JPS62253144A - Silver halide color photographic sensitive material having improved pressure resistance - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity, little fog and superior pressure resistance by specifying the pAg of a specified silver chloride phase and the pAg of a specified silver bromide phase in a silver halide emulsion layer having a high silver chloride content. CONSTITUTION:At least one emulsion layer of this sensitive material contains silver halide particles having <=80mol% silver chloride content as a whole and contg. a phase having <=95mol% silver chloride content and a phase having <=80mol% silver bromide content. The pAg of the former phase is 3.0-6.5 and the pAg of the latter phase is 5.0-7.0. The preferred difference between both the pAg values is <=0.5, especially 1-1.5. The pAg values are controlled with silver nitrate, sodium chloride or potassium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field 1 The present invention relates to ``silver halide color photographic photosensitive material 11'', particularly a silver halide color photographic photosensitive material with high sensitivity, low fog, and excellent pressure resistance. Regarding 1.

[Background of the Invention] Concerning applying chemical sensitization to the surface of internal latent image type silver halide grains capable of preferentially forming a latent image inside the silver halide grains, and using the resulting product as a negative-working silver halide emulsion. , various proposals have been made.

Specifically, Japanese Patent Publication No. 5G-36978 discloses that the surface of internal latent image type silver halide grains formed by a conversion method is chemically sensitized to contain a color coupler. It is also disclosed that by incorporating a color coupler into this type of so-called conversion emulsion, a color photographic material having high sensitivity, good river edge properties, and high gradation can be obtained. however,
This type of conversion emulsion may cause fog in unexposed areas when pressure is applied to the photographic material.
A particularly serious problem is that the image density decreases or increases in exposed areas.

This point is also described in JP-A-59-140444%. Furthermore, the results of extensive studies on conversion emulsions by the present inventors show that conversion emulsions cause a significant decrease in image density (desensitization), especially in exposed areas, when a photographic light-sensitive material is subjected to strong pressure before being exposed. Moreover, after being exposed to light, especially when subjected to strong pressure in a developer, it is easy to increase the image density in image areas or cause significant fogging (sensitization) in non-image areas. there were.

JP-A No. 52-18309 discloses a method in which a silver salt and a halide salt are reacted on silver halide grains which are partially composed of a sparingly soluble silver salt having at least a larger solubility product. A method for preparing silver halide emulsions with partial conversion of silver grains is presented.

The silver halide emulsion thus obtained has high sensitivity and a high maximum density.

However, even with the silver halide emulsion obtained in this way, if unfavorable pressure is applied before or after imagewise exposure, although it is somewhat improved compared to the conversion emulsion, it still exhibits poor photographic performance. It has unfavorable performance problems. , especially when receiving 1 before imagewise exposure.
-J has little effect on desensitization to pressure.

JP-A-60-136735 discloses a method for producing a silver halide emulsion in which a shell consisting of silver bromide is formed on a core consisting essentially of silver chloride after lowering rlAg. It is characterized as a silver halide having two distinct layers of halide composition. However, regarding the silver halide emulsion of this scale, there is no mention of chemical sensitization of the silver halide grain surface, nor is there any mention of the pressure resistance of the silver halide emulsion. Further, the halogen composition of the shell is substantially only silver bromide, and in the examples pure silver bromide is used for the shell.

[Object of the present invention] An object of the present invention is to solve the problems of the prior art described above, and to provide a silver halide color photographic light-sensitive material that has high sensitivity, low fog, and excellent pressure resistance. It is in.

[Structure of the Invention] The object of the invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers contains silver chloride as a whole. phase having a silver chloride content of 80 mol% or more and a silver chloride content of 95 mol% or more and a silver bromide content of 80 mol% or more.
containing silver halide grains having a phase of mol % or more,
In the silver halide grains, a phase having a silver chloride content of 95 mol% or more is formed in the range of l)A 113.0 to 6.5, and a phase having a silver bromide content of 80 mol% or more is formed in the range of I)A. (15,0～
7.0.

[Specific structure of the invention] The present invention will be explained in detail below.

The silver halide grains used in the present invention (hereinafter referred to as silver halide grains of the present invention) have a total silver chloride content of 80
It is mol% or more, and preferably in the range of 85 mol% or more to 99 mol%.

The silver chloride content in the silver halide grains of the present invention is 95
It is particularly preferable that the phase containing 97 to 100 mol % of silver chloride is contained in the mol % or more phase.

It is particularly preferable that the phase having a silver bromide content of 80 mol % or more in the silver halide grains of the present invention contains 90 to 100 mol % of silver bromide.

The silver halide grains of the present invention particularly preferably have a core-shell type structure in which a phase with a silver chloride content of 95 mol% or more is arranged in the core part and a phase with a silver bromide content of 80 mol% or more is arranged in the shell part. .

Further, the silver halide grains of the present invention can also form three or more phases or three or more phases or three or more phases by mole % or more.

The thickness of the phase with a silver bromide content of 80 mol% or more is preferably 0.001 to 0.02 up, and the thickness of the phase with a silver chloride content of 95 mol% or more (abbreviated as B) is preferably 0.001 to 0.02 up. The condition of −□≧0.95 A+8 is preferable.

The silver halide grains of the present invention have a silver chloride content of 95 mol%
The above phase is IIA (formed in the range of 13.0 to 6.5, and the phase with a silver oxide content of 80 mol% or more is pAgs, o
-70.

In particular, IIA (1 (hereinafter referred to as +1A!+(R)) and silver bromide content of 8 when forming a phase with a silver chloride content of 95 mol% or more
In the relationship of IIIAIIJ (hereinafter referred to as Mg (A)) when a phase of 0 mol% or more is formed, △pΔa=p△a (13>-pAc+ (△)), ΔpA (l is 0.5 It is preferably 1 or more and 1.5 or less, particularly preferably 1 or more and 1.5 or less.

To control 11AQ, silver nitrate, sodium chloride, or potassium chloride is preferable.

When forming the silver halide grains of the present invention, the pH is 4.
The following is preferable, and the temperature is preferably 40 to 60°C.

The silver halide grains of the present invention may be used alone or in combination with other silver halide grains.

When the silver halide grains of the present invention are used in combination with silver halide grains other than the present invention, the total projected area occupied by all the silver halide grains of the silver halide emulsion layer containing the silver halide grains of the present invention is The ratio of the projected area occupied by the silver halide grains of the invention is preferably 50% or more, more preferably 75% or more.

Silver halide emulsion using silver halide grains of the present invention (
Hereinafter, this will be referred to as the silver halide emulsion of the present invention. ) is a mixture of halide ions and silver ions at the same time, and while considering the critical growth rate of silver halide crystals, the pH in the mixing pot, 1) A (I is controlled by the controller). In order to make the particle size distribution uniform, it is preferable to generate the particles by sequentially adding them at the same time.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

Examples of the silver halide solvent include ammonia, thioether, thiourea, thiourea derivatives such as 4-substituted thiourea, and imidazole derivatives. Regarding thioethers, U.S. Pat. Nos. 3.271.157 and 3.7
No. 90.387, No. 3,574,628Q, etc. can be referred to.

When the solvent is other than ammonia, the amount of the solvent used is 10-3 to 1.0% by weight of the reaction solution, especially 10-2 to 10-1.
Weight percent is preferred. In the case of ammonia, it can be selected arbitrarily.

The silver halide grains of the present invention may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a root shape. . In these particles, any ratio of (100) and (111) planes can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains of the present invention (grain size represents the diameter of a circle with an area equal to the projected area) is 3μ
m or less, particularly preferably 1 μm or less, and most preferably 0.8 μm or less.

In the silver halide emulsion of the present invention, it is preferable to add noble metal ions inside the grains. The noble metal salt is preferably an iridium salt, a rhodium salt, a gold salt, a cadmium salt, or a lead salt, with an iridium salt being particularly preferred. The amount of these noble metal salts added is preferably 10-9 to 10-5 mol, preferably 10-8 to 10-6 mol, per mol of silver halide.

The silver halide emulsion of the present invention requires chemical sensitization of silver halide grains by a conventional method.

That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a negative metal sensitization method using gold or other negative metal compounds, etc. are used alone or in combination, but at least a sulfur sensitizer must be used. is particularly preferred.

Suitable chemical sensitization methods include, for example, British Patent No. 618.
No. 061, No. 1,315,755, - No. 1,39
6,696, Japanese Patent Publication No. 44-15748, U.S. Patent No. 1.574.944, U.S. Patent No. 1.623,499,
No. 1,673,522, No. 2,278,947, No. 2.399.083, No. 2,410,689@, No. 2
, No. 419,974, No. 2,448,060, No. 2,
No. 487,850, No. 2.5181698, No. 2.5
No. 21,926, No. 2,642,361, No. 2.69
No. 4,637, No. 2,728,668, No. 2,7
No. 39,060, No. 2.743.182, No. 2.74
3.183, 2,983,609, 2,983
, No. 610, No. 3,021,215, No. 3.026.
No. 203, No. 3.297.446, No. 3,297
, No. 447, No. 3, No. 361, No. 564, No. 3, 4
No. 11,914, No. 3.554.757, No. 3,5
No. 65,631, 3. ! No. 165,633, 3.5
No. 91,385, No. 3.656.955, No. 3□76
1, No. 267, No. 3.7721031, No. 3, 8
57.71'1, 3.891, 446, 3
．． No. 901,714, No. 3,904,415, No. 901,714, No. 3,904,415, No.
3.930.867, 3,984, 2.49, 4,054,457, 4.067, 740, Research Disclosure
Losure ) No. 12008, No. 13452, No. 13654, T. H. James [The Theory of the Photographic Process J (
T.H.

James; The Theory of
the p photographicProcess
) (4th Ed, Macmillan
It is preferable to carry out sensitization using a chemical sensitizer or sensitization method described in, eg, 1977) pp. 67-76.

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

Furthermore, these sensitizing dyes can be used for purposes such as gradation adjustment and development adjustment in addition to their original spectral sensitizing effect.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, These include penzoxozal nucleus, naphthothiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thiooxysilidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
．． No. 912.329, No. 3, No. 656.959, No. 3
, No. 672,897, No. 3,694,217, No. 4
, No. 025,349, No. 4,046,572, British Patent No. 1.242.588, Japanese Patent Publication No. 14030/1973,
Examples include those described in No. 52-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, US Pat.
．． No. 201, No. 2, No. 072.908, No. 2,739
, No. 149, No. 2.945.763, British Patent 50
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 5,979. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 78, No. 2,442,710, No. 2.454,6
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 29, No. 2.776, and No. 280. Furthermore, U.S. Patent Nos. 2,213,995 and 2,493,
No. 748, No. 2.519.001, West Germany ii'f
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in US Pat. No. 929,080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, and No. 43-4933.
No. 43-4936, No. 44-32753, No. 45-2
No. 5831, No. 45-26747, No. 46-1162
No. 7, No. 46-18107, No. 47-8741,
No. 47-11114, No. 47-25379, No. 47
-37443, 48-28293, 48-38
No. 406, No. 48-38407, No. 48-38408
No. 48-41203, No. 48-41204, No. 49-6207, No. 50-40662, No. 53-
No. 12375, No. 54-34535, No. 55-156
No. 9, JP-A No. 50-33220, JP-A No. 50-33828
No. 50-38526, No. 51-107127, No. 51-115820, No. 51-135528
No. 51-151527, No. 52-23931, No. 52-51!132, No. 52-104916,
Same 52. -1 (No. 14917, No. 52-109925, No. 52-110618, No. 54-80118, No. 56-25728, No. 57-1483, No. 58-
No. 10753, No. 58-91445, No. 58-153
No. 4126, No. 59-114533, No. 59-116
6, '15, No. 59-116647, U.S. Patent No. 2
．． No. 688.545, No. 2,977.229, No. 3.
397.060@, No. 3,506,443, No. 3.5
No. 78.447, No. 3,672,898, No. 3,67
9.428, 3.769.301, 3.81
No. 4.609 and No. 3.837,862.

Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( For example, U.S. Pat.
, 437,510), cadmium salts, azaindene compounds, aminosudirbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,3
No. 90 and No. 3.635.721). U.S. Patent No. 3,615.613, U.S. Patent No. 3,615
, No. 641, No. 3,617,295, No. 3.635,
The combinations described in No. 721 are particularly useful.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As antifoggants and stabilizers, US Pat. No. 2,713
．． No. 541, No. 2.743.180, No. 2.143
．． Pentazaindenes described in US Patent No. 181, US Patent Nos. 2,716,062 and 2,444,607,
2,444,605, 2,756,147,
No. 2,835,581, No. 2,852,375, Research Disclosure (Research[)i
Tetrazaindenes described in U.S. Pat. No. 14851, triazaindenes described in U.S. Pat.
Azaindenes such as polymerized azaindenes described in US Pat. No. 1142; thiazolium salts described in US Pat. 3.148.067
Pyrylium salts described in No. 1986-406
Quaternary onium salts such as phosphonium salts described in US Pat. No. 65: US Pat. No. 2.403,927, US Pat.
, No. 897, No. 3.708.303, Japanese Unexamined Patent Publication No. 1983-
135835, mercapto-tetrazoles, mercapto-1-lyazoles, and mercaptodiazoles described in US Pat. No. 2,824.
001, mercaptobenzthiazoles and mercaptobenzimidazoles described in U.S. Pat. No. 3□397.987, and mercaptooxadiazoles described in U.S. Pat. No. 2,843,491. mercapto-substituted hezolocyclic compounds such as the mercaptothiadiazoles described in U.S. Patent No. 3.364.028; U.S. Pat. No. 3.236.65
No. 2, catechols described in Japanese Patent Publication No. 43-10256, resorcinols described in Japanese Patent Publication No. 56-44413, and polyhydroxybenzenes such as nisdel gallate described in Japanese Patent Publication No. 43-4133; Tetrazoles described in West German Patent No. 1,189,380, triazoles described in U.S. Pat. No. 3,157,509, benztriazoles described in U.S. Pat. No. 2,704,721, U.S. Urazoles described in Patent No. 3.287.135, U.S. Patent No. 3.10614
61, U.S. Patent No. 2.27
1,229, azoles such as polymerized benztriazoles described in JP-A No. 59-90844, and U.S. Patent No. 3.161.5.
Pyrimidines described in US Pat. No. 15, U.S. Patent No. 2.75
Heterocyclic compounds such as 3-pyrazolidones described in U.S. Pat. No. 1,297, and polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat. 59-137
No. 945, No. 140445, British Patent No. 1,356,
No. 142, U.S. Patent No. 3.575.699, U.S. Patent No. 3.6
Various inhibitor precursors described in US Pat. No. 49,267, etc.; sulfinic acids and sulfonic acid derivatives described in US Pat. No. 3,047,393; sea
, 2e3@, 2,839, 405, 2.488.
There are inorganic salts described in No. 709 and No. 2,728,663.

As the binder (or protective colloid) for the silver halide emulsion of the present invention, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, and cellulose derivatives may also be used. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as monopolymers or copolymers can also be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bulletin of Society of Photography of Japan (Bull)
, Soc, Sct, Phot, Japan)
Oxygen-treated gelatin as described in No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Examples of gelatin derivatives include gelatin, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, -polyalkyleonoxides, and epoxy compounds. Those obtained by reacting compounds are used. Specific examples include U.S. Patent No. 2,614,928;
No. 3,132,945, No. 3,186.846, No. 3,312,553, British Patent No. 861,414, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42 -26845 etc.

Proteins include albumin and casein; cellulose derivatives include hydroxyethyl cellulose, carboxymethyl 12) reulose, cellulose sulfate,
As the sugar derivative, sodium alginate and starch layer conductor are preferred.

The graft polymer of gelatin and other polymers may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. A grafted material can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, human oxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
, No. 763,625, No. 2,831,767, No. 2,
No. 956.884, etc.

Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N-
Single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.
For example, West German Patent Application (OLS) 2,312,708
No. 3,620,751, U.S. Patent No. 3,879
, No. 205, and Japanese Patent Publication No. 43-7561.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added to the processing solution to harden the photosensitive material to such an extent that it is not necessary to add a hardening agent, but it is also possible to add a hardening agent to the processing solution.

Hardening agents include aldehyde-based, aziridine-based (for example, PB Report, 19,921, U.S. Pat. No. 2.950)
, No. 197, No. 2,964,404, No. 2,98
Specifications of No. 3,611 and No. 3,271,175, Japanese Patent Publication No. 46-40898, and Japanese Patent Publication No. 91315-1988
Isoxazole type (for example, those described in U.S. Pat. No. 331,609),
Epoxy systems (e.g. U.S. Patent No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1.0
33.518, those described in Japanese Patent Publication No. 4g-35495), vinyl sulfone type (for example, P
B Report 19.920, West German Patent No. 1.100,94
No. 2, No. 2,337,412, No. 2,545,7
No. 22, No. 2,635,518, No. 2.742.30
No. 8, No. 2.749,260, British Patent No. 1,251
, No. 091, Japanese Patent Application No. 45-54236, No. 48-11
0996, U.S. Patent No. 3.539.644, U.S. Patent No. 3
．． 490,911), acryloyl type (for example, those described in Japanese Patent Application No. 48-27949 and U.S. Patent No. 3,640,720),
Carbodiimide systems (e.g., U.S. Pat. No. 2,938,8
No. 92, No. 4,043,818, No. 4,061,49
9, the specifications of Japanese Patent Publication No. 46-38715, and the specification of Japanese Patent Application No. 49-15095), triazine series (for example, West German Patent Nos. 2,410,973 and 2)
, 553,915, U.S. Patent No. 3,325,287, and JP-A-52-12722), polymer type (for example, British Patent No. 822.061M)
, U.S. Patent No. 3.623.878, U.S. Patent No. 3.396.0
No. 29, 3.226.234 specifications, Tokuko Sho 4
No. 7-18578, No. 18579, No. 47-4889
6), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and (N-methylol-based) hardening agents can be used alone or in combination. As a useful combination technology, for example, West German Patent No. 2
, No. 447,587, No. 2.505.746, No. 2.
514.245@, U.S. Patent No. 4,047,957;
Specifications of No. 3,832,181 and No. 3.840.370, JP-A No. 48-43319, and No. 50-6306
No. 2, No. 52-127329, Special Publication No. 48-3236
Combinations described in each publication of No. 4 may be mentioned.

When the silver halide emulsion of the present invention is used for color photographic sensitization, aromatic primary
A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of a grade amine developer (for example, a p-phenylenediamine derivative or an aminephenol derivative). The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are quaternary, in which four molecules of silver ions need to be reduced in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or D that releases development inhibitors during development to improve image sharpness and image graininess.
An IR coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and release a development inhibitor at the same time.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and is bonded in such a way that the inhibitor is released by intramolecular nucleophilic reaction or intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Furthermore, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and hivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 4g-94432, No. 50-87650, No. 51-3631, No. 52-
No. 115219, No. 54-99433, No. 54-1
No. 33329, No. 56-30127, U.S. Patent No. 2,
No. 875,057, No. 3,253,924, No. 3, 2
65.506, 3,408,194, 3.
No. 551.15S, No. 3,551,156, No. 3,6
No. 64,841, No. 3,725,072, No. 3.73
No. 0.722, No. 3,891,445, No. 3.900
．． No. 483, No. 3.929.484, No. 3.93
3.500, 3, 973.968, 3,9
No. 90,896, No. 4,012,259, No. 4,0
No. 22,620, No. 4,029,508, No. 4,05
No. 7,432, No. 4,106,942, No. 4,133
, No. 958, No. 4.2691936, No. 4,286
, No. 053, No. 4,304,845, No. 4.31
No. 4,023, No. 4.336.327, No. 4,3
No. 56,258, No. 4,386,155, No. 4,40
This is described in No. 1,752, etc.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers, and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-164.
No. 882, No. 58-167326, No. 58-206
No. 321, No. 58-214863, No. 58-21
No. 7339, No. 59-24653, Special Publication No. 40-60
No. 31, No. 40-6035, No. 45-40757,
47-27411, 49-37854, JP-A-50-13041, 51-26541, 51-
No. 37646, No. 51-105820, No. 52-42
No. 121, No. 53-123129, No. 53-125
No. 835, No. 53-129035, No. 54-485
No. 40, No. 56-29236, No. 56-75648, No. 57-4z9so, No. 57-35858, No. 5
γ-146251, 59-99437, British Patent No. 1,252,418, US Patent No. 2,600.78
No. 8, No. 3,005.712, No. 3,062,653
No. 3.127.269, No. 3,214,437, No. 3.253.924, No. 3,311,476, No. 3,419,391, No. 3, 519.429, 3,558,319, 3,582,322
No. 3. e15. soe number, 3,658,544, 3.705.896, 3.725,067,
3.758.309, 3,823.156, 3,834,908, 3,891,445,
3.907,571, 3,926,631,
No. 3,928,044, No. 3.935.015, No. 3,960,571, No. 4,076.533, No. 4
．． No. 133,686, No. 4,237,217, No. 4,
No. 241.168, No. 4,264.723, No. 4
, No. 301,235, No. 4,310,623, etc.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1,543,040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838, British Patent Publication No. 50-137137, No. 51-146828, No. 53-105226, No. 54-115230,
No. 56-29235, No. 56-104333, No. 56-126833, No. 57-133650, No. 5
No. 7-155538, No. 57-204545, No. 58
-118643, 59-31953, 59-3
No. 1954, No. 59-59656, No. 59-124
No. 341, No. 59-166956, U.S. Patent Nos. 2 and 3
No. 69,929, No. 2,423,730, No. 2,43
No. 4,272, No. 2,474,293, No. 2,698
, No. 794, No. 2,772,162, No. 2,801.
No. 171, No. 2,895,826, No. 3,253,9
No. 24, No. 3,311,476, No. 3,458,3
No. 15, No. 3,476.563, No. 3,591,3
No. 83, No. 3,737,316, No. 3.758,30
No. 8, No. 3,767.411, No. 3,790,384
No. 3.8801661, No. 3.926.634, No. 4,004,929, No. 4,009.035,
4,012,258, 4,052,212, 4,124,396, 4,134.7ff6, 4,138,258, 4,146,396,
4,149,886, 4,178.183, 4,205,990, 4,254,212,
4.264,722, 4,288,532, 4,296,199, 4,296,200, 4.299.914, 4.333.999,
These are described in 4,334,011, 4,386.455, 4,401.752, 4,427.767, etc.

In addition to the above-mentioned compounds, various photographic additives can be added to the silver halide photographic material containing the silver halide emulsion of the present invention.

Examples of such agents include ultraviolet absorbers (e.g., benzophenone compounds, benzotriazole compounds, etc.), development accelerators (e.g., 1-aryl-3-pyrazolidone compounds, etc.), surfactants (e.g., alkylnaphthalene sulfonates, (argyl succinate sulfonate, itaconate, polyalkylene oxide compounds, etc.),
Water-soluble anti-irradiation dyeing Fl (e.g. azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds, triphenylmethane compounds, etc.)
, film property improvers (e.g. glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin, etc.), color clouding preventive agents (diffusion-resistant hydroquinone compounds, etc.), dye image stabilizers (e.g. hydroquinone derivatives, gallic acid derivatives, etc.) , phenolic compounds, hydroxychroman compounds, polyalkylpiperidine compounds, aromatic amine compounds, etc.), water-soluble or oil-soluble optical brighteners, background color wI regulators (oil-soluble coloring dyes, etc.), etc. .

Small dye-forming couplers, colored couplers, DIR couplers, DI that need to be adsorbed onto the surface of silver halide crystals
Among R compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be treated using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to various methods for dispersing hydrophobic additives such as couplers. 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 water-soluble additive as necessary. The mixture is dissolved using a hydrophilic binder such as an aqueous gelatin solution, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or ultrasonic device. After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

The ratio of high boiling point organic solvent to low boiling point organic solvent is 1:0.1 to 1:50. More preferably, the ratio is 1:1 to 1:20.

Examples of high boiling point oils include those 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 liquid solvent is used.

Examples of high-boiling organic solvents that can be used include U.S. Pat. No. 2,322,027, U.S. Pat. No. 262, No. 2.852.383, No. 3.554.755, No. 3.676, No. 137, No. 3
, No. 676.142, No. 3.700.454, No. 3.
748.141, 3.779.765, 3.8
37.863, British Patent No. 958,441, 1 and 2
No. 22,753, No. 0122,538,889, JP-A-47-1031, JP-A No. 49-90523, JP-A No. 50-2
No. 3823, No. 51-26037, No. 51-2792
No. 1, No. 51-27922, No. 51-26035,
No. 51-26036, No. 50-62632, No. 5
No. 3-1520, No. 53-1521, No. 53-15
No. 127, No. 54-119921, No. 54-1199
22, No. 55-25051, No. 55-36869, No. 56-190119, No. 56-81836, Japanese Patent Publication No. 48-29060, or in place of the 1° high boiling point solvent. Examples of low boiling point or water-soluble organic solvents that can be used include those described in US Pat. No. 2,801,171 and US Pat. No. 2,949,360. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc.
In addition, water-soluble organic solvents include aretone, methyl isobutyl ketone, β-■ toxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl Examples include ether, phenoxyethanol and the like.

Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylnaphthalene sulfones, alkyl sulfonates, alkyl sulfates, argyl phosphates, sulfosuccinates, and sulfoalkyl polyoxyethylenes. Anionic surfactants such as alkylphenyl ethers, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids,
and amphoteric surfactants such as alkyl betaines, etc.
It is preferable to use cationic surfactants such as and quaternary ammonium salts. Specific examples of these surfactants can be found in "Surfactant Handbook" (Sangyo Tosho, 1966)
) and [Emulsifier, emulsification equipment research, technical data collection] (
(Wagaku Panronsha, 1978).

As a latex dispersion method, for example, US Patent No. 4.19
No. 9,363, No. 4,214,047, No. 4,203
．． No. 716, No. 4,247,627, Japanese Unexamined Patent Publication No. 1977-7
No. 4538, No. 51-59942, No. 51-5994
The method described in No. 3, No. 54-32552, etc. is preferred.

Any known method can be used for developing the photographic material containing the silver halide emulsion of the present invention.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution. A web method, a method of performing viscous development processing, etc. may be used.

Color support processing includes a color development process, a bleaching process, a fixing process, and if necessary a water washing process, and/or
Alternatively, a stabilization process is performed, but instead of a process using a bleach solution or a process process using a fixer, a 1-bath bleach-fix solution can be used to carry out the bleach-fix process (). It is also possible to carry out a monobath treatment process using a one-bath development, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath.

In combination with these treatment steps, a predural treatment step, its neutralization T, lli! , a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material instead of the color developing agent or its precursor, and the developing treatment is performed with an activator solution.
Instead of monobath treatment, activator treatment, bleaching, and fixing treatments may be performed simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as the final step, which is either a water washing process, a stabilization process, a water washing process, or a stabilization process.) Color development process - Bleaching process Constant coloring process - Color development process Processing process - Bleach-fixing process/pre-film treatment process - Neutralization process One-color development process - Stop-fixing process - Water washing process - Bleach process Constant fixation process - Water washing process - Post-hardening process Process - Color development process - Water washing process - Supplementary color visual image process - Stop process - Bleach process Constant fixation process - Monobath process - Activator process - Bleach-fix process - Activator process - Bleach Treatment Step Constant Fixation Treatment Step [Examples of the Invention] The present invention will be described in detail below with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.

(Example-1) The following five types of solutions were prepared.

(I) Gelatin 5.2g Add water to make 150d.

(II) NaCff1 19.97° Add water 3
Finished with 40 crowns.

(I[[) A(+NO358,00(+Add water to finish to 340d.

(■) K B r 1.400 Add water to 11
．． 7711! Finish it.

(V) ACI NO32,00 (11 water added
．． Finished at 771g.

251 of liquid (I)! , and liquid (■) and liquid (III) were added thereto over 60 minutes using the controlled double jet method, followed by addition (■) and liquid (V) over 10 minutes. (11L, 1)H in the container was 3.0, the temperature was maintained at 50°C, IIA (+ is shown in Table 1), and the resulting halogenated particles were all cubic crystals with an average particle size of was 0.70 μm on each side.

Table 1 Sodium thiosulfate per mole of silver halide for each emulsion 1. Chemical sensitization was carried out by adding 10 -5 mol of 1X, and spectral sensitization was carried out by adding blue-sensitive sensitizing dye [BSD-1] in an amount of 3.0 x 10 -> mol per mol of silver halide. A coating solution was prepared by adding 0.4 mol of yellow coupler [Y-1] per mol of silver halide dissolved in dibutyl phthalate, and the coating solution was coated on a resin-coated paper support by Xu Bu Yinso as metallic silver T 3 ．． Omo/dm gelatin 1300/
(Conditions were adjusted so that In'), and 10 g/dt' of gelatin was further coated on the soil as a protective layer.

Each of these samples was subjected to wedge exposure according to a conventional method, and then processed using the color development process and processing solution described below.

5II-1 rθ Color development processing step 1, color development (35℃) 45 seconds 2, bleach-fixing (35℃) 45 seconds 3, washing with water 30-34℃ 90 seconds 4, drying 50-80℃ 60 seconds color development Liquid pure water aoo1g ethylene glycol 101QN,N-diethylhydroxylamine 100potassium chloride
2ON-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2° Potassium carbonate
30 (add 1 water and add 11 gold stones)
and adjust to pl-110,08.

Bleach-fix solution The reflection density of the yellow dye image formed on each sample was measured using a Sakura color densitometer model PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.) using the attached blue filter.
Sensitivity and fog were determined from the characteristic curve. The results are shown in Table 2. Sensitivity represents relative sensitivity when sample 4 is taken as 100.

<Pressure resistance> A: Samples 1 to 4 were tested using a scratch strength tester (manufactured by Heldon Co., Ltd.) with a needle of 0.3 Illffl at the tip of 50 (
After applying pressure with a constant load of +, a white light simulated exposure is performed and a color development process is performed. The obtained sample was scanned with a microdensitometer, and the density change ΔD at the portion to which a load was applied was measured at a reflection density of 0.8.

B: Samples 1 to 4 were exposed to a wedge of blue light and then placed in water maintained at 38°C using a needle with a tip of 0.5+nm in the same manner as above.
After applying a constant load, a color development process is performed. The obtained sample was scanned with a microdensitometer in the same manner as in A, and the change in m degree ΔD of the part where the load was applied at 1 in 1 degree 0.8 was measured.

Table 2 As is clear from Table 2, samples No. 1, No. 1 of the present invention
It can be seen that Sample No. 12 has higher sensitivity, lower fog, and excellent pressure resistance than Comparative Sample No. 0.4. No.

In No. 3, silver halide grains were formed in accordance with the method disclosed in JP-A-60-136735, but although it had high sensitivity, it was found that fog was high and pressure resistance was poor. Therefore, when forming a phase with a silver chloride content of 95 mol% or more (hereinafter referred to as high silver bromide content layer), the pAo should be set to 3.0 to 6.5. It can be seen that the effect of the present invention is achieved by setting I) AU to 5.0 to 7.0 when forming a high silver bromide content layer. In particular, the difference between pAo at the time of forming the high silver chloride content phase and 11A (+) at the time of forming the high silver bromide content layer is 1.0 to 1.
5: Sample No. 11 shows that the effect of the present invention is even better.
asked from NO12.

[Example-21 Silver halide grains were produced in the same manner as in Example 1, with the addition time of liquid (■) and liquid (Ill) being 20 minutes.

The resulting particles were cubic and had a side of 0.40 μm. However, I) All during formation is the same as in Example 1. Emulsion p4o, A', B', C', D'
Tozuru. Each emulsion was chemically sensitized by adding 1.2X 10-5 moles of sodium diosulfate per mole of silver halide, and green-sensitive sensitizing dye [GSD-11 (1.6X 10 moles per mole of silver halide) was added to each emulsion. → mol) or red-sensitive sensitizing dye [R8D-1] (1.4×10 −5 mol per mol of silver halide) was added.

5D-1 SD-1 A sample of a silver halide color photographic light-sensitive material was prepared by sequentially coating the following constituent layers on a polyethylene laminate paper support from the support side.

1st layer...Blue-sensitive silver chlorobromide emulsion layer 1.2 (1/u2 gelatin, blue-sensitive silver chlorobromide used in Example-1 (silver equivalent 0.30 (1/v') and 0.
Yellow coupler (Y-1) dissolved in dioctyl phthalate (0.50 (1/12) per mole of silver halide).
40 mol).

2nd layer: Intermediate layer 0.7 (1/l' gelatin, 10 m (1/12) irradiation dye represented by Al-1 below and 5
m (1/12 layer containing a dye represented by Al-2 below.

3rd layer... Green-sensitive silver chlorobromide emulsion layer 1.25(]/TI' gelatin, silver halide emulsion sensitized with the above-mentioned green-sensitive sensitizing dye (3.29/v2 in terms of silver)
) and 0.5 (+/TI') of magenta coupler [M-1] dissolved in a u mixture of dibutyl phthalate and ethyl acetate.
] (0.25 mol per mol of silver halide).

4th layer...intermediate layer 1.2Q/1' gelatin-containing layer 5th layer...red-sensitive silver chlorobromide emulsion layer 1.4(]/11' gelatin, red-sensitive sensitized above) Dye-sensitized silver halide emulsion (silver equivalent: 2.0 (1/f)
) and 0.45 g/v2 of a cyan coupler represented by C-1 below dissolved in dioctyl phthalate-1 of 0.20 (1/n2).

6th layer...light absorption layer 1.0(]/11' of gelatin and 0.20(1/m
0,30 (1/m
UV absorber Tinuvin 328 (manufactured by Ciba Geigy)
Layer 7 containing protective layer 0.5 (1/w' layer containing gelatin [C, 1] I [A I-1] lAl-2] Wedge exposure was carried out according to the usual method. After the color development process used in Example 1, the reflection densities of the yellow, magenta, and cyan dye images formed on each sample were measured using F-type blue, green, and red filters, and the characteristic curves were Sensitivity fog was determined. The sensitivity is defined as the sensitivity of each photosensitive emulsion layer of sample No. 088 as 100. The pressure resistance is the same as in Example 1 except that each sample was exposed to blue, green, and red light. As is clear from the results in Table 3, sample No. 5 of the present invention
, N 0.6 has higher sensitivity and lower fog than comparative samples No. 7, No. 8, and has excellent pressure resistance.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedure rlljF 1 (Method) % Formula %] 2. Name of the invention Silver halide color photographic light-sensitive material with improved pressure resistance 3. Relationship with the case of the person who missed the correction Special r [Applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Co., Ltd. Representative Director
1st move Inchu 4, Agent 102 Address 1-1 Kudankita 4-chome, Chiyogawa-ku, Tokyo (Delivery date) 1986 06 fJ 2 /I 6, Procedures subject to amendment? rli Seien (spontaneous) 1985 Patent Application No. 97502 2 Name of the invention Silver halide color photographic light-sensitive material with improved pressure resistance 3 Relationship with the person making the amendment case Patent applicant address Nishi, Shinjuku-ku, Tokyo Shinjuku 1-26-2 Name
<127> Roku Konishi Photo Industry Co., Ltd. Representative Director
Keigyu Amako 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 6. Contents of amendment (1) 4th line from the bottom of page 40 of the specification r・3. Om
g/dm..." was changed to "...3,0mg/
(K...” What?

(2) On page 47, line 6 of the specification [...(Silver equivalent 0.3
0 (1/12)...'' is 1... (Silver conversion 3.
0 (1/vr2)...] is spelled.

　　　　　d

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a total silver chloride content of 80 mol% or more, and chloride It contains silver halide grains having a phase with a silver content of 95 mol% or more and a phase with a silver bromide content of 80 mol% or more, and the silver halide grains have a silver chloride content of 95 mol% or more. Phase pAg3.0~
6.5, and a phase having a silver bromide content of 80 mol% or more is formed in a pAg range of 5.0 to 7.0. .