JPH02153342A - Silver halide photographic sensitive material having excellent allowance to fluctuation in processing conditions - Google Patents

Abstract

PURPOSE:To decrease the fluctuation in photographic performance arising from a fluctuation in development conditions by incorporating 2 kinds of emulsions subjected to chemical ripening respectively at pAg values of specific ranges into the photosensitive material. CONSTITUTION:The emulsion subjected to the substantial chemical ripening at the pAg value within a 6.0 to 8.8 range is incorporated into >=1 layers of the emulsion layers of the title photosensitive material and the emulsion subjected to the substantial chemical ripening at the pAg value within a 8.9 to 11.0 range is incorporated into >=1 layers of the emulsion layers. The chemical sensitization can be executed by making combination use of one noble metal and sulfur sensitizers. The adjustment of the pAg of the emulsions can be executed by adding silver ions or halide ions which control the removal rate of soluble salts after the end of the growth of the silver halide particles in the emulsions or adding a pAg value increasing agent (e.g.: thiocyanate) to the emulsions.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
It is an object of the present invention to provide a silver halide photographic light-sensitive material whose photographic performance changes little due to changes in development processing conditions.

[Background of the invention]

The progress of silver halide photographic materials in recent years has been remarkable, and the trend toward higher sensitivity and higher image quality shows no signs of stopping. On the other hand, consumer needs for photographic materials are also becoming more diverse, and in order to meet these needs, the importance of silver halide emulsions, which can easily control gradation, has been highlighted. Furthermore, in recent years, it has become increasingly desirable to provide photographic performance that is stable against fluctuations in development processing conditions, such as developer temperature and development time.

As a method for obtaining a photographic light-sensitive material with high sensitivity and high image quality, for example, a method using a tabular silver halide emulsion having an average aspect ratio of 8 or more as disclosed in JP-A-58-113934; Or, JP-A-60-1
A method using a core/shell type emulsion having a high silver iodide content inside the grains as disclosed in Japanese Patent No. 43331 is known.

However, these emulsions had drawbacks mainly in processing properties. In other words, tabular grains having a high aspect ratio have too high development activity regardless of the average silver iodide content of the total grain due to their morphological properties, and it is extremely difficult to obtain a desired gradation. Ta. On the other hand, the core/shell type emulsion disclosed in JP-A No. 60-143331 certainly has excellent graininess, but the effects of the invention described in the specification are as follows:
"High development activity" was not obtained; on the contrary, the development activity was lowered, probably due to the high average silver iodide content, and it was still difficult to control the gradation. Attempts to increase development activity by lowering the average silver iodide content led to a vicious cycle in which sensitivity decreased.

As described above, in the prior art, it has been impossible to easily control the development processing characteristics of photographic materials using high-performance silver halide emulsions.

[Purpose of the invention]

In view of the above problems, it is an object of the present invention to provide a silver halide photographic material having excellent stability in development processing.

[Structure of the Invention] As a result of extensive research, the present inventors have discovered that the above object can be solved by using the silver halide emulsion shown below, and have accomplished the present invention.

That is, an object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the emulsion layers is subjected to substantial chemical ripening with a pAg value of 6.0 to 8. .8, and at least one of the emulsion layers has been subjected to substantial chemical ripening to a pAg value of 8.9 to 1O35. This has been achieved using a silver halide photographic light-sensitive material.

The present invention is based on the following findings discovered by the present inventors. In other words, it is well known among those skilled in the art that when chemically ripening an emulsion, the setting of l) Ag has a sufficient effect on how the chemical ripening takes place;
A sensitization method in which ripening is carried out at about 4 to 5 times has been known for a long time. However, if chemical ripening is simply carried out by setting a low pkg, chemical ripening will be completed in a short time, but fog will become unstable, for example, fog will increase due to storage over time, or the same chemical aging will occur. There are problems with reproducibility when applying

However, after various studies by the present inventors, pA
If two types of silver halide emulsions that have undergone substantial chemical ripening with g values in the ranges of 6.0 to 8.8 and 8.9 to 11.0 are combined, the halogenated emulsions used alone can be We have discovered that a silver halide emulsion with superior processing stability can be obtained when using a combination of a silver emulsion or an emulsion that has been chemically ripened within the same pAg range, and has led to the present invention. be.

The present invention will be described in more detail below.

In the present invention, chemical ripening refers to sensitizing silver halide grains using a chemical sensitizer when forming a silver halide emulsion.

In the present invention, chemical ripening can be achieved by any chemical sensitization means, and the chemical sensitizer used is not particularly limited.

Chemical sensitizers that can be advantageously used in the present invention include noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds such as sodium thiosulfate, thiogen, and allyl isothiocyanate can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

As a chemical sensitizer that can more fully exhibit the objectives and effects of the present invention, a combination of a noble metal sensitizer and a sulfur sensitizer is preferred.

The amount of chemical sensitizer added when chemically ripening the silver halide emulsion according to the present invention depends on the silver halide grains used.
It can be set as appropriate.

Next, substantial chemical ripening as used in the present invention will be explained.

In the present invention, the step of starting chemical sensitization refers to the step of adding a chemical sensitizer, and in this step, the time when the chemical sensitizer is added is the time to start chemical sensitization.

Moreover, the chemical sensitization described above can be stopped by methods known in the art. As a method to terminate chemical sensitization,
Methods such as lowering the temperature, lowering the pH, and using a chemical sensitization stopper are known, but in consideration of the stability of the emulsion, etc., the method using a chemical sensitization stopper is preferable. Examples of chemical sensitization stoppers include halides (e.g., potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (e.g., 4-hydroxy-6-methyl-1,3,3a , 7-chitrazaindene, etc.) are known. These compounds may be used alone or in combination.

The time when these operations for terminating chemical sensitization are performed is the end of chemical sensitization.

In the present invention, the term "substantial chemical ripening time" refers to the time between the start of chemical sensitization and the end of chemical sensitization.

In the present invention, silver halide emulsions subjected to chemical ripening within two types of pAg ranges are used. One of the emulsions is
Substantial chemical ripening is carried out at a pAg value of 6.0 to 8.8, preferably in the range of 7.0 to 8.2, more preferably in the range of 7.4 to 8.0. It is within.

The other emulsion was subjected to substantial chemical ripening of 8.9~
11.0, but the preferred value is 9.0-10
．． It is within the range of 5.

The pAg value during substantial chemical ripening preferably satisfies the above conditions for at least 1/3 of the substantial chemical ripening time, particularly for at least 2/3 of the first half of this substantial chemical ripening time. It is preferable to satisfy the following.

In the present invention, the pAg of the emulsion subjected to chemical ripening is adjusted to the above value in order to control the removal rate when unnecessary soluble salts are removed after the growth of silver halide grains in the emulsion is completed. , or adding silver ions or halide ions. Alternatively, a desired pAg value can be set using a compound other than halide ions that forms a poorly soluble salt with silver ions (hereinafter abbreviated as pAg value increasing agent).

The pAg value increasing agent will be explained in detail below.

As a pAg value increasing agent, when performing chemical ripening at a pAg of 6.0 to 8.8, it can be added to increase the pAg value by at least 0.02 (and preferably 0.05) or more1)
There is no particular limitation as long as it is a compound other than halide ions that increases the Ag value. However, particularly preferred compound groups include thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, selenone anates such as sodium selenocyanate and sodium selenocyanate, sodium carbonate and
There are carbonates such as potassium carbonate, and sulfites such as sodium sulfite and potassium sulfite. Among these, the most preferred compound group is thiocyanate.

The amount of these pAg increasing agents added varies depending on the composition, grain size, crystal habit, etc. of the silver halide emulsion used, but is usually preferably 0.0005 to 1.0 g per mole of silver halide, and more preferably. is 0.001 to 0.5 g, particularly preferably 0.005 to 0.2 g.

Further, the pAg increasing agent may be added either before or after the start of the actual chemical ripening, but if it is after the start, it is preferably added in the first half of the actual chemical ripening time. Particularly preferred is the case where it is added prior to the addition of the chemical sensitizer.

Two types of silver halide emulsions used in the present invention (
One side has a pAg of 6.0 to 8.8. The other one is 8.9-11.0
2) can be used in photographic materials having at least one silver halide emulsion layer, but it is preferably used in adjacent emulsion layers, and more Preferably, it is used in the same photosensitive layer, and most preferably, it is used separately in upper and lower layers of the same photosensitive layer.

The silver halide color photographic light-sensitive material of the present invention may contain various other components in addition to the above-mentioned essential components.

In the present invention, the silver halide emulsion includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any materials used in ordinary silver halide emulsions, such as silver chloroiodobromide and silver chloride, can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred. .

The photosensitive silver halide grains used in the above silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are prepared, or they may be grown by various commonly used methods.

Further, the silver halide grains may be changed in halogen composition by using a conversion method at any step of their formation.

The silver halide grains described above can contain various metal elements inside the grains and/or on the grain surfaces, and can also be provided with reduction sensitizing nuclei by placing them in a suitable reducing atmosphere.

Further, the silver halide emulsion may be one in which unnecessary soluble salts have been removed after the growth of silver halide grains has been completed, or it may be one in which unnecessary soluble salts are contained.

In the present invention, the silver halide grains in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is primarily formed inside the grains. Further, it may be in any crystal form.

The average grain size of the silver halide grains is 0.05 to 3.
The thickness is preferably 0 μm, more preferably 0.1 to 20 μm.

In the present invention, the silver halide emulsion having any grain size distribution can be used. In other words, emulsions with a wide grain size distribution ("polydisperse emulsions")
or an emulsion with a narrow particle size distribution (referred to as a "monodisperse emulsion").

The silver halide emulsion described above may be a mixture of two or more silver halide emulsions formed separately.

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

Further, when the silver halide photographic light-sensitive material of the present invention is used for color purposes, it may be for monochrome use or for multicolor use. Multicolor silver halide photographic light-sensitive materials usually use magenta, magenta,
It has a structure in which a silver halide emulsion layer containing yellow and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. can be set arbitrarily depending on the important performance and purpose of use.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure's RD-17643 and RD- shown in the table below.
Examples include compounds described in 18716.

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filters Dye brighteners Hardeners Coating aids Surfactants Plasticizers Slip agents Static inhibitors Matting agents Binder RD-17643 Page Classification Page 23 I[[648 23IV 64B Right 29 XXI 648-24
Vl 649 // 25 ■ 25 ■ 25-26 ■ // 24 V 26 X 651 right 26-27 n 650 right 26-27
XI 650 right 27 A dye-forming coupler that forms a dye by performing a coupling reaction with an oxidized product of a group primary amine developer (for example, a p-)22-diamine derivative or an aminophenol derivative) is used. 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. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DLR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the group is separated by the coupling reaction. Intramolecular nucleophilic reaction,
Included are those in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Also, 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.

Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.
, 408° No. 194, No. 3,551.155, No. 3,
No. 582,322, No. 3,725゜072, No. 3,8
91,445, West German Patent No. 1,547.868, West German Patent Application No. 2,219.917, West German Patent Application No. 2,261.36L
No. 2゜414.006, British Patent No. 1,425.0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 50-6341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21327, No. 51
-102636, 52-82424, 52-1
No. 15219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
3゜062.653, 3,127,269, 3,311,476, 3゜419.391, 3
, 519,429, 3,558,319, 3゜582.322, 3,615,506, 3,8
No. 34,908, No. 3891.445, West German patent 1,
No. 810,464, West German Patent Application (OLS) 2,408
, No. 665, No. 2,417,945, No. 2,418,
No. 959, No. 2,424,467, Special Publication No. 1977-1960
No. 31, JP-A-49-74027, JP-A No. 49-7402
No. 8, No. 49-129538, No. 50-60233, No. 50-159336, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-
No. 58922, No. 53-55122, patent application No. 55-1
Examples include those described in No. 10943.

As the cyan dye-forming coupler, known phenolic or naphthol couplers can be used.

For example, phenolic couplers substituted with an alkyl group, acylamino group, or ureido group, naphthol couplers formed from a 5-aminonaphthol skeleton, diisomeric naphthol couplers with an oxygen atom introduced as a leaving group, etc. Ru.

Specific examples of cyan color forming couplers that can be used include, for example, U.S. Patent No. 3,779.763, Patent No. 58-98731,
No. 60-37557, U.S. Patent No. 2,895.326, U.S. Patent No. 60-225155, U.S. Patent No. 60-222853,
No. 59-185335, U.S. Patent No. 3°488, 193
No. 60-237448, No. 53-52423,
No. 54-48237, No. 56-27147, Equity 4
9-11572, Patent No. 61-3142, Patent No. 61-9
652-3, 61.39045, 61-501
No. 36, No. 61-99141, No. 61-105545
Examples include those listed in the issue.

Examples of light-sensitive materials to which the silver halide photographic light-sensitive material of the present invention can be applied include various color and black-and-white light-sensitive materials. For example, color photosensitive materials such as color negative film, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive film, heat development film, silver dye bridge film, X-ray photography film, squirrel film, color photosensitive material, etc. It can be used in photosensitive materials for black and white photography such as micro photography, general photography, and black and white photographic paper.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

The amount of silver halide photographic light-sensitive material added is expressed in weight (g) per 1I112 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Layer structure of samples No. 1: 1st layer; antihalation layer (HC-1) black colloidal silver 0.20 UV absorber (UV-1)
0.20 High boiling point solvent (OiL 1 ) 0.20
Gelatin 1.5 2nd layer; Intermediate layer (IL-1) t+V absorber (tlV-1) 0.0
1 High boiling point solvent (Oiff-1) 0.0
1 Gelatin 1.5 Third layer - low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.9 Silver iodobromide emulsion (Ea+-2) 0.6 Sensitizing dye (
S-1) 2.5X10-' (mol/1 mole of silver) 0.5X 10-' (mol/1 mole of silver) 0.5X 10-' (mol/1 mole of silver) Sensitizing dye (S-3) Sensitizing dye (S-2) Cyan coupler (C-1) Cyan coupler CC-2) Colored cyan coupler (CC DIR compound (D-1) High boiling point solvent (OiQ-1) Gelatin 4th layer; High sensitivity red sensitivity Emulsion layer (RH) Silver iodobromide emulsion (Em-3) Sensitizing dye (S-1) 2, OX 10-' (mol/silver 2, OX 10-' (mol/silver 1, OX 10-') Mol/silver 1.0 0.05 1) 0.05 0.002 0.5 1.5 Sensitizing dye (S-2) Sensitizing dye (S-3) Cyan coupler (C-2) Cyan coupler (C -3') Colored cyan coupler (CC-1) DIR compound (D-2) High boiling point solvent (OiQ-1) Gelatin 2.0 1 mol) 1 mol) 1 mol) 0.015 0.25 0.015 0 .05 0.3 1.5 5th layer: Intermediate layer (IL-2) 6th gelatin layer: Low-sensitivity green-sensitive emulsion layer (L) Silver iodobromide emulsion (Em-1) 0.5 1.0 Sensitizing dye (S-4) 5XlO-' (mol/silver 1 mol) Sensitizing dye (s-5) 1xlO-' (mol/silver 1 mol) Magenta coupler (M-1) 0.5 colored magenta coupler ( CM-1) DIR compound (D-3) DIR compound (D-4) High boiling point solvent (Oil2-2) Gelatin 7th layer; Intermediate layer (IL-3) Gelatin 8th layer; High sensitivity green-sensitive emulsion layer ( Silver iodobromide emulsion (Ell-3) Sensitizing dye (S-6) 1.5X 10-'0.0I O2O3 0,020 0,4 0,8 1,3 (mol/1 mol of silver) Yellow coupler (Y-1) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (D-2) 0.01 High boiling point solvent (
01ρ-3) 0.3 gelatin
1.0 11th layer; High sensitivity blue sensitive emulsion I
I (Bl() Silver iodobromide emulsion (Em-4)
0.8 Sensitizing dye (s-9) 1xlo-4 (mol/1 mol of silver) Sensitizing dye (S-10) 3 x 10 (mol/silver)
1 mole of silver) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2”) 0.05 High boiling point solvent (OiQ-3) 0.1 Gelatin 1.1 12th layer; 1st protective layer (PRO -1) Fine grain silver iodobromide emulsion (average grain size 0.08 μmAg 12 mol%) 0.4 UV absorber (UV-1) 0.10 (mol/
2) 0.05 Magenta coupler (M-3) 0.15 Colored magenta coupler (CM -2) Magenta coupler (M Sensitizing dye (S -8) Sensitizing dye (S -7) DIR compound (D-3) High boiling point solvent (Oi (2-3) Gelatin 9th layer; Yellow filter layer (yc ) Yellow colloidal silver stain inhibitor (SC-1) High boiling point solvent (Oiff-3) Gelatin 1st O layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-1) 0.25 sensitizing dye (S-10)
7 (Oiff-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 13th layer; 2nd protective layer (PRO-2) Interface Activator (SU-1) 0.005 Alkali-soluble matting agent (average particle size 3 μm) 1.10 Gelatin 0.6 Em-1: Average particle size 0.46 μm 1 average silver iodide 7.0 mol%, monodispersed Silver surface emulsion Em-2: average grain size 0.3
0 μm 1 Average silver iodide content 2.0 mol%, monodisperse, uniform composition emulsion Em-3: Average grain size 0.81 μm Average silver iodide content...7.0 mol% Monodisperse surface Low silver iodide-containing emulsion E+o-4: average grain size 0.95 μm, average silver iodide content...8.0 mol%, monodisperse (width of distribution 14%) surface low silver iodide (0.5 mol %)-containing emulsion In addition to the above composition, a coating aid Su-2, a stabilizer 5tb-1, and an antifoggant AF-1 were added to each layer.

In addition, the silver halide emulsion of Sample-1 old Em-1-E+a-4 was chemically ripened by keeping the temperature of the reaction tank at 55°0 and adding ammonium thiocyanate, sodium thiosulfate, and chloroauric acid. was applied. pAg value during chemical ripening is 9,
2 and aged for 90 minutes.

In addition, the silver halide emulsions used in the 1st O layer and the 11th layer of sample-101 were replaced with silver halide emulsions whose pAg during chemical ripening was changed as shown below.
-106 were prepared and shown in Table-■.

Using Em-5Em-1, the pAg during chemical ripening was 7.
pAg during chemical ripening was adjusted to 7.5 using Em-6Em-4.
(1) Weight ratio of emulsion adjusted to 5 Breakdown of compounds used (CI, ), So.

(Ct(z)sso)HN(C2Hs)3(CHriIs
O,e (CHJ4SOxe(CtHs)xNHΦ(CHz)s
sOINa (01=)xso,e (CHJsSOsHN(CJi)1 l C,I(.

0 ■ 0 ■ C- ■ Cθ Cα Q Q M-2 Cθ Q H H u NaO,5-C-COoC,H,1 CH.

C00CaH+7 u C- H 0it ■ JV C2H.

S ■ ((CH2=CH302CHz) 5ccLsOz
(Clb square rN (C1lz) 2SO3Ku Na03S-C-COOCH2 (CF2CF,) IHC
C00Ctb(CFzCFz)31(IQ H CsH+5(t) IQ i12 S tab - ■ HF Each of the samples -101 to 106 thus prepared was exposed to wedge light using white light, and then the following development process was performed. .Also, for color development processing, the standard development time is 3.
In addition to minutes and 15 seconds, 3 minutes and 3 minutes and 30 seconds are also processed.
;.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixing for 3 minutes and 15 seconds. Washing for 6 minutes and 30 seconds. Stabilization for 3 minutes and 15 seconds. Drying for 1 minute and 30 seconds. The composition of the processing liquid used in each processing step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroquineluamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37 .5g sodium bromide 1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make if.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 m (2 Add water to make 1Q, and adjust to pH -6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 14, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5
mQ Konidax (Konica) 7. Add 511112 water to make lQ.

The blue density of each sample obtained was measured and the gamma value was determined.

The gamma value is expressed by the slope of a straight line connecting the minimum density +0.2 to the density 1.5 in the optical range.

Table 2 shows this result and the variation range of gamma value depending on development time.
Shown below.

Table 2 As is clear from Table 2, the sample of the present invention had a smaller gamma fluctuation range than the comparative sample, and a remarkable improvement effect on processing fluctuation was observed.

Furthermore, similar experiments were conducted with a red-sensitive emulsion layer and a green-sensitive emulsion layer, and similar good results were obtained, confirming that the effects of the present invention are exerted regardless of the difference in color sensitivity. .

Example 2 A multilayer color photosensitive material sample 201 (comparison) was prepared by sequentially coating each layer having the composition shown below on a subbed triacetyl cellulose film support from the support side. The amount of each component applied is indicated by "gets".

However, silver halide is shown in the coating amount in terms of silver, and coupler is shown in the number of moles per 1 mole of silver.

1st layer: antihalation layer UV absorber TJ -10,3 UV absorber U -20,4 High boiling point solvent 0-1 1.0 Black colloidal silver 0.24 Gelatin
2.0 Second layer: Intermediate layer 2.5-di-t-octylhydroquinone 0.1
High boiling point solvent 0-1 0.2 Gelatin 1.0 Third layer: Low sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (5-1) and (5
-2) spectrally sensitized silver iodobromide (Ag14 mol%
Average particle size 0.25μm) 0.5
Coupler Cp-10,1 High boiling point solvent 0-2 0.6 Gelatin 1.3 Fourth layer: High sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (5-1) and (5
-2) Silver iodobromide spectrally sensitized (Agl 2 mol% average grain size 0.60 μff1)
0.8 Coupler Cp-10,2 High boiling point solvent 0-2 1.21.8 Gelatin 5th layer: Intermediate layer 2.5-E-octylhydroquine 0.1 High boiling point solvent 0-1 0. 2 gelatin
0.9 6th layer: Low sensitivity green-sensitive silver halide emulsion layer Green sensitizing dye (5-3) and (5-4
) spectrally sensitized silver iodobromide (Agl 4 mol % average particle size 0.25 μm) 0.6 coupler Cp-20,04 coupler Cp-30,01 high boiling point solvent 0-3 0.5 gelatin 1. 4 Seventh layer: Highly sensitive green-sensitive silver halide emulsion layer Green sensitizing dye (5-3) and (5
-4) Silver iodobromide spectrally sensitized (Agl 2 mol% average grain size 0.60 μm) 0.
9 Coupler Cp-20,10 Coupler Cp-30,02 High boiling point solvent 0-3 1.91.5 Gelatin 8th layer: Same as intermediate layer 5th layer 9th layer: Yellow filter layer Yellow colloidal silver 2.5- Di-t-octylhydroquinone high boiling point solvent 0
-1 Gelatin 10th layer: low sensitivity blue-sensitive silver halide emulsion layer Silver iodobromide (Agl
4 mol% average grain size 0.35 μm) Coupler Cp-4 High boiling point solvent 0-3 Gelatin 11th layer: Highly sensitive blue-sensitive silver halide emulsion layer Silver bromide (Ag12
Mol% average particle size 0.90 μm) Coupler Cp-4 High boiling point solvent 0-3 Gelatin 0.1 0.1 0.2 0.9 0.6 0.3 0.6 1.3 0.9 0.5 1.4 2.1 12th layer: 1st protective layer UV absorber U-10,3 UV absorber U-20,4 High boiling point solvent 0-3 0.62.5-
Sheet t-octylhydroquinone 0.1 gelatin
1.2 13th layer: second protective layer average grain size 0.08 μm 1 non-photosensitive fine-grain silver halide emulsion made of silver iodobromide containing 1 mol % of silver iodide
0.3 Polymethyl methacrylate particles (diameter 1.5 μm) Surfactant-1 Gelatin 0.7 In addition to the above composition, gelatin hardening agent-1 and a surfactant were added to each layer.

(Compounds used) Ultraviolet absorber U-1 Ultraviolet absorber U Sensitizing dye S Sensitizing dye S (CHt)sSOz″ (CH,), SO, Na Capragelatin hardening agent ■ Surfactant ■ NaO, 5-C )ICOOCRl(CFICFri3HC
H,C00CR2(CF,CF,)1)1 Sensitizing dye S Sensitizing dye S Coupler cp High boiling point solvent 0 C,H.

C,H.

High boiling point solvent 0 - High boiling point solvent 0 In addition, the silver halide emulsion in the photosensitive silver halide emulsion layer of sample 201 was prepared by maintaining the temperature of the reaction tank at 55°C, and containing ammonium thiocyanate, sodium thiosulfate, and chloroauric acid. was added for chemical ripening.

chemistry The pAg value during aging was adjusted to 9.0, and aging was performed for 90 minutes.

In addition, the silver halide emulsion used in the 10th layer and 11th layer of sample 201 was as shown below in 1) A during chemical ripening.
Sample-2 by replacing with a silver halide emulsion with different g
02 to 20G were produced and shown in Table 3.

Em-7 sample 201 10th layer silver halide emulsion Ea
+-8 sample 201 11th layer silver halide emulsion Em-
pAg during chemical ripening was adjusted to 7.7 using 9Em-7 pAg during chemical ripening using Ea-1o En+-8
Adjustment to 7.7 Table 3 (1): Emulsion weight ratio Each of the samples 201 to 202 thus prepared was wedge exposed using white light and then subjected to the following development treatment. Regarding the first development processing time, in addition to the standard 6 minutes, processing was performed for 4 minutes, 5 minutes, 7 minutes, and 8 minutes.

Processing process Processing time Processing temperature First development
6 minutes 38°C water washing
2/ll1 inversion
21/〃Color development 611〃Tone
Conditioning 2//l/bleaching
61111 established
4 tt tt water
Washing 4〃/l stable
ll/Normal wet/dry
Drying I used in the above treatment step: The composition of the treatment liquid is as follows.

First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g sodium carbonate (l hydrate)
30g Droxymethyl-g 2.5g 1.2g tQ 000tQ l-Phenyl-4-methyl-4-hy3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and transfer the liquid Nitrilotrimethylene Phosphonic acid, hexasodium salt Stannous chloride (dihydrate) p-Aminephenol Sodium hydroxide Color developer with the addition of glacial acetic acid Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide iodide Potassium (0.1% solution) Anti-g g 0.1 g g 5 mQ 1000 m12 g 6 g g 0 mQ Sodium hydroxide 3 g Citrazic acid 1.5 g N-ethyl-
Adjust by adding N-β-methanesulfonamidoethyl-2,2-ethylenedithiodietano water Liquid sodium sulfite sodium ethylenediaminetetraacetate 1g g 000mQ 2g Rum (dihydrate) g 0,4m0 3m (2 000mQ Thioglycerin Bleach by adding glacial acetic acid water Sodium ethylenediaminetetraacetate (dihydrate) g Iron(II) ammonium (2) ethylenediaminetetraacetate
water salt) 120g ammonium bromide ioog add water
1000m12 fixation liquid ammonium thiosulfate 80g sodium sulfite 5g sodium bisulfite 5g add water
1000 mff stable liquid formalin (37% by weight) 5 mI
2 Konidax (manufactured by Konica Corporation) 5m12
For each sample obtained by adding water to 100100O, the blue density was measured, and the relative sensitivity and gamma value were determined.

The relative sensitivity is determined by calculating the reciprocal of the exposure amount required to obtain a blue density of 1.0, and using the first development time of 6 minutes for each sample as the standard (100), and using the other samples as the standard. It is expressed as relative sensitivity versus

Furthermore, the gamma value was expressed by the slope when connecting a straight line from a density of 0.5 to a density of 1.0 in the optical range.

These results and the variation range of relative sensitivity and gamma value are shown below.
4.

As is clear from Table 4, the sample of the present invention had a smaller gamma fluctuation width than the comparative sample, and a remarkable improvement effect was observed in processing fluctuation. Furthermore, the samples of the present invention had uniform sensitivity changes due to changes in the first development time, indicating that the emulsions had excellent performance in terms of sensitivity development characteristics.

Furthermore, similar experiments were conducted with a red-sensitive emulsion layer and a green-sensitive emulsion layer, and similar good results were obtained, confirming that the effects of the present invention are exerted regardless of the difference in color sensitivity. .

Example 3 Color reversal photosensitive material sample 3 was prepared by providing the following 1st to 11th layers on a paper support coated with polyethylene on both sides.
02 (comparative sample) was prepared. The coating amount of each component is g/m
Shown as 2. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Black colloidal silver -0,10 gelatin
-1,5 2nd layer (1st red-sensitive layer) Cyan coupler! ! Antifading agent High boiling point solvent Red sensitizing dye (S t: AgBr1 (Agl-I-I 1, S 3.0 mol%.

---0,080 ---0,16 --- 0.12 --0.06 0.18 2) Spectrally sensitized with average particle size 0.4 μm) ---0,14 -0,81 Gelatin 3rd layer cyan power / anti-fading agent high boiling point solvent red sensitizing dye (S) AgBr1 (Agl (2nd red sensitive layer) Blur C-1---0,043 C-2---0゜085 A-1---0,064 A-2---0,032 o -1---0,097 -1,5-2) with spectral sensitization of 3.0 mol% and average particle size of 0 .8 μm) -0,16 Gelatin -0,98 4th layer (first intermediate layer) Color mixing inhibitor AN tt AN high boiling point solvent
〇- Gelatin 5th layer (first green-sensitive layer) Magenta coupler C- Anti-fading agent 8- // A- High boiling point solvent O- Green sensitizing dye (S-3) AgBrl (Agl 3.0 mol%.

Gelatin 6th layer (second green-sensitive layer) Magenta coupler C- Anti-fading agent 8- // A- High boiling point solvent 〇- Green sensitizing dye (S-3) AgBrl (Agl 3.0 mol%.

■ −0,020 0,060 0,13 −0,90 3−−−0,25 3−−−0,067 4−−−0,12 1−−−0,19 average spectrally sensitized Particle size: 0,4 μm) ---0,15 0,93 3 ---0,15 3 ---0,040 4 ---0,070 1-1-0,11 average spectrally sensitized Particle size: 0.7 μm) Gelatin 7th layer (second intermediate layer) Yellow colloidal silver color mixing inhibitor AN // AN high boiling point solvent
0 Gelatin 8th layer (first blue-sensitive layer) Yellow coupler C- Anti-fading agent A- // A High boiling point solvent
〇- Blue sensitizing dye (S-4) AgBrl (Agl 3.0 mol%.

Gelatin 9th layer (second blue-sensitive layer) Yellow coupler C Anti-fading agent A- ---0,15 ---0,83 ■ 0.20 0.014 0.046 0.096 0.90 4 --- -0.24 1 ---0.096 5 ---0.048 3 ---0.048 Spectrally sensitized average particle size 0.4 μm) ---0,15 ---0,95 ■ ---0,32 ---0,13 tt A 5
---0.064 High boiling point solvent 0-3 ---
-0.064 AgBr1 spectrally sensitized with blue sensitizing dye (S-4) (Agl 3.0 mol%, average particle size 0.8
μl11) -0,13 Gelatin -0,93 1st theta layer (
UV absorbing layer) UV absorber U -1---0,45//
U-2---0,15 color mixing inhibitor AN
-1---0,033 High boiling point solvent 0-3
---0.37 gelatin -1,
87 Eleventh layer (protective layer) Gelatin -0,50 However, in addition to the above, surfactant, hardener, isoCH.

CH.

AN AN-2 Di-2-ethyl hequinulftale Di-isodecyl phthalate Di-nonyl phthalate S ■ C2H.

(CH2), 5O1e (CH3)3SO3゜The silver halide emulsion used in each color-sensitive layer was
It was prepared by the method of Example 1 of Publication No. 78447.

After desalting and washing with water, each emulsion was heated at 55°C in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate.
Optimal chemical ripening was performed at pAg 9.8.

In addition, the silver halide emulsion used in the fifth and sixth layers of sample-301 was replaced with a silver halide emulsion in which 1) Ag was changed during chemical ripening as shown below.
2 to 306 were prepared and shown in Table 5.

Em-11 Sample-301 5th layer silver halide emulsion Em-
12tt 301 6th layer //Em-13Em
PAg during chemical ripening using Em-11 was adjusted to 7.1 l) Ag during chemical ripening using Em-12 was adjusted to 7.1 Table (1) Weight ratio of emulsions Each of the emulsions prepared in this way Samples 301 to 306 were subjected to wedge exposure using white light and then subjected to the following development treatment.

In addition, regarding the first development process, 1 minute of the standard development time
In addition to 5 seconds, 1 minute and 1 minute 30 second treatments were also performed.

First development (monochrome development) 1 minute 15 seconds (38°C) Washing with water 1 minute 3
0 second light fog IQO (2ux or more 1 second or more 2nd development (color development) 2 minutes 15 seconds (38°C) Wash with water 4
5 seconds bleach fixing 2 minutes (38°C) water
Washing: 2 minutes and 15 seconds The composition of the treatment liquid used in the above treatment step is as follows.

(First developer) Potassium sulfite 3.0g Sodium thiocyanate 1.0g Sodium bromide 2.4g Potassium iodine
8.0ffig potassium hydroxide (48%) 6.2mQ potassium carbonate
14g sodium bicarbonate
12g1-phenyl-4-methyl-
4-hydroxymethyl 3-pyrazolidone
1.5g hydroquinone monosulfonate
Add 23.3g water 1.
012 (pH 9,65) (Color developing solution) Benzyl alcohol ethylene glycol Potassium carbonate (anhydrous) Potassium hydroxide 14.6 aff 12.6 + aQ 6 g 1.4 g Sothorium sulfite 1.6 g This result and the variation range of gamma value depending on development time 3.6-
Cythiaoctane-1.8-diol 0.24g Hydroquinylamine sulfate 2.6g4-N
-Ethyl-N-β-(methanesulfonamidoethyl)-
Add 5.0g of 2-methyl-p-phinydiamine sesquisulfate and water.
i, oI2 (bleach-fix solution) 1.56 molar solution of ammonium salt of ethylenediaminetetraacetate diiron complex 115+oQ
Sodium metabisulfite 15.4g Ammonium thiosulfate (58%) 126IIIQ5-mercapto-1,2,4-triazole 0.4g Add water to 1.012 (pH = 6.
5) The blue density was measured for each sample obtained, and the gamma value was determined. The gamma value is expressed by the slope when connecting the density of 1°5 in the optical range with a straight line from the point of density 0.5.

are shown in Table-6.

As is clear from Table 6, the sample of the present invention had a smaller gamma fluctuation width than the comparative sample, and a remarkable improvement effect on processing fluctuation was observed.

Furthermore, when similar experiments were conducted with a blue-sensitive emulsion layer and a red-sensitive emulsion layer, similarly good results were obtained, confirming that the effects of the present invention are exerted regardless of the difference in color sensitivity. .

〔Effect of the invention〕

As mentioned above, the silver halide photographic material of the present invention has excellent gamma stability over changes in development time.
The silver halide photographic material of the present invention can be made highly stable in processing.

hand continuation amendment July 10, 1999

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers is subjected to substantial chemical ripening with a pAg value of 6.0 to 8.
A silver halide emulsion with a pAg value of 8.9 and at least one layer of the emulsion layer are subjected to substantial chemical ripening with a pAg value of 8.9.
A silver halide photographic light-sensitive material, characterized in that it contains an emulsion applied within the range of 11.0 to 11.0.