JPH0444037A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material contg. a colorless one equiv. coupler which has high dyestuff forming efficiency by utilizing the group to be eliminated by reaction of a coupler and the oxidant of a developing agent by incorporating the specific coupler into this photosensitive material. CONSTITUTION:This photosensitive material contains the compd. expressed by formula I. In the formula I, Cp denotes a residual coupler group exclusive of the hydrogen atom at the active point; L denotes a combination group; n denotes 0 or 1 integer; X denotes an oxygen atom or sulfur atom; Y denotes a group contg. a phosphorus atom or silicon atom, has R3, R4 via the phosphorus atom or silicon atom and is bonded to a carbon atom. R1 to R4 denote a hydrogen atom or substituent. The silver halide photographic sensitive material contg. the colorless one equiv. coupler which has the high dyestuff forming efficiency by utilizing the group to be eliminated by reaction of the coupler and the oxidant of the developing agent is obtd. in this way.

Description

Detailed Description of the Invention U Industrial Field of Application The present invention has a group that is eliminated by reaction with an oxidized developing agent,
The eliminated group is β-oxyphosphonic acid ester or β-
The present invention relates to a silver halide photographic material containing a coupler that forms a dye via an oxyalkylsilane intermediate.

[Prior Art] Although the image quality of silver halide color photographic light-sensitive materials has improved significantly in recent years, the sharpness is still not satisfactory. Thinner films are being considered as one means of improving sharpness. In particular, in the case of a silver halide emulsion layer that is closer to the support, the light scattering bus from the surface of the light-sensitive material becomes longer, so it is known that thinning the film by reducing the amount of binder is an effective means of improving sharpness. . As means for achieving a thin film, techniques such as polymer couplers described in Japanese Patent Application No. 59-28745 and highly color-forming low molecular weight couplers described in Japanese Patent Application No. 59-195234 are used to reduce the amount of oil or gelatin. Techniques are known to reduce the amount.

[Problems to be Solved by the Invention] However, none of them were satisfactory in terms of color development, desilvering properties during processing, etc. Also, patent application No. 62-200349,
No. 62-204257 and Japanese Patent Application No. 1-134454 disclose that by blocking the auxochrome of the dye, the maximum absorption wavelength is temporarily shifted to the shorter wavelength side, and the reaction with the oxidized product of the developing agent is caused by the use of ordinary azomethine. Monoequivalent couplers have been described that release one molecule of dye in addition to the dye. Although these couplers have significantly improved coloring properties compared to conventional couplers, the hue of the dye bound to the coupler has not yet shifted sufficiently, so the coupler itself absorbs visible light, resulting in undesirable effects such as desensitization. No development is occurring. Also, poor storage stability is a major problem. Therefore, even when such conventional couplers are used in color negative films, the couplers themselves are colored, so that the manner in which they can be used is extremely limited. Furthermore, it could not be used for photosensitive materials for direct observation, such as reversal and color papers.

The coupler of the present invention generates another molecule of dye in addition to the normally produced azomethine dye upon reaction with an oxidized developing agent, and the mechanism for producing the second molecule of dye is thought to be as follows.

Due to the reaction between the coupler and the oxidized developing agent, Cp-L, L
-X bonds are sequentially cleaved to release ■.

The released ■ undergoes an intramolecular concerted elimination reaction of X and Y to produce the dye ■.

An object of the present invention is to provide a silver halide photographic photosensitive material containing a new colorless monoequivalent coupler with high dye-forming efficiency by utilizing a group that is eliminated by the reaction between the coupler and an oxidized developing agent. It is in.

[Means for Solving the Problems] The objects of the present invention have been achieved by a silver halide photographic feed characterized by containing a compound represented by the following general formula (1).

General formula (1) [In the formula, Cp represents a coupler residue excluding the hydrogen atom at the active site, and L represents a linking group. n represents an integer of O or 1. X represents an oxygen atom or a sulfur atom. Y represents a group containing a phosphorus atom or a silicon atom, and Rs via the phosphorus atom or silicon atom.

It is bonded to the carbon atom containing R4. R1-R4
represents a hydrogen atom or a substituent. ] Above - general formula I)
will be explained in more detail.

The coupler residue Cp can be any group that reacts with oxidized developing agent to release a linking group. It contains coupler residues used in conventional color-forming couplers that produce colored products on reaction with oxidized developing agent and coupler groups that produce colorless products on reaction with oxidized color-forming developing agent. Both types of couplers are known to those skilled in the art. The coupler residues may be stabilized with oil-soluble groups or fatty end groups, or may be unstabilized. It may be monomeric or it may be a dimeric, oligomeric or polymeric coupler residue.

The group below -L- is attached to the coupler residue at any position where a group released from the coupler by reaction with oxidized developing agent can be attached. L may be such that it releases said group by an intramolecular nucleophilic reaction of the type described in U.S. Pat. No. 4,248,962;
It may also be of any type that involves electron transfer along a conjugated chain as described in US Pat. No. 4,409,323. Regarding the coupler residue represented by Cp, typical yellow coupler residues are disclosed in U.S. Patent No. 2,29
8.443, 2,407,210, 2.87
No. 5057, No. 3,048,194, No. 3,26
No. 5,506, No. 3,447,928, and Farbk
upplereine literalurvers
jecht Agfa Mitteilung (Ba
ndII) ) 1 Engineering, pp. 2-126 (1961). Among these, acylacetanilides, such as benzoylacetanilide and pivaloylacetanilide, are preferred.

Representative magenta coupler residues include U.S. Patent Nos. 2,369,489 and 2,343,703;
2.311,182, 2.600, 78
No. 8, No. 2,908,573, No. 3,062,6
No. 53, No. 3,152.896, No. 3519.4
No. 29, No. 3,725,067, No. 4,540,
No. 654, JP-A-59-162548 and the above Fa
rbkupplereineLiteraturuve
rsiecht Agfa Mittejlung (
BandlI) pages 126-156 (1961). Among these, pyrazolones or pyrazoloazoles (eg, pyrazolotriazole, pyrazoloimidazole, etc.) are preferred.

Representative cyan coupler residues include U.S. Pat. No. 2.367.531, U.S. Pat. No. 2,423,730,
Same No. 2.474,293, No. 2,772,162, No. 2,395826, No. 3,002,836, No. 3.034,892, No. 3041.236, No. 4,666.999 and the aforementioned Farbkup
pIereine Literatuversie
cht Agfa Mitteilung (Band I
I) pages 156-175 (1961). Among these, phenols and naphthols are preferred.

Representative coupler residues that form substantially colorless products include British Patent Section 861,138, U.S. Pat. No. 3,632,345, and U.S. Pat.
No. 1, No. 3,958,993, and No. 3,691
, No. 959, etc. Among these, cyclic carbonyl compounds are preferred.

The linking group represented by
It may contain a group capable of controlling the reaction rate between the oxidized product of the developing agent and the oxidized form of the developing agent, the diffusion rate of the groups below X released from Cp, and the release rate of the groups below X. Typical linking groups include those that release a group of Examples include those which release groups of X or less by an electron transfer reaction along a conjugated chain, as disclosed in JP-A-56-114946 and JP-A-57-154234. Others: JP-A-57-188035, JP-A No. 5B-98
No. 728, No. 59-206834, No. 60-7112
No. 9, No. 60-214358, No. 50-225844
No. 60-233649 (No. 130, No. 60-233649)
Also included are the linking groups disclosed in No. 60-237446 and No. 60-237447.

As the yellow coupler residue represented by Cp in general formula (I), those represented by the following general formulas (H) and (N) are preferred. [In the formula, * indicates an active point. ] General formula (n) General formula (II+) In the two general formulas (II) and (m), R5R6 each represents an alkyl group, a cycloalkyl group, a heterocyclic group, or a halogen atom; The heterocyclic group may be bonded via an oxygen atom, nitrogen atom or sulfur atom. Furthermore, the alkyl group, cycloalkyl group, and heterocyclic group may be bonded via the bonding groups listed below. That is, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfamoylcarbonyl group, carbonyloxy group, oxycarbonyl group, ureido group, thioureido group, thioamide group,
Sulfone group, sulfonyloxy group, etc. Further, the alkyl group, cycloalkyl group, aryl group, and heterocyclic group may further have a substituent described below. That is, halogen atoms, nitro groups, cyano groups, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups,
Aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carboxyl group, sulfone group, sulfamoyl group, carbamoyl group, acylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, Arylthio group, alkylthio group, alkylamino group, anilino group, hydroxy group, imide group, acyl group, etc.

When there are two or more R6 and R6, they may be the same or different.

The magenta coupler residue represented by Cp in the general formula (T) is represented by the following general formulas (IV), (V), (
VT) or (■) is preferred. [In the formula, * indicates an active point. ]General formula rV) General formula (vr) -N-N In the above general formulas (TV) to (■), R7, R, has the same meaning as R,,R, in general formula (II), (■[) be.

Cyan coupler residues represented by Cp in general formula (I) include the following general formulas (Vlll), (IX), (
Those represented by X) are preferred. [In the formula, * indicates an active point. ] General formula (■) General formula (V) General formula (IX) General formula (X) In the above (■■) to (X), R11 and Rlo are general formula (TI), R of (1■), It is synonymous with R.

The linking group represented by -L- in general formula (T) is preferably one represented by the following general formulas (XI) to (XIV). [In the formula, * indicates an active point. ] General formula (XI) In the formula, R11 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group, and A1 represents an oxygen atom or -NR'.

R' represents an alkyl group, a hydroxy group, an alkoxy group, or a sulfonyl group. Z is a 5- to 7-membered carbocyclic ring (e.g. indanone, cyclopentanone, cyclohexanone, etc.) or a heterocyclic ring (e.g. piperidone, pyrrolidone,
Represents a group of nonmetallic atoms necessary to form hydrocarbostyryl, etc.). [In the formula, * indicates an active point. 1 General formula (XI) 2 Rx2 Rls CCH In the formula, R12 and A2 are respectively synonymous with R and A□ in general formula (XI), and RL8 is an alkyl group, an aryl group, a heterocyclic group, a cyano group, Represents a hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylamino group, dialkylamino group, or anilino group.

[In the formula, * indicates an active point. ] General formula (x nr) R,4-CH-R1s In the formula, R14 and Rlr may be the same group or different groups, such as an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group , represents a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammonium mil group or -NAa.

A8 represents 11 nonmetallic atoms necessary to form a 5- to 7-membered heterocycle (eg, phthalimide, triazole, tetrazole, etc.) together with the nitrogen atom.

[In the formula, * indicates an active point. ] General formula (XTV) In the formula, R16 is an alkyl group, an aryl group, an anilino group,
B represents an alkylamino group or an alkoxy group, and B represents an oxygen atom, a sulfur atom or a nitrogen atom.

Linking groups useful in the present invention include the following general formula: Including, but not limited to.

General Formula (XV) In the formula, W represents an atomic group necessary to complete a benzene ring or naphthalene ring which may have a substituent. L+ represents 10, S, or NRIG-, and is bonded to the coupling position of the coupler residue represented by Cp in the general formula (1), and is R engineering.

RIB, R, is a hydrogen atom, an alkyl group, or an aryR
Represents the Efur group. Moreover, the -C- group is substituted at the ortho position or para position with respect to Ll, and is bonded to X.

General formula (XVI) -G In the formula, R21R2o and R2+ have the same meanings as L+, R+□, and RIll in general formula (XV), respectively. R22 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a heterocyclic residue;
3 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue,
Indicates an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group. In addition, this linking group connects the C-
Bonds to X via a group.

Next, an example of a linking group that releases a group of X or less by an intramolecular nucleophilic substitution reaction is shown by the general formula (X■).

General formula (X■) Nu -E In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur, or nitrogen atom, and in the general formula (I), Cp
It is bonded to the coupling position of the coupler residue represented by . E is an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group, and is bonded to X. Z has a steric relationship between the nucleophilic group Nu and the electrophilic group E, and after the nucleophilic group Nu is released from the coupler residue represented by Cp in the general formula (I), a three-membered ring or It is a linking group that can undergo an intramolecular nucleophilic reaction with the formation of a 7-membered ring and thereby release a group below X.

R to R4 in the general formula (1) will be explained in detail. R□ to R4 represent a hydrogen atom or a substituent.

R1-R4 may represent the same group or different groups. Examples of substituents include alkyl groups such as methyl group and ethyl group, aryl groups such as phenyl group, p-anisyl group, and naphthyl group, heteroaryl groups such as pyridyl group and thiazolyl group, alkoxyl groups such as methoxyl group and ethoxyl group, Amino group, 1'i dimethylamino group, di(hydroxyethyl)amino group,
Alkylamino groups such as acetoxyethylamino group and cyanoethylamino group, alkylcarbamoyl group, arylcarbamoyl group, acylamino group, aroylamino group,
Sulfonylamino groups such as ureido groups, methylsulfonylamino groups and phenylsulfonylamino groups; alkylsulfonyl groups such as nitro groups, cyano groups and methylsulfonyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and etquincarbonyl groups; and phenoxycarbonyl groups. group, p-
It represents an aryloxycarbonyl group such as a chlorophenoxycarbonyl group, an alkoxysulfonyl group such as a butoxysulfonyl group, an aryloxysulfonyl group such as a phenoxysulfonyl group, but is not limited to these. A preferable combination of R-R4 preferably has at least one aryl group or heteroaryl group and one or more electron-withdrawing substituents such as a cyano group and an ethoxycarbonyl group. Moreover, it is preferable that at least one of R-R4 contains a group having a total of 1 to 30 carbon atoms.

Y is (R240) 2P-, [(R24N) 2] 2
It represents substituents such as P(R2,)3P+-, (R2i)-8i-, but is not limited thereto. R24 represents an alkyl group such as a methyl group, an ethyl group, or an isopropyl group, or an aryl group such as a phenyl group or a tolyl group, but is not limited thereto.

Specific examples of the coupler of the present invention are shown below, but the coupler is not limited thereto.

Compound Example NHCOCI2H25 2;3 OC,, H25 OCI2I (25 NH3○2C□H3°) The coupler of the present invention can be prepared by methods known in the organic synthesis industry. Specific synthesis examples are shown below.

(Synthesis example) Synthesis of exemplified compound (10) 2-chloro-5-dodecyloxycarbonyl α-(4-
Hydroxymethyl-2-nitrophenoxy)-α-(4
-MeI-xybenzoyl)acetanilide (a) (
3.24 g, 5 mmol) and N,N-dimethylaminopyridine were dissolved in toluene, and phosgene gas was blown into the solution while stirring under water cooling. After about 5 minutes, the phosgene gas was stopped, the temperature was returned to room temperature, and the mixture was stirred for 3 hours. Toluene was distilled off under reduced pressure to obtain a colorless oily substance (b).

Trimethylsilylmalononitrile (0.69g.

5 mmol) in tetrahydrofuran (TI-IF
) Dissolve in 30 cc, cool to 70°C, and add n-butyllithium (5 mmol) dropwise. p-Dodecyloxybenzaldehyde (0.68g, 5 mmol)
was dissolved in 5 cc of THF and added dropwise. Keep at -50°C and stir for 1 hour. (b) was dissolved in 5 cc of THF and added dropwise. Stir at the same temperature for 3 hours. The temperature is returned to room temperature, and THF is distilled off under reduced pressure. The mixture was subjected to silica gel chromatography and eluted with ethyl acetate/hexane to give 1.52 g of Exemplified Compound (10) as colorless crystals. The structure of the obtained Compound 1 (10) was confirmed by nuclear magnetic resonance spectrum (NMR) and mass spectrum (MASS spectrum).

Synthesis Scheme C1θ (c) (d) C1σ The coupler of the present invention may be contained in a photographic light-sensitive material and/or a photographic processing solution such as a developer, but is preferably contained in a photographic light-sensitive material.

Photographic materials containing couplers of the invention may be single elements containing one silver halide emulsion layer on a support, or they may be multilayer, multicolor elements.

Here, the coupler of the present invention reacts with the oxidized color developing agent produced by developing silver halide in the silver halide emulsion layer to produce two dye molecules, or these silver halide emulsion layers In addition to the couplers of the present invention, other photographic couplers such as conventional dye-forming couplers, inhibitor-releasing couplers, and masking couplers that form like-colored dyes may also be included. Typical are red-sensitive silver halide emulsion layer units containing one or more cyan dye-forming couplers, green-sensitive silver halide emulsion layer units containing one or more magenta dye-forming couplers, and one or more yellow emulsion layer units. This is a photographic light-sensitive material containing a blue-sensitive silver halide emulsion unit containing a dye-forming coupler on a support.

Each of these silver halide emulsion layer units may also consist of two or more layers, and these layers may contain other photographic couplers used in the art, such as those described above.

The couplers used in the present invention and various other couplers can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in different combinations. It can also be introduced into two or more layers.

The amount of the coupler added according to the present invention is 2 per added layer.
X 10-' to lX10-'' moles are preferred.

In addition, when using couplers that form pigments of similar colors,
The addition of the coupler is preferably from 0,001 to 20 moles per mole of the coupler of the present invention.

The couplers used in the present invention can be introduced into photosensitive feeds by various known dispersion methods. For example, typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method.

In the oil-in-water dispersion method, after dissolving in either a high-boiling organic solvent or a low-boiling organic solvent with a boiling point of 175°C or higher, either alone or in a mixture of both, water or an aqueous gelatin solution is added in the presence of a surfactant. etc. Finely disperse the coupler in an aqueous medium. Examples of high boiling point organic solvents are U.S. Pat.
It is described in No. 027, etc. Dispersion may be accompanied by layer inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Photographic exposure of the present invention 4;! As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the material, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

The photographic emulsion layer of the photographic light-sensitive material of the present invention may contain any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver halides for color photography feeds are silver iodobromide or silver iodochlorobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 12 mole percent silver iodide. For photographic materials for printing, silver bromide, silver chlorobromide and silver iodochlorobromide are preferred.

Silver halide grains in photographic emulsions may be so-called regular grains with regular crystal structures such as cubic, octahedral, or tetradecahedral, or may have irregular crystal systems such as spherical. It may be a crystal, a crystal with crystal defects such as twin planes, or a composite form thereof. The grain size of the silver halide is typically such that emulsions have silver halide grains larger than about 0.1 micron, at least about 95% by weight of which are within ±40% of the average grain diameter. Average particle diameter is approximately 0.2
Emulsions that are 5 to 2 microns in size and have at least about 95% by weight or at least about 95% by number of silver halide grains within the average grain diameter ±20% can be used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), 1st
4, pp. 24B-257 (1970): U.S. Patent No. 4
, 434,226, 4,414.310, 4,433,048, 4,439,520, and British Patent No. 2,112,157. It can be prepared. The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in this process is Research Disclosure N.

No. 17643 and No. 18716. Known photographic additives that can be used in the present invention are also described in the two Research Disclosures mentioned above.

Further, the support used in the present invention may be any support used in photographic materials, but typically cellulose acetate film, polyvinyl acetate film, polyethylene terephthalate film,
Flexible supports such as polymeric films or paper supports may also be used.

The color developing solution used in the photographic light-sensitive material of the present invention has the composition of a general color developing solution containing an aromatic primary amine developing agent.

The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash, soda carbonate, potassium carbonate,
Tertiary sodium phosphate, potash, potassium metaborate, borax, etc. are used alone or in combination.

Color developing solutions usually contain sulfites, which are used as preservatives.
For example, sodium sulfite, sodium bisulfite) or hydroxylamine can be added.

If necessary, any development accelerator can be added to the color developing solution.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Potassium ferricyanide, iron (Ilf) lithium ethylenediaminetetraacetate, and ammonium iron (TII) ethylenediaminetetraacetate are particularly useful as bleaching agents. Aminopolycarboxylic acid iron (Tff) complexes are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent No. 3.04252
Various additives can be added, including the bleaching accelerators described in Specification No. 0, Specification No. 3,241,966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 8836-1983, etc. .

The fixing bath contains 30 g/r to 200 g/r of ammonium salt, sodium salt, and potassium salt of thiosulfate as a fixing agent.
g/, Q, and may also contain pTrH agents such as sulfites, acetates, borates, phosphates, and carbonates. The pH of the fixer is 3-10, more preferably 5-9.

[Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per m' unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

Example 1 Multilayer color photographic element sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetylcellulose film support from the support side.

Sample-1 (comparison) 1st layer; antihalation layer (HC) Black colloidal silver 0.15 UV absorber (
UV-1) 0.20 colored coupler (CC
-1) 0.02 high boiling point solvent (Oil -1)
0.20 High starvation point solvent (Oil-2) 0.
203! -J Ceratin 1.6 2nd layer; Intermediate layer (T L -1) Gelatin 1.3 3rd layer; Low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (Em-1)
0.4 Silver iodobromide emulsion (Em-2) 0.
3 Sensitizing dye (S-1) 3.2x 10-' (mol/silver 1 mol) Sensitizing dye (S-1)
-2) 3.2X10-' (mol/silver 1 mol) sensitizing dye (S-
3) 0.2X]O-' (mol/mol of silver) cyan coupler (C-1) 0.50 cyan coupler (C-2
) 0.13 colored cyan coupler (C(,
-1) 0.07 DIR compound (D-1) 0.006 DIR compound CD-2) 0.01 High i'lli point solvent (Oil -1) 0.55 Additive (SC-1
) 0.003 gelatin
1° 4th layer; High sensitivity red-sensitive emulsion layer (R-I-T) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (1-1) 1.7XlO-' (mol/silver 1 mole) sensitizing dye (S-
2) 1.6X10-' (mol/silver 1 mol) sensitizing dye (S-
3) 0, lX10-' (mol/silver 1 mol) Cyan coupler (C-2) 0.23 Colored cyan coupler (C(,1) 0.03 DIR compound (D-2) 0.02 High boiling point solvent ( Oil -1) 0.25 Additive (S(, -
1) 0.003 gelatin
1゜5th layer; Intermediate layer (II, -2) Gelatin o8 8th: Low-sensitivity green-sensitive emulsion layer ((, -L) Silver iodobromide emulsion (Em-1) 0.64↓ 7th layer io Silver bromide emulsion (Em-2) 0.2 sensitizing dye (
S-4,) 6.7xlO-' (mol/silver 1 mol) Sensitizing dye (S-
5) 0.8X10-' (mol/silver 1 mol) magenta coupler (M-1) 0.17 magenta coupler (M-2
) 0.43 Colored Magenta Coupler (CM-
1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.70 Additive (SC-1)
0.003 Seratin
10 High sensitivity green-sensitive emulsion layer (G-H) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (
S-6) 1, lX10-' (mol/silver 1 mol) sensitizing dye (S-
7) 2.0XlO-' (mol/silver 1 mol) sensitizing dye (S-
8) 0.3X10-' (mol/mol of silver) Magenta coupler (M-1) 0.03 Magenta coupler (M-2
) 0.13 Colored Magenta Coupler (CM-1
)0.04 DIR compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Additive (SC-
1) 0.003 gelatin
1.0 8th layer; yellow filter layer (yc)
Yellow colloidal silver 01 Additive (T(S -1) 0.07 Additive (H8-2) 0.07 Additive (S(, -
2) 0.12 high boiling point solvent (Oil-2)
0.15 gelatin 1
0 9th layer; low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em -1) 0.25 Silver iodobromide emulsion (Em
-2) 0.25 sensitizing dye (S-9) ・111 10th layer 11th layer 5.8X10-' (mol/silver 1 mol) Yellow coupler (I-1) O,'ll'ZDIR compound (D
-1) 0.003DIR compound (D -2)
0.006 high boiling point solvent (Oil-2)
0.18 Additive (SC-1) 0.0
04 gelatin 13 ・High sensitivity blue-sensitive emulsion layer (B-I() Silver iodobromide emulsion (Em-4) 0.5 sensitizing dye (
S-10) 3.0X 10-4 (mol/silver 1 mol) sensitizing dye (S-
11) 1.2X10-' (mol/silver 1 mol) yellow coupler (Y-1) 0.28 high boiling point solvent (Oil-2)
0.05 additive (SC-1)
0.002 Gelatin 1.0 1st
-Protective layer (p Ro-1) Silver iodobromide emulsion (Em-5) 0.3 ultraviolet absorber (UV-1) O,Q7 ultraviolet absorber (UV-
2) 0.1 additive (MS-1)
0.2 Additive (H3-2) 0.1 High boiling point solvent (Oil-1,) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin
08 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent 0.13 (average particle size 2
μm) Polymethyl methacrylate-1-002 (average particle size 3 μm) Slip agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (SU-
2) 0.02 gelatin
0.5 In addition to the above composition, each layer also contains a coating aid SU.
4. Dispersion aid 5U-3, hardener H-1, H-2, stabilizer 5T-1, preservative DI-1, antifoggant AF-1, A
F-2, dyes Al-1 and Al-2 were added as appropriate.

Also, It is.

It is.

m-1 m-2 m-2E: m-4 The emulsions used in the second test were as follows: Monodisperse emulsions with internal height deformation Average Agl content: 7055 μm Average △gI content: 2 0.36 μm Average Δgl content 8 0.84 μm Average Agl content 8 1.02 μm 5 mol% 5 mol% 0 mol% 5 mol% Octahedron Octahedron Octahedron Octahedron C=1 0M-1 4J D-2 UV-2 ■S 5'0゜S (Jl ■1-2 [(CH2=CHS O2CH2), CCH25O,C
H, CH3I, N CH, CH25O, KU-3 (Alkanol Na○, 5-CH-COOCH2 (CF, CF2), H
CH2C00CH2(CF2CF2)-H0ij! -3 I-1 I-2 I-4 INaO= SC-COOC-Hl 7CH,
-COOC, H.

5T-1 Mixture AX-1 MW: 30,000 F-1 F-2 In addition, yellow coupler Y-1 in the 9th and 10th layers of sample 1 was replaced with equimolar amount of Kabra shown in Table 1. Samples 2 to 6 were prepared in the same manner as Sample 1 except for the following.

Samples 1 to 6 were each subjected to wedge exposure and then subjected to the following development treatment.

Processing process (38°C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the treatment solution was as follows.

[Color developer 4-amino-3methyl-N-ethyl-N (β-hydroxyethyl) aniline sulfate 475g5! J Anhydrous sulfite 425g Hydroxylamine 1/2 sulfate 20g Anhydrous potassium carbonate 375g Sodium bromide
1.3g nitrilotriic acid tristrium salt (regia salt) 2.5g potassium hydroxide 1.0g Add water to make one volume, and adjust to pH 10.0 using potassium hydroxide.

[Bleach solution] Ethyleneaminetetraacetic acid & 3(nr) ammonium salt
100g Ethylenediaminetetraacetic acid ammonium salt 00g 150.0g 10.0m Ammonium bromide glacial acetic acid water was added to the mixture overnight, and the pH was adjusted to 6.0.

[Fixer] Ammonium thiosulfate (50% aqueous solution) 162m12
Add 12.4 g of anhydrous sodium sulfite water, leave overnight, and adjust the pH to 6.5 using acetic acid.

[Stabilizing liquid coformalin (37% aqueous solution) 15 m Cuconidax (manufactured by Konica Corporation) 7.5 m, add 9 water to make one volume.

The sensitivity (Sl) and maximum density (D max) of the thus obtained yellow dye image were evaluated. Sensitivity S1 is expressed as a relative value when the sensitivity of Sample 1 is set to 100.

In addition, the blue densities of samples 1 to 6, which were not subjected to any development processing but were subjected to only bleaching, fixing, and subsequent processing, are shown at the same time. This is expressed as DoB. The results are also shown in Table 1.

6↓ Table 1 As shown in Table 1, the coupler of the present invention has higher sensitivity and color development than Y-1. Also ¥-2. It has higher sensitivity than Y-3, and because the coupler itself is not colored, coloring in the blue region as in the comparative couplers Y-2 and Y-3 is not observed.

The structure of the comparative coupler used in the Examples is shown below.

[Effects of the Invention] According to the present invention, a silver halogen photographic photosensitive material containing a new colorless single-function coupler having high dye-forming efficiency by utilizing a group that is eliminated by the reaction between the coupler and an oxidized developing agent. material can be provided.

G,′]

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing a coupler represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, C_p represents a coupler residue excluding the hydrogen atom at the active site, and L represents a linking group. n represents an integer of 0 or 1. X represents an oxygen atom or a sulfur atom. Y represents a group containing a phosphorus atom or a silicon atom, and is bonded to the carbon atom containing R_3 and R_4 via the phosphorus atom or silicon atom. R_1 to R_4 represent a hydrogen atom or a substituent. ]