JPH03230149A - Image forming method - Google Patents

Abstract

PURPOSE:To enhance the gradation reproducibility and max. density of a color image by short-time exposure by sensitizing a high silver chloride emulsion contg. particles free from a phase in which silver bromide is locally present near the vertexes with a prescribed amt. of a gold compd. and using the sensitized emulsion. CONSTITUTION:A color photographic sensitive material is exposed for <=10<-4> sec and developed to form a color image. The sensitive material contains an emulsion contg. clean silver halide particles free from a phase in which silver bromide is locally present near the vertexes and made of silver chlorobromide having >=95 mol% silver chloride content. The emulsion has been sensitized with a gold compd. (e.g. chloroauric acid) used by 5X10<-7>-5X10<-4> mol per 1 mol silver halide. The silver halide can be formed in the presence of a water soluble iridium compd. and blue-, green- and red-sensitive emulsions can be spectrally sensitized with prescribed sensitizing dyes, respectively.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for obtaining a color image with gradation from soft information having a reflective support and a silver genide color. The present invention relates to a method for quickly obtaining color images with excellent quality.

[Background of the invention]

Today, in the field of Electro-X, due to significant advances in imaging devices such as CCDs and magnetic recording media, it is now possible to take photographs with the same ease as conventional silver halide photography, and immediately display them on a TV for enjoyment. It has made this possible. Also, in the field of printing and plate-making, advancements in scanners have made it easy to read the original image with a scanner and then edit, modify, change contrast, enlarge/reduce, etc. while viewing the color display. Now you can.

In this way, recording and processing images as electrical signals is becoming widespread not only in the industrial field but also in general society.

However, simply displaying images on a television is still insufficient, and various methods have been put into practical use, such as electrophotographic methods, which require images recorded on paper.

Even in these fields, silver halide photographic light-sensitive materials have rich tonality that is far superior to other methods, and they have excellent descriptive power.

JP-A No. 62-35352 discloses that a silver halide color photographic light-sensitive material is scanned and exposed, and then developed.
Discloses a method for forming color images, published in Japanese Patent Application Laid-open No. 1983
No. 197947 discloses a recording material that forms a color image by developing after scanning exposure, in which a photosensitive material containing silver halide grains with a silver chloride content of 95 mol% is exposed to LED light or laser light. This indicates that an image is formed by performing imagewise exposure using a photoreceptor and then developing with a specific developer for a short period of 45 seconds.

However, according to studies conducted by the present inventors, images obtained when a photosensitive material having the above structure is developed for a short period of time have soft gradations and a low maximum density.
- It was found that the image quality was extremely low compared to a color image obtained by exposure for 2 seconds or more, and there was a problem in practical use.

Furthermore, Japanese Patent Application Laid-Open No. 2-18548 discloses that gold sensitization is applied to silver halide having a localized silver bromide phase to prevent image quality deterioration during multiple exposure. It was found that the pressure resistance was significantly inferior and there was a problem in practical use.

As a result of intensive research, the present inventors have found that the silver halide grains contained in the photosensitive material are clean silver halide grains that do not have a localized silver bromide phase near the grain apex, and contain silver chloride. 5 X 10-' to 5 X 10 per mole of silver halide during the chemical ripening process.
The present inventors have discovered that by incorporating a gold compound in the amount of 1.5 molar, that is, gold sensitization, it is possible to obtain images with high contrast and high maximum density, as well as photosensitive materials with good pressure resistance, and have completed the present invention. Ta.

Although it is not clear why such an improvement is achieved by using specific silver halide grains and by applying a specific amount of gold sensitization, it is possible to suppress latent image bleaching caused by silver chloride development. It is presumed that pressure resistance does not deteriorate even if gold sensitization is performed because silver 10ogenide prevents a decrease in density and has few internal defects.

[Purpose of the invention]

An object of the present invention is to provide a method for obtaining an image with excellent gradation reproducibility and high maximum density in a short exposure time of 10-' seconds or less.

[Structure of the invention]

The above object of the present invention was achieved by exposing a silver halide photographic light-sensitive material having the following structure for a time of 10-' seconds or less and then developing it.

The silver halide photographic light-sensitive material according to the present invention contains a yellow color-forming coupler, a magenta color-forming coupler, and a cyan color-forming coupler on a reflective support, and further contains silver bromide in the vicinity of the grain vertices in a layer constituting the photographic light-sensitive material. Clean silver halide grains with no localized phase and silver chloride content of 95
Silver chlorobromide grains with a mole % or more are gold sensitized by further adding 5 X 10-' to 5 X 10-' moles of a gold compound per mole of silver halide during the chemical sensitization process. It is characterized by

[Specific structure of the invention]

The silver halide grains of the present invention must have a silver chloride content of 95 mol % or more, a silver bromide content of 5 mol % or less, and a silver iodide content of 0.5 mol %. % or less. More preferably, the silver bromide content is 0.
1 to 2 mol% silver chlorobromide.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. It may also be used in combination with silver halide grains having a silver chloride content of 95 mol % or less.

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more according to the present invention, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 95 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains of the present invention must be uniform from the inside to the outside of the grains (defined and referred to as "clean emulsion").
No. 6, No. 58-108533, No. 60-222844
In the case of composite silver halide grains having a phase with a high silver bromide content as described in No. 60-222845 and No. 60-222845,
When used in combination with gold sensitization, pressure resistance deteriorates significantly, which is not preferable.

The grain size of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic properties such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm1, more preferably 0.
．． It is in the range of 25 to 1.2 μm. Note that the particle size can be measured by various methods commonly used in the technical field.

Typical methods include Loveland's "Particle Size Analysis Method" (A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122) or the aforementioned method by Mies, The. Theory, Knowledge, Photographic Ink Process (3rd edition, published by Macmillan (1)
966), Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is
This is a coefficient indicating the breadth of particle size distribution, and is defined by the following formula.

Here, ri represents the particle size on each side of the particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than cubic or spherical.
It represents the diameter when the projected image is converted into a circular image of the circumferential area.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737 and The Journal on Photographic Science (J.

Octahedron, tetradecahedron, 1
Particles having a shape such as a dihedron can also be prepared and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Metal ions may be added using lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts. In particular, it is desirable to add an iridium salt to form particles in the presence of the iridium compound.

In the present invention, forming silver halide in the presence of a water-soluble iridium compound means adding the iridium compound at any stage of nucleation, growth, or physical ripening of silver halide. Specific methods include a method in which an iridium compound is added to the mother liquor before nucleation, a method in which an iridium compound is added in a rush during the growth of silver halide, or a method in which an iridium compound is added in a solution of a soluble silver salt and/or a soluble halide solution. Examples include a method of adding it to a soluble halide solution, or a method of adding it to a soluble halide solution immediately before physical ripening after completion of growth, but a method of adding it to a soluble halide solution is preferable in terms of obtaining the effects of the present invention. Further, the iridium compound may be added in divided stages. As the iridium compound to be added, a mixed solution of two or more different iridium compounds may be used. Alternatively, two or more different solutions of iridium compounds may be added at different stages.

In the present invention, the amount of iridium compound added is 1 O-mol of iridium compound per mol of silver halide.
The range is preferably from 9 to 10-' mol, more preferably from 10-8 to 1
A range of 0-' moles is more preferred. If the amount is less than this, the effect of the present invention will not be sufficiently exhibited, and if it is more than this, desensitization, fogging, etc. will occur, which is not preferable.

The iridium compound used in the present invention is not particularly limited, but from the viewpoint of compound stability, safety, economical efficiency, etc., industrially possible and preferable compounds include halogenated iridium (III) compounds, halogenated iridium <N) Examples include compounds and iridium complex salts having a ligand and a cyte halogen, amines, oxalate, etc. Examples are given below, but the present invention is not limited thereto.

Iridium trichloride, iridium tribromide, potassium hexachloroiridium (III), iridium sulfate (Ill
) Ammonium, Iridium disulfate (I[[) Potassium, Iridium trisulfate (I[[) Tripotassium, Iridium sulfate (I[[), Trioxalatoiridium (In),
Iridium tetrachloride, tetrabromide, iridium, potassium hexachloroiridium (IV), ammonium hexachloroiridium (IV), potassium iridium (TV), trioxalatoiridium (IV) In the present invention, any of these compounds may be used. You can choose one of them, or you can use them in combination as needed. These iridium compounds are used by being dissolved in water or a water-miscible solvent, but a method that is often used to stabilize solutions of iridium compounds, that is, hydrogen halide (
For example, hydrochloric acid, hydrochloric acid, etc.) or alkali halides (
For example, a method of adding potassium chloride, sodium chloride, potassium bromide, etc. can be used.

The silver halide grains used in the 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 formed inside the grain as a gap. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitization methods can be used alone or in combination, but at least gold sensitization is essential.

Furthermore, it is more preferable to use sulfur sensitization together.

Gold compounds that can be used as gold sensitizers include, but are not limited to, chloroauric acid, sodium chloroaurate, gold potassium thiosulfate, and the like.

The amount of gold compound added to the silver halide emulsion according to the present invention is 5 x 10-' to 5 x per mole of silver halide.
10-3 mol, preferably 2X to-'~I
The concentration is X 10-' molar. More preferably, 2.
6X 10-' to 4X 10-' moles, most preferably 2.6X 10-' to 9 X 10-' moles.

In order to add a gold compound to a silver halide emulsion, it may be added after being dissolved in a suitable solvent such as water or ethanol.

The gold compound according to the present invention is added during the production process of a silver halide emulsion, and the addition timing is arbitrary until the end of the chemical sensitization (or chemical ripening) stopping process in the production process. The excellent effects of the present invention can be obtained by adding it to.

Here, the chemical sensitization termination step (or also referred to as the chemical sensitization termination step) refers to the step of adding a chemical sensitization stopper to the sensitization step. In this case, simultaneously with the addition of a chemical sensitization stopper or
It includes within 10 minutes before and after (nearby), preferably at the same time or within 5 minutes before and after.

Specifically, the arbitrary period until the end of the chemical sensitization stopping step is before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation and before the start of chemical sensitization. It may be carried out at any time selected from the period up to this point, during chemical sensitization, and until the end of chemical sensitization. Preferably, from the end of silver halide grain formation to the start of chemical sensitization,
It is added at any time selected from during chemical sensitization and until the end of chemical sensitization. The entire amount may be added at one time, or may be added in multiple portions.

In the silver halide emulsion of the present invention, compounds called antifoggants and stabilizers are added in order to optimally apply chemical sensitization and to prevent a decrease in sensitivity and the occurrence of capri during storage or development of the light-sensitive material. be able to.

These compounds include 4-hydroxy-6-methyl-1゜3.3a, 7-chitrazaindene, 3-methylbenzothiazole, ■-phenyl-5-mercaptotetrazole, and many heterocyclic compounds and mercapto compounds. It is being

In the case of flash exposure, the exposure time described in the present invention refers to the time when the intensity of light changes over time, and from the time when it reaches its maximum value of 172, it decreases to 1 of that maximum value.
72, and in cases such as scanning exposure with laser light, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value in the spatial variation of the intensity of the light flux, When the diameter of the luminous flux is defined as the distance between two points where the outer edge of the luminous flux intersects with a line that is parallel to the scanning line and passes through the point where the light intensity is maximum, the exposure time is calculated by (diameter of the luminous flux)/(scanning speed). shall be.

Scanning exposure using a linear light source can be considered in the same way as the case of laser light described above.

Types of light sources include xenon discharge tubes and cathode ray tubes (CR).
T), light emitting diode, tungsten halogen lamp,
Any known light source such as a mercury high-pressure discharge tube or a laser can be used. Among these, gas lasers such as helium-neon, argon, and helium-cadmium, semiconductor lasers such as gallium arsenide phosphorus, and combinations thereof with nonlinear optical elements are preferably used.

Laser printer devices that are considered to be applicable to such systems include, for example, Japanese Patent Application Laid-Open No. 55-4071,
No. 59-11062, Japanese Patent Publication No. 56-14963, No. 56-40822, European Patent No. 77410, Institute of Electronics and Communication Engineers Technical Research Report Vol. 80. No. 244 and Film and Television Technology 1984/6 (382), 34-3
It is described on page 6 etc. There is something.

The preferred range of excellent gradation reproducibility and high maximum density, which is the objective of the present invention, is when sensitometry is performed on a sample that has been wedge exposed for 10-4 seconds or less and then developed. , at least in the exposure range of l: 100, the Y, M, and C6 coloring densities are below the density at which color turbidity occurs (due to the overlap of the inherent sensitivity ranges, the M coloring occurs simultaneously when the Y coloring occurs). It means that the average gradation of the straight line portion in the exposure range is at least 1.6, and the average gradation (tan value of the coloring density with respect to the exposure amount at a density of 0.3 to 1.5) is 0.9 or more.

In particular, for the above-mentioned color turbidity, the silver chloride content is 95 mol%.
Photographic materials containing the above silver halide emulsions are advantageous.

The silver halide photographic light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific wavelength region of 400 to 900 nm in combination with a yellow color-forming coupler, a magenta color-forming coupler, and a cyan color-forming coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is expressed by the following general formula (A), and it is expected that the following will occur: 1. In the general formula [A], Zll and z1□ are benzoxazole nucleus, naphthoxazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyridine, respectively. It represents a group of atoms necessary to form a nucleus or a quinoline nucleus, but these heterocycles also include those having substituents.

Examples of substituents on the heterocycle formed by Zll and zl include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, or an alkoxycarbonyl group. Among these substituents, preferred substituents are halogen atom, a cyan group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred substituents are a cyano atom, a cyano-methyl group, an ethyl group, a methoxy group, or an ethoxy group.

R21 and R2□ each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a carbon atom number. 1 to 4 sulfoalkyl groups. Further, R23 is selected from a hydrogen atom, a methyl group, and an ethyl group. Xe represents an anion, and a represents 0 or 1.

Among the sensitizing dyes represented by the general formula (A), particularly useful dyes are the sensitizing dyes represented by the following general formula [A'].

General Formula [A'] Here, Y and Y2 each represent an atomic group necessary to complete a benzene ring or a naphthalene ring which may be substituted.

The benzene ring and naphthalene ring formed by Yl and Y2 include those having a substituent, and the substituent is preferably a halogen atom, a hydroxyl group, a cyano group, an aryl group,
It is an alkyl group, an alkoxy group or an alkoxycarbonyl group. More preferred substituents are a halogen atom, a cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. It is.

R21, R22, R23, Xe and α general formula CA)”
I? Same as shown.

Amplified general formula () represented by general formula [A] used in the present invention () A-9 A-10 -11 -12 -13 4 5 -16 -17 -18 -19 -20 1 2 -23 -24 A- 25 A-26 -27 -28 When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the following general formula CB).

General formula CB) In the formula, Zll and Zl each represent an atomic group necessary to form a benzene ring or a naphthalene ring fused to an oxazole. The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups, or alkoxy groups. More preferred substituents are halogen atoms,
These are phenyl group and methoxy group, and the most preferred substituent is phenyl group.

According to a preferred embodiment of the present invention, Zll and 2□ together represent a benzene ring fused to an oxazole ring;
The 5-position of one benzene ring is substituted with a phenyl group, or the 5-position of one benzene ring is substituted with a phenyl group, and the 5-position of the other benzene ring is substituted with a halogen atom. Rll and R2□ each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group. More preferably, R11 and R2□ are each an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferred is a sulfoethyl group.

R2, is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
Preferably represents a hydrogen atom or an ethyl group.

X and e represent anions, such as chlorine, odor CH, So
, , C2H65O, and other anions.

n represents I or O. However, when the compound forms an inner salt, n represents O.

Specific examples of the natural dye represented by the general formula [B) that are preferably used in the present invention are shown below.

-1 -2 -3 -4 5 -6 -8 -9 -10 -11 2 (CH2)2503H-N (2H5)3 When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion,
Spectral sensitization is preferably carried out using a sensitizing dye represented by the following general formula [C] or a sensitizing dye represented by the following general formula (D).

General formula (C) General formula CD) In the formula, R represents a hydrogen atom or an alkyl group, R8-R4
represent an alkyl group and an aryl group, respectively, and z111
124 and Z represent an atomic group necessary to form a benzene ring or a 7talene ring fused to a thiazole ring or selenazole ring, respectively, Z3 represents a hydrocarbon atomic group necessary to form a 6-membered ring, a represents l or 2, 2 represents a sulfur atom or a selenium atom, and xe represents an anion.

In the above general formula, the alkyl group represented by R includes a methyl group, an ethyl group, and a propyl group, and R is preferably a hydrogen atom, a methyl group, or an ethyl group. Particularly preferred are a hydrogen atom and an ethyl group.

Further, R, , R, , R, and R4 are each a linear or branched alkyl group, and this alkyl group may have a substituent. (e.g. methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy-γ-sulfopropyl, sulfatepropyl, allyl, benzyl, etc.) or an aryl group, and this aryl group may have a substituent.

(for example, phenyl, carboxyphenyl, sulfophenyl, etc.), and represents a group selected from Z l + Z x, Z 4
The heterocyclic nucleus formed by and Z may have a substituent, and preferred examples of the substituent are a
It is an aryl group, an alkyl group, or an alkoxy group, and more preferably a halogen atom (for example, a chlorine atom), a phenyl group, or a methoxy group.

CH35o,, c, H, so, etc.), and ff1i
Represents l or 2.

However, when the compound forms an inner salt, Q represents 1.

Hereinafter, the general formula [CD and C
Typical examples of the sensitizing dye represented by D) are -1 -2 -3 -4 CH2C; H2 () is I'l 5 C2H.

re -5 -6- 7- -9 -10 -11 -12 C, Hl JS ■e C-13 C-14 -1 -2 -4 -5 -7 The above general formula [A), CB), [C ) or CD) The amount of the sensitizing dye added is not particularly limited, but it is preferably used in the range of 1X10-7 to 1X10-'' mol per 1 mol of silver halide, and more preferably the addition of the sensitizing dye As the method, methods well known in the art can be used.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), and in some cases diluted with water; In some cases they can also be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibrations for this dissolution.

Furthermore, the sensitizing dye used in the present invention is disclosed in U.S. Patent No. 3.46.
9.987, a method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion, as described in Japanese Patent Publication No. 46/24185, etc. Alternatively, a method may be used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added.

Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other addition methods include U.S. Patent Nos. 2,912.345 and 3,342.
．． No. 605, No. 2,996.287, No. 3,425.
The method described in No. 835 and the like can also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvents, and these solutions may be mixed or added separately before being added to the silver halide emulsion. good. When adding them separately, the order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

It is advantageous to use gelatin as the binder (or [1 colloid)] of 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.

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

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer may be contained in the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. be able to.

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-)22-diamine derivative, aminophenol derivative, etc.). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in 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 than those described above.The dye image-forming couplers used in the present invention are not particularly limited, and various couplers may be used. However, the compounds described in the following patents are included as representative examples.

Yellow dye image-forming couplers include acylacetamide type and benzoylmethane type 4-equivalent or 2-equivalent couplers, which are described, for example, in US Pat. No. 2,778.
No. 658, No. 2,875,057, No. 2,908゜5
No. 73, No. 2,908.513, No. 3,227,15
No. 5, No. 3,227゜550, No. 3,253,924
No. 3,265.506, No. 3,277゜155, No. 3,341,331, No. 3,369,895,
3, 384.

No. 657, No. 3,408,194, No. 3,415.6
No. 52, No. 3,447°928, No. 3,551.15
No. 5, No. 3,582.322, No. 3,725°072
German Patent No. 1,547.868, German Patent No. 2,057,
No. 941, No. 2,162.899, No. 2,163.8
No. 12, No. 2,213.461, No. 2,219,91
No. 7, No. 2,261,361, No. 2,263.875
No., Special Publication No. 13576, Japanese Patent Publication No. 48-2943
No. 2, No. 48-66834, No. 49-10736,
No. 49-122335, No. 50-28834, No. 5
No. 0-132926, No. 55-144240, No. 56
-87041.

Examples of magenta dye-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers of the 5-pyrazolone series, pyrazolotriazole series, pyrazolinobenzimidazole series, indacylon series, and cyanoacetyl series; No. 2,600,788, 3.
No. 061,432, No. 3,062,653, No. 3,1
No. 27,269, No. 3,311,476, No. 3.15
No. 2.896, No. 3,419.391, No. 3,519
, No. 429, No. 3,558,318, No. 3,684.
No. 514, No. 3,705.896, No. 3,888.6
No. 80, No. 3,907.571, No. 3,928.04
No. 4, No. 3,930.861, No. 3,930.816
No. 3,933,500, JP-A-4949639, JP-A No. 49-111631, JP-A No. 49-129538,
No. 51-112341, No. 52-58922, No. 5
No. 5-62454, No. 55-118034, No. 56-
No. 38643, No. 56-135841, Special Publication No. 1977
-60479, 52-34937, 55-29
No. 421, No. 55-35696, British Patent No. 1,247
．． 493, Belgian Patent No. 792.525, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 1987-125.732, Japanese Patent Publication No. 59-228,2
No. 52, No. 59-162.548, No. 59-171.
No. 956, No. 60-33,552, No. 60-43,6
No. 59, West German Patent No. 1,070.030 and U.S. Patent No. 3
, No. 725,067, etc.

Typical cyan dye-forming couplers are phenolic and naphthol-based 4-equivalent or 2-equivalent type cyan dye image-forming couplers, and are described in U.S. Pat. , No. 598,
2,367.531, 2,369,929, 2,423,730, 2,474,293, 2
, 476.008, 2,498.466, 2,
No. 545,687, No. 2,728,660, No. 2,7
No. 72,162, No. 2,895,826, No. 2,97
6.146, 3,002,836, 3,419
, No. 390, No. 3,446,622, No. 3,476.
No. 563, No. 3,737,316, No. 3,758,3
No. 08, No. 3,839.044, British Patent No. 478,9
No. 91, No. 945,542, No. 1,084,480, No. 1,377.233, No. 1,388.024, No. 1,543゜040, and JP-A-47-374
No. 25, No. 50-10135, No. 50-25228, No. 50-112038, No. 50-117422,
No. 50-130441, No. 51-6551, No. 51
-37647 No. 4, No. 51-52828, No. 51-1
No. 08841, No. 53-109630, No. 54-48
No. 237, No. 54-66129, No. 54-13193
No. 1, No. 55-32071, No. 59-146050, No. 59-31953, and No. 60-117249.

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. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is acceptable.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, oil-in-water emulsion dispersion, etc. can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or Dissolve using a water-soluble organic solvent and emulsify using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jet mixer, or ultrasonic device. After being dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Anionic surfactants, nonionic surfactants, and cationic surfactants are 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 a machine or ultrasound. 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 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 layer of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

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.

The silver halide emulsion layer of a /% silver halide photosensitive material using the silver halide emulsion of the present invention and/or other hydrophilic colloid layer can be used to reduce the gloss of the photosensitive material, increase the addibility, A matting agent can be added to prevent scratching.

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 a light-sensitive material using the silver halide emulsion 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 colloid layers.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

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

A preferred embodiment is a water-resistant photographic base paper in which both sides of the base paper are coated with polyolefin. This polyolefin-coated photographic base paper has a large effect on the image quality (white background, sharpness, etc.) of the finished print, and the hue of the white background is particularly important. Various proposals have been made to improve white discoloration. For example, adding a colorant to the emulsion layer to improve brightness and hue (surface reflectance characteristics such as L*, a book, b*, etc.) There is a method of adjusting the coloring agent within the range, or a method of adding a colorant to the photographic base paper as described in JP-A-53-19021, but the latter method is more preferable for the present invention.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
Direct or (support surface adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, anti-tension properties, friction properties,
and/or may be coated via one or more subbing layers to improve 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 extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenolic and p-7x unilene diamine 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. Alternatively, these compounds are generally present in a concentration of from about 0.1 g to about 30 g per gram of color developer lα, preferably from about 1 g to about 15 g per gram of color developer lα.
Use at a concentration of g.

The color developing agent used in the color developer is typically an aromatic primary amine compound, especially p-phenylenediamine, and a preferred example is N,N-diethyl-p-phenylenediamine hydrochloride. salt, N-ethyl-
p-phenylenediamine hydrochloride, N+N-'; , I
f Ru-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-hydroxyethylaminoaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene These color developing agents may include sulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)-3-methyl-4-aminoaniline, etc. ) may be used alone or in combination of two or more, or one or more of these color developing agents and other black and white developing agents such as hydroquinone,
It may be used in combination with 1-phenyl-3-pyrazolidone and N-methyl-p-aminophenols. in this case,
The amount of the color developing agent added is in the range of 0.2 to 2 mol, preferably in the range of 0.4 to 0.7 mol, per 1 mol of silver halide contained in the color photographic light-sensitive material.

When the silver halide color photographic light-sensitive material of the present invention is subjected to color development processing, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4- Aminoanilisulfates are particularly preferred.

In addition to the above-mentioned color developing solution, the color developing solution includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, and N,N-diethylhydroxylamine. , N
, N-bis(methoxyethyl)hydroxylamine, triethanolamine, jetanolamine glycose,
Preservatives such as potassium sulfite, methanol, ethanol,
Contain, as necessary, various photographic additives known in the photographic field such as organic solvents such as butanol, ethylene glycol, and diethylene glycol, development regulators such as citradinic acid and polyethylene glycol, and heavy metal ion hiding agents and development accelerators. I can do it.

In addition, sulfite ions such as sodium sulfite and potassium sulfite as preservatives for color developing solutions are used in relatively large amounts (for example, when the color developing solution contains benzyl alcohol, which is a coloring property improver). Approximately 0.01 per IQ
However, if the benzyl alcohol in the color developer contains only about 0 to about 5 mQ per 112 of the color developer, the sulfite ion concentration will be It needs to be about 0.004 mol or less.

The silver halide color photographic light-sensitive material of the present invention is preferably developed with a color developing solution that does not contain any water-soluble bromide or contains a very small amount of water-soluble bromide. When an excess of water-soluble bromide is contained, the development speed of the silver halide color photographic light-sensitive material decreases. The bromide ion concentration in the color developer is approximately 0.1 g or less, preferably 0.05 g or less per color developer Iρ, in terms of potassium bromide.

When the photosensitive material of the present invention is continuously processed while continuously replenishing the color developer replenisher, if a small amount of bromide ions are eluted from the color photosensitive material as a result of development,
A small amount of bromide ions accumulate in the color developer,
Even in this case, it is preferable to appropriately select the replenishment ratio of the color developer replenisher to the total amount of bromide contained in the light-sensitive material so that the amount of bromide ions in the color developer falls within the above range.

It is preferable to use a water-soluble chloride as a development regulator in the color developing solution.

The water-soluble chloride used is used in an amount of 0.5 to 5 g, preferably 1 to 3 g, per color developer IQ in terms of potassium chloride.

In the color developing solution, an organic development inhibitor described in JP-A No. 58-95345 can be further used within a range that does not impair the present invention. Preferably, adenine and guanine are used in the color developing solution in an amount of 0 to 0.02 g/12.

The pH of the developer of the present invention is preferably 9.5 or higher, more preferably 13 or lower. It has been conventionally known that development is accelerated by increasing the pH of the developer, but the silver halide color photographic light-sensitive material of the present invention provides sufficient rapid developability even at a pH of 11 or less. It will be done.

The temperature of the color developer is 15-45°C, preferably 20-45°C.
It is carried out between 0°C.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment.

Many compounds are used as bleaching agents, but iron (
(■), Kobal-1-(DI), copper (■), etc., especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid Aminopolycarboxylic acids such as, malonic acid, tartaric acid, malic acid, diglycolic acid, metal complex salts such as dithioglycolic acid, hepterythyanates, dichromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and thioether.

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

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

The stabilizing liquid used in the stabilization treatment can contain a PHR regulator, a chelating agent, a fungicide, and the like. For these specific conditions, reference may be made to JP-A-58-134636 and the like.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 Each layer having the structure shown in Table 1 was laminated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side (the side on which the photographic constituent layer was coated). A multilayer silver halide color photographic material was prepared. The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (YY-1) 26.7g, dye image stabilizer (ST-1) 10.0g1 (ST-2
) 6.67g, additive (HQ-1) 0.67g and high boiling point organic solvent (DNP) 6.67g, ethyl acetate 60+
mQ was added and dissolved, and this solution was mixed with 20% surfactant (SU
1) A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of a 10% gelatin aqueous solution containing 7rn(l) using an ultrasonic homogenizer. This dispersion was prepared as a blue-sensitive silver halide emulsion under the following conditions. (Silver 1
(containing 0g) to prepare a first layer coating solution.

The second to seventh layer coating solutions are also the same as the first layer coating solution in Table-1.
They were added to the first, third and sixth layer coating solutions, respectively.

CH.

WR-1 B OP NP IDP V.P. Dioctyl phthalate dinonyl 7 crate diisodecyl phthalate Polyvinylpyrrolidone Q-1 Q-2 OC,HI T-4 CH.

CH.

(2) As a hardening agent, H-1 was added to the second and fourth layers, and H-2 was added to the seventh layer.

-1 C(CHxSO*CH-CH*)a o, 07 g/m" [Preparation method of blue-sensitive silver halide emulsion] The following (liquid A) was added to 1000 mΩ of a 2% aqueous gelatin solution kept at 40°C.
and (Solution B) were simultaneously added over 30 minutes while controlling pAg = 6.5, pH-3.0, and the following (Solution C) and (Solution D) were added at pAg = 7.3, pH-5. , 5 over 180 minutes.

At this time, pAg was controlled using an aqueous solution of thorium described in JP-A-59-45437.

(Liquid A) Sodium chloride 3.42g Potassium bromide 0.03g Add water 200mff (Liquid B) Add silver nitrate 10g water 200mff (Liquid C) Sodium chloride 102.7g Potassium bromide Add 1.0g water 600m12 (Liquid D) Add 300g of silver nitrate to water After adding 600mff, desalt using a 5% aqueous solution of Demol N manufactured by Kako Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mix with an aqueous gelatin solution to obtain an average A monodispersed cubic emulsion EMP-1 having a grain size of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol % was obtained.

The following compound was used for the above emulsion EMP-1, and 50°
Chemical ripening was performed at C for 90 minutes to obtain a blue-sensitive silver halide emulsion (EmA).

Sodium thiosulfate 0.8 mg 1 mol 1 mol A
Auric acid 0.5 mg 1 mol 1 mol A fixer SB 5 6 X 10-' mo/L = / mol AgX sensitizing dye D-15
AgX [Method for preparing green-sensitive silver halide emulsion] (Liquid A)
Same as EMP-1 except for changing the addition time of (B solution) and (C solution) and (D solution), average particle size 0.43 μm 1 coefficient of variation = 0.08, silver chloride content rate 9
A monodispersed cubic emulsion EMP-2 with a concentration of 9.5 mol % was obtained.

For EMP-2, the following compound was used at 55 °C for 12
After chemical ripening for 0 minutes, a green-sensitive silver halide emulsion (Em
B).

Sodium thiosulfate 1.5 mg 1 mol 1 mol A Auric acid 1.0 mg 1 mol 1 mol A fixer SB -56X 10-' mol 1 mol AgX sensitizing dye D 2 4XIQ-'-F-ru 1 mol A
gX [Preparation method of red-sensitive silver halide emulsion] Same as EMP-1 except for changing the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D). Average particle size 0
．． 50μm1 coefficient of variation -0.08, silver chloride content 99.
A 5 mol % monodisperse cubic emulsion EMP3 was obtained.

90 at 60°0 using the following compound for EMP-3.
A red-sensitive silver halide emulsion (Em C
) was obtained.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixative SB -56x 10-' mol/mol AgX
Sensitizing dye D -38, Ox 10-'mol 1 mol Ag
X-1 D B-5 Next, in the same manner, the halogen compositions in liquids A and C were changed as shown in Table 2, and the chloroauric acid in the chemical sensitization process was changed to the system with addition. , and silver halide emulsions without additives were also prepared in combination to produce EmD-EmZ.

The obtained silver halide emulsions were combined as shown in Table 3 and coated in the composition shown in Table 1 above.

The prepared sample was measured with EG&G sensitometer mark Vl (
EG&G Electro-Optics Co., Ltd.), the following development process was performed by applying 0.9 x 10' second standing light through an optical wedge, and the resulting sample was measured with a PDA-65 densitometer (manufactured by Konica Corporation). , sensitometry was performed. The maximum concentration (Dm
ax) and the difference (Δγ) in the average slope of the characteristic curve between concentrations 0.3 and 1.5.

The results are shown in Table-3.

Processing process Temperature Time Development color development 35.0±0.3°C 45 seconds bleach fixing
35.0±0.5℃ 45 seconds stabilization 30~34
Dry for 90 seconds at °C 60-80'0
The formulations of the color developing solution, bleach-fixing solution and stabilizing solution used for 60 seconds are as follows.

(Color developer) Pure water 800mQ Triethanolamine 10gN,N-diethylhydroxylamine 10g Potassium chloride 2g Potassium sulfite
0.3g 1-Hydroxyethylidene 1,1-diphosphonic acid Catechol-3,5-disulfonic acid disodium salt N-ethyl-N-β-methanesulfonamiethyl-3-
Methyl-4-amine aniline sulfate optical brightener (4,4'-diaminosulfonic acid derivative) Add water to bring the total amount to IQ.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate Ammonium thiosulfate ethylenediaminetetraacetate (70% aqueous solution) Ammonium sulfite (40% aqueous solution) Add water to bring the total volume to la, pH-6 with potassium carbonate glacial acetic acid, Adjust to 2.

Adjusted to pH-10.10 Stilbene 1.0g 1.0g 1.0g 4.5g 1.0g 0g 3g 100mff 27.5m12 Rum or (stabilizing liquid) 5-chloro-2-methyl-4-inthiazoline- 3-one ethylene glycol 1-hydroxyethylidene-1,1-diphosphonate ethylenediaminetetraacetic acid Ammonium hydroxide (20% aqueous solution) Ammonium sulfite optical brightener (4,4'-diaminostilbendisulfonic acid derivative) Add water to total amount is IQ, sulfuric acid or hydration power 1.0g 1.0g 2.0g 1.0g 3.0g 3.0g 1.5g Table Furthermore, using sample 5.6.7.8, CP manufactured by Konica Corporation
The following process was performed using a K-18 color paper developer, and Δγ and I) max were measured in the same manner.

Color development 38±0.3℃ 3 minutes 30 seconds bleach fixing
Stabilized at 35±0.5°C for 1 minute and 30 seconds 30~35°
From C3 minutes onwards, the following was discovered.

(1) Sample 1.3 of the present invention subjected to gold sensitization is B.

G, R3 layer average slope (Δγ), maximum concentration (Dmax)
It was found that Samples 2 and 4, which were not gold sensitized, had low Δγ and Dmax and did not satisfy the Δγ + Drnax value for obtaining high-quality prints. .

(2) Comparative sample 5,6°7 using an emulsion with a high Br ratio
．． In the development process used in Table 3, Sample No. 8 had low Δγ and low Dmax regardless of the presence or absence of gold sensitization, which is unsatisfactory.

When these samples are developed with CPK-18, Δγ and Dmax become high, which indicates that these samples lack rapid developability because they use emulsions with a high Br ratio. It was also found that there was no difference between the samples with and without gold sensitization.

However, even in the CPK-18 treatment, color turbidity occurred in the blue-sensitive layer (Y color development), and sample 1 of the present invention
．． Dmax did not reach 3, and it is clear that the sample of the present invention is comprehensively superior in terms of high image quality and rapid processing.

Example 2 A blue-sensitive silver halide emulsion was prepared according to the following method.

[Preparation method of blue-sensitive silver halide emulsion] Based on the formulation of EMP-1 used in Example-1, l(
, IrCQ, were added at 2.1 x 10-'' mol 1 mol AgX.

■ K21r, p (1m not added -E
MP-4■ K21rC12,2,1x10-'mol 1
Mol Agx as C solution.

During addition of D solution, rush addition at 90 minutes...EMP-5 ■ K11
rC(1@2.lX IQ-”mol 1 mol AgX to C
Preliminary addition to the liquid...EMP-6 The following compound was added to the above emulsion EMP-4, 5, and 6.
Chemical ripening was performed at °C for an optimum time to obtain blue-sensitive silver halide emulsions (EmA-1 to EmA-18).

Sodium thiosulfate 0.8 mg 1 mol Ag
X Chloroauric acid Holes listed in Table-5
Agent SB-55x 1 (f'7/MobAgXD-
4 (Illustrative sensitizing dye A-2) 0.7X 10-J 1 mol Ag
A silver halide photographic light-sensitive material was obtained by coating with the following layer structure (the green-sensitive emulsion in the third layer was EmB, and the red-sensitive emulsion in the fifth layer was EmC).

These samples were then exposed and processed in the same manner as in Example 1 to obtain the Δγ and Dmax values shown in Table 6.

From Table 6, in comparison, the sample of the present invention has a Δγ.

Both Dmax showed high values, reproducing the fact that gold sensitization has a remarkable effect, and it was found that the effect of the present invention was dependent on the amount of gold compound added. Furthermore, the effect of the present invention is further enhanced by adding an iridium compound (KzlrC (1 g)) during physical ripening, and the addition of an iridium compound is more effective in EMP-6 than in rush addition such as EMP-5. It has been found that the effect is stronger when added to a halide solution such as

Example 3 The same procedure as in Example 2 was carried out for green-sensitive emulsions and red-sensitive emulsions, and the gold-sensitized samples and the iridium compound-added emulsions had high Δγ and high Dmax. -2 results were obtained.

In particular, it was demonstrated that the effect of the present invention was even higher in the sample coated with an emulsion in which an iridium compound was added to the halide solution in advance.

Example 4 After preparing a silver chlorobromide emulsion with a silver chloride content of 99.5 mol% using the same formulation as EMP-6, a silver chloride bromide emulsion was prepared using the same formulation as EMP-6.
Before chemical sensitization according to the description in No. 31, blue-sensitive sensitizing dye D-1 was added in an amount of 5 x 10-' 1 mol AgX, and then silver bromide ultrafine grain emulsion (grain size 0.05 μm) was added.
was added in an amount of 1 mol % in terms of silver, and then the sensitizers shown in Table 7 were added to perform chemical sensitization. (This emulsion is EmA-
19 to EmA-24. )EmA-16 as a comparison, the structures of these prepared emulsions were investigated by X-ray diffraction, electron microscopy, and EDX, and it was found that EmA-16
had a uniform composition from the grain surface to the inside, but it was confirmed that EmA-19 to EmA-24 had a localized silver bromide phase with a high silver bromide content near the grain apex. Ta.

These blue-sensitive silver halide emulsions were coated in the same layer structure as in Example 2 to obtain a silver halide color photographic light-sensitive material. (Samples 37-42) Also, samples 31-3 similar to samples 25-30 of Example-2 using E mA -13-18.
6 was also created.

Samples 31 to 42 were exposed and processed in the same manner as in Example-2, and Δγ and Dmax were determined.

Furthermore, a pressure resistance test was conducted using Samples 25 to 30 as comparative samples. The test was carried out using a Hayton scratch meter equipped with a 0.1+nmI diamond stylus, applying pressure to the surface of the sample by changing the load, and then developing and judging the quality of the pressure resistance based on the load at which fogging occurred. Table 8 shows that samples 37 to 42 having a silver bromide localized phase show the effect of the present invention (high Δγ) compared to samples 32 to 36 of the present invention.
, high Dmax), a similar effect is observed by applying gold sensitization, but it was found that gold sensitization significantly caused Brella shear fog to occur, which was a practical problem.

Samples 32 to 36 of the present invention have high Δγ and high Dmax,
In addition, the occurrence of brella shear fog is also low.

Example-5 Using the blue-sensitive emulsion of the present invention used in Example-2, the green-sensitive emulsion of the present invention and the red-sensitive emulsion of the present invention used in Example-3, the color tone of the layer structure of Example-3 was 4-node agent (WR-1, WB-1
) was coated on polyolefin coated paper which had been treated with white charcoal using the method described in JP-A-53-19021 to obtain a sample.

Using this sample, a commercially available laser printer (approx.
Scanning was performed at a scanning speed of 1.6 m/sec with a laser beam having a beam diameter of 80 μm at a pitch of 100 μm, and the exposure method sample was shown in Example-1. Processing was performed to obtain a color image. The exposure time at this time was calculated to be equivalent to 5×10 −' seconds.

The obtained color image had excellent gradation, high Dmax, and was an excellent color image. In addition, the combination of the photographic base paper used in this example and the removal of the color tone modifier improves the brightness of the white background and provides a color image with an excellent S/N ratio, making it suitable for printing with a laser printer. It was found that the image quality was more favorable.

Claims (1)

[Claims] In a photographic light-sensitive material having a silver halide photographic emulsion layer containing a yellow color-forming coupler, a magenta color-forming coupler, and a cyan color-forming coupler on a reflective support, the silver halide grains contained in the photographic light-sensitive material have odor in the vicinity of the grain vertices. It is a clean silver halide grain having no localized silver phase, and has a silver chloride content of 95 mol% or more of silver chlorobromide, and further has a silver chloride content of 5 x 10^-^ per mol of silver halide. 7~5x
A photographic light-sensitive material that has been gold-sensitized by adding 10^-^4 moles of a gold compound during the chemical sensitization process is 10^-^
- An image forming method characterized in that an image is obtained by exposing for a time of 4 seconds or less and then developing.