JPH0481843A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and rapid processability and to obtain the max. density by incorporating a high-chloride silver halide emulsion layer on a base and incorporating a specific yellow coupler into photograph constituting layers. CONSTITUTION:This photosensitive material contains the high-chloride silver halide emulsion layer on the base and contains the yellow coupler expressed by formula therein. In the formula, RA denotes an alkyl group, cycloalkyl group; RB denotes an alkyl group, cycloalkyl group, acyl group or aryl group; RC denotes a group which can be substd. with a benzene ring; RD denotes an alkyl group; J denotes -N(RE)CO- or -CON(RE)- (RE denotes a hydrogen atom, alkyl group, aryl group or heterocyclic group); X1 denotes a group which can be eliminated at the time of coupling; (n) denotes 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material which has excellent color reproducibility and rapid processability, and which can provide a sufficient maximum density.

[Background of the Invention] After exposing a silver cohalide photographic material to light, color development is performed, whereby an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye, resulting in color development. An image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

Yellow image forming couplers include penzoylacetanilide and pivaloylacetanilide compounds,
For example, US Pat. No. 2,875.057, US Pat. No. 3.265,
No. 506, No. 3,408,194, No. 3,551.1
No. 55, No. 3,582,322, No. 3,725.07
No. 2, No. 3,891,445, West German Patent No. 1,547,
No. 868, West German Application Publication No. 2,219゜917, No. 2,
No. 261,361, No. 2,414,006, British Patent No. 1,425.020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 4g-73147, No. 5
No. 1-102036, No. 5゜-13341, No. 50-
No. 123342, No. 50-130442, No. 51-2
No. 1827, No. 50-87650, No. 52-8242
No. 4, No. 52-115219, etc. are used.

On the other hand, shortening processing time has become an important issue in recent years. In other words, photographic elements are processed by running processing in automatic processing machines installed in each laboratory, or as part of improving services for users.
It is required that the product be processed and returned to the user on the same day that the product is received.In recent years, it has become necessary to return the product several hours or even tens of minutes after receiving the product. There is a strong demand for shorter delivery times.

However, the yellow couplers conventionally used are not suitable for rapid processing, and developability deteriorates especially when high chloride silver halide emulsions are used, making it impossible to obtain sufficient maximum density. It became clear that there was a serious problem.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent color reproducibility and rapid processability, and which can provide a sufficient maximum density.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a photographic constituent layer containing at least one high chloride silver halide emulsion layer on a support, in which the photographic constituent layer has the following general formula CY-■] This is achieved by a silver halide photographic material containing at least one yellow coupler shown in the following.

General formula CY-1 below] , RD represents an alkyl group, and J li -N CO
- or -CON-(RE +; i hydrogen RE
RE represents an atom, an alkyl group, an aryl group, or a heterocyclic group. )
, Xl represents a group that can be separated upon coupling with an oxidized form of a developing agent, and n represents 0 or 1. ] [Specific structure of the invention] The present invention will be described in detail below.

In the present invention, a high chloride silver halide emulsion is defined as a 90% silver halide emulsion.
It means silver chlorobromide, silver chloroiodobromide, silver chloroiodide, or silver chloride emulsion containing silver chloride in a mole % or more.

The content of silver iodide is preferably 1 mol % or less, and more preferably no silver iodide is contained. The content of silver bromide is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less.
-0.01 mol% is most preferred.

There are no particular restrictions on the distribution state of silver iodide and silver bromide in silver halide grains, and they may be localized at the center, surface, or in between, or may be distributed on the average. good.

Methods for preparing silver halide grains include acidic method, neutral method,
Any method such as the ammonia method is preferably used. Further, silver halide solvents other than the ammonia method may be used. The particles may be grown all at once, or may be grown after seed particles are created.

The method of creating and growing the seed particles may be the same or different.

Silver halide emulsions contain halide ions and silver ions,
They may be mixed at the same time, or one may be mixed in a liquid in which the other is present.

The silver halide emulsion according to the present invention may be a mixture of two or more separately formed silver halide emulsions.

The particle size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse, with monodisperse being preferred.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, please refer to Research Disc.
Disclosure (hereinafter abbreviated as RD) 176
It can be carried out based on the method described in No. 43, Item (■).

The average grain size of the silver halide grains of the present invention (grain size represents the diameter of a circle with an area equal to the projected area) is 5 μm
The thickness is preferably 1 μm or less, particularly preferably 1 μm or less.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods.

Also, for example, British Patent No. 618,061, British Patent No. 1,315,755, British Patent No. 1,396,696
Specification, Japanese Patent Publication No. 44-15748, U.S. Patent Box No. 1.574.944, U.S. Patent No. 1,623,499
No. 1,623.499 specification, No. 1,
No. 673.522, No. 2.278,947, No. 2.399,083, No. 2.41
Specification No. 0,689, Specification No. 2,419,974, Specification No. 2.448,060, Specification No. 2,487,
Specification No. 850, Specification No. 2,518,698, Specification No. 2,521.926, Specification No. 2,642,36
Specification No. 1, Specification No. 2,694.637, No. 2
, 728.668, 2.739.060, 2,983,610, 8.0
No. 21,215, No. 3,026,203, No. 3.297,4411i, No. 3,2
Specification No. 97,447, Specification No. 3,361,564, Specification No. 3,411,914, Specification No. 3,554
．． Specification No. 757, Specification No. 3,565.631,
Specification No. 3,565.633, No. 3.591,3
Specification No. 85, Specification No. 3,656,955, Specification No. 3.761.267, Specification No. 8,772,031
Specification of No. 3.11157.711, Specification of No. L191,446, No. 3,001,714
Specification No. 3,904,415, No. L9
Specification No. 30.867, Specification No. 3,984.249, Specification No. 4,054,457, Specification No. 4.067
．． Specification No. 740, RD No. 12008, RD No. 13452
No. 13564, by T. H. James "The
Theory orthePhotographic
process (4th Ed, Macmill
an.

It is preferable to carry out chemical sensitization as described in 1977), pages 67 to 76.

Next, the yellow coupler represented by the general formula CY-13 contained in the high chloride silver halide emulsion layer according to the present invention will be explained.

In the general formula [Y-I], examples of the alkyl group represented by RA include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an F-decyl group. This R.A.
The alkyl group represented by also includes those having a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, and a hydroxy group. etc.

Examples of the cycloalkyl group represented by RA include a cyclopropyl group, a cyclohexyl group, and an adamantyl group.

Particularly preferred as RA is a branched alkyl group.

In the general formula (Y-H, an alkyl group represented by RB,
Examples of the cycloalkyl group include the same groups as RA,
Examples of the aryl group include phenyl group.

The alkyl group, cycloalkyl group, and aryl group represented by RB include those having the same substituents as RA.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group, and a benzoyl group.

RB is preferably an alkyl group or an aryl group,
Particularly preferred is an alkyl group.

In the general formula [Y-1), the groups that can be substituted on the Hensen ring represented by Rc include halogen atoms (e.g. chlorine atom), alkyl groups, alkoxy groups (e.g. methoxy group)
, an aryloxy group, an acyloxy group, an acylamino group, a carbamoyl group, an alkylsulfonamide F group, an arylsulfonamide group, a sulfamoyl group, and an imide group.

n is 0 or 1.

In the general formula [Y-1], the alkyl group represented by RD includes linear and branched alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, t- Butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-
Decyl group, linear and branched dodecyl group, tridecyl group,
Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a tocosyl group, a tetradecyl group, and a hexanoyl group. Particularly preferred among these alkyl groups are those having 8 to 20 carbon atoms.

In the general formula [Y-1), J represents -NCO- or -CON-, and RE is RE
RE represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the alkyl group represented by R6 include methyl group, ethyl group, isopropyl group, t-butyl group, and dodecyl group.

Further, examples of the aryl group represented by RE include a phenyl group and a naphthyl group.

These alkyl groups or aryl groups represented by RE include those having substituents.

This substituent is not particularly limited, and typical examples include halogen atom, alkyl group, aryl group (e.g., phenyl group, p-methoxyphenyl group, naphthyl group, etc.), alkoxy group, and aryloxy group. , alkylthio group, arylthio group, alkylsulfonyl group,
Examples include arylsulfonyl group, acylamino group, etc.
Further examples include a carbamoyl group that may have a substituent, an acyl group, a sulfonamide group, a sulfamoyl group that may have a substituent, a hydroxy group, a nitrile group, and the like.

In the general formula CY-I), Xl represents a group that leaves during the coupling reaction with the oxidized form of the developing agent, and represents, for example, a group of the following general formula [Y-nE or [Y-m].

General formula [Y-nl RF In the formula, R4 represents an aryl group or a heterocyclic group including those having a substituent.

General Formula (ym) In the formula, Zl represents a group of nonmetallic atoms necessary to form a 5- to 6-membered ring in cooperation with the nitrogen atom.

Here, the atomic groups necessary to form the nonmetallic atomic group include, for example, methylene, methine, substituted methine, 〉C-0,
-NH--N--0-5S O2- and the like.

Among the groups represented by the general formula [Y-Ill or [Y-I[I], particularly preferred are the following general formulas (Y-rV) to [
Y-IX: A group represented by l.

General formula [Y-IV] In the formula, R1 is a carboxyl group, an ester group, an acyl group,
It represents an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl group, or the same substituent as the group represented by Rc above, and g represents an integer of 0 to 5.

When g is 2 or more, R may be the same or different.

General formula (y-v) General formula (Y-Vl: 1 represents an arylsulfinyl group, an alkylsulfonamide group, an arylsulfonamide group, a carbonic acid group, and these groups may be the same or different. Good too.

Furthermore, R3 and RK may form a ring.

General formula [Y-■] General formula [Y-■] General formula [Y-■] In [Y-■] and [Y-■], RJ and RK are hydrogen atom, halogen atom,
Alkyl group, alkoxy group, aryl group, heterocyclic group,
carboxylic acid ester group, amino group, acylamino group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, where z2 is a heteroatom (e.g. -N
H-O--S-, etc.), and RL has the same meaning as R1. RM is an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group,
Represents an arylsulfonyl group.

General formula [Y-IX: 1 /\, O C Zi In the formula, W is a hetero atom (e.g. -NH-N--0--5
-, etc.), sulfonyl, car group, and Z3 is -W-N-
Represents a group of nonmetallic atoms necessary to form a 5- to 6-membered ring in cooperation with Co-. RN s RO% RP is the R1
and represents a group similar to RK.

Further, RNXRo and RP may form a ring together with a part of Z3.

The yellow coupler of the present invention preferably has a ballast group. A ballast group is an organic group that provides diffusion resistance to the coupler, and includes an alkyl group with 6 or more carbon atoms,
Examples include an aryl group having 10 or more carbon atoms, and an aryl group substituted with a linear or branched alkyl group having 10 or more carbon atoms in total. All of these are
RB, Rc, Ro in the general formula [YI], or a group included in the above description as a partial structure thereof.

Among the general formulas [Y-IV:l to [Y-■], the most preferable one is represented by the general formula [Y-IXI].

The yellow coupler represented by the general formula (Y-1) according to the present invention can be synthesized by a conventionally known method.

Further, the yellow coupler represented by the general formula CY-I: ] according to the present invention can be used alone or in combination of two or more, or can be used in combination with another type of yellow coupler.

Further, the yellow coupler according to the present invention can be used in a range of usually about I x 10 -3 mol - about 1 mol, preferably l x 10 -2 mol - 8 x 10' mol per 1 mol of silver halide. .

Next, 2 represented by the general formula CY-I used in the present invention
Although typical examples of equivalent yellow couplers are shown, the present invention is not limited thereto.

Margins Below In order to incorporate the yellow coupler according to the present invention into the photographic light-sensitive material of the present invention, known techniques used for ordinary yellow couplers can be applied. It is preferable to dissolve the coupler in a high-boiling point solvent and, if necessary, in combination with a low-boiling point solvent, disperse the coupler in the form of fine particles, and add it to the silver halide emulsion according to the present invention. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

When the photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a cyan coupler are used in addition to the yellow coupler of the present invention. Magenta coupler There are no particular restrictions on the cyan coupler, and known ones can be used.

As the magenta coupler, for example, 5-pyrazolone couplers, pyralopenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be used.

Examples of cyan couplers include naphthol couplers.
Phenolic couplers and imidazole couplers can be used.

The silver halide photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

The silver halide photographic material of the present invention may contain various other photographic additives.

For example, antifoggants, development accelerators, development retarders, bleach accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, interfaces. Activators, plasticizers, wetting agents, etc. can be used. (RD
No. 17643 can be referred to. ) Furthermore, by coupling with a competing coupler and an oxidized form of a developing agent, a development accelerator,
Photographically useful fragments such as bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers Compounds that release can be used.

Examples of the support for the silver halide photographic material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, polyester film such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide film, polycarbonate film, and polystyrene. There are films, etc., and in the case of a transparent support, a reflective layer may be used together.

These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. It is also possible to use a simultaneous coating method of two or more layers as described in U.S. Pat. No. 2,781,791 and U.S. Pat. No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. It is preferable to do so.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids can be used as binders in these constituent layers, and gelatin is preferably used. In addition, the various photographic additives mentioned in the explanation of the emulsion layer can be contained in the layer.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion of the present invention, and any commonly known processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; Although the silver halide color photographic light-sensitive material of the present invention may be processed using any method including water washing and/or stabilization processing, the silver halide color photographic light-sensitive material of the present invention can be processed in the steps of color development, bleach-fixing, and water washing (or stabilization). Suitable for rapid processing.

〔Example〕

Although specific examples of the present invention are described above, the embodiments of the present invention are not limited to these.

Example 1 Silver halide color photographic light-sensitive material samples Magnet 1 to Magnet 15 were prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1...1.2g/rrr gelatin, 0.3
2g/rr? A blue-sensitive silver halide emulsion (silver chloride content is shown in Table 1) of 1.0 mmol/I dissolved in 0.50 g/rrr of dioctyl phthalate (in terms of silver, the same applies hereinafter) is shown in Table 1. Layer containing yellow coupler.

Layer 2...1.2g/rf gelatin, 10mg
/rrr irradiation dye (AI-1), 25m
An intermediate layer consisting of g/g (AI-2).

Layer 3 - 1.25 g/rd gelatin, 0.
A layer containing 22 g/rrr of green-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.62 g/rrf of magenta coupler (M-A) dissolved in 0.30 g/rrr of dioctyl phthalate.

Layer 4: Intermediate layer consisting of 1.2 g/rrr of gelatin.

Layer 5---1,40g/go gelatin, 0.2
A layer containing 0 g/rf of red-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.45 g/rf of cyan coupler (C-A) dissolved in 0.20 g/rrf of triro-octyl phosphate. .

Layer 6: Layer containing 0.5 g/d of gelatin.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-5-) riazine sodium was added in layers 2.4 and 6.
Each was added in an amount of 0.017g per 1g of gelatin.

Margin below (Y-A) (AI-2) (M-A) (C-A) I (AI-1) N! 035C82N)] OOH The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konica Corporation).
After wedge exposure using a 100% wafer, the highest density of the blue-sensitive emulsion layer (
Dmax) was measured.

The results are shown in Table-1.

Processing process> Temperature color development @ 34.7± Bleach-fixing 347± Stabilization 30~ Drying 60~ Degrees 0.3℃ 0.5℃ 34℃ 80℃ Time 30 seconds and 45 seconds 50 seconds 90 seconds 60 seconds Color developer> Pure water
800mj triethanolamine
8g N,N-diethylhydroxyamine
5g potassium chloride 2g
N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium sulfite
0.2g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total amount to 11, and adjust the pH to 10.2.

Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100mj ammonium sulfite (40% solution) 27.5ml Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid. , add water to make a total volume of 1 p.

Stabilizing liquid> 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g Add water to make 1g, and adjust pn to 7, 1g with sulfuric acid or potassium hydroxide. 0
Adjust to.

Next, the color reproducibility of the samples Nα1 to 1kL5 was evaluated by the following method.

First, color negative film (Konica Color GX-1,0
0: Konica Corporation) and camera (Konica FT-IMO)
TOR: manufactured by Konica Corporation) was used to photograph a color checker manufactured by Macbeth. Subsequently, a color negative development process (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was printed on a Konica color printer CL-P 2000.
(manufactured by Konica Corporation) for the above samples No. 1 to Nα.
15 with a size of 82m1 x 117mm,
A practical print was obtained by processing in the same manner as above (however, the color development time was 45 seconds). Printer conditions during printing were set for each sample so that gray on the color checker turned gray on the print.

The color reproducibility of the obtained practical prints was visually evaluated. The results are summarized in Table-1.

As is clear from Margin Table 1 below, Samples 1.3 and 5 using silver halide other than those of the present invention were inferior in development speed;
Even with 5 seconds of development, a sufficient maximum density cannot be obtained, and the color reproducibility is also unfavorable.

On the other hand, although improvement in color reproducibility and maximum density was observed in Sample No. 2 using the silver halide of the present invention and a yellow coupler other than the present invention, the color reproducibility of green and yellow was far from satisfactory, and The maximum density in 30 seconds development is also insufficient.

On the other hand, sample No. 4.6.7.8.9 using the silver halide of the present invention and the yellow coupler of the present invention, l
0111.12.13.14 and 15 both have very good color reproducibility, and it can be seen that a sufficiently high maximum density can be obtained even in a very short development time of 30 seconds.

[Effects of the Invention] According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material that is excellent in color reproducibility and rapid processability and provides a sufficient maximum density.

Table Em-1: Silver chlorobromide Em-2 containing 90 mol% of AgBr
: Silver chlorobromide Em-3:A containing 1 mol% of AgBrO
Silver chlorobromide Δ containing gBr 0.5 mol% Color reproducibility (hue, color ■ Insufficient O Color reproducibility (hue, color is good ◎ Color reproducibility (hue, color very good)

Claims (1)

[Scope of Claims] A photographic constituent layer comprising at least one high chloride silver halide emulsion layer is provided on a support, and a yellow coupler represented by the following general formula [Y-I] is contained in the photographic constituent layer. A silver halide photographic material containing at least one of the following. General formula [Y-I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a group that can be substituted on the benzene ring, R_D represents an alkyl group, J is ▲ formula,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_E represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. It represents a group that can be separated during ringing, and n represents 0 or 1. ]