JPH01209448A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color formability and light resistance by incorporating a yellow coupler having a specific cyclic amine part as at least one partial structure into the above material. CONSTITUTION:This material contains the yellow coupler having the cyclic amine part expressed by the formula I as at least one partial structure. In the formula I, R11 denotes a hydrogen atom., alkyl group, alkenyl group, alkinyl group or acyl group, R12-R14 respectively denote a hydrogen atom. or alkyl group; X denotes a bivalent combination group such as -O-, -S- or -SO2-. The light resistance is thereby improved without impairing the color formability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material using a novel yellow coupler.

[Background of the invention]

As a yellow coupler used for forming a yellow dye in a silver halide color photographic material (hereinafter referred to as a color photographic material), α-
Acylacetanilides (eg pivaloylacetanilide, benzoylacetanilide) are common.

Couplers used in color photosensitive materials are required to have many properties, including the following. In other words, the silver halide emulsion should not be used as a coupler or reduce its sensitivity, it should not react with other additives in the emulsion, it should not decompose during long-term storage in the emulsion, and it should react quickly with the color developing agent to improve the color density. In addition, the formed dye should be stable against external conditions such as light, heat, and humidity, and the color development in the unexposed area should be as low as possible. Couplers must also not cause discoloration, staining, or fading.

To date, various efforts have been made in the molecular design of couplers in order to improve these properties.

For example, regarding the structure of ballast groups, Japanese Patent Publication No. 56-444
No. 20, JP-A-55-93153, JP-A No. 56-7424
No. 9, No. 56-74250, No. 58-21738, etc., include alkoxycarbonyl groups, N-substituted or unsubstituted alkylsulfonamide groups, and arylsulfonamide groups.
It has been proposed to improve color development by introducing a sulfonyl group or the like.

Further, JP-A-62-297846 discloses a technique for improving the light resistance of a dye by introducing a specific phenol group into the molecule of a yellow coupler.

However, this alone does not fully satisfy the above properties, and it is extremely difficult to satisfy both color development and image storage properties (particularly light fastness), which have been considered contradictory properties in this field. Ta.

Color development is especially important in rapid processing, which has recently become popular.Therefore, there is a strong desire to develop and use couplers that have excellent light resistance without impairing color development.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color photosensitive material containing a novel yellow coupler with excellent color development.

A second object of the present invention is to provide a color photosensitive material containing a novel yellow coupler that has excellent light resistance and good image storage stability.

[Structure of the invention]

The above objects of the present invention have been achieved by a color photosensitive material containing a yellow coupler having at least one cyclic amine moiety as a partial structure represented by the following general formula CI).

General formula [1] In the formula, R11 is a hydrogen atom, an alkyl group, an alkenyl group,
An alkynyl group or an acyl group, R121Rl) and R1 each represent a hydrogen atom or an alkyl group, and X represents a divalent linking group.

The present invention will be explained in more detail below.

Examples of the alkyl group represented by R11 include methyl group,
Ethyl group, propyl group, butyl group, pentyl group, benzyl group, etc., alkenyl group such as vinyl group, allyl group, impropenyl group, etc., and alkynyl group such as ethynyl group, propynyl group, etc., acyl group Examples include formyl group, acetyl group, propionyl group, butyryl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, and the like.

Examples of the divalent linking group represented by X include -o-, -s
-, -5o2- and -N- (R represents a hydrogen atom, an alkyl group or an acyl group).

R1 is preferably a hydrogen atom or an alkyl group,
R82 to R1 are preferably a hydrogen atom or a methyl group.

The yellow coupler used in the color photosensitive material of the present invention may be any type known in the art to form a yellow dye by reaction with an oxidized product of a color developing agent (for example, α
-acylacetamide type, β-ketoacetate type, N
, N-malondiamide type, etc.), and the cyclic amine moiety represented by the general formula CI) may be located at any position (for example, R1 to R of the coupler represented by the general formula (I[) described later).
', a part of Y), or one coupler may contain two or more of these bonds.

Further, the present invention also includes a case where a yellow coupler having a bond represented by general formula [1] as a partial structure is bonded at any site to form a dimer or more multimer.

Among the yellow couplers having at least one moiety represented by the general formula [I] as a partial structure, preferred general formula (n), where R' is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a bridged carbonized represents a hydrogen compound residue; R2 represents a halogen atom, an alkoxy group, an aryloxy group, or an acyloxy group; R3 and R4 each represent a substituent; L represents a divalent linking group, m and Q
each represents 0 or l. Y represents a hydrogen atom or a group that can be separated by reaction with a color developing agent.

General formula (n) will be explained in detail below.

The alkyl group represented by R1 is a linear chain having 1 to 36 carbon atoms or a branched alkyl group such as methyl, ethyl,
1-furovir, t-butyl, 2-ethylhexyl, t-
Six groups include octyl, dodecyl, benzyl, and phenethyl. Examples of the alkenyl group include an alkenyl group having 3 to 24 carbon atoms (e.g. allyl, 2,4-pentagenyl group, etc.); examples of the cycloalkyl group include a cycloalkyl group having 5 to 24 carbon atoms (e.g. cyclopentyl, cyclohexyl group, etc.); Preferred examples of the aryl group include phenyl group and naphthyl group. Further, as the bridged hydrocarbon compound residue, for example, bicyclo[2,11]butane-
■-yl, tricyclo[3,3,1,13.7]decane=1-yl, 7,7-dimethyl-bicyclo[2,2,1
]hebutan-1-yl and the like.

These groups further include those having substituents, such as /) rogene atoms and amino, nitro,
The six groups include cyano, hydroxyl, carpoxyl, alkyl, aryl, alkoxy, aryloxy, alkylthio, acyl, acylamino, acylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkylamino, arylamino, alkoxycarbonyl, etc. can.

Preferred R1 is a branched alkyl group or a substituted aryl group.

Examples of the halogen atom represented by R2 include chlorine, bromine, fluorine, and iodine atoms; examples of the alkoxy group include methoxy, ethoxy, octyloxy, and dodecyloxy; and examples of the aryloxy group include phenoxy, etc. Examples of the acyloxy group include acetyloxy,
Examples include benzoyloxy group.

Preferred R2 is a halogen atom or an alkoxy group.

R3 is not particularly limited as long as it is a group that can be substituted on the benzene ring, but specifically includes a halogen atom, alkyl, alkoxy, alkylthio, aryl, acyl, acylamino, sulfonamide, sulfonyl, carbamoyl, sulfamoyl, ureido, alkoxycarbonyl, nitro , cyano, carboxyl group, etc. These groups further include those having a substituent, and examples of the substituent include the same groups as those explained for R1 above.

Preferred R3 is a halogen atom, an alkyl group or an alkoxy group.

Examples of the substituent represented by R4 include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, heterocyclic groups, spiro compound residues, bridged hydrocarbon compound residues, etc. It will be done.

The alkyl, alkenyl, cycloalkyl, aryl, and bridged hydrocarbon compound residues represented by R4 include the same groups as those explained for R1 above.

The alkynyl group represented by R4 has 2 to 36 carbon atoms.
, the cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred. The heterocyclic group is preferably 5- to 7-membered, and may have a substituent or be fused. Specific examples include 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl groups. Examples of spiro compound residues include spiro[3
, 37hebutan-■-yl group, and the like.

L may be any divalent linking group commonly used in the art, preferably a group containing a carbonyl or sulfonyl group. Specific examples include alkyloxycarbonyl, aryloxycarbonyl, and N-substituted or unsubstituted acylamino, sulfonamide, carbamoyl, and sulfamoyl groups.

In the general formula (n), Y represents a hydrogen atom or a group that can be separated by reaction (coupling) with a color developing agent, and this split-off group is well known in the art, and a typical example is a halogen atom. , an alkoxy group, an aryloxy group, an arylthio group, and a 5- to 6-membered nitrogen-containing heterocyclic group, but preferably the following general formula CII [
) or (IV).

General formula (III) 〇R5 R5 represents an aryl group or a heterocyclic group including one having a substituent.

General formula [■], Par ゛′・, Zl ゛・1. -8. /'21 represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle together with N. The atomic groups forming this atomic group include RR -Co-, -NH-, -N=, -0-, -S-, -
Examples include So□-.

Among the above general formulas (II[) and (IV), the following general formulas (V) to [■] are particularly preferred.

General formula [V].

In the formula, R6 represents a hydroxyl group, a carboxyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a group similar to R3 in the general formula (n),
p represents an integer of 1 to 5.

When p is 2 or more, a plurality of R1's may be the same or different.

General formula [VI), d-゛・, In the formula, Z2 represents an atomic group necessary to form an imidazole, pyrazole, or triazole ring together with the nitrogen atom, and R
7 is a hydrogen atom, a halogen atom, or alkyl, alkoxy, aryl, heterocycle, amino, acylamino, carboxyl, alkoxycarbonyl, alkylsulfonyl,
Represents each layer of arylsulfonyl, alkylsulfinyl or arylsulfinyl. q represents an integer of 1 or 2, and when q is 2, two R7s may be the same or different.

General formula [■] represents Z, ' or ÷CRIO-, and R'', R' and R'' each represent the same group as R7 in the general formula (Vl). Z represents an atomic group necessary to form a 5- to 6-membered ring together with -W-N-Co-. Further, Ra, R1 or RIG may form a ring together with a part of Z.

Hereinafter, typical examples of yellow couplers (hereinafter referred to as couplers of the present invention) having at least one cyclic amine moiety represented by the general formula CI) as a partial structure will be shown.
The present invention is hereby limited to 0 + m
(q cv) zLI
″) coto ω0 ■
B +-I
C%J0 -I C%J
So Moan Z
To c+IJC'J
No -ro
To 2 NC
%J Next, a typical synthesis example of the coupler of the present invention will be shown.

Synthesis Example (Synthesis of Exemplary Coupler 9) Cθ (1) 299 and (2) 17g were combined with pyridine 100I+I
The mixture was heated and dissolved in FF and heated at 70 to 80°C for 5 hours. After cooling, the reaction solution was poured into 500ml of water (2), and the oily portion was extracted with ethyl acetate and thoroughly washed with water.The ethyl acetate layer was then separated, dried over Na25O, concentrated, and the residue was subjected to column chromatography. Purify it to produce a white solid (3
) 319 was obtained.

Next, (3) 31 g was dissolved in chloroform, and 4.3 raQ of sulfuryl chloride was added dropwise over 20 minutes while cooling with water.
The mixture was further stirred for 30 minutes. The reaction solution was washed with water, concentrated, and the crude product (
4) Obtained 329. This was dissolved in 150 m of ethyl acetate (2), and 9.5 g of (5) was added thereto, followed by heating under reflux for 3.5 hours.

After filtering off insoluble materials, the organic layer was separated, washed with water, and treated with Na2SO
After drying at step 4, it was concentrated. 30 g of white crystals were obtained by recrystallizing the residue with methanol.

The above white crystal was fixed by NMR, MASS spectrum, and elemental analysis, and the result was consistent with Exemplary Coupler 9.

The above yellow couplers of the present invention can be used alone or in combination of two or more.

The yellow coupler of the present invention is useful as a so-called protected dispersion type coupler, which is used by dissolving in a high boiling point organic solvent such as dibutyl phthalate or tricresyl phosphate, which has a boiling point of 175°C or higher and is difficult to miscible with water. Furthermore, without using the above-mentioned high-boiling point organic solvents, substantially water-insoluble low-boiling point organic solvents such as ethyl acetate and butyl acetate, or water-soluble low-boiling point organic solvents such as methanol, ethanol, methyl cellosolve, and methyl isobutyl ketone can be used. It can also be used by dissolving only in a boiling point organic solvent.

Further, the yellow coupler of the present invention can be used as a coupler for use in the so-called diffusion transfer method, in which a photosensitive element having a photosensitive layer is brought into contact with a processing solution for the purpose of blocking light, etc., to form a transferred image on the image receiving layer of the image receiving element. You can also do that.

Moreover, the yellow coupler of the present invention is
No. 585, U.S. Patent No. 3,486,890, Research Disc + - (Research Disc
It can also be used in the dye image forming methods described in US Pat.

That is, the yellow coupler of the present invention and the aromatic primary amine developing agent are both contained in a light-sensitive material, and after imagewise exposure, color development is carried out by processing with an alkaline activation bath or heat treatment. , it is possible to obtain a dye image with good gradation.

Conventionally known methods can be used to incorporate the yellow coupler of the present invention into the silver halide emulsion of a color light-sensitive material. For example, when using the protect dispersion method as described above, the solution is dissolved in a high boiling point organic solvent such as tricresyl phosphate or dibutyl phthalate, or a low boiling point organic solvent such as ethyl acetate or butyl propionate, alone or in combination. , mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed in a high-speed rotary mixer or colloid mill, added directly to a silver halide emulsion, coated on a support and dried, or the above emulsified dispersion After setting, it is shredded and the low boiling point solvent is removed by means such as washing with water, and then this is added to the emulsion, coated on a support and dried. In this case, generally 10 to 30 of the yellow coupler of the present invention is added per mole of silver halide.
Although it is preferable to add 0 g, it goes without saying that this may be varied depending on the purpose of application.

The color light-sensitive material to which the present invention is applied may be any material regardless of type or purpose. For example, it can be particularly advantageously used in multilayer negative color photosensitive materials, color print photosensitive materials, or reversal color photosensitive materials. The silver halide used at this time is any of the silver halide emulsions commonly used, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. can be used.

The silver halide emulsion is chemically enhanced by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

The silver halide photographic material according to the present invention may contain other color couplers together with the yellow coupler of the present invention in order to form a multicolor image. Other useful couplers include, for example, 5-pyrazolone magenta couplers, phenolic or naphthol cyan couplers, and the like. In combination with these couplers, it is also possible to use azo-type colored couplers, osazone-type compounds, development dye-releasing couplers, etc. for auto-masking. Further, at this time, it is desirable to use a desired colorless coupler, which is colorless before color development, together with the above-mentioned masking coupler.

Furthermore, various couplers such as so-called competing couplers, DIR couplers, and BAR (Biasch Accelerator R) are used to improve photographic properties.
It may also include a coupler called a leasing coupler or the like.

In the present invention, examples of the magenta coupler that can be used in combination with the yellow coupler of the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds.

Examples of cyan couplers that can be used in combination with the yellow coupler of the present invention include phenol compounds, naphthol compounds substituted with -0-aryl at the active site, and naphthol compounds.

The color photosensitive material of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet inhibitor, which are commonly used in photosensitive materials,
Antistatic agents, capping agents, surfactants, etc. can be used.

An image can be formed on the color photosensitive material of the present invention by subjecting it to a color development process known in the art.

The color light-sensitive material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath.

After color development, the color photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

〔Effect of the invention〕

The color photosensitive material containing the yellow coupler according to the present invention has excellent color development and good light resistance.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 As shown in Table 1, each of the yellow couplers of the present invention (indicated by the numbers of the above-mentioned exemplary couplers) and the following comparative couplers were prepared in 3. 10-2 moles of OX were added to a mixture of dibutyl phthalate and 40 mQ of ethyl acetate corresponding to 1/4 weight of each yellow coupler, heated to 50 °C,
Dissolved.

This solution was mixed with 10 mQ of a 10% aqueous solution of Alkanol-B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 m+2 of a 5% aqueous gelatin solution, and passed through a colloid mill several times to emulsify and prepare a dispersion.

This dispersion was added to 500 ml of gelatin silver chlorobromide emulsion, and 0.25 m of silver chlorobromide was coated on polyethylene laminated paper.
Samples 1 to 8 of silver halide photographic light-sensitive materials were prepared by coating and drying so as to give a weight ratio of g/m'. This sample was wedge exposed in a conventional manner and processed according to the following steps and processing solution formulation.

[Processing process] Processing temperature Processing time Color development 38°0 3 minutes 30 seconds Bleach fixing
Wash at 33°C for 1 minute and 30 seconds.
Dry at 25-30°C for 2 minutes 75-80'0 2 minutes [Color photographic developer] Benzyl alcohol 15me Ethylene glycol 15m (! Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride
0.2g potassium carbonate
30.0g hydroxylamine sulfate 3.0g polyphosphoric acid (TPPS)
2.5g 3-methyl-4-amino-N
-Ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide
Add 2.0g water to make the total volume lQ, p
Adjust to H1o, 20.

[Bleach-fix solution]

Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml12 Ammonium sulfite (40% solution) 27,5+J Adjust to pH 7.1 with potassium carbonate or glacial acetic acid, add water. Let the total amount be lQ.

Phenol compound comparative coupler A (coupler described in JP-A-62-297846) Comparison coupler B (coupler described in JP-A-56-74249) Sensitometric results of dye images of each sample after development processing are shown in Table 1. The sensitivity is the reciprocal of the exposure amount that gives a density of fog + 0.1, and is expressed as a relative sensitivity when the sensitivity of sample 1 is taken as 100.

Further, the density of the dye image after exposure for 100 hours (at an initial density of 1.0) was measured using a xenon fade meter to determine the dye residual rate. The results are also shown in Table 1.

As is clear from Table 1, the samples using the couplers of the present invention were excellent in both sensitivity and maximum density and exhibited good color development. Furthermore, it has excellent light resistance.

Example 2 After corona discharge was applied to a paper support coated with polyethylene on both sides, the following seven layers were sequentially applied from the support side,
Multilayer color photographic paper sample 9 was prepared. Note that the amount added in the photosensitive material is per 1 m2. In addition, silver halide was expressed as a silver equivalent value.

Layer L: 1.5 g of gelatin, 0.33 g of blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol%, average grain size 0.65 μm)
), 1, IX 10-3 moles of comparative yellow coupler A
and 0.015g of HQ-1 shown below dissolved in
, 25 g of dioctyl 7-thale 1- (DOP).

Layer 2...1. Og gelatin, and 0.09g I
A layer containing 006 g of DOP in which Q-1 was dissolved.

Layer 3: 1.3 g of gelatin, 0.27 g of green-sensitive silver chlorobromide emulsion (silver bromide 50 mol%, average grain size 0.45 μm)
), 0.28 DOPlo in which 0.59X 10-3 moles of the following magenta coupler M-1 and 0.015 g of HQ-1 were dissolved, 15 g of the following anti-irradiation dye A
Layer containing ID-1.

Layer 4...1.5g of gelatin, 0.8g of the following ultraviolet absorber UV-1 and 0.04g of TLQ-1 were dissolved.
, 6g (7) layer containing DOP.

Layer 5: 1.3 g of gelatin, 0.3 g of red-sensitive silver chlorobromide emulsion (silver bromide 50 mol%, average grain size 0.35 μm)
, 0.75X 10-3 mol of the following cyan coupler C-
1 and 0.2 g of D dissolved in 0.005 g of IIQ-1
Layer containing OP.

Layer 6: 0,01 in which 1.0g of gelatin, 0.4g of ultraviolet absorber UV-2 and 0.01g of HQ-1 were dissolved.
Layer containing 5g of DOP.

Layer 7...1. A layer containing Og of gelatin, 0-015g of filter dye AID-2 below.

H I2 I2 ID-1 ID-2 NaO,5C)I, NHOOH U■-1 Open C4H9(t) C+Hs(t) Sample 90 Samples were prepared in the same manner except that the coupler A in layer 1 was changed as shown in Table 2. IO~14 was created.

After each sample was exposed to blue light, green light, and red light through a continuous wedge, it was developed using the same processing steps as in Example 1. The results of sensitometry of the resulting dye image and light fastness test similar to Example 1 are shown in Table 2 for the blue-sensitive layer.

In addition, comparative couplers A and B are the same as in Example 1,
The sensitivity is a relative sensitivity when the sensitivity of sample 9 is set as 100.

As is clear from the results in Table 2, the samples using the yellow coupler of the present invention in multilayer color photosensitive materials also showed
It provides a dye image with superior color development and light fastness compared to those using comparative couplers.

Also, instead of the example yellow coupler 3 of sample 11, 1
The effect of the present invention was also observed when 1.17.19.26 was used.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising a yellow coupler having at least one cyclic amine moiety represented by the following general formula [I] as a partial structure. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_1 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an acyl group,
_1_3 and R_1_4 each represent a hydrogen atom or an alkyl group, and X represents a divalent linking group. ]