WO1987004809A1

WO1987004809A1 - Color image forming process

Info

Publication number: WO1987004809A1
Application number: PCT/JP1987/000062
Authority: WO
Inventors: Osamu Takahashi; Hideaki Naruse; Jun Arakawa; Jiro Yamaguchi
Original assignee: Fuji Photo Film Company Limited
Priority date: 1986-01-30
Filing date: 1987-01-29
Publication date: 1987-08-13
Also published as: AU596149B2; EP0258443B1; JPS62175747A; EP0258443A1; AU6936287A; EP0258443A4; JPH0614180B2

Abstract

A color image-forming process which comprises processing an imagewise exposed color paper containing an anionic surfactant having a fluorine-substituted aliphatic group as a hydrophobic group and an -SO3M or -OSO3M group (wherein M represents hydrogen or cation) as a hydrophilic group with a substantially benzyl alcohol-free color developer. In the case of processing the above-described color paper containing the fluorine-substituted anionic surfactant, color images with high coloraton density can be obtained in a short time even when the paper is processed with a color developer which substantially does not contain a development promoter causing environmental pollution.

Description

Specification

Force image formation method

〔 Technical field 〕

The present invention relates to a method for forming a color image using a halogenated color light-sensitive material, and particularly to a color image forming method using a benzene and / or alcohol to reduce the processing time. It relates to a forming method.

[Background technology]

In order to form a color photographic image, a photographic power blur of five colors of yellow, magenta and cyan is contained in the photosensitive layer, and after exposure, it is processed with a color developing solution containing a color developing agent. In this process, the oxidized aromatic primary amine reacts with the coupler to give a coloring dye by a coupling reaction.In this case, it is necessary to give as high a coloring density as possible within a limited development time. It is necessary.

In order to obtain a high color density, use a coupler whose coupling speed is as high as possible, or use a silver halide emulsion which is easy to develop and has a large amount of developed silver per unit coating amount. Is usually achieved by using a color developing solution having a high developing speed.

In order to speed up the development of silver halide emulsions, it is easy to think of increasing the silver chloride content of silver halide. It has disadvantages that can easily occur. In order to increase the amount of developed silver, it is conceivable to increase the above-mentioned silver chloride content or to enhance chemical sensitization. However, in this case, there is a disadvantage that capri easily occurs. Reducing the grain size of silver halide emulsions also speeds up development Although this is a means, it has a fatal drawback of lowering sensitivity. Methods using silver chloride emulsions are described in, for example, JP-A-58-95545, JP-A-59-23232, and JP-A-60-91940. There is a problem that gradation adjustment is difficult

—On the other hand, various measures have been taken to speed up the development of color developing solutions. Among them, various additives have been studied to accelerate the penetration of the color developing agent into the dispersed oil droplets and promote the color development, and in particular, the addition of penzyl alcohol to the color developing solution has been studied. However, the method of accelerating color development is currently used for color photographic light-sensitive materials, especially for color sensitization, because of its great effect of promoting color formation. Widely used in one process.

However, when pen alcohol is used, its solubility in water is low, so that diethylene glycol, triethylene glycol, alkanolamine and the like are required as solvents. However, since these compounds, including penzir alcohol, have high pollution load values B0D and C0D, it is necessary to remove pen-real alcohol for the purpose of reducing pollution load. preferable.

Further, even if the solvent is used, it takes time to dissolve the pen-zir alcohol, and therefore it is better not to use the pen-zir alcohol for the purpose of reducing the liquid preparation work.

In addition, when benzyl alcohol is introduced into a bleaching bath or a bleach-fixing bath, which is a post-bath, it causes the formation of the cyan pigment πτ ico-dye and causes a decrease in color density. In the latter case, since the washing speed of the developing solution component is slowed down, the image storability of the photosensitive material may be adversely affected. Therefore, the above reasons It is preferable to use benzyl alcohol. Conventionally, in color development, processing was usually performed in 3 to 4 minutes. However, with the recent reduction in finish delivery time and reduction in lab work, reduction in processing time has been desired.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

In order to solve this problem, various color development accelerators (for example, U.S. Pat. Nos. 295Q970, 5151247,

2 ^ 49093, 24304925, 403075,> 1119, 462, UK Patent 144 (¾998, same

No. 1, 4 5 4 13 No. 5, JP-A No. 53-158 581, No. 55-62 50, 55 No. 55-62, 51 No. 55-624 No. 52, No. 55-6244 53, No. 51-1242, No. 55-49772) It was not possible to obtain the coloring intensity.

A method incorporating 3-virazolines is used (for example, the method described in JP-A-60-26338, JP-A-60-1584844, JP-A-60-158446). However, it has the disadvantage that the sensitivity is lowered during the life and fog is generated.

In addition, a method of incorporating a color developing scheme (for example, US Pat.

No. 3 7 1 9 4 9 2, No. 3 3 4 2 5 5 9 No. 3 3 4 5 9 7 No., Japanese Unexamined Patent Publication No. Sho 56-63 25, No. 56-161 3 33, Even if the methods described in Nos. 57-977531 and 57-783565 are used, the color development is delayed and capri is generated. Disadvantage] ?, Not the right way.

Various methods have been proposed for developing a reflective silver halide color photographic light-sensitive material using a color developing solution which does not contain benzyl alcohol at all or whose addition amount is greatly reduced. Been? For example, JP-A-57-200370, JP-A-59-487755, JP-A-59-174748, JP-A-59-i77553 and JP-A-6073 -26 3 39, 60- 17 2 0 42, 58- 3 13 34, JP 49-294 6 1, etc.

Surfactants used in conventional color photographic light-sensitive materials subjected to such color development processing include: sanonin; sulfosuccinic acid; anolekybenzenesnolefonic acid such as dodecylbenzenesnolefonic acid; alkylnaphthalene Sulfonic acid; Sorbitan sesquiyl oleate; Sorbitan monolaurate; Anionic and nonionic surfactants such as alkylene oxide derivatives o

In this way, when using a conventional surfactant, a color developer containing substantially no benzyl alcohol can be used to process a color light-sensitive material within 2 minutes and 30 seconds. It was insufficient for the purpose of obtaining a color photograph with a high maximum color density (Dma ^) and a low minimum color density (Dinin) with little sensitivity and gradation change.

Accordingly, a first object of the present invention is to provide an image forming method which can provide a high color density in a short time even when a color developer containing substantially no benzyl alcohol is used. .

A second object of the present invention is to reduce the generation of capri and to speed up development. An object of the present invention is to provide an image forming method.

A third object of the present invention is to provide a color image forming method in which changes in sensitivity and gradation are small.

[Disclosure of the Invention] The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the following special carbon-fluorinated anionic surfactant was added to a silver halide emulsion layer or a neighboring silver halide emulsion layer. In the case of processing the photographic paper in the layer, it has been found that a high color density can be obtained in a short time even if a color developing solution substantially containing benzyl alcohol is used, thereby achieving the present invention. did.

That is, the present invention has at least one silver halide emulsion layer on a reflective support, and the emulsion layer or a layer adjacent thereto has a fluorine-substituted fatty acid having 4 to 18 carbon atoms as a hydrophobic group in the molecule. have a family group, and as the parent-aqueous base - S_〇 ₃ M or - 0s0 ₃ M c π Gen Kaginka error (where M is a is hydrogen atom or a cation) containing Anion surfactant having After exposure, photographic light-sensitive material contains benzyl alcohol substantially. 力 O is an image forming method that is characterized by developing in a color developer for 2 minutes and 30 seconds or less.

In the present invention, substantially containing benzyl alcohol means that the concentration of benzyl alcohol in the developer is 0.5 or less.

Preferable anionic surfactants in the present invention can be represented by the following general formula.

(Rf) _n (B) _m -X [[] Here, the fluorine-substituted alkyl group or Aruke of 4-1 8 carbon atoms - indicates Le group, X is - S0 ₃ M or -〇_S0 ₃ M (M is hydrogen atom or a cation) represents, B Is a divalent to trivalent organic residue. For example, a divalent or trivalent aliphatic hydrocarbon group (for example, alkylene group or alkylene group in which the titylene in the alkylene group is partially substituted with an aromatic group), aryl Diene groups (eg, phenylene, 1,4-naphthylene, 2-hydroxy-1,4-naphthylene, etc.), divalent heterocyclic groups (eg, divalent benzimidazoyl group, 1- Alkenylbenzmidazol-2-yl, etc.), but Β also represents a divalent or trivalent organic residue and a divalent bonding group (eg, -C0-0-,

-〇一 CO-, -NR-G0-. One G0-NR-, one S0 ₂ NR-, where R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms.

R

I

Group (I j, (S〇 2— N— — 0—〇〇) ₂ R ₂ —, -C00R _1- , -R ₁ 0-C0-R _1- , -CONH-R ^, -S0 ₂ NR -R _1- , represents ο

Here, the above-mentioned divalent aliphatic hydrocarbon group, arylene group, and divalent heterocyclic group are represented, and R ₂ represents a trivalent aliphatic hydrocarbon group.

n is an integer of 1-2, and m represents 0 or 1. Next, some specific examples of the above-mentioned anionic surfactant particularly useful in the present invention are shown.

(-1)

CF. (CF _? ) ₇ SO _? _NCH _5! CH ₂ CH ₂ S03Na (A-2)

CF ₃ (CF ₂ ) ₇ S0 ₂ N (CH ₂ ) ₄ S0 ₃ K

° 2 ^H 5

(-3)

H (CF ₂ ) ₆ CH ₂ 0 (CH ₂ ) ₃ S0 ₃ Na

( - Four )

H (QF ₂ ) ₅ CH ₂ 0 (CH ₂ ) ₃ S〇 ₃ Na

(A-5)

H (CF ₂ ) _1Q CH ₂ 0 (CH ₂ ) ₃ S0 ₃ H'N (CH ₃ ) ₃

(A-6)

〇F ₃ (CF ₂ ) ₇ S0 ₂ NCH ₂ CH ₂ 〇 (CH ₂ CH ₂ 〇) _n (CH ₂ ) ₃ S0 ₃ Na

C ₃ H ₇ n = 1

(A-7) n

n = 3

(A-8) »

n = 5

(A-9) it

n = 1 0

(A-10)

_{_{_{CF 3 (CF 2) 6 C0NHCH}}} 2 CH 2 0 (GH 2) 3 S0 3 Na (A - 1 1)

(A- 12)

CH ₂ C00CH ₂ (CF ₂ ) ₈ H CHC〇〇〇H ₂ (CF ₂ ) ₈ H

S0 ₃ Na

(A-13)

(A-17

N

(CF ₂ ) ₆ CF ₃

Na0 ₃ S

G H.

(-18) ( ₂ ) ₆ H

I 〇,

CH 3

H

7

CH _₂ 0 (CH _{2 2)} Roh _₃ 3S0 ₃ 3N. A

(-19)

GH C00GH ₂ CH ₂ NS0 ₂ (CF ₂ ) ₇ CF ₃

I CHC00GH ₂ CH ₂ NS0 ₂ (GF ₂ ) ₇ CF ₃

SO Na C3H7

(A-20)

GF ₃ (GF ₂ ) ₇ SO Na

(A-21)

GF ₃ (GF ₂ ) ₇ S0 ₃ K (A-22)

(A-23)

CF ₃ (GF ₂ ) ₆ C00 (CH ₂ ) ₃ S0 ₃ Na (A-24)

C ₁₆ H ₃₃ -CHC00CH ₂ (CF ₂ ) ₄ H

S〇. Na

(A-28)

^C 2 ^F 5 ^CF 3 ^GF 3

CF ₃ -C—〇 = 〇— 0CH ₂ CH ₂ S0 ₃ Na C ₂ F ₅

(A-29)

^C 2 ^F 5 ^CF 3 ^CF 3

III CF ₃ -C- C = C-0CH ₂ CH ₂ 0S0 ₃ Na

^C 2 ^F 5 These compounds used in the present invention are described, for example, in U.S. Pat.

2 · 5 5 ¾ 7 1 5 issue, the same _second! 5 6 7 0 1 No. 1, the second ₁ ₇₃₂₎ 3 9 No. 8, the second 7 6 4 6 0 No. 2, the second> 8 0 8 6 6

No. 2 809, 998, No. 2 <913 776, No. 291 ¾ 528, No. 2> 933, 450, No. 293, 0 98, No.

Nos. 957, 031, JP-A-479894, JP-A-55-089, and JP-B-45-37304, JP-A-47-9 Nos. 6 to 13 ^w J. Gliem. Soc, 1950, p. 2789, and 1957, p. 2574 and 2640, ^w J. Amer. Chem. Soc, "7. 9, page 2549 (1957).

Some of these carbon-containing surfactants containing carbon fluoride used in the present invention are commercially available from Dainippon Ink Chemical Industry Co., Ltd. under the trade name of Megafac F (for example, F-109). , F-110 and F-115), and are commercially available from Imperial Chemical Industries, Ltd. under the trade name of Monflor (for example, Monflor 31).

The anionic surfactant containing carbon fluoride used in the present invention is added to one or both of an oil-soluble photographic additive (eg, force blur, etc.) solution and a colloid aqueous solution as far as the solubility permits. can do.

In the present invention, a DIR non-coloring power blur, an ultraviolet absorber, an anti-fading agent, a color mixing inhibitor, a stain inhibitor, an antioxidant, and the like can coexist in an oil droplet containing a coupler.

The surfactant used in the present invention is used alone. Can be used in combination with other surfactants. In some cases, it may be preferable to use it in combination with some other surfactant.

The fluorine-substituted anionic surfactant used in the present invention can be used in combination with a so-called fluorine-unsubstituted anionic surfactant and a non- or non-ionic surfactant.

As is the -S0 ₃ M Moshigu a hydrophobic group (not substituted with fluorine hydrophobic group) from 8 carbon atoms to 3 0 per molecule Anion surfactant of the French Motona substituted - 0S0 ₃ M (M has the same meaning as defined above α] medium) arbitrary preferable to use a compound having both a. This type of compound is described in Ryohei Oda and Kazuhiro Teramura, “Synthesis and Application of Surfactants” (Horizontal Edition) and AW Perry,

ourface Active Agents, Inters cience Putilications Inc.

See New York.

As the nonionic surfactant, it is preferable to use a nonionic surfactant described in JP-A-48-30933 and a fatty acid ester-based surfactant of a polyhydric alcohol. The fatty acid ester-based surfactant of the polyhydric alcohol preferably has at least two, preferably at least three, hydroxyl groups, and more preferably has 6 to 25 carbon atoms of the fatty acid. Specifically, the fatty acid ester nonionic surfactant of nrubitan described in US Pat. No. 3,676,141 is advantageously used in the present invention.

Specific examples of the above-mentioned fluorine-unsubstituted anionic surfactant include the following compounds.

(A-1) C ₁₂ H ₂₅ 0S0 ₃ Na _{(A - 2) C 14 H} 29 0S0 3 Na

(-3) Roast oil

_{(A - 4) C 12 H} 25 C0NHCH 2 CH 2 0S0 3 Na

(A-5) C _lo H. ₅ S0. Na

_{(A- 6) C 1 .H,} 9 S0 3 Na

_{_{A - 7) C 8 H 17}} CH 2 0CH 2 CH 2 S0 3 Na

(A- 8) Na0 ₃ S-GH-COOC ₈ H ₁₇

CH ₂ -GOOC ₈ H ₁₇

(A-10) C ₁₃ H ₂₇ CONH S0 ₃ Na

Where represents -CH

In the CH invention, at least one fluorine-substituted surface active agent for use in the present invention, the hydrophobic group and -S0 ₃ M also properly from 8 carbon atoms to 3 0 per molecule - OS0 ₃ M Group (where M has the same meaning as in the above [I]). It is particularly preferred to use at least one and at least one of Z or sorbitan fatty acid ester nonionic surfactants.

In the present invention, it is necessary to heat and melt the capillaries before emulsification, or to dissolve them in an organic solvent to make them liquid. Those that can be directly emulsified by melting are limited to compounds having a melting point of about 91C or less.

As an organic solvent (ie, a so-called oil component) used for finely dispersing the force puller in an aqueous medium, a solvent which is practically insoluble in water and has a boiling point of 190 TC or more at normal pressure is useful. This type of organic solvent can be selected from carboxylic esters, phosphoric esters, carboxylic amides', ethers, and substituted hydrocarbons. Specific examples thereof include di-n-butyl phthalate ester, di-iso-butynophthal ester, di-meth-oxyethyl phthal ester, di-n-butyl adipate ester, Disoctylazelenate, tri-n-butynolephthate monooleate, butynolaureate, di-n-cenomycinate, tricresyl phosphate, tri-n-butylphosphate Esters, triinooctyl phosphoric esters, N · N-methyl cuff. Amyl acid, N-N-dimethyl palmitic acid amide, n-futinole-m-bentatecinolele feninolee 1-tenole, ethinole-2.4-tert-butynolephenyl ether and salts There is a dani paraffin.

In the present invention, a low-boiling solvent (having a boiling point of 130 or less at room pressure) or a solvent having a low boiling point in addition to such a solvent for dissolving the power brush is used. It may be advantageous to use a water-soluble high-boiling solvent in combination. For example, propylene carbonate, ethyl acetate, butyl acetate, ethyl propyl. Acid esters, sec-butynoleanolone, tetrahydrofuran, cyclohexanone, dimethylhonolenamim, dimethylsulfoxyside ', methylseptol sorb and the like.

As the emulsifying device used for carrying out the present invention, a device that applies a large shear force to the treatment liquid or a device that applies high-intensity ultrasonic energy is suitable. In particular, a colloid, a mill, a homogenizer, a capillary emulsifier, a liquid siren, an electromagnetic strain type ultrasonic generator, and an emulsifier having a woolman whistle can give good results.

As the photographic layer containing the fluorine-substituted anion surfactant used in the present invention, a silver halide emulsion layer and / or a layer adjacent thereto are preferable, and a silver halide emulsion layer is particularly preferable.

The amount of the fluorine-substituted anionic surfactant used in the present invention depends on the type of the coupler to be used, the type of the other coexisting additive, the type and the amount of the dispersing solvent, and in some cases, the other surfactant used in combination. Although it depends on the type and amount of the agent, it is generally preferred that the dispersing substance (that is, a solution in which a coloring agent and other oil-soluble photographic additives are dissolved in a dispersing solvent) be 0.2 to 50% by weight.

As the substance coexisting with the coupler, an oil-soluble copying agent additive such as an anti-fading agent, an ultraviolet absorber, a DIR coupler, an antioxidant and the like can be contained.

The term "reflective support" used in the present invention means a material which enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer, Such a reflective support is made of a support coated with a hydrophobic resin containing a light-reflective material such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, or the like, or a light-reflective material. Warabi containing dispersed content includes those using an aqueous resin as a support. For example, a parasite paper, ^ ethylene-coated nylon, ^ reprovylene-based synthetic paper, a transparent support with a reflective layer or with a reflective material, for example, a glass plate, a 'ten-ethylene terephthalate, ≡1 ^ Acid cellulose, slightly acid cellulose, etc. ^ polyester film, ^ rearm, film, carbonate film, ^ polystyrene film etc.), these supports are used Select according to the purpose.

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

O o

The processing time of the color development process in the present invention is as short as 2 minutes and 30 seconds or less. Preferred processing times are 30 seconds to 2 minutes. Here, the processing time is the time from when the photosensitive material comes into contact with the developing solution until it comes into contact with the next bath.

The color developing solution used in the developing process of the present invention is preferably an aqueous alkaline solution mainly containing an aromatic primary amine color developing solution. As the color developing agent, p-phenylenediamine-based compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-ethylenirinine, and 3-methinolen-4-in. Amino-ethyl-N-?-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-- Amidoethylaniline, 3-methyl-4-amino-N-ethyl-N-^-methoxshetylaniline and their sulfates, hydrochlorides, phosphates or p -Toluene sulfonate, tetraphenyl borate, p- (t-octyl) benzene sulfonate and the like. Particularly preferred are 3-meter-4-amino-N-ethynole-N-β-methansulfonamichinolinaleline and salts thereof.

Examples of aminophenol derivatives include _0- aminophenol, -aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol, Contains 2-year-old 3-amino-3,4-dimethylbenzene.

In addition, L.F.A.kaaon, 'Ph.oto rapiiic Processing Chemistry ", Focal Press, pp. 226-229, U.S. Patent S19 S015, ^ δθ ^ βθΑ And those described in JP-A-48-64933, etc. If necessary, two or more color developing agents can be used in combination.

The processing temperature of the color developer in the present invention is preferably from 301C to 50C, more preferably from 33C to 45C.

As the development accelerator, various compounds other than those substantially containing benzyl alcohol may be used. For example, U.S. Patent No. S64 & 604, Japanese Patent Publication No. 44-9503, US Patent

ヒ Various types of birds represented by 1 7 1, 2 4 7 Rimedium compounds and other cationic compounds, genuine dyes such as phenosafuranine, neutral salts such as thallium nitrate and nitric acid rims, and Japanese Patent Publication No. 44-93034 , U.S. Pat.No. 5,399,900, 2 ^ 531 ^ 832 Nos. 2 and 9> Q970 and Nos. 2 and 5> 77, 127 described in Nos. 2 and 5 77, 127, respectively. Compounds, thioether-based compounds described in U.S. Pat.No.2,012,242, and other compounds described in JP-A-58-15693, and JP-A-60-224,344. .

In short-time development processing as in the present invention, not only means for accelerating development but also technology for preventing development capri are important issues. As antifoggants in the present invention, preferred are alkali metal halides such as lithium bromide, sodium bromide and potassium iodide, and organic antifoggants. Examples of organic force inhibitor include, for example, benzotriazole, 6-nitonibenzene, zonole, 5-nitroysonda, zonole, and 5-methinobenzone azonole. 5 — Two Trozenzo Triazono, 5 — Black Mouth-Benzotho Triazono, 2 — Thiazoli Nore-Benzimida, Monozono, 2- Thiazolylme Chinole-Benzimidazo, Hydroxyaza Nitrogen-containing heterocyclic compounds such as sodolidine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazoneol, 2 —menolecaptobenzimidazole and 2-mercaptobenzothiazol, furthermore Mercapto-substituted aromatic compounds, such as salicylic 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 developing solution of the present invention may be a pH buffer such as an alkali metal carbonate, borate or phosphate; hydroxypropylamine, triethanolamine, West German patent application. (0 LS) No. 2,622,950, preservatives such as sulphite or bisulphite; organic solvents such as diethylene glycol; dye-forming agents; competitive couplers; Dry nucleating agents, such as nucleating agents; auxiliary developing agents, such as 1-phenyl-3-virazolidone; saccharifying agents; ethylenediaminetetraacetic acid, nitric acid triacetic acid, silicone Patent application title: Rohexanediaminetetraacetic acid, iminoniacetic acid, N-hydroxymethylethylenediamintrisulfuric acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid

Amino ^ carboxylic acid, represented by the compound described in No. 58-195 5 845, 1-hydroxylidene-1,1,1'-diphosphonic acid, lysate (ResearctL Disclosure.) / 1817 (May 1979) Organic phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine -N, N, Ν ', -tetra Methylene phosphonic acid rumino aminophosphonic acid, JP-A-52-102, JP-A-53-4-2730, JP-A-54-II1127, JP-A-55- No. 40, No. 4, No. 55-402, No. 55, No. 55-1, 26, No. 41, No. 55, No. 65, No. 55, No. 55-No.

6 5 9 5 6 and Research Disclosure

(Research. Disclosure) l 18170 (May 1979) may contain a chelating agent such as phosphonocarboxylic acid.

In addition, the color developing bath is divided into two or more parts as necessary, and the replenisher is added from the first or last bath to shorten the development time and reduce the amount of replenishment. May be.

ラー現像ゲン通常通常通常通常通常通常通常 Is done. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing) or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (II), cobalt (H), chromium (VI), copper (n), peracids, quinones, and nitroso compounds. . For example, ferricyanide, bichromate, organic complexes of iron (DI) or copartite (（), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ditrilotriic acid Complex salts of aminocarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and linoleic acid; persulfates, manganates; and α-sophenol. Can be used. Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate (I) sodium and ethylenediaminetetraacetate (II) ammonium, triethylenetetramineironpentapentanate (III) ammonium, Persulfates are particularly useful. Ethylenediaminetetraacetic acid (H) complex salt is useful in both an independent bleaching solution and a single bath bleach-fixing solution.

Various accelerators may be used in the bleaching solution or the bleach-fixing solution, if necessary. For example, bromine ion, iodine ion, and US patent

¾ 7053, JP-B No. 45-856, JP-A-49-26659, JP-A-53-32753, JP-B53-36233 As shown in JP-A-53-37010 and thiourea-based compounds, or JP-A-53-124424, JP-A-53-95631, JP-A-5-3-5 No. 7 831, No. 53-3 2 7 3 6, No. 5 3-6 5 7 32, No. 5 4-5 2 5 3 4 and U.S. Patent No.

¾ 9 9 5 5 5 9 9 9 9 JP-A-49-5964, JP-A-50-140201, JP-A-53-284426, JP-A-53-114416, Heterocyclic compounds described in JP-A-53-104432 and JP-A-54-357272, or JP-A-52-20832, JP-A-55 Thioether compounds described in JP-A-25064 and JP-A-55-26506, or quaternary amines described in JP-A-48-84440 Or compounds such as thiocarbamoyls described in JP-A-49-42349. Examples of the fixing agent include thiocyanate sulfate, thiocyanate, thiocyanate compounds, thiamine ureas, and a large amount of iodide. It is used. As a preservative for the bleach-fixing solution or the fixing solution, sulfite, bisulfite or a carbonyl-bisulfite adduct is preferred.

After the bleach-fixing process or the fixing process, a washing process is usually performed. In the washing step, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, hard water softeners such as inorganic phosphoric acid, amino-carboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and pie-proofing agents to prevent the occurrence of various bacterium algae and power plants, and magnesium If necessary, a hardening agent represented by a salt / aluminum salt or a surfactant for preventing drying load and unevenness can be added. Or LE West Photographic 'Science' And 'Engineering' (Phot. Sci. And Eng.), Vol. 9, No. 6, (1965) And the like. In particular, a sword that is a sharpener or anti-binder is effective. Also, in the washing process It is also possible to save water by using a multi-stage (for example, 2 to 5 stages) countercurrent method.

Further, after or instead of the water washing step, a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 may be carried out. In the case of this process, 2 to 9 countercurrent baths are required. Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, buffers for adjusting membrane pH (eg, borate, metaborate, borax, phosphate, carbonate, hydroxylation, sodium hydroxide, ammonia water, monocarbonate) Acids, dicarboxylic acids, polycarbonates, etc.) and formalin. Other, water softeners optionally (inorganic-phosphate, amino ^ Li carboxylic acids, organic-phosphate, amino ^ Rihosuhon acid, and phosphonocarboxylic acid), killing KinHitoshi ¹ j (Proxel, Lee Sochiazoron, A surfactant, a fluorescent brightener, a hardener, and the like may be added, for example, 4-thiazolylbenzimidazole, halogenide phenolbenzotriazoles and the like.

Further, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like can be added as a membrane pH adjuster after the treatment. '

The color coupler incorporated in the light-sensitive material preferably has a palladium group or is remarkable to have a diffusion resistance. The two-equivalent color coupler substituted with a leaving group can reduce the amount of coated silver. A coupler, a non-color coupler or a coupler that has an appropriate diffusibility DIR couplers releasing an image inhibitor or couplers releasing a development accelerator can also be used.

Examples of yellow couplers that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples thereof are described in U.S. Patent Nos. 2,407,210, 2,870,057, and 2,626,506. In the present invention, the use of two-equivalent yellow couplers is preferred, as described in U.S. Pat. Nos. 4,040,194, 4,447,928, and 93,501. Nos. 4,702,620 and 4,432,024, and U.S. Pat.Nos. 440,175,2, and 432,024. , RD 18053 (April 1979), UK Patent No.

No. 142 0 20, West German Application Publication No. 2> 2 1 ¾ 9 17 No. 2> 26 I 3 61 No. 232 587 No.

A typical example is a nitrogen pull-out type yellow puller described in No. 4 3 8 1 No. 2. The a-piparoylacetide-based coupler is excellent in the fastness of a coloring dye, particularly in light fastness, while the α-benzoylacetanilide-based coupler can obtain a high color density.

The magenta couplers usable in the present invention include oil-protected, orzinazo-based or cyanoacetyl-based, preferably 5-birazolone- and birazolo-azo-based, such as, bisazolo-triazols. Kabbler. 5-hee. In lazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are used in view of the hue and color density of the coloring dye. Preferable examples thereof include U.S. Pat.Nos. 2,311,082, SSa TOS, 60Q788, 290-573, and ¾062. «No. 653, No. 5152>, No. 896 and No. 1993. As the hard-to-removal group of the 2-equivalent 5-biazoline coupler, a nitrogen atom leaving group described in US Pat. No. 4,310,619 or US Pat. No. 4,351,89 The arylthio group described in No. 7 is preferred. In addition, a 5-pirazolone-based plastic having a pallas group described in European Patent No. 73636 can obtain a high color density.

Birazoloazole couplers include U.S. Patent No.

ヒ 36 ¾ 8 7 9 Lazo mouth venzimidazoles, preferably birazolo [5,1-] as described in US Patent No. a72067. ] [1,2,4] Triazoles, Research, and Device Closures 2 4 2 2 0 0 (June 1984) June 2008, Zilotetriazoles and Research Disclosures

And pyrazolipid virazoles described in 24,230 (June, 1984). The imidazo [1,2-] virazoles described in European Patent No. 11-741 are preferred in view of the low yellow absorption of the coloring dye and the light fastness, and European Patent No. 1 Birazolo [1,5--] [1,2,4] triazole described in 1-860 is particularly preferred.

Cyan couplers usable in the present invention include oil-protected naphthol-based couplers and phenol-based couplers. The naphthalene-based couplers described in U.S. Pat. No. 2,474,293. And, preferably, U.S. Pat. And Nos.> 22-233 and 4,292,000 are examples of oxygen-equivalent double-equivalent naphthol-based couplers. Specific examples of phenolic couplers are described in U.S. Pat.No. 2,369,929, U.S. Pat.No. 2> 80 L171, U.S. Pat. No. Humidity and temperature-resistant cyan couplers are preferred for use in the present invention, and are exemplified by U.S. Pat.

Phenol cyan couplers having an alkyl group or more at the meta-position of the phenol nucleus described in 772,002, phenolic cyan couplers, U.S. Pat. No. ^ TT ^ ISS, U.S. Pat. No. 08, No. * 12 & 396, No. 4, 334011, No. 4327, 173, German Patent Publication No. 2,59-Diacylamino-substituted phenolic couplers described in JP-A-59-1666956 and the like, and U.S. Pat.Nos. 4,446,622, 433,993, and 4,394. 4 5 5 5 9 and

No. 4,42,769, and the like. These are phenol-based compounds having a phenyl group at the 2-position and an acylamino group at the 5-position.

Granularity can be improved by using a power blur in which the coloring dye has an appropriate diffusibility. Examples of such a dye-diffusing power brush are disclosed in U.S. Pat. No. 4,362,37 and British Patent No. 12-570, and specific examples of the magenta power brush are disclosed in European Patent No. 9557. No. 0 and West German Patent Application No. 234,533 describe specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the above special couplers are dimers or more May be formed. ^ A typical example of a reimaged dye forming power brush is U.S. Pat.

4 »0 8 Q 2 11 described in No. 1. Specific examples of homemilimated magenta couplers are described in UK Patent No. 2> 102; 173 and US Pat. No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material. The above can also be introduced.

The standard amount of color coupler used is that of photosensitive silver halide.

1 mol] J 0.01 to 1 mol, preferably 0.01 to 0.5 mol for yellow couplers, and 0.03 to 0.3 for magenta couplers. Moles, and 0.02 to 0.3 moles in the Zian force puller.

The light-sensitive material used in the present invention may be a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an asconolevic acid derivative, or a colorless antifoggant or color mixture inhibitor. It may contain a coupler, a sulfonamide, a phenol compound and the like.

A well-known discoloration inhibitor can be used in the light-sensitive material processed in the present invention. Examples of organic discoloration inhibitors include hydroquinones, 61-hydroxychromans, 5-hydroxycoumarins, and sucrose. Mouth chromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylated xybenzenes, aminophenols, hindered doors Representative examples include amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. In addition, metal complexes represented by (bis-salicyaldaldoximato) nickel complexes and (bis-N, N-dialkyldithiol-rubamat nickel complexes) can also be used.

To prevent the deterioration of the yellow dye image due to heat, humidity and light, a compound having both a hindered amine and a hindered phenol partial structure in the same molecule as described in U.S. Pat. Give good results. Further, in order to prevent the deterioration of the azenta dye image, in particular, the deterioration due to light, use is made of spiroindanes described in JP-A-56-15964, and JP-A-55-89835. Hydroquinone esters or monoether-substituted σ-mans described in (1) give favorable results.

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

The amount of the UV absorber applied may be sufficient to provide photostability to the cyan dye image, but if it is used in large amounts, yellowing will occur in the unexposed areas (white areas) of the color photographic material. in is located may result ', usually favored properly 1 X 1 0 ^{- 4} mol /饥² ~ ² X 1 0- ³ mol / m ^2, in particular 5 X 1 0- ⁴ Monore Zm ² ~: 1. 5 X It is set in the range of 1 0 ³ mole Zm ^2.

In a usual color paper layer of a light-sensitive material, an ultraviolet absorber is contained in one or both layers of the red-sensitive emulsion layer containing a cyan coupler, preferably in both layers. Between the green and red layers When an ultraviolet absorber is added to the intermediate layer, it may be co-emulsified with a color mixing inhibitor. When an ultraviolet 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 flute of any particle size.

In the light-sensitive material to be processed in the present invention, an ultraviolet absorber can be added to the hydrophilic π-side layer.

The light-sensitive material to be processed in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as anti-irradiation or halation. The photographic emulsion layer or other hydrophilic color or layer of the photographic material to be processed in the present invention may contain any of stilbene, triazine, thiazole or coumarin brighteners. A water-soluble one may be used, and a water-insoluble brightener may be used in the form of a dispersion.

As described above, the light-sensitive material used in the present invention can be applied to a multilayer multicolor photographic material having at least two different spectral sensitivities on a support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one real-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as needed. Each emulsion layer in the previous period may be composed of two 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 used in the present invention includes a protective layer, an intermediate layer, a filter layer, an anti-halation layer, and a pack layer in addition to the silver halide emulsion layer. ¾ It is preferable to appropriately provide any auxiliary layer.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material used in the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. .

For example, gelatin derivatives, proteins such as graphitic oligomers of gelatin and other macromolecules, albumin, casein, etc .; Cellulose derivatives such as sulfates, sugar derivatives such as sodium alginate and starch derivatives; vinyl alcohol, polyvinyl alcohol partial acetal, and ^ -N-Bilhi. Mouth or copolymers such as lidone, acrylic acid, polymethacrylic acid, polyacrylamide, polyvinylamide, polyvinyl razol, etc. Many types of synthetic hydrophilic polymer substances can be used.

As gelatin, lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan. 16 and 30 (1966) may be used. A hydrolyzate or enzymatic hydrolyzate of gelatin can also be used. In addition to the additives described above, the light-sensitive material of the present invention may further contain various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors, lubricants, mordants, mats Agents, antistatic agents, plasticizers, or other useful photographic materials. Various additives may be added. A representative example of these additives is Research 'Disclosure 1 176 4 3 (1972 January 1 February) and the same. 1 8 7 16 (January 19, 1997).

In the present invention, silver chlorobromide, silver chloride, silver chloroiodobromide, silver bromide, silver iodobromide and the like are used as α-halogenated silver, and preferably silver iodide is substantially contained. Silver bromide, silver chlorobromide, and silver chloride]), and more preferably silver chlorobromide having a silver bromide content of 20 to 98 mol. Further, for the purpose of processing in a shorter time, it is preferable to use silver chloride and silver chlorobromide having a silver chloride content of 90 mol or more, particularly 95 mol or more.

The silver halide grains used in the present invention may have a phase different from the inside and the surface layer, may have a multi-phase structure having a bonding structure, or the whole grains may be composed of a uniform phase. They may be mixed. .

Average grain size of silver halide grains used in the present invention (in the case of spherical or nearly spherical grains, the grain diameter is used, and in the case of cubic grains, the ridge length is defined as the grain size, and the average is based on the projected area) Is preferably 2 or less and 0.1 or more, and particularly preferably 1 or less and 0.15 or more. The grain size distribution may be either narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is 20 or less, particularly preferably. It is preferable to use so-called monodispersed silver halide emulsions having a size of 15 or less in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more monodisperse silver halide emulsions having different grain sizes in the emulsion layer having substantially the same color sensitivity (the monodispersity The above-mentioned fluctuation rate is preferable) is mixed in the same layer or multi-layer coated in another layer be able to. Further, two or more polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The shape of the silver halide grains used in the present invention may be cubic, octahedral, dodecahedral, or tetradecahedral, or may have regular crystals, or may be irregular such as spherical. (Irregular) It may have a crystal form, or a compound form of these crystal forms, but preferably has a regular ¾ crystal such as a cube or a tetrahedron. Further, tabular grains may be used. In particular, an emulsion in which tabular grains having a ratio of length to thickness of 5 or more, particularly 8 or more, occupy 50% or more of the total projected area of the grains may be used. An emulsion comprising a mixture of these various crystal forms may be used. These various types of emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains, but the former is preferred.

The photographic emulsion used in the light-sensitive material processed in the present invention is P.

G-laf kide s, Ghmiet et Pliysiqae Pliotographiq e Paul Montel, 1967), G-.F.Duff in, Pliotogra-phic Emulsion Cliemi stry (Focal Press, 196) 6 years), by V.L. Ze lilonan et al, Making and Coating Pliotograpiclic Emulsion (published by Focal Press, 1964). it can. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble salt is a one-sided mixing method, a simultaneous mixing method, or a combination thereof. May be used. particle Can be formed in excess of silver ion (so-called reverse mixing method). It is also possible to use a method to keep the pA _g in the liquid phase in which the wafer androgenic halide as one type of simultaneous mixing method constant, to Wachiiwayuru Con Bok Rolled, a double jet Bok method. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Further, a so-called conversion method including a process of converting silver halide haptogen that has already been formed into silver halide having a lower solubility product until the process of forming silver halide halides is completed. Emulsions prepared and emulsions which have undergone the same halogen exchange after completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening, potassium salt, zinc salt, copper salt, iron salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its salt. Salt and the like may coexist.

The silver halide emulsion is usually subjected to physical ripening, desalting and chemical ripening after grain formation, and then used for coating.

Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 2,711,157, JP-A-5-123660, JP-A-5-3-8240) Thia ethers and thien compounds described in JP-A-53-144319, JP-A-54-107171 or JP-A-54-155828) Can be used for precipitation, physical ripening, and chemical ripening. In order to remove the soluble silver salt from the emulsion after physical ripening, a washing method such as a Nudell washing method, a flow-setting method or an ultra-leakage method is used. The silver halide emulsion used in the light-sensitive material to be processed in the present invention contains a compound containing sulfur capable of reacting with active gelatin or silver (eg, sulphate sulfate, thioureas, mercapto compounds, rhodanines). Sulfur sensitization method used; Reduction sensitization method using a reducing substance (for example, stannous salt, amines, hydrazine derivative, formamidine sulphinic acid, silani conjugate); metal compound (for example, gold) in addition to鍺塩can be used _{P t, l r, P d} , Rh, or in combination with etc. F e which periodic table f metals complex salts) noble metal sensitization method ¾ using alone.

Of the above chemical sensitizations, sulfur sensitization alone is preferred.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the color light-sensitive material used in the present invention are spectrally sensitized by a methine dye or the like so as to have color sensitivity. Dyes used include cyanine dyes, melocyanin dyes, complex cyanine dyes, complex melocyanin dyes, holo-larocyanin dyes, hemicyanin dyes, styryl dyes, and hemiokinol dyes. Included. Particularly useful dyes are those belonging to cyanine dyes, melocyanine dyes and complex melocyanine dyes. As these dyes, any of nuclei usually used in cyanine dyes as basic heterocyclic nuclei can be applied. That is, a viroline nucleus, an oxazoline nucleus, a thiazoline nucleus, and a nucleus. Such as a roll nucleus, an aged oxazoline nucleus, a thiazo-mononuclear nucleus, a serenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridin nucleus; Nuclei in which rings are fused; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, ie, inlenin nucleus, benzind'renin nucleus, ind, mononuclear nucleus, Azole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Melocyanine dyes or complex melo and cyanine dyes have a pyrazolin-5-one nucleus, a chi-hydantoin nucleus, and a 2-thio-xoxazolidin-2,4-di-nucleus having a ketomethylene structure. Five- to six-membered heterocyclic nuclei such as nuclei, thiazolidin-2,4-dione nuclei, rhodanine nuclei, and genius parbituric acid nuclei can be applied. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 6,985,545, 2,977,229, 3,977,060, 5,522> 052, 552 Nos. 7, 641, 61, 293, 62, 964, 664, 680, ^ β Τ ^ δθ δ, 679, 428, 7 No. 377, No. 769, 301, No. 814, 609, No. 837, 862, No. 4, 02707, UK Patent 1,344, No. 281, No. 507, 803, No. 43-4936, No. 53-123, No. 5, JP-A No. 52-110, 188, No. 52 -It is described in No. 10992.

Along with the sensitizing dye, the emulsion may contain a dye which itself has no spectral sensitizing action or a substance which does not substantially absorb visible light and exhibits supersensitization.

BEST MODE FOR IMPLEMENTATION]

^ Below, the present invention will be described according to examples]) It is not limited to these.

Example 1.

The yellow coupler (Y-1) 2 4.09 was dissolved by adding ethyl acetate 3 and a solvent: 7 dibutyl tartrate 12 4.0 as a solvent, and using this solution as an emulsifying dispersant, the following comparative compound R-1 The solution was added to a solution of 10 (dibutyl naphthalene sulfonato sodium) in 10 2 aqueous gelatin solution containing 10π, and emulsified and dispersed by a high-speed stirrer.

Adding the whole amount of the emulsified dispersion to Ruru silver chlorobromide emulsion from Br 8 0 (Ag 7 0 containing) silver coating amount 0.3 1 i / n on both sides so as to become ² laminated with Riechiren paper support on Then, a gelatin layer was provided on the top of this coating layer to prepare a comparative sample (A).

Next, samples (B) to (R) were prepared as follows.

Sample (B)

The same sample as the sample (A) except that 1.0-1 of the exemplified compound A-1 of the present invention is used as the emulsifying dispersant in the glue of R-1.

Sample (_C)

As an emulsifying and dispersing agent, R 1 Kawa! ) Is an exemplary compound A of the present invention.

-Sample same as sample (A) except that 1.0 is used for 9 ^

Sample (D)

The same sample as sample (A) except that 1.0-1 of Exemplified Compound A-11 of the present invention was used instead of R-1 as an emulsifying dispersant

Sample (E_

As an emulsifying and dispersing agent, the exemplary compound of the present invention A- Sample identical to sample (A) except using 20 ^ 1.0 ^

Sample (F)

The same sample as sample (A) except that 1.0-1 of Exemplified Compound A-26 of the present invention was used instead of R-1 as an emulsifying dispersant

Furthermore, instead of the yellow coupler (Y-1) of the samples (A) to (F), the samples (G) to (!) Were obtained using a magenta coupler (M-1) and a cyan coupler (C-1). And (M) to (R).

When a magenta coupler was used, the silver coating amount of the silver chlorobromide emulsion composed of 0.37 / m ² Br 75 mol was 0.209 / ² , the cyan coating amount was 0.33 / ² , the silver coating amount of silver chlorobromide emulsion comprising br 7 0 mo was 0.28 ¼ ^2.

Y-1

2) ₃ H / c ₅ H ₁₁ (t) /

I c

OH M-

CH ₃ 0. OC ₈ H ₁₇

N- ■ NH S O · 'No'

\ /

G ₈ H ₁₇ (t)

C

Comparative compound R-l

These samples were given a step exposure for sensitometry. Thereafter, Experiments of Processing A and Processing B were carried out using the color developing solutions (A) and (B) as shown below. The contents of the processing A and B are distinguished by the difference between the contents of the color developing solutions (A) and (B), and the contents of the other processing steps are the same for both A and B. (Processing process) Temperature (time) Current solution 3 8 2.0 minutes Bleach-fix solution 3 3 1.5 minutes Rinse 2 8-3 51: 3.0 minutes

(Developer formulation)

Color developer (A)

Diethylene triamine 5 vinegar 5 Na salt 2.0 ^ Benzinole T-record 15 m Diethylene ricone 1 Ome

Na S0 2.09

KB r 0.5 ^ Head's xylamine sulfate 3.0 ^

4-amino-3 -methyl-N-ethyl-N

[(Methanesulfonamide) ethyl]

-Phenylenediamine sulfate 5.0 ^

Na ₂ G0 ₃ (1 monohydrate) 3 0.0 optical brightener (scan 1.0 ^ water were added total amount of 1000 ^

({¾10.1) Color developer (B)

Diethylene triamine 5 acetic acid 5 Na salt 2.0

KBr 0.5 -9 hydr, roxylamine sulfate 3.09

4-Amino-3-methyl-N-ethyl

^[51 - (methanesulfonamido Ami de) Echiru]

P-phenylenediamine 'sulfate 5.09

Na ₂ C03 (Monohydrate) 30.09 Fluorescent brightener (Still pen type) 1.0 ^ Add water to 1000 me

(Bleach-fix solution formulation)

Ammonium sulfate (54wt) 150 / κ

NH ₄ [Fe (I) (EDTA)] 55 ^

EDTA2Na 4

1000 で in total with water

(pH 6.9) The evaluation of photographic properties was performed with two items, the maximum intensity (Dmax) and the minimum disturbance (Dmin). The results are shown in Table I. Table-1 Photographic properties Sample coupler i Emulsifier / dispersant Treatment A Treatment B

Dmin Dmas Dmin • Dmas

(Note 1) Samples (B) to (F), (H) to (L), and (N) to {R)

What has been developed is the present invention. From the results in Table 1, it can be seen that the samples of the present invention have the highest concentration and are almost the same as those of the treatment A even in the treatment B with a high concentration of benzyl alcohol, regardless of whether the yellow coupler, the magenta coupler or the cyan coupler is used. It can be seen that they exhibit the same coloring properties.

Example 2.

Comparative multilayer photographic paper (A) having the layer configuration shown in Table 2 was prepared on a paper support laminated on both sides with ethylene.

The coating solution was prepared as follows.

Preparation of first layer coating solution

To yellow coupler ( _a ) 19.1 ^ and color image stabilizer () 4.49 were added and dissolved ethyl acetate 27. 2 and solvent (c) 7.9, and this solution was used as an emulsifying dispersant. It was added to 10 85 aqueous gelatin solution containing 10 10 sodium dibutylnaphthalenesulfonate (R-1) and emulsified and dispersed by a continuous stirrer to obtain an emulsified dispersion.

On the other hand, silver chlorobromide emulsion blue-sensitive sensitizing dye shown below in (silver bromide 8 0 mole silver 7 0 ¾-containing) silver chlorobromide 1 mole per] 9, 7. 0 X 1 ( Γ 4 90 mol was prepared as a real layer emulsion by adding mol.

The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted so as to obtain the composition shown in Table 2, thereby preparing a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardener for each layer, a 1-year-old xy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as spectral sensitizers for each emulsion. Blue-sensitive emulsion layer

Na

Rogeni匕銀1 mo This 1) 7.0 X 10- ⁴ mo添方opening) Green-sensitive emulsion layer

S0 ₃ HN (C ₂ H ₅ ) ₃

(Halo dangin 1 mo this J? 4.0 X 10 ^_4 mo addition [])

S〇 ₃ HN (C ₂ H ₅ ) ₃

(C opening Gen halide 1 mo This 7.0 X 10- ⁵ mo添力π) Red-sensitive emulsion layer

Θ

^C 2 ^H 5 ^G 2 ^H 5

(Silver silver halide 1 mo per 1.0 X 10 ^_4 mo support!)

The following dyes were used as the anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer:

S0 ₃ K so ₃ K Red-sensitive emulsion layer:

H 5.C 2.OOC

SO3K The structural formulas of the compounds used in this example are as follows:]) "L-) 0

(a) I yellow cuff

(¾) Color image stabilizer

(c) Solvent

(d) color mixing inhibitor

(Θ) Magenta coupler

\

8d ₁₇ (t)

(f) Color image stabilizer

(g) Solvent

C ₈ H ₁₇ 0 † -P

2: 1 mixture (weight ratio) (H) UV absorber / \ — c) soluble

Medium

₇ 1: 5: 3 mixture (molar ratio)

Color mixing inhibitor

QH

〇 ₇ (t)

(t) C ₈ H ₁₇ I

8 ¹⁷ OH

(iso CcH ^ O ^ -P ^ O

(k) Cyan coupler

〇

(£) UV absorber

: 3: 3 mixture (molar ratio)

(m) Solvent

! Table one two-layer main Ru for the pair formed using "& green first _- the seventh layer gelatin 1.33 ^ m ^_2:

(3 layers of protection) Acryl-modified 0.17 "copolymer of polyvinyl alcohol (degree of modification 17)

i sound n

Layer 6 Gelatin 0.54 "

(UV absorbing layer) 'UV absorbing agent (H); 0.21 "

Solvent (j) \ 0.09 cc _m ² ; i fifth layer I silver chlorobromide emulsion (70 mol of silver bromide) silver: I 0.239 m 2; (red sensitive layer Zephthene 0.98 '

Cyan coupler (k) 0.30 "Color image stabilizer 0.17" Solvent M 0.23CC T ² 4th layer Gelatin

(UV Sugar:) UV Absorber) 0.62 "

Anti-color mixing agent (i) 0.05 "solvent (0.26 _cm ² silver chlorobromide emulsion (75 mol of silver) silver: I 0.13 ¼ ² gelatin i 1.80 magenta cuff. ;! 0.20 "solvent (g) 0.68 cc _m ² second layer - gelatin of 0.99 ^ / m ² (color mixing preventing layer) color mixing preventing layer (0.08 i first layer 'silver chlorobromide emulsion (Nioii 80 mol) of silver 0.27 ^ m ² : (blue sensitive layer) gelatin 1.86 "

(A) 0.71 f Color image stabilizer (9) 0.19 ": Solvent (c) 0.34 cc / _m ² support Polyethylene laminated paper (white pigment (TiO2 and blue Contains taste dye Next, photosensitive materials (B) to (D) were prepared as shown below.

Photosensitive material B

In the first, third and fifth layers of the light-sensitive material (A), R-1 was used as the emulsifier and dispersant. Same photosensitive material-photosensitive material C

In the first, third and fifth layers of the light-sensitive material (A), the light-sensitive material (A) was used except that 1.2-1 of the exemplary compound A-9 of the present invention was used as an emulsifying dispersant in the glue j of R-1. Same photosensitive material

Photosensitive material D

In the first, third and fifth layers of the light-sensitive material (A), the same as the light-sensitive material (A) except that Ex. Compound A-26 of the present invention was used as an emulsifying dispersant instead of R-1 in 1.2 ^. Photosensitive material

Using a sensitometer (FWH type, Fuji Photo Film Co., Ltd., color temperature of light source ¾200 ° K) on these samples, the gradation for sensitometry is passed through blue, green, and red filters. Exposure was given. The exposure at this time was performed so that the exposure amount was 250 GMS with an exposure time of 0.5 second.

Thereafter, Experiments of Processes A and B were performed using the color developing solutions (A) and (B) as shown below.

The photographic properties were evaluated by changing the development time from the color development, bleach-fix, and washing steps to 1, 2, and 3 minutes. The contents of the processing A and B represent the difference between the color developing solutions A and B, and the other processing contents are the same for both A and B.

Evaluation of photographic properties, relative sensitivity, gradation, maximum density (Dm _a2 :), minimum Concentration (Dmin) was performed for 4 items. The relative sensitivity is a relative value where the sensitivity at a color development time of 2 minutes in process A of each photosensitive layer of each photosensitive material is 100. The sensitivity was expressed as a relative value of the reciprocal of the exposure required to give a density obtained by adding 0.5 to the minimum density. The gradation was expressed as a density difference from the sensitivity point to a point increased by 0.5 by the logarithm of the exposure (iogE :).

The results are shown in Table 3 (A) and (B).

(Process) (Temperature) (Time). Image solution 381C 1.0-3.0 minutes

33 at 1.5 minutes Rinse 28-35 C 3.0 minutes

(Developer formulation)

Color developer (A)

Diethylenetriamine 5 Enzymatic acid 5 Na salt 2.0 ^ Ben, Nore or Nore 15 m Jetylene glycolon 10w £ Na ₂ S0, 2.0 ^

KBr 0.5 ^ Hydroxylamine sulfate 3.0 ^

4-Amino-3-Methyl-N-ethyl N-

(^-(Methanesulfonamide,) ethyl)-

P-Ferenylene Dipamine << Sulfate 5.0 ^

Na ₂ C0 ₃ (1 monohydrate) 30.0 ^ optical brightener (Suchirupen system) 1.0 100 Water to make the total amount On ^

(PH I O.1) Color developer (B)

Diethylenetriamine 5 drunk acid 5 Na salt 2.0 ^

Na ₂ SO 2.0 i

KB r 0.5 ^ Hydroxylamine sulfate 3.0 4-Amino-3- 3-methyl N-ethyl-N

[^-(Methanesulfonamide) ethyl]

p-phenylenediamine sulfate 5.0 ^

Na ₂ C0 ₃ (1 monohydrate) 30.0 ^ fluorescent whitening agent 100 in a total volume added (Suchirupen system) 1.0 ^ Water

(pHl O.1)

(Bleach-fix solution formulation)

Ammonium thiosulfate (54wt) 150m £

NH ₄ e (I) (EDTA)]

EDTA2Na

1000¾ with water

(pH6.9) Table 3 A Process A Photo-emulsification-Development time 1 minute 2 minutes 3 minutes Material Dispersant relative:

, Another gradation D thigh D «¾ i gradation, D 羅 D∞t gradation: D D

53 059; 0.10 1.78 100 052 0.10! 184 106! 1.00! 0.11 186

A R- 65 1.14 0.10234 100 1.16 Oil 2.40: 111! 1.19 0.112.43

68 1240.10250 100 126 0.11 253; 114! 128 0.10254

B ₍ 57 jO.97; 0.09! 1.81! 100 1.0110.10; 1.87116 is .10 | 0.11 159 j ^; !!!

B G-; Α · 71; 1.25; 0 ュ 0 ^: 235; 100; 128: 0 ュ 0244130 131; 0.11 2.46

74 1.37 0.10; 251 100: 1.39; 010; 255,125; 1.41! 0.11 257

55 0.93; 0.101.81 100 0.97 0.10 1.87 j 111 1.05 0.10,1.89

G A-9 68 1.20 0.10; 237 100 i 1.220.09 2.43 17 125 10.11: 246

71 1.30 0.10! 253 100 1.320.10 256: 119 1.3410.101257

B j 60 1.00 iO.10 2.02 100 1.02 010 1.89117 1.12 0.10 1.92 j

DG; A- 26:76 12710.10 2.39! 100 1.28! 0.1012.45122 1.33 0.1012.49 R!: 77! L.38: 0.10 | 2.55; 100 U.40 0.10 _; 258125: 1.43 ^! 0.10259 Table 3 Process B Process A Photosensitive emulsification Developing time 1 minute: 2 minutes 3 minutes

: Simplified translation relative 1 'relative' _ relative

Another [5 g¾ D mm D «¾c Dmm D« a ΏΜΙ

Sensitivity:

B 46 0/78 0 new 0: 1.57 72 050 0.10; 1.60 87 050 0.10 1.70

A G; R- 1, 61 1.0θ! Θ10 | 2Ό5 72 1.10 0 0: 2.07 92 112 0.10 211

1 ¹

R |; 59 1.10; 010: 221 75 ill 5 0.10-220 94 120 010 230

^: .; 1

j

I i ί

B! : 49 0.85 0 8! 1.74 107 1.06 0.09 '1.79 85 1.08 0.09: 186

Β 1 G Α- 1 66 1.10 0.08 228 i 120 126 0.10 239: 90 ^: 128; 0.09 2.43 R 64: 1.21 0.08 2.46 115 1.35: 0.09! 2.49! 92; 1.39; 0.09 254

Β, 48 0.9010.09 1.73! 103; 1.03 0.09 1.841105 1.05 0.10: 1.87

;

CG Α—9! 64! 1.05: 0.09 223 i 109 j 120 0.09 2.43! 111 122 0.10 ^: 2.45 R: 62 1.16 0.09 2221111; 1.27! 0.09 253 113! 1.31 0.10: 255

B; 52 0.88 0.09 1.75 110 11:08 10 1.86 113 1.10 ^! 0.10 1.88 jj

G A- 26; 69 1.12 0.09 225 116! 1.30 i 0.10 245! 118 1.32 0102.47 R 67 ί 1.23: 0.09 2.78 117; 1.39; 253: 120 i 1.41 0.10 257

(Note 1) The present invention is obtained by developing photosensitive materials (B), (G) and (D) by processing B. As is clear from Table S, the photosensitive materials (B) to (D) used in the present invention are comparative photosensitive materials. It can be seen that the performance of Treatment B, which is small and does not contain benzyl alcohol, is comparable to that of Treatment A.

Further, in the light-sensitive materials (B) to (D) of the present invention, even in a high bromine content emulsion whose development progresses relatively slowly, good photographic properties can be obtained in a processing time of 2 minutes even in processing B containing benzyl alcohol. showed that. Therefore, it can be seen that the development is further shortened in the emulsion having a high chlorine content.

[Industrial applicability]

According to the practice of the present invention], by substantially eliminating pen-zyl alcohol, the pollution load is reduced, the preparation of the solution is reduced, and the effect of eliminating the decrease in the concentration due to the cyan dye remaining in the silicone body is eliminated. It has. In addition, the use of the silver halide emulsion of the present invention provides an effect that high Dmax, low Dmin, and sensitivity and photographic properties with little gradation change can be obtained without using j? And benzyl alcohol. Have

Claims

The scope of the claims

1. At least one silver halide emulsion layer on a reflective support, or a fluorine-substituted aliphatic group having 4 to 18 carbon atoms as a hydrophobic group in a molecule of the emulsion layer or an adjacent layer. a, and as the hydrophilic group - the 0s0 ₃ M (wherein M is a hydrogen atom or a cation on) of silver halide color photographic material containing a Anion surfactant having - S_〇 ₃ M or A color image forming method characterized in that after the image exposure, development processing is performed in a developer substantially free of benzyl alcohol in a time of 2 minutes and 30 seconds or less.

2. The color image forming method according to claim 1, wherein the anionic surfactant is a surfactant represented by the following general formula (1).

(Rf) _n (B) _m -X (1)

Here Rf is a fluorine-substituted alkyl group or an One-containing substituted alkenyl group of 4-1 8 carbon atoms, X is - S_〇 ₃ M or - 0S_〇 ₃ M (M is a hydrogen atom or a Chikarachisain B) represents a divalent or trivalent organic residue or a polyvalent group in which a divalent or trivalent organic residue is bonded to a divalent bonding group, n is 1 or 2, and m is 0 or 1. Represents

3. The divalent or trivalent organic residue represented by B is a divalent or trivalent aliphatic hydrocarbon group, an arylene group, or a divalent hetero π-ring group. The image forming method according to the above item.

4. When the polyvalent group represented by B is

R

(SO ^ -NR ^ O-GO) .R ₂ -,-GOORi-,

-R ^ -CO-R ^, -C0NH-R _χ or -S0 ₂ NR-R _1- (where R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and is a divalent aliphatic hydrocarbon group, an arylene group, or a divalent heterocyclic group. And R ₂ represents a trivalent aliphatic hydrocarbon group.) The color image forming method according to claim 2, wherein

5. The method according to claim 1, wherein the π-genated silver emulsion or an adjacent layer thereof contains a fluorine-unsubstituted anionic surfactant and / or a nonionic surfactant together with the anionic surfactant. Color image forming method.

6. Buddha Motona substituted § - one surfactant and a hydrophobic group having a carbon number of 8-3 0 in the molecule - S0 ₃ M or - 0s0 ₃ Anion soluble surface Buddha Motona substituted with a group M 6. The image forming method according to claim 5, which is an activator.

7. The color image forming method according to claim 5, wherein the nonionic surfactant is a sorbitan fatty acid ester-based nonionic surfactant.

8. The color image forming method according to claim 1, wherein the color developing solution is an aqueous solution containing an aromatic primary amine color developing agent as a main component.

9. A silver halide photo having at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one real silver halide emulsion layer on a reflective support. In a color image forming method in which a photosensitive material is subjected to color development, bleaching and fixing or bleach-fixing, washing with water and Z or stabilizing treatment after image exposure, the emulsion layer or its tunneling layer has hydrophobicity in the molecule. 4 to 4 carbon atoms Having 1 8 fluorine substituted aliphatic group, and as the hydrophilic group - S0 ₃ M or - 0s0 ₃ M (wherein M is a hydrogen atom or a cation on) contain Anion surfactant having A color image forming method characterized in that color development is performed in a color developer substantially containing benzyl alcohol in a time of 2 minutes and 30 seconds or less.

10. The color image forming method according to claim 9, wherein the anionic surfactant is a surfactant represented by the following general formula (1).

_{_{(Rf) n (B) m}} -X (1) wherein Rf represents a fluorine-substituted alkyl group or an One-containing substituted alkenyl group of 4-1 8 carbon atoms, X is - S0 ₃ M or -〇_S0 ₃ M (M represents a hydrogen atom or a hydrogen atom); B represents a divalent or trivalent organic residue or a polyvalent group in which a divalent or trivalent organic residue is bonded to a divalent bonding group. , N represents 1 or 2, m represents 0 or 1.

11. The divalent or trivalent organic residue represented by B is a divalent or trivalent aliphatic hydrocarbon group, an arylene group, or a divalent heterocyclic group. The color image forming method described in the above section.

12. When the polyvalent group represented by B is R

I

(SOg-NR ^ O-CO) ₂ R ₂ -.-COORi —,

-R, 0-C0-R,-,-C0NH-R ₁ or -S0 ₂ NR-R _1- (where R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and is a divalent Represents an aliphatic hydrocarbon group, an arylene group, or a divalent heterocyclic group, and R ₂ is 3 10. The color image forming method according to claim 10, which represents a monovalent aliphatic hydrocarbon group).

13. The ninth aspect of the present invention, wherein the silver halide emulsion or an adjacent layer thereof contains a fluorine-substituted anionic surfactant and a Z or non-ionic surfactant together with the anionic surfactant. The image forming method according to the above item.

14. French Motona substituted Anion surfactant and a hydrophobic group having a carbon number of 8 to 3 0 in the molecule - S 0 ₃ M or - 0 S 0 ₃ French Motona substitution § having an M group - The color image forming method according to claim 13, which is an on-active surfactant.

15. The colorant according to claim 13, wherein the nonionic surfactant is a nonionic surfactant of a fatty acid ester type of sorbitan.

16. The image forming method according to claim 9, wherein the color developing solution is an aqueous solution mainly containing an aromatic primary amine color developing agent.

17. The color image forming method according to claim 1, wherein silver halide is mainly used to form a latent image on the surface of the grains.

18. The color image forming method according to claim 1, wherein the color developing solution contains benzyl alcohol at all.

19. The color image forming method according to claim 8, wherein the aromatic primary amine color developing solution is a P-phenylenediamine compound.

20.p-Phenylenediamine compound is 3-methyl-4-amino-ethyl-N--methansulfonamide 10. The method according to claim 19, wherein the method is phosphorus or 3-methyl-4-amino-1-N-ethyl-N-hydroxyethylaniline.

21. The method according to claim 19, wherein the p-phenylenediamine-based compound is 3-methyl-4-amino-N-ethynole — methansulfonamine ethynoleiraline.

22. The color image forming method according to claim 1, wherein an anionic surfactant is contained in the silver halide emulsion layer.

23. An anionic surfactant is added to the silver halide emulsion layer and / or an adjacent layer in a ratio of 0.2 to 50% by weight of the hydrophobic substance emulsified and dispersed in the layer. The method for forming a color image according to claim 1, wherein said method is contained.