JPS61233742A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material using a phenolic compd. capable of forming a cyan dye good in spectral absorption characteristics by incorporating a specified cyan coupler. CONSTITUTION:The silver halide photographic sensitive material contains a cyan coupler represented by formula [I] in which X is H, halogen, or acylamino; Y is alkyl or a group represented by formula [II]; Z is a non metallic atomic group necessary to form a 5- or 6-membered ring together with 2 carbon of the phenol ring and 0; R1 is alkyl, cycloalkyl, aryl, or a heterocyclic group; and -W- is -CO-, -SO2-, -COCOO-, or -CONH-. The formed dye is extremely fast against heat, light, or humidity, and extremely good in color developing performance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material, and in detail,
This invention relates to a silver halide photographic material containing a novel active site substitution type cyan coupler that has excellent color development, no color staining, excellent light resistance, and excellent fastness against heat and moisture. .

(Background of the Invention) Generally, in a silver halide color photographic light-sensitive material, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and an oxidized product of the color developing agent is generated at this time. A dye image can be obtained by coupling the dye with a coupler that forms yellow, magenta, and cyan dyes.

Cyan couplers that are widely used to form the cyan dyes are phenolic and naphthol based compounds. In particular, what is desired to be improved in the phenolic compound used for the final image is that the cyan dye formed first has good spectral absorption characteristics, that is, the green region of the absorption spectrum (particularly at 500nm).
■The absorption of light (~550nl) is small and the maximum absorption wavelength is long wavelength (640nm~660rv>), and the cyan dye formed second has sufficient fastness against light, heat, and moisture. and, under these storage conditions, there is little contamination in the uncolored areas. Thirdly, the coloring property is good, that is, it has sufficient coloring sensitivity and coloring density.

Therefore, many proposals have been made to improve these points. In particular, 2,5-diacylaminophenol compounds are attracting attention as having excellent properties regarding the second point, sufficient fastness against heat and moisture. For example, U.S. Patent No. 2,772
, 162, 2,895.826, etc. 2,5-diacyl having a fluorine-substituted aliphatic carboxylic acid amide group at the 2-position of the phenol and an acylamino group at the 5-position, etc. It is an aminophenol compound. These specific compounds, known as 2,5-diacylaminophenol compounds, do produce cyan dyes with excellent heat resistance and excellent spectral absorption properties, but the color forming properties of the couplers themselves and the coloring properties of the dyes are poor. It has a serious drawback of extremely poor light resistance.

Therefore, in order to improve these drawbacks, a 112-equivalent coupler was proposed in which a fluorine atom was introduced at the 4-position of the phenol ring that undergoes the coupling reaction with the oxidized product of the color developing agent. , 758,308. Although these couplers exhibit excellent color development, they have the undesirable property of causing yellow staining when exposed to light.

In addition, 2,5-diacylaminophenol compounds having a pentafluorobenzamide group at the 2-position of the phenol ring are disclosed in U.S. Pat. Nos. 3,758,308 and 3,88.
0,661, and on the other hand, 2,5-diacylaminophenol compounds having an 0-sulfonamidobenzamide group at the 2-position of phenols are described in JP-A-56-80045. has been done. Although these 2,5-diacylaminophenol compounds are satisfactory in terms of spectral absorption characteristics, they are not necessarily sufficient in terms of dye fastness.

In addition, 2 with a sulfonamide group at the 5-position of the phenol ring
, 5-diacylaminophenol compounds have been developed, such as those disclosed in JP-A-53-109630 and JP-A-55-1.
No. 63537, No. 5B-22235, No. 56-993
No. 41, No. 56-116030, No. 56-55945
No. 56-80054. Further, a 2,5-diacylaminophenol compound having a benzamide group substituted with at least one fluorine atom at the 2-position of the phenol ring is disclosed in JP-A-56-161.
It is described in Publication No. 542. However, although the dyes produced from these compounds have excellent fastness to heat and moisture, they have insufficient fastness to light.

In each case, the above-mentioned 2,5-diacylaminophenol compounds are 2-acylamino-4,6-dichloro-5-methylphenol compounds (US Pat. No. 2,801), which have been in practical use for many years. , No. 171)
The dye is much less fast to light than the cyan coupler.

Also, 2.5- described in JP-A-59-139352
Although diacylaminophenol cyan couplers have improved light fastness, they are still not satisfactory.

On the other hand, the cyan coupler based on 2-7 cylamino-4,6-dichloro-5-methylphenol (the coupler described in U.S. Pat. No. 2,801,171) is more robust against heat and humidity than the diacylaminophenol-based cyan coupler. is much lower.

Furthermore, the 2-7 cylamino-4,6-dichloro-5-ethylphenol-based (coupler described in Japanese Patent Publication No. 11572/1972) cyan coupler has further improved fastness to light, heat, and humidity. However, from a researcher's perspective, it is still not sufficient.

Furthermore, 6-azilamino-twohydroxy-benzodioxin cyan coupler (British Patent No. 2.109.3)
The coupler described in No. 138) has a problem with the second point of fastness to heat and moisture.

(Object of the Invention) A first object of the present invention is to provide a silver halide photographic material using a phenolic compound capable of forming a cyan dye having good spectral absorption characteristics.

The second object is to provide a silver halide photographic material in which the obtained dye image has sufficient fastness against light, heat, and humidity.

The third object is to provide a silver halide photographic material having high sensitivity and color density.

(Structure of the Invention) The above object of the present invention is achieved by a silver halide photographic material containing a cyan coupler represented by the following general formula [I].

General formula [1] In the formula, X represents a hydrogen atom, a halogen atom or an acylamino group, Y represents an alkyl group or a group represented by the following general formula [II], and 2 represents a phenol core of the general formula [I] represents a group of nonmetallic atoms that can form a 5- to 6-membered ring together with two carbon atoms and an oxygen atom.

General formula [I[] -NH-W-R.

In the formula, R4 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and -W- is -CO-1-8
Represents O2-1-cocoo- or -CONH-.

(Specific Structure of the Invention) In the general formula [I], X represents a hydrogen atom, a halogen atom, or an acylamino group, and examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the acylamino group include an acetamido group and a propanamide group. X
Among the hydrogen atom, halogen atom, and acylamino group represented by, halogen atom is preferred, and chlorine atom is particularly preferred.

In the general formula [I], Y represents an alkyl group or a group represented by the general formula [n], preferably a group represented by the general formula [II].

In the general formula [II], R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group,
-W- represents -CO-1-502-1-Cocoo-* or -CONI-1-, but -W-tL/r bar co-1-CONH- is preferred *L, <, and is-C
O- is particularly preferred.

The alkyl group represented by R5 has 1 to 30 carbon atoms.
straight-chain or branched alkyl groups, such as methyl, ethyl, isopropyl, t-butyl, octyl,
Examples include dodecyl group, eicosyl group, and triacontyl group. This alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryloxy group, an alkylsulfonyl group, and an acylamim L alkoxy j1 hydroxyl group. As an example, γ-(2,4
Examples include -di-t-amylphenoxypropyl group, β-(dodecylsulfonyl)ethyl group, phenoxymethyl group, and methoxyethyl group.

The cycloalkyl group represented by R1 can be a cyclohexyl group or the like.

A specific example of the aryl group represented by R1 is a phenyl group. This phenyl group can have a substituent, and examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, an amide group, etc. Examples of the phenyl group having such a substituent include p -methoxyphenyl group, dodecyloxyphenyl group, p-(
Examples include γ-(2,4-di-t-amylphenoxy)butyrylamino)phenyl group, 0-chlorophenyl group, p-tolyl group, mesityl (trimethylphenyl) group, and the like.

Specific examples of the heterocyclic group represented by R1 include a furyl group, a pyranyl group, a chenyl group, a pyridyl group, and a 2-day-pyrrolyl group.

Among the alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R1, the alkyl group is particularly preferred. Among the alkyl groups, γ-(2゜4-di [-acylphenoxy)propyl group, α-(2,4-di t
-amylphenoxy)propyl group, α-2,4-di-t-butylphenoxy)propyl group, etc. are particularly preferred.

In the general formula CI], 2 is 5 to 6 together with two carbon atoms and an oxygen atom of the phenol core of the general formula [I].
Represents a group of non-gold atoms that can form a membered ring,
The 5- to 6-membered ring formed containing Z is preferably a 5- to 6-membered ring that does not contain any heteroatoms other than the oxygen atom. The 5- to 6-membered ring formed by including 2 is W! such as an alkyl group or an alkoxy group. It may have a substituent.

As the 5- to 6-membered ring formed containing Z, cyclic compound derivatives such as benzofuran, 2,3-dihydrobenzofuran, 1,2-benzobilane, 3,4-dihydro=1,2-benzobilane are particularly preferable. .

Typical specific examples of the cyan coupler represented by the general formula (1) of the present invention are shown below in the margins.

However, the present invention is not limited thereto.

Example cyan coupler α1)
(a) Hs Cslm O Hs Hs The cyan coupler represented by the general formula [I] of the present invention can be obtained by various methods, but may be obtained by using 5-hydroxybenzofuran (5-hydroxycoumarone), 5-hydroxy Synthesized as derivatives of coumaran (5-hydroxy-2,3-dihydrobenzofuran), 6-hydroxy-2H-1-benzobilane (6-hydroxychromene), 6-hydroxychroman, 6-hydroxybenzofuran, 5-hydroxyoxazole, etc. can.

The synthesis of the above derivatives is described, for example, in West German Patent No. 730.790.
No. 736,797, U.S. Patent No. 2,259,3
No. 11, British Patent No. 748,223, Dutch Patent No. 6,512,311, Tetrahedron 1970, 2
Vol. 6, pp. 879-886, Japan Chemical Journal Vol. 73, 282
286 (1952) and the like can be used.

Typical synthesis examples of the cyan coupler of the present invention will be described below.

Synthesis Example-1 (Synthesis of intermediate 5-hydroxy-6-nitrocoumaran) 300 J of nitric acid (specific gravity...1) in 600 mfl of water.
．． 42) and keep at -5 to 0°C. 27.29-5
- Add human O-xycoumaran in small portions over 45 minutes.

After stirring at the same temperature for 30 minutes, 2! Pour the reaction solution into ice water. After extraction with ether, the ether layer was washed with 5% sodium hydrogen carbonate, the ether was distilled off, and the mixture was isolated and purified by column chromatography.

20.89 (yield 57.5%) of 5-hydroxy-6-nitrocoumaran was obtained.

Synthesis Example 2 (Synthesis of Exemplary Cyan Coupler (10)) 200g of 5-hydroxy-6-nitrocoumaran was dissolved in 100IIIp of tetrahydro7ran, 1g of 5% palladium on carbon was added, and the mixture was hydrogenated at room temperature and pressure.

The reaction solution was filtered, and tetrahydrofuran was distilled off. 2001 g of acetonitrile and 9.0 g of pyridine were added to the residue, and 18.79 g of α-(2,4-di-[-amylphenoxy)butanoic acid chloride] was added dropwise with N.

After stirring for 1 hour, the reaction solution was poured into ice water 20011, and the crystals were filtered, washed with water, and air-dried. Recrystallization from a mixture of benzene and hexane yielded 5-hydroxy-6-[α-(2,4-di-t-amylphenoxy)butanamide lacumaran (illustrative coupler (10)) (36,01) (yield 72%). )
) was obtained.

Synthesis Example-3 (Synthesis of Exemplary Cyan Coupler (1)) 15g
1 soml of 5-hydroxy-6-[α-(2,4-di-t-amylphenoxy]butanamide lacumalan)
was dissolved in chloroform, and 4.5Q sulfuryl chloride was added dropwise at a temperature below 10°C. - After standing overnight, wash with water, distill off chloroform, and recrystallize from methanol to 13.217
<Yield 82%) of 4-chloro-5-hydroxy-〇-
[α-(2,4-di[-amylphenoxy)butanamide]coumaran (exemplified coupler (1)) was obtained.

Such couplers are generally lipophilic, and in order to incorporate them into sensitive materials, they need to be incorporated into photosensitive materials using the general formula [
At least one of the cyan couplers of the present invention represented by [1]
The silver halide emulsion (generally a red-sensitive emulsion layer or a layer adjacent thereto) of a sensitive material is made by dissolving the two in a solution having a boiling point such as '8'.

The coupler of the present invention can be incorporated into the emulsion layer of a color sensitive material using a conventionally known method, such as a high boiling point organic solvent with a boiling point of 115°C or higher such as tricresyl phosphate or dibutyl phthalate, or a high boiling point organic solvent such as butyl acetate or butyl propionate. After dissolving the coupler of the present invention in each of the low boiling point solvents alone or optionally in a mixture thereof, the couplers are mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotating mixer, After emulsifying using a dispersing means such as a colloid mill, the silver halide emulsion used in the present invention is prepared by adding it to silver halide! It can be made by I.

In this way, when the above-mentioned coupler is contained in the photosensitive layer of a photosensitive material, it has the advantage of improving color staining etc. because it shows no bad interaction with color development and has particularly good reactivity. . Furthermore, the dye obtained using the coupler of the present invention satisfies the above-mentioned excellent color absorption properties.

The amount of the cyan coupler according to the present invention to be added to the silver halide photographic light-sensitive material used in the present invention is 1 per mole of silver.
It is preferably added in a range of X10 mol to 1 x 10 mol, more preferably in a range of 5 x 10 mol to 5 x 10 mol.

The silver halide photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, and the like.

The silver halide color photographic light-sensitive material of the present invention may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, magenta, yellow, and cyan couplers containing at least lfl of the cyan coupler of the present invention are usually contained as photographic couplers. The silver halide emulsion layer and the non-photosensitive layer have a structure in which all the layers are arranged on the support in an appropriate number and order, but the number and order of layers can be changed as appropriate depending on the important performance and purpose of use. You may do so.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
)H and pAQ may be produced by sequentially and simultaneously adding them while controlling them. After growth, a conversion method may be used to change the halogen composition of one particle.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and by placing them in an appropriate reducing atmosphere, metal ions can be added to the inside of the particles and/or on the surface of the particles. Can provide reduction-sensitized nuclei.

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 be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, l: 1,0,01 plane and [1,i,1
] Any aspect ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. It's okay.

In the silver halide containing the coupler of the present invention, spectral sensitizing dyes that are advantageously used to impart photosensitivity in the wavelength range required for red-sensitive emulsions include, for example, U.S. Pat. No. 2.270,378, No. 2.44'2,710, No. 2,454,62
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 9 and No. 2,776.280.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing capri during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add a hardening agent to the processing solution to the extent that it can harden the photosensitive material, but it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming dye is formed for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazoles, and open-chain acylacetonitrile couplers. In addition to the couplers of the present invention, examples of cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either 2-equivalence may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied by dispersing a hydrophobic compound such as a coupler, and is usually mixed with a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary with a low-boiling point and/or water-soluble organic solvent. After emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, It can be added to the hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include phenol derivatives, phthalate esters, phosphate esters, which do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

6 Anionic surfactants and nonionic surfactants can be used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. , cationic surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

In the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention, an ultraviolet absorber is added to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to U light. It may also include.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention, the gloss of the photosensitive material is reduced and the addability is increased.
A matting agent can be added to prevent the sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide color photographic light-sensitive material of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

Photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention, coating property improvement,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

In the photographic material using the silver halide emulsion of the present invention, the photographic emulsion layer and other layers include a baryta layer or a flexible reflective support such as paper or synthetic paper laminated with an α-olephne polymer, cellulose acetate, Cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
It can be applied to films made of semi-synthetic or synthetic polymers such as polycarbonate and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be used directly or (adhesiveness, antistatic property, dimensional stability, resistance It may be applied via one or more subbing layers (to improve abrasion, hardness, antihalation, frictional properties and/or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times range from 1 ms to 1 ms, which is normally used in cameras, as well as exposures shorter than 1 µs, such as exposures of 100 µs to 1 µs using cathode ray tubes or xenon flash lamps. It is also possible to make exposures longer than 1 second. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be used to form an image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic proscenes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.11 g to about 30 g per fl of color developer solution, preferably about 1 g to about 1 g per fl of color developer solution.
Use at a concentration of approximately 1.5 g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-〇-phenylenediamine salt, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-human O-oxyethylaminoaniline, 4-
Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amino-based color developer, the color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bimetal vim
Salts, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually above 7, most commonly about 10.
〜about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. III
As the bleaching agent used in the whitening process, a metal complex salt of an organic acid is used, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time developing color in the uncolored areas of the color former. Its composition is aminopolycarboxylic acid or ilM, organic acids such as citric acid, iron,
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt.

Specific representative examples of these include the following:

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [61 Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid Sodium salt The bleach used is as mentioned above! It contains a metal complex salt of I acid as a bleaching agent and can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, DH of borate, oxalate, acetate, carbonate, phosphate, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, bisulfite 1i11
1! Sulfites such as potassium, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate , potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and other various salts may be contained alone or in combination.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution,
Bubbling of air or oxygen may be carried out in the bleach-fixing bath and in the storage tank of the bleach-fixing replenisher, if desired, or a suitable oxidizing agent such as hydrogen peroxide, bromine am, persulfate, etc. may be added as appropriate. May be added.

(Specific Effects of the Invention) According to the present invention, a cyan dye m image having a maximum absorption wavelength of 640 to 660 nw can be obtained;
The absorption at 0n- is extremely small and an extremely good cyan dye image can be obtained.

The dyes formed are also extremely robust to heat, light, and moisture.

Furthermore, the coloring property is also very good.

(Specific Examples of the Invention) Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Using couplers of the present invention and comparative couplers as shown in Table 1 below, 10 g of each coupler was added to a mixture of 5 lJl of dibutyl phthalate and 30 Ill of ethyl acetate, and heated to 60°C. Completely dissolved. This mixed solution was mixed with 5 rafts of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified using a colloid mill to prepare a dispersion of each coupler. This coupler dispersion was then added to 500 g of gelatin-silver chlorobromide (containing 20 mol% silver bromide) emulsion, coated on polyethylene-coated paper, and dried to form six types of silver halide color photographic light-sensitive materials. It was created. These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing.

[Color development process] Color development: 30°C, 3 minutes and 30 seconds Bleach-fixing: 30°C, 1 minute and 30 seconds Washing: 30°C, 2 minutes The composition of each processing solution in the color development process is as follows.

[Color developer composition] 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5g benzyl alcohol
Sodium hexametaphosphate at 15°C 2.
5g anhydrous sodium sulfite 1,85Q sodium bromide 1.4g potassium bromide o, s g borax
39. Add IQ water to make 1 no.
Adjust to p)l 10,3 using sodium hydroxide.

[Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 61.0 g Ethylenediaminetetraacetic acid diammonium salt s, o g Thio-T
Ammonium a-acid 124.50 Metahypertium 1iiIIIi! ! Sodium 13.5 (
J Anhydrous sodium sulfite Add 2.7g of water to make 1J/.

Photographic characteristics were established for each sample obtained after processing.

The results are shown in Table 1.

Note that the sensitivity values in the table are expressed as relative sensitivities with the sensitivity of sample No. 014 set as 100.

This measurement was performed using a PDA-60 type densitometer [Konishi Roku Photo Industry ■]
[manufactured by] was used.

Comparative coupler (A) Comparative coupler (B) Comparative coupler (C) Table 1 As is clear from the results in Table 1, all of the samples of the present invention have higher sensitivity and higher maximum density than the comparative samples. I understand that. Note that all samples had maximum wavelengths in the range of 640 to 660 nm.

Example 21 Samples 7 to 12 in which six types of cyan dye images were formed were obtained in the same manner as in Example 1 using the couplers of the present invention and comparative couplers as shown in Table 2.

Then, light resistance, heat resistance, and moisture resistance were examined.

The results obtained are shown in Table 2.

Light resistance is measured after 200 hours of irradiation of each image with a xenon fade meter, heat resistance is measured after 2 weeks at 77°C, and humidity resistance is measured after 2 weeks at 60°C and relative humidity of 70% at the initial temperature. The respective residual concentrations at 1.0 are shown. (Each Residual Density %) In addition, Steen expressed the rate of increase in blue density in the unexposed area of the sample subjected to the light exposure test as a percentage.

In Table 2, comparative couplers (A), (8) and <C) are the same as those used in Example 1.

As is clear from the results in Table 2, the samples of the present invention are excellent in light resistance, heat resistance, and moisture resistance, and furthermore, the occurrence of staining is small.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare sample No. 13.

Layer 1... 1.2 (1/12 gelatin, 0.32o
A blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%) of /m2 (in terms of silver, the same applies hereinafter), a yellow coupler of 0,80111/II' (Y -1) A layer containing.

Layer 2... 0.70a/m2 gelatin, 12u/
l” anti-irradiation dye (AI-1), 6
An intermediate layer consisting of (AI-2> of raQ/-.

Layer 3 --- 1.25 Mm2 (7) t'5 tin, 0.2
5 g/12 green sensitive silver chlorobromide emulsion (silver bromide content 70 mol %), layer containing 0,62Q/- magenta coupler (M-1) dissolved in 0.30 MI dioctyl phthalate.

Layer 4: Intermediate layer consisting of 1.20 g/m2 of gelatin.

Layer 5... 1.20o/Q12 gelatin, 0.3
A layer containing 0 g/i2 red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol %), 9 G X 10 mol/■ of the exemplary cyan coupler (1) dissolved in 0620 Q/m dioctyl phthalate.

Layer 6... 1. OOM-gelatin and 0.20M ■
0,300/I2 dissolved in dioctyl phthalate of 2
A layer containing an ultraviolet absorber (UV-1).

Layer 7: Layer containing o, sog/l gelatin.

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-5-h riazine was added to I12.4 and 7 in an amount of 0.017 g per 1 g of gelatin, respectively.

The following margins: Y-1) :M-1) L (AI-1) (AI-2) (UV-1) CIIHII(t) The multicolor color photographic material sample 13 obtained above was used as Example 1. Similar treatment was performed. It was confirmed that the sample obtained after the treatment had excellent photographic properties, light resistance, heat resistance, and moisture resistance.

Claims (1)

[Scope of Claims] A silver halide photographic material containing a cyan coupler represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a hydrogen atom, a halogen atom, or an acylamino group, Y represents an alkyl group or a group represented by the following general formula [II], and Z represents a group of nonmetallic atoms that can form a 5- to 6-membered ring together with the two carbon atoms and oxygen atom of the phenol core of general formula [I]. General formula [II] -NH-W-R_1 In the formula, R_1 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and -W- represents -CO-, -
Represents SO_2-, -COCOO- or -CONH-.