JPH03103849A - Cyan dye forming coupler and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PURPOSE:To enhance light and heat fastness and to sharpen absorption of a dye by using a cyan dye forming coupler specified in structure. CONSTITUTION:The cyan dye forming coupler to be used is represented by formula I in which R1 is an aliphatic, aromatic, or heterocyclic group; R2 is a group substitutable on the hetero ring; X is H or a group releasable at the time of coupling; Y is a divalent group, such as amido or ester bond; Z is a dissociable group; n1 is 0 or 1; and each of A - E is a C or N atom; thus permitting light and heat fastness and absorption characteristics of a color development dye to be enhanced, an absorption wave form to be sharpened, and color reproduction performance to be improved.

Description

Detailed Description of the Invention (Industrial Field of Use) The present invention relates to a novel shea/dye-forming coupler used in silver halide color photographic materials, and a silver halide photographic light-sensitive material containing the coupler. It is related to the department.

(Prior art) After a silver halide photosensitive material is exposed to light, it is subjected to a color development process, whereby a developing agent such as an aromatic primary amine oxidized by silver halide reacts with a dye-shaped bottom coupler. A color image is formed.

Generally, in this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and red, color images of yellow, maze/ta, and cyan, which are complementary colors, are formed, respectively.

Phenols or nutols are often used as shear/color image forming couplers.

However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, US special? 2nd and 3rd t7.3
3/No. 2,362, Octopus 2, No. 1123,
The color images obtained using the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 7.30 and U.S. Pat. 77j, /A. 2, 193, 1.26 of the book,! - Color images obtained with diacylaminone phenol shea/couplers generally have poor light fastness;
-Hydroxy-conaphthamide cyan couplers generally have insufficient both light and thermal (particularly moist heat) rigidity.

To improve the drawbacks of such cyan dye-forming couplers, for example, U.S. Pat. , t♂6, j-hydroxy-2-acyl-nocarbostyrylsia/l-hydroxy-2-acyl as described in U.S. Pat. No. 30.4'23
3-7 acylaminooxy/dolkabun - hydroxy-3-acylamino+2.3-? Hydro 7,
Developed 3-benzimidazole-1-o/coupler! has been done. These couplers have excellent light fastness and heat fastness. These couplers are specific couplers having a heteroatom in the color-forming mother nucleus, but any ring having a dissociative group for color-forming is equivalent to phenol.

On the other hand, as couplers in which a heteroatom is introduced into a ring with a dissociable group, 3-hydroxypyridine and co,z-dihydroxypyridine are only disclosed in US Pat. No. 2,223, θOg. However, the absorption wavelength of the 3-hydroxyviridine compound described in this US patent is on the very short wavelength side, and the absorption peak is also broad. Furthermore, this 3-hydroxypyridine is also water-soluble. Therefore, 3-hydroxypyridi/ could not be used as a so-called cyan coupler.

(Problems to be Solved by the Invention) Therefore, the purpose of the present invention is to
3-Hydroxy- as described in No.
6-Acylaminocarbonuteryl C-A-A/Coupler and U.S. Patent No. II,1130.112
Bi-hydroxy-3-acylaminooxy/Dole coupler described in No. 3. It has excellent light fastness and heat fastness similar to monoacylamino-2,3-dihydro-7,3-penzimidazole-co-on couplers, and has excellent absorption characteristics for coloring dyes (
That is, the object of the present invention is to provide a novel shear/coupler with a sharp absorption waveform and improved reproducibility of dark brown colors.

Another object of the present invention is to provide a silver halide color photosensitive material R'k containing such a novel cyan coupler.

(Means for Solving the Problems) The object of the present invention is to provide a cyan dye-forming cazoler represented by the following general formula [I], [■] or (III) and a silver halide color photographic photosensitive material containing the coupler. It was effectively achieved by the materials department.

(In the formula, R1 represents an aliphatic group, an aromatic group, or a multicyclic group; R2 represents a group or atom that can be substituted for a heterocycle;
X represents a hydrogen atom or a coupling-off group; Y represents a divalent linking group containing at least seven amide bonds and/or ester bonds; 2 represents a dissociative group; Hn1 represents θ or/i'l; is 7, R1 and R2 may form a ring (at least 7 of iR1, R, 2 and
is a heterocyclic residue group in which R1, R2 or X is eliminated in the general formula CI)/or li. It can also be included as two or more substituents. AX BX CXD and E each represent a carbon atom or a nitrogen atom, and two of A-H are nitrogen atoms. )? In the formula, 90 represents an aliphatic group, an aromatic group, or a polycyclic group; R2 represents a group or atom that can be substituted on the pyridine ring; X represents a hydrogen atom or a coupling-off group; Y represents at least /represents a divalent linking group containing two amide bonds and/or ester bonds; Z represents a dissociative group; i''2
represents O,/or Ko; if n2 is 2, two R
2 may be the same group or atom or different groups or atoms, and the two 82 may form a ring base;
When n2 is 7 or more, R0 and 2 may form a ring. At least 7 of R2 and X represent the general formula [1
) out of which R1, R2 or X is removed, the remaining pyridyl fund 7
Or, it may be included as a substituent of more than one substituent. (If the other seven R2 can be bonded to the nitrogen atom of the pyridyl ring, and in this case, the hydroxyl group bonded to the ortho or para position can also become a siketone due to tautomerism.) The cyan couplers represented by formulas 1), [■], and (III) will be described in detail.

R1 is preferably an aliphatic group having 36 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (e.g., 7enyl, na7thyl), or a heterocyclic group (e.g., 3-pyridyl, 2-furyl). , morpholino).

In this specification, the term "aliphatic group" refers to a linear, branched, or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. . Representative examples include methyl, ethyl, butyl, dodecyl, octadecyl, icosenyl,
iso-proyl, tert-butyl, iert-octyl, tert-dodecyl, cyclohexyl, cyclope/thyl, allyl, vinyl, 2-hexadecenyl, propagyl/0-yl.

In addition, "aromatic group" refers to a monocyclic or polycyclic condensed aromatic hydrocarbon group, and "heterocyclic group" refers to not only carbon atoms (, (J, S', N, P, etc.) A cyclic group containing at least 7 heteroatoms in the ring, in which a 3- to ♂-membered ring, preferably a j- or t-membered ring, may be fused with other heterocycles, and heterocycles may be fused together. May be fused with benzene/ring.1
It also includes cyclic groups without aromaticity.

The aliphatic group, aromatic group, and heterocyclic group represented by R12 can further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy, comethoxyethoxy), an aryloxy group (e.g., j,4L-di-tert- amylphenoxy, 2-chlorophenoxy, l-cyanenoxy)
, alkenyloxy group (e.g. 2-probenyloxy)
, ami7 group (e.g. butylamino, dimethylamino, anilino, N-metheranilino), acyl group (e.g. acetyl, be/zoyl), ester group (e.g. butoxycarbonyl, phenoxycarbonyl, acetyloxy, penzoyloxy, butoxy) sulfonyl, toluene-nulfonyloxy), ado groups (e.g. acetelano, ethylcarbamoyl, dimethylcarbamoyl, meta/nulpo/amide, bunalsulfamoyl), sulfamide groups (e.g. diprobylsulfamoylamino), imido-containing (e.g. succi/imide, hydantoinyl), ureido groups (e.g. phenylureido, dimeterureido), aliphatic or aromatic sulfonyl groups (e.g. meta/nulfonyl, phenylnulfonyl), aliphatic or aromatic thio groups ( For example, it may be substituted with a group selected from eteltheo, 7enylthio), hydroxy group, cyano group, carboxy group, nitro group, nurpho group, halog/atom, etc.

Next, }t2 represents a group that is transferred to the nuclear heterocycle, and preferred specific examples include aliphatic groups (such as methyl, ethyl, butyl, dodecyl, etc.), aromatic groups (
(e.g. phenyl, naphthyl), heterocyclic groups (e.g. 3-pyridino, 2-furyl), alkoxy groups (e.g. methoxy, 2-methoxyethoxy), ? lyloxy groups (e.g. 2,←-di-tert-amylphenoxy, 2-chlorophenoxy, cucyanophenoxy), alkenyloxy groups (e.g. λ-propenyloxy), amino groups (e.g. buteramino, dimeteramino, anilino, N -metheranilino), acyl groups (e.g. acetyl, be/zoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, penzoyloxy, phthoxysulfonyl, toluene/nulfonyloxy), amide groups (e.g. acetelamino, ethylcarbamoyl) , dimetercarbamoyl, methanesulfonamide, butylsulfamoyl), null-7 amide groups (e.g. dizolobylnulfamoylamino), imide groups (e.g. succi/imide, hydantoinyl groups), ureido groups, aliphatic or aromatic Examples include a group sulfonyl group, an aliphatic or aromatic theo group, a hydroxy group, a cyano group, a carboxy group, and a halogen atom.

Specific examples of the groups listed above are the same as those exemplified for R■. Also, R2 can be present on the nitrogen chain in the heterocycle, and in this case, fL
Examples of 2 include an aliphatic group, an aromatic group, a multicyclic group, an acyl group, a nulfonyl group, an aliphatic or aromatic oxy group, and an amino group. In this case, when the ortho or para position of the nitrogen atom in the heterocycle is a hydroxyl group, the tautomerism of the hydroxyl group expressed as a cyclic keto/keto ring is also included in the present invention.

1/4'- Furthermore, when X represents a coupling-off group (hereinafter referred to as a leaving group), examples include coupling active carbon via oxygen, nitrogen, sulfur or carbon atom gold, and an aliphatic group. , aromatic group, group bonding with heterocyclic group, aliphatic group,
Aromatic or heterocyclic sulfonyl group, aliphatic/aromatic or "a. 7Fj: bonds to a ring carbonyl group"
) fr group, halogen atom, aromatic azo group, etc., the aliphatic, aromatic or heterocyclic group contained in these leaving groups may be substituted with a substituent permissible for R1, and these When there are two or more substituents, they may be the same or different, and these substituents may further have an acceptable substituent for R1.

Specific examples of coupling-off groups include halogen/atom (e.g. fluorine, chlorine, bromine), alco? (e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonyl ethoxy), aryloxy group (e.g., methoxyphenoxy, ≠-methoxyphenoxy, l-carboxyphenoxy) , acyloxy groups (e.g. acetoxy,
tetradecanoyloxy, penzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methane-nulfonyloxy, toluene/sulfonyloxy), acylamino groups (e.g. dichloroacetelano, heptafluorobuterylamino), aliphatic or Aromatic nulfonamide groups (e.g. meta/nulfo/amino, p-toluene/nulfonylamino), alkoxycarbonyloxy groups (e.g. ethoxyluponyloxy, be/zyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g. 7-enoxycarbonyloxy) ), aliphatic/aromatic or heterocyclic theo groups (e.g. eteltheo, phenyltheo, tetrazolylthio), carbamoylamino groups (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino), 3- or 2-membered arsenic hetero groups Tamaki (
For example, imidazolyl, virazolyl, triazolyl, tetrazolyl, /, . 2-dihydro-2-oxo/-pyridyl), imide groups (e.g. succi/imide, hydantoynyl), aromatic azo groups (e.g. phenylazo), etc.
! ) These groups may be further substituted with a group allowed as a substituent for R1.

There are also bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or keto/group as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

Y is a divalent linking group containing at least an amide bond or an ester bond, and specifically, e. Examples include S(J■−N−. Here, ′kL3
Muyo and R4 represent a hydrogen atom, an aliphatic group, an aromatic group or a multicyclic group.

In the same general formulas [I] to EI Jll), it is preferable that there is no substituent on the nitrogen atom in the heterocycle. General formula (
I] to C Il[ J, preferably Y is -N I C U- (bonded to the pyridi/ring through the nitrogen atom).

In general formulas LI) to (III), preferred X is a hydrogen atom, a halog/atom, an aliphatic or aromatic oxy group,
Aliphatic or aromatic thio group, aliphatic or aromatic oxy/carbonyloxy group, aliphatic or aromatic acyloxy group, aliphatic or -7g-? It is an aromatic sulfonyloxy group.

When a ring is formed between 几■, 几■ and R2, the preferable number of ring members is 3 to 7 members, and! and a two-membered ring are more preferred, and the ring may be a ring containing gold at an N or O atom outside a carbocyclic ring, and aromatic 'k! It is not necessary to have it.

2 is the acid dissociation constant PKa! to 7.2 dissociative groups, which may be substituted with hydroxyl, aliphatic, aromatic or heterocyclic groups, at least/preferably (7 or 2 electron-absorbing groups, e.g. acyl group, cyano group)
Indicates an active methyl/group with .

Zf'i. Preferably, it is a hydroxyl group or an aromatic sulfonado group, particularly preferably a hydroxyl group.

In order to stably introduce Cazolar into color photographic materials, so-called balanute groups having ♂ or more carbon atoms are added to R1 and R2.
, XX, Z. It is good to have at least seven of them.

The couplers of the present invention include at least 7 of R1, about 2, and
is the one-pronged formula [R1, ? of I,1~(Ill)? A heterocyclic group (formula CII) from which 2 or X is removed (pyridyl group in (Ill)) may also be included as a substituent. That is, the coupler of the present invention includes oligomers and polymers in which at least seven of R1, R2, and X include a heterocyclic group represented by the following formula. Here, among the couplers of the present invention, R■, 几2 or X of the general formula 1)
A compound containing seven heterocyclic groups from which is removed is called a trimer containing two dimers. Examples of the polymer include vinyl polymers containing at least seven of the above three types of heterocyclic groups in 1-t2 or X, and the number average degree of polymerization of the polymer is, for example, about 70. ~/
,0θO.

Specific examples of the cyan coupler of the present invention are shown below, but the present invention is not limited thereto.

I-(1) 1-(2) α −+2　／− 1 + 2 + 2 - I-(3) 1-(4) I-(5) 1-(9) ■100 ■One α◇ F α C5 ■, 1 (re − +2J 1 One child - I-(6) I-(7) I-(8) ■-(6) I-(13 α α one. 2. Ko 6 - ? 5H1■(t 冫 ■-(1 yen ■-(4) I-(17) Ill) 1-H) ■-(d) ? 5H1■ (Re 1 + 2 7 α -Cotter ■-(f) I-QI ■- (Foundation) ■-(7) α α -2 ♂One -3　0　- C8H17(t) ■-(a) ■－(self) SC}l2CH20H ■-(d) ■－(self) ■-(c) α ■-(7) − 3 3 − ■-(E) I-Jυ C5H11(t) 0 ■−■ −3 ≠ − ■－(self) 11-(4) n-(5) 1 - (6) -3 7- 01-i II-(1) II-(2) ■-(3) II-(7) n-(8) I1-(9) -3　r　ー ? 5H1 ■ (Re n-an ■One αD ■-(6) ■-(to) II-(17) ■－(self) -32- Card / One ■－(self) ■−α→ ■100 ■-(a) n-an α 1φ　O　1 Ichig 2 ? 5H■1(t) n-@ ■10 ■-(c) ■-(4) ■Ilsan 4t 3- n-H ■-(E) ■One (a) 11I-(1) 111-(2) 111-(3) α -+X- ? 5H■1(t) 1-(4) F III-(5) Ill - (6) Ichigu 7- [1-(11 m-a], l α ■-(6) Ce -4t? I[[-(7) C.I.V. 1I[-(8) III-(9) -Gza- ■One alpha east III-Cl 110G -! O one ■－(self) ? 5H■1(t) 111-(I Ka ■One (g) 1-@ α ■-(E) ■-(c) −! 3- ■-00 ■Ichikan α ■−Qυ ■－(self) Ct ■-(d) α ■-(E) C8H17 (re -j4'- ■-(E) α ■-(4) ■One (goods) ■Ichikan III-C33 The synthesis method of the present invention will be explained below.

The coupler of the present invention is For example, the following to mu You can meet them by following the route shown.

-37-0H C5Hll (R-3♂-Y' represents an amino group or carboxyl group, R2,
n, A, B, CXDX E has the same meaning as above.
represents a hydrogen atom or a halogen atom.

When Y' is an amino group, it is reacted with an acid chloride, and when Y' is a carboxyl group, a cybond is formed with amines by a known dehydration condensation method, and a diffusion-resistant group (Balla
st) Introduce l. Leaving group (X)'f if necessary
It may be introduced before or preferably after the introduction of the r-diffusion-resistant group.

The starting material 3-hydroxypyridine derivative is Pylestai/Handbook del Olga'/:r
-7 Chemie (Bet lsteins Hand
buchder Organischen Chem
ie) or the literature cited therein.

The specific laws and regulations of the coupler of the present invention will be described below.

Example 1 (Illustrative compound (1-/)) Co-amino-3-hydroxyvirazine (/) under a nitrogen stream
/． /lil,0. /OmOI) of acetonitrile (/
θOwe) solution in the presence of pyridine (/Ornl)-32, j-(J,4(1-di-t-amylphenoxy)
Monolactyl chloride (JJ.It, 0,
/Omol) and heated under reflux for 3 hours. After cooling, dilute hydrochloric acid (.20Otnl) was added and extracted three times with ethyl acetate. The organic layer is washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and recrystallized from acetonitrile to give the exemplified compound (
I-/) (jg.3t 13 liters) was obtained.

Synthesis Example 2 (Exemplary Compound (1--2)) Guaminocochlor! -Hydroxypyridine ( /A .0?,
0. //mol) and J-(.2,≠-di-t-amylphenoxy)monohexanoyl chloride (gO.jr,
o. //mol)i reaction The reaction was carried out under the same conditions as in Example/ to obtain an oil-based compound (i--N(3'?.rr, I1'4t modification)).

Synthesis Example 3 (Illustrative Compound (I-/l) Guamino-3-hydroxypyridazi7 (//.i
yX o. iomol) and 2-(hexadeca/nulfonylamino)penzoyl chloride (lIII, -AO- 32, O.zOmol) were reacted under the same conditions as in Synthesis Example/, to obtain the exemplified compound (I-/o)Cy-a. θ2, t/
%) of oil fall products were obtained.

Synthesis Example 4 (Exemplary Compound (II-/)) 3-Aminoguhydroxybily9y (//.OfXO.
/OmO1) f. 2-amino-3-hydroxypyrazi/
The exemplified compound (
]]-/) (30.3?7l%) was obtained.

Synthesis Example 5 (Exemplary coupler (n--!)) Under the same reaction conditions as in the synthesis example,! -Aminocochloride-hydroxypyridi7(/41.ψi10.lOmOl) and j-
(.2,!-di-t-amylphenoxy)hexanoyl chloride (3t.ty,o./Omo I) was reacted to form the exemplary coupler (II--2) (-?za.9f
T, the. 2%) of an oil was obtained.

Synthesis Example 6 (Exemplary coupler (1-/)) Under nitrogen stream, 3
-aminocohydroxypyridine (//.0?,0.
/Omo1) in acetonitrile (/θo,1) in the presence of viridiy (/Otttl). 2-(.2.
4-di-t-amylphenoxy) lactate chloride (3
3. ♂f, 0. /Omol)i was added dropwise, and the mixture was heated under reflux for 1 hour. After cooling, normal hydrochloric acid (200 ml) was added, and the mixture was extracted three times with ethyl acetate. The organic layer is washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and recrystallized from acetonitrile (/JOtrtl) to give the exemplary coupler ([1-/) (33.01
&'0%) was obtained.

Coupling Example 7 (Exemplary coupler (■-)) Coupling Under the same reaction conditions as in Coupling Example 2, 3-amino! -Chlorocohydride mouth xybilidi/(/←.lIf,0./Omol
) and J-(J,44-di-t-amylphenoxy)hex/noyl chloride (36.6?, 0./Omol)
f react, example coupler (III--2) (g0.32
, g3%) was obtained.

Other couplers can also be combined under similar conditions.

Most of the couplers of the present invention are oil-soluble, and it is generally preferable to dissolve them in a high boiling point solvent (if necessary, use a low boiling point solvent together), emulsify and disperse them in an aqueous gelatin solution, and add them to a silver halide emulsion. . In addition, in the case where it is soluble in an alkaline aqueous solution, it can be dissolved in an alkaline aqueous solution together with a developing agent and other additives and used for image formation as so-called external mold development.

On the other hand, using a developing agent and an alkali together (with addition of an organic solvent if necessary), oxidation coupling/gluing with an oxidizing agent (e.g., persulfate, silver nitrate, nitrous acid or its salt), or using the general formula ( When X in 1) to (■) is a hydrogen atom, the dye can be synthesized by condensation using p-nitrosoanrine and alkali or acetic anhydride, and this can be used as a cyan dye for various purposes (e.g. filters). ,
It can be used as a dye for paints, paints, images and information recording or printing).

When added to a silver halide emulsion, a hydroquino/derivative, an ultraviolet absorber, a known anti-fading agent, etc. may be used in combination, if necessary, to adjust and improve color development or storage stability.

4 3 - Same as above, the high boiling point solvent has a melting point of less than ioo0c (
Any substance that can dissolve the coupler with a boiling point of /gO0C or more (preferably igo0c or more) can be used, examples of which include phosphoric acid esters (for example, tricresyl phosphate, trioctyl phosphate, tricyclohexyl phosphate),
Organic acid-C esters (e.g. dibutyl phthalate, diocterphthalate, dicyclohexyl phthalate, totesylbe/soate, bis(.2-ethylhexyl) sebacate), ethers, (including eboxy), amides and amines. They may also be cyclic. Furthermore, a high boiling point solvent used in the oil-in-water dispersion method described below can also be used.

Next, the silver halide color photographic material of the present invention will be explained.

In the silver halide color photographic material of the present invention, at least/layer of the light-sensitive material has the general formula CII, (n)'E
or (III).

These couplers can be added to -A3- to the silver halide emulsion N sensitive to the visible or infrared region or to its adjacent layer, but in order to achieve the object of the present invention, it is preferable to add the photosensitive silver halide emulsion N to the layer adjacent thereto. This is an emulsion layer.

The photosensitive material of the present invention can be applied to any processing process that uses a color developer.

For example, it can be applied to the processing of color paper, color reversal paper, color positive film, color negative film, color reversal film, color direct positive photosensitive material, and the like. In particular, application to color paper and color reversal paper is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride.

The halogen composition of the emulsion may be different or equal among the grains, but if an emulsion having an equal halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [Single layer 6G or multiple layers] A particle with a so-called stacked structure in which the halogen composition is different, or a structure having a non-layered part with a different halogen composition inside or on the particle surface (if it is on the particle surface, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used.

In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, mixed crystals are formed due to compositional differences, resulting in unclear boundaries. Alternatively, the structure may be actively made to have continuous structural changes.

The halogen composition differs depending on the type of photosensitive material to which it is applied. For example, printing materials such as color paper are mainly based on silver chlorobromide emulsions, while photographic materials such as color negatives are mainly based on silver iodobromide emulsions. used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized layers can be located inside the particle, or on the edge, corner, or surface of the particle surface, but one preferred example is a layer that has grown epitaxially on a part of the corner of the particle. .

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle size is expressed as the particle diameter, and in the case of cubic particles, the ridge length is used as the particle size, and the particle size is expressed as an average based on the projected area.

In the case of tabular grains, it is also expressed in terms of spheres. ) is preferably 2 μm or less and 0.1 μm or more, particularly preferably 1.
It is 5 μm or less and 0.15 μm or more.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r ) crystals or those in which these coexist, or those with irregular crystal shapes such as spherical shapes, or composites of these crystal shapes. good. Also, tabular grains may be used.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No. 17643
(December 1978), pp. 22-23, 'I. Emulsion preparation
dtypes)”, and the same No. 18716 (1
(November 979), 648 pages, "Physics and Chemistry of Photography" by P. Glafki, published by Beaumontel (P.
des , Chemie et Physique P
photograhique, Paul Montel
, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi)
n, Photographic Emulsion Ch
emistry (Focal Press.1966
)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V. L. Zelikman et al.
tal. , Making and Coatin
gPhotographic Emulsion, F
ocal Press 1964).

70 U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, No. 434,226, No. 4,414,310, No. 4,
433,048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may consist of different halide groups, or it may have a layered structure, or silver halides of different compositions may be bonded together by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No.
17643 and the same No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD 17643 RD 18
7161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers Page 649 Right column 4 Brightening agents Page 24 5 Anti-fogging Agent Pages 24-25 Page 649 Right column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column~
Ilter dye, page 650, left column, ultraviolet absorber 7, stain inhibitor, page 25, right column, page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
A compound that can be immobilized can be produced by reacting with formaldehyde as described in No. 35,503, and specific examples thereof are given in the aforementioned Research Disclosure (RD) No. 35,503. 1 7
6 4 3, ■10-G.

As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
428,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476,
760, U.S. Patent No. 3,973,968, U.S. Patent No. 4,
Preferred are those described in European Patent No. 314,023, European Patent No. 4,511,649, European Patent No. 249,473A, and the like.

As magenta couplers, 5-pyrazolone and virazoloazole compounds are preferred, and US Pat.
No. 0,619, European Patent No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, European Patent No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1983
0-4 3 6 5 9, 61-72238,
No. 60-35730, No. 55-118034, No. 6
Particularly preferred are those described in US Pat. No. 0-185951, US Pat. No. 4,500,630, US Pat. No. 4,735'40,654, US Pat. .

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4, 296, 200, No. 2, 3
No. 69,929, No. 2,801,171, No. 2,
No. 772,162, No. 2,895,826, No. 3
, No. 772, 002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, European Patent No. 249,453A, US Patent No. 3,446,622, European Patent No. 4,333,999
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690,8
No. 89, No. 4, 254, 212, No. 4,
Preferably, those described in No. 296,199, JP-A-6142658, etc.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure No. 17643
Section 1G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat.
．． 146,368 is preferred. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774.181, and developing agents as described in U.S. Pat. No. 4,777.1'20. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with the dye to form a dye.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576,910, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-1. ．． No. 54234, No. 60-18424
No. 8, No. 6 3-3 7346, No. 6 3-3 7
350, U.S. Pat. No. 4,248,962, U.S. Patent No. 4,
Those described in No. 782,012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , 4.31.0.618, etc., JP-A-60-185
D described in No. 950, JP-A-6224252, etc.
IR redox compound releasing power puller, DIR coupler releasing power puller DIR coupler releasing redox compound or DIR redox releasing redox compound, releasing a dye that recolors after separation as described in European Patent Nos. 173,302A and 313,308A. Cabra, R. D. No.
l1449, 24241, JP-A-61-201247
No. 4, U.S. Pat.
553,477, a coupler that releases a leuco dye as described in JP-A No. 63-75747, a coupler that releases a fluorescent dye as described in U.S. Pat. No. 4,774,181, etc. Can be mentioned.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

77 Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and others. In addition, the process and effects of latex dispersion as one of the polymer dispersion methods, and specific examples of latex for impregnation are as follows:
U.S. Patent No. 4,199,363, West German Patent Application (OLS) No. 2. 541, 274 and 2,541,230, etc., and PCT International Publication No. W○8 regarding dispersion methods using organic solvent soluble polymers.
It is described in the specification of 8/0 07 2 3.

Examples of organic solvents used in the above-mentioned oil-in-water dispersion method include phthalic acid alkyl esters (dibutyl phthalate,
dioctyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters ( (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or with a boiling point of about 30°C -150°C organic solvents such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0.001 to 1 mole for yellow couplers. Ol to 0.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The color photosensitive material of the present invention includes JP-A No. 63-12577.
1,2-penzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chlorobenzoate, described in No. 47, No. 62-272248, and JP-A-1-80941. It is preferable to add various preservatives or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)penzimidazole.

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. For details on the support and coating method, see Research Disclosure Volume 176 Item 1764
3 Section XV (p.27) Section X■ (p.28) (197
(December 1988 issue).

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Furthermore, metal complexes such as (bissalicylaldoximato)nickel complexes and (bis-N,N-dialkyldithiocarbamato)nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are covered by U.S. Patent No. 2,360,2
No. 90, No. 2,418,613, No. 2,700,
No. 453, No. 2,701,197, No. 2,728
, No. 2,732,300, No. 2,735,765, No. 3,982,944, No. 4,430,425, British Patent No. 1,363,92
No. 1, U.S. Patent No. 2,710,801, U.S. Patent No. 2.81
6,028, etc., and 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3,432,30.
No. 0, No. 3,573,050, No. 3,574,6
No. 27, No. 3, 698, 909, No. 3,
No. 764,337, JP-A-52-152225, etc., and spiroindanes are disclosed in U.S. Patent No. 4,360,58.
No. 9, p-alkoxyphenols are disclosed in U.S. Patent No. 2,
No. 735,765, British Patent No. 2,066,975;
Hindered phenols are disclosed in U.S. Pat.
No. 0,455, JP-A No. 5 2-7 2 2 2 4,
U.S. Patent No. 4,228,235, Japanese Patent Publication No. 52-6623
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Nos. 3 and 45, respectively.
No. 7,079, No. 4,332,886, Special Publication No. 1982
-21144, etc., and hindered amines are disclosed in U.S. Patent Nos. 3,336,135 and 4,268,5.
93, British Patent No. 1,326,889, British Patent No. 1,3
No. 54,31382, No. 1,410,846, Special Publication No. 5 1-142
No. 0, JP-A No. 58-114036, JP-A No. 59-5 3
8 4 6, U.S. Pat. No. 59-78344, etc., and metal complexes are disclosed in U.S. Pat.
No. 1,155, British Patent No. 2,027,731 (A)
They are listed in each number. These compounds are
Usually 5 to 1 for each corresponding color coupler
The objective can be achieved by co-emulsifying 0.00% by weight with a coupler and adding it to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, penzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. Nos. 3,705,805 and 3,707,395), (as described in US Pat. No. 4,045,229), butadiene compounds (such as those described in US Pat. No. 4,045,229), or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, penzotriazole compounds substituted with the aforementioned aryl group are preferred.

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

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N,-diethylaniline, 3 -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or I)-1 luenesulfonates, etc. can be mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains pH buffering agents such as alkali metal carbonates, boric acid 85 salts or phosphates, development inhibitors such as bromide salts, iodide salts, penzimidazoles, penzothiazoles or mercapto compounds. It also generally contains an antifoggant or the like. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazites,
Triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo[2,2,
2] Various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competing couplers sodium boron. fogging agents such as hydride, auxiliary developing agents such as 1-phenyl-3-virazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids; for example,
Ethylenediaminetetraacetic acid, nitri86rotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l
-Hydoxyethylidene-1. 1 diphosphonic acid, nitrilo-N, N, N-}rimethylenephosphonic acid,
Representative examples include ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer may contain known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol, alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3 liters per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenishing solution,
It can also be less than mf. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Further, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (I).
Compounds of polyvalent metals such as [I), chromium (■), and copper (n), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (I[) or cobalt (I[[)];
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(.III) complexes and persulfates, including ethylenediaminetetraacetic acid iron(III) complexes, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(II[) complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I[[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

Bleach solutions, bleach-fix solutions, and their pre-baths must contain 89% A bleach accelerator can be used if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290,812, JP-A No. 53-95630, Research Disclosure No. No. 17,129 (19
Compounds having a mercapto group or disulfide bond as described in Jpn. Pat.
Thiourea derivatives described in No. 561; JP-A-5-8-1
6 235; West German Patent No. 2,748
, 430; polyamine compounds described in Japanese Patent Publication No. 45-88-36; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West Patent No. 1,290,812, JP-A-5-3-
The compounds described in No. 9 5 6 30 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalof the Society of Mo
tion Picture and Televisi
on Engineers Vol. 64, p. 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, JP-A-5 7=8 5 4
Inchiazolone compounds and cyabendazole compounds described in No. 2, chlorine-based disinfectants such as chlorinated sodium incyanurate, and other penzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J (1986), Sankyo Publishing, Hygiene ``Microbial sterilization, sterilization, and anti-mold technology J (1982) edited by Japan Society of Industrial Engineers, Japan Society of Antibacterial and Anti-Mold Agents ``Encyclopedia of antibacterial and anti-mildew agents J''
(1986) may also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 5-7-8-5-4-3 and 5-8-
1 4 834, 6 0-2 2 0 3 4 5
All known methods described in this issue can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing 93. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3.34
Indoaniline compounds described in No. 2,597, No. 3,
No. 342,599, Research Disclosure 14
, 850 and 15,159, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and JP-A-53-135628. Examples include urethane compounds.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Virazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-643'39 and JP-A No. 57-144.
No. 547, and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Furthermore, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,226,770 or U.S. Patent No. 3,67-4,499 may be carried out. good.

The present invention will be further explained below with reference to Examples.

Example 1 Coupler of the present invention (1-/). 2. 09 with ethyl acetate 20@l and ethanol/! d, and added sodium carbonate 32 dissolved in 30 ml of water. While stirring, add Gu(ethyl, methanesulfonamide etheramino) 10-toluidi/monohydrate sesquisulfate 2.4
After adding Lff, ammonium persulfate 2.7tf water/
It was dissolved in 6〃d and added dropwise.

After stirring at room temperature for 30 minutes, water/Oθwtlf was added to separate the layers. The ethyl acetate layer was washed three times with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure at room temperature. A small amount of salmon was immediately dissolved in chloroform and passed through a silica gel column to obtain a cyan fraction.

When the solvent was distilled off under reduced pressure at room temperature, a dark blue powdery dye was obtained.

Couplers (I-.2), (I-J), in the same way as above
(II-/), (l[l-/), (III-2
) and the following comparative couplers (C-/), (C-,!) were used to combine the dyes.

Table 7 shows the results of measuring the solution absorption spectra of the dyes. Also coupler (1-/) and comparative cazoler (C-/)
The spectrum of is shown in Figure 1.

As can be seen from Figure 1 and Table 7, the absorption of the dye obtained from the coupler of the present invention is very sharp and has a vivid hue, and the molar extinction coefficient (ε) is also high. Recognize.

Comparative coupler (C-/) Comparative coupler (C--i') Example 2 Coupler of the invention (1-/)/Or, dibutyl 7-thalerate ioy and ethyl acetate 20 rdf j 00C
The solution obtained by heating was emulsified in a gelatin solution 1j'Of containing /meddecylbenze/sodium sulfonate water bath solution lrd'ii.

Next, this emulsified dispersion was mixed with red-sensitive silver chlorobromide emulsion -22-(BrjO%)/*Jl (containing 7f in Ag), sodium dodecylbenzenesulfonate was added as a coating aid, and both sides were laminated with polyethylene. It was coated on a coated paper support. The amount of coupler applied was set to φoomg7m. On top of this layer is a gelatin protective layer (gelatin:, y/t
/m )f was applied, and this was designated as sample A.

In place of the above coupler (1-/), a film was prepared by the same procedure using the same molar amount of turnip 2-(Table 2)'fr: of the present invention. These were designated as samples B and -U in this order. or,
As comparative examples, comparative cazolers (C-/), (C-2
), (C-3), (C-da) and (C-t)2 were used to prepare sample V-Z.

Each sample was exposed to light using a continuous sensitometric wedge and then subjected to the following development treatment.

Color development process (33°C) / Color development ・・・・・・3 minutes 30 seconds 2 Bleach fixing ・・・・・・7 minutes 30 seconds 3 Washing with water
...Group 2 minutes 30 seconds The treatment steps used in each step are as follows.

1/θO 1 color developer benzyl alcohol diethyl/glycol ethylene diamine acetic acid sodium sulfite anhydrous potassium carbonate hydroxylamine/sulfate potassium bromide l-amino-N-ethyl-N-(β-methanesulfonamitoethyl)-m-toluidine sesqui Add sulfuric acid monohydrate water /β (pH Comparative coupler (C-J) / θ /!.θ- ♂ .Otrtl ! .θ 1 2 .0? 30 f 3 .θ ? 0.tf 3.0? .2) (C-g) (C-z)? White fixer Ethylene diamine acetate/ferric guacetate Sodium sulfite Sodium thiosulfate (70%) φ. Ot l Q i s. All the samples coated with the coupler of the present invention after the /l treatment with the addition of oy /30yte water exhibited a bright cyan to blue hue.

Next, I was able to comment on the test O robustness after treatment.

That is, Table 2 shows the residual rate of the dye ek degree when the sample was left in the dark at /OO0C for /θ days and when it was exposed to light using a xenon fade meter (/00,000 lux) for 7 weeks.

/03- Example 3 did. The coating liquid was prepared from steel as follows.

First layer coating solution preparation Yellow coupler (1!xY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (C
pd-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 c of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing c. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.
A 3:7 mixture of 88 yuan and 0.70p (silver molar ratio). The coefficient of variation of particle size distribution is 0.08 and 0.08.
10. Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below per 1 mol of silver for the large emulsion. Add 10-' moles of OX, and for small size emulsions, 2.5X each
A sample was prepared in which sulfur sensitization was performed after adding IO-' moles.

The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved, and a first coating liquid was prepared so as to form the composition shown below. was prepared.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first N coating solution. As the gelatin hardening agent for each layer, 1-oxy-3.5-dichloro-s-}riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer SO3θ SO3H-N(C2115)3 (CH2)4 (CLL S03θ SO3NII(CJs)3 (2.O Green-sensitive emulsion layer 105 Red-sensitive emulsion layer 106 (2.5X10-' mole each for small-size emulsions) (4.OX10-' mole per mole of silver halide for large-size emulsions, small-size emulsion) 5.6 for
X10-' mol) and (per mole of silver halide, 0.9X10-' mol for large size emulsions and 1 for small size emulsions)
．． IX10-' mol) To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-' mol per mol of silver halide.

(per mole of halogenated 81, ?.OX10-' mol for large-sized emulsions, and 1.OX10-' mol for small-sized emulsions) Also, blue-sensitive emulsion layer, green-sensitive emulsion layer, For the red-sensitive emulsion layer, l-(5-methylureidophenyl)5-mercaptotetrazole was added at a concentration of B.
5 X 10"' moles, 7.7 X 10-' moles, 2.
5×10-” moles were added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1.3.3a,7-tetrazaindene was added per mole of silver halide, respectively, to IXIO-
'mol and 2X10-'mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coated amount in terms of silver.

Support Polyethylene lagonate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a blue dye (ulmarine blue)] First N (blue sensitive layer) Said silver chlorobromide emulsion 0.30 gelatin 1. 86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.3
Five-color image stabilizer (Cpd-7)'
0.06 Second layer (color mixing prevention N) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6 solvent (Solv-4) 0
．． 08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size o.55Ilm
and 0.39ttmO 10
9 (Ag molar ratio). The coefficient of variation of particle size distribution is 0.10
and 0.08, each emulsion contains AgBrO. 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer ((:pd-2) 0.03 Color image stabilizer (Cpd- 3) 0.1
Five-color image stabilizer (Cpd-4) 0
．． 02 color image stabilizer (Cpd-9)
0. 02 solvent (Solν-2)
0.40 Fourth layer (UV absorption N) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.0
5 Solvent (Solv-5) 0
．． 24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 14 mixtures of one with an average grain size of 0.58 and one with an average grain size of 0.45 ImO (Ag molar ratio). The coefficient of variation of the grain size distribution is 0 .09 and 0.11,
Each emulsion contained 8 gBr O. 6 mol% was locally contained on a part of the grain surface)' 0.23 Gelatin 1.34 Cyan coupler (ExC) ' 0.32 Color image stabilizer (Cpd-6) 0. 1
7-color image stabilizer (Cpd-7)'
0.40 color image stabilizer (Cpd-8>'
0.04 solvent (Solv-6)
0. 15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.02
Solvent (Solv-5) 0.
08 Seventh layer (protective layer) Gelatin l. 33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
>0. 17 Liquid paraffin ゛ 0.03 (ExY) 1:1 mixture with yellow coupler (molar ratio) 113 (ExC) Cyan coupler R=C. 2:4:4 mixture by weight of HS, C4H9 and 0H (Cpd-1) Color image stabilizer ([!xM) 1:1 mixture (molar ratio) of magenta coupler 114 (Cpd-2) Color image stabilizer Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor 0H (Cpd-6) 2:4:4 mixture of color image stabilizers (weight ratio) (Cpd -7) Color image stabilizer? Cll■-CI! )-CONIIC411q(L) Average molecular weight 60,000 (Cpd-8) Color image stabilizer: I:/(Mo1v ratio) total average 117 (So Iν 1) Solv-2) Solv-2: ■ Mixture (volume ratio) (Solv-4) Solvent (Cpd-9) Color image stabilizer (UV-1) Ultraviolet absorber 118 (Solv-5) Solvent COOCsH+y (CHz)s J COOCsH+, (Solv-6) Solvent sample IO+2~/O♂ Same as sample /0/ except that the cyan coupler in the j-th layer of sample /O/ (comparison) was replaced with the cazolers of the present invention listed in Table 1 of Example 2, respectively. A sample was prepared.

After exposing the above-mentioned photosensitive material through the Kusaku Kusahi, it was processed in the following steps.

Color development 33°C Bleach constant N 30-3t0C stable■ 30-37°C stable■ 30-37°C stable■
30-37°C Stable ■ 30-37°C Drying 70-rj 0c (Stable ■ → ■ (Qp Tank countercurrent system and each treatment liquid combination or the following sequence.

Color developer water etre/diami/tetraacetic acid 4'j seconds 3 seconds. 20 seconds 20 seconds. It took 20 seconds, 30 seconds, and 20 seconds. ) ♂θθml ko . θ 2 triethanolamine/sodium chloride potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-l-aminoanili/sulfate N,N-dietherhydroxylamine! , 6-dihydroxybe/zene/,. 2,4Z-}Linulphonic acid fluorescent brightener (lI-,V'-diamine Add water to pH (,+t °C) Bleach-fix solution water Ammonium theosulfate (70m) Sodium sulfite ♂ .oy / .g V +2 3 ? !.Of ge. Sodium 3t glacial acetic acid
Add rr water
/000ml9H(.2j'C)
J,3 Stable liquid formalin (37%) 0. /t formalin-sulfite adduct 0.723-chlorocomethyl←-intiazoli/-3-one 0.02i comethyl-guinthiazolin-3-1o7 o. N,N-bis(carboxymethyl)hydrazine instead of xylamino7. Similar results were obtained using O Y/l.

[Brief explanation of drawings]

Figure 7 shows the coupler (I-/) and the comparative coupler (C-/).
This is the absorption spectrum of the dye obtained from ).

Claims (3)

[Claims] (1) A cyan dye-forming coupler represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R_1 represents an aliphatic group, aromatic group, or heterocyclic group; R_2 represents a group or atom that can be substituted for a heterocycle; X is hydrogen Represents an atom or a coupling-off group; Y
represents a divalent linking group containing at least one amide bond and/or ester bond; Z represents a dissociative group; n
1 represents 0 or 1; if n_1 is 1, R_1 and R
_2 may form a ring; at least one of R_1, R_2 and X is R_1, R_2 in the general formula [I]
It may also contain one or more heterocyclic residues from which 2 or X has been removed as a substituent. A, B, C, D, and E each represent a carbon atom or a nitrogen atom, and the other two of A to E are nitrogen atoms. ) (2) A cyan dye-forming coupler represented by the following general formula [II] or [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (In the formula, R_1 represents an aliphatic group, aromatic group, or heterocyclic group; R_2 is a pyridine ring represents a group or atom that can be substituted with; X represents a hydrogen atom or a coupling-off group;
Y represents a divalent linking group containing at least one amide bond and/or ester bond; Z represents a dissociative group;
n_2 represents 0, 1 or 2; if n_2 is 2,
The two R_2 may be the same group or atom or different groups or atoms, and the two R_2 may form a ring; when n_2 is 1 or more, R_1 and B_2 form a ring. may be formed; at least one of R_1, R_2 and X is R_1 in general formula [II] or [III];
R_2 or X may contain one or more pyridyl residues as substituents; n_2 is 2, one R_2 is a hydroxyl group, and the hydroxyl group is in the ortho position to the nitrogen atom of the pyridyl ring. Or when bonded to the para position, another R_2 can be bonded to the nitrogen atom of the pyridyl ring, and in this case, the hydroxyl group bonded to the ortho or para position may become a ketone due to tautomerism. can. ) (3) Formula [I] according to claim (1) or (2), [
A silver halide photographic material containing at least one cyan dye-forming coupler represented by [II] or [III].