atoms are representative. and is preferable.

In addition, as the arylcarbamoylamino group, unsubstituted phenylcarbazoylamino groups such as phenylcarbamoylamino groups, halogen-substituted phenylcarbamoyl groups represented by p-cyanophenylcarbamoylamino groups and p-chlorophenylcarbamoylamino groups, etc. are substituted phenylcarbamoylamino groups. Preferred as a carbazoyl group.

The alkyl of the alkyloxycarbonylamino group is preferably an unsubstituted alkyl having 1 to 22 carbon atoms such as a methyl group, ethyl group, butyl group, or dodecyl group, and the imide group is a succinimide group, a phthalimide group, or an alkyl thereof. Substituted products and the like are preferred.

The alkyl of the alkylcarbamoyl group and alkylsulfamoyl group is a butyl group, a dodecyl group, and the ring carbon atom fi
an alkyl carbamoyl group having an unsubstituted alkyl group such as an alkyl group of 1 to 22 or an alkyl sulfur 1 moyl group;
Also, phenoxy-substituted alkyl groups such as r-(2,4-di-t-amylphenoxy)butyl groups, substituted alkylcarbamoyl groups having alkoxy-substituted alkyl groups such as n-dodecyloxyprobyl groups, and substituted alkyl groups. A sulfamoyl group is preferred.

Arylcarbamoyl groups and arylsulfo-monoyl groups include phenylcarbamoyl groups, unsubstituted arylsulfamoyl groups such as phenylsulfamoyl groups, unsubstituted arylsulfamoyl groups, phenylcarbamoyl groups substituted with alkyl groups or halogen atoms, and phenylsulfamoyl groups. Preferred are phenylcarbamoyl groups represented by famoyl groups and substituted phenylsulfasoyl groups.

Further, as the alkoxy group of the alkoxycarbonyl group and the alkoxysulfonyl group, each of which may be substituted, a C1-22 alkoxy group represented by a methoxy group, an ethoxy group, a butoxy group, and the like is preferable.

Representative examples of pyrazolopyridin-5-one dyes used in the present invention are listed below.

Margin below (1 day) DC, 11,.

NHL; OCt tHts The pyrazolopyrimidin-5-one dye represented by the formula [1] is a coupler represented by the following formula [1[] and the phenylenediamine color developer represented by the following formula [II+]. It can be synthesized by oxidative coupling of the main drug in the presence of an oxidizing agent.

Formula [II] II.

[Here, R, , R, and R9 represent the same meaning as defined in the above-mentioned general formula [1].

X represents a hydrogen atom or a substituent group that is released by reaction with an oxidized product of a color developing agent.] General number +n] [Here, R R.

OJ: HiRa represents the same meaning as defined in general formula [11] This coupling reaction is preferably carried out under basic conditions, and the reaction medium is an organic solvent, an aqueous organic solvent, Alternatively, the oxidizing agent may be any one having a potential to oxidize p-phenylenediamine, whether organic or inorganic. Examples of the oxidizing agent include silver halide, hydrogen peroxide, manganese dioxide,
Inorganic oxidizing agents such as A potassium sulfate and oxygen, as well as various organic oxidizing agents such as NBS and chloramine T, can be used.

The conocoupling reaction was performed by T. H. James 41
i”Tha Theory of the Photo
graphlc Process (4th edition) (Mac
mNlan, 1977), a leuco dye is formed by the nucleophilic attack of the coupler anion on the reactive species formed by oxidation of phenylenediamine or aminophenol, and then the azomethine dye is converted into azomethine dye. It is believed that

Furthermore, the pyrazolopyrimidin-5-one coupler represented by the general formula [II''J described above is disclosed in Japanese Patent Application No. 62-2034.
51 and can be synthesized by the method described therein.

Typical specific synthesis examples of the dyes used in the present invention are shown below.

Synthesis of dye (compound 2) The pyrazolopyrimidin-5-one compound (1) is
It was synthesized according to the method described in the above-mentioned patent application specification.

1.7 g of compound (1) was dissolved in 100 μl of ethyl acetate, and an aqueous solution IIL containing 60 g of potassium carbonate was added. Then, while stirring at room temperature, 4-amino-3-methyl-
N-ethyl-N-(β-methanesulfonamidoethyl)
Aniline 3/2 sulfate monohydrate 6.5g aqueous solution 100
+aj was added. Add 1.4g of silver powder to this reaction solution,
Further, while stirring at room temperature, 20 mN of 2% hydrogen peroxide solution was gradually added. After stirring at room temperature for 30 minutes, the ethyl acetate layer was taken out, the solvent was distilled off, and the resulting residue was recrystallized from toluene to obtain 1.3 g of compound (2).

Synthesis of Dye (Compound 5) Compound 5 Pyrazolopyrimidin-5-one compound (11) was synthesized according to the method described in the above-mentioned patent application specification.

2.1 g of compound (II) was dissolved in ethyl acetate, and 1 ft of water containing 60 g of potassium carbonate was added thereto. Then, while stirring at room temperature, 4-amino-3-methyl-N-ethyl-N -(β-Hydroxyethyl)aniline sulfate (5.0 g) in water (100 μl) was added.

This reaction (1.5 g of silver chloride powder was added to the solution, stirred at room temperature for 30 minutes, the ethyl acetate layer was taken out, the solvent was distilled off, and the resulting residue was recrystallized with a mixed solvent of toluene and hexane. As a result, 1.4 g of compound (5) was obtained.

The pyrazolopyrimidin-5-one dye used in the present invention uses a coupler represented by the above formula [II] as a cyan coupler used in silver halide color photographic light-sensitive materials, for example, and a coupler represented by the above formula [II+]. It is also useful as a photographic dye for producing a cyan image by developing with a color developing solution containing a phenylenediamine-based color developing agent, and coupling the developing agent oxidized by exposed silver halide with the coupler. be.

The pyrazolopyrimidin-5-one dye used in the present invention is also used as a filter dye for photography, and is
It is also useful as a cyan dye for images in thermal transfer processes, inkjet methods, color electrophotography, printing, etc. as shown in Nos. 511-205798 and 58-2190116, etc., and is particularly used in thermal transfer recording materials. Ru.

In order to improve the stability of the dye used in the present invention against light or heat, a known stabilizer can be used in combination. Such stabilizers include, for example, U.S. Pat.
35,016 and 3.9112.944, U.S. Pat.
, 216 and JP-A-55-21004, JP-A-54-14
5530, GB 2,077.455 and GB 2.06L8 [1
Spiroindane derivatives and methylenedioxybenzene conductors described in No. 8, U.S. Patent No. 3,784°33
No. 7, No. 3.412, 1fIQ No. 3,574,
No. 627, No. 3,573.050, Japanese Unexamined Patent Publication No. 1973-1
No. 52225, No. 53-20327 and No. 53-1
Chroman talk conductor, Spirocoumaron talk conductor and Kumaran talk conductor described in No. 770, Japanese Patent Application Laid-open No. 55-6321, British Patent No. 1,347,556, British Patent Publication No. 2
, 066.975 and Japanese Patent Publication No. 54123:17 and P
- Aminophenol conductor, bisphenol derivatives described in Japanese Patent Publication No. 48-31625 and U.S. Pat. No. 3,700,455, and U.S. Pat.
Examples include metal complexes as described in No. 8 and the like.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example Sample 1 was prepared by coating a gelatin layer containing a comparative dye (^) dissolved in dioctyl phthalate on a paper support laminated on both sides with polyethylene so that the reflection density was approximately 1.5. Next, Samples 2 to 11 were prepared in exactly the same manner as in Sample 1, except that the comparative dye (^) was replaced with the dye shown in the table.

Samples 1-1 obtained above! Spectral absorption maximum wavelength (λ, □) and reflection density at 420n■ (Dλ4
．． . ) and a reflection density of 075, the half-width (WH), which is the difference between one point on the longer wavelength side than λsmg and one point on the shorter wavelength side than λ,□, was measured, and the spectral absorption characteristics were studied.

The smaller the value of Dλ420, the less asymmetric absorption in the green region, and the smaller the value of wH, the sharper the absorption and the better the spectral absorption characteristics.

In addition, each of the above coated samples was heated at high temperature (60℃, 80%R).
1;) Leave it in the atmosphere for 20 days to improve the heat resistance and
We investigated moisture resistance. The obtained results are also shown in the table. However, the heat resistance and humidity resistance of the coated dye is expressed as the percentage of dye remaining after the heat resistance and humidity resistance test for an initial density of 1.5. A type densitometer (manufactured by Konica Corporation) was used.

Comparative dye (A) Table 1 As is clear from the results in the table, the dye-coated samples used in the present invention all have very small half-value widths and small asymmetric absorption compared to the comparative dye-coated samples. , it can be seen that it has excellent spectral absorption characteristics. Furthermore, it can be seen that it has a high dye residual rate, excellent heat resistance and moisture resistance, and is robust.

[Effects of the Invention] The pyrazolopyrimidin-5-one dye used in the present invention has an extremely good hue and has high fastness to heat and humidity. Compared to the cyan dye, the sub-absorption in the edge region is greatly reduced in hue, there is less irregular absorption, and it has excellent spectral absorption characteristics. Furthermore, since it is a fast dye with good heat resistance and moisture resistance, it is well used in heat-sensitive transfer recording materials.

Patent applicant Co Nika Co., Ltd. Representative patent attorney: Miki Nakashima, Yugai (1 person)

Claims (1)

[Claims] A dye for thermal transfer recording represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It may form a ring. R_3, R_4, R_5 and R_6 are each a hydrogen atom,
Represents a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group. Further, R_1 and R_4, and R_2 and R_6 may be combined with each other to form a 5- or 6-membered ring. R_7, R_8
and R_9 each represent a monovalent substituent. ]