CN1030010C - Silver halide color photographic materials - Google Patents

Abstract

A silver halide color photographic material which comprises a support having at least one silver halide color photographic emulsion layer coated thereon and containing at least one compound represented by the general formula (I) and at least one compound represented by the general formula (II) in at least one of hydrophilic layers provided on the support. The materials give stable color images in long storage, high sharpness, high sensitivity and low fogging property because of using new dyes and couplers.

Description

Silver halide color photographic materials

The present invention relates to silver-halide color photoelement; The silver-halide color photoelement of usefulness specifically relates to take a picture; More specifically say to relate to such class silver-halide color photoelement, they can form (hereinafter being referred to as sharpness) color image of the clear distinctness with long-time storage stability, and have ISO and than the photographic fog of low degree.

Normally in silver halide, add spectral sensitizer and with the silver-halide color photoelement spectral sensitization according to subtractive primary colour.Responsive to blueness.In green sensitive and silver halide emulsion layer, contain the colour coupler that can form weld, magenta dye and cyan dye respectively to red sensitive.Silver-halide color photoelement carries out after the imaging exposure, develops with the colour developing solution that contains the primary aromatic amine color developer, bathes with the certain shadow of bleaching then and handles, and can obtain image.

Yet resulting color image is always unstable to light, heat or moisture content.Especially blue or green dye image, its dark bleaching level is more visual and the magenta dye image is all serious than weld under the effect of heat or moisture content, and this will change color balance.This is a very big problem (for example, this photograph can become light red brown between storage period in the photo album) in actual use.

For addressing the above problem JP-A-56-80045(BrP 2066494; Symbol JP-A representative used herein " uncensored disclosed Japanese patent application "), JP-A-56-104333(BrP 2068943), JP-B-57-37857(US4333999) (symbol used herein " JP-B " representative " uncensored Japanese patent application "), JP-A-58-105229(US4430423) and JP-A-60-24547(US456777) point out, 2 and 5 colour couplers that are substituted with acylamino-at the phenol phenyl ring, as " 2; 5-diamido phenol " colour coupler, be very suitable for as the colour coupler that can form durable colour-fast blue or green dye image.On 5 of phenol, have C ₂Or more the phenols cyan colour coupler of senior alkyl also can form durable non-fading blue or green dye image.

These phenols cyan colour couplers are applicable to the high and good colour phhotograpy image of storge quality of preparation color fastness to heat very much, in addition, the photosensitive material of this class colour coupler of known employing has processing stability and excellent color reprodubility, and this should give the credit to especially, and cyan density remains unchanged in bleaching-photographic fixing processing procedure.

Therefore, above-mentioned phenols colour coupler is the preferred compound that can form the colour coupler of blue or green dyestuff in color sensitive material.

Select the standard conditions of cyan colour coupler to comprise the spectral absorption characteristics of photostability, dyestuff and to the influence of photosensitive property.Desirable cyan colour coupler should satisfy all these character.

On the other hand, another the required critical nature of color sensitive material that is used for photo is an image quality, and image quality is influenced greatly by sharpness.

For improving the sharpness of color image, adopt following two technical measures usually.The first prevents the phenomenon that fogged by the image that halation causes.During passing silver halide emulsion layer or the light of scattering afterwards, on the interface of silver emulsion and matrix or on the photosensitive material surface of silver halide emulsion layer, be reflected, this part reflected light is imported in the silver halide emulsion layer again, thereby cause above-mentioned halation phenomenon, another measure is to prevent the phenomenon that fogged by the image that irradiation causes, this irradiation be since in the silver halide emulsion layer the lip-deep scattered light of silver halide caused.

The silver-halide color photoelement of photograph usefulness normally adopts the above-mentioned method that prevents irradiation.

For preventing irradiation, that silver halide emulsion layer is painted.Usually these want painted emulsion layer to contain hydrophilic colloid, thereby it is painted to carry out to comprise water-soluble dye in these emulsion layers usually.Described dyestuff should satisfy following condition.

(1) these dyestuffs must have the appropriate spectral absorption character that adapts with its purposes.

(2) these dyestuffs must be the photochemistry inertia, promptly can not produce chemical action to silver halide emulsion layer, for example can not reduce light sensitivity, weaken latent image and cause photographic fog.

(3) these dyestuffs must fade or dissolve and be removed in the sensitization processing procedure, and can not cause undesirable color on the photosensitive material of handling.

For seeking to satisfy the dyestuff of above-mentioned condition, those skilled in the art study widely, and found following dyestuff, the oxonol dyestuff that promptly contains pyrazolone or barbituric acid nuclear, in BrP 506385,1177429,1311884,1338799,138,537 1,1467214,1433102 and 1553516, JP-A-48-85103(BrP 1373026), JP-A-49-114420(BrP 1433102), JP-A-55-161233 and JPA-59-111640, United States Patent (USP) 3247127, introduce above-mentioned dyestuff is existing in 3469985 and 4078933; United States Patent (USP) 2533472 and 3379533 and BrP 1278621 another kind of oxonol dyestuff is disclosed; BrP 575691,680631,599623,786907,907125 and 1045609, United States Patent (USP) 4255326 and JP-A-59-211043 have introduced azo dyes; JP-A-50-100116, JP-A-54-118247, BrP 2014598 and 750031 has been introduced azomethine dyes; United States Patent (USP) 2865752 has been introduced anthraquinone dye; United States Patent (USP) 2538009,2688541 and 2538008, BrP 584609 and 1210252, JP-A-50-40625, JP-A-51-3623, JP-A-51-10927, JP-A-54-118247, JP-A-48-3286 and JP-A-59-37303 have introduced inferior 2-allyl dyestuff; JP-B-28-3082, JP-B-44-16594 and JP-B-59-28898 have introduced styryl dye; BrP 446583 and 1335422 and JP-B-59-228250 introduced triarylmethane dye; BrP 1075653,1153341,1284730,1475282 and 1542807 has been introduced merocyanine dyes; United States Patent (USP) 2843486 and 3294539 has been introduced cyanine dye.

In these dyestuffs, the oxonol dyestuff that contains two pyrazolone nuclears has been used for color sensitive material, and as the dyestuff that a class is suitable for, they can be faded in containing the solution of sulphite, and what adverse influence photosensitive emulsion is not almost had.

Yet many oxonol dyestuffs that contain two pyrazolone nuclears all have weak point, and promptly they can make silver emulsion or the undesirable sensitization of some zone generation of the silver emulsion of spectral sensitization, make light sensitivity descend, and increase photographic fog.This is likely because spectral sensitizer has wherein come off.

In addition, (the recent required time of this processing is shorter) can left behind some dyestuffs after development treatment.For addressing this problem, the someone proposes to adopt the dyestuff reactive high to sulfite ion.But these dyestuffs are defectiveness also, and promptly they are stable inadequately in wafer, and density can descend the photosensitive effect that can not get wishing after storage a period of time.

In addition, the colour coupler in above-mentioned dyestuff and heat-resisting look jail (as above-mentioned 2,5-diamido phenol colour coupler) is used with and can be reduced light sensitivity and increase photographic fog.This is a very big problem in actual use.JP-A-60-225155 discloses and uses 2 with, 5-diamido phenol colour coupler and the specific prepared photosensitive material of oxonol dyestuff have high anti-dark fadedness, fabulous sharpness, good latent image stability and high whiteness (low photographic fog), but have found that above-mentioned sharpness and the photographic fog aspect and unsatisfactory of being combined in.

The purpose of this invention is to provide a kind of silver-halide color photoelement that contains photothermographic silver halide, this material can provide the stable color image of standing storage, has high definition, ISO and low photographic fog.It realizes that by means of a kind of new type water-solubility dyestuff this dyestuff is treated to fade easily, has storage stability, and to the photographic property of above-mentioned silver halide emulsion layer without any adverse effect.

The objective of the invention is to realize by a kind of like this silver-halide color photoelement, this photosensitive material comprise supporting mass and at least one deck be coated in silver-halide color sensitive emulsion layer on the supporting mass, and in one deck at least invests hydrophilic colloid layer on the supporting mass, contain the compound shown in compound shown at least a following general formula (I) and at least a following general formula (II):

R wherein ₁And R ₂Expression-COOR separately ₅Or-CO

; R ₃And R ₄Represent hydrogen or alkyl separately; R ₅And R ₆Represent hydrogen, alkyl, aryl or R separately ₅And R ₆5 or 6 yuan of rings of common formation; Q ₁And Q ₂Represent aryl (divalent or 3 valencys) separately; X ₁And X ₂Represent divalence keyed jointing group or a chemical bond separately; Y ₁And Y ₂Represent sulfonic acid group or hydroxy-acid group separately; L ₁, L ₂And L ₃Represent methine separately; m ₁And m ₂Represent 1 or 2 separately; N represents 0,1 or 2; P ₁And P ₂Represent 0,1,2,3 or 4 separately; S and S represent 1 or 2 separately;

Y wherein ₃Expression-NHCO-or-CONH-; R ₈Expression aliphatic group, aromatic group, heterocyclic group, replacement or unsubstituted fragrant amine groups; X ₃Expression hydrogen, halogen atom, alkoxy grp or acylamino-group; R ₇Expression alkyl (containing two or more carbon atoms) or acylamino-or expression are with R ₇With X ₃Combine and form nonmetallic atom group required when 5-7 is first to be encircled; The group that Z can remove when representing hydrogen atom or a kind of and oxidized developing agent coupling.

In the present invention, term " alkyl (or moieties) ", " aryl (or aryl moiety) " and " aromatic group " are represented that replace and unsubstituted corresponding group separately.

Below the dyestuff shown in the formula (I) is described in detail.

In formula (I), R ₁And R ₂Expression-COOR separately ₅Or R ₅

-CON-R ₆; R ₃And R ₄Represent hydrogen or alkyl (as methyl, ethyl) separately; R ₅And R ₆Represent hydrogen separately, unsubstituted alkyl is [as methyl, ethyl, isopropyl, butyl), (substituent example has sulfo group (as the sulphur methyl to the alkyl that replaces, sulfoethyl), carboxyl is (as ethyloic, carboxyethyl), hydroxyl is (as hydroxyethyl, 1, the 2-dihydroxypropyl), alkoxy is (as methoxyethyl, ethoxyethyl), halogen atom is [as fluorine, chlorine, bromine is (as the 2-chloroethyl, the 2-bromoethyl, 2,2, the 2-trifluoroethyl)], cyano group (as cyanoethyl), aliphatic series or aromatic sulfonyl (as the methylsulfonyl ethyl), nitro is (as 2-nitro butyl, 2-nitro-2-methyl-propyl), amino unsubstituted or that replace through alkyl (as methyl or ethyl) is (as dimethylaminoethyl, the lignocaine propyl group), aryl is (as benzyl, right-the benzyl chloride base)]; [substituent example has sulfo group (as right-sulfophenyl to the phenyl of phenyl and replacement, adjacent, right-two sulfophenyls), carboxyl is (as right-carboxy phenyl, between-carboxy phenyl), hydroxyl is (as right-hydroxyphenyl, between-hydroxyphenyl), alkoxy is (as right-methoxyphenyl, between-ethoxyl phenenyl), halogen atom is (as right-chlorphenyl, right-bromophenyl, right-fluorophenyl), cyano group is (as right-benzonitrile base, neighbour-benzonitrile base), nitro is (as p-nitrophenyl, the m-nitro base), the amino that does not replace or replace through alkyl (as methyl or ethyl) is (as to dimethylamino phenyl, to the lignocaine phenyl), alkyl is (as p-methylphenyl, between tolyl)].Work as R ₁And R ₂Expression-COOR ₅, and R ₅During expression hydrogen, R ₁And R ₂Be carboxyl, they not only can form free acid, and can salify (as sodium salt, sylvite, ammonium salt, quaternary ammonium salt).

R ₅And R ₆Also can form 5 or 6 yuan of rings, as morpholino, piperidino.Q ₁And Q ₂Represent that separately [substituent example has C for phenyl that the unsubstituted aryl of 2 or 3 valencys (as phenyl, naphthyl), 2 or 3 valencys replace _1-4Alkyl, C _1-4Alkoxy; halogen atom (chlorine; bromine; fluorine); aliphatic series or aromatic amine formoxyl (as the ethylamino formoxyl); aliphatic series or aromatics sulfamoyl (as the ethyl sulfamoyl); cyano group; nitro; alkyl sulphonyl (as mesyl); aryl sulfonyl (as benzenesulfonyl); the amino (as dimethylamino) unsubstituted or hydrocarbon alkyl (as methyl and ethyl) replaces; aliphatic series or aromatics acylamino-(as acetylamino); aliphatic series or aromatics sulfonamido (as the first sulfonamido)].Q ₁And Q ₂Can with other parts at any position bonding.X ₁And X ₂Represent divalence keyed jointing group separately, specifically represent following groups:

, or chemical bond, wherein a R ^' ₇Expression hydrogen, C _1-5Alkyl, or C _1-5[described substituent example has C to the alkyl that (total carbon atom number) replaces _1-3Alkoxy, sulfo group (as sulfoethyl, sulfopropyl), carboxyl (as carboxyethyl), cyano group, hydroxyl (as hydroxyethyl), amino, aliphatic series or aromatics sulfonamido (as the first sulfonamido), aliphatic series or aromatics acylamino-(Carbonamido) (as acetylamino), aliphatic series or aromatic amine formoxyl (as the ethylamino phosphinylidyne), aliphatic series or aromatics sulfamoyl (as the second sulfamoyl) unsubstituted or that replace through alkyl (as methyl and ethyl)].Y ₁And Y ₂Represent sulfonic group or carboxylic acid group separately, they not only can form free acid, but and salify (as sodium salt, sylvite, ammonium salt, quaternary ammonium salt), L ₁, L ₂And L ₃The methine (described substituting group comprises methyl, ethyl and phenyl) of representing methine or replacement separately.m ₁And m ₂Represent 1 or 2 separately; N represents 0,1 or 2; P ₁And P ₂Represent 0,1,2,3 or 4 separately; S ₁And S ₂Represent 1 or 2 separately.

In the compound shown in the formula (I), R ₃And R ₄Preferably hydrogen or methyl separately; R ₅And R ₆Hydrogen preferably separately, C _1-4Alkyl, C _1-6[described substituting group is sulfo group, carboxyl, hydroxyl, C preferably for the alkyl that replaces _1-2Alkoxy, chlorine atom, cyano group, amino, C _1-4Alkyl amino], [described substituting group is sulfo group, carboxyl, C preferably for phenyl or substituted-phenyl _1-4Alkoxy, chlorine atom, cyano group, C _1-4Alkyl, amino, C _1-4Alkyl amino], R ₅And R ₆Preferably can also form one 5 yuan or 6 yuan of rings (as morpholino ring pyrolidine ring, piperidine ring), Q ₁And Q ₂Separately preferably the phenylene of phenylene, replacement [described substituting group is C preferably _1-4Alkyl, C _1-4Alkoxy, halogen atom (as chlorine, bromine, fluorine), C _1-4Dialkyl amido].

As n, m ₁, m ₂, P ₁, P ₂, S ₁And S ₂Respectively do for oneself greater than 1 several the time, the group that is marked separately by them can be identical also can be different.

X ₁And X ₂Preferably separately expression-O-,

Or chemical bond, wherein a R ^' ₇Preferably hydrogen, C _1-5The C of alkyl or replacement _1-5[described substituting group comprises C to alkyl _1-3Alkoxy, cyano group, hydroxyl and C _1-4Alkyl amino].

In addition, in the dyestuff shown in the formula (I), m wherein most preferably ₁=m ₂A little dyestuffs of=1.

Because thereby the present invention is suitable for adopting can be dissolved in the dyestuff that treating fluid is easy to spin off from photosensitive material, so the contained carbon number of alkyl and aryl is preferably fewer.

Be examples for compounds shown in the formula (I) below, but they are not construed as limiting the scope of the invention.

The compound of formula (I) can be synthetic by the whole bag of tricks, for example, in the presence of alkali, make pyrazolone shown in the formula (III) and formula (IV is a), the compound shown in (IV b), (IV c), (the IV d) or (IV e) carries out condensation:

R wherein ₁, R ₃, Q ₁, X ₁, Y ₁, L ₁, L ₂, m ₁, n, P ₁And S ₁As defined above; Z represents hydrogen, nitro, halogen atom (as chlorine, bromine) R ₈Expression hydrogen, alkyl (as methyl, ethyl), phenyl; X represents negative ion (as chloride, bromide, iodide, perchlorate, dimethyl suflfate, ethyl-sulfate, tosilate).Other compound shown in the formula (I) can be by synthetic with above-mentioned similar methods.

The example of used alkali comprises pyridine, piperidines, triethylamine, triethanolamine, sodium acetate and potassium acetate in the above-mentioned condensation reaction.

Carry out the used appearance agent of above-mentioned condensation reaction and comprise the potpourri of alcohol (as methyl alcohol, ethanol, isopropyl alcohol), acid amides (as dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone), nitrile (as acetonitrile), dimethyl sulfoxide, ethylene glycol, ethers (as glycol monoethyl ether, ethylene glycol diethyl ether), water and water and above-mentioned solvent.The ratio of solvent in described potpourri is preferably 1-100 part (volume) (water of each part volume relatively).

Temperature of reaction can be selected to the solvent for use boiling spread at 0 ℃.

Reaction time visual response temperature and deciding is usually in about 30 minutes to 3 days scope.

The consumption of pyrazolone in above-mentioned condensation reaction shown in the formula (III), with respect to every mole of formula (IV a), the compound shown in (IV b), (IV c), (the IV d) or (IV e), be the 0.1-3 mole.

Introduce the synthesis example of compound shown in the formula (I) below.

Synthesis example 1(compound 3)

In 50ml ethanol, add 5.2g3-carbethoxyl group-1-(2-sulphur benzyl) pyrazolin-5-one, and then add 4.2ml triethylamine and the 1.5g MDA diphenylamine (malondialdehyde dianilate) that contracts.This mixture heated was refluxed 3 hours, obtain a kind of uniform solution.Under agitation the 15ml methanol solution that is dissolved with the 1.2g sodium acetate is added in the above-mentioned hot solution.Add the 25ml isopropyl alcohol to above-mentioned solution then, be settled out the mulberry crystallization.This crystallization is leached, use washed with isopropyl alcohol, get 2g compound 3 after the drying.

Fusing point: be higher than 300 ℃

${\lambda }^{H^{2}O}{}_{\mathrm{m\; a\; x}}$ : 551nm ε: 6.73 * 10 ⁴(ε is an extinction index)

Synthesis example 2(compound 8)

Preparation is by 7.4g3-carboxyl-1-(2-sulphur benzyl) potpourri formed of pyrazolin-5-one, 50ml methyl alcohol and 7.5ml triethylamine, with ice-cooled.Add 2.8g glutaraldehyde two anil hydrogen chloride to this potpourri, stirred 3 hours.And then add the 50ml methanol solution that is dissolved with the 4.2g sodium acetate, then add the 25ml isopropanol precipitating and go out the mulberry crystallization.This crystallization is leached, use washed with isopropyl alcohol, get 5.4g compound 8 after the drying.

Fusing point: be higher than 300 ℃

：626nmε：7.89×10 ⁴

The diffusible cyan colour coupler of compound right and wrong shown in the formula (II).

Synthesis example 3(compound 10)

Preparation is by 8g3-(2-hydroxyethylamino formoxyl)-1-(2-sulphur benzyl) potpourri formed of pyrazoline, 30ml methyl alcohol 3.8ml triethylamine, and with its cooling.Add 3g glutaraldehyde two anils to this solution, add the 2ml acetic anhydride then.Make this potpourri in room temperature reaction 1 hour, add the 20ml isopropanol precipitating then and go out the black crystallization.Crystallization is leached, use washed with isopropyl alcohol, get 6.1g compound 10 after the drying.

Fusing point: be higher than 300 ℃

：633nmε：8.8×10 ⁴

Synthesis example 4(compound 18)

Acyl system is by 8g3-carboxyl-1-[2-(4-sulfophenyl) ethyl] potpourri that pyrazolin-5-one, 50ml methyl alcohol and 7ml triethylamine are formed, add 1.6gN then, N '-diphenyl methylether hydrogen chloride heated two hours, formed a kind of uniform solution.Add the 50ml methanol solution that is dissolved with the 4.5g sodium acetate to this solution, add the 20ml isopropanol precipitating then and go out yellow crystal.This crystallization is leached, use washed with isopropyl alcohol, get 4g compound 18 after the drying.

Fusing point: be higher than 300 ℃

：452nmε：2.10×10 ⁴

Synthesis example 5(compound 12)

Compound 12 be by the method identical with synthesis example 2 by 3-carbethoxyl group-1-(2,4-disulfo benzyl) the pyrazolin-5-one preparation.

Fusing point: be higher than 300 ℃

：640nmε：7.02×10 ⁴

Synthesis example 6(compound 20)

Compound 20 is by 3-carboxyl-1-[2-(4-sulfo group butoxy by the method identical with synthesis example 2) benzyl] the pyrazolin-5-one preparation.

Fusing point: 264-269 ℃ (decomposition)

：628nmε：7.39×10 ⁴

The diffusible cyan colour coupler of these compound right and wrong shown in the formula (II).

Introduce the compound of formula (II) below in detail.

In formula (II), R ₈Expression chain or cyclic aliphatic group preferably have 1-32 carbon atom (the total number of carbon atoms), as methyl, butyl, pentadecyl, cyclohexyl; Aromatic group preferably has 6-32 carbon atom (the total number of carbon atoms), as phenyl, naphthyl; Heterocyclic group preferably contains N, and at least one among O and the S is as the first ring of heteroatomic 5-7, as 2-pyridine radicals, 3-pyridine radicals, 2-furyl, 2-oxazolyl; Or substituted-amino, the preferably amino that replaces by at least one alkyl and aryl.Above-mentioned these groups can replace; substituting group is selected from alkyl; aryl; alkoxy or aryloxy group are (as methoxyl; dodecyloxy; methoxyethoxy; phenoxy group; 2; 4-two tertiary pentyl phenoxy groups; 3-tertiary butyl-4-hydroxy phenoxy group; naphthoxy); carboxyl; alkyl carbonyl or aromatic carbonyl are (as acetyl group; tetradecane acyl group; benzoyl); alkoxy carbonyl group or aryloxy carbonyl are (as methoxycarbonyl group; benzyloxycarbonyl group; carbobenzoxy); aliphatic series or aromatics acyloxy are (as acetyl group; benzoyloxy; phenyl carbonyl oxygen base); aliphatic series or aromatics sulfamoyl (N-ethyl sulfamoyl; N-octadecyl sulfamoyl); aliphatic series or aromatic amine formoxyl are (as N-ethylamino formoxyl; N, N-methyl dodecyl carbamyl); aliphatic series or aromatics sulfoamino-group are (as the first sulfoamino-group; the benzene sulfoamino-group); aliphatic series or aromatics acylamino-are (as acetylamino; benzamido; carbethoxyl group amino; the phenylamino carbonylamino); imino group (succinimido; the glycolylurea base); aliphatic series or aromatic sulfonyl (as mesyl); hydroxyl; cyano group; nitro and halogen atom.

In this manual, term " aliphatic group " expression straight chain, side chain or alicyclic hydrocarbon group, they can be saturated, and are also undersaturated, as alkyl, alkenyl or alkynyl.

In formula (II), R ₇Expression C _2-20(sum) alkyl (as ethyl, butyl, pentadecyl), aliphatic series or aromatics acylamino-(as myristoyl amino, benzamido (benzolylamino), 2-(2,4-two tertiary pentyl phenoxy groups) butyrylamino).

In formula (II), X ₃Expression hydrogen, halogen atom (as Cl, Br, F), aliphatic group (as methyl, propyl group, allyl), alkoxy (as methoxyl, butoxy), aliphatic series or aromatics acylamino-(as acetylamino).

R ₇And X ₃Can form one jointly and form the required nonmetallic atom group of 5-7 unit ring, as among forming carbocyclic ring or preferably containing N, O and S at least one as heteroatomic heterocycle (as phenyl ring, lactam nucleus)

In formula (II); Z represents hydrogen or coupling-leaving group, as halogen atom (F; Cl; Br); alkoxy is (as ethoxy; dodecyloxy; methoxy carbamyl ylmethoxy; the carboxyl propoxyl group; the methylsulfonyl ethoxy); aryloxy group is (as the 4-chlorophenoxy; 4-methoxyl phenoxy group; 4-carboxyl phenoxy group); aliphatic series or aromatics acyloxy are (as acetoxyl group; tetradecane acyl-oxygen base; benzoyloxy); aliphatic series or aromatics sulfonyloxy are (as mesyloxy; tosyloxy); acylamino-is (as dichloro acetamino; the heptyl butyrylamino; methanesulfonamido; tosyl amino); alkyl oxy carbonyl oxygen is (as ethoxy carbonyl oxygen base; benzyloxy carbonyl oxygen base); virtue oxygen carbonyl oxygen base (as carbonyl phenoxy oxygen base); aliphatic series or aromatics thio group are (as ethylmercapto group; thiophenyl); heterocycle thio group (as the tetrazolium sulfenyl); imino group is (as succinimido; the glycolylurea base); at least the heterocycle that contains a N atom is (as the 1-pyrazolyl; 1-Phenyltriazole base); aromatics azido (as phenylazo).These leaving groups can contain the group that is suitable for sensitization.

R in the formula (II) ₇C preferably _2-15Alkyl, C _2-4Alkyl is good especially.

Z is preferably hydrogen or halogen atom in the formula (II), and halogen atom is better.

X in the formula (II) ₃Hydrogen atom preferably.

The ring that is become with X-shaped by the seal ring radicals R in formula (II) is 5 yuan of hydroxyindole rings preferably.

The compound of formula (II) and synthetic method thereof in following patent literature existing report, as United States Patent (USP) 4564590,2895826,4557999,4565777,4124396,4613564,4327173,4564586,4430423, JP-A-61-39045, JP-A-62-70846, JP-A-61-390441 and JP-A-62-257158.

Following is the example of The compounds of this invention shown in the formula (II), and the scope of the invention is not so limited.

The dyestuff of formula (I) can any effective dose be used as filter dye, anti-irradiation dyestuff or anti-halo dye, and its consumption preferably can guarantee to provide the optical density (whole hydrophilic colloid layer) of 0.05-3.0.Can in any procedure of processing before the light sensitive layer composition is coated to supporting mass, add above-mentioned dyestuff.

Be to prevent the spectral absorption harmful to spectral sensitizer, the dyestuff that preferably uses n=1 in the formula (I) is as green sensitizing dye, and the dyestuff that uses n=2 wherein is as red sensitizing dye.

Dyestuff of the present invention can be adopted some known methods be scattered at least one hydrophilic colloid layer, i.e. emulsion layer and other hydrophilic colloid layer (middle layer, protective seam, the antihalation layer that comprises back sheet and filter layer).

(1) a kind of method is that dyestuff of the present invention directly is dissolved in or is scattered in the coating composition of emulsion layer and hydrophilic colloid layer, or dyestuff of the present invention is dissolved in or is scattered in aqueous solution or the solvent, solution or the dispersion liquid with gained is used for emulsion layer or hydrophilic colloid layer then.Dye soluble of the present invention is in appropriate solvent, as methyl alcohol, ethanol, propyl alcohol, methyl cellosolve, halohydrin (seeing JP-A-48-9715 and U.S.3756830), acetone, water, pyridine or their potpourri.The solution of gained can be added in emulsion or the hydrophilic colloid solution.

(2) another kind of method is that the hydrophile copolymers that has with used dyestuff ion opposite charges is sneaked in some layer as mordant, by the reaction between this polymkeric substance and the dye molecule dyestuff is positioned in the specific layer.

The term " polymer " mordant " expression: the polymkeric substance that contains secondary and tertiary amine base; have the polymkeric substance of nitrogen heterocyclic ring part; and contain the polymkeric substance of these cation group in season, the molecular weight of these polymkeric substance is more than 5000 or 5000, is preferably more than 10000 or 10000.

For example, the mordant of Shi Yonging comprises described vinylpyridine polymer of US254564 and vinylpyridine cationic polymer; The described vinyl imidazole cationic polymer of US4124386; US3625694 described can with the crosslinked polymer mordant of gelatin; The described water of US3958995 and JP-A-54-115228 is the colloidal sol type polymer mordant not; The described water-soluble mordant of US3898088; US4168976 described can with the active mordant of dyestuff covalent bonding; The BrP 685475 described polymkeric substance that obtain by the alefinically unsaturated compounds that contains dialkylaminoalkyl ester residue; The reaction product of BrP 685475 described polyvinyl alkyl ketone and aminoguanidine; The described polymkeric substance that obtains by 2-methyl isophthalic acid-vinyl imidazole of US3445231.

(3) also having a kind of method is to utilize the surfactant dissolves compound.Described surfactant is oligomer or polymkeric substance.

Submit on January 26th, 1984 by Fuji Photo Film Co.Ltd. at JP-A-60-158437() 19 pages to 27 pages of instructions describe above-mentioned oligomer and polymkeric substance in detail.The hydrosol of the lipophilic polymer described in the JP-A-51-39835 also can add in the above-mentioned hydrophilic colloid dispersion liquid that obtains.

With respect to every mole of silver halide in the silver halide emulsion layer that contains cyan colour coupler, the consumption of cyan colour coupler shown in the formula (II) can be in the 0.1-1 molar range, preferably the 0.2-0.5 mole.

The cyan colour coupler of formula (II) is dissolved in high boiling organic solvent, and as phthalic acid ester solvent, phosphate (salt) solvent, fatty acid ester solvent, the solution with gained is scattered in the hydrophilic colloid medium that will add in the silver emulsion again.

For improving the storge quality of silver-halide color photoelement, can be to wherein adding benzotriazole UV absorbers and water insoluble and dissolve in the polymkeric substance of organic solvent.Specifically, use these polymkeric substance can improve dark fadedness effectively.The most suitable polymkeric substance is that those are at the polymkeric substance described in the JP-A-61-162813.

Hydrophilic colloid comprises common gelatin and any other colloid that becomes known for photosensitive material.

The present invention can adopt any as the silver halide raw material among silver bromide, iodine silver bromide, iodine chlorine silver bromide, chlorine silver bromide and the silver chloride.For carrying out fast processing, specifically, contain the 90%(mole) or more (preferably 98%(moles) or more) the chlorine silver bromide of silver chloride is preferred.This chlorine silver bromide can contain a small amount of silver iodide, but does not preferably contain silver iodide.

The used silver halide particle of the present invention can be the form of regular crystal, as cube and octahedron, also can be random crystal, as spherical peaceful sheet, or its array configuration.Also can use the potpourri of particle, but preferably have the silver halide particle of regular crystal form with different crystal form.

The used silver halide particle of the present invention can comprise different phases or homogeneous phase at internal layer with the top layer.These particles can be mainly to form latent image (promptly negative emulsion) in its surface, or mainly within it portion form latent image (be internal latent image emulsion, give atomizing rotating emulsion (previously fogged direct reversal emulsion)).These particles preferably can mainly form latent image in its surface.

Used silver emulsion plain film shape grain emulsion preferably among the present invention, wherein thickness is equal to or less than 0.5 μ m, preferably be equal to or less than 0.3 μ m, diameter preferably is equal to or greater than 0.6 μ m, and the average diameter thickness rate is equal to or greater than 5 particle and accounts for more than 50% or 50% of whole projected area; Or the emulsion of monodispersity, make statistic bias coefficient (s/d ratio, s: standard deviation, d: the distribution diameter of projected area approximate circle) be equal to or less than 20%.Also two or more plain film shape grain emulsions or monodispersity emulsion can be used with.

The used photosensitive emulsion of the present invention can be prepared by known method, as at P.Glafkides, " Chimie er physique Photographique ", (Paul Montel co., Ltd., 1967), G.F.Duffin, " Photographic Emulsion Chemistry " (Focal Press, 1966), and V.L.Zelikman, the method for being introduced in " Making and Coating Photographic Emulsion " (Focal Press, 1964).

When forming silver halide particle, for controlling the growth of these particles, can use ag halide solvent, as ammonia, sulphur cyanogen potassium, sulphur cyanogen ammonium, sulfide compound (as described in US3271157,3574628,3704130,4297439,4276374), sulphur compound (as described in JP-A-53-144319, JP-A-53-82408, JP-A-55-77737) and amines (as described in JP-A-54-100717).

Form or physics slaking silver halide particle process in, can have following material, as the iron complex of complex, molysite or its salt of complex, rhodium salt or its salt of cadmium salt, zinc salt, thallium salt, iridium salt or its salt.

Silver emulsion is normally through chemical sensitization, for example press the method that " Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden " (Akademisch Verlagsgesellshaft, 1968) 675-734 page or leaf that H.Frieser edits is introduced.

That is to say, can adopt by vulcanizing the method for sensitizing, as thiosulfate (ester), thiourea, thin based compound, rhodanine compound with the sulfocompound of active gelatin or silver reaction; Carry out the method for reduction sensitization by reducible material, as tin salt, amine, hydrazine derivate, carbonamidine sulphurous acid, silane compound; Carry out the method for noble metal sensitizing by precious metal chemical complex or their potpourri, as the complex of group VIII metal (as Pt, Ir, Pd) in gold complex and other periodic table.

In order in production, preservation or the processing procedure of photosensitive material, to prevent photographic fog, or stable photographic property, can contain various compounds in the used silver halide magenta-sensitive emulsion of the present invention as anti-photographic fog agent and stabilizing agent, for example, azole compounds is as benzothiazolium salt, nitroindoline compound, triazole type, benzotriazole and benzimidazoles compound (especially those contain nitro and halogenic substituent); Heterocycle is dredged based compound, as dredging basic thiazolium compounds, dredge basic benzothiazoles, dredging basic benzimidazole, dredges basic thiadiazole, thin basic tetrazolium class (especially 1-phenyl-5-dredges basic tetrazolium) and thin yl pyrimidines class; The heterocycle that contains water soluble group (as carboxyl and sulfuryl) is dredged based compound; Thioketone (thioketo), as _ azoles quinoline sulphur (oxazolinethion); Azepine indenes class is as the purine (especially (1,3,3a, 7) purine of 4-hydroxyl replacement); Benzene thiosulfonic acid; Phenylsulfinyl.

Silver halide magenta-sensitive emulsion of the present invention can contain colour former agent, the compound of using as these colour couplers of cyan colour coupler, magenta colour coupler, yellow colour coupler and dispersion.

That is to say that silver halide magenta-sensitive emulsion of the present invention can contain in the colour development process by produce colored compound with aromatics primary amine developer (as the p-phenylene diamine derivative, p-aminophenol derivative) oxidative coupling.For example; 5-pyrazolone colour coupler, pyrazolo benzimidazole (pyrazolobenzimidazole) colour coupler are arranged; cyano group acetocoumarin (cyanoacet ylcumarone) colour coupler; the Pyrazolotriazole colour coupler, and as the open chain acyl group acetonitrile of magenta colour coupler with as the acyl group acetamide colour coupler of yellow colour coupler.

These colour couplers preferably contain the hydrophilic radical non-dispersive colour coupler of (being called the ballast group) in its molecule.These colour couplers can be 4 equivalents or 2 equivalents of silver ion, or have the coloured quality agent of colour correction effect, or can discharge the colour coupler (so-called DIR colour coupler) of development restrainer in developing process.

Non-DIR colour coupler can contain colourless DIR coupling compound, and this compound can form colourless product and discharge development restrainer by coupling reaction.Also can add ultraviolet light absorber and anti-fading agent, as cinnamate and 2-(2-hydroxyphenyl) benzotriazole.

These anti-fading agents comprise the compound that following patent literature is introduced: US3432300,3573045,3574627,3700455,3764337,3935016,4254216,4268593,4430425,4465757,4465765,4518679, BrP 1347556, British patent gazette (not examination) 2066975, JP-A-52-152225, JP-A-53-17729, JP-A-53-20327, JP-A-54-145530, JP-A-55-6321, JP-A-55-21004, JP-A-61-72246, JP-A-61-73152, JP-A-61-90155, JP-A-61-90156, JP-A-61-145554.

Photosensitive emulsion of the present invention can contain the polyoxy alkylidene or derivatives thereof, as ether, ester and amine; Sulfide compound, thiomorpholine class, quarternary ammonium salt compound, urethane derivatives, urea derivative, imdazole derivatives and 3-pyrazolidone develop to improve photosensitivity and contrast (Contrast) or to quicken.

Except dyestuff disclosed in this invention, also can contain known water-soluble dye (as oxonol dyestuff, hemioxonol dyestuff and merocyanine dyes) in the silver halide magenta-sensitive emulsion of the present invention, as filter dye or anti-irradiation dyestuff.Known cyanine dye, merocyanine dyes and half cyanine dye also can be used as spectral sensitizer.

Photosensitive emulsion of the present invention can contain various surfactants, as applying auxiliary agent and antistatic agent, to improve smooth property, to help to disperse emulsion, prevent bonding and improve photographic property (as quickening to develop, provide high-contrast (contrast) and photosensitivity).Photosensitive material of the present invention also can contain various adjuvants; as anti-fading agent, rigidizer, colored antifoggant; ultraviolet absorber and protective colloid, as gelatin, these are in Research Disclosure Vol.176(1978. XII) the existing introduction among the RD-17643.

The emulsion of making is coated on the suitable supporting mass, for example herbarium paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic substrate or glass plate.

Photosensitive silve halide material of the present invention comprises colored positive photoresist film, chromatics paper, colored negative film, color reverse film (can contain colour coupler, can not contain) yet, the photosensitive material that is used for mask-making technology is (as lithographic printing (lith) film, the lithographic printing duplicate film), the photochromics that is used for cathode-ray tube display (as is used for the photochromics that the emulsion X ray writes down, use the direct or indirect photographic material of screen), the photosensitive material that is used for silver salt diffusion transport process is used for the photosensitive material of colored diffusion transport process, the photosensitive material that is used for dyestuff transmission course and inhibitor transmission course, the photosensitive material that is used for the silver dye bleach process, be used to write down the photosensitive material of print image, the photosensitive material that is used for direct impression, be used for heat-developed photosensitive material and the photosensitive material that is used for physical development.

The exposure process that forms photographic image can adopt any known light source to carry out, for example, and natural light (sunlight), tungsten lamp, fluorescent light, mercury vapor light, xenon arc lamp, carbon lamp, xenon flash lamp and cathode-ray tube (CRT) flying-spot scanner.Time shutter is generally 1/1000-30 second, but also can be less than 1/1000 second, and when for example using xenon flash lamp or cathode-ray tube (CRT), the time shutter is 1/10 ⁴-1/10 ⁶Second, the time shutter also may be greater than 30 seconds.If necessary, can control the spectral component of the light that is used for exposing by chromatic filter.Available laser explosure.In addition, can also adopt the light that sends by X ray, gamma-rays or alpha ray Ji Fa Phosphonium light body to expose.

The photograph of photosensitive material of the present invention was handled and can be adopted known method and treating fluid to carry out, as described in Research DisclosureNO.176 28-30 page or leaf (RD-17643).Take a picture to handle and to form silver halide image (monochrome photography processing) or color image (colored) according to resembling processing.Treatment temperature but also can be hanged down 18 ℃ or be higher than 50 ℃ usually between 18-50 ℃.

The present invention handles the method for color sensitive image without any restriction to processing.Say that generally conventional method comprises following several, method (a): exposure, colour development, bleaching-photographic fixing, if necessary, carry out rinsing and stabilization; Method (b): exposure, with the developer solution that contains the black-and-white development agent develop, uniform exposure, colour development, bleaching-photographic fixing, if necessary, carry out rinsing and stabilization; Method (c): expose, develop, further develop, bleach-photographic fixing, if necessary, carry out rinsing and stabilization with the colour developing solution that contains Alevaire (as borohydride sodium) with the developer solution that contains the black-and-white development agent.

The used aromatics primary amine color developer of colour developing solution comprises those known color developer that is widely used in various autochromy processes, for example amino phenol and p-phenylene diamine derivatives among the present invention.Preferably using the p-phenylene diamine derivative, below is its typical example, and these are not construed as limiting the scope of the invention.

D-1 N, N-diethyl-p-phenylenediamine (PPD)

D-2 2-amino-5-lignocaine toluene

D-3 2-amino-5-(N-ethyl n-bay amino) toluene

D-4 4-[N-ethyl-N-(beta-hydroxyethyl) amino] aniline

D-5 2-methyl-4-[N-ethyl-N-(beta-hydroxyethyl) amino] aniline

D-6 N-ethyl-N-(β-methanesulfonamido ethyl)-3-methyl-4-amino aniline

D-7 N-(2-amino-5-lignocaine phenyl ethyl) Methanesulfomide

D-8 N, N-dimethyl-p-phenylenediamine (PPD)

D-9 4-amino-3-methyl-N-ethyl-N-methoxyethyl aniline

D-10 4-amino-3-methyl-N-ethyl-N-β-ethoxyethyl aniline

D-11 4-amino-3-methyl-N-ethyl-N-β-Ding oxygen ethylaniline

These p-phenylene diamine derivatives also can be the forms of salt, as sulfate, hydrochloride, sulphite and tosilate.Above-claimed cpd is existing the introduction in US2193015,2552241,2566271,2592364,3656950 and 3698525.In per 1 liter of developer solution, the consumption of above-mentioned aromatics primary amine color developer is generally about 0.1-20g, preferably about 0.5-10g.

Used colour developing solution can contain the known azanol for people among the present invention.

Azanol can unhindered amina in colour developing solution form use, but generally be to use, as their sulfuric ester, oxalate, chloride, phosphate, carbonic ester and acetic acid esters with the form of acid salt aqueous solution.Azanol can replace, and also can be unsubstituted.Nitrogen-atoms in the azanol can replace with alkyl.

In per 1 liter of colour developing solution, the addition of azanol is 0-10g, is preferably 0-5g.As long as can keep the stability of colour developing solution, the azanol consumption is few more good more.

Can add sulphite as preservative agent, as sodium sulphite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium metabisulfite and carbonyl sulfite derivative.In every liter of developer solution, the consumption of above-mentioned preservative agent is 0-20g, preferably 0-5g.As long as can keep the stability of colour developing solution, this consumption is few more good more.

Other preservative agent that can mention has, the described aromatics polyol of JP-A-52-49828, JP-A-56-47038, JP-A-56-32140, JP-A-59-160142 and US3746544; US3615503 and BrP 1306176 described hydroxypropanone-classes; The described alpha-amido carbonyls of JP-A-52-143020 and JP-A-53-89425; The described various metals of JP-A-57-44148 and JP-A-57-53749; The described various carbohydrates of JP-A-52-102727; The described hydroxamic acid of JP-A-27638; The described α of JP-A-59-160141, α '-dicarbonyl compound; The described salicylic acid of JP-A-59-180588; The described alkanolamine of JP-A-54-3532; The described gluconic acid derivative of JP-A-56-75647; With the described polyalkyleneimine of JP-A-56-94349.Hydrazine-N, N-oxalic acid also are preferred.If necessary, two or more above-mentioned preservative agents can be mixed use.Specifically, preferably with 4, a 5-dihydroxy-benzenedisulfonic acid, polyethyleneimine and triethanolamine are added in the developer solution together.

Used colour developing solution among the present invention, the pH value is that 9-12 is better, 9-11 is better, and can contain other known compound as the developer solution component.

The 11-19 page or leaf describes the kind and the consumption of preservative agent, buffering agent, sequestrant, development accelerant, antifoggant and whitening agent in detail among the JP-A-62-63526.

In the present invention, colour developing solution is at 20-50 ℃, uses under the best 30-40 ℃ of treatment temperature, the processing cycle is 20 seconds to 5 minutes, and preferably 30 seconds to 4 minutes, every square metre of used development amount of photosensitive material was 30-1000ml, best 60-400ml, consumption is less relatively good.

Desilverization process among the present invention is normally carried out as follows, generally comprises blanching step-photographic fixing step, photographic fixing step-bleaching-photographic fixing step, blanching step-bleaching-photographic fixing and bleaching-photographic fixing step.Desilverization step was carried out 2 minutes or was less than 2 minutes, preferably 15-90 second.

The present invention can adopt the adjuvant of the described bleaching liquid of 20-25 page or leaf, bleaching-stop bath, stop bath and respective amount among the JP-A-62-63526.

Rinsing after the desilverization and/or stabilization also can by with JP-A-62-63526 in the described identical method of 25-29 page or leaf carry out.

Following example can more detailed explanation the present invention, but the present invention is not limited to these examples.Except as otherwise noted, all umbers, number percent and ratio be all by weight herein.

Example 1

Tygon has sample (1) as the multi layer colour positive of lower floor's structure with preparation on the lamination of the two sides of paper substrate

Layer structure

The composition of each layer provides hereinafter.Numeral is meant the amount (g/m of coating ³), the amount of silver emulsion is calculated according to silver content.The amount of cyan colour coupler and dyestuff in mole/square metre.

Supporting mass

The laminated paper of tygon, wherein the tygon on the ground floor one side contains white pigments (TiO ₂) and blue dyestuff (ultramarine).

Ground floor (to blue responsive silver halide emulsion layer)

Contain spectral sensitizer (Sen-1)

Single chlorine silver bromide emulsion (EM-1) 0.16 that disperses

Contain spectral sensitizer (Sen1)

Single chlorine silver bromide emulsion (EM-2) 0.1 that disperses

Antifoggant (Cpd-1) 0.004

Gelatin 1.83

Yellow colour coupler (ExY) 0.83

Dye image stabilizing agent (Cpd-2) 0.03

Polymkeric substance (Cpd-3) 0.08

Solvent (Solv-2 and Solv-2, volume ratio is 1: 1) 0.35

Rigidizer (Hd) 0.02

The second layer (anti-colour mixture layer)

Gelatin 1.25

Anti-blending agent (Cpd-4) 0.04

Solvent (Solv-3 and Solv-4, volume ratio is 1: 1) 0.20

Rigidizer (Hd) 0.02

The 3rd layer (to the silver halide emulsion layer of green sensitive)

Contain spectral sensitizer (Sen-2,3)

Single chlorine silver bromide emulsion (EM-3) 0.05 that disperses

Contain spectral sensitizer (Sen-2,3)

Single chlorine silver bromide emulsion (EM-4) 0.11 that disperses

Antifoggant (Cpd-5) 0.001

Gelatin 1.79

Magenta colour coupler (ExM) 0.32

Dye image stabilizing agent (Cpd-6) 0.20

Dye image stabilizing agent (Cpd-7) 0.03

Dye image stabilizing agent (Cpd-8) 0.03

Solvent (Solv-3 and Solv-5, volume ratio is 1: 2) 0.65

Rigidizer (Hd) 0.01

The 4th layer (UV-absorbing layer)

Gelatin 1.58

Ultraviolet light absorber be (VU-1/2/3's

Mol ratio is 1: 4: 4) 0.62

Anti-blending agent (Cpd-4) 0.05

Solvent (Solv-6) 0.34

Dyestuff (Dy-1) 1.8 * 10 ^-4

(mole/square metre)

Dyestuff (Dy-2) 2.0 * 10 ^-4

(mole/square metre)

Rigidizer (Hd) 0.01

Layer 5 (to the silver halide emulsion layer of red sensitive)

Contain spectral sensitizer (Sen-4,5)

Single chlorine silver bromide emulsion (EM-5) 0.07 that disperses

Contain spectral sensitizer (Sen-4,5)

Single chlorine silver bromide emulsion (EM-6) 0.15 that disperses

Antifoggant (Cpd-9) 0.0002

Gelatin 1.34

Cyan colour coupler 6.7 * 10 in the table 2 ^-4

(mole/square metre)

Ultraviolet light absorber be (UV-1/3/4's

Mol ratio is 1: 3: 3) 0.17

Polymkeric substance (Cpd-3) 0.33

Solvent (Solv-1) 0.23

Rigidizer (Hd) 0.01

Layer 6 (UV-absorbing layer)

Gelatin 0.53

Ultraviolet light absorber be (UV-1/2/3's

Mol ratio is 1: 4: 4) 0.21

Solvent (Solv-6) 0.08

Rigidizer 0.01

Layer 7 (protective seam)

Gelatin 1.33

The ethenol copolymer of acryloyl group modification

(modification degree: 17%) 0.17

Whiteruss 0.03

Silver emulsion (EM-1) used in the above-mentioned sample is prepared as follows:

(solution 1)

H ₂O 1000ml

NaCl 5.5g

Gelatin 25g

(solution 2)

Sulfuric acid (1N) 20ml

(solution 3)

1% aqueous solution 2ml of following formula: compound

(solution 4)

KBr 2.80g

NaCl 0.34g

Adding water makes cumulative volume reach 140ml

(solution 5)

AgNO ₃5g

Adding water makes cumulative volume reach 140ml

(solution 6)

KBr 67.20g

NaCl 8.26g

K ₂The IrCl(0.001% aqueous solution) 0.7ml

Adding water makes cumulative volume reach 320ml

(solution 7)

AgNO ₃120g

NH ₄NO ₃(50% aqueous solution) 2ml

Adding water makes cumulative volume reach 320ml.

Solution 1 is heated to 74 ℃,, then solution 4 and 5 was added in 9 minutes in the above-mentioned solution simultaneously, after 10 minutes solution 6 and 7 was added in the above-mentioned solution within 45 minutes simultaneously to wherein adding solution 2 and 3.After interpolation finishes mixed solution was left standstill 5 minutes cooling and desalination.The gelatin that adds entry and dispersion transfers to 6.2 with pH, obtains a kind of single dispersed cubic crystallographic system chlorine silver bromide emulsion, and its particle mean size is 0.96 μ m, and Z-factor (s/d, s are standard deviations, and d is a particle mean size) is 0.08, and silver bromide accounts for the 80%(mole).With sodium thiosulfate this emulsion is optimized chemical sensitization.

Method according to the above-mentioned emulsion of preparation (EM-1) prepares other chlorine silver bromide emulsion (EM-2)-(EM-6), and difference is a compound amount, and temperature and time changes to some extent.

Below table 1 details of these emulsions is shown.

Table 1

The average Br content deviation of emulsion crystal formation

Title granularity (mole %) coefficient

（μm）

EM-1 cube 0.96 80 0.08

EM-2 cube 0.64 80 0.07

EM-3 cube 0.52 95 0.08

EM-4 cube 0.40 95 0.09

EM-5 cube 0.44 70 0.09

EM-6 cube 0.36 70 0.08

Z-factor=standard deviation/particle mean size

Sample (2)-(7) are by the method identical with above-mentioned sample (1) preparation, and difference is the cyan colour coupler in dyestuff and the layer 5 in having changed the 4th layer.The composition of dyestuff and cyan colour coupler is table 2 illustrate.The numbering that provides in the numbering that please notes dyestuff and cyan colour coupler and the example is corresponding.Following cyan colour coupler (c) is used for contrast.

Cyan colour coupler (c)

Table 2

Sample dyestuff cyan colour coupler

(consumption: mol/m ²) (6.7 * 10 ²Mol/m ²)

(1) Dy-1(1.8 * 10 ^-5) (C) contrast

Dy-2（1.8×10 ^-5）

(2) " C-3 contrast

(3) I-37(1.8 * 10) ^-5(C) contrast

I-10（2.0×10） ^-5

(4) " C-3 the present invention

(5) " c-1 the present invention

(6) " c-2, the C-3(the present invention that rubs

You were than 1: 1)

(7) I-5(1.8 * 10 ^-5) C-3 the present invention

I-5（2.0×10 ^-5）

(Ltd. makes, the colour temperature of light source for FWH type, Fl Photo FilmCO.: 3200K) by red filter sample (1)-(7) sensitization is exposed with sensitometer.In this case, the time shutter is 0.1 second, obtains the exposure of 250CMS.Expose to determine sharpness by a wedge, the blue or green density that obtains is 1.5.

After the exposure, carry out each step of following colour development, bleaching-photographic fixing and rinsing.

The treatment step temperature (℃) time

Colour development 33 3 minutes and 30 seconds

Bleaching-photographic fixing 33 1 minutes and 30 seconds

Rinsing 24-34 3 minutes

Dry 70-80 1 minute

Shown in every kind for the treatment of fluid composed as follows:

Colour developing solution

Water 800ml

Diethylene-triamine pentaacetic acid 1.0g

Nitrilotriacetic acid(NTA) 1.5g

Benzylalcohol 15ml

Diglycol 10ml

Sodium sulphite 2.0g

Potassium bromide 0.5g

Sal tartari 30g

N-ethyl-N-(β-methanesulfonamido ethyl)-3-

Methyl-4-amino aniline sulfuric ester 5.0g

Hydroxylamine sulfate ester 4.0g

Whitening agent (WHITEX 4B, Sumitomo Chemical

Co., Ltd. makes) 1.0g

Adding water makes cumulative volume reach 1000ml

Ph（25℃） 10.20

Bleaching-fixing bath

Water 400ml

ATS (Ammonium thiosulphate) (70% aqueous solution) 150ml

Sodium sulphite 18g

Ethylene diaminetetraacetic acid iron (III) ammonium 55g

Ethylene diaminetetraacetic acid disodium 5g

Adding water makes cumulative volume reach 1000ml

pH（25℃） 6.70

Developed in above-mentioned sample (1)-(7), estimate its photonasty, fog density, sharpness and fadedness then.In this case, to be 1.0 o'clock relative sensitivity numerical value be decided to be 100 with the relative sensitivity of sample (1) obtains as reference in density; Fog density numerical value is to be 3 minutes 30 seconds and intensifying processing time to be to obtain under two kinds of situations of 7 minutes at development time; Definition values is by measure C.T.F(contrast transfer function under the spatial frequency of 15 circulation/mm) (%) obtain, definition values is high more good more.The sample of the value of secretly fading after with every kind of development placed under 80 ℃, 70% relative humidity condition and obtained in 14 days, and color density is the density percent that 2.0 part was obtained in 14 days before the evaluation test.The results are shown in table 3.

(table 3 is seen below the literary composition back)

Can be clear that from table 3 sample of having used cyan colour coupler and dyestuff with of the present invention is the photosensitive material with high photosensitivity, low photographic fog, high definition and good anti-dark fadedness.

Example 2

The sample (8) that has following composition by the method preparation identical with example 1.

Ground floor (to blue responsive silver halide emulsion layer)

Contain spectral sensitizer (Sen-6)

Single chlorine silver bromide emulsion (EM-7) 0.27 that disperses

Gelatin 1.86

Yellow colour coupler (ExY) 0.82

Solvent (Solv-4) 0.35

Rigidizer (Hd)

The second layer (anti-colour mixture layer)

Gelatin 0.99

Anti-blending agent 0.06

Solvent (Solv-3 and Solv-4, volume ratio is 1: 1) 0.12

Rigidizer (Hd) 0.02

The 3rd layer (to the silver halide emulsion layer of green sensitive)

Contain spectral sensitizer (Sen-7,3)

Single chlorine silver bromide emulsion (EM-8) 0.45 that disperses

Gelatin 1.24

Magenta colour coupler (ExM) 0.35

Dye image stabilizing agent (Cpd-6) 0.20

Dye image stabilizing agent (Cpd-7) 0.03

Dye image stabilizing agent (Cpd-8) 0.03

Solvent (Solv-3 and Solv-5, volume ratio is 1: 2) 0.65

Rigidizer (Hd) 0.01

The 4th layer (UV-absorbing layer)

Gelatin 1.58

Ultraviolet light absorber (the mole of VU-1/2/3

Than being 1: 4: 4) 0.62

Anti-blending agent (Cpd-4) 0.05

Solvent (Solv-6) 0.34

Dyestuff (Dy-1) 1.8 * 10 ^-5

(mole/square metre)

Dyestuff (Dy-2) 2.0 * 10 ^-5

(mole/square metre)

Rigidizer (Hd) 0.01

Layer 5 (to the silver halide agent layer of red sensitive)

Contain spectral sensitizer (Sen-4,5)

Single chlorine silver bromide emulsion (EM-9) 0.20 that disperses

Gelatin 0.92

Cyan colour coupler (table 5) 6.7 * 10 ^-4

(mole/square metre)

Polymkeric substance (Cpd-3) 0.30

Ultraviolet light absorber (the mole of VU-1/3/4

Than being 1: 3: 3) 0.17

Solvent (Solv-4) 0.20

Rigidizer (Hd) 0.01

Layer 6 (UV-absorbing layer)

Gelatin 0.53

Ultraviolet light absorber (the mole of VU-1/2/3

Than being 1: 4: 4) 0.21

Solvent (Solv-6) 0.08

Rigidizer (Hd) 0.01

Layer 7 (protective seam)

Gelatin 1.33

The ethenol copolymer of acetyl group modification

(modification degree 17%) 0.17

Whiteruss 0.03

The details of AgBrCl particle is shown in table 4 in the used silver emulsion of above-mentioned sample.

Table 4

Emulsion crystal formation average particle Br(content) deviation

Degree (μ m) (mole %) coefficient

EM-7 cube 0.85 0.6 0.10

EM-8 cube 0.45 1.0 0.09

EM-9 cube 0.34 1.8 0.10

Z-factor=standard deviation/particle mean size

Prepare sample (8)-(12) by same procedure, difference is dyestuff in having changed the 4th layer and the cyan colour coupler in the layer 5.Their composition is shown in table 5.

Table 5

Sample dyestuff cyan colour coupler

(consumption mol/m ²) (6.7 * 10 ^-4Mol/m ²)

(8) Dy-1(1.8 * 10) (C) contrast

Dy-2（2.0×10）

(9) 〃 C-1 contrast

(10) I-37(1.8 * 10) (C) contrast

I-10（2.0×10）

(11) 〃 C-1 the present invention

(12) 〃 (C), C-14 the present invention

(mol ratio is 1: 1)

With sample (8)-(12) exposure, and, obtain measured value with example 1 described mode by following step process.

The treatment step temperature (℃) time

Colour development 35 45 seconds

Bleaching-photographic fixing 30-35 45 seconds

Rinsing (1) 30-35 20 seconds

Rinsing (2) 30-35 20 seconds

Rinsing (3) 30-35 20 seconds

Rinsing (4) 30-35 30 seconds

Dry 70-80 60 seconds

(adopting 3 barrels of countercurrent rinsings (4) → (1) system)

Every kind for the treatment of fluid composed as follows:

Colour developing solution

Water 800ml

Ethylenediamine-N, N, N ', N '-tetramethylene phosphonic acid 1.5g

Triethylenediamine (1, the 4-diazabicylo

(2,2,2) octane) 5.0g

Sodium chloride 1.4g

Sal tartari 25g

N-ethyl-N-(β-methanesulfonamido ethyl)-the 3-methyl

-4-amino aniline sulfuric ester 5.0g

N, N-diethyl hydroxylamine 4.2g

Whitening agent (UVITEX CK, Ciba Geigy CO., Ltd.

Make) 2.0g

Adding water makes cumulative volume reach 1000ml

pH（25℃） 10.10

Bleaching-fixing bath

Water 400ml

ATS (Ammonium thiosulphate) (70%) 100ml

Sodium sulphite 18g

Ethylenediamine tetraacetic acid iron (III) ammonium 55g

Disodium ethylene diamine tetraacetate 3g

Ammonium bromide 40g

Glacial acetic acid 8g

Adding water makes cumulative volume reach 1000ml

pH（25℃） 5.5

Rinsing is bathed

Ion exchange water (wherein calcium and content of magnesium are respectively 3ppm or are less than 3ppm).

Developed in sample (8)-(12), measure performance by example 1 identical mode, sensitivity value is decided to be 100 with the relative sensitivity of sample (8) to be made reference and arrives, and the formed photographic fog value of intensifying processing is that development time obtains when being 90 seconds.The results are shown in table 6.

(table 6 is seen the literary composition back)

Can be clear that from table 6 sample that contains cyan colour coupler and dyestuff is good photosensitive material, they have ISO, low photographic fog value, high definition and good anti-dark fadedness.

Example 3

For measuring the stability of dyestuff of the present invention in film, the sample (2) of example 1 and 2, (4), (7), (9) and (11) were left standstill for two weeks under 35 ℃ and 80% relative humidity condition, measure the percent of remaining dyestuff then.The results are shown in table 7.

Table 7

The percent of the remaining dyestuff of sample

(2) 80 contrasts

(4) 95 the present invention

(7) 92 the present invention

(9) 82 contrasts

(11) 95 the present invention

The result shows that dyestuff of the present invention has good stable in film.

The present invention can provide a kind of silver-halide color photoelement, hydrophilic colloid layer wherein to contain new dyestuff, treated being easy to of this class dyestuff faded, still have stability after depositing over a long time, and to the photographic property of photosensitive emulsion, particularly to light sensitivity and photographic fog without any adverse influence.In addition, the present invention can provide a kind of silver-halide color photoelement that contains the red sensitive emulsion layer, and this emulsion layer has good anti-dark fadedness, high definition, ISO and low photographic fog.

Abovely describe the present invention in detail with reference to embodiment, clearly those skilled in the art also can make some improvement and change, but these all belong to base region of the present invention.

Table 6

Sample light sensitivity photographic fog value sharpness is secretly faded

3.5 minutes 7 minutes

(8) 100 0.09 0.12 29.0 75 contrasts

(9) 87 0.09 0.13 28.9 88 contrasts

(10) 107 0.08 0.09 33.0 75 contrasts

(11) 123 0.08 0.09 34.0 92 the present invention

(12) 120 0.08 0.09 33.8 90 the present invention

Table 3

The dark fadedness of sample light sensitivity photographic fog value sharpness

3.5 minutes 7 minutes

(1) 100 0.09 0.12 29.5 74 contrast

(2) 91 0.09 0.13 29.3 87 contrasts

(3) 107 0.08 0.09 33.2 76 contrasts

(4) 120 0.08 0.09 34.0 89 the present invention

(5) 117 0.08 0.09 33.9 92 the present invention

(6) 120 0.08 0.09 33.9 88 the present invention

(7) 115 0.08 0.09 33.8 89 the present invention

Claims (12)

1, a kind of silver-halide color photoelement, contain supporting mass and at least one deck be coated in silver-halide color sensitive emulsion layer on the supporting mass, contain the compound shown in compound shown at least a general formula (I) and at least a general formula (II) in the hydrophilic colloid layer of one deck at least on this supporting mass:

R wherein ₁And R ₂Expression-COOR separately ₅Or

R ₃And R ₄Represent hydrogen or alkyl separately; R ₅And R ₆Represent hydrogen, alkyl, aryl separately, or R ₅And R ₆Common formation one 5 yuan or 6 yuan of rings; Q ₁And Q ₂The expression aryl; X ₁And X ₂Represent divalence keyed jointing group or chemical bond separately; Y ₁And Y ₂Represent sulfonic group or hydroxy-acid group separately; L ₁, L ₂And L ₃Represent methine separately; m ₁And m ₂Represent 1 or 2 separately; N represents 0,1 or 2; P ₁And P ₂Represent 0,1,2,3 or 4 separately; S ₁And S ₂Represent 1 or 2 separately;

Y wherein ₃Expression-NHCO-or-CONH-; R ₈Expression aliphatic group, aromatic group, heterocyclic group or replacement or unsubstituted virtue are amino; X ₃Expression hydrogen, halogen atom, alkoxy or acylamino-; R ₇Expression contains the alkyl, acylamino-of two or more carbon atoms or with X ₃With R ₇Combine and form a required nonmetallic atom group of 5-7 unit ring; Z represents hydrogen or a kind of group that can leave away when with the coupling of oxidation colour developer, described silver halide emulsion layer includes the bromine silver chloride of 90% (mole) or above silver chloride.

2, by the silver-halide color photoelement of claim 1, wherein said silver halide emulsion layer comprises and contains the 98%(mole) or the bromine silver chloride of above silver chloride.

3, by the silver-halide color photoelement of claim 1, the consumption of wherein said formula (I) compound is as the criterion with the optical density that 0.05-3.0 can be provided.

4, by the silver-halide color photoelement of claim 1, wherein at least one hydrophilic colloid layer, be mixed with described formula (I) compound.

5, press the silver-halide color photoelement of claim 1, the consumption of wherein said formula (II) compound, every mole of silver halide with respect in the silver halide emulsion layer that contains this compound is the 0.1-1 mole.

6, press the silver-halide color photoelement of claim 1, wherein R ₅Or R ₆Represented alkyl is the alkyl that replaces, and described substituting group is selected from: sulfo group, carboxyl, hydroxyl, alkoxy, halogen atom, cyano group, aliphatic series or aromatic sulfonyl, nitro, amino and aryl unsubstituted or that replace through alkyl.

7, press the silver-halide color photoelement of claim 1, wherein R ₅Or R ₆Represented aryl is a phenyl unsubstituted or that replaced by following radicals, and described substituting group is selected from: sulfo group, carboxyl, hydroxyl, alkoxy, halogen atom, cyano group, nitro, amino and alkyl unsubstituted or that replace through alkyl.

8, press the silver-halide color photoelement of claim 1, wherein R ₁And R ₂Each self-forming sodium salt, sylvite, ammonium salt or quaternary ammonium salt.

9, press the silver-halide color photoelement of claim 1, wherein Q ₁Or Q ₂Represented aryl is the phenyl of divalent or 3 valency phenyl or naphthyls or replacement, and described substituting group is selected from: C _1-4Alkyl, C _1-4Alkoxy, halogen atom, aliphatic series or aromatic amine formoxyl, aliphatic series or aromatics sulfamoyl, cyano group, nitro, alkyl sulphonyl, aryl sulfonyl, amino, aliphatic series or aromatics acylamino-, aliphatic series or aromatics sulfonamido unsubstituted or that replace through alkyl.

10, press the silver-halide color photoelement of claim 1, wherein X ₁And X ₂Expression separately

Or chemical bond, wherein a R ¹ ₇Expression hydrogen, C _1-5Alkyl, add up to C _1-5Substituted alkyl, described substituting group is selected from C _1-3Alkoxy, sulfo group, carboxyl, cyano group, hydroxyl, amino, aliphatic series or aromatics acylamino-, aliphatic series or aromatic amine formoxyl and aliphatic series or aromatics sulfamoyl unsubstituted or that replace through alkyl.

11, press the silver-halide color photoelement of claim 1, wherein Y ₁And Y ₂Represent sulfonic group or carboxylic acid group separately, they can form free acid or salt.

12, press the silver-halide color photoelement of claim 1, wherein L ₁, L ₂And L ₃The methine of representing methine or replacement separately, substituting group are selected from methyl, ethyl and phenyl.