JPS59184341A - Method for processing color photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To reduce a change in photographic properties while using a developing soln. after the lapse of time and to improve stability during processing by processing a color phtosensitive silver halide material with a color developing soln. contg. aromatic primary amine as a color developing agent, a aspecified decomposition inhibitor and a chelating agent. CONSTITUTION:A color phtosensitive silver halide material is processed with a color developing soln. contg. aromatic primary amine as a color developing agent, 0.01-0.6g/l compound represented by formula I as a decomposition inhibitor and a compound selected from a group consisting of compounds represented by formulae II-IV. The color developing agent and org. components such as hydroxylamine in the developing soln. are well protected from decomposition in the presence of heavy metallic ions such as Fe and Cu ions. The developing soln. has sufficient power to sequester Ca and Mg ions in the presence of these ions, and it does not form a precipitate and does not get cloudy. In the formulae, m is 1, 2 or 3, n is 1 or 2, R is lower alkyl, and M is H, an alkali metallic atom or ammonium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing silver halide color light-sensitive materials. More specifically, it relates to a method for processing silver halide color light-sensitive materials with significantly improved stability.

In the processing of silver halide color light-sensitive materials, color developers play an important role in determining the photographic properties of the light-sensitive materials.

The liquid generally contains an aromatic primary amine developing agent that couples with a coupler to form a dye.
It is well known that this compound is oxidized over time by oxygen in the air or metal ions in the developer, and does not affect photographic properties. Therefore, it is well known that sulfite is used as an antioxidant in color developing agents. Since the coupling between the developing agent and the coupler is significantly inhibited, the amount used is limited and cannot be used in large amounts as in the case of the T1 black and white developer.

Additionally, hydroxylamines can be used as antioxidants along with sulfites, as described in US Pat. However, the presence of heavy metal ions such as iron and copper ions tends to accelerate the decomposition of hydroxylamines and produce ammonia, and the ammonia produced in this way has an adverse effect on the properties of color photographs, as is well known. Therefore, even when hydroxylamines are used, the stability of color developers is often insufficient.

On the other hand, it is well known that color developers use carbonate buffers and phosphate buffers because they require an alkaline pH of 9 to pH/;t, but calcium and magnesium ions derived from water or calcium eluted from photosensitive materials The solubility of the metal ions in the buffer is extremely low, resulting in white precipitates in the color developer, causing problems such as adhesion to photosensitive paulownia materials and clogging of filters in automatic processors. A bay agent is essential.

As mentioned above, in color developers, the decomposition of organic components such as color developing agents and hydroxylamines is prevented,
In addition, it is necessary to have sufficient ability to hide calcium ions and magnesium ions.A number of methods have been proposed in the past as methods for preventing the decomposition of color developing agents and hydroxylamines.

For example, the method using hydroxamic acid described in JP-A No. 2-22 and 3♂, the same! 2-'19F, a method using a dihydroxynaphthalene compound described in the 2j specification, 3.2-'/θ, a method using a saccharide described in the 27.27 specification, and a method described in the 2j Goo 3 No. 32 specification The same method using alkanolamines! g-9g-3 The method using polyalkyleneimine described in the specification of No. 9, same! 2-
A method using the α-aminocarbonyl compound described in No. 302θ and No. 63-79412j,
<-7j Nigu No. 2 and the same! A method using oxycarboxylic acids represented by nocurconic acid, described in the specification of Targ/Kug♂, U.S. Patent No. 3/Oh 03 and British Patent No. 130
#/7 is a method using hydroxy 7cetone or dihydroxyacetone described in the specification, US Patent No. 3?230/7
A method using 2-anilinoethanol described in the specification,
Tokukai Akira! t-47θ3? No. and same! T-3,2/￥0 and US Patent No. 32! Kuku details 1. Although many methods have been proposed, such as the method using the aromatic polyhydroxy compound described above, in all of them, the stabilization of the color developer is insufficient, the compound is expensive, or the amount used is large.
), or the compound itself affects photographic properties, making it impossible to obtain practically satisfactory results.

On the other hand, many compounds are known as metal ion hiding agents (chelating agents) used in developing solutions.

Examples of inorganic chelating agents include sodium tripolyphosphate,
Sodium hexametaphosphate, sodium tetrapolyphosphate, and the like are well known, but they have a drawback that they have low calcium hiding and f ability and cause calcium precipitation when the color developer is aged.

Examples of aminopolycarboxylic acid chelating agents include nitrilotriacetic acid and ethylenediaminetetraacetic acid.
These have the disadvantage that they have a low calcium hiding power and that the iron complex itself promotes the decomposition of color developing agents and hydroxylamine. U.S. Patent, 2 and 730
/ as stated in the Gwa issue.

3-diaminopro-t-nortetraacetic acid has low water solubility and low calcium hiding power, making it unsatisfactory. 4 to 1. Kaisho J, 2-. /, -monocyclohexanediamine-N, N, N', N'-tetraacetic acid, and the same! Binuhydroxyethylenediamine diacetic acid described in No. 7-10212 has relatively little decomposition of color developing agents and hydroxylamine, but has low calcium hiding/f ability, and is a very expensive compound, so it is not suitable for color developing solutions. impractical to use. In addition, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid represented by the general formula (1) of the present invention are disclosed in US Patent No. 34t, 22
Although it is described in the issue, the effect of preventing the decomposition of color developing agents and hydroxylamines (both of which are insufficient).

As an organic phosphonic acid chelating agent, Re5earc
h Disclosure /l! ? /No.70, Tokukai Akira! --/θ272 Otsu issue, j3-g 273θ issue, same! ni-19734t7, same! Da/yu//ko 2, same jj-
No. 024, same-f! -'7023, same jj-29
and No. 23, same j! -/21.2g/issue.

Same J, taa! '? ! ! No., No. J-4 on JJ-,
1 Tsutsumi J7-779293, the same tag No. 7725, and West German Patent No. 10G J373, all of which have low hiding power of calcium and prevention of decomposition of color developing agents and hydroxylamine. However, it is not practical because it is opaque and expensive.

In addition, ethylenediamine represented by the general formula (■) of the present invention
N,N,N',Nl-tetranoterenephosphonic acid is Re
Although this is exemplified in U.S. Patent No. 5EarchDisclosure/3G No. 10 and U.S. Pat.

Further, hydroxyalkylidene diphosphonic acid represented by the general formula (It) is exemplified in U.S. Pat. Patent 3794t
As described in the specification of No. J9/1999, there is a drawback that salts that are sparingly soluble with calcium ions and sodium ions or potassium ions are formed, so a means for preventing the formation of precipitates has been proposed.

For example, as described in U.S. Pat.
Lithium ions are very expensive and their usage is limited, and at the same time, the chelating agent hides calcium ions and magnesium ions in color developers. However, if you use it again, the above-mentioned precipitate will still be formed and the Litecum-Ionreli effect will often be opaque.

In addition, as another means for preventing grain sinking, US Pat. No. 3,994,17
No. 30 and Japanese Patent Application Laid-Open No. 7332/1997, methods of using the chelating agent in combination with other aminopolyphosphonic acids or caminopolycarboxylic acids are also proposed, but Although this method can prevent precipitation, it promotes the decomposition of color developing agents and hydroxylamines, so it cannot be said to be an appropriate method.

Furthermore, alkylene diamine di(O
-Hydroxyphenylacetic acid) is the share B (-ke3-909
Described in No. 00 1. However, the compound significantly prevents the decomposition of developing agents and bitroxylamine7.
'7F has low electrical conductivity and is expensive, so its usage is limited (1. It has the disadvantage of low calcium hiding ability. Other gylating agents (ethylene diamine) Sodium tetraacetate, sodium nitrilotriacetate, sodium tripolyphosphate, and sodium hexametaphosphate) are described in the patent.
In this case as well, the decomposition of hydroxylamines is accelerated and calcium precipitates occur, making it impractical.

As mentioned above, there is a method for stabilizing color developing solutions, for example, preventing the decomposition of color developing agents and hydroxylamines, and preventing precipitation of lucium ions and Fuguishium ions. However, a satisfactory and practical means for determining the light intensity has not yet been found.

Therefore, it is an object of the present invention to solve the problem that the '11 component in a color developer such as a two-color developing agent or hydroxylamine is decomposed by light due to the presence of heavy metals such as iron and copper. The object of the present invention is to provide a photographic processing method for obtaining a color X-ray image using a protected color developer.

The second object of the present invention is to provide a color developer which has sufficient hiding power for metal ions in the presence of calcium ions and magnesium ions and which does not cause precipitation or cloudiness, and a color developer using the same. An object of the present invention is to provide a photographic processing method for obtaining a color photographic image.

The above purpose is to develop a silver halide color light-sensitive material into (1) an aromatic primary amine color developer-E agent, (2) at least one compound represented by the following general formula (1) with O3
θ/~0, , <f/'IJ, and (3) selected from the group consisting of compounds 7)h represented by the general formula (■) in 1-, general formula (1), and general formula (IV) It has been found that this can be achieved by processing with a color developer containing at least one compound ('-).

C00M COOM General formula (If) H General formula (jl) CH2C00M General formula (■) In the formula, m represents an integer from / to 3, n represents/or
represents a lower alkyl group (preferably one with up to 3 carbon atoms, such as a methyl group, an ethyl group, etc.), and M may be the same or different and represents a hydrogen atom, an alkali metal atom (sodium atom, potassium atom, lithium atom, etc.). ) or represents ammonium.

Specific examples of the compound represented by general formula (1) include the following.

1-/-2 Specific examples of the compounds represented by formulas (If) to (ff) include the following.

fl-/ CH3 H2O5P-C-PO3H2 H 1[-,2 2H5 1[-3 CH2C00H ■-da CH2C00H ■-j ■-Otsu The compound of general formula (1) is alkylene diamine di(0-
known as hydroxyl ethyl acetate). The amount of the compound to be added is θ per liter of color developer, 0/~θ, preferably Q, θ/~θ, more preferably o, θt1.
io~0.30? It is.

A commercially available product can be used as the present compound.

The compound of general formula (II) is /-hydroxyetheri7'
f 7- / , / i) Oh 7-□-
one,. - The amount of the compound added is preferably 0.10 to θ1, more preferably 0°3 per color developer/l.
0~ko, Of.

The compound of general formula (I) is known as diethylenetriamiso-pentaacetic acid, triethylenetetramine-hexaacetic acid, etc., and the amount of the compound added is preferably 0.7 θ per liter of color developer! , 0? , more preferably 72-32. It is particularly preferred to use it in the form of its sodium salt.

The compound of general formula (IY) is ethylenediamine-N.

It is known as N,N',N'-tetramethylenephosphonic acid, and the amount of the compound added is preferably in the color developer/
θ per l, /θ~! , 01, more preferably θ, JO-
2, θ2.

Among the compounds of general formulas (II) to (IV), compounds of general formulas (It) and (TV> are preferred.Also, compounds of general formulas (II) to
Two or more of the compounds of l) may be used in combination.

Aromatic primary amine color developing agents used in the present invention are known and widely used in a number of color development processes. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below.
It is not limited.

D-/N,N-diethyl-ri-phenylenediamine D-22-amino-j-diethylaminotoluene D-3-monoamino-t-(N-ethenol, -N-laurylamino)toluene D-gu [ N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-sx-methyl-gu [N-ethyl-N-(β-hydroxyethyl)aminocoaniline D- to N-ethyl-N-(β- N,N-dimethyl-p-phenylenediamine D-9 guamino -3-Methyl-N-ethel-N-methoxyenalaniline D'-10guamino-3-methyl-N-ethel-N-
β-Ethoxyethyl 7niline D-// Kuamino-3-methyl-N-ethel-N-
β-Sotoxyetheraniline The p-phenylenediamine derivative of E et al. may also be a salt such as a sulfate, a hydrochloride, a sulfite, or a p-)luenesulfonate. The above compound is disclosed in U.S. Patent No. 2793
θ/! No. 2. f3; 22g/issue, same, 231.42
7/ issue, same + 2j ri 23? gu, 95θ on the same 3rd day,
It is described in Waza No. 525 in the same 3. The amount of the aromatic-grade amine developing agent used is about 0.00% per liter of developer solution. /1
~ about 207, more preferably about o, sy ~ about 10? The concentration is

As is well known, the color developer used in the present invention preferably contains hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. Hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of hydroxylamines may be substituted with an alkyl group. Preferred hydroxylamines are compounds of the following formula.

H -N-H'', R is a hydrogen atom or an alkyl group having 7 to 3 carbon atoms (preferably or optionally substituted carbon/
~3 alkyl group).

The above compound may be a water-soluble acid salt. It is particularly preferred that R is a hydrogen atom. Preferably, the amount of calories added to the compound is 0.1 to 0.1 per liter of color developer. ~ Co θg more preferably /f! ~10? It is.

Specific examples of the hydroxylamine used in the present invention include the following compounds.

-1 H -NH H-coH CH3N)-1 H-,? The color developer used in the present invention preferably has a pH of 9.
~/, 2, more preferably 9 ~//, θ, and the color developer (2) may contain other (=compounds of known developer components).

For example, as an alkaline agent and a pI-1 buffer, caustic soda, caustic potash, soda carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, potassium metaborate, borax, etc. are used alone or in combination. .

In addition, for the purpose of providing buffering capacity, for formulation convenience, or to increase ionic strength, it may be added to Various salts are used, such as alkali nitrate, alkali sulfate, etc.

Color developer (- means necessary (2) Any development accelerator can be added. For example, U.S. Pat. Various birimidium compounds and other catheonic compounds represented by No., cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 4T'l-9304, U.S. Patent No. 23339-0 ,
2S3/ and 32, 29!0970, 2377
Polyethylene glycol and its derivatives described in No. 127,
Nonionic compounds such as polythioethers,
&-9! θ9, Belgian patent /, /2J'tλ organic solvents and organic amines, ethanolamine, ethylenediamine, jetanolamine, etc., as well as F,
Written by A. Mason [PhotographicPro
cessing ChemistryJ P41O-
<t 3(pocal Press-: [, andon
-i 91 l) The accelerators described in D can be used. In addition, 2 US patents! /3-7417
Benzyl alcohol, phenyl ether alcohol, Journal of the Photographic Society of Japan, Volume 4, Page 2 (7952)
Pyridine, ammonia, hydrazine, amines, etc. described in 2010) are also useful development accelerators. Also, three US patents θ/
The thioether compounds described in No. 2G No. 2 may also be used. Among these, ethylenediamine, benzyl alcohol, and thioether compounds are particularly preferred.

Additionally, sodium sulfite, potassium sulfite, potassium bisulfite, or sodium bisulfite, which are commonly used as preservatives, can be added.

In the present invention, any necessary antifoggant can be added to the color developer. Examples of the antifoggant include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants. Examples of organic antifoggants include benzotriazole, nitrobenzimidazole, !-nitroisoindacyk, !-)tylbenzotriazole, and !-). Nitrogen-containing to terocyclic compounds such as -nitrobenzotriazole, j-chlorobenzotriazole, J-'f azolyrubenzimidazole, cortiazolylmethyl-benzimidazole, hydroxyazaindolizine, and/-phenyl-! Mercapto-substituted heterocyclic compounds such as -mercaptotetrazole, comelcabutobenzimidazole, comelcabutobenzotheazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heterocyclic compounds.

These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

1 In the case of reversal color processing, competing couplers in the color developer include citrazic acid, J acid, H
Acids etc. are useful. For example, U.S. Patent 274t,
2 r 3.2 issue, special public Sho Guku 9! θri issue, same Gugu 9! Ot No. 9307, U.S. Patent No. 3j20
No. 90, No. 0.2/2 on No. 31, No. 3g! Compounds described in No. 732 and the like can be used.

Alkali metal borohydride, amine borane, ethylene diamine, etc. can be used as the brushing agent. Other compounds described in Sections 4t7-j, f', r/ can be used.

As a compensating developer, p-aminophenol, N-benzyl-p-aminophenol, /-phenyl-3-pyrazolidones, etc. can be used.

The analogy is Tokusho Gu5-gu/Gua! No., Glow 7903
The compounds described in No. 2 are useful.

The color photographic processing method of the present invention is described in U.S. Patent No. 3.22.7.
．． fj1 and 3.227. It can also be used in diffusion transfer color photography using the method described in No. fjλ.

In this case, the coupler may or needs to diffuse into other layers during the processing step.

The processing method of the present invention is an internal development method in which a coloring agent is contained in the photosensitive material (US Pat. No. 2,376,679, US Pat.
22027 and 2/θ//7/), as well as the so-called external development method in which a coloring agent is present in the developer (U.S. Pat.
．． 2627 / No., same, lj9ko24t3 and same,
No. 2390970) (- is also applicable.

Therefore, the processing method of the present invention can be applied to a color developing bath/flum, a color bath, a color positive film, and a color film.

Common materials such as transfer film) and silver-based color photographic materials chairs! It can also be applied to the main process.

In the method of the present invention, processing steps such as image-exposed color negative film, color positive film, color 1/e-, etc. are usually (1) color development → bleaching → water washing → fixing → water washing → stabilization-drying (2) color Develop → Wash with water → Bleach and stabilize → Wash with water → Stabilize →
Drying (3) The basic process is color development → stop and fix → bleach and fix → washing → stabilization → drying. Further, a bath, a hardening bath, etc. may be provided before color development, and water washing after color development, water washing after bleaching, stabilization bath, etc. can be omitted.

On the other hand, the processing steps for color reversal films are usually (4)
Black and white development → Stop → Water washing → Kaburashi → Color development → Stop → Water washing → Bleaching → Water washing → Fixing → Water washing → Stabilization → Drying (5) Black and white development → Water washing → Water washing → Color development → Water washing →
The basic process is promotion → bleaching → fixation → water conditions → stabilization → drying. Steps (4) and (5) may further include a pre-bath, a pre-hardening bath, a neutralization tower, etc. Alternatively, a bleach-fixing bath may be used. Further, a stop bath, a stabilizing bath, a water wash after a color developing bath, a water wash bath after a bleach bath, an accelerator bath, etc. can be omitted. For the sword brush bath, brushing agents such as t-butylamine borane sodium borohydride, tin-amino polycarboxylic acid complex salts, aqueous sodium boron, etc. can be used. By doing so, the brush bath can be omitted.Also,
The brush bath can also be changed to re-exposure.

In the photographic processing method of the present invention, the steps shown in (1) to (5) above are useful, but the present invention does not include the steps (
= Not limited.

Moreover, the color development process is usually 20 to 0c.

The test is carried out under conditions of 3θ seconds to 1Q minutes.

The silver halide color photographic light-sensitive material used in the present invention is suitable for all color photographic light-sensitive materials that involve a color development process, such as color negative film, color paper, color positive film, and color reversal film.

The photographic emulsion used in the present invention is P, QLafkide.
Written by Chimie et Physique Photo
ographique (Paul M, onte1, 79g2), G, F.

Photographic Emuls by Duffin
ion Chemistry (The pocal
Press, /rigg year), V, T., Zelikm
Mak ing and Co by an et al.
a t ing Photographic Emuls
ion (The FocaL Press, /9
It can be prepared using the method described. That is, any of the acid method, neutral method, ammonia method, etc. may be used, and it can also be prepared by reacting a soluble silver salt with a soluble halogen salt. The formats are one-sided mixed method, simultaneous mixed method,
Any combination thereof may be used.

It is also possible to use a method in which particles are formed under an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which the pA and g in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrod-Dazur jet method can also be used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride may be used as silver 1110.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a talicum salt, an iridium salt or a complex salt thereof, a [-T dicum salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The photographic emulsion used in the present invention includes methine dyes and other (
2, it may be spectrally sensitized. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holopolar-cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Useful sensitizing dyes include, for example, German patent 929, 0? No. θ, US Patent λ, 23/, +, t♂ calyx, same.

Gu93,7ri! No., same, f03.77 No. Otsu, same,
6/9.0θ/ issue, same, 9/2,329, same 3. To Nio, Tao No. 9, Tao No. 31 and 22. and No. 27, same 3. Go9
Gu, No. 277, Same Gu, 0.2 spear, 3 Gu No. 9, Ma, θ dago,! No. 72, British Patent/.

2 Octopus, J Toto No., Special Public Sho Gu Goo/G No. 030, plj
J--2 Guzagugu: This is what is described in 2.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization1, a representative example of which is disclosed in U.S. Pat. Ko, 6;/za, No. 593, same.

No. 977.229, No. 3, No. 397.060, No. 3
, No. 322.052, 39. Da27. No. 77, No. 3
．． AI7.293, 3. 2 and 9 Gogu issue, 31
eg Otsu≦lritto0, same 3,372. ! 9♂ issue, same 3
．． Za79. l/! , No. 2r, 3, 703.

No. 372, same? , 7/:9, 3θ/ issue, same 3. and/g,
Go No. 09, same 3. Za37. ,! ? 1st issue, same gu.

02, No. 707, British Patent/, 3 Google 1.2 Za No. 7,
Same/, j'07. Za 93, special public Akihiro 3-g 23 Otsu,
Same, f3-/, 2.37! No., Tokukai Akira! λ-//θ is described in No. 72, and Tako-/θ is described in No. 9.2it.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. An example is an aminostilbene compound substituted with a nitrogen-containing heterologous group (for example, U.S. Patent No. 933,39θ, 3.t3
! , No. 72/), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,2, No. 3,610), cadmium salts, azaindenated metals, and the like. U.S. Patent 3, g/j.

73, 3. T/! , Nigutsu issue, same 3. Za/7.2
ri No. 5, same 3. The combinations described in Items 3 and 7 are particularly useful.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein trout proteins; cellulose conductors such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate salts, etc., sugars such as sodium alginate, starch derivatives, etc. Derivatives: Various synthetic highly hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyhinyl alcohol partial acetal, poly N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

Typical synthetic hydrophilic polymer substances are, for example, West German Patent Application (OLS) 2,... /, 2, 7θ1, US Patent 3. 2θ, 2O/No., 3. and 79, 2θj,
Special Public Show E3-7. t is as described in No. 1.

The invention can also be applied to multilayer, multicolor photographic materials having at least one different spectrally sensitive layer on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
and at least one blue-sensitive emulsion layer. The JlIn order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used in some cases. You can also do that.

The photosensitive material used in the present invention may contain a water-soluble dye as a filter dye in the hydrophilic CO layer for prevention of irradiation and other various purposes. Dyes include oxonol dyes, hemioxonol dyes, steryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Among them, ogisonol dyes; hemimegisonol dyes and merocyanine dyes are useful.

Specific examples of dyes that can be used include the British patent str<t, gθ
ri issue, same i, /77 +729 issue, Tokukai Show ¥ to -zama 730 issue, same ¥9-99#20, same gu 9- // Doug 20 issue, same! Co/θza, No. 775, U.S. Patent Co., 27
4t, 7 and co-number, same, 333, ri2 co-number, same, rij4. Za2ri No. 3. /gl.

/,! ? 'No. 2, No. 3, No. /77.07, No. 3. Cog 7, /, No. 2.7, Same 3. ! Gu θ, ZaI No. 7, same 3゜! ? ! , 7θgu issue, same 3. T, f3.90! No. 3.
7/6', Gua, No. 2, same number, θ7/, No. 3/2, same number, θ70.3!2 (2).

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, US Pat. No. 2,31.0. ．． 29
No. 0, same 2. Ri/za 1g/3, same 2. e>73,3/
Gu No. 2, 2θ/, /wa No. 7, No. 2, 2.70 Gu, 77
No. 3, same, 7.2, and No. 52, same, 732. ,?
θθ No., λ, 73. f, 71゜evening issue, same, 710
, ♂0/issue-2 same, ♂/6. θko? No., British Patent/
, 3A3. Ha.f-droquinone derivatives described in U.S. Pat. '1. f7,022, same 3,0
- Gallic acid derivatives described in 21.2, No. 2, etc.,
U.S. Patent No. 2.23s, >35, 3°69? , 9θ9
No., Special Public Shogu 9-2θri No. 77, same! p-alkoxyphenols described in Co. No. 3623, U.S. Pat.
, 4732, 3θO No. 3, . 3-73, 03
θ No. 3. j7 gu, 27th issue, 3, 2 ni gu, 337
p-oxyphenol derivatives described in JP-A No. 2-36g33, JP-A No. 62-/G7-3, JP-A No. 2-36G3, JP-A No. 700.755, U.S. Patent No. 3, 700.755
There are bisphenols listed in this issue.

Photosensitive ladles made using the present invention may include UV absorbers in the hydrophilic colloid layer, such as benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,333.79F). ), terteazolidone compounds (e.g. U.S. Pat. No. 3,3/41, 79
Number 4, number 3, 3 octopus.

6? ), benzophenone compounds (e.g., those described in JP-A No. 27J'), cinnamate ester compounds (e.g., U.S. Patent No. 3°7θt,
tros issue, 3.707.37j),
Butadiene compounds (e.g., U.S. Pat.
No. 9) or benzoxyzole compounds (such as those described in US Pat. No. 3.700, '1.!r, f) can be used. Furthermore, US patent 3
．． Tap, No. 762, JP-A-Sho J4T-Gr, 33J
Those listed in item ' can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used.

These UV absorbers may be mordanted into certain layers.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion. Specific examples of fluorescent brighteners are disclosed in U.S. Patent No. 2,432,7θ/,
Same 3, 2A9. fgu No. 0, same 3, 3! No. 102, British patent! ! It is described in No. 2,07 O, Ibid., No. 3/9,763, etc.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a coupler that can develop color by oxidative coupling with an aromatic 7th class amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) during color development processing.

For example, as a magenta coupler, US patent λ.

60θ, 2 and 2, same, 9za 3, 1θt, same 3, θ
λ, S3, 3. /27. ．． 2A9 No. 3, 3
//, 4t7 Otsu, same 3. g/9,3wa/issue, same 3. !
/9. '729, 3. ! 3♂, 3/9 issue, same 3,
! r, No. 2.3.22, 3. AI! .

sot issue, same 3. Za3g, Riθzago, same 3. ? 9/, Guy! No., West German Patent/, and/θ, 4tgZ No., West German Patent Application (OLS) -2, GuOl, Bebe No. 5, Same, 21g/7,9g! No. 2. gu/r, ri No. 59, same, gu 2
Gu, Gu No. 47, Special Public Show Gu0-g037, Special Public Show! /-
No. 2072, Doyoichi-S! ? No. 22, same +t9-/1
9. ! t3za issue, same geta-7ri 027, same jθ-/!
No. 93jt, No. 2/2/Okogu, No. 4t9-741
Same as 02! 0-g0233, 577 on the same O/-2
No. J333/22, patent application Shojter//θ94t3
This is what is described in .

As yellow couplers, compounds of the benzoylacetanilide and biparoylacetanilide F series are advantageous. Specific examples of yellow couplers that can be used include US Patent λ,/
7J-, No. 067. Same 3゜2g! , No. 30. Same 3. Gu0za, No. 797. Same 3,! 3/, /j, f, same 3
．． evening? No. 2.322.

3,72r, No. 072, 31za No. 97,771. West German patent/! 4t7,! No. tF, West German Application Publication Co., Ltd., 2
/9, 9/7 issue, same, 2AI, 34/ issue, same 2. the law of nature/
Gu, oo/No. 3, British Patent/, Gu! , No. 0.2.0,
Special public Akira! /-10713, JP-A-4T7 1 piece t/33
No., same Gu and -73/G No. 2, same! /-10,2,/s3
No., jθ-634t1, same! 0- / 2334
T No. 2, same! θ-/30 Guguco, 37-. 2//
Core issue, same! It was written in the θ-za7za S0 issue, the same 32-#24-gu issue, the same Okoh//Yu2/ri issue, etc.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

Specific examples include U.S. Patent No. 9,929, U.S. Pat.
! , 2/ , No. 90♂, same, F9j,? λ No. 3
, 03 gu, za 92 issue, 3, 3//, gua ni issue, 3.
Gu! F, No. 3/j, same 3. Gua g.

Jtj issue, 3.3?3,97/issue, 3. j9/, 3
No. 73, 3, 747.777, same g.

θOg, RI No. 29, West German patent application (:0LS), 2°G/G, F3θ No., same, RI 34t, 322, JP-A-Shogu f-j? ? 3 and issue, same S/-λOtsu 03gu issue, same guza-j
O#j issue, same/-/4t+zakoto issue, same! 2-19 Go 2y No. 90932, Same,! ? -/j-3!
3J'' and the same No. j2-2θg!yj.

As a colored coupler, for example, U.S. Patent 3° & 74
, j Otsu O issue, 2,327. No. 0r, No. 3.03, and No. 92, Special public Sho Doug-20 Fu No. 3, No. 3F-, 22
No. 33j, same number 2-//30, same number 32, 7
No., JP-A-6/-2603 specification, same! Hugues 2
/2/ issue specification, West German patent application (OLS), 2. g/r
, 962 may be used as DIR couplers, such as those described in U.S. Pat.
．． No. 33, same 3. Ni/7, No. 297, same”
3,70/, 7,3 issue, f@3, 790,
3.41, 3. 32.3g! No., West German patent application (
OLS) λ, 4t/g, θθ6, same, g! g, 30
/ issue, same 2. Gu! No. 329, British Patent No. 963.4t
! Gu issue, Tokukai Sho! 9A241 to Ko, same 9-722
No. 335, Tokuko Sho J-/-/1. Those listed in No. 7 can be used.

In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, US Pat. No. 3,297, 4t! No. 3.379.
No. 329, West German Patent Application (tJLs) Yu, Gu/7.9/
No. 3, JP-A No. 32-/j, No. 277, JP-A-33-9/
/ Items listed in No. 4 can be used.

Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in λ or more different layers.

These couplers are generally present in amounts ranging from 2X/θ-3 moles per mole of silver in the emulsion layer! x/θ-1 mole, preferably /X10'' mole to 3-X/θ-1 mole.

Example / The following color developing solution was prepared.

Distilled water 700ml 1J anhydrous sodium sulfite 2. Tough trisodium phosphate decahydrate Salt θ, θ Sodium bromide θ・9 is potassium iodide (θ
,/person in charge) 90.0ml caustic soda
3. Of Dag-Mino-N-Ether-N
- (β-methanesulfonamidoethyl)-3-methyl-guaminoaniline //, θ7 additive (
(See Table 1) Add distilled water for 10 oomlp
H=//, match to ts.

This color developer is added as F.-book ions/pPm (F
ecg3 solution) 200 ppm GC as Ca+ ion
a(NO3)2 solution) was added and stored at 4tOOC for 74 days. .

Thereafter, the concentration of the color developing agent was analyzed by serimetry, and the presence or absence of precipitation was confirmed. The results are shown in Table 1.

According to the present invention, not only the deterioration of the color developing agent is significantly prevented, but also the precipitation caused by calcium is not generated.

Example 2 The following color developer was prepared.

Distilled water 200ml Benzyl alcohol 79ml diethylene glycol 10ml Sodium sulfite, 2y Potassium bromide o,! 1 Sodium carbonate
301N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-guaminoaniline sulfone)! ,,0# Hydroxylamine sulfate (No, / not included), oy additive (
(See Table 2) Add distilled water to 7000ml pH
: Set at 10.00.

State Toko color developer (Fe ion/ppm (F
eC/! 3 solution), and 200p as Ca+ ion.
pm (Ca(NO3)2 solution) was added and heated at θ°C for 2
Stored for 0 days.

Thereafter, the a degree of hydroxylamine and color developing agent was analyzed, and the presence or absence of precipitation was confirmed.

The results are shown in the second layer.

Although the presence of hydroxylamine significantly prevents the deterioration of the color developing agent (NO,/and 2), the present invention, which uses a specific compound represented by the general formula in combination, prevents the deterioration of hydroxylamine and the color developing agent. This is significantly prevented, and no precipitate attributable to calcium is formed.

Example 3 The following first layer (lowest layer) to t@th (top layer) were coated on a paper support laminated on both sides with polyethylene to prepare a multilayer color photosensitive material.

(In the table, mW/m represents the coating amount.) */ Uncoupler: 2-[α-(2, monoamylphenoxy)butanamide]-g, 6-dichloro-o-methylphenol *λ Solvent diphosphoric acid- Trinonyl ester *3 Ultraviolet absorber: 2-(2-hydroxy-3-sec-butyl-1-1-buternohenyl)penztriazole*gmainta coupler: i-(,:z,y,za-trichlorophenyl) -3- [Kokuroguchi-! -tetradecanamide]anilinocobylazolinoj-one*j Coupler solvent diphosphoric acid-0-cresyl ester*B Yellow color 1-y-: α-pivaloyl-α-(2
, Gudioxo-5,! -dimethyloxolidin-3-yl)- λ-chloro5-[α-(2゜goozi-t-amylphenoxy)butanamide]acetani; Lido After exposing the above sensitive material through an optical wedge, it was processed in the following step. .

Treatment process (33°C) The components of each treatment liquid are as follows.

The color developer of NO9/-N (1, // used in the color developer example) was prepared immediately after preparation and after 20 days at 4 to °C.
I used the.

Bleach-fix ammonium thiosulfate /2'1. l? Sodium metabisulfite /3.39 Anhydrous sodium sulfite 2.72 Add j2 water to EDTA ferric ammonium salt /θθθ
nV.

The pH was adjusted to 4.7-6.

Next, the light reflection densities of yellow, magenta, and cyan were measured using a Fuji self-recording densitometer.

Color development C The photographic properties processed immediately after preparing the solution at night are taken as the standard, and the changes in photographic properties after the solution ages (Dmin and D: = 2.θ
Table 3 shows the change in optical density at the point .

As shown in Table 3, the present invention, which uses the compound represented by the general formula, not only stabilizes the developer and prevents precipitation, but also maintains the photographic properties of the developer even after aging. The changes were two times smaller, and the stability of the process was significantly improved.

Patent Applicant: Fuji Photo Film Co., Ltd. April 731, Showa N. Commissioner of the Japan Patent Office 1, Indication of Case: Showa Jr. Patent Application No. TYθ7V
No. 2, Name of the invention Processing method for silver halide color light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Amendment Subject: Column 5 of the "Detailed Description of the Invention" of the description, Contents of the Amendment All entries in the "Detailed Description of the Invention" section of the description are amended as follows.

(1) Delete "ammonia" in the 7th line of page 2.2.

(2) "Color development → washing → bleach-fixing →" on page 2J-page 17 is corrected to "color development → bleach-fixing →".

(3) Delete "Also, wash with water after color development" on page 26, lines 2-3.

(4) Correct “stability” in the second line of page jλ to “stabilization”.

Procedural amendment, official book Showa to ¥+1 [( Mr. Commissioner of the Japan Patent Office 1, Indication of case Showa! to 2013 patent application No. 7.2, Name of invention Processing method for silver halide color light-sensitive materials 3 , Relationship to the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Hiroshi Fuji Photo Film Co., Ltd. Subject of amendment ``Detailed Description of the Invention'' column of the specification! Contents of the Amendment On page 1j, line r from the bottom of the specification, ``preferably 00O7~θ.&Oj'' is corrected to ``preferably 0.0/~0.30''.

Claims (1)

[Scope of Claims] A silver halide color light-sensitive material comprising: (1) an aromatic primary amine color developing agent; (2) at least one compound represented by the following general formula (1); /l and (3) the following general formula (It
), a color developer containing at least one compound selected from the group consisting of compounds represented by general formula (I) and general formula (IV). Method. General formula (1) %Formula% General formula (It) M2O3P-C-PO3M2H General formula (1) General formula 1') (In the formula, m represents an integer of / to 3, n represents / or R represents a lower alkyl group, and M may be the same or different and represents a hydrogen atom, an alkali metal atom or ammonium.)