JPS62201436A - Color image forming method - Google Patents

Abstract

PURPOSE:To enable high color density to be formed in a short time by color developing a photosensitive material with a processing solution containing substantially no benzyl alcohol in the presence of a specified compound. CONSTITUTION:The silver halide color photographic sensitive material provided with at least one of photosensitive layers containing a color coupler on a reflective support is color developed after imagewise exposure within a developing time of 2min 30sec. With a color developing solution containing substantially no benzyl alcohol in the presence of the compound represented by formula I in which X is H, optionally substituted alkyl, alkoxy, aryloxy, or amino; Y is optionally substituted alkyl or aryl; and n is an integer of 1-3. Said compound is added in an amount varied dependent on the contents of the composition of the photosensitive material, but when it is added into the photosensitive layer or nonphotosensitive layer of the photosensitive material, it is added, preferably, in an amount of 10<-4>-10mol% of silver halide contained in the photosensitive material, and when it is contained in the color developing solution, it is added, preferably, in an amount of 5X10<-9>-1.5X10<-1>mol/l.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a color image forming method, and more particularly to a color image forming method that causes less environmental pollution and allows rapid processing.

<Prior art> As a color image forming method, silver rhodanide color photographic light-sensitive materials (silver rhodanide color photographic materials) having a hydrophilic colloid layer containing a color coupler dissolved in a high-boiling organic solvent in the form of oil droplets have been conventionally used. After imagewise exposure, the exposed silver halide grains are developed by the color developing agent. ``(Reducing silver ions in silver halide)--A coupling reaction between the oxidized product of an aromatic primary amine compound and the above color coupler is performed to form a dye, and a color image is formed. What you get is well known.

In recent years, demands for improved productivity have been increasing in the photographic industry, and the problem of how to quickly process a large number of prints has always been the most important issue. In order to solve these problems, shortening the processing time for photosensitive materials, especially shortening the processing time for color photographic paper, is considered to be the most effective means.

In order to achieve such a reduction in development processing time, it is necessary to provide as high a color density as possible within a limited development time. An effective way to achieve this is to increase the coupling speed as high as possible.

It is known that the coupling reaction rate depends on both the reactivity of the color coupler used and the permeability of the aromatic primary amine compound, which is the color developing agent, into oil droplets (including the coupler). .

For these reasons, various methods have been studied to increase the rate of penetration of color developing agents into oil droplets.

Among these methods, the method of increasing the development speed by adding benzyl alcohol to color development is currently widely used in the processing of color photographic paper because of its great effect of promoting color development.

<Problems to be Solved by the Invention> When benzyl alcohol is used for convenience, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as a solvent due to its low water solubility. However, these compounds, including benzyl alcohol, have a pollution burden value of BOD-? Since the COD is high, it is preferable to remove indyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if the solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Also, a bleaching bath in which benzyl alcohol is used as a post-bath.

Alternatively, if it is brought into the bleach-fixing bath, it causes the formation of leuco dye of N'an dye, which causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the processed light-sensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development has generally been processed in 3 to 1 minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, there has been a desire to shorten the processing time.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, the color density will be significantly lowered and additional work will be necessary.

To solve this problem, various proprietary color development accelerators (for example, U.S. Pat. No. 0,920, U.S. Pat.
, / 4t7, same u, 4t9. (, No. 903.

λ, 30g, No. 925, u, 03r, No. 076,
Same da, 119. Dawo No. 2, British Patent/, gri! , da13
No., JP-A-53-15♂31, same! ! -g holder No. 0, same j-J
Ko'If1 issue, same jj-g February issue, same jj-j2gF
No. 3, special public show 11-/2 << No. 22, same evening! -97j
Even when used in combination with the compound described in No. 1, sufficient color density could not be obtained.

In addition, methods for incorporating 3-pyrazolidones (e.g., ttf
y!
- Even when used with raw eel, it has disadvantages such as decreased sensitivity and fogging.

In addition, there is also a method of incorporating a coloring GL image main system (for example, US special tF
37tq da 92, 33g 2! ! No. 9, 3Jy2s
No. 97, JP-A No. 4-6231, JT-/4/33
No. 2-92! Even if the method described in No. J1, No. J7-rJjtj, etc. is used, it is not an appropriate method because it has the drawbacks that color development is delayed and fog is generated.

On the other hand, regarding acylphenol derivatives, it has been reported in Japanese Patent Application Laid-open No. 55-4352 that some structures have the ability to prevent color fogging.
No. 1, No. 61-27539, but there is no mention of the development accelerating effect in short-time processing, and JP-A-54-65535 does not mention the development accelerating effect of acylphenol derivatives. However, only a slight accelerating effect has been observed in treatment systems where benzyl alcohol is present.

Accordingly, an object of the present invention is to provide a color image forming method that provides high color density in a short time even when using a color developing solution that does not substantially contain benzyl alcohol.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide color photographic material having at least one photosensitive layer containing a coupler on a reflective support after imagewise exposure. , achieved by a color image forming method characterized by processing with a color developer substantially free of benzyl alcohol in the presence of a compound represented by the following general formula (I) for a developing time of within 2 minutes and 30 seconds. Ta.

General formula (I) +1 (wherein, X represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an aryloxy group, or an amino group; Y represents a substituted or unsubstituted alkyl group or aryl group) , n is an integer of 1 to 3.) In the present invention, "containing substantially no benzyl alcohol" means that the concentration of benzyl alcohol in the color developer is 2.
ml/9- or less, preferably less than 0.5 mjL/JL, and more preferably not contained at all.

Next, the acylphenol derivative represented by the general formula (I) used in the present invention will be explained.

The alkyl group represented by X in general formula (I) preferably has 1 to 30 carbon atoms, particularly 1 to 2 carbon atoms.
0 linear, mono-branched or cyclic alkyl group. Specifically, methyl group, ethyl group.

Propyl group, 1so-butyl group, tert-butyl group,
Examples include tert-octyl group. The alkoxy group represented by X preferably has 1 carbon number
-30, particularly an alkoxy group having a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms.

Specifically, a methoxy group, an ethoxy group, a 1so-propoxy group, a dobusyloxy group, a hexadecyloxy group, etc. can be mentioned as examples. Represented by X. The aryloxy group is preferably a phenoxy group, and this aryloxy group may be substituted with an alkyl group, an alkoxy group, an amino group, an amide group, etc. Specifically,
Examples include phenoxy group, 4-methoxyphenoxy group, and 3-methylphenoxy group. The amino group represented by X may be substituted with an alkyl group, an aryl group, etc., and A-isomers include an amino group, an N,N-diethylamino group, an N,N-dibutylamino group, and a N-dibutylamino group.

Examples include N-diphenylamino group.

In general formula (I), Y is a substituted or unsubstituted alkyl group,
The alkyl group represented by Y representing an aryl group preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group is an aryl group, an alkoxy group, or an alkoxycarbonyl group.

Optionally substituted with carboxyl group, amide group, etc., specifically, methyl group, ethyl group, propyl group, ta
Examples include rt-butyl group, carboxyethyl group, pentadecyl group, and benzyl group.

The aryl group represented by Y preferably has 6 to 10 carbon atoms.
, especially the phenyl group. Specifically, this aryl group may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, or the like.

Fueni Jl/1. %, 2-naphthyl group, 4-hydroxyphenyl group, 2-methoxyphenyl group, 4-methylphenyl group, 2.4-dihydroxyphenyl group, 4-hexadecyloxy group, 3-1':decyl group.

Examples include 3-tetradecanamide group.

n in general formula (I) is a number from 1 to 3.

X in general formula (r) is a hydrogen atom.

It is preferably an alkyl group or an alkoxy group, and most preferably a hydrogen atom.

Y in general formula (I) is most preferably an aryl group.

Specific examples of the compound represented by general formula (I) are shown below.
However, the present invention is limited to the following compounds' (9++11
+ A considerable number of the compounds represented by the general formula (I) used in the present invention can be obtained as commercial products. Furthermore, these compounds can be synthesized according to the method described in JP-A-54-65535.

It has been known that the compound represented by the general formula (I) used in the present invention has a development accelerating effect when processed with a processing solution containing benzyl alcohol. However, the effect is not so great, and the general formula (
The remarkable development accelerating effect of the compound represented by I) was a surprising effect that could not have been expected from the prior art.

In the present invention, color development in the presence of at least one compound represented by the general formula (I) can be carried out as follows.

That is, it can be carried out by making the compound represented by the general formula (I) exist in at least one of the light-sensitive layer or non-light-sensitive layer of the silver halide color photographic light-sensitive material and/or in the color developing solution. When added to a photosensitive material, it is preferable to add it to a layer close to the support.

The amount of the compound represented by general formula (I) used in the present invention varies depending on the composition of the light-sensitive material, but when it is added to the light-sensitive layer or non-light-sensitive layer of the light-sensitive material, It is preferably in the range of 10 mol to 10' mol per mol of silver halide contained in the compound, more preferably lo-5
It ranges from mol to 1O-2 mol. When used by adding it to a color developing solution, the range is preferably from 5xlO-g mol/vertical to 1.5xlO'mol/visual, more preferably 5xlO'mol/! It ranges from L to 1.5X10-2 mol/liter.

The pH of the color developing solution used in the present invention is different from that of the conventional one.The "reflective support" used in the present invention is a material that enhances reflectivity to make the dye image formed in the silver halide emulsion layer clearer. Such reflective supports include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, or those containing original reflective substances dispersed therein. This includes those using hydrophobic resin as a support. For example, baryta paper, polyethylene coating, covering paper, polypropylene synthetic paper 1 Transparent support 1 with a reflective layer or a reflective material 1 For example, glass plate, polyethylene terephthalate, cellulose triacetate, cellulose nitrate, etc. There are polyester films, polyamide films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use.

Next, a processing step (image forming step) in the present invention will be described.

The color development process in the present invention has a short processing time of 2 minutes and 30 seconds or less. Preferred processing time:! It is O-5 minutes to λ minutes. Processing here at Ini +1°.

The period is when the photosensitive material is in contact with the color developer.

This is the time until contact with the next bath, and includes the time required to move between columns.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phinidine diamine compounds are preferably used, and representative examples thereof include 3-methyl-so-amino-N, N-diethylaniline-3-methyl-l-amino-N-ethyl- N-
β-Hydroquinlethylaniline, 3-methyl-g-
7E/-N-1-f-N-β-methanesulfonamidoethylaniline, 3-methyl-guamino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p -) x7 sulfonate, tetraphenylborate, p-(t-octele)benzenesulfonate, and the like.

Examples of aminophenol conductors include 0-aminophenol, p-aminophenol, and daminophenol.
Examples include methylphenol, λ-amino-3-methylphenol, kookine-3-amino-/, and dimethylbenzene.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
1963) (L, F, λ.

Pwlason, ” Pltotograpltic
l'rocessingUbcmist,ry''
, Focal Press) -226'2
2 pages, U.S. Patent Co., No. 193.01j, Ibid.

! Those described in Tako, No. 3 Buri, JP-A-Kokai Shoda/Buri No. 933, etc. may be used. If necessary, color developing main systems of Komi or higher may be used in combination.

The processing temperature of the color developer in the present invention is 300C'
-3o0(: is preferable, and 3r'c to daj0C is more preferable.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, US Patent Co., 4/, ≦Ou No., Special Publication Showa 19!
No. 03, U.S. Patent No. 3.72), various pyrimidiram compounds represented by 2%t2 and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Tokko Sho KK -93
No. 0, US patent! No. 33.990, same, j3/
, No. 32, No. 910, 970, λ.

Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. J77.127,
Thioether compounds described in U.S. Pat. ♂-1! Otsu939. Similarly, the compound described in No. 0-2203St'1 can be mentioned.

In addition, in short-time development processing as in the present invention,
An important issue is not only a means to accelerate development, but also a technique to prevent development fog. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic antifoggants include benzotriazole, g-nitrobenzimidazole, and! -nitroindazole, j-methylbenzotriazole, j-nitropensotriazole, j-ri-o-hey 7”)
9 Azole, 2-thiazolyl-benzimidazole, λ
-Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and l-
Phenyl! Mercapto-substituted heterocyclic compounds such as -mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and also mercapto-substituted aromatic compounds of thiosalicylic acid can be used. Particularly preferred are halides.

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

In addition, the color developer in the present invention includes pH buffering agents such as alkali metal carbonates, borates, or phosphates: hydroxylamici, triethanolamine, West German Patent Application (OLS) No. 22950 Preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; Auxiliary agents such as ('It drugs: viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, hexanediaminetetraacetic acid, iminodiacetic acid, N-hydroquinemethylethylenediaminetriacetic acid, diethylenetriaminepentate acid, trietylenetetramine hexaacetic acid) Acetic acid and aminopolycarboxylic acids such as the compounds described in JP-A-5R-IQS/US, etc.
-Hydroxyethylidene-1,lr-diphosphonic acid, Research Disclosure
Disclosure) Scrap 1. Hyakki phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine-N, N, N described in f/70 (Yuzuki / 97)
Aminophosphonic acids such as ', N'-tetramethylenephosphonic acid, JP-A No. 102721r, same! 3-
No. 172730, same j goo/, 2//27, same ta j-
Da 02 da issue.

61-'40-21, same! ! - No. 12629, same number j - ≦ 59j! No. 696is.

and Research Disclosure (ILcsearch Disclosure) A
A chelating agent such as a phosphonocarboxylic acid described in Tx/J'/70 (I Taffeta, June 2006) may be included.

In addition, the color developing bath is divided into λ or more parts as necessary.
The color developing PIli source solution may be supplemented from the first bath or the last bath to shorten the development time and reduce the amount of replenishment.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching process may be carried out simultaneously with the fixing process or separately. For bleaching, compounds of polyvalent metals such as iron (III), cobalt (■), chromium (■), and steel (!l), peracids, quinones, and 2) oiso compounds are used. For example, ferrinanide, dichromate, organic complex salts of iron(1) or copal(III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid.

Aminopolycarboxylic acids such as l,3-diamino-2-propatoltetraacetic acid or complex salts of (r-organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitronephenol, etc.) may be used. Of these, potassium ferricyanide, iron ethylenediaminetetraacetate (
III) Sodium and iron ethylenediaminetetraacetate (1
) Ammonium.

Triethylenetetramine iron (111) ammonium pentaacetate, persulfate salt is particularly useful. Ethylenediaminetetraacetic acid 1(III) complex salt is useful in both stand-alone bleach solutions and -bath bleach constant N solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleaching window 11i1& as required. For example, in addition to bromide ion and iodide ion, US Pat.
-727j Ta No. 63-3t233 and same evening J-
37 (thiourea-based compounds as shown in Particular No. 7/Otsu No.
-m31, same j3-ta 2♂31, same j3-3ko 23
No. 6, Suta No. 3-6J732, Suta No. 2J3St, and U.S. Patent No. J,/93. No. ♂5, thiol-based compounds as shown in books I+lIl, etc., or No. KK in JP-A No. 59, jO-/'10/29, No. 3-2r%t2, No. 3-2r%t2, 13-/%/12J No. 53
-IOH, No. 232, the heterocyclic compound described in IOH, No. 727, etc., or JP-A-Sho! Two 20
No. 232, same j! -2to≦da issue, and the same! j-243
The thioether compounds described in the specification of JP-A No. 06, etc., the quaternary amines described in the specification of JP-A-4T/-/KKKO, or the thiocarbamoyls described in the specification of JP-A-2Jgt, etc. Compounds may also be used.

As the constant N agent, thiosulfates, thiocyatsates, thioether compounds dithioureas, large amounts of iodides, etc. can be used, but thiosulfates are generally used. As the preservative for the bleach-fixing solution and the fixing solution, sulfites, bisulfites, or cal6yl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, hard water rejuvenation M such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. A hardening agent typified by , a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L
,, E, West), Photographic Science and Engineering ()'hot-8ci,
and Eng,), Volume 9, No. 6-(/9
Compounds described in 6) etc. may be added. The addition of chelating agents and anti-piping agents is particularly effective. In addition, it is also possible to save one amount of water by using a countercurrent method in the water washing process (=multistage (for example, 2 to 5 stages)).

Also, after or instead of the water washing process, JP-A-37-
A multi-stage countercurrent stabilization treatment process as described in No. 164tJ may also be implemented. In the case of this process.

A ~9 m countercurrent column is required. Each Tml compound is added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers to adjust membrane p I-1 (e.g.

borate, metaborate, borax, phosphate, carbonate,
Ink is made by using potassium hydroxide, sulfur hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
(aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (Proxel, intiazolone, diluteazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), surfactants, fluorescent brighteners, hardening agents, etc. May be added.

In addition, ammonium chloride,
Various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, and ammonium thiosulfate may also be added.

The silver halide emulsion used in the present invention has an average grain size of o, iμ expressed by the diameter of an equivalent circle in projection.
It is preferably from m to 2 μm, and most preferably from 0.2 μm to 7.3 μm. Preferably, the emulsion is a monodisperse emulsion, and the grain size distribution expressed by the degree of monodispersion is the ratio of the statistical standard deviation (S) to the average grain size (d) (S/d
) is preferably 0°2 or less, more preferably 0.1!
It is as follows.

The silver halide emulsion used in the present invention may have any halogen composition, but preferably consists of silver bromide and/or silver chlorobromide containing substantially no silver iodide, and more preferably chloride. It is a silver chlorobromide emulsion containing 2 moles or more and 98 moles or less of silver 1 arsenic, more preferably 15 moles or more and less than 98 moles.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
) crystal? :It may be something you have.

Further, it may have an irregular crystal shape such as a spherical shape, or it may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 2 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used.

These various emulsions may be either a surface layer image type in which an m image is mainly formed on the surface or an internal ff1ll type in which an m image is formed inside one grain.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J (L', 01al'kides)" by Grafkide.

Chimie et Physique PhoL
ographique (published by Paul Monte1, /'07)], by Duffin [Photographic Emulsion Chemistry J (0
, F. Du [in Photographic Emu
lsion Chemistry (Focal Pr.
ess, /9J4)], Zelikman et al., "Production and Coating of Photographic Emulsions J (V, L.

Making and by Zelikman eL al.
Coaling )'oLographic Emul
sin (published by Focal l'ress, / 9L!,
It can be prepared using the method described in 2010). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble rhodan salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It's okay. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase produced by silver rodanide is kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, milk 7f11 prepared by a so-called conversion method, which involves a process of converting the silver halide already formed before the completion of the silver halide grain formation process into silver rhodanide (2) having a smaller solubility product. Also, emulsions which have been subjected to similar halogen conversion after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting.

Silver halide emulsions are usually physically ripened after grain formation.

It is desalted and chemically ripened before use for coating.

Known silver halide bath agents (e.g. ammonia, rhodankali or US Pat. No. 3,27/, 152, JP-A-Shoj
/ - / 23≦O, JP-A-Shoj3-/2da0♂,
Tokukai Showa 6! -/4t9tJ/9, Tokukai Sho r<t-1o
No. 0717 or Tokukai Showa 5K -/Evening! ! 2/, etc.) can be used in precipitation, physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, 70 Cure Yon sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and a sulfur-containing compound that can react with silver (for example, thiosulfate 2
Thioureas, followed by mercapto compounds.

sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine d'4, formamidine sulfinic acid, silane IIZ compound); metal compounds (e.g. , in addition to the total complex salt, l'
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as t, 1r, Pd, ILIt, Pe, etc. can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

In order for the color photographic light-sensitive material of the present invention to satisfy the target gradation, two or more types of monodisperse silver halide emulsions (monodisperse (preferably those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated in separate layers. Furthermore, polydisperse silver halide emulsions of λ or more types or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The uninvented blue-sensitive, green-sensitive and red-sensitive emulsions are each sensitized by methine dyes and other dyes.
Melonanine pigment, complex anine pigment, complex merocyanine pigment, hoa-boranine pigment, hemicyanine pigment, steryl pigment.

and hemi, oquinol dyes. Particularly useful dyes are those belonging to the merocyanine dyes, melonanine dyes and complex merocyanine dyes.

For these pigments, any of the nuclei commonly used for N-anine pigments can be used as basic heterogeneous WJ nuclei. Namely, pyrroline nucleus, oxasili/nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, and imidazole nucleus.

Tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, cochoxazolidine-λ
, 9t-dione bales, thiazolidine, l-dione nuclei,
It can be applied to 5-membered heterocyclic nuclei such as rhodanine nuclei and thiobarbic acid nuclei.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is the US patent λ
, ni♂♂, s<tr issue, same 2゜977, . 2+29 issue,
3,397.0 θ, J, 622.0 octopus, 3. Octopus 2.6 da/issue.

Same 3. ≦/7.29J No. 3. tko♂, No. 969, same 3. ttt, t, ro issue, 3.672.19/no. 3, 479, s2/no., j, 703°322
No. 3.26, No. 301, J, //da, No. 609, No. 3. ♂37. rt number, same da.

02t, No. 707, British Patent/, 3gg,, zl1
No., same /, j07, /173, special public show% t3-riwa No. 36, same 63-/23? No. J, JP-A-52-1to
6i, No. 1, Z2-10 Tata No. 2J.

Along with sensitizing dyes, there are also dyes that do not have a sensitizing effect or substances that do not substantially absorb visible light.
The emulsion may be enriched with substances exhibiting supersensitization.

The sensitizing dye in the present invention may be added at any step up to coating the silver halide emulsion on the support. That is, it can be added at any step such as during or after grain formation of the silver halide emulsion, before or after chemical sensitization, or at the step of adding additives for preparing a coating solution.

Further, the sensitizing dyes may be added separately in advance to each of the qi-dispersed emulsions used in combination in the present invention, or the dyes may be added after the emulsions are mixed. The former example where it is added to is more preferred.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A divalent color coupler substituted with a leaving group can reduce the amount of silver coated than a nominal color coupler whose coupling active position is a hydrogen atom. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2. ≠0
No. 7,210, No. 2,17j, No. 067 and No. J, 21. J, No. 306, etc. In the present invention, it is preferable to use a two-wheel yellow coupler,
U.S. Patent No. 3. ≠ (7J', /5'4! No. J, $447.921, No. 3.33,301 and Hiroshi, O here.

Oxygen atom separation type yellow couplers described in No. 6coO, etc., or Japanese Patent Publication No. 1977-/(77J-R, U.S. Patent No. DA, ≠0/, 75J, U.S. Patent No. /979 μ month), British Patent No. 1
．． Hiroλj, No. 020, West German Application Publication 2. Colli, Ri 1
No. 7, No. 2,161.361, No.-132,
Typical examples include the nitrogen atom separation type yellow couplers described in No. 517 and No. 2°≠33,112. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness.
On the other hand, α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. ! - Pyrazolone couplers are preferably those in which the 3-position is 14-substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. , same No. J.

J413.703, No. 2,600.71#, No. J, No. 901.173, No. 3,062. T! No. 3,
Same 3rd. l! λ, No. 19z and No. 3゜234.01
/ No. etc. As a leaving group for a two-equivalent r-t lazolone coupler, U.S. Pat. t/
The nitrogen atom leaving group described in No. 1 or U.S. Patent No.
The arylthio group described in No. 31/, rri No. 7 is preferred. Also, European Patent No. 73. It has a pallast group as described in jj No. 4! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
362,1172, preferably pyrazolo[s, 1-c) [t, S, ≠] triazoles as described in U.S. Pat. (
Pyrazolotetrazoles and Research Disclosure 24A JOC/91
Examples include pyrazolopyrazoles described in the year μ year. Imidazo(/
, ub) pyrazoles are preferred, such as pyrazolo [/] as described in European Patent No. 11, rtO.

5-b) (/, x, ψ) triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers. ≠7≠.

Naphthol couplers described in λri No. 3, preferably U.S. Pat.

Alternative examples include the oxygen atom-eliminating type two-equivalent naphthol-based kazolers described in Kou Kou No. 6,326, Kou No. 1T, 2.9T, and No. 200. Further, specific examples of phenolic couplers include U.S. Pat.
No. U, 712. /No. 62, No. 2. r9j, 12
It is written in No. 4 etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. A phenolic cyan coupler having a phenolic cyan coupler, °U.S. Pat. No. 2,772. /lp No. 2, No. J, 761.3
01 issue, same@gu, /koro, 3rd issue, same number ψ, 33μ,
0//, No. 327°773, West German Patent Publications No. 3, 3, 7, and Japanese Patent Application Sho SR-μ Co. No. 47/, etc., j-diacyl amino substituted phenols system couplers and U.S. Patent No. J, get, 622
No. 33! , Tuck issue, same issue, ≠! /,j
j'2, ≠, ≠27, 7.47, etc., which have a phenylureido group at the co-position and! These include phenolic couplers having an acylamino group at the - position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in U.S. Pat. No. 44. Specific examples of magenta couplers are found in JA4°237 and British Patent Nos. 170 and 170, as well as in European Patent No. 24, J7 (7) and German Published Application No. 3,23.

No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. J, 'tj/
, 1r No. 20 and 1r No. u, oro.

It is described in No. λii. Specific examples of polymerized magenta couplers are described in British Patent No. U, 102,773 and US Patent No. tA, 367, Cof2.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer, or in combination with different types of couplers, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into two or more layers.

The coupler used in the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, either a high-boiling organic solvent with a boiling point of 17 r'c or more and a so-called auxiliary solvent with a low boiling point are dissolved in one liquid alone or in a mixture of the two, and then water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling organic solvents are described in, for example, US Patent No. J, 312.027. Dispersion and Kid phase inversion may be involved, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before further application.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl 7-talate, dicyclohexyl phthalate, di-λ-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid a()-liphenyl phos-7ate , tricresyl phosphate, coethylhexyl diphenyl phosphate, tricyclohexyl phosphate, 1J-r-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichlorob, bilbosphate, di-x-ethylhexyl phenyl phosphonate Such)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, λ-ethylhexyl-p-
hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, -94L-di-tcrt-amylphenol, etc.), aliphatic carboxylic acid esters (dioctylase, etc.) ester, glyceral tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl 7-tertoxyj-1 crt-octylaniline, etc.), hydrocarbons (・t-roughin, dodecyl citrate, etc.), , diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is approximately 30''
Organic solvents having a molecular weight of C or more, preferably to'c or more and about /lo oc or less can be used, and typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, coethoxy7 ethyl acetate,
Examples include dimethylformamide.

Examples of the process, effects, and latex for impregnation of latex dispersion methods are described in U.S. Patent No. μ,/Tata.

No. 363, West German Percentage License (ULS) No. x, r<t/
.

No. 274 and No. 2 of the same. z4ti, No. 230, etc.

Standard usage for color couplers @C ranges from 0.00/ to 1 mole per mole of photosensitive silver halide, preferably from 0.0/ to O0j0/ for yellow couplers and from 0.0/ to O0/ for magenta couplers. 0.003 to 0
．． 3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychroman E, j-hydroxycoumarans, spirochroman, p-alkoxyphenols,
Hindered phenol flame centered on bisphenols Typical examples include gallic acid derivatives, methylene dioxybenzenes, amine phenol momme, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. It will be done. Further, metal complexes such as (bissalicylaldoximado)nickel complexes and (bis-N,N-dialkyldithiocarbamado)nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
Compounds having a hindered amine and a hindered phenol fractional structure in the same molecule, such as those described in U.S. Pat. In order to still prevent the deterioration of the magenta dye image, especially the deterioration caused by light, spiroindans described in JP-A No. Shojt-/j9t≠μ, and hydroquinone diethers or monomers described in JP-A No. Shoj3-r9Ijj Ether substituted chromans are the preferred result for total thickness.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The coating amount of the ultraviolet absorber may be sufficient as long as it imparts photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, usually preferably /X 10-'
mol/m2 ~ coX/(7-3 morph m2, especially jXIO
It is set in the range of 'mol/m2 to ljx/0 mol/m2.

In the usual color e.xi.- sensitive material layer structure, an ultraviolet absorber is contained in either layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each of the above emulsion layers may be separated from λ or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a pack layer.

As the binder or protective colloid that can be used in the emulsion 14 or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as alginate, starch derivatives;
Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyhinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Substances can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Enzyme-treated gelatin as described in Japan, A/&, page 30 (t yt&) may also be used;
Hydrolyzed gelatin and enzymatically decomposed products can also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure lygu
3ct/71/month) and 7/J (/7/year//month).

(Example) The present invention will be explained in more detail below with reference to Examples.

Example 1 A multilayer color photographic paper having the layer structure shown in the table was prepared on a paper support laminated on both sides with polyethylene. Application II
! tFi was prepared as follows.

Preparation of first layer coating solution Yellow cazoler (a) /li, /f and color image stabilizer (b)
) +, < cf to ethyl acetate to 27.2rne and solvent (c
) 7.

This solution was emulsified and dispersed in an aqueous IO% gelatin solution/Ijml IC containing 1 ml of sodium 10-tidedecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (silver bromide JfOmo 1%, containing 1 g 70f/kg) per silver chlorobromide/mo I.
．． 0.times.10-' mol was added to make a milk powder, and θy was prepared. A first layer coating solution was prepared by mixing and dissolving the emulsified dispersion and the one with milk, and setting the gelatin concentration to g4ffl so as to have the composition shown in Table 1.

The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first J@ coating liquid. l-oxy-J,j-dichloro-s-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (7.0×10-'mol added per silver halide/mo) Green-sensitive emulsion layer (4C, 0×10-'mol added per silver halide/mo) (7.0× per silver halide tmo) / 0-5 mol added) Red-sensitive emulsion layer (halogenated @ 1 mol/, 0x10-'mo! added) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler) Color image stabilizer (c) Solvent H <e) Magenta coupler (0 Color image stabilizer (k) Uncoupler α (kl) (7+) Color image stabilizer (m) Solvent α (k2) C4H8(t) This was designated as sample A. Compounds (3), (9), and (11) of the present invention were added to the coating solution for the first layer of sample A as shown in Table 2, respectively. B, C, and D. Sample E was prepared by adding the compound (18) of the present invention to the coating liquids of the first to sixth layers of sample A as shown in Table 2.

These samples A to E were exposed to light through an optical wedge and red, green, and blue filters, and were treated with the following color developers (a) to (d) (a) to (d) as shown in Table 3. Got the results.

The evaluation of photographic properties was based on the results of treatment (a). In other words, the sensitivity is defined as the reciprocal of the exposure amount required to give the minimum density plus 0.5, and the processing (
The sensitivity in a) was set as 100, and the results in other treatments were expressed as relative values to this. In addition, in order to evaluate color development, treatment (a) was also used as a standard. That is, sample A
The exposure amount that gave a coloring density of 1.50 in the treatment (a) of each layer was determined, and the coloring density of each sample in each treatment at this exposure amount was used as a measure of coloring property.

(Processing process) (Temperature) (Time) Developer solution 38℃ 2.0 minutes Bleach-fix solution
Wash with water at 38°C for 1.0 minutes 2B-35'C for 3.0 minutes (Developer formulation) Color developer (a) Diethylenetriaminepentaacetic acid/5Na 2.0g Benzyl alcohol 15m diethylene glycol 10m Naz so3
2. OgKBr
1.0g hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-
Ethyl-N-[β-(methanesulfonamido)ethyl]
-p-phenylenediamine sulfate s, 0gNa2
CO3 (-water salt) 30.0g Fluorescent brightener (stilbene type) 1.0g Add water for a total of 1000rnfL (pH 1o, 2) Color developer (b) Diethylenetriaminepentaacetic acid/5Na 2.0gNa
25o3 2. OgKBr
1.0g hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate s,
OgN az CO3 (-water salt) 30
．． 0g Fluorescent brightener (Stilbene type) 1.0
g Add water and the total amount is 1000 m (
pH 1o, 2) Color developer (c) Diethylenetriamine five vinegar brew, 5Na 2-0g Benzyl alcohol 15mJL diethylene glycol Ion Mi Na z
S O32, Og KBr 1.0g Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate s, Og compound (7)
0.05g Na2CO3 (-water salt)
30.0g optical brightener (stilbene type) i
, Add 0g water to make a total of 1000m (p) ILo, 2) Color developer (d) Diethylenetriaminepentaacetic acid/5Na 2.0gNa
25o3 2. OgKBr
1.0g Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamide)
ethyl]-p-phenylenediamine sulfate 5. O
g Compound (7) 0.05gN
a2CO3 (-water salt) 30.0g Fluorescent brightener (stilbene type) Add 1.0g water to make a total of 1000ml (pH 10,2
) (Bleach-fix solution formulation) Ammonium thiosulfate (54wt%) 50mR Na2SO3 15g NH4[Fe (m) (EDTA)] 55gE
DTA ・2Na Add 4g of water to make a total of 1000ml (pH 6,
9) From the results in Table 3, when color development processing is performed in the presence of the compound represented by the general formula (I) of the present invention, the development processing time is 2 minutes even when using a color development solution from which benzyl alcohol has been removed. It can be seen that it has sufficient color development. Also,
It is also clear that the development accelerating effect of the compounds according to the invention is more pronounced when treated with a treatment solution in the absence of benzyl alcohol than when treated with a treatment solution in the presence of benzyl alcohol.

Example 2 Example 1 refers to the compounds (
When we conducted the same experiment except for replacing 7) with (3) and changing the amount added to 1g of O, we obtained the same results as 1.
The effectiveness of the present invention was confirmed.

(Effects of the Invention) According to the method of the present invention, by substantially eliminating benzyl alcohol, the pollution load can be significantly reduced, the liquid preparation work is reduced, and the concentration decrease due to cyan dye remaining in the leuco form is eliminated. be able to. Furthermore, by shortening the development time, a large amount of color prints can be processed quickly and productivity can be dramatically improved. Further, according to the present invention, color prints with good color development and high contrast can be obtained even when processing is performed for a short time of 2 minutes and 30 seconds using a color developer that does not substantially contain benzyl alcohol.

Claims (1)

[Scope of Claims] In developing a silver halide photographic material having at least one light-sensitive silver halide emulsion layer containing a color coupler on a reflective support, after imagewise exposure, substantially benzyl alcohol is used. A method for forming a color image, which is characterized in that color development is carried out in the presence of a compound represented by the following general formula (I) using a color developing solution that does not contain . General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. represents an alkyl group or an aryl group, n is an integer of 1 to 3.)