JP2519026B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic which is excellent in various characteristics related to silver halide emulsion technology and has a remarkably high degree of perfection. It relates to a photosensitive material.

[Prior Art] Generally, an imagewise exposed silver halide grain is treated with an oxidation product of an aromatic primary amine developing agent and a color former (coupler).
A silver halide photographic light-sensitive material capable of forming a dye image by a coupling reaction with is well known and widely used in the field of color photography.

However, as the times have changed and mass production in laboratories and speeding up are strongly demanded, robustness in various photographic characteristics is required as a silver halide photographic light-sensitive material in order to respond to these advances. It has started to be done.

For example, in color photographic paper, high sensitivity for shortening printing time, resistance to latent image regression due to diversification and complexity of lab work, performance fluctuation during transport and storage of roll and seal photographic paper , Resistance to various process fluctuations due to low replenishment as a measure to reduce running costs in the fogging resistance processing process for rapid processing at high temperature, and scratches and pressure in the automatic processor due to high speed conveyance of the automatic processor. It is desired to improve resistance to increase / decrease sensation caused by. Furthermore, the color photographic paper must satisfy all the items in the above-mentioned various characteristics, and even one of the performances cannot be deteriorated.

Moreover, although the above-mentioned various characteristics seem to be independent of each other, it is well known that if some means for improving the photographic characteristics is adopted, other photographic characteristics are deteriorated.

For example, the use of monodisperse emulsions has recently been attracting attention in order to achieve high sensitivity, but in some emulsions, the storability of samples over time and the temperature dependence during exposure may deteriorate. .

Furthermore, a technique of combining a specific sensitizing dye and a black and white silver halide developing agent in order to improve the above-mentioned storability is disclosed in JP-A 58-58
No. 176637, the effect on the enhancement of sensitivity and stability is insufficient, and the latent image degrading property of some emulsions may be deteriorated.

By the way, adding a compound represented by the general formula [I] of the present invention to a silver halide emulsion layer is
British Patent No. 2,054,187, U.S. Patent No. 3,582,333, No.
No. 3,671,248, No. 3,902,905, No. 3,522,053, and JP-A Nos. 56-52743 and 58-28741. However, these are for the purpose of developing property, prevention of fogging, etc., and there is no description about improvement of sensitivity deterioration during storage with time and other effects in the present invention.

Furthermore, there is a technique for controlling the gradation of particularly a highlight portion (leg portion) by combining a specific phthalate ester high boiling point organic solvent with a silver halide emulsion having a narrow grain size distribution. Although it is proposed in JP-A-58-40550, it is different from the object of the present invention. Furthermore, if the high-boiling organic solvent is applied to such a silver halide grain having a narrow grain size distribution, the coloring property is It only decreased, and no good result was obtained.

As described above, since there are strong reciprocal factors particularly in the improvement of emulsion technology, the development of a silver halide photographic light-sensitive material having a remarkably high degree of perfection from the viewpoint of the above various characteristics is strongly desired at present. is there.

[Object of the Invention] A first object of the present invention is to provide a silver halide photographic light-sensitive material having improved sensitivity, latent image regression resistance, storability of the light-sensitive material, and improved photo identification such as pressure fog. It is in.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having improved processing fluctuation resistance.

A third object of the present invention is to provide a silver halide photographic light-sensitive material excellent in other photographic characteristics.

Other objects of the present invention will be apparent from the following description.

In view of the above-mentioned present situation, the present inventors have made various studies on a silver halide photographic light-sensitive material capable of satisfying all the above-mentioned various characteristics, and as a result, the above-mentioned various objects have been found to be [100].
Planes and [111] planes, and monodisperse silver halide grains having a K value represented by the following formula A in the range of 3 ≦ K ≦ 600, and a high dielectric constant of less than 6.0. At least one silver halide emulsion layer containing a boiling organic solvent
This is achieved by a silver halide photographic light-sensitive material having a layer and containing a compound represented by the following general formula [I].

Expression [A] General formula [I] In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, a sulfonic acid group (including a salt thereof) or a monovalent organic group. A ₁ , A ₂ and A ₃ are each a nitrogen atom, or [R ₄ represents a hydrogen atom, a halogen atom, a sulfonic acid group (including a salt thereof) or a monovalent organic group. ]] Is represented.

X ₁ and X ₂ are each a hydroxyl group or —NR ₅ R ₆
[R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aryl group or an alkylcarbonyl group, respectively, or R ₅
And R ₆ may combine with each other to form a ring. ]] Is represented.

Further, R ₁ , R ₂ , R ₃ and R ₄ may combine with each other to form a ring, and further, at least one of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ and R ₅ And may combine with at least one of the groups represented by R ₆ to form a ring.
n ₁ , n ₂ and n ₃ each represent an integer of 0 to 3.

[Specific Structure of the Invention] The silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the light-sensitive material of the present invention) will be described in detail below.

First, the halogen atom represented by R ₁ , R ₂ , R ₃ and R ₄ in the general formula [I] is, for example, a chlorine atom, a bromine atom or the like, and typical examples of the monovalent organic group are:
For example, hydroxyl group, cyano group, amino group, alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, dodecyl group, benzyl group, phenethyl group, etc.), alkenyl group (eg, propenyl group, etc.), alkoxy group (eg, Methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, allyloxy group, benzyloxy group, etc.), aryl group (for example, phenyl group, tolyl group, naphthyl group, chlorophenyl group, cyclohexylphenyl group, cyanophenyl group, etc.), Aryloxy group (eg, phenoxy group, tolyloxy group, naphthoxy group, chlorophenyloxy group, hydroxyphenyloxy group, etc.), alkylsulfamoyl group (eg, methylsulfamoyl group, ethylsulfamoyl group, benzylsulfamoyl group, etc.) , Arylsul Amoyl group (eg phenylsulfamoyl group, naphthylsulfamoyl group etc.), hydroxycarbonyl group, alkylcarbonyl group (eg methylcarbonyl group, ethylcarbonyl group, pentylcarbonyl group etc.), arylcarbonyl group (eg phenylcarbonyl group, Tolylcarbonyl group, naphthylcarbonyl group, etc.), heterocyclic group (for example, furyl group, thiazolyl group,
Imidazolyl group, succinimide group, benzoxazolyl group, phthalimido group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), heterothio group (eg, thiazolylthio group) , Imidazolylthio group, triazolylthio group, benzoxazolylthio group, benzthiazolylthio group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthyloxy group) Carbonyl group, etc.), alkylcarbonylamino group (eg, methylcarbonylamino group, ethylcarbonylamino group, etc.),
Arylcarbonylamino group (eg, benzoylamino group, naphthoylamino group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, etc.) ,
Alkylacyloxy group (eg acetyloxy group, cyclohexylcarbonyloxy group etc.), arylacyloxy group (eg benzoyloxy group etc.), alkylamino group (eg ethylamino group, dimethylamino group, diethanolamino group etc.), arylamino group ( For example, anilino group etc.), alkylcarbamoyl group (eg ethylcarbamoyl group etc.), arylcarbamoyl group (eg phenylcarbamoyl group etc.), alkylsulfonamide group (eg methylsulfonamide group, ethylsulfonamide group etc.), arylsulfonamide Examples thereof include groups (eg benzenesulfonamide group), cycloalkyl groups (eg cyclohexyl group), cycloalkyloxy groups (eg cyclohexyloxy group) and the like.

In the above general formula [I], R ₁ , R ₂ , R ₃ and R ₄ form a bonding ring, and at least one of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ and R ₅ and R ₆ Examples of the bond ring formed with at least one of the groups represented by: are aromatic rings (eg, benzene ring, naphthalene ring, etc.), cycloolefin rings (eg, cyclohexene ring, etc.), heterocycles (eg, furan ring, imidazole ring, etc.) ) And the like.

The alkyl group represented by R ₅ and R ₆ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.), and these alkyl groups are substituted. When it has a group, as the substituent, a hydroxyl group, a hydroxycarbonyl group, a cyano group, an aryl group (for example, a phenyl group, a tolyl group, etc.), an alkyloxycarbonyl group (for example, an ethoxycarbonyl group, a hexadecyloxycarbonyl group, etc.), Aryloxycarbonyl group (eg, phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylsulfonamide group (eg, methanesulfonamide group, etc.), acylamino group (eg, acetamide group, benzamide group, etc.), alkoxy group ( For example, methoxy group, benzyloxy group, etc.), An aryloxy group (for example, phenoxy group etc.), a sulfonyl group (for example, methanesulfonyl group etc.) and the like can be mentioned.

The aryl group represented by R ₅ and R ₆ is, for example, a phenyl group, a naphthyl group or the like, preferably a phenyl group. When the phenyl group has a substituent, examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), a hydroxyl group, a nitro group, a cyano group, a hydroxycarbonyl group, an alkyl group (a linear or branched alkyl group). Group, for example, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc., alkoxy group (eg methoxy group, ethoxy group, propoxy group) , Butoxy group, pentyloxy group) and the like.

Examples of the alkylcarbonyl group represented by R ₅ and R ₆ include a methylcarbonyl group and a butylcarbonyl group.

Among the compounds represented by the general formula [I] used in the present invention, the compounds represented by the following general formula [II] or [III] can be preferably used.

General formula [II] In the formula, R ₇ represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), or an aryl group (preferably a phenyl group), and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each Hydrogen atom, alkyl group (preferably having 1 carbon atom)
~ 4 alkyl group), an aryl group (preferably a phenyl group), or a hydroxyl group. The alkyl group may have a substituent, and as the substituent, for example, a halogen atom, a hydroxyl group, a carboxyl group,
An amino group etc. can be mentioned. The aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group and a hydroxycarbonyl group.

General formula [III] In the formula, R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom, a halogen atom, a sulfonic acid group (including a salt thereof), or a monovalent organic group.

However, at least one of R ₁₂ , R ₁₄ and R ₁₆ is a hydroxyl group or —NR ₁₇ R ₁₈ (R ₁₇ and R ₁₈ have the same meanings as R ₅ and R ₆ in the above formula [I], respectively. )
Is. Further, R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may combine with each other to form a ring.

Further, the monovalent organic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is represented by R ₁ , R ₂ , R ₃ and R ₄ in the general formula [I].
It has the same meaning as the monovalent organic group represented by.

Among the compounds represented by the general formula [III], the compound represented by the following general formula [IV] is more preferable.

General formula [IV] In the formula, R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an alkylcarbonyloxy group or an alkyloxycarbonyl. Represents a group.

In the general formula [IV], examples of the alkyl group represented by R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and a hydroxyethyl group. As the alkoxy group, for example, a methoxy group, an ethoxy group, a butoxy group and the like can be mentioned, as the cycloalkyl group, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and as a cycloalkyloxy group, for example , A cyclopentyloxy group, a cyclohexyloxy group and the like, the aryl group includes, for example, a phenyl group, a hydroxyphenyl group, a tolyl group and the like, and the aryloxy group includes, for example, a phenoxy group and a tolyloxy group. As the alkylcarbonyloxy group,
Examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, and the like, and examples of the alkyloxycarbonyl group include a methyloxycarbonyl group, a propylethyloxycarbonyl group, a propyloxycarbonyl group, and the like. Further, R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ may combine with each other to form a ring.

Next, specific examples of the compound represented by the general formula [I] will be listed, but the compounds are not limited to these.

The compound represented by the general formula [I] (hereinafter referred to as the compound [I] of the present invention) used in the present invention is a compound known as a developing agent in the art except for a part thereof, and can be easily prepared by a known method. Can be synthesized.

To incorporate the compound [I] of the present invention into a silver halide photographic light-sensitive material, it is dissolved in water or an organic solvent which is optionally miscible with water (for example, methanol, ethanol, etc.) or an organic solvent ( It may be dissolved in water (not necessarily miscible) and then dispersed in a hydrophilic colloid or added as a solution or dispersion. The addition amount is preferably 1.0 × 10 ^{−4 to} 1.0 mol, and more preferably 1.2 × 10 ^{−3 to} 1.0 × 10 ⁻¹ mol, per mol of silver halide. The time of addition may be any time from the time of preparation of the silver halide emulsion to the time of coating, but it is preferably the time from the completion of chemical ripening of the silver halide emulsion to the time of coating.
The place of addition may be any layer of a light-sensitive silver halide emulsion layer or a non-light-sensitive hydrophilic colloid layer, but is preferably a layer containing the light-sensitive silver halide emulsion used in the present invention, or It can be added in the non-photosensitive hydrophilic colloid layer adjacent to the emulsion layer.

Next, the silver halide grains according to the present invention will be described.

The "monodisperse silver halide grains" used in the present specification mean that the shape of each silver halide grain looks uniform when the emulsion is observed by an electron micrograph, and the grain size is uniform, and The ratio S / of the standard deviation S of the particle size distribution to the average particle size is 0.20 or less. The standard deviation S of the particle size distribution is calculated according to the following equation.

Further, the average grain size referred to here is, in the case of spherical silver halide grains, the diameter thereof, or in the case of grains having a shape other than a cube or a sphere, when the projected image is converted into a circular image having the same area. The mean value of the diameters, where each particle size is ri and the number is ni, defined as:

The above particle diameter can be measured by various methods generally used in the technical field for the above purpose. As a typical method, Loveland's “Particle Size Analysis Method”, ASTM Symposium on Light Microscopy, 1955, pp. 94-122 or “Theory of Photographic Processes” co-authored by Mies and James,
It is described in Chapter 2 of the third edition, published by Macmillan Company (1966). This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The relationship between grain size distributions is described in "The Empirical Relationship between Sensitometric and Grain Size Distributions in Photographic Emulsions", The Photographic Journal, Volume LXXIX, (1949), pages 330-338, Tribelli and Smith. You can determine this in the manner described.

The average particle size of the monodisperse particles used in the present invention is not particularly limited in essence of the invention, but is preferably 0.1 to 2.0 μm when measured according to the above method,
More preferably, it is in the range of 0.2 to 1.6 μm.

[100] face and [111] face of the silver halide grain according to the present invention
The ratio of planes corresponds to the [100] plane of the silver halide grain using Cu-Ka rays as X-rays in X-ray diffraction analysis [20].
The intensity of the diffraction lines (observed at diffraction angles (2θ) of about 30.9 ° and 55.0 °, respectively) attributed to the [222] plane corresponding to the [0] plane and the [111] plane were measured, and their ratios were measured. K
Is determined according to the following formula, the value is preferably 3 ≦ K ≦ 600, more preferably 10 ≦ K ≦ 400,
Particularly preferably, those having a range of 20≤K≤200 are used. Incidentally, the definition of the surface of the silver halide grain in the present invention is described, for example, in “Bretan of the Society.
Powder Scientific X-ray Diffraction Analysis of Emulsions Containing Silver Halide Grains Oriented and Applied on a Base Plate, as described in "Scientific Photography of Japan", Vol. 13, page 5. According to the diffraction diagram obtained by.

The composition of the silver halide grains according to the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. From the viewpoint of sensitivity, developability and desilvering property, silver chlorobromide can be preferably used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure having different inside and outside.

The silver halide grains according to the present invention can be prepared by controlling pAg, temperature, addition rate or the like or by selecting various grain forming conditions, and can be prepared by a normal single jet method or a double jet method. it can. Any of known methods such as an acid method, a neutral method, an ammonia method, and a conversion method may be used, and a reverse mixing method may be used. Further, the silver halide grains of the present invention may be so-called core / shell type silver halide grains.

Further, these silver halide grains may be of a type in which a latent image is mainly formed on the surface or may be of a type in which the latent image is formed inside the grain.

As the high boiling point organic solvent used in the present invention, any compound having a dielectric constant of less than 6.0 can be used. The lower limit is not particularly limited, but the dielectric constant is preferably 1.9 or more. For example, phthalates with a dielectric constant of less than 6.0,
Examples include esters such as phosphoric acid esters, organic acid amides, ketones, and hydrocarbon compounds.

Further, in the present invention, it is preferably a high boiling organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less. More preferably, the phthalic acid ester or phosphoric acid ester in the high boiling point organic solvent is used. The organic solvent is
It may be a mixture of two or more kinds, and in this case, the dielectric constant of the mixture may be less than 6.0. The dielectric constant in the present invention indicates the dielectric constant at 30 ° C. Examples of the high boiling point organic solvent that can be used in combination in the present invention include dibutyl phthalate, dimethyl phthalate, tricresyl phosphate, tributyl phosphate and the like.

Examples of the phthalic acid ester advantageously used in the present invention include those represented by the following general formula [V].

General formula [V] In the formula, R ₂₃ and R ₂₄ each represent an alkyl group, an alkenyl group or an aryl group. However, R ₂₃ and R ₂₄
The total number of carbon atoms of the group represented by is 9 to 32.
More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, the alkyl groups represented by R ₂₃ and R ₂₄ in the above general formula [V] are linear or branched, and include, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. , Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. The aryl group represented by R ₂₃ and R ₂₄ is a phenyl group, a naphthyl group and the like, and the alkenyl group is a hexenyl group, a heptenyl group, octadecenyl and the like. These alkyl group, alkenyl group and aryl group may have a single or a plurality of substituents, the substituent of the alkyl group and alkenyl group,
Examples thereof include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an alkenyl group. , And an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

Examples of the phosphoric acid ester advantageously used in the present invention include those represented by the following general formula [VI].

General formula [VI] In the formula, R ₂₅ , R ₂₆ and R ₂₇ each represent an alkyl group, an alkenyl group or an aryl group. However, R
The total number of carbon atoms represented by ₂₅ , R ₂₆ and R ₂₇ is 24 to 54.

The alkyl group represented by R ₂₅ , R ₂₆ and R ₂₇ in the general formula [VI] is, for example, a butyl group, a pentyl group, a hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like.

These alkyl group, alkenyl group and aryl group may have a single or a plurality of substituents. Preferably R ₂₅ , R ₂₆ and R ₂₇ are alkyl groups, for example, 2-ethylhexyl group, n-octyl group, 3,5,5-
Trimethylhexyl group, n-nonyl group, n-decyl group,
Examples thereof include a sec-decyl group, a sec-dodecyl group, a t-octyl group and the like.

Specific examples of the organic solvent according to the present invention are shown below, but the present invention is not limited thereto.

Exemplified organic solvent The high boiling organic solvent according to the present invention can be used in an amount of 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, per 1 mol of silver halide.

The method of incorporating a high-boiling point organic solvent having a dielectric constant of less than 6.0 in the silver halide emulsion layer according to the present invention includes, for example, at least one of the high-boiling point organic solvents, or at least one of the high-boiling point organic solvents and a coupler, and an ultraviolet ray. After mixing and dissolving with a low boiling point organic solvent, if necessary, together with a hydrophobic additive such as an absorber, a dye image stabilizer and a color mixing inhibitor,
It can be added to a silver halide emulsion after being mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed using a high speed rotating mixer, a colloid mill or an ultrasonic disperser.

The emulsion containing the silver halide grains according to the present invention may or may not be physically ripened,
The emulsion is usually prepared after precipitation formation or after physical ripening.
Water-soluble salts are removed, and as a means used for that purpose, inorganic salts having polyvalent anions (for example, ammonium sulfate and magnesium sulfate), anionic surfactants can be used even if the noodle washing method which has been known for a long time is used. Alternatively, a precipitation method using polystyrene sulfone, another anionic polymer, or a gelatin derivative such as an aliphatic- or aromatic-acylated gelatin may be used.

The above emulsion used in the present invention can be chemically sensitized by a method commonly used by those skilled in the art. For example, The Theory of Photographic P by Mees
The method described in the textbook such as rocess) or other known methods can be used. That is, a compound containing sulfur capable of reacting with silver ions, such as thiosulfate, or U.S. Patent Nos. 1,574,944 and 2,278,947.
No. 2, No. 2,410,689, No. 3,189,458, No. 3,501,31
3, the compounds described in French Patent No. 2,059,245 and the like, or a sulfur sensitizing method using active gelatin, and reducing substances, for example, stannous salts described in US Pat. No. 2,487,850, US patents. No. 2,518,698, No. 2,5
No. 21,925, No. 2,521,926, No. 2,419,973, No. 2,
Amines described in U.S. Pat.
Iminoaminomethanesulfinic acids described in No. 83,610,
Silane compounds described in U.S. Pat. No. 2,694,637, or the first volume of the Journal of Photographic Science (1953)
The reduction sensitization method by the method of HW Wood described on page 163 or below, or the gold sensitization method using gold salt or gold thiosulfate described in US Pat. No. 2,399,083, etc. may be used alone or in combination. it can. Also, instead of or in addition to the sulfur sensitization method, U.S. Pat.
The selenium sensitization method described in the publication can also be used. Among the chemical sensitization methods that can be used in the present invention, the sulfur sensitization method is particularly preferably used.

The light-sensitive material of the present invention is preferably spectrally sensitized using various optical sensitizers in addition to the above-mentioned sensitizers. As the optical sensitizer used for this purpose, for example, cyanine dyes, merocyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes are known, but particularly useful dyes are cyanine dyes and merocyanine dyes. is there. These sensitizing dyes may be used alone or in combination.

Particularly, examples of the sensitizing dye contained in the color light-sensitive material include, for example, U.S. Pat. Nos. 2,526,632 and 2,503,776.
No. 2,493,748, 3,384,486, 3,480,43
No. 4, No. 3,573,916, and No. 3,582,338, etc. are described in detail.

The silver halide emulsion used in the present invention may be a so-called surface latent image type emulsion having a photosensitive nucleus formed on the grain surface by the chemical ripening, or after the photosensitive nucleus is formed,
Further, it may be an internal latent image type emulsion in which a silver halide is precipitated to have a photosensitive nucleus inside the grain. The internal latent image type emulsion may of course be an emulsion prepared by a conversion method without chemical ripening.

In the silver halide emulsion used in the present invention, gelatin is advantageously used as a protective colloid, and in this case, inactive gelatin is particularly advantageous. Further, a photographically inactive gelatin derivative (eg, phthalated gelatin) can be used in place of gelatin.

The silver halide emulsion used in the present invention contains tetrazaindenes, mercapto, for the purpose of preventing fog during the production process, storage of the light-sensitive material, or at each stage of development processing, or stabilizing photographic performance. A compound such as tetrazole may be contained.

The coupler contained in the silver halide photographic light-sensitive material of the present invention is any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidized product of a developing agent. Can also be used, but the following are particularly representative.

As a coupler for forming a coupling product having a spectral absorption maximum wavelength in a wavelength range of 350 nm to 500 nm, those known to those skilled in the art are typically known as so-called yellow couplers, for example, U.S. Pat.No. 2,186,849, No. 2,322,027, No. 2,728,685, No. 2,875,057,
No. 3,265,506, No. 3,277,155, No. 3,408,194
No. 3,415,652, No. 3,447,928, No. 3,664,84
No. 1, No. 3,770,446, No. 3,778,277, No. 3,849,1
No. 40, No. 3,894,875, British Patent No. 778,089, No. 80
No. 8,276, No. 875,476, No. 1,402,511, No. 1,42
Specifications of 1,126 and 2,513,832 and Japanese Patent Publication No. 49
-13576, JP-A-48-29432, 48-66834, 49-107
36, 49-122335, 50-28834, 50-132926
No. 50, No. 50-138832, No. 51-3631, No. 51-17438, No. 51
-26038, 51-26039, 51-50734, 51-53825
No. 51, No. 51-75521, No. 51-89728, No. 51-102636, No. 5
1-107137, 51-117031, 51-122439, 51-143
No. 319, No. 53-9529, No. 53-82332, No. 53-135625,
53-145619, 54-23528, 54-48541, 54-65
No. 035, No. 54-133329, No. 55-598.

As a coupler that forms a coupling product having a spectral absorption maximum wavelength in the wavelength range of 500 nm to 600 nm, one known in the art as a so-called magenta coupler is typical, for example, U.S. Pat.No. 1,969,479. , The same
No. 2,213,986, No. 2,294,909, No. 2,338,677, No. 2,340,763, No. 2,343,703, No. 2,359,332,
No. 2,411,951, No. 2,435,550, No. 2,592,303
No. 2, No. 2,600,788, No. 2,618,641, No. 2,619,41
No. 9, No. 2,673,801, No. 2,691,659, No. 2,803,5
No. 54, No. 2,829,975, No. 2,866,706, No. 2,881,
No. 167, No. 2,895,826, No. 3,062,653, No. 3,12
No. 7,269, No. 3,214,437, No. 3,253,924, No. 3,3
No. 11,476, No. 3,419,391, No. 3,486,894, No. 3,
No. 519,429, No. 3,558,318, No. 3,617,291, No. 5
3,684,514, 3,705,896, 3,725,067, 3,888,680, British Patent 720,284, 737,700
No. 813,866, 892,886, 918,128,
No. 1,019,117, No. 1,042,832, No. 1,047,612
No. 1,398,828 and 1,398,979 specifications,
West German Patent Publication No. 814,996, No. 1,070,030, Belgian Patent No. 724,427, JP-A-46-60479, No. 49-29639,
49-111631, 49-129538, 50-13041, 50-1
16471, 50-159336, 51-3232, 51-3233,
51-10935, 51-16924, 51-20826, 51-265
No. 41, No. 51-30228, No. 51-36938, No. 51-37230, No. 51-37230
51-37646, 51-39039, 51-44927, 51-10434
No. 4, No. 51-105820, No. 51-108842, No. 51-112341,
51-112342, 51-112343, 51-112344, 51-
117032, 51-126831, 52-31738, 53-9122
No. 53, No. 53-55122, No. 53-75930, No. 53-86214, No. 53
-125835, 53-123129, 54-56429 and 57-3
5,858 and various publications and research disclosure magazines (1
(June 984) Volume 242, paragraphs 24,220 and 24,230.

As a coupler that forms a coupling product having a spectral absorption maximum wavelength in the wavelength range of 600 nm to 750 nm, one known in the art as a so-called cyan coupler is typical, and U.S. Pat. 2,356,475
Issue No. 2,362,598, No. 2,367,531, No. 2,369,92
No. 9, No. 2,423,730, No. 2,474,293, No. 2,476,0
No. 08, No. 2,498,466, No. 2,545,687, No. 2,728,
No. 660, No. 2,772,162, No. 2,895,826, No. 2,97
No. 6,146, No. 3,002,836, No. 3,419,390, No. 3,4
46,622, 3,476,563, 3,737,316, 3,
No. 758,308, No. 3,839,044, British Patent No. 478,991,
No. 945,542, No. 1,084,480, No. 1,377,233,
Nos. 1,388,024 and 1,543,040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, and
50-112038, 50-117422, 50-130441, 51-65
No. 51, No. 51-37647, No. 51-52828, No. 51-108841,
53-109630, 54-48237, 54-66129, 54-13
1931 and 55-32071.

Further, the silver halide emulsion layer containing the silver halide grains according to the present invention may further contain silver halide grains other than the silver halide grains according to the present invention. The ratio of silver halide grains to all grains is preferably 50% or more, more preferably 80% by weight.
It is above, and more preferably 100%.

The silver halide photographic light-sensitive material used in the present invention is produced by coating a silver halide photographic emulsion layer and, if necessary, a non-photosensitive layer on a support. It is preferable to use a reflective support in order to achieve the effects of the present invention. As the support, for example, a film of paper, baryta paper, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, or the like, or two or more types of substrates such as a laminate of paper and polyolefin (polyethylene, polypropylene, etc.) A laminated film or the like is used. Then, this support may be subjected to various surface modification treatments in order to improve the adhesion to the silver halide emulsion. For example, those subjected to surface treatment such as electron impact treatment or undercoating treatment for providing an undercoat layer are used. Of the above-mentioned supports, it is preferable to use either baryta paper, polyethylene-coated paper, titanium oxide-containing polyethylene terephthalate support, electron beam-curable resin-coated paper or polypropylene paper.

To coat and dry a silver halide emulsion on this support, a commonly known coating method, for example, a dip coating method,
It is applied by a method such as a roller application method, a bead application method or a curtain flow application method, and then dried.

The layers constituting the silver halide photographic light-sensitive material of the present invention basically include, as light-sensitive layers, a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion. Layer, an intermediate layer as a non-photosensitive layer, a protective layer,
There are various photographic component layers such as filter layers, antihalation layers, backing layers and the like. In this case, each photosensitive emulsion layer may be composed of a mixture of two or more kinds of silver halides having different sensitivities, or may be composed of two or more kinds of layers.

More specifically, the multicolor silver halide color photographic light-sensitive material of the present invention comprises a blue-sensitive layer, a non-photosensitive layer (first intermediate layer), a green-sensitive layer and a non-photosensitive layer (second An intermediate layer), a red-sensitive layer, a non-photosensitive layer containing an ultraviolet absorber (third intermediate layer) and a protective layer may be used.

After exposing the photographic light-sensitive material of the present invention, various photographic processing methods are used for color development. The processing temperature and time are
The temperature is appropriately set, and the temperature may be room temperature, or lower than room temperature, for example, 18 ° C. or lower, or higher than room temperature, higher than 30 ° C., for example, around 40 ° C., or even higher than 50 ° C. The temperature in the high-temperature rapid processing is 33 ° C. or higher, but the effect of the present invention can be obtained in this case as well.

For color development, as a color developing agent, for example, N, N-
Dimethyl-p-phenylenediamine, N, N-diethyl-
p-phenylenediamine, N-carbamidomethyl-N-
Methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N-carboxymethyl-2-methyl-p-phenylenediamine, N-carbamidomethyl- N-ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2
-Methyl-p-aminophenol, 3-acetylamino-2-aminodimethylaniline, N-ethyl-N-β-
Methanesulfonamidoethyl-4-aminoaniline, N
-Ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-aminoaniline, sodium salt of N-methyl-N-β-sulfoethyl-p-phenylenediamine and the like can be used.

The silver halide photographic light-sensitive material of the present invention may contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer. Color developing agent precursor is a compound capable of forming a color developing agent under alkaline conditions, a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include sugar amine reactant precursors and urethane type precursors. The precursors of these aromatic primary amine color developing agents are described in, for example, US Pat.
No. 599, No. 2,507,114, No. 2,695,234, No. 3,71
9,492, British Patent 803,783, JP-A-53-135628,
54-79035, Research Disclosure
15,159, 12,146, and 13,924.

It is necessary to add these aromatic primary amine color developing agents or their precursors in an amount such that sufficient color can be obtained during development processing. This amount varies largely depending on the type of the light-sensitive material, but is generally between 0.1 and 5 mol, preferably 0.5 mol, per mol of the light-sensitive silver halide.
It is used in the range of 3 to 3 moles. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone or the like, and it can be added in a high solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate. It may be added as an emulsified dispersion using a boiling point organic solvent, or may be added by impregnating a latex polymer as described in Research Disclosure, Item 14850.

The silver halide photographic light-sensitive material of the present invention is usually bleach-fixed and washed with water after color development processing. Many compounds are used as bleaching agents, among which iron (II
I), cobalt (III) and other polyvalent metal compounds, among others,
Complex salts of these polyvalent metal cations and organic acids, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid, diglycolic acid, dithio. Metal complex salts such as glycolic acid, ferricyanates, dichromates, etc. may be used alone or in an appropriate combination. Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto.

[Examples] Example 1 A silver halide formed by a double jet method with silver chlorobromide (containing 30 mol% of silver chloride) having an average particle size of 0.42 µ and having [100] faces and [111] faces. Monodisperse emulsion A consisting of grains (S / = 0.11), monodisperse emulsion B consisting of octahedral crystals
(S / = 0.13), monodisperse emulsion C (S /
= 0.13) and polydisperse (S / = 0.34) twin emulsion D were prepared, respectively.

To each of the above emulsions A, B, C and D, sodium thiosulfate and a sensitizing dye shown below were added in an amount of 3 × 10 ^-4 mol per mol of the above-mentioned silver chlorobromide to obtain the optimum emulsion. Chemical sensitization and spectral sensitization were performed under the conditions.

The following dispersions of cyan couplers, the following hardeners and coating aids were added to each emulsion thus obtained to prepare coating solutions. The amount of hardener added is 0.01 g /
It was 1 g of gelatin.

The addition amount of the compound [I] in the coating solution is 1 mol of silver chlorobromide.
It was 8 × 10 ⁻³ mol per mol.

Then, a coating solution having the following composition and a coating solution for a gelatin protective layer were coated on polyethylene-coated paper and dried to prepare Samples 1 to 9.

<Cyan coupler> <Sensitizing dye> The following tests (1) to (5) were performed on the obtained samples.

(1) Sensitometric characteristic test Nine kinds of coated samples were subjected to a sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.
After exposing red light through the optical wedge using KS-7 type),
The treatment was performed according to the following treatment steps.

[Color developer composition] Pure 700 ml Benzyl alcohol 15 ml Diethyl alcohol 15 ml Hydroxyamine sulfate 2 g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.4g Potassium carbonate 30g Potassium bromide 0.4g Potassium chloride 0.5g Potassium sulfite 2g Add pure water to make it 1 (pH = 10.2) [Bleaching fixer composition] Ethylenediaminetetraacetic acid ammonium ammonium 61g Ethylenediaminetetraacetic acid 2ammonium 5g Ammonium thiosulfate 125g Sodium metabisulfite 13g Sodium sulfite 2.7g Add water to make 1 (pH = 7.2) For each sample obtained, relative sensitivity and minimum reflection density (fog) Photoelectric density It was measured using a total (PDA-60 type manufactured by Konishi Rokusha Kogyo Co., Ltd.).

(2) Latent image degradability As in (1) above, the sample exposed through the optical wedge was
After standing for 24 hours under the conditions of ° C and 20% RH, the treatment and the concentration measurement were carried out in the same manner as in the above (1). The magnitude of latent image regression is represented by the density value after standing when the density when processed immediately after exposure is 1.0.

(3) Preservation property with time After leaving the sample under conditions of 40 ° C and 80% RH for 10 days, exposure, treatment and measurement were performed in the same manner as in (1) above, and the sensitivities before and after aging were compared to obtain a ratio. Displayed as (%).

(4) Pressure effect test during wetting After exposing the exposed sample to pure water at 33 ° C. for 3 minutes,
Using a Haydon Scratch Strength Tester Model 18 (manufactured by Shinto Kagaku Co., Ltd.), scratches are performed at each load of 5, 10, 20, 30 and 50 g. After the sample was dried and subjected to the same treatment as described above, the load required for the occurrence of increase / decrease (sensitization was indicated by + and desensitization was indicated by −) was examined.

(5) Processing fluctuation resistance test The amount of potassium bromide in the color developer composition is 1.0 /
A sensitometric characteristic test of (1) above was performed using a color developing solution having the same composition as that of the color developing solution except that the composition was changed to 1. The ratio (%) of the sensitivity obtained in the test of (5) to the sensitivity obtained in the test of (1) above is shown as a treatment variation resistance test.

The results obtained in each of the tests (1) to (5) are shown in Table 2.

From Table 2 above, there is a tendency that the storage stability with time is improved by the use of the compound (I), but with respect to Samples 2 and 9 outside the present invention, not only the degree of the improvement is small but also the latent image degrading property is deteriorated. have done. Further, in Samples 8 and 9 using the polydisperse silver halide emulsion, the sensitivity was low and the degree of fog was large. On the other hand, in Samples 4 and 5 of the present invention, the latent image degrading property is improved rather than deteriorated even though the compound (I) is used, and at the same time, it shows a great effect on the storage stability over time. . Further, the other photographic characteristics of Samples 4 and 5 of the present invention are also at a sufficiently satisfactory level, and it is clear that there is no defect in various performances and the degree of perfection is extremely high. Sample 6 was prepared from a monodisperse emulsion consisting of octahedral crystals, but this sample is inferior in pressure effect and processing fluctuation resistance. Further, in Sample 7 prepared from the monodisperse emulsion composed of cubic crystals, the fog was slightly increased, and the sensitivity was insufficient. Also, the pressure effect and fluctuation resistance are poor.

Example 2 A sample was prepared with the layer structure shown in Table 3 below.

Samples 1 to 5 were prepared by changing the above sample as follows.

Further, the three kinds of silver halide emulsions used here were prepared as follows.

<Red Sensitive Emulsion> Using the emulsion A in Example 1, the cyan coupler is the cyan coupler and the following cyan coupler is 1: 1 by weight.
It was prepared in the same manner as in Example 1 except that the above was used in combination.

<Green Sensitive Emulsion> Emulsion A in Example 1 was used, and a sensitizing dye and a coupler were prepared in the same manner as in Example 1 except that the compounds shown below were used.

(Sensitizing dye) (Magenta coupler) <Blue Sensitive Emulsion> Using emulsion A in Example 1, a sensitizing dye and a coupler were prepared in the same manner as in Example 1 except that the compounds shown below were used.

(Sensitizing dye) (Yellow coupler) (UV absorber) Table 4 shows the results obtained by performing the same tests (1) to (5) as in Example 1 on the obtained five types of samples except that the exposure was performed using white light.

From Table 4, it was confirmed that the improving effect of the present invention can be exerted even in a multilayer sample composed of a plurality of silver halide emulsions. Further, it was clearly found that the compound (1) -added layer was obtained in the same manner whether it was added to the silver halide emulsion layer or the intermediate layer.

Other than changing the pAg value when silver halide grains are produced,
The following monodisperse emulsions E to H were prepared in the same manner as in Example 1.

Emulsion name Average grain size K value E 0.42 μ 1.1 F 0.42 μ 9.3 G 0.42 μ 320 H 0.42 μ 980 The above emulsions D to G and emulsions A to C of Example 1 were chemically sensitized in the same manner as in Example 1. , And spectral sensitization.

Using the emulsion thus obtained, the composition of Table 5 was used to prepare Sample 11
~ 17 created. However, I-26 was used as the compound (I) and H-6 according to the present invention was used as the high-boiling point organic solvent, and the same constitution as in Example 1 was used. The obtained sample was evaluated for sensitometry, latent image degrading property, storability with time, pressure effect at the time of wetting, and process fluctuation resistance by the same method as in Example 1. The results are shown in Table 5.

From the above results, only when the K value is within the range of the present invention,
It can be seen that there are no defects in various performances and the degree of perfection is high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kaoru Onodera 28, Horinouchi, Odawara City, Konishi Roku Photo Industry Co., Ltd. (56) References JP-A-58-28741 (JP, A) JP-A-58-40550 (JP) , A) Japanese Patent Laid-Open No. 58-50533 (JP, A) edited by The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Salt Photographed Edition" (issued on January 30, 1979), Corona Publishing Co., Ltd., No. 150. Page to page 169

Claims (1)

(57) [Claims] 1. A monodisperse silver halide grain having a [100] plane and a [111] plane and having a K value represented by the following formula A in the range of 3 ≦ K ≦ 600, and Dielectric constant is 6.
A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a high-boiling organic solvent having a value of less than 0 and containing a compound represented by the following general formula [I]. Expression [A] General formula [I] In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, a sulfonic acid group (including a salt thereof) or a monovalent organic group. A ₁ , A ₂ and A ₃ are each a nitrogen atom, or [R ₄ represents a hydrogen atom, a halogen atom, a sulfonic acid group (including a salt thereof) or a monovalent organic group. ]] Is represented. X ₁ and X ₂ are a hydroxyl group or —NR ₅ R ₆ [R
₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or an alkylcarbonyl group, or R ₅ and R ₆ may combine with each other to form a ring. ]] Is represented. Further, R ₁ , R ₂ , R ₃ and R ₄ may combine with each other to form a ring, and further, at least one of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ and R ₅ and It may combine with at least one group represented by R ₆ to form a ring. n ₁ , n ₂
And n ₃ each represent an integer of 0 to 3.