CN1497342A - Silver halide colour photographic sensitive material - Google Patents

Abstract

The silver halide color photographic sensitive material has, on a support, unit blue-, green- and red- sensitive silver halide emulsion layers each consisting of two or more photosensitive emulsion layers having the same color sensitivity but different from each other in sensitivity and contains one or more of the compounds of formula (I) or (II), wherein >=60% of the total projected area of silver halide grains contained in one or more of the photosensitive emulsion layers is occupied by tabular grains having an aspect ratio of >=5.0. In the formula (I) or (II), R<SB>1</SB>represents a substituent; n represents an integer of 0-6; R<SB>2</SB>represents alkyl or aryl; R<SB>3</SB>represents 1-3 (m) independent substituents (the sum total of the Hammett's substituent constants [sigma]<SB>p</SB>of all the symbols R<SB>3</SB>is >=0.1); m represents an integer of 1-3; R<SB>4</SB>and R<SB>5</SB>each represent H, alkyl, alkeny, alkynyl or aryl; and INH represents the residue of a mercaptotetrazole, mercaptotriazole or mercaptothiadiazole derivative or the like.

Description

Silver halide colour photographic sensitive material

Technical field

The invention relates to silver halide colour photographic sensitive material.More detailed saying is about high sensitivity, graininess, the sensitive photographic material that clarity is good, the color and luster repeatability is good.

Background technology

Silver halide colour photographic sensitive material, in order to improve the interests of colored negative film to the user, more and more require high sensitivityization, but in recent years, owing to can adapt to the film and the infiltration that has the compact camera of image electronic enlarging function of the band lens of various conditions of exposures easy and simply, particularly photographic sensitivity (ISO sensitivity) is usually used really at the photographic high speed film more than 800.

On the one hand, performance as silver halide photographic sensitive material, be only second to sensitivity, the most important thing is clarity and color and luster repeatability, as the means of improving clarity and color and luster repeatability, known have the oxysome with color development development host to carry out coupling reaction, discharges the DIR colour coupler (coupler) of development restrainer.And know by containing these in the emulsion, utilize edge effect to improve clarity, utilize the double-layer effect to improve the color and luster repeatability, (for example, Patent Document 1).Yet, the DIR colour coupler of record in these special permissions, by with the coupling reaction of development host oxysome, discharge development restrainer, simultaneously also form the azomethine pigment, thus the use layer and the use amount of DIR colour coupler restricted greatly, so be the high technology of widespread use hardly.

As a kind of method that addresses this problem, a kind of scheme has been proposed, promptly, after development host oxysome coupling reaction, ask the nucleus substitution reaction in the molecule that nitrogen-atoms by origin autography host causes, form the cyclisation product, and discharge the DIR colour coupler (for example, Patent Document 2) of development restrainer.The DIR of record becomes mixture in this special permission, does not in fact form colour, owing to can discharge development restrainer, does not use layer and do not restrict, and can be described as the high technology of widespread use.

On the other hand, a kind of high sensitivity is disclosed, granular and clarity is good, the technology that pressure patience is good, be that the ISO sensitivity is at the photosensitive material more than 320, on the emulsion layer away from supporter, the diameter of equivalent circle that uses particle and the ratio (aspect ratio) of thickness are more than 5 and have a tabular particle (for example, Patent Document 3) of dislocation line.Yet, utilize this technology, DIR becomes mixture to be difficult to reach realization edge effect and double-layer effect, the DIR that puts down in writing in the above-mentioned special permission becomes the mixture performance, also be inadequate in the high sensitivity photosensitive material, so the technology before using is difficult to realize sufficient clarity and color and luster repeatability for the high sensitivity photosensitive material.

[Patent Document 1] spy opens flat 4-278942 communique

[Patent Document 2] Europe special permission 950922A1 instructions

[Patent Document 3] spy opens flat 5-341459 communique

Summary of the invention

The purpose of this invention is to provide a kind of high sensitivity, clarity, graininess are good, and the color and luster repeatability obtains abundant improved colour photographic sensitive material.

Present inventors found that and utilize following formation through further investigation, can reach above-mentioned purpose of the present invention.

(1) a kind of silver halide colour photographic sensitive material, have the unit sense indigo plant silver halide emulsion layer that 2 layer or more colour sensitivity layer constitute different on the supporter by each light sensitivity, unit sense green property silver halide emulsion layer and the red property of unit sense silver emulsion, it is characterized in that, this silver halide colour photographic sensitive material, at least contain a kind by the compound of remembering the expression of general formula (I) or general formula (II) down, and more than 60% of full projected area of contained silver halide particle at least 1 layer of this photosensitive emulsion layer, occupied at the tabular particle more than 5.0 by the diameter of equivalent circle of particle ratio with thickness.

[changing 2]

In the formula, R ₁Expression can be replaced in the substituting group on the naphthalene nucleus, and n represents the integer of 0-6, and n is 2 when above, each R ₁Can be the same or different.R ₂The expression alkyl or aryl.R ₁And R ₂Also can be in conjunction with forming ring.R ₃Be m the independent substituting group that closes with fragrant oxygen loops, all R ₃The summation of Hami special substituent constant σ p value elect as more than 0.1, herein, R ₃And R ₅Also can be in conjunction with forming ring.M represents the integer of 1-3.M is 2 or 3 o'clock, each R ₃Can be the same or different.R ₄Represent hydrogen atom, alkyl (comprising naphthenic base), alkenyl (comprising cycloalkenyl), alkynyl or aryl respectively separately with R5.INH represents mercapto-tetrazole derivant, mercapto-triazole derivant, dimercaptothiodiazole derivant, mercapto oxdiazole derivative, thyroidan derivant, Qiu oxazole derivatives, mercaptoimidazole derivant, sulfhydryl benzimidazole derivative, mercaptobenzothiazolderivative derivative, mercaptobenzoxazole derivant, terazole derivatives, 1,2,3-triazole derivative, 1,2, the residue of 4-triazole derivative or benzotriazole derivatives.

(2) according to the silver halide colour photographic sensitive material of putting down in writing in (1), it is characterized in that in the above-mentioned silver-halide color photoelement, more than 60% of the full projected area of at least 1 layer of contained silver halide particle in the photosensitive emulsion layer is to be occupied at the tabular particle more than 8.0 by the diameter of equivalent circle of the particle ratio with thickness.

(3) according to the silver halide colour photographic sensitive material of record in (1) or (2), it is characterized in that above-mentioned tabular silver halide particle, per 1 particle has 10 above dislocation lines.

(4) silver halide colour photographic sensitive material of each record in basis (1)-(3), it is characterized in that contained emulsion at least 1 layer of photosensitive emulsion layer of this silver halide colour photographic sensitive material, be with the tabular particle of (111) face as principal plane, the silver iodide containing ratio on the top layer of this tabular particle partly is I at principal plane ₁Mole % is I at lateral parts ₂During mole %, I ₂/ I ₁＜1 particle accounts for more than 50% of total silver halide particle projected area.

(5) according to the silver halide colour photographic sensitive material of each record in (1)-(4), the ISO light sensitivity that it is characterized in that above-mentioned silver halide colour photographic sensitive material is more than 640.

Embodiment

Below DIR colour coupler used in the silver halide colour photographic sensitive material of the present invention is elaborated.

In above-mentioned general formula (I) and the formula (II), R ₁It is the substituting group that can be replaced on the naphthalene; for example, as enumerating halogen atom; alkyl (comprises naphthenic base; bicyclic alkyl); alkenyl (comprises cycloalkenyl; bicyclic alkenyl); alkynyl; aryl; heterocyclic radical; cyano group; nitro; alkoxy; aryloxy group; heterocyclic oxy group; acyloxy; carbamoyloxy; alkyl oxy carbonyl oxygen; virtue oxygen carbonyl oxygen base; acylamino-; aminocarbonyl amino; alkoxycarbonyl amido; aryloxy carbonyl amino; sulfamoylamino group; alkyl and Arenesulfonyl amino; alkylthio group; arylthio; the heterocycle sulfenyl; sulfamoyl; sulfo group; alkyl and aryl sulfinyl; alkyl and aryl sulfonyl; acyl group; aryloxy carbonyl; alkoxy carbonyl group; carbamyl; imide; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino; silicyl.

More detailed saying, R ₁Expression halogen atom (for example, chlorine atom, bromine atoms, iodine atom), alkyl [replacement or the unsubstituted alkyl of expression straight chain, side chain, ring-type].Alkyl (the alkyl of preferred 1-30 carbon atom, for example, methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, eicosyl, the 2-chloroethyl, the 2-cyanoethyl, the 2-ethylhexyl), naphthenic base (replacement or the unsubstituted naphthenic base of preferred 3-30 carbon atom, for example, cyclohexyl, cyclopentyl, 4-dodecyl cyclohexyl), (preferred carbon number is replacement or the unsubstituted bicyclic alkyl of 5-30 to bicyclic alkyl, promptly, from being the dicyclo alkane of 5-30, removes carbon number the monad radical of 1 hydrogen atom, for example, dicyclo [1,2,2] heptane-2-base, dicyclo [2,2,2] octane-3-yl), also comprise ring structure tricyclic structure how etc.The following alkyl in Shuo Ming the substituting group (for example, the alkyl of alkylthio group) is also represented the alkyl of this conception of species], alkenyl [replacement or the unsubstituted alkenyl of expression straight chain, side chain, ring-type.(preferred carbon number is replacement or the unsubstituted alkenyl of 2-30 to alkenyl; for example; vinyl; allyl; isopentene; dragon ox base; oil base); (preferred carbon number is replacement or the unsubstituted cycloalkenyl of 3-30 to cycloalkenyl; promptly; remove carbon number and be the monad radical of a hydrogen atom of 3～30 loop chain shape alkene; for example; 2-cyclopentene-1-base; 2-cyclohexene-1-yl); bicyclic alkenyl (replaces or unsubstituted bicyclic alkenyl; preferred carbon number is replacement or the unsubstituted bicyclic alkenyl of 5-30; promptly; remove the monad radical of a hydrogen atom of dicyclo chain alkene with two keys; for example; dicyclo [2; 2; 1] hept-2-ene"-1-base; dicyclo [2; 2; 2] oct-2-ene-4-yl)]; (preferred carbon number is replacement or the unsubstituted alkynyl of 2-30 to alkynyl; for example; ethinyl; propinyl; the trimethyl silyl ethinyl); (preferred carbon number is replacement or the unsubstituted aryl of 6-30 to aryl; for example; phenyl; p-methylphenyl; naphthyl; the m-chlorphenyl; o-hexadecanoyl aminophenyl); heterocyclic radical is (preferably from the replacement of 5 yuan or 6 yuan or unsubstituted; remove the monad radical of a hydrogen atom in the heterogeneous ring compound of aromatic series or non-aromatic; also can aromatic rings such as benzene be arranged condensation; more preferably carbon number is 5 yuan or 6 yuan of aromatic heterocycles of 3-30; for example; the 2-furyl; the 2-thienyl; the 2-pyrimidine radicals; the 2-[4-morpholinodithio base; pyrrolidinyl; pyrrolidone-base; morpholinyl; morpholino); cyano group; nitro; (preferred carbon number is replacement or the unsubstituted alkoxy of 1-30 to alkoxy; for example; methoxyl; ethoxy; isopropoxy; tert-butoxy; n-octyloxy; the 2-methoxyethoxy); (preferred carbon number is replacement or the unsubstituted aryloxy group of 6-30 to aryloxy group; for example; phenoxy group; the 2-methylphenoxy; 4-tert-butyl group phenoxy group; the 3-nitro-phenoxy; 2-myristoyl amino-benzene oxygen); (preferred carbon number is replacement or the unsubstituted heterocyclic oxy group of 2-30 to heterocyclic oxy group; 1-phenyltetrazole-5-oxygen base; the 2-tetrahydro-pyran oxy); acyloxy (preferred formyloxy; carbon number is replacement or the unsubstituted alkyl carbonyl oxygen base of 2-30; carbon number is replacement or the unsubstituted aryl-carbonyl oxygen of 7-30; for example, formyloxy; acetoxyl group; propionyloxy; stearoyl-oxy; benzoyloxy group; p-anisyl carbonyl oxygen base); carbamoyloxy (replacement or the unsubstituted carbamoyloxy of preferred carbon number 1-30, for example; N; N-dimethylamino formyloxy; N, N-diethylamino formyloxy; morpholino carbonyl oxygen base; N, the amino carbonyl oxygen of N-two-n-octyl group base; N-n-octyl group carbamoyloxy); alkyl oxy carbonyl oxygen (replacement or the unsubstituted alkyl oxy carbonyl oxygen of preferred carbon number 2-30; for example; methoxy carbonyl oxygen base; ethoxy carbonyl oxygen base; tertiary butyloxycarbonyl oxygen base; n-octyl group carbonyl oxygen base); virtue oxygen carbonyl oxygen base (replacement or the unsubstituted fragrant oxygen carbonyl oxygen base of preferred carbon number 7-30; for example; phenoxy group carbonyl oxygen base; to methoxy phenoxy carbonyl oxygen base; to (n-hexadecane oxygen base) carbonyl phenoxy oxygen base); amide group (preferred, formoxyl amino; carbon number is replacement or the unsubstituted alkyl amide group of 2-30; carbon number is replacement or the unsubstituted aryl amido group of 7-30, for example; formamido group; acetylamino; propionamido; lauroyl amino; benzoyl amino; 3; 4,5-three-(the hot oxygen phenyl of n-) amide group); the aminoacyl amido (replacement or the unsubstituted aminoacyl amido of preferred carbon number 1-30, for example; carbamyl amino; N; N-dimethylamino amide group; N, N-lignocaine amide group; the morpholino amide group); the alcoxyl amide group (replacement or the unsubstituted alcoxyl amide group of preferred carbon number 2-30, for example; the methoxy amide group; the ethoxy amide group; uncle's fourth oxanamide base; n-octadecane oxanamide base; N-methyl-methoxy amide group); virtue oxanamide base (replacement or the unsubstituted fragrant oxanamide base of preferred carbon atom 7-30; for example, benzene oxanamide base; to the clofexan base; m-(n-octyloxy) benzene oxanamide base); sulfamoylamino group (replacement or the unsubstituted sulfamoylamino group of preferred carbon number 0-30, for example; sulfamoylamino group; N; N-dimethylamino sulfonamido; N-n-octyl group sulfamoylamino group); (preferred carbon atom is replacement or the unsubstituted alkyl sulfonamido of 1-30 for alkyl and Arenesulfonyl amino; carbon number is replacement or the unsubstituted Arenesulfonyl amino of 6-30, for example, and sulfonyloxy methyl amino; the butyl sulfonamido; the phenyl sulfonamido; 2; 3; 5-trichlorophenyl sulfonamido; p-aminomethyl phenyl sulfonamido); alkylthio group (replacement or the unsubstituted alkylthio group of preferred carbon number 1-30; for example, methyl mercapto; ethylmercapto group; n-hexadecane sulfenyl); arylthio (replacement or the unsubstituted arylthio of preferred carbon number 6-30, for example; thiophenyl; p-chlorobenzene sulfenyl; m-methoxy thiophenyl); heterocycle sulfenyl (replacement or the unsubstituted heterocycle sulfenyl of preferred carbon number 2-30; for example, 2-[4-morpholinodithio base sulfenyl; 1-phenyltetrazole-5-base sulfenyl); sulfamoyl (the replacement sulfamoyl of preferred carbon number 2-30 carbon atom, for example; N-(3-dodecane oxygen propyl group) sulfamoyl; N; N-dimethylamino sulfonyl, N-(N '-the phenyl amino formoxyl) sulfamoyl); sulfo group; alkyl and aryl sulfinyl (replacement or the unsubstituted alkyl sulfinyl of preferred carbon number 1-30; the replacement of carbon number 6-30 or unsubstituted aryl sulfinyl, for example; methyl sulfinyl; the ethylsulfinyl-1 base; the phenyl sulfinyl; p-aminomethyl phenyl sulfinyl); alkyl and aryl sulfonyl (replacement or the unsubstituted alkyl sulfonyl of preferred carbon number 1-30; the replacement of carbon number 6-30 or unsubstituted aryl sulfonyl; for example, methyl sulphonyl; ethylsulfonyl; phenyl sulfonyl; p-aminomethyl phenyl sulfonyl); acyl group (preferred formoxyl, the replacement of carbon number 2-30 or unsubstituted alkyl carbonyl; the replacement of carbon number 7-30 or unsubstituted aryl carbonyl; for example; acetyl group; propiono; the 2-chloracetyl; stearyl; benzoyl group; p-(n-octyloxy) phenylcarbonyl group); aryloxy carbonyl (replacement or the unsubstituted aryloxy carbonyl of preferred carbon number 7-30; for example; carbobenzoxy; o-chlorophenoxy carbonyl; m-nitro-phenoxy carbonyl; p-(tert-butyl group) phenyloxycarbonyl); alkoxy carbonyl group (replacement or the unsubstituted alkoxy carbonyl group of preferred carbon number 2-30, for example, methoxycarbonyl group; carbethoxyl group; tertbutyloxycarbonyl; n-octadecane oxygen carbonyl); carbamyl (replacement or the unsubstituted carbamyl of preferred carbon number 1-30; for example; carbamyl; N-methylamino formoxyl; N; the N-formyl-dimethylamino; N, N-two-(n-octyl group) carbamyl; N-(o-methoxyphenyl) carbamyl); N-(o-tetradecane oxygen phenyl) carbamyl); N-(p-acyl aminophenyl) anisyl) carbamyl); imide (preferred, the N-succinimide; N-phenol acid imide); (preferred carbon number is the replacement phosphinyl of 2-30 to phosphinyl; two octyloxy phosphinyls for example; the diethoxy phosphinyl); (preferred carbon number is the replacement phosphinyl oxygen base of 2-30 to phosphinyl oxygen base; two phenoxy group phosphinyl oxygen bases for example; two octyloxy phosphinyl oxygen bases); (preferred carbon number is the replacement phosphinyl amino of 2-30, for example dimethoxy phosphinyl amino to phosphinyl amino; dimethylamino phosphinyl amino); silicyl (preferred, the replacement silicyl of carbon number 3-30; for example, trimethyl silyl; t-butyldimethylsilyl; the phenyl dimetylsilyl).

Among the above-mentioned functional group, have the functional group of hydrogen atom, can remove behind the hydrogen atom and replaced by above-mentioned base again.As such functional group, can enumerate alkylamidoalkyl sulfonyl, aryl amido group sulfonyl, the amino carbonyl of alkyl sulfonyl, Arenesulfonyl amino carbonyl.As the example, can enumerate the amino carbonyl of sulfonyloxy methyl, p-aminomethyl phenyl sulfonyl-amino-carbnyl, acetylamino sulfonyl, benzoyl amino-sulfonyl.

R ₁Preferably halogen atom, cyano group, amide group, sulfamoyl, carbamyl are more preferably amide group, sulfamoyl, carbamyl, and good especially is carbamyl.

N represents the integer of 0-6, and n is 2 when above, each R ₁Can be identical, also can be different.N is preferably 1, at this moment, and R ₁Preferably in formula (I), replace on the α position of hydroxyl.

R ₂The expression alkyl or aryl.To being described in more detail of alkyl and aryl, with above-mentioned R ₁In the same meaning told about.R ₂Preferably carbon number is replacement or the unsubstituted alkyl of 1-30, is more preferably the unsubstituted alkyl of carbon number 1-20.R ₂Can with R ₁In conjunction with forming ring.Encircle preferably 5-7 unit ring.R ₃Meaning and above-mentioned R ₁In tell about identical, the summation of separately Hami special substituent constant σ p value is more than 0.1.

The summation of Hami special substituent constant σ p value is preferably 0.1-1.6,0.1-1.0 more preferably, and especially good is 0.2-0.8.This σ p value when this scope, the best time that can obtain disengaging development restrainer.When σ p value is the big value of forward, disengage constantly very slowly, during little value, understand too fast.

At this, the special substituent constant in the Hami of using in this instructions is done some explanations.The special principle in Hami is nineteen thirty-five, by the special a kind of principle of experience advocated in L.P. Hami, at reaction and the balance of benzene derivative, quantitatively discusses substituent influence, thinks that even to this day this principle of experience is widely effective.The substituent constant of obtaining according to the special principle in Hami has σ p value and σ m value, these most values all can find in general scientific and technological book, for example, " the chemical handbook of Lange " the 12nd edition in the J.A.Dean volume, 1979 (McGraw-Hill) and " chemical field " supplementary issue, No. 122,96-103 page or leaf all have detailed introduction in 1979 (Nan Guangtang).Though utilize Hami special substituent constant σ p to limit and illustrate each substituting group among the present invention, but this does not also mean that some substituting group that only limits to see, its value is arranged in the document in above-mentioned scientific and technological book, even also comprise in the document unknown its value certainly, but according to the special principle mensuration in Hami the time, fall into substituting group in its scope.From now on, σ p value, σ m value are just represented this meaning.

R ₃Be preferably selected from alkyl, alkenyl, halogen atom, cyano group, nitro, amide group, sulfamoyl, alkyl and aryl sulfinyl, alkyl and aryl sulfonyl, acyl group, aryloxy carbonyl.Alkoxy carbonyl group, carbamyl.Better be selected from halogen atom, cyano group, nitro, sulfamoyl, alkoxy carbonyl group.Preferably be selected from halogen atom, nitro.

R ₃And R ₅Also can be in conjunction with forming ring.This ring also can have substituting group, preferably 5-6 unit ring.

M represents the integer of 1-3, preferably 1,2.M is 2 or 3 o'clock, and each R3 can be identical, also can be different.

R ₄And R ₅Represent hydrogen atom, alkyl (comprising naphthenic base), alkenyl (comprising cycloalkenyl), alkynyl, aryl respectively separately.

More detailed saying, R ₄And R ₅Expression hydrogen atom, alkyl [replacement or the unsubstituted alkyl of expression straight chain, side chain, ring-type.Alkyl (the alkyl of preferred carbon number 1-8, for example, methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), naphthenic base (replacement or the unsubstituted naphthenic base of preferred carbon number 3-8, for example, cyclohexyl, cyclopentyl)], alkenyl [replacement or the unsubstituted alkenyl of expression straight chain, side chain, ring-type.Alkenyl (replacement or the unsubstituted alkenyl of preferred carbon number 2-8, for example, vinyl, allyl, isopentene), (replacement or the unsubstituted cycloalkenyl of preferred carbon number 3-8 promptly, are removed the monad radical of a hydrogen atom to cycloalkenyl in the loop chain alkene with carbon number 3-8.For example, 2-cyclopentene-1-base, 2-cyclohexene-1-yl)], alkynyl is (preferred, carbon number is replacement or the unsubstituted alkynyl of 2-8, for example, acetylene, propine, trimethyl silyl ethinyl), (preferred carbon number is replacement or the unsubstituted aryl of 6-12 to aryl, for example, phenyl, p-methylphenyl, naphthyl, m-chlorphenyl).

R ₄And R ₅Preferably hydrogen atom or alkyl.

In above-mentioned functional group,, further replace with following substituting group again after also hydrogen atom can being removed for functional group with hydrogen atom.Promptly; (for example can enumerate halogen atom; fluorine atom; the chlorine atom; bromine atoms; the iodine atom); sulfo group; cyano group; nitro; alkyl (for example; methyl; ethyl; hexyl); alkenyl (for example; vinyl); alkynyl (for example; ethinyl); aryl (for example; phenyl; tolyl; naphthyl); alkoxy (for example; methoxyl; ethoxy; octyloxy); aryloxy group (for example; phenoxy group; naphthoxy); acyl group (for example; acetyl group; propiono; benzoyl group); the alkyl or aryl sulfonyl (for example; mesyl; benzenesulfonyl); amide group (for example; acetamido; Benzamido); carbamyl (for example; carbamyl; N-amino-carbonyl; N; N-dimethylamino carbonyl; N-phenylamino carbonyl); alkoxy carbonyl group (for example; methoxycarbonyl group; carbethoxyl group; hot oxygen carbonyl); aryloxy carbonyl (for example; carbobenzoxy; naphthalene oxygen carbonyl); acyloxy (for example; acetoxyl group; benzoyloxy group); the alcoxyl amide group (for example; the methoxy amide group; fourth oxanamide base); aminoacyl amido (for example, N-methylamino amide group; N-phenylamino amide group).

INH represents mercapto-tetrazole derivant, mercapto-triazole derivant, dimercaptothiodiazole derivant, mercapto oxdiazole derivative, thyroidan derivant, Qiu oxazole derivatives, mercaptoimidazole derivant, sulfhydryl benzimidazole derivative, mercaptobenzothiazolderivative derivative, mercaptobenzoxazole derivant, terazole derivatives, 1,2,3-triazole derivative, 1,2, the residue of 4-triazole derivative or 124 Triazole derivant.

The residue of preferred expression mercapto-tetrazole derivant, mercapto-triazole derivant, dimercaptothiodiazole derivant, sulfydryl Er oxazole derivant.

Below show the residue concrete example of the said derivative of representing by INH, but the present invention is not limited to these.INH can be in following formula ^*Mark combines with the DIR colour coupler.

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Change 4

R in the formula ₆-R ₈Represent hydrogen atom or substituting group respectively separately.By R ₆-R ₈The substituent example of expression and above-mentioned by R ₁-R ₅The base of expression has under the situation of hydrogen atom, and it is identical that hydrogen atom is removed the example of enumerating as its substituting group when further replacing.P represents the integer of 0-4, preferred 0-2.

Below show the preferred example of the derivant that INH is provided, but be not limited to these.

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Below, list the compound concrete example with general formula (I) expression of the present invention, but be not limited to these.

[changing 22]

[changing 23]

[changing 24]

[changing 25]

[changing 26]

[changing 27]

[changing 28]

[changing 29]

[changing 30]

Below list the concrete example of the compound of representing with general formula (II) among the present invention, but be not limited to these.

[changing 31]

[changing 32]

[changing 33]

[changing 34]

[changing 35]

Below tell about the concrete synthetic method of coupling agent of the present invention.

The coupling agent of examples of compounds (24) is synthetic

Coupling agent according to following flow process synthetic compound example (24).

Change 36

The coupling agent of compound (24) is synthetic

Synthesizing of compound (24b)

To the ethyl acetate solution of compound 24a (10g) that uses the method identical to obtain and dimethylaniline (2.8g) (in 60 milliliters (following note is made " mL ") with the compound (41b) put down in writing in the European patent 950922A1 instructions, 10 ℃ are added carbonic acid two (trichloromethyl) ester (2.3g) down, stirred 2 hours.Reactant liquor is joined in acetonitrile (50mL)/1N salt sour water (50mL), stirred 1 hour.The crystallization that filtration is separated out after cleaning with acetonitrile, by drying, obtains compound 24b (10.2g).

Synthesizing of compound (24c)

In the toluene (80mL) and THF (20mL) mixed solution of compound 24b (10g) and 4-hydroxyl-3-nitro benzaldehyde (6.2g), add DBU (5.6g), at nitrogen stream, under 80 ℃, stirred 2 hours.After reactant liquor is cooled to 30 ℃, join in ethyl acetate (100mL)/1N salt sour water (200mL), carry out layering.Organic layer is cleaned with 5% aqueous sodium carbonate, and after dried over mgso, decompression concentrates down.To concentrate raffinate with silica gel chromatographic column (eluting solvent: ethyl acetate/normal hexane=1/2) make with extra care, obtain compound 24c (9.9g).

Synthesizing of compound (24d)

In the methyl alcohol (38mL) and tetrahydrofuran (8mL) mixed solution of compound 24c (9.5g), 10 ℃ are added sodium borohydride (0.95g) down, stirred 1 hour.Reactant liquor is joined in ethyl acetate (60mL)/1N salt sour water (120mL).The washing organic layer, after dried over mgso, concentrating under reduced pressure.With silica gel chromatographic column (eluting solvent: after ethyl acetate/normal hexane=1/1) refining,, obtain compound 24d (8.4g) by by acetonitrile crystallization again.

Synthesizing of compound (24e)

In methylene chloride (35mL) solution of compound 24d (8g), under 10 ℃, drip methylene chloride (15mL) solution of phosphorus tribromide (3.2g), stirred 4 hours.Reactant liquor is joined in ethyl acetate (200mL)/1N salt sour water (200mL).The washing organic layer, after dried over mgso, concentrating under reduced pressure.To concentrate raffinate with the crystallization again of ethyl acetate/acetonitrile system, obtain

Compound 24e (7.4g).

Synthesizing of compound (24)

To mercapto-tetrazole derivant A (3.1g) and N, in N,N-dimethylacetamide (30mL) solution of N-diisopropyl-N-ethamine (1.8g), under 10 ℃, add N,N-dimethylacetamide (20mL) solution of compound 24e (7g), 25 ℃ were stirred 2 hours down.Reactant liquor is joined in ethyl acetate (100mL)/1N salt sour water (100mL).Organic layer is cleaned with 5% aqueous sodium carbonate, after dried over mgso, concentrating under reduced pressure.By concentrating raffinate with silica gel chromatographic column (eluting solvent: ethyl acetate/normal hexane=1/2) make with extra care, obtain the example compound (24) (utilizing ultimate analysis, NMR and Mass spectrum to carry out compound identification) of 6.2g.

The coupling agent of examples of compounds (53) is synthetic

Coupling agent by following flow process synthetic compound example (53).

Change 37

The coupling agent of compound (53) is synthetic

Synthesizing of compound (53a)

In the toluene (220mL) of compound 24b (28g) and 2-hydroxyl-5-nitro benzaldehyde (22g) and THF (55mL) mixed solution, add DBU (20g), nitrogen stream, 80 ℃ were stirred 4 hours down.After reactant liquor is cooled to 30 ℃, join in ethyl acetate (300mL)/1N salt sour water (300mL), carry out layering.Organic layer is cleaned with 5% aqueous sodium carbonate, after dried over mgso, concentrating under reduced pressure.With concentrate with silica gel chromatographic column (eluting solvent: ethyl acetate/normal hexane=1/3) make with extra care, obtain compound 53a (26g).

Synthesizing of compound (53b)

In the methyl alcohol (120mL) and tetrahydrofuran (30mL) mixed solution of compound 53a (26g), 10 ℃ are added sodium borohydride (2.7g) down, stirred 1 hour.Reactant liquor is joined in ethyl acetate (300mL)/1N salt sour water (300mL).The washing organic layer, after dried over mgso, concentrating under reduced pressure.To concentrate raffinate with silica gel chromatographic column (eluting solvent: ethyl acetate/normal hexane=1/2) make with extra care after, with acetonitrile crystallization again, obtain compound 53b (16g) again.

Synthesizing of compound (53c)

In methylene chloride (80mL) solution of compound 53b (16g), 10 ℃ are added phosphorus tribromide (6.4g) down, stirred 8 hours.Reactant liquor is joined in ethyl acetate (300mL)/1N salt sour water (300mL).The washing organic layer, after dried over mgso, concentrating under reduced pressure.To concentrate raffinate with silica gel chromatographic column (eluting solvent: ethyl acetate/normal hexane=1/3) make with extra care, obtain compound 53c (13.1g).

Synthesizing of compound (53)

To mercapto oxdiazole derivative B (6.3g) and N, in N,N-dimethylacetamide (60mL) solution of N-diisopropyl-N-ethamine (4.6g), under 10 ℃, add N,N-dimethylacetamide (30mL) solution of compound 53c (13g), 25 ℃ were stirred 2 hours down.Reactant liquor is joined in ethyl acetate (200mL)/1N salt sour water (200mL), organic layer is cleaned with 5% aqueous sodium carbonate, after dried over mgso, concentrating under reduced pressure, to concentrate raffinate with silica gel chromatographic column (eluting solvent: ethyl acetate/hexane=1/3) make with extra care, obtain 9.1g example compound (53) (utilizing ultimate analysis, NMR and Mass spectrum to carry out compound identification).

Coupling agent (to call coupling agent of the present invention in the following text) with general formula (I) and formula (II) expression of the present invention can be used in any layer in the photosensitive material.Promptly; (for example can be used in photosensitive layer (feel indigo plant emulsion layer, the green property emulsion layer of sense, the red property emulsion layer of sense, divide the photo sensitivity distribution different double-layer effect alms giver (donor) layers), non-photosensitive layer with these main photosensitive layers; protective seam, yellow filtering layer, middle layer, anti-halo layer) in any layer.When same colour sensitivity layer be divided into sensitivity different more than 2 layers the time, described coupling agent can be added to high sensitivity layer, any layer in minimum sensitivity layer or the middle sensitivity layer also can add in all layers.Preferably be used in photosensitive layer and/or with the non-photosensitive layer of photosensitive layer adjacency in.

The consumption of coupling agent of the present invention in photosensitive material is 5 * 10 ^-4-2g/m ²Coating weight, be preferably 1 * 10 ^-3-1g/m ²Scope, more preferably 5 * 10 ^-3-5 * 10 ^-1G/m ²Scope.

About the use of coupling agent of the present invention, can adopt known any process for dispersing according to compound to photosensitive material.For example, can be used as under alkali-soluble situation that alkaline aqueous solution adds or be dissolved in organic solvent that water mixes in the form method of adding, or adopt oil droplet dispersion method, solid dispersion method etc. in the water of use high boiling organic solvent.

Coupling agent of the present invention can use separately, also can more than 2 kinds and use.Also can will be used for more than 2 layers with a kind of compound.And then, also can with the compound and the usefulness of other useful groups of known release photograph or its presoma, also can use with the coexistence of following coupling agent or other adjuvants.These can suitably be selected according to the performance requirement to photosensitive material.

The specific photograph sensitivity of colour photographic sensitive material of the present invention preferably more than 640, better more than 800, when using more than 1000, just realizes that effect of the present invention says, and is preferred especially.

Silver-colored amount in the colour photographic sensitive material of the present invention is preferably 6-10g/m ², 6-9g/m more preferably ²Said herein silver-colored amount is the amount that the amount of total silver such as silver halide and argent is converted into silver.Can use the silver-colored amount in known any methods analyst photosensitive material, though can use any method,, for example, the ultimate analysis of use fluorescent X-ray method etc. are the easiest.

The thickness of colour photographic sensitive material of the present invention is represented with the summation of the hydrophilic colloid layer holostrome of photonasty silver halide emulsion layer on the supporter.Thickness preferably more than 22 μ m, 23-27 μ m more preferably.

The mensuration of thickness is to use scanning electron microscope, and pair cross-section carries out macrophotography and tries to achieve.

Used colour photographic sensitive material among the present invention, preferably on supporter, has the red property of unit sense silver halide emulsion layer, the green property of unit sense silver halide emulsion layer, unit sense indigo plant silver halide emulsion layer, and constituent parts colour sensitivity layer is made of the different silver halide emulsion layer more than 2 layers of sensitivity, the total projection area of contained silver halide particle is more than 60% in one deck at least of this emulsion layer, the tabular silver halide particle of ratio more than 5.0 that is diameter of equivalent circle and the thickness of particle occupies, the diameter of equivalent circle of this particle is preferred more than 8.0 with the ratio of thickness, better more than 10.0, be preferably in more than 12.0.The upper limit as the diameter of equivalent circle of particle and the ratio of thickness is preferably 200.The diameter of equivalent circle of so-called particle is the area diameter projected income value that removes this particle with the thickness of particle with the ratio of thickness.When too small, sensitivity is very low with the ratio of thickness for the diameter of equivalent circle of particle; When excessive,, cause sensitivity reduction, pressure patience, storage stability to worsen by the intrinsic desensitization that pigment causes, very undesirable.

Below tabular silver halide particle used among the present invention is elaborated.

The composition of the tabular silver emulsion that the present invention is used does not have particular restriction, but can preferably use the tabular particle emulsion of iodine silver bromide or chlorine iodine silver bromide.

Among the present invention, tabular silver halide particle (below be also referred to as dull and stereotyped particle) is meant the silver halide particle of the principal plane with 2 relative parallel (111).Dull and stereotyped particle of the present invention has 1 twin plane or the parallel double crystal face more than 2.So-called twin plane is meant when the whole lattice-site ion in the both sides of (111) face exists mirror image to concern, should just be called twin plane by (111) face.

This flat board particle during from particle, presents triangle, hexagonal configuration, or they have the toroidal of fillet, has parallel each other outside surface.

The area diameter projected and the thickness of dull and stereotyped particle are to utilize replica method to take the TEM photo, obtain to have to be equal to the diameter of a circle (area diameter projected) of area and thickness with each particle projected area and to obtain.At this moment, thickness is to be calculated by the length gauge that duplicates image (shade).

Used silver halide particle among the present invention, its area diameter projected is preferably 0.2-20 μ m, 0.3-15 μ m more preferably, especially good is 0.6-10.0 μ m.

The diameter that is equivalent to ball is preferably 0.2-5.0 μ m, more preferably 0.6-4 μ m.What is called is equivalent to the diameter of ball, is meant the diameter that has with the isopyknic ball of each particle volume.

Emulsion of the present invention is preferably monodispersed.The coefficient of alteration of the diameter that is equivalent to ball of all silver halide particles of the present invention is below 30%, preferably below 25%.During the flat board particle, the coefficient of alteration of area diameter projected is also very important, and the coefficient of alteration of the area diameter projected of all silver halide particles of the present invention is preferably below 30%, better below 25%.The coefficient of alteration of the thickness of dull and stereotyped particle is preferably below 30%, better below 25%.So-called coefficient of alteration is to remove the value that the distribution standard deviation of each silver halide particle equivalent diameter obtains with average equivalent diameter, perhaps, with the distribution standard deviation income value of average thickness except that each dull and stereotyped particle thickness, multiply by 100 value again.

The twin plane spacing of the dull and stereotyped particle that emulsion of the present invention is contained, can suitably select as requested, preferably below the 0.012 μ m that puts down in writing in No. 5219720 instructions of United States Patent (USP), maybe can put down in writing, the ratio of (111) principal plane spacing/twin plane spacing is taken as more than 15 as special opening in the flat 5-249585 communique.

Coefficient of alteration as the twin plane spacing of all dull and stereotyped particles of emulsion of the present invention is preferably 3-25%, 3-20% more preferably, and especially good is 3-15%.The coefficient of alteration of so-called twin plane spacing is deviation (standard deviation) income value that removes the twin plane spacing thickness of each tabular particle with average twin plane spacing, takes advantage of 100 value again.The coefficient of alteration that the twin plane spacing of master plate shape particle distributes surpasses at 25% o'clock, and interparticle homogeneity is very bad, is lower than at 3% o'clock, is difficult to modulate emulsion.

Among the present invention, the silver iodide containing ratio in the silver halide particle is for the total silver amount in the particle, and preferred 0.5 mole more than the %, below the solid solution boundary, more preferably 1-20 mole %.The silver chloride containing ratio is for the total silver amount in the particle, preferred 0-10 mole %.

Among the present invention, the top layer of so-called silver halide particle is meant to comprise the silver halide particle surface, from this silver halide particle surface to the dark silver halide layer of 5nm.The top layer of the principal plane part of so-called dull and stereotyped particle, be meant from the profile of principal plane in face inboard more than the 10nm, and to the dark particle inside of 5nm, the top layer of so-called lateral parts, be meant from the profile of particle side in face inboard more than the 10nm, and to the dark particle inside of 5nm.

Among the present invention, the silver iodide containing ratio on the top layer of so-called silver halide particle is meant and uses said method, the arithmetic mean of the silver iodide containing ratio that 5 positions on top layer are measured.In the top layer of principal plane part silver iodide containing ratio is measured, the spacing between 5 position measuring points, reach measure particle be equivalent to more than 1/10 of circular diameter.During the top layer of lateral parts was measured, the measuring point spacing at 5 positions reached and measures more than 1/10 of particle thickness.

Among the present invention, adopt following method, measure the principal plane part of silver halide particle, the silver iodide containing ratio on the respectively top layer of lateral parts.

With dull and stereotyped particle, be cut into disc perpendicular to principal plane, make on the cross section principal plane part and the lateral parts on top layer all have 2 respectively, and measure from cross-wise direction irradiation electron ray, promptly, the particle that utilizes centrifuging to take out from emulsion or photosensitive material is coated on the triacetyl cellulose supporter, uses the resin embedding particle again., be positioned on the copper mesh that posts support membrane from this sample cutting 50nm slab with the ultra-thin section cutter.

With analytical electron microscope spot diameter (diameter) is narrowed down to the following point of 2nm and analyze, to measure the silver iodide containing ratio in this particle established part.Silver halide particle to known containing ratio is handled equally, makes inspection amount line, by obtaining the ratio of Ag intensity and I intensity in advance, calculates the silver iodide containing ratio.As the analysis line source of analytical electron microscope, it is thermionic better than using to use electron-dense electric field emission type electron gun, and by spot diameter is narrowed down to below the 1nm, the halogen that can analyze small part is at an easy rate formed.

When dull and stereotyped particle being cut into disk perpendicular to principal plane, but the position of the circle of contact where no matter be present in, as long as undertaken by the said determination method just no problem, can be at any position circle of contact.

Silver halide particle of the present invention, the silver iodide containing ratio with top layer partly is taken as I at principal plane ₁Mole % is taken as I at lateral parts ₂During mole %, I ₂/ I ₁＜1 tabular silver halide particle occupies more than 50% of total silver halide particle projected area contained in the emulsion layer.

And then, I ₁And I ₂Relation, preferred I ₂/ I ₁＜0.8, better I ₂/ I ₁＜0.6, best I ₂/ I ₁＜0.4.

In addition, I ₁Do not comprise 0 mole of %, preferably less than 30 moles of %, better at 8-20 mole %, on the other hand, I ₂Comprise 0 mole of %, preferably less than 7 moles of %.

Present inventors found that through further investigation the above-mentioned silver halide particle that uses among the present invention is by improving clarity and color and luster repeatability with the invention described above combination of compounds.

Below the modulator approach of silver emulsion of the present invention is told about in detail.

Modulated process as silver halide emulsion particles of the present invention comprises (a) fundamental particle forming process and this process particle forming process (b) of carrying out and then.(b) process can be that (b1) imports dislocation process, (b2) and limit the importing process of bight dislocation or (b3) any process in the extension cohesive process, can be at least one process wherein, also can be the combination of two above processes.

At first, (a) fundamental particle forming process is described.Used silver amount during fundamental particle forms, the final total silver amount with respect to using in particle forms can adopt any value, is preferably 20-95%, more preferably more than the 30-90%.The average silver iodide containing ratio of fundamental particle can be below 0-30 mole %, below the preferred 0-25 mole %, more preferably below the 0-20 mole %.As required, fundamental particle also can form core/shell structure.

The growth of fundamental particle can be undertaken by two gunitees that silver salt solution and halogen aqueous solution are added simultaneously, at this moment, in order to prevent because of the iodide ion skewness causes the growth dislocation, preferred stirring reaction container and the dilution concentration of adding solution equably.And the pAg when improving growth also is preferred.At this moment, pAg is preferably more than 7.0, more preferably more than 7.4.

Preferred method is when adding silver salt solution and halogen aqueous solution, is added on the silver iodide particulate of reaction vessel external modulation simultaneously.At this moment, the preferred 50-90 of growth temperature ℃, more preferably 60-85 ℃.The silver iodide particulate that adds can be modulated, in advance Yi Bian Yi Bian also can modulate interpolation continuously.The modulator approach of this moment can be opened the method for putting down in writing in the flat 10-43570 communique with reference to the spy.

The silver iodide particulate average particle size that adds is 0.01-0.1 μ m, is preferably 0.02-0.08 μ m.The silver iodide containing ratio of fundamental particle can change according to the amount of the silver iodide particulate that adds.

Also can add iodine silver bromide particulate, to replace adding silver salt solution and halogen aqueous solution.At this moment, be equal to the silver iodide amount of required fundamental particle, can obtain to have the fundamental particle of required silver iodide containing ratio by the silver iodide amount that makes particulate.Iodine silver bromide particulate can be modulated in advance, but preferably the limit interpolation is modulated on the limit continuously.The average particle size of the iodine silver bromide particulate that adds is 0.005-0.05 μ m, is preferably 0.01-0.03 μ m.Temperature during growth is 60-90 ℃, preferred 70-85 ℃.

Below (b) process is described.

At first, (b1) process is described.(b1) process comprises the 1st shell process and the 2nd shell process.On above-mentioned fundamental particle surface, the 1st shell is set.With respect to final total silver amount used in particle forms, the ratio of the 1st shell is 1 mole of %-10 mole % preferably, and its average silver iodide containing ratio is 20 moles of %-100 mole %.With respect to total silver amount, the ratio of the 1st shell is more preferably 1 mole of %-5 mole %, and its average silver iodide containing ratio is 25 moles of %-100 mole %.The 1st shell is with two gunitees to the growth of fundamental particle basically, adds silver nitrate aqueous solution and the halogen aqueous solution that contains iodide and bromide.Perhaps, with two gunitees, add silver nitrate aqueous solution and the halogen aqueous solution that contains iodide.Perhaps, with single gunite, add the halogen aqueous solution that contains iodide.

Can use above any method, also can be their combination, from the average silver iodide containing ratio of the 1st shell as can be known, when forming the 1st shell, except iodine silver bromide mixed crystal, also can separate out silver iodide.Under any circumstance, usually, when then forming the 2nd shell, silver iodide disappear, and all become iodine silver bromide mixed crystal.

As the method for optimizing that forms the 1st shell, the iodine silver bromide of interpolation or silver iodide particulate are arranged, carry out the method for slaking dissolving.And then, as preferable methods, the silver iodide of interpolation particulate is arranged, add the method for silver nitrate aqueous solution or interpolation silver nitrate aqueous solution and halogen aqueous solution subsequently.In this case, owing to added silver nitrate aqueous solution, promoted the dissolving of silver iodide particulates, still, as the 1st shell, making silver iodide containing ratio wherein is 100 moles of % with the silver amount of the silver iodide particulate that adds.Calculate the silver nitrate aqueous solution of interpolation, with it as the 2nd shell.The silver iodide particulate preferably adds rapidly.

What is called is added the silver iodide particulate rapidly, is meant that total silver iodide particulate that the formation shell is used added in 10 minutes, had more preferably added in 7 minutes.This condition can be according to kind, the concentration of protecting colloid agent such as the temperature of adding system, pBr, pH, gelatin, have or not ag halide solvent, kind, and concentration etc. change, and as mentioned above, the time is short more good more.During interpolation, preferably do not add silver salt solutions such as silver nitrate in fact.During interpolation the preferred 40-90 of the temperature of system ℃, more preferably 50-80 ℃.

The silver halide grains of using among the present invention, in fact, preferably silver iodide are limited to when forming mixed crystal, also can contain silver bromide and/or silver chloride.100% silver iodide preferably.Silver iodide can obtain β body, γ body and the α body of No. 4672026 record of United States Patent (USP) or the crystalline texture of similar α body.Among the present invention, its crystalline texture is not had particular restriction, can use the potpourri of β body and γ body, preferably use the β body.The silver iodide particulate can be that No. the 5004679th, United States Patent (USP) waits in the instructions and puts down in writing, form before adding, also can be through common water-washing process, any can.Among the present invention, the preferred emulsion particles that uses through common water-washing process.The silver iodide particulate can use United States Patent (USP) to wait for No. 4672026 the method for putting down in writing in the instructions to be easy to form.PI value when preferred employing forms particle keeps constant and carries out the silver salt solution of particle formation and two injection additive processs of iodide salt aqueous solution.Herein, pI is the logarithm of the I-ion concentration inverse of system.Do not have particular restriction for the having or not of the kind of protecting colloid agent such as temperature, pI, pH, gelatin, concentration, ag halide solvent, kind, concentration etc., but the size of particle more preferably below 0.07 μ m, will be more suitable for the present invention below 0.1 μ m.Owing to be particulate, the shape of particle can not be specific fully, but the coefficient of alteration of particle size distribution is preferably below 25%.Particularly 20% when following, and effect of the present invention is remarkable.Herein, the size of silver iodide particulate and Size Distribution are that the silver iodide particulate is positioned in online that electron microscope observation uses, and do not adopt the carbon replica method, try to achieve but directly utilize penetrant method to observe.This is because particle size is very little, so utilize the carbon replica method to observe the cause that will produce very big error at measurment.Particle size is defined as to have with the observation particle and is equal to the projected area diameter of a circle.About the distribution of particle size, also use this to be equal to the projected area circular diameter and try to achieve.The most effective silver iodide particle size is below 0.06 μ m among the present invention, and more than the 0.02 μ m, the coefficient of alteration of particle size distribution is below 18%.

The silver iodide particulate after above-mentioned particle forms, preferably waits the concentration that common washing and protecting colloid agent such as adjustment pH, pI, gelatin are carried out in record in the instructions for No. 2614929 according to United States Patent (USP), and the silver iodide concentration that contains is adjusted.PH is preferably 5-7.The pI value is preferably set to the solubleness that makes silver iodide and reaches minimum pI value, perhaps high than this value pI value.As the protecting colloid agent, preferably using mean molecular weight is about 100,000 common gelatin.The better mean molecular weight that uses is at the low molecular weight gelatine below 20,000.Use if the gelatin that above-mentioned molecular weight is different mixes, obtain effect preferably sometimes.The gelatin amount of every 1kg emulsion is preferably 10-100g, more preferably 20-80g.The silver amount that converts with silver atoms of every 1kg emulsion is preferably 10-100g, more preferably 20-80g.Gelatin amount and/or silver amount, the preferred value of selecting to be suitable for adding rapidly the silver iodide particulate.

The emulsion that contains the silver iodide particulate, normally add the dissolving back in advance, but must fully improve the stirring efficiency of system when adding.The stirring rotation number of setting preferably is higher than common revolution.Produce bubble in order to prevent to stir, it is effective adding defoamer.Specifically can use the embodiment of No. 5275929 instructions of United States Patent (USP) to wait the defoamer of telling about.

As the better method that forms the 1st shell, can use the iodide ion releasing agent of putting down in writing in No. 5496694 instructions of United States Patent (USP), to replace iodide ion in the past to supply with method (adding the method for free iodide ion), Yi Bian form the silver halide phase that contains silver iodide on one side generate iodide ion rapidly.

The iodide ion releasing agent, by with the reaction of iodide ion release regulator (alkali and/or nucleopilic reagent), discharge iodide ion, but can enumerate following chemical species as the nucleopilic reagent that uses this moment.For example can enumerate hydroxide ion, sulfurous acid ion, hydramine, thiosulfuric acid ion, pyrosulfurous acid ion, hydroximic acid, oximes, dihydroxy benzenes class, thio-alcohol, sulfinate, carboxylate, ammonia, amine, alcohols, urea class, Thiourea, phenols, hydrazine class, hydrazides class, Semicarbazido class, phosphine class, sulfide-based.

By concentration, adding method or the reacting liquid temperature of control alkali or nucleopilic reagent, can control release rate, the release time of iodide ion.As alkali alkaline hydrated oxide preferably.

The preferred concentration range for that generates used iodide ion releasing agent of iodide ion and iodide ion release regulator rapidly is 1 * 10 ^-7-20M, more preferably 1 * 10 ^-5-10M, more preferably 1 * 10 ^-4-5M, be preferably 1 * 10 especially ^-3-2M.

When concentration surpasses 20M, the iodide ion releasing agent that molecular weight is big and the addition of iodide ion releasing agent, with respect to the capacity of particle formation container, can be too many, so undesirable.

When being lower than 1 * 10 ^-7During M, iodide ion release reaction speed can slow down, and is difficult to generate the iodide ion releasing agent rapidly, so also undesirable.

Preferred temperature range is 30-80 ℃, more preferably 35-75 ℃, is preferably 35-60 ℃ especially.

Under temperature surpassed 80 ℃ high temperature, the release reaction speed of iodide ion can be exceedingly fast usually, and had been lower than under 30 ℃ the low temperature, and the release reaction speed of iodide ion is extremely slow again usually, and service condition is restricted, extremely undesirable respectively.

When discharging iodide ion, use under the situation of alkali, also can utilize the pH of solution to change.At this moment, the fine control iodide ion release rate of energy, the pH preferable range of release time are 2-12, and more preferably 3-11 is preferably 5-10 especially, most preferably are that the pH after regulating is 7.5-10.0.Under the neutrallty condition of pH7, utilize the hydroxide ion of the ionic product decision of water to play the effect of correctives.

Also at this moment nucleopilic reagent and alkali and usefulness, also can be controlled at pH in the above-mentioned scope release rate, the release time of control iodide ion.

Discharge the iodine atomic time with the iodide ion form from the iodide ion releasing agent, can discharge whole iodine atoms, a part is not decomposed and residual.

On the above-mentioned dull and stereotyped particle that is provided with the 1st shell, the 2nd shell is set further, for being used for final total silver amount that particle forms, the ratio of the 2nd shell is 10-40 mole %, its average silver iodide containing ratio is 0-5 mole %, for total silver amount, the ratio of the 2nd shell is 15-30 mole % more preferably, and its average silver iodide containing ratio is 0-3 mole %.Be provided with the 2nd shell of growing on the dull and stereotyped particle of the 1st shell, can be on the direction of the diameter of equivalent circle that improves this flat board particle particle and the ratio of thickness, also can on the direction of the diameter of equivalent circle that reduces particle and the ratio of thickness, grow.Basically say, add silver nitrate aqueous solution and the halogen aqueous solution that contains bromide, carry out the growth of the 2nd shell by two gunitees.Perhaps, after interpolation contains the halogen aqueous solution of bromide, add silver nitrate aqueous solution with single gunite.Kind, concentration, the ag halide solvent of protecting colloid agent such as the temperature of system, pH, gelatin has or not, kind, concentration etc. can change in wide range.For pBr, among the present invention, the pBr when the 2nd hull shape become to finish, the pBr when preferably being higher than the 2nd hull shape and becoming the initial stage.PBr when the 2nd hull shape becomes the initial stage is preferably below 2.9, and the pBr when the 2nd hull shape becomes to finish is preferably more than 1.7.More preferably the 2nd hull shape become the initial stage pBr below 2.5, the pBr when the 2nd hull shape become to finish is more than 1.9.Most preferably, the 2nd hull shape becomes the pBr at initial stage below 2.3, more than 1.PBr when preferably, the 2nd hull shape becomes to finish is more than 2.1, below 4.5.

In (b1) procedure division, preferably there is dislocation line.

About the dislocation line of dull and stereotyped particle, for example can be according to J.F.Hamilton, Phot.Sci.Eng., 11,57 (1967) or T.Shiozawa, J.Soc.Phot.Sci.Japan, the method of using infiltration type electron microscope Direct observation at low temperatures of record in 35,213 (1972).Promptly, for making particle not be subjected to producing the pressure of dislocation line degree, from emulsion, take out silver halide particle carefully, then it is positioned in electron microscope observation with online, and for the damage that prevents to cause (printing output etc.) by electron ray under the state of cooling samples, utilize penetrant method, observe, at this moment, the thickness of particle is thick more, and electron ray is difficult to see through more, so utilize high-pressure type (for the thick particle of 0.25 μ m, accelerating potential is more than 200KV) electron microscope, can observe more clearly.

By the photo of the particle that utilizes this method gained,, obtain the position and the quantity of dislocation line to each particle when seeing perpendicular to the direction of principal plane.Dislocation line preferably is present near the edge part of dull and stereotyped particle.Near the so-called edge part, being hexagon outer peripheral portion (marginal portion) and its inside part of dull and stereotyped particle, that is, is the part of growing in (b1) process.The dislocation line that is present in edge part, preferably per 1 particle is average more than 10, and it is average more than 20 to be more preferably per 1 particle.If intensive existence of dislocation line or dislocation line intersect mutually, when then observing, can not count the dislocation line number of clear per 1 particle sometimes exactly.But, even in this case, also can count to roughly degree such as 10,20,30, can exist several situation to differentiate clearly with having only.Average about the dislocation line number of per 1 particle can go out the dislocation line number to 100 above populations, and it is average to obtain its number.

Below describe about the importing process that limits the bight dislocation.

As first kind of form, have only to utilizing the method for iodide dissolving near the summit; As second kind of form, the method for adding silver salt solution and iodide salt solution is simultaneously arranged; As the third form, near the only method to dissolving the summit of ag halide solvent of using is arranged; As the 4th kind of form, the method through the halogen conversion is arranged.

Below, describe about the method for utilizing iodide ion dissolving of first kind of form.

When adding iodide ion in fundamental particle, dissolving has fillet near each apex of fundamental particle.Then, add liquor argenti nitratis ophthalmicus and bromide solution simultaneously, perhaps, the mixed liquor of liquor argenti nitratis ophthalmicus and bromide solution and iodide solution makes the particle further growth, imports dislocation in the vicinity, summit.About this method, can open flat 4-14954 number and special opening put down in writing in flat 9-189974 number each communique with reference to the spy.

In this form, the iodide ion total amount of being added will be removed this iodide ion total mole number income value with total silver amount molal quantity of fundamental particle and take advantage of 100 value as I again ₁₀₂When (mole %), effectively dissolve angle from obtaining the present invention, with respect to the silver iodide containing ratio I of fundamental particle ₁₀₁(mole %), (I ₁₀₂-I ₁₀₁) preferably satisfy 0-8, more preferably 0-4.

In this form, the iodide ion concentration of interpolation is preferably low, specifically, concentration preferably below 0.2 mol, 0.1 mol more preferably.

In addition, the pAg when adding iodide ion is preferred more than 8.0, more preferably more than 8.5.

Add iodide ion, after the apex of dissolving fundamental particle, continue to add separately liquor argenti nitratis ophthalmicus, perhaps, add liquor argenti nitratis ophthalmicus and bromide solution simultaneously, or, the mixed liquor of liquor argenti nitratis ophthalmicus and bromide solution and iodide solution, make the particle further growth, near the summit, import dislocation.

The method of adding silver salt solution and iodide salt solution in the time of about second kind of form describes.With respect to fundamental particle, add silver salt solution and iodide salt solution rapidly, can make silver iodide or silver iodide contain the high silver halide of rate and carry out the extension generation in the apex of particle.At this moment, the best interpolation time of silver salt solution and iodide salt solution is 0.2-0.5 minute, more preferably 0.5-2 minute.About this method, can open write up in the flat 4-149541 communique with reference to the spy.

After adding the apex of silver salt solution and iodide salt solution dissolving fundamental particle simultaneously, continue to add separately liquor argenti nitratis ophthalmicus, perhaps, add liquor argenti nitratis ophthalmicus and bromide solution simultaneously, or, the mixed liquor of liquor argenti nitratis ophthalmicus and bromide solution and iodide solution makes the particle further growth, is importing dislocation near the place, summit.

Method about the use ag halide solvent of the third form describes.

After joining ag halide solvent in the dispersion medium that contains fundamental particle, add silver salt solution and iodide salt solution simultaneously, make in the fundamental particle apex by the ag halide solvent dissolving, silver iodide or silver iodide contain the high silver halide preferred growth of rate.At this moment, there is no need to add rapidly silver salt solution and iodide salt solution.About the method, can open write up in the flat 4-149541 communique with reference to the spy.

After adding ag halide solvent dissolving fundamental particle apex, continue to add separately liquor argenti nitratis ophthalmicus, perhaps add liquor argenti nitratis ophthalmicus and bromide solution simultaneously, the perhaps mixed liquor of liquor argenti nitratis ophthalmicus and bromide solution and iodide solution, make the particle further growth, importing dislocation near the place, summit.

Below describe about the method for passing through the halogen conversion of the 4th kind of form.

This method is, by in fundamental particle, adding epitaxial growth position supporting agent (below be called the side direction body), for example special sensitizing coloring matter and the water-soluble iodate thing of putting down in writing in the clear 58-108526 communique of opening, and delay at apex formation the outer of silver chloride of fundamental particle, add iodide ion again, the method that makes silver chloride carry out the halogen conversion to silver iodide or the high silver halide of silver iodide containing ratio.The side direction body can be a sensitizing coloring matter, also can be water-soluble thiocyanate ion, but preferably water-soluble iodate thing ion.Employed iodide ion is 0.0005-1 mole % for fundamental particle, is preferably 0.001-0.5 mole %.After adding iodide ion, add silver salt solution and chloride salt solution simultaneously, thereby form the silver chloride of extension in the apex of fundamental particle.

Describe about the halogen conversion that forms by iodide ion.By adding halide ion, make the big silver halide of solubleness form the littler silver halide of solubleness, be transformed into the littler silver halide of solubleness.This process is called the halogen conversion, and is for example, on the books in No. 4142900 instructionss of United States Patent (USP).Utilize iodide ion among the present invention,, form the silver iodide phase in the fundamental particle apex portion by to carrying out the halogen conversion selectively at the epitaxially grown silver chloride of the apex portion of fundamental particle.Seeing the spy for details opens and puts down in writing in the flat 4-149541 communique.

By adding iodide ion, make at the epitaxially grown silver chloride of fundamental particle apex portion after silver iodide carry out the halogen conversion mutually, then add liquor argenti nitratis ophthalmicus separately, perhaps add liquor argenti nitratis ophthalmicus and bromide solution simultaneously, or the mixed liquor of liquor argenti nitratis ophthalmicus and bromide solution and iodide solution, make the particle further growth, importing dislocation near the place, summit.

The particle that forms in (b2) process is partly gone up and is preferably had dislocation line.Dislocation line preferably is present near the bight of dull and stereotyped particle.Near the so-called bight, be meant that there is the location point of X% at the straight line center that is formed by connecting from center and each summit with particle, when drop wire is made on the limit that forms each summit, centers on the three-D part that forms by this vertical line and this limit.The preferred 50-100 of this X value, more preferably 75-100.The dislocation line that is present in edge part preferably on average has more than 10 in per 1 particle, and more preferably per 1 particle on average has more than 20.If intensive existence of dislocation line or dislocation line intersect mutually, then when observing, can not accurately count to the dislocation line number of per 1 particle sometimes.But, even in this case, also can count to roughly degree such as 10,20,30, can exist several situation to differentiate clearly with having only.Average about the dislocation line number of per 1 particle can go out the dislocation line number to 100 above populations, and it is average to obtain its number.

Below (b3) extension engaging process is described.

Form mutually about silver halide epitaxy to fundamental particle, as putting down in writing in No. 4435501 instructions of United States Patent (USP), select the position of silver salt epitaxy by being adsorbed on side direction bodies such as the lip-deep iodide ion of fundamental particle, aminoazaindene or beam split sensitizing coloring matter, for example can form in the edge or the bight of fundamental particle.In the Te Kaiping 8-69069 communique, on the selecteed position of slab-foundation particle as thin as a wafer, form the silver salt epitaxy phase, because this extension is on good terms and carries out optimum chemical sensitization, so reached high sensitization.

Among the present invention, particularly preferably be, use these methods to make fundamental particle of the present invention carry out height and help to change.The side direction body can use amino azaindene, or the beam split sensitizing coloring matter, but more preferably uses iodide ion or thiocyanate ion.

By changing the addition of iodide ion or thiocyanate ion, the formation position of silver salt epitaxy phase can be limited to the edge or the bight of fundamental particle.

The addition of iodide ion is 0.0005-1.0 mole % for the silver amount of fundamental particle, is preferably 0.001-0.5 mole %.The amount of thiocyanate ion is 0.01-0.2 mole % for the silver amount of fundamental particle, is preferably 0.02-0.1 mole %.

After having added these side direction bodies, add silver salt solution and chloride salt solution again, form silver chloride extension phase.The temperature of this moment is preferably 40-70 ℃, more preferably 45-60 ℃.The pAg of this moment is preferably below 7.5, better below 6.5.By using the side direction body, can be in the bight of fundamental particle, or edge part forms the extension phase of silver chloride.For the emulsion that obtains like this, open flat 8-69069 communique record according to the spy, can implement the chemical sensitization height to extension phase selectivity ground helps to change and its height is helped to change, but also can form the silver chloride extension mutually after, continue to add simultaneously silver salt solution and halide salt solution, further growth, further height helps to change.At this moment the halogen aqueous solution of Tian Jiaing is a bromide salt solution, or the mixed liquor of bromide salt solution and iodide salt solution.The temperature of this moment is preferably 40-80 ℃, more preferably 45-70 ℃.The pAg of this moment is preferably 5.5-9.5, more preferably 6.0-9.0.

The extension phase that forms in (b3) process is characterized in that, basically, on the fundamental particle outside that forms, forms formation with the halogen different with fundamental particle in (a) process.The composition of extension phase is AgCl, AgBrCl or AgBrCl I preferably.More preferably, import special " adulterant (metal complex) " put down in writing in the flat 8-69069 communique of opening in extension on mutually.The position that extension is grown mutually can be at least a portion in the bight, edge part, principal plane portion of fundamental particle, also can be to stride a plurality of positions.Preferably choose just bight, or be edge part, the perhaps form of bight and edge part.

In the part of (b3) process, can there be dislocation line, but more preferably has dislocation line.Dislocation line preferably is present in the junction surface of fundamental particle and epitaxial growth portion, or epitaxy part.The dislocation line that is present in junction surface or epitaxy part on average has more than 10 in preferred per 1 particle, and being more preferably in per 1 particle on average has more than 20.If intensive existence of dislocation line or dislocation line intersect mutually, then when observing, can not accurately count to the dislocation line number of per 1 particle sometimes.But, even in this case, also can count to roughly degree such as 10,20,30, can exist several situation to differentiate clearly with having only.Average about the dislocation line number of per 1 particle can go out the dislocation line number to 100 above populations, and it is average to obtain its number.

Dull and stereotyped particle of the present invention, interparticle dislocation line quantity is preferred evenly to distribute.In the emulsion of the present invention, the silver halide particle that per 1 particle contains 10 above dislocation lines accounts for the 100%-50% (number) of all particles, preferred 100-70%, preferred especially 100-90%.

When being lower than 50%, interparticle homogenieity is undesirable.

When asking for the particle ratio that contains dislocation line and dislocation number of lines among the present invention, preferably at least 100 particle Direct observation dislocation lines are tried to achieve,, especially preferably the particle more than 300 is observed and tried to achieve more preferably to 200 above particles.

Can operate tabular particle of the present invention, make and finishing the back from (b) process, top layer principal plane silver iodide containing ratio I partly to the chemical sensitization process ₁The silver iodide containing ratio I of mole % and lateral parts ₂Mole % satisfies I ₂/ I ₁＜1.

As an example, for the tabular silver halide particle of modulating in advance, can consider on side surface direction, behind the low silver halide phase preferred growth of silver iodide containing ratio, the silver halide that the silver iodide containing ratio is high on the principal plane direction step of growing mutually again, perhaps, on the principal plane direction, behind the high silver halide phase preferred growth of silver iodide containing ratio, the step of the silver halide that growth silver iodide containing ratio is low on side surface direction again.

Respectively in the method for principal plane direction or side surface direction preferred growth tabular silver halide particle, most important have following 2 points, (i) particle shape of the tabular silver halide particle of modulating for growing, halogen is formed, side structure, also have and (ii) be growth, the silver ion of supplying with in system, halide ion or the halogen of silver halide grains emulsion that becomes their supply source are formed, the size of silver halide grains, the selection of the temperature in the adding conditional of silver halide grains, the reaction system, pBr, concentration, stirring, gelatin concentration etc.

For example, during preferred growth, pBr is preferably 1.0-2.5 on side surface direction, and gelatin concentration is preferably 0.5-2.0%, and on the principal plane direction during preferred growth, pBr is preferably 2.5-4.5.

Under situation of the present invention, for thickness and the silver halide of evenly and in heterogeneity controlling silver halide particle principal plane part and the respectively top layer of lateral parts between particle and in the particle are formed, preferable methods is to utilize ion to supply with method, by supplying with silver halide grains, utilize the silver halide particle of its dissolving in growth to supply with the method for silver ion, halide ion.

Silver halide grains, can add the particulate that the regulation halogen is formed that has of modulation in advance rapidly, also can modulate the mixer of particulate being used for outside being arranged on the growth response container, supply with silver ion and halide ion and carry out hybrid reaction, the method that add in the growth response container on modulation particulate limit, limit.

Emulsion of the present invention is preferably removed and/or ultrafiltration concentration salt.

" ultrafiltration " speech is according to M.Cheyan work " Ultra filtration Handbook " (テ Network ノ ミ Star Network) publishing house's 1986 annuals) in the definition of paying use.In this filtration method, generally use film, this film can pass through unwanted material.For example be, in making the process of silver emulsion, make as desired material such as silver halide particles and can not pass through, and salt not etc. is passed through, use the process for purification of functional membrane like this.

Ultrafiltration comprises in order to remove unnecessary solubility salt, and cleans and/or concentrated silver emulsion.These processes be silver emulsion by making dispersion by pressurized ultra filtration membrane spare, and make unnecessary salt, thereby the residue (emulsion) that obtains being formed by silver halide particle and spreading agent carries out by semi-permeable diaphragm.

Thisly optionally separating, is to the synthetic semipermeable membrane press solution that makes, selectively by all molecules below the specific dimensions, and residual than its big molecule with hydraulic pressure.Among the present invention, the pressure of the silver emulsion that contacts with ultra filtration membrane is preferably 1-10kg/cm ²

Silver halide that precipitates in peptizator and unnecessary salt utilize in the known method supply container.Then this liquid is passed through flowmeter, with being pumped in the ultra filtration membrane spare, unnecessary salt is discharged to see through liquid, and when the cycling pattern, residue is back in the container.In another kind of mode, a plurality of ultra filtration membrane spares are connected in series, the residue from leading portion film spare can be fed in the source line of next film spare.

By each film spare, make liquid continue stream forward, if will wash, this liquid can be diluted once more with solvent, in addition,, then do not need solution is diluted once more if will concentrate.

Ultrafiltration preferably makes the dispersion liquid in the reaction vessel, with this semipermeability ultra filtration membrane contact on one side circulation on one side, crosscut semi permeability ultra filtration membrane produces pressure differential.Film can only see through the following molecule of specific dimensions, and will be retained in the dispersion liquid than its big molecule and silver halide, contains the suitable film of this size pore, can be 500-300000 from molecular cut off, chooses in the film of preferably about 500-100000 molecular weight ranges.

The dispersion liquid pressure that contacts with ultra filtration membrane can change in wide range.As representational, the reaction vessel pressure that contacts with ultra filtration membrane is 7.0kg/cm ², the top hole pressure of trapped substance is 0.7kg/cm ²Below.The pressure differential of crosscut film, representational, be 2.8-4.2kg/cm ²Much less, according to the structure of reaction vessel and ultra filtration membrane, the viscosity of dispersion liquid, the concentration of trapped substance and required trapped substance purity, the pressure operation outside above-mentioned scope is certainly also within the present technique category.

The film that uses in the ultrafiltration, representational is that thin layer with superfine little vesicular structure is supported on than on its thick porous matter synthem and the anisotropic membrane that contains.These useful films can be various polymer substances, for example, Polyvinylchloride, poly carboxylic acid vinyl acetate, polyvinyl formate, polyvinyl acetate (PVA), polyvinyl alcohol (PVA), polysulfones, polyvinylether, polyacrylamide, polyacrylonitrile, PMAm, polyimide, polyester, poly-fluothane support, for example, teflon, and Kynoar and cellulosic polymer, for example, cellulose and cellulose esters, for example, cellulose acetate, cellulose butyrate and cellulose acetate butyrate etc.

For side surface direction/principal plane direction, make the silver halide phase time that different halogens are formed respectively, as above-mentioned, preferably use ultrafiltration, remove the operation of salt not, ion etc. aptly.

Form side's silver halide mutually after, remove remaining surplus or unwanted halide ion, preventing that unwanted conversion takes place in the manufacture process afterwards, and forming the opposing party's silver halide phase time, can control its halogen easily and form.Utilize washing, desalination process or film separate does not need material except that desalt, ion etc. operation, preferably after fundamental particle forms and after any one party of side surface direction/principal plane direction is upwards grown, carry out after perhaps the silver halide layer of forming arbitrarily forms, especially preferably after above-mentioned each silver halide forming process finishes, carry out.

If will suppress the principal plane direction of tabular silver halide particle or the growth of side surface direction, except the growth conditions of controlling above-mentioned silver halide particle, also can be on the specific crystal surface of silver halide particle, absorption is called the silver halide growth inhibitor, the adjuvant of crystal habit inhibitor or inhibitor, have face and select the pigment of adsorbability, adsorbability materials such as inhibitor preferably use in non-adsorption plane.

The protective colloid that uses during as modulation emulsion of the present invention though use above-mentioned gelatin favourable, in addition, also can use hydrophilic colloid.

For example, can use gelatine derivative, gelatin and other high molecular graft polymer, the protein of albumin, casein class; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfuric acid ester class, sugar derivativess such as sodium alginate, starch derivative; Multiple synthetic hydrophilic polymer materials such as the single or multipolymer of polyvinyl alcohol (PVA), polyvinyl alcohol (PVA) part acetal, poly--the N-vinylpyrrolidone, polyacrylic acid, polymethylacrylic acid, polyacrylamide, polyvinyl imidazole, tygon pyrazoles etc.

Emulsion of the present invention is preferably washed for desalination, and is dispersed in the protecting colloid of new preparation.As protective colloid,, equally also can use other natural polymers or synthetic high polymer except that gelatin though can use gelatin.Kind as gelatin, can use alkali treated gelatin, carry out the gelatin (methionine content is below 40 μ mol/g) of oxidation processes with the methionine base in the oxidized gelatin molecules such as hydrogen peroxide, amido modified gelatin of the present invention (for example, phthalic acid (Off Le) is changed gelatin, trihemellitic acid gelatin, amber acidifying gelatin, maleinization gelatin, acidifying gelatin).Also can use the spy to open as required to put down in writing in the flat 11-237704 communique, in the molecular weight distribution of utilizing パ ギ-Fa to measure, contain 30% above molecular weight 280,000 above composition lime treatment skeleton gelatin.For example, also can use European patent No. 758758 and No. 5733718 each instructions of United States Patent (USP) in the starch put down in writing.Natural polymer has the IX item of special fair 7-111550 communique, (researchdisclosure) the 176th volume, No.17643 (in Dec, 1978) to put down in writing.Washing temperature can be selected according to purpose, preferably selects in 5-50 ℃ of scope.PH during washing also can select according to purpose, preferably selects in the 2-10 scope, more preferably the scope of 3-8.PAg during washing also can select as requested, preferably selects between 5-10.As method for washing, can from ヌ-De Le WATER-WASHING METHOD, the dialysis of using semi-permeable diaphragm, centrifugal separation, condensation sedimentation, ion exchange process, ultrafiltration etc., select to use.Also can from the method for using sulfate, method with an organic solvent, the method for use water-soluble polymers, the method for use gelatine derivative etc., select for solidifying the precipitation method.

The present invention is when forming particle, also can there be following polymkeric substance, for example, Te Kaiping 5-173268 number, with 5-173269 number, with 5-173270 number, with 5-173271 number, with 6-202258 number, with the poly-alkylene oxide block multipolymer of putting down in writing in 7-175147 number each communique, perhaps specially permit the poly-alkylene oxide block copolymer of putting down in writing in No. 3089578 instructions.The life period of this polymkeric substance can be any time in the particle modulation, if the commitment that forms at particle uses, then it is effective.

In modulation during emulsion of the present invention, for example, when particle forms, when desalination processes, chemical sensitization, be coated with before, preferably have metal cation salt as required.Under the situation of in particle, mixing, preferably when particle forms, add and during as the modification of particle surface or chemical sensitizer, after particle forms, add before chemical sensitization finishes.When all particles mixes, only can select for example can to use Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, Bi to the particle core or the method for only shell portion being mixed.These metals, so long as particle when forming with just can adding that the dissolving salt form exists, as ammonium salt, acetate, nitrate, sulfate, phosphate, hydroxysalt or 6 coordination complex salts, 4 coordination complex salts etc.CdBr is for example arranged ₂, CdCl ₂, Cd (NO ₃) ₂, Pb (NO ₃) ₂, Pb (CH ₃COO) ₂, K ₄[Fe (CN) ₆], (NH ₄) ₄[Fe (CN) ₆], K ₂IrCl ₆, (NH ₄) ₃RhCl ₆, K ₄Ru (CN) ₆As the ligand of coordination compound, can from halogen, water, cyano group, cyanate, thiocyanate, nitro, sulfo-nitro, oxo, carbonyl, choose.These metallic compounds use a kind of only, also can be used in combination more than 2 kinds or 3 kinds.

After metallic compound is preferably dissolved in water or the suitable organic solvent such as methyl alcohol, acetone, add.Solution-stabilized in order to make, can adopt the method for adding aqueous solution of hydrogen halide (for example, HCl, HBr) or alkali halide (for example, KCl, NaCl, KBr, NaBr).Also can add soda acid etc. as required.Metallic compound can add to before particle forms in the reaction vessel, also can add in the process that particle forms.To water soluble silver salt (for example, AgNO ₃) or the middle interpolation of alkali halide aqueous solution (for example, NaCl, KBr, KI), also can in forming, add continuously silver halide particle.And then preparation and water soluble silver salt, alkali halide be solution independently, can add continuously the suitable period in particle forms.Preferably various adding methods are made up.

The method of the chalcogen compound of putting down in writing in adding as No. 3772031 instructions of United States Patent (USP) in the emulsion modulation also is effective sometimes.Except S, Se, Te, also can there be cyanogen salt, sulfo-cyanogen salt, selenium cyanic acid, carbonate, phosphate, acetate.

Silver halide particle of the present invention can be implemented at least a kind in sulphur sensitizing, selenium sensitizing, tellurium sensitizing, golden sensitizing, palladium sensitizing or noble metal sensitizing, the reduction sensitization in the arbitrary process in the manufacture process of silver emulsion.According in which process, carrying out chemical sensitization, can modulate the emulsion of various types.The pattern of imbedding chemical sensitization nuclear in particle inside is arranged, be embedded to apart from the pattern of the more shallow position of particle surface or the pattern of making chemical sensitization nuclear on the surface.Emulsion of the present invention can be selected the position of chemical sensitization nuclear as required, but usually preferably, make at least a chemical sensitization nuclear near near surface.

Among the present invention, a kind of preferred embodiment of chemical sensitization is the independent sensitizing or the combination sensitizing of chalcogen sensitizing and noble metal sensitizing, also can be as T.H.James work (Journalphotographicprocess), the 4th edition, Macmillan society periodical,, (T.H.James, The Theory of the photographic process in 1977,4th ed, Macmillan, 1977) record in the 67-76 page or leaf, the use active gelatin carries out, in addition, as ResearchDiscloswre, 120 volumes, in April, 1974,12008; Research Discloswre, 34 volumes, in June, 1975,13452, No. the 2642361st, United States Patent (USP), with No. 3297446, with No. 3772031, with the 3857711st, with No. 3901714, with No. 4266018 and with No. 3904415, and each instructions of No. the 1315755th, BrP in record, under pAg5-10, pH 5-8 and temperature 30-80 ℃, use several combinations of sulphur, selenium, tellurium, gold, platinum, palladium, iridium or these sensitizers.In the noble metal sensitizing, can use precious metal salts such as gold, platinum, palladium, iridium, wherein preferably golden sensitizing, palladium sensitizing and both also usefulness.

In golden sensitizing, can use P.Grafkides work, the golden salt of record among No. 307105, the Chimie et physiqnePhotographiqwe (Paul Mohtel society periodical, 1987, the 5th edition), Research Discloswre will 307 volumes etc.

Specifically, except the chlorination auric acid, the chlorine potassium oleate, outside the oil potassium thiocyanate, also can use No. the 2642361st, United States Patent (USP) (aurosulfo and Auric selenide etc.), with No. 3503749 (having the mercaptan gold of water-soluble base etc.), with No. 5049484 (two (methyl hydantoin hydrochlorate) gold complex etc.), with No. 5049485 (intermediate ion mercaptan gold complex, for example, 1,4,5-trimethyl-1,2,4-trisazo--3-mercaptan gold complex etc.), the heterocycle gold complex of the big ring-type in same No. 5252455 and same No. 5391717, with No. 5620841, with No. 5700631, with No. 5759760, with No. 5759761, with No. 5912111, with No. 5912112, with No. 5939245, Te Kaiping 1-147537 number, with 8-69074 number, with 8-69075 number, with 9-269554 number, special public clear 45-29274 number, Deutsches Wirtschafts Patent DD-264524A, with 264525A number, with 265474A number, with 298321A number, the spy opens 2001-75214 number, with 2001-75215 number, with 2001-75216 number, with 2001-75217 number, gold compound with record in 2001-75218 number.

Palladium compound is meant divalence or tetravalence palladium salt.Preferred palladium compound, available R ₂PdX ₆Or R ₂PdX ₄Expression.Wherein, R represents hydrogen atom, alkali metal atom or ammonium.X represents halogen atom, expression chlorine, bromine or iodine atom.K is specifically arranged ₂PdCl ₄, (NH ₄) ₂PdCl ₆, Na ₂PdCl ₄, (NH ₄) ₂PdCl ₄, Li ₂PdCl ₄, Na ₂PdCl ₆Or K ₂PdBr ₄Gold compound and palladium compound are preferably also used with thiocyanate or selenium cyanate.

In sulphur sensitizing, use unsettled sulphur compound, can use the P.Grafkides work, the unstable sulphur compound of record in No. 307105, Chimieet physique photographique (Paul Montel society system, 1987, the 5th edition), ResearchDisclosure will 307 volumes etc.

Specifically, (for example can use thiosulfate, sodium thiosulfate), sulphur urine class (for example, diphenyl sulphur urine, triethyl sulphur urine, N-ethyl-N '-(4-methyl-2-thiazole) sulphur urine, dicarboxyl methyl-dimethyl disulfide urine, ethyloic-trimethyl thiourea), the sulfonyl amine (for example, the sulphur acetamide), the rhodanine class (for example, the diethyl rhodanine, 5-benzal-N-ethyl rhodanine), hydrogen phosphide is sulfide-based (for example, trimethyl hydrogen phosphide sulfide), the thiohydantoin class, 4-oxo-oxazolidines-2-thion (thion) class, disulfides or multiple sulfides are (for example, dimorpholine disulfide, cystine, six sulfanes-thion (thion)), sulfhydryl compound (for example, halfcystine), polythionate, known sulphur compounds such as element shape sulphur and active gelatin etc.Good especially is thiosulfate, sulphur urine class, hydrogen phosphide is sulfide-based and the rhodanine class.

In selenium sensitizing, use unsettled selenium compound, can use special public clear 43-13489 number, with 44-15748 number, spy open flat 4-25832 number, with 4-109340 number, with 4-271341 number, with 5-40324 number, with 5-11385 number, with 6-51415 number, with 6-175258 number, with 6-180478 number, with 6-208186 number, with 6-208184 number, with 6-317867 number, with 7-92599 number, with 7-98483 number, with the selenium compound of putting down in writing in the communique such as 7-140579 number.

Specifically; can use the colloidal metallic selenium; the selenourea class (for example; N; N-dimethyl selenourea; fluoroform carbonyl-trimethyl selenourea; acetyl-trimethyl selenourea); the selenium amide-type (for example; the selenium acid amides; N; N-diethyl phenyl selenium acid amides); hydrogen phosphide selenide (selenide) class (for example; triphenyl phosphatization hydrogen selenium compound; pentafluorophenyl group-triphenyl phosphatization hydrogen selenide); the selenium phosphoric acid ester (for example; three-p-, three selenium phosphates; three-n-butyl selenium phosphate); the selenium ketone (for example; the selenium benzophenone); different selenium cyanate; the selenium carboxylic acids; selenium ester class (for example; methoxyphenyl selenono-2,2-dimethoxy cyclohexane ester); diacyl selenide class etc.And then can use special public clear 46-4553 number, with the non-unstable selenium compound of record in the 52-34492 communique etc., for example, selenous acid, selenium cyanic acid class (for example, Potassium Selenocyanate), selenazoles class, selenium compound class.Good especially is hydrogen phosphide selenide (selenide) class, selenourea class, selenium ester class and selenium cyanic acid class.

In tellurium sensitizing, use unsettled tellurium compound, can use the spy open flat 4-224595 number, with 4-271341 number, with 4-333043 number, with 5-303157 number, with 6-27573 number, with 6-175258 number, with 6-180476 number, with 6-208186 number, with 6-208184 number, with 6-317867 number, with the unstable tellurium compound of putting down in writing in the communique such as 7-140579 number.

Specifically; (for example can use hydrogen phosphide telluride class; butyl-diisopropyl hydrogen phosphide telluride; tributyl hydrogen phosphide telluride; three fourth oxygen hydrogen phosphide tellurides; ethoxy-diphenyl phosphatization hydrogen telluride); diacyl (two) telluride class (for example; two (xenyl carbamyl) two tellurides; two (N-phenyl-N-methylamino formoxyl) two tellurides; two (N-phenyl-N-methylamino formoxyl) telluride; two (N-phenyl-N-benzylamino formoxyl) telluride; two (carbethoxyl group) telluride); the tellurium ureas (for example; N; N '-dimethyl ethene tellurium urea; N, N '-diphenylethlene tellurium urea); the tellurium amide-type; tellurium ester class etc.

As useful chemical sensitization auxiliary agent, can use as azepine indenes, azepine pyridazine, aza-pyrimidine etc. and in the chemical sensitization process, suppress overexposure, and increase the known compound of sensitivity.The example of chemical sensitization additive modification agent, be recorded in United States Patent (USP) No. 2131038, with No. 3411914, open clear 58-126526 communique and above-mentioned ダ Off イ Application work " photographic emulsion chemistry " with No. 3554757 instructions, spy, in the 138-143 page or leaf.

The golden sensitizer that uses among the present invention and the use amount of chalcogen sensitizer can change according to used silver halide particle and Chemical Sensitization etc., but per 1 mole of silver halide are 10 ^-8-10 ^-2The mole, be preferably 10 ^-7-10 ^-3About mole.

To silver emulsion of the present invention, preferably in particle forms, after particle forms, and before chemical sensitization or in the chemical sensitization, or after the chemical sensitization, carry out reduction sensitization.

Said herein reduction sensitization can be selected any in the following method,, adds the method for reduction sensitization agent in silver emulsion that is; The method that is known as silver-colored slaking of growth or slaking in the low pAg environment of pAg1-7; The method that is known as high pH slaking of growth or slaking in the high pH environment of pH8-11.Also can be also with the method more than two kinds.

From regulating the angle of reduction sensitization level knifeedge, the method for adding the reduction sensitization agent is a preferable methods.

As the reduction sensitization agent, for example known have tin salt, ascorbic acid and derivant thereof, amine and polyamine class, hydrazine derivate, formamidine sulfinic acid, silane compound, a monoborane compound.For reduction sensitization of the present invention, can select these known reduction sensitization agent for use, also can be also with the compound more than 2 kinds.As the reduction sensitization agent, preferred compound is a stannous chloride, thiourea dioxide, dimethyl amine monoborane, ascorbic acid and derivant thereof.The addition of reduction sensitization agent is created conditions owing to depend on emulsion, so need to select addition, per 1 mole silver halide is 10 ^-7-10 ^-3Mole.

The reduction sensitization agent for example can be dissolved in the organic solvents such as water or alcohols, glycols, ketone, ester class, amide-type, and add in particle growth.Also can add in the reaction vessel in advance, but preferable methods is to add in the suitable moment of particle growth.Can the reduction sensitization agent be added in water soluble silver salt or the halid aqueous solution of water-soluble alkaline in advance, also can use these aqueous solution precipitation silver halide particles.Be accompanied by the growth of particle, can be divided into and add the reduction sensitization agent solution several times, also can add for a long time continuously, these all are preferable methods.

In the emulsion manufacture process of the present invention, the preferred oxygenant that uses silver.So-called oxygenant to silver is meant to have to act on the compound that argent is converted into the effect of silver ion.Especially effectively, can be the secondary product that in the forming process of silver halide particle and chemical sensitization process, produces the compound that atomic little silver particles is transformed into silver ion.The silver ion that generate this moment can form the silver salt that is insoluble in water, and for example, silver halide, silver sulfide, silver selenide etc. perhaps form silver salt soluble in water, as silver nitrate etc.To the oxygenant of silver, can be inorganics, also can be organism.As inorganic oxygenant, ozone, hydrogen peroxide and addition product thereof (for example, NaBO is for example arranged ₂H ₂O ₂3H ₂O, 2NaCO ₃3H ₂O ₂, Na ₄P ₂O ₇2H ₂O ₂, 2Na ₂SO ₄H ₂O ₂2H ₂O), peracid salt (for example, K ₂S ₂O ₈, K ₂C ₂O ₆, K ₂P ₂O ₈), peroxide coordination compound (for example, K ₂[Ti (O ₂) C ₂O ₄] 3H ₂O, 4K ₂SO ₄Ti (O ₂) OHSO ₄2H ₂O, Na ₃[VO (O ₂) (C ₂H ₄) ₂] 6H ₂O), permanganate (for example, KMnO ₄), chromate (for example, K ₂Cr ₂O ₇) wait halogenss such as oxysalt, iodine or bromine, cross halate (for example, periodic acid potassium), the slaine (for example, potassium ferricyanate) and the thiosulfonate of high atomicity.

As organic oxygenant, quinones such as picture paraquinones have been exemplified, as the compound (for example, N-bromine succinimide, toluene-sodium-sulfonchloramide, chloramine B) of organic peroxides such as peracetic acid and perbenzoic acid, release reactive halogen.

Preferred oxidant of the present invention is the inorganic oxide of ozone, hydrogen peroxide and addition product thereof, halogen element, thiosulfonate and the organic oxidizing agent of quinones.Preferred form is also to use with above-mentioned reduction sensitization agent with to the oxygenant of silver.Also can from following method, select to use, that is, use the method for implementing reduction sensitization behind the oxygenant again, otherwise or with its method, perhaps both coexistent methods.These methods can be selected in the particle forming process or in the chemical sensitization process to use.

For the photographic emulsion that uses among the present invention, for prevent photosensitive material in manufacture process, preserve in or take a picture and photographic fog occurs in handling, perhaps make the photographic property stabilization, can contain all cpds.Multiple known photographic fog be can add and the thiazoles of agent or stabilizing agent, for example benzothiazolium salt, nitro glyoxaline, nitrobenzimidazole class, chloro benzimidazole class, bromobenzene and imidazoles, thyroidan class, mercaptobenzothiazoler class, mercaptobenzimidazole class, dimercaptothiodiazole class, aminotriazole(ATA) class, benzotriazole, nitrobenzene triazole type, mercapto-tetrazole class (particularly 1-phenyl-5-mercapto-tetrazole) prevented; Sulfhydryl miazines; The mercapto-triazine class; Thioketal compound such as oxide phosphorus thion for example; Azepine indenes class, for example benzotriazole class, purine class (particularly the 4-hydroxyl replaces (1,3,3a, 7) purine class), pentaaza indenes class etc.For example, can use United States Patent (USP) No. 3954474, with the compound of putting down in writing in No. 3982947 instructions, the special public clear 52-28660 communique.Have as a kind of of preferred compound, open the compound of putting down in writing in the clear 63-212932 communique the spy.Antifoggant and stabilizing agent can be according to purposes, particle form preceding, particle form in, any period during the dispersion of particle after forming back, water-washing process, washing, before the chemical sensitization, in the chemical sensitization, after the chemical sensitization, before the coating adds.By in the emulsion modulation, adding, except realizing antifog originally and stabilization effect, also can be used in the brilliant wall of control particle, reduce particle size, reduce the dissolubility of particle, control chemical sensitization, multiple purposes such as control pigment arrangement.

The photographic emulsion that uses among the present invention preferably utilizes methine pigment and other pigment to carry out beam split sensitizing, can bring into play effect of the present invention.For used pigment, comprise anthocyanidin, merocyanine pigment, compound flower cyanine, composite part anthocyanidin, holopolar form (holo polar) anthocyanidin, half anthocyanidin, styrene pigment and half oxonols pigment.Useful especially pigment is the pigment that belongs to anthocyanidin, merocyanine pigment and composite part anthocyanidin.In these pigments, can use any nuclear that is generally used in the anthocyanidin class as alkaline heteronucleus.Promptly, can use pyrrolin He, oxazoline nuclear, sulphur azoles quinoline nuclear, pyrrole nucleus, oxazole nuclear, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazolium nuclear, pyridine nucleus, in these nuclears, merged ester ring type hydrocarbon ring nuclear, and in these nuclears, merged the nuclear of aromatic hydrocarbon ring, that is, for example can be suitable for indolenine nuclear, benzo indolenine nuclear, indole nucleus, benzoxazole nuclear, Nai Bing oxazole nuclear, benzothiazole nucleus, aphthothiazoles nuclear, benzo selenazole nucleus, benzimidazole nucleus, quinoline nuclei, on carbon atom, also can have substituting group at these nuclears.

In merocyanine pigment or the composite part anthocyanidin, as nuclear with ketone methylene structure, for example can use pyrazolin-5-one nuclear, thiohydantoin nuclear, 2-Liu Dai oxazolidine-2 ,-4-diketone nuclear, thiazolidine-2, the 5-6 unit heteronucleus of 4-diketone nuclear, rhodanine nuclear, thiobarbituric acid nuclear.

These sensitizing coloring matters can use separately, also it can be used in combination, and the combination of sensitizing coloring matter is especially normally used with the purpose of rich shade sensitizing.Its typical example, United States Patent (USP) there be No. 2688545, with No. 2977229, with No. 3397060, with No. 3522052, with No. 3527641, with No. 3617293, with No. 3628964, with No. 3666480, with No. 3672898, with No. 3679428, with No. 3703377, with No. 3769301, with No. 3814609, with No. 3837862, with No. 4026707, No. the 1344281st, BrP, each instructions with No. 1507803, special public clear 43-4936 number, with 53-12375 number, the spy opens clear 52-110618 number, with what put down in writing in 52-109925 number each communique.

In emulsion, can together contain pigment or the actual material that does not absorb the demonstration rich shade sensitizing of visible light that self does not have the beam split sensibilization with sensitizing coloring matter.

Adding the time of sensitizing coloring matter in emulsion, can be any stage that up to the present is considered to effective emulsion modulation.Normally in finishing the back time before coating, chemical sensitization adds, as the record in No. the 3628969th, United States Patent (USP) and No. 4225666 each instructions, can add simultaneously with chemical sensitizer, beam split sensitizing and chemical sensitization are carried out simultaneously, also can open in the clear 58-113928 communique and put down in writing as the spy, before chemical sensitization, add, also can before generating the silver halide particle precipitation fully, add, beginning beam split sensitizing.And then also can in No. 4225666 instructions of United States Patent (USP), disclose, these above-claimed cpds are added respectively, promptly, before chemical sensitization, add the part of these compounds, remaining part adds after chemical sensitization, with disclosed method in No. 4183756 instructions of United States Patent (USP) is representative, also can add in any moment in silver halide particle forms.

Can add 4 * 10 in per 1 mole of silver halide ^-6～8 * 10 ^-3Mole.

But the sub-property of the power supply that also can use fragmentation sensitizer.The sub-property sensitizer of powering is recorded in the following document, promptly, No. the 5747235th, United States Patent (USP), with No. 5747236, with No. 6054260, No. 5994051, European patent 786692A1, with each instructions of 893732A1, the spy open 2000-181001 number, spy open 2000-180999 number, spy open 2000-181002 number, spy open 2000-181000 number, with 2000-221626 number, with 2000-221628 number each communique.But the sub-property of the power supply of fragmentation sensitizer can use in any moment in the photosensitive material manufacture process.When for example particle forms, when desalination processes, chemical sensitization, before the coating etc.In these processes, also can be divided into for several times and adding.Compound of the present invention adds after being preferably dissolved in water-soluble solvent such as water, methyl alcohol, ethanol or their mixed solvent again.When being dissolved in the water, for if improve or reduce the compound that pH will make solubleness improve, interpolation again after also can improving or reduce pH and dissolving.But the sub-property of the power supply of fragmentation sensitizer preferably uses in emulsion layer, but also can add in protective seam and the middle layer when adding emulsion layer to, makes it diffusion during coating.The interpolation time of The compounds of this invention, all it doesn't matter before and after the interpolation of sensitizing coloring matter, and the ratio that it is contained in silver halide emulsion layer for per 1 mole silver halide, is 1 * 10 ^-9～5 * 10 ^-2Mole is preferably 1 * 10 ^-8～2 * 10 ^-3Mole.

But when using the sub-property of the power supply sensitizer of fragmentation, preferably use the keeping quality modifying agent.The keeping quality modifying agent preferably uses the spy to open flat 11-119364 number, spy and opens the compound of putting down in writing in 2001-42466 number each communique.

In photosensitive material of the present invention,, in addition, also can use various adjuvants according to purpose though can use above-mentioned various adjuvant.

These adjuvants are documented in (researchdisclosure)-Item 17643 (in Dec, 1978), in more detail with Item 18716 (in November, 1979) with among the Item 308119 (in Dec, 1989), and its each situation is as shown in the table.

	Additive types	RD17643	RD18716	RD308119
					1	Chemical sensitizer	23 pages	648 pages of right hurdles	996 pages
2	Sensitivity rising agent		The same
					3	Divide light sensitizer, rich shade sensitizer	The 23-24 page or leaf	Page right hurdle, 648 pages of right hurdles-649	The right side, 996 right sides-998
4	Whitening agent	24 pages	647 pages of right hurdles	998 right sides
					5	Photographic fog prevents agent and stabilizing agent	The 24-25 page or leaf	649 pages of right hurdles	The right side, 998 right sides-1000
6	Light absorber, filter dye, ultraviolet light absorber	The 25-26 page or leaf	Page left hurdle, 649 pages of right hurdles-650	The right side, 1003 left sides-1003
					7	The anti-coloring agent	25 pages of right hurdles	650 L-R hurdles	1002 right sides
8	The pigment image stabilizing agent	25 pages		1002 right sides
					9	Hard coat agent	26 pages	651 pages of left hurdles	A left side, 1004 right sides-1005
10	Bonding agent	26 pages	The same	The right side, 1003 right sides-1004

11	Plastifier, lubricant	27 pages	650 pages of right hurdles	The right side, 1006 left sides-1006
					12	Coating additive, surfactant	The 26-27 page or leaf	The same	A left side, 1005 left sides-1006
13	Antistatic agent	27 pages	The same	A left side, 1006 right sides-1007
					14	Deluster			A left side, 1008 left sides-1009

In addition, cause the deterioration of photographic property in order to prevent formaldehyde gas, that preferably puts down in writing in No. 4411987, United States Patent (USP) of interpolation and same No. 4435503 instructions in photosensitive material can compound immobilized with formaldehyde reaction.

The present invention can use various color couplers, and instantiation is above-mentioned (researchdisclosure) No.17643, and VII-C～G and same No.307105 put down in writing in the patent of putting down in writing among VII-C～G.

As yellow coupler, preferably, for example No. the 3933501st, United States Patent (USP), with No. 4022620, with No. 4326024, with No. 4401752, with No. 4248961, special public clear 58-10739 number, No. the 1425020th, BrP, with No. 1476760, No. the 3973968th, United States Patent (USP), with No. 4314023, with records such as No. 4511649, European patent 249473A number.

Magenta coupling agent, the preferably compound of 5-pyrazolone and pyrazoles azole series.Put down in writing in the preferably following document, that is, No. the 4310619th, United States Patent (USP), with No. 4351897, No. the 73636th, European patent, No. the 3061432nd, United States Patent (USP), with No. 3725067, researchdisclosure No.24220 (in June, 1984), the spy opens clear 60-33552 number, researchdisclosure No.24230 (in June, 1984), the spy opens clear 60-43659 number, with 61-72238 number, with 60-35730 number, with 55-118034 number, with 60-185951 number, No. the 4500630th, United States Patent (USP), with No. 4540654, with No. 4556630, put down in writing in international open WO88/04795 number.

As the cyan coupling agent, it is coupling agent that phenol system and naphthalene are arranged, put down in writing in the preferably following document, that is, No. the 4052212nd, United States Patent (USP), with No. 4146396, with No. 4228233, with No. 4296200, with No. 2369929, with No. 2801171, with No. 2772162, with No. 2895826, with No. 3772002, with No. 3758308, with No. 4334011, with No. 4327173, Deutsches Reichs-Patent discloses No. 3329729, European patent 121365A number, with 249453A number, No. the 3446622nd, United States Patent (USP), with No. 4333999, with No. 4775616, with No. 4451559, with No. 4427767, with No. 4690889, with No. 4254212, with No. 4296199, the spy opens clear 61-42658 number record such as grade.

Form the representative instance of coupling agent as the pigment that is aggregated materialization, as No. the 3451820th, United States Patent (USP), with No. 4080211, with No. 4367282, with No. 4409320, with record in No. 4576910, No. the 2102137th, BrP, European patent 341188A number.

Have suitable diffusible coupling agent as the color development pigment, preferably No. the 4366237th, United States Patent (USP), No. the 2125570th, BrP, No. 96570, European patent, Deutsches Reichs-Patent (disclosing) are put down in writing for No. 3234533.

What be used to revise the color development pigment does not need the color coupler that absorbs, preferably the VII-G item of researchdisclosure No.17643, with the VII-G item of No.307105, No. the 4163670th, United States Patent (USP), special public clear 57-39413 number, No. the 4004929th, United States Patent (USP), with No. 4138258, No. 1146368 record of BrP.Preferred use record in No. the 4774181st, the United States Patent (USP) utilize coupling the time iridescent that discharges usually revise the color development pigment do not need the coupling agent that absorbs, or the conduct of No. 4777120 record of United States Patent (USP) breaks away from base and has the coupling agent that can form the precursor base of pigment with the reaction of development host.

Be accompanied by coupling, discharge the compound of the residue that is useful on photograph, also can preferably use in the present invention.The DIR colour coupler of released development inhibitor, except the present invention, preferred also with the patent of putting down in writing in above-mentioned RD17643, VII-F item and same No.307105, the VII-F item; The spy opens clear 57-151944 number; With 57-154234 number; With 60-184248 number; With 63-37346 number; With 63-37350 number; No. the 4248962nd, United States Patent (USP); Put down in writing in same No. 4782012.

Discharge the coupling agent of making nuclear agent or development accelerant with the image shape when developing, preferably No. the 2097140th, BrP, with No. 2131188, spy open clear 59-157638 number, with record in 59-170840 number.Be more preferably the spy open clear 60-107029 number, with 60-252340 number, spy open flat 1-44940 number, carry out redox reaction with the oxysome with development host of record in 1-45687 number, discharge the compound of か ぶ ら せ agent, development accelerant, ag halide solvent etc.

In addition, as spendable coupling agent in the photosensitive material of the present invention, the competitive coupling agent that record in No. the 4130427th, the United States Patent (USP) is arranged, No. the 4283472nd, United States Patent (USP), with No. 4338393, with many equivalents coupling agent of putting down in writing in No. 4310618 grade, the spy opens clear 60-185950 number, the spy opens the coupling agent of the release DIR redox compound of putting down in writing in the clear 62-24252 grade, discharge the coupling agent of DIR colour coupler, discharge the redox compound of DIR colour coupler or discharge the redox redox compound of DIR, European patent 173302A number, the coupling agent that carries out the pigment of secondary color after the disengaging that discharges with record in 313308A number, RD.No.11449, with 24241, the spy opens the coupling agent of the release bleach boosters of putting down in writing in the clear 61-201247 grade, the coupling agent of the release ligand of putting down in writing in No. 4555477 grade of United States Patent (USP), the spy opens the coupling agent of the colourless pigment of release of record in clear 63-75747 number, the coupling agent of the release fluorchrome of record in No. the 4774181st, the United States Patent (USP).

The coupling agent that uses among the present invention can utilize various known process for dispersing to import in the photosensitive material.

Oil droplet is scattered in the example of employed high boiling solvent in the method in the water, and record in No. the 2322027th, the United States Patent (USP) is for example arranged.

Be scattered in as oil droplet and use in the method in the water, boiling point under the normal pressure is at the instantiation of the high boiling organic solvent more than 175 ℃, there is phthalate (for example, dibutyl phthalate, dicyclohexyl phthalic ester, two-2-ethylhexyl phthalic ester, decyl phthalic ester, two (2,4-two-tertiary pentyl phenyl) phthalic ester, two (2,4-two-tertiary pentyl phenyl) different phthalic ester, two (1,1-diethyl propyl group) phthalic ester); The ester class of Phosphoric acid or phosphonic acid (for example, triphenyl, trimethylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, thricyclohexyl phosphate, three-ethylhexyl dihydrogen phosphate, dotriacontyl phosphate, tri butylethyl phosphate, trichlorine propyl phosphate, two-2-ethylhexyl phenyl phosphate ester); Benzoate class (for example, 2-ethylhexyl benzoic ether, dodecyl benzoic ether, 2-ethylhexyl-P-hydroxybenzoate); Amide-type (for example, N, N-diethyl dodecane acid amides, N, N-diethyl lauramide, N-myristyl pyrrolidone); Alcohols or phenols (for example, isooctadecanol, 2,4-two-tertiary pentyl phenol); Aliphatic carboxylic acid esters,'s class (for example, two (2-ethylhexyl) sebacate, dioctyl salicylate, glycerine tributyl, isostearoyl base laurate, trioctylphosphine citrate); Anil (for example, N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline), hydro carbons examples such as (for example, paraffin, dodecyl benzene, diisopropyl naphthalenes).As secondary solvent, for example can use boiling point more than 30 ℃, preferred more than 50 ℃ and the organic solvent below 160 ℃, as typical case, for example, ester acetoacetic ester, ester acid butyl ester, ethyl propionate, butanone, cyclohexanone, acetate 2-ethoxy ethyl ester, dimethyl formamide are arranged.

The instantiation of the process of latex dispersion method, effect and dipping latex, for example be recorded in United States Patent (USP) No. 4199363, No. the 2541274th, Deutsches Reichs-Patent application (OLS) and with in No. 2541230.

Also can add phenylethyl alcohol or spy in color sensitive material of the present invention opens clear 63-257747 number, with 62-272248 number with special open record in flat 1-80941 number, for example 1,2-benzisothiazole-3-ketone, n-butyl-P-hydroxy benzenes acid esters, phenol, 4-chloro-3, various antiseptics or mildewproof agents such as 5-dimethyl phenol, 2-Phenoxyethanol, 2-(4-thiazoline) benzimidazole.

The present invention is applicable to various color sensitive materials.For example, as representational enumerate colour negative that general usefulness or film use, magic lantern with or TV colour reversal film, colour paper, colour positive and the colour reversal photographic paper used.The present invention especially preferably is applicable to the color dub film.

Spendable suitable supporter among the present invention, for example, 28 pages of above-mentioned R.D.No.17643, with page left hurdle, 647 pages of right hurdles to 648 of No.18716 with record in 879 pages of No.307105.

Photosensitive material of the present invention on the opposition side with emulsion layer side, is provided with preferably that total drying is thick to be the hydrophilic colloid layer (being called backing layer) of 2-20 μ m.Preferably contain as above-mentioned optical absorbing agent, filter dye, ultraviolet light absorber, antistatic agent, hard coat agent, bonding agent, plastifier, lubricant, coating additive, surfactant in this backing layer.The water swelling rate of this backing layer is preferably 50-250%.

Colour photographic sensitive material of the present invention can utilize the 28-29 page or leaf of above-mentioned RD.No.17643, with the usual method of putting down in writing in the 651 pages of left hurdles～right hurdle of No.18716 and the 880-881 page or leaf with No.307105, carries out development treatment.

Used color development developer solution in the development treatment of photosensitive material of the present invention is that color development development host is the alkaline aqueous solution of major component with primary aromatic amine preferably.As this color development development host, also available chlorine phenol system compound, but preferably use penylene two amine compounds, as its typical example, 3-methyl-4-amino-N is arranged, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-amsacrine ethylaniline, 3-methyl-4-amino-N-ethyl-'beta '-methoxy ethylaniline, and their sulfate, hydrochloride or tosilate etc.Wherein, the sulfate of 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline preferably, these compounds according to purpose also can and with more than 2 kinds.

The color development developer solution for example contains pH buffering agent, chloride salt, bromide salt, iodide salt, benzimidazoles such as alkali-metal carbonate, borate or phosphate usually, and development restrainer such as benzothiazoles or sulfhydryl compound or photographic fog prevent agent.As required, can use hydramine, diethyl hydramine, sulphite, N, various antioxidants such as hydrazine classes such as N-dicarboxyl methyl hydrazine, phenyl semicarbazide, triethanolamine, catechol sulfonic acid class; Organic solvent such as ethylene glycol, diglycol; Development accelerants such as benzylalcohol, polyglycol, quarternary ammonium salt, amine; Pigment forms coupling agent, competition coupling agent, 1-phenyl-auxiliary development hosts such as 3-pyrazolidone; Viscosity is paid agent; Aminopolycarboxylic, amino polyphosphonic acid, alkyl phosphonic acid, phosphine carboxylic acid are the various integrated agents of representative.As integrated agent, for example can enumerate ethylenediamine tetraacetic acid, triacetamide as typical example, diethylene-triamine pentaacetic acid, CDTA, hydroxyethyl imido-acetic acid, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, nitrilo--N, N, N-trimethylene phosphonic, ethylenediamine-N, N, N, N-tetramethylene phosphonic acid, ethylenediamine-two (o-hydroxyphenyl acetate) and salt thereof.

When implementing the counter-rotating processing, after carrying out black-and-white development, carry out color development usually and develop.For this black-and-white developer, for example can be used alone or in combination dihydroxy benzenes classes such as quinhydrones, for example, 3-pyrazolidine ketone such as 1-phenyl-3-pyrazolidone or, for example, N-methyl-known black-and-white development hosts such as aminophenols such as P-amino phenol.The pH of these color development developer solutions and black-and-white developer is generally 9-12.The magnitude of recruitment of these developer solutions is though according to handled colour photographic sensitive material and difference generally is that per 1 square metre photosensitive material is below 3 liters, by reducing the bromide ion concentration of replenishing in the liquid, also can be taken as below the 500ml.When reducing magnitude of recruitment, utilize the contact area that reduces treating fluid and air, can prevent liquid evaporation, air oxidation.

The contact area of photograph treating fluid and air in treatment trough can be by representing with undefined aperture opening ratio.That is,

Aperture opening ratio=[contact area (the cm for the treatment of fluid and air ²)] ÷ [capacity (cm for the treatment of fluid ³)].

Above-mentioned aperture opening ratio is preferably below 0.1, more preferably 0.001-0.05.As the method that reduces this aperture opening ratio, for example, be provided with the method for veils such as floating head except handling on the liquid level in the photograph of treatment trough, also can there be the spy to open the method for the use movable cover of putting down in writing in the flat 1-82033 communique; The spy opens the slit developing method of putting down in writing in the clear 63-216050 communique.Reduce aperture opening ratio, be not only applicable to color development and develop and two processes of black-and-white development, and be applicable to each follow-up process, for example, in all processes of bleaching, blix, photographic fixing, washing, stabilization.By using the method for accumulating that suppresses bromide ion in the developer solution, also can reduce magnitude of recruitment.

The time of color development development treatment is set between 2-5 minute usually, by forming the luminous development host of high pH of high temperature and use high concentration, also can further shorten the processing time.

Photographic emulsion layer after color development develops is handled by bleaching usually.Bleaching is handled and the photographic fixing processing can be carried out (blix processing) simultaneously, also can carry out respectively.For fast processing, also can use in bleaching and handle the disposal route that the after bleaching photographic fixing is handled.And then handle the continuous blix Lip river of two grooves, blix carries out that photographic fixing is handled before handling or, blix is bleached processing after handling, and can at random implement according to purpose.As bleaching agent, for example can use iron polyvalent metal compounds such as (III), peracid (particularly, sodium peroxydisulfate is suitable for film with colored negative film), benzoquinones class, nitro compound.As representational bleaching agent, for example can use organic complex salt of iron (III), for example, ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, CDTA, methyliminodiacetic acid, 1, the complex salt of aminopolycarboxylic classes such as 3-diaminopropanetetraacetic acid, glycoletherdiaminotetraacetic acid, perhaps for example with the complex salt of citric acid, tartrate, malic acid.In these, consider that with ethylenediamine tetraacetic acid iron (III) complex salt, and 1,3-diaminopropanetetraacetic acid iron (III) complex salt is that aminopolycarboxylic iron (III) complex salt of representative is ideal from fast processing and antipollution aspect.And then amino carboxylic acid iron (III) complex salt is particularly useful in bleaching liquid or the bleach-fixing liquid.Use the bleaching liquid of these aminopolycarboxylic iron (III) complex salts or the pH of bleach-fixing liquid, be generally 4.0-8,, also can under low pH, handle for fast processing.

In bleaching liquid, bleach-fixing liquid and their above-mentioned body lotion, as required, can use bleach boosters.Useful bleach boosters instantiation can use to be put down in writing in following instructions and the communique, for example can use United States Patent (USP) No. 389385, No. the 1290812nd, Deutsches Reichs-Patent, with No. 2059988, spy open clear 53-32736 number, with 53-57831 number, with 53-37418 number, with 53-72623 number, with 53-95630 number, with 53-95631 number, with 53-104232 number, with 53-124424 number, with 53-141623 number, with the compound with sulfydryl or disulfide group of record in 53-18426 number, researchdisclosure No.17129 number (in July, 1978); The spy opens the tetrahydrothiazole derivates of clear 51-140129 number record; The spy open clear 45-8506 number, spy open clear 52-20832 number, with the thiourea derivative of record in No. the 3706561st, 53-32735 number, United States Patent (USP); No. the 1127715th, Deutsches Reichs-Patent, spy open the iodide salt of record in clear 58-16235 number; No. the 966410th, Deutsches Reichs-Patent, with the polyoxyethylene compound class of record in No. 2748430; The polyamino compound of special public clear 45-8836 number record; In addition, the spy open clear 49-40943 number, with 49-59644 number, with 53-94927 number, with 54-35727 number, with 55-26506 number, with the compound of record in 58-163940 number; Bromide ion etc.Wherein, from the very big viewpoint of facilitation effect, the compound with sulfydryl or disulfide group it is desirable to especially for desirable, No. 3893858 instructions of United States Patent (USP), Deutsches Reichs-Patent No. 1290812 instructions, spy open the compound of putting down in writing in the clear 53-95630 communique.Further it is desirable to the compound of putting down in writing in No. 4552884 instructions of United States Patent (USP).These bleach boosters can add in the photosensitive material.When the color sensitive material to photography usefulness carried out blix, these bleach boosters were effective especially.

In bleaching liquid and the bleach-fixing liquid, painted for preventing to bleach except above-claimed cpd, preferably contain organic acid.Good especially organic acid be acid ionization constant (pKa) for the compound of 2-5, specifically have, for example acetate, propionic acid, glycolic acid.

As the fixer that uses in stop bath and the bleach-fixing liquid, for example can enumerate thiosulfate, thiocyanate, thioether based compound, Thiourea, a large amount of iodide salt.Wherein, use thiosulfate usually, most widely used is ATS (Ammonium thiosulphate).In addition, thiosulfate is preferably also used with thiocyanate, thioether based compound, thiocarbamide.As the antioxidant of stop bath and bleaching/fixing bath, the sulfinic acid compound of record in sulphite, hydrosulfite, the heavy sulphurous acid addition product of carbonyl or the European patent 294769A number preferably.Stable for what bathe, preferably in stop bath and bleach-fixing liquid, add various aminopolycarboxylic classes or organic phosphine acids.

Among the present invention, in order to adjust pH, preferably adding pKa with the 0.1-10 mol in stop bath or bleach-fixing liquid is the compound of 6.0-9.0, preferably as imidazoles such as imidazoles, 1-methylimidazole, 1-ethyl imidazol(e), glyoxal ethylines.

Total desilverization process time is short more good more in the scope that does not produce the bad desilverization.The preferred time is 1-3 minute, more preferably 1-2 minute.In addition, treatment temperature is 25-50 ℃, is preferably 35-45 ℃.In the temperature range of the best, can improve desilverization speed, and, can effectively prevent to handle the back and take place painted.

In desilverization process, preferably strengthen as far as possible and stir.As the concrete grammar that strengthen to stir, have and use special collision method and the special spinning solution of putting down in writing in the clear 62-183460 communique of putting down in writing in the clear 62-183461 communique of opening of opening to the emulsion side inject process liquid stream of photosensitive material, improve the method for mixing effect.And then, Yi Bian can enumerate the wind-screen wiper blade that is located in the body lotion contact with the emulsion surface, mobile photosensitive material on one side, by in emulsion surface formation turbulent flow, the method for raising mixing effect and increase the method for total treating fluid circular flow.This stirring raising method to bleaching liquid, bleach-fixing liquid, stop bath is any all is effective.Think that this is that its result can improve the cause of desilverization speed because stirring can improve the speed of supplying with bleaching agent and fixer in the emulsion film.Above-mentioned stirring raising method, more effective than the situation of using bleach boosters, can significantly increase facilitation effect, and utilize bleach boosters can eliminate the photographic fixing inhibition.

The automatic processing machine that uses in the developing photosensitive material of the present invention, preferably have the spy open clear 60-191257 number, with 60-191258 number, with the handling apparatus for photosensitive material of putting down in writing in 60-191259 number each communique.Open in the clear 60-191257 communique as above-mentioned spy and to put down in writing, this conveying device can significantly reduce in the past body lotion body lotion carrier band treating fluid backward, prevents that the effect of performance degradation for the treatment of fluid is remarkable.This effect is for the processing time and the minimizing treating fluid magnitude of recruitment of each process of shortening, and is effective especially.

Silver halide colour photographic sensitive material of the present invention is after the desilverization is handled, general through washing and stabilization process.Washing amount in the water-washing process is according to characteristic (for example, depending on as material therefors such as coupling agents), the purposes of photosensitive material, and then, for example, according to the arbitrary way of the quantity (progression) of washing temperature, rinsing bowl, adverse current, following current, other various conditions can be set in very wide scope.Wherein, according to Journal of the Society of Motion Picture andTelevision Engineers the 64th volume, the method for record in (May nineteen fifty-five number) is P.248-253 obtained the relation of rinsing bowl number and the water yield in the multi-stage countercurrent mode.

According to the multi-stage countercurrent mode of putting down in writing in the above-mentioned document, can reduce the washing amount significantly, but since increased water in groove hold-up time and diseaseful breeding, the suspension that occurs generating is attached to the problem on the photosensitive material.In color sensitive material of the present invention is handled, as the countermeasure that solves this kind problem, can use the spy to open the minimizing calcium ion of putting down in writing in the clear 62-288838 communique, the method for magnesium ion, very effective.Also can use the spy to open to put down in writing in the clear 57-8542 communique, be germifuge for example as chlorine such as isothiazoline (イ ソ チ ア ゾ ロ Application) compound or thiabendazole (サ イ ア ベ Application ダ ゾ-Le) class, chlorination fulminuric acid sodium, in addition, for example, can use as benzotriazole etc., hole mouth feelings work " fungi-proofing anti-little dose chemistry " (1986) three is published altogether, health technology can be compiled " sterilization of microorganism, sterilization, mildew-resistant technology " (nineteen eighty-two) industrial technology meeting, germifuge of putting down in writing in " fungi-proofing mildewproof agent topical reference book " (1986) is compiled by Japanese fungi-proofing mildew-resistant association.

The pH of the washing water during photosensitive material of the present invention is handled is 4-9, is preferably 5-8.Washing temperature and washing time, for example can be according to the characteristic of photosensitive material, purposes is carried out all settings, generally be, be 20 seconds-10 minutes at 15-45 ℃, be 30 seconds-5 minutes preferably at 25-40 ℃.For photosensitive material of the present invention, also can directly handle to replace above-mentioned washing with stabilizing solution.For such stabilization processes, can use the spy open clear 57-8543 number, with 58-14834 number, with all known methods of putting down in writing in 60-220345 number each communique.

And the above-mentioned washing that continues is handled, and also carries out stabilization processes sometimes.As its example, can enumerate as the stable body lotion final body lotion, that contain colorant stabilizer and surfactant of photography with color sensitive material.As colorant stabilizer, aldehydes, N-methylol compound, hexamethylenetetramine or aldehyde sulphurous acid addition products such as formaldehyde or valeral are for example arranged.In these stabilizer baths, can add various sequestrants and mildewproof agent.

The above-mentioned additional overflowing liquid that causes that is accompanied by washing and/or stabilizing solution also can utilize in other processes such as desilverization process again.

For example, in the processing of using automatic processing machine, when above-mentioned each treating fluid was concentrated because of evaporation, it was concentrated to compensate preferably to add water.

Silver halide colour photographic sensitive material of the present invention for the simplification handled and rapid, also can include color development development host.In order to include, preferably use the various presomas of color development development host.For example, the indenes aniline based compound of putting down in writing in No. 3342597 instructions of United States Patent (USP) is arranged, for example: with No. 3342599 instructions, researchdisclosure No.14850 with the schiff base type compound of putting down in writing among the No.15159, open the urethane based compound of putting down in writing in the clear 53-135628 communique with the metal salt complex, the spy that put down in writing in the pure aldehyde compound of putting down in writing among the No.13924, No. 3719492 instructions of United States Patent (USP).

Silver-halide color photoelement of the present invention as required, develops in order to promote color development, also can include various 1-phenyl-3-pyrazolidine ketone.Exemplary compounds for example is to open clear 56-64339 communique the spy, with the 57-144547 communique with put down in writing in the 58-115438 communique.

Various treating fluid of the present invention can use in 10-50 ℃.The temperature of generally held standard is 33-38 ℃, adopts higher temperature, can promote to handle, and shortens the processing time, otherwise, if adopt more low temperature, can improve the stability of image quality and improvement treating fluid.

Photosensitive silve halide material of the present invention, also applicable to United States Patent (USP) No. 4500626 instructions, spy open clear 60-133449 communique, with the 59-218443 communique, with the heat developing photo sensitive material of record in 61-238056 communique, the European patent 210660A2 instructions etc.

Silver halide colour photographic sensitive material of the present invention when the film (film) of the band lens of record installs in being applied to special fair 2-32615 communique, real fair 3-39784 communique etc., is easy to realize more effective effect.

Embodiment

Below, enumerate embodiment and be described more specifically the present invention.But the present invention is not subjected to the qualification of these embodiment.

Embodiment 1

1) modulation of emulsion

(emulsion kind)

Open the emulsion 1C that puts down in writing among the embodiment 1 of flat 11-174606 communique for the spy, the addition of the silver iodide particulate in the modulated growth processes, make the total silver amount silver iodide containing ratio in the particle after the growth course end is reached 10 moles of %, modulated the dull and stereotyped particle of silver halide thus.After the washing, add gelatin, adjust pH and be 5.7, pAg is 8.8, the silver-colored reduced mass of every 1kg emulsion is that 131.8g, gelatin quality are 64.1g, has formed the emulsion kind.The emulsion that obtains is that ratio by the diameter of equivalent circle of 10 moles of % of average silver iodide containing ratio, average ball equivalent diameter 0.7 μ m, averaged particles and thickness is the particle that 28 particle constitutes.

(Em-A1)

With the trihemellitic acid rate is 97% trihemellitic acid gelatin 46g, the aqueous solution that contains 1.7gKBr of 1211ml, remains under 75 ℃, carries out high degree of agitation.After adding the above-mentioned emulsion kind of 48g, add the rotten silicone oil (Japanese ユ ニ カ-Co., Ltd.'s goods, L7602) of 0.3g.Add H ₂SO ₄, pH is adjusted into 5.5 after, with two gunitees, in 12 minutes, add and contain AgNO ₃7.0g aqueous solution 67.6mL and contain the KBr of 10 moles of %KI and the mixed aqueous solution of KI, making flow accelerate to final flow is 3.5 times of initial stage flow.At this moment, with respect to saturated calomel electrode, silver-colored current potential is remained on+20mV.After adding 2mg sodium benzenethiosulfonate and 2mg thiourea dioxide, use two gunitees again, add in 143 minutes and contain AgNO ₃The aqueous solution 762mL of 170g and contain the KBr of 10 moles of %KI and the mixed aqueous solution of KI, making flow accelerate to final flow is 3.0 times of initial stage flow.At this moment, with respect to saturated calomel electrode, silver-colored current potential is remained on+20mV.With two gunitees, add in 11 minutes and contain AgNO ₃23.4g aqueous solution 75mL and KBr aqueous solution.At this moment, with respect to saturated calomel electrode, silver-colored current potential is remained on-10mV.Be warmed up to 82 ℃, add KBr, silver-colored current potential is adjusted into-80mV after, adding with the KI mass conversion is the emulsion that contains 0.037 μ m particle size silver iodide particulate of 2.28g.After adding end, in 10 minutes, add 100.2mL at once and contain 23.4g AgNO ₃Aqueous solution.In 5 minutes of the interpolation initial stage, silver-colored current potential is remained on-80mV with the KBr aqueous solution.After the washing, add gelatin, 40 ℃ are adjusted pH down is 5.8, and pAg is 8.7.After adding compound 1 and 2, be warmed up to 60 ℃.After adding sensitizing coloring matter ExS-1 and ExS-2, add potassium rhodanide, chlorination auric acid, sodium thiosulfate, N, N-dimethyl selenourea (N, N-ヂ メ チ Le セ レ ノ ウ レ ア) carries out the optimum chemical sensitization.When chemical sensitization finishes, add the compound F 17-hydroxy-corticosterone-2 of compound 1 and following announcement.So-called herein optimum chemical sensitization is meant for per 1 mole of silver halide, from 10 ^-1～10 ^-8Select sensitizing coloring matter and all cpds in the addition scope of mole.

This emulsion is, average ball equivalent diameter is 1.70 μ m, and the average equivalent circular diameter is 2.80 μ m, with (111) face of the diameter of equivalent circle of averaged particles and the ratio 4.8 of thickness dull and stereotyped particle as principal plane.

With the limit cooling in liquid nitrogen of gained particle, the limit is observed with TEM, the result observes, in projected area,, account for 90% of sum with the interior particle of dislocation line that do not exist 80% from the particle core, and in projected area, from the particle peripheral part, at 20% particle periphery, per 1 particle has the dislocation line more than 10.

According to the method for record herein, utilize to use the analytic electron microscope method of electric field emission type electron gun, measure the silver iodide containing ratio I on the top layer of gained particle ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 40% of total projection area with (111) face.

Change 38

Change 39

Change 40

Compound 1

Change 41

Compound 2

(Em-A2)

(modulation of iodine silver bromide fine grain emulsion)

The 1000mL solution that will contain 0.3g KBr, 30g gelatin is warmed up to 45 ℃, fully stirs.Then adding 700mL simultaneously contains 148g AgNO ₃Silver nitrate aqueous solution and 700mL contain the halide solution of 96.3g KBr, 10.1g KI, Yi Bian keep the flow velocity of 47.5mL/min, Yi Bian continue to add 10 minutes.Carry out common desalination, add gelatin.Tiao Zhi emulsion is to be 7 moles of % by average silver iodide containing ratio like this, and average particle size is the emulsion (iodine silver bromide fine grain emulsion) that the iodine silver bromide particulate of 0.04 μ m constitutes.

(modulation of silver bromide fine grain emulsion)

In the modulation of above-mentioned iodine silver bromide fine grain emulsion,, carry out same modulation except only halide solution being become the KBr.Tiao Zhi emulsion is to be the emulsion (silver bromide fine grain emulsion) that the silver bromide particulate of 0.05 μ m forms by average particle size like this.

(modulation of Em-A2)

For above-mentioned (Em-A1), washing is warmed up to 60 ℃ after finishing, and with KBr solution silver-colored current potential is remained on-35mV with respect to saturated calomel electrode.Subsequently, add the average particle size 0.04 μ m that obtains as above-mentioned modulation, the iodine silver bromide fine grain emulsion of average 7 moles of % of silver iodide containing ratio, make its amount reach 2 moles of %, carry out slaking in 30 minutes with respect to total silver amount.After confirming that the particulate that adds dissolves fully, utilize common sedimentation washing to carry out desalination.Then, be warmed up to 60 ℃ again, silver-colored current potential remained on-77mV with respect to saturated calomel electrode with KBr solution.Afterwards, add silver bromide fine grain emulsion, make its amount reach 3 moles of %, carry out slaking in 10 minutes with respect to total silver amount as the average particle size 0.05 μ m of above-mentioned modulation, in addition, the same Em-A2 that modulated with (Em-A1).

The particle that one side obtains with cooled with liquid nitrogen, observe with TEM on one side, the result observes, in projected area,, account for 90% of sum with the interior particle of dislocation line that do not exist 80% from the particle core, and in projected area, from the particle peripheral part, at 20% particle periphery, per 1 particle has the dislocation line more than 10.

According to the method for record herein, utilize to use the analytic electron microscope method of electric field emission type electron gun, measure the silver iodide containing ratio I on the top layer of gained particle ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 80% of total projection area with (111) face.In addition, I ₂/ I ₁＜0.8 be that the particle of principal plane accounts for 65% of total projection area with (111) face

(Em-J1)

To contain weight-average molecular weight and be about 15000 low-molecular-weight oxidation processes gelatin 1.6g, the aqueous solution 1300mL of KBr1.0g, and remain on 58 ℃, adjusting pH is 9, fully stirs.With two gunitees, add in 30 seconds and contain 1.3g AgNO ₃Aqueous solution and contain 1.1g KBr and the 0.7g weight-average molecular weight is the aqueous solution of 15000 low-molecular-weight oxidation processes gelatin, the formation of examining.Add 6.6g KBr then, be warmed up to 78 ℃, slaking.After slaking finished, adding 15.0g was the gelatin that 100,000 alkali treated gelatin carries out chemical modification with succinic anhydride to weight-average molecular weight, subsequently, pH is adjusted to 5.5.Again with two gunitees, in 30 minutes, add 230mL and contain 29.3g AgNO ₃Aqueous solution and contain the aqueous solution of 15.8g KBr and 1.92KI.At this moment, silver-colored current potential is remained on-20mV with respect to saturated calomel electrode.And then, accelerate flow with two gunitees, in 37 minutes, add and contain 64.5g AgNO ₃Aqueous solution and the 233mL aqueous solution that contains 42.3g KBr and 5.14g KI, and final flow reaches 1.33 times of the initial stage flow.At this moment, during the interpolation, the silver position is remained on-20mV.Then, keep silver-colored current potential to be-10mV, in 35 minutes, contain 70.8g AgNO simultaneously with two gunitees interpolations ₃Aqueous solution and KBr aqueous solution.

After cooling the temperature to 40 ℃, add 4.9g compound 2, add the sodium sulfite aqueous solution of 32mL 0.8M again.Then adjust pH 9.0, kept 5 minutes with the NaOH aqueous solution.After temperature is raised to 55 ℃, use H ₂SO ₄Modulation pH is 5.5.Add 1mg benzene thiosulfonic acid sodium, adding the 13g calcium concentration is the lime treatment gelatin of 1ppm.After adding end, in 20 minutes, the limit is added 250mL and is contained 71.0g AgNO ₃Aqueous solution and KBr aqueous solution, the limit remains on silver-colored current potential+75mv.At this moment, with respect to 1 moles of silver, add 1.0 * 10 ^-5The potassium ferrocyanide and 1 * 10 of mole ^-8The K of mole ₂IrCl ₆

After the washing, add gelatin, adjust down that pH is 6.5, pAg is 8.8 for 40 ℃.After being warmed up to 56 ℃, after adding sensitizing coloring matter ExS-3, ExS-4, ExS-5 and compound 2, add potassium rhodanide, chlorination auric acid, sodium thiosulfate, N again, N-dimethyl selenourea and following compound F 17-hydroxy-corticosterone-11, and then add compound 3, carry out optimum chemical sensitization.When finishing, chemical sensitization adds following compound F 17-hydroxy-corticosterone-2.

This emulsion is average ball equivalent diameter 1.33 μ m, average equivalent circular diameter 2.63 μ m, the ratio 11.4 of the diameter of equivalent circle of averaged particles and thickness with the dull and stereotyped particle of (111) face as principal plane.

The particle that obtains with cooled with liquid nitrogen, one side are observed with TEM on one side, the result observes, in projected area, from the particle core, account for 90% of sum 80% with the interior particle of dislocation line that do not exist, and in projected area, from the particle peripheral part, at 20% particle periphery, per 1 particle has the dislocation line more than 10.

According to the method for record herein, utilize to use the analytic electron microscope method of electric field emission type electron gun, measure the silver iodide containing ratio I on the top layer of gained particle ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 38% of total projection area with (111) face.

Change 42

Compound 3

Change 43

Change 44

Change 45

(Em-J2)

For above-mentioned (Em-J1), washing is warmed up to 60 ℃ after finishing, and uses KBr solution, is equivalent to saturated calomel electrode, and silver-colored current potential is remained on-35mV.Afterwards, add average particle size 0.04 μ m, the iodine silver bromide fine grain emulsion of average 7 moles of % of silver iodide containing ratio makes the silver amount of interpolation reach 2 moles of %, slaking 30 minutes with respect to total silver amount.Confirm that the particulate that adds dissolves fully, and implement to be warmed up to 60 ℃ again after the ultrafiltration operation, silver-colored current potential is remained on-75mV with respect to saturated calomel electrode with KBr.Afterwards, adding average particle size is the silver bromide fine grain emulsion of 0.05 μ m, and makes the silver amount of interpolation reach 4 moles of % with respect to total silver amount, slaking 10 minutes, in addition, the same Em-J2 that modulated with (Em-J1).

In above-mentioned ultrafiltration operation, ultra filtration membrane has used the Port-Le Off イ Le ト ロ Application ultra filtration membrane of the molecular cut off of Japanese Port Le Co., Ltd. system as 100K.Pressure to ultra filtration membrane is high more, filters piece more, when too high, can cause film rupture, so suitable pressure is 1-10kg/cm ²

According to the method for record herein,, measure the silver iodide containing ratio I on the top layer of gained particle with the analytic electron microscope method of using the electric field emission type electron gun ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 75% of total projection area with (111) face.In addition, I ₂/ I ₁＜0.7 be that the particle of principal plane accounts for 65% of total projection area with (111) face.

(Em-P1)

To contain the phthalic acid rate and be 97%, weight-average molecular weight is 100,000 O-phthalic acidifying gelatin 0.38g and the aqueous solution 1200mL of 0.99g KBr remains on 60 ℃, and pH is adjusted into 2, fully stir.With two gunitees, interpolation contains 1.96g AgNO in 30 seconds ₃Aqueous solution and contain the aqueous solution of 1.97g KBr, 0.172g KI.After treating that slaking finishes, add contain among the every 1g of 12.8g 35 micromole's methionine, weight-average molecular weight is about gelatin 100,000, amino carried out the trihemellitic acidization of chemical modification with trihemellitic acid.After PH adjusted to 5.9, add KBr 2.99g, NaCl 6.2g.Add in 35 minutes with two gunitees and to contain 27.3gAgNO ₃Aqueous solution 60.7mL and KBr aqueous solution.At this moment, with respect to saturated calomel electrode, silver-colored current potential is remained on-30mV.Then, in the stirring apparatus outside being arranged on reaction vessel, add simultaneously and contain 65.6g AgNO ₃Aqueous solution and to contain KBr and KI and weight average molecule be 20,000 aqueous gelatin solution, the iodine silver bromide fine grain emulsion of 6.5 moles of % of modulation silver iodide containing ratio added this iodine silver bromide fine grain emulsion in the reaction vessel in 62 minutes simultaneously.At this moment, silver-colored current potential is remained on ± 0mV with respect to saturated calomel electrode.

After adding the 1.5mg thiourea dioxide,, in 13 minutes, add 132mL and contain 41.8g AgNO with two gunitees ₃Aqueous solution and KBr aqueous solution.Adjust the water-soluble liquid measure of KBr of adding, the silver-colored current potential that adds when finishing is reached+40mV.After adding 2mg benzene thiosulfonic acid sodium, add KBr, silver-colored current potential is adjusted into-100mV.With the KI mass conversion, add the above-mentioned silver iodide fine grain emulsion of 6.2g.After adding end, in 8 minutes, add 300mL at once and contain 88.5g AgNO ₃Aqueous solution.Adjust the addition of KBr aqueous solution, the current potential that adds when finishing is reached+60mV.After the washing, add gelatin, under 40 ℃, adjust pH and be 6.5, pAg is 8.2.After being warmed up to 61 ℃, add sensitizing coloring matter ExS-6, ExS-7, ExS-8, compound 3, add K again ₂IrCl ₆, potassium rhodanide, chlorination auric acid, sodium thiosulfate, hexafluoro phenyl diphenylphosphine hydrogen selenide, compound 1, carry out optimum chemical sensitization.When finishing, chemical sensitization adds F-2.

The particle that obtains with cooled with liquid nitrogen, observe with TEM simultaneously, the result observes, in projected area,, account for 90% of total population with the interior particle of dislocation line that do not exist 80% from the particle core, and in projected area, from the particle peripheral part, at 20% particle periphery, per 1 particle has the dislocation line more than 10.

According to the method for record herein,, measure the silver iodide containing ratio I on the top layer of gained particle with the analytic electron microscope method of using the electric field emission type electron gun ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 46% of total projection area with (111) face.

Change 46

Change 47

Change 48

(Em-P2)

To above-mentioned (Em-P1), washing is warmed up to 60 ℃ after finishing, and usefulness KBr solution with respect to saturated calomel electrode, remains on silver-colored current potential-35mV.Afterwards, add the iodine silver bromide fine grain emulsion of above-mentioned average particle size 0.04 μ m, average 7 moles of % of silver iodide containing ratio, and make the silver amount of interpolation reach 2 moles of %, slaking 30 minutes with respect to total silver amount.The particulate that confirm to add dissolves fully, and after similarly implementing the ultrafiltration operation with (Em-J2), is warming up to 60 ℃ again, uses KBr solution, and silver-colored current potential with respect to saturated calomel electrode, is remained on-70mV.Afterwards, adding above-mentioned average particle size is the silver bromide fine grain emulsion of 0.05 μ m, and makes the silver amount of interpolation reach 5 moles of % with respect to total silver amount, and in addition slaking 10 minutes, is modulated into Em-P2 with (Em-P1) the samely.

The particle that one side obtains with cooled with liquid nitrogen, observe with TEM on one side, the result observes, in projected area,, account for 90% of total population with the interior particle of dislocation line that do not exist 80% from the particle core, and in projected area, from the particle peripheral part, at 20% particle periphery, per 1 particle has the dislocation line more than 10.

According to the method for record herein,, measure the silver iodide containing ratio I on the top layer of gained particle with the analytic electron microscope method of using the electric field emission type electron gun ₁And I ₂, its result, I ₂/ I ₁＜1.0 be that the particle of principal plane accounts for 60% of total projection area with (111) face.In addition, I ₂/ I ₁＜0.9 be that the particle of principal plane accounts for 52% of total projection area with (111) face.

As above Tiao Zhi emulsion Em-A1-A2, the feature of J1-J2, P1-P2 particle is shown in table 1.

Table 1

Emulsion	Average ball equivalent diameter μ m	Average equivalent circular diameter μ m	The coefficient of alteration of diameter of equivalent circle	The ratio of the diameter of equivalent circle of averaged particles and thickness	????I 1Mean value	????I 2/I 1＜1 account for the ratio (%) of total projection area as the particle of principal plane with (111) face	Dislocation line (bar/particle)	Remarks
									Em-A1	??1.70	??2.80	??28	????4.8	????5.5	????40％	Article 10, more than	The comparison emulsion of A2
Em-A2	??1.70	??2.80	??28	????4.8	????5.0	????80％	Article 10, more than	The silver iodide containing ratio regulation emulsion on top layer
									Em-J1	??1.33	??2.63	??25	????11.4	????4.8	????38％	Article 10, more than	The comparison emulsion of J2
Em-J2	??1.33	??2.63	??25	????11.4	????6.0	????75％	Article 10, more than	The silver iodide containing ratio regulation emulsion on top layer
									Em-P1	??1.30	??3.80	??22	????38.0	????4.0	????46％	Article 10, more than	The comparison emulsion of P2
Em-P2	??1.30	??3.80	??22	????38.0	????5.5	????60％	Article 10, more than	The silver iodide containing ratio regulation emulsion on top layer

(more than 60% of total projection area of the ratio 7 expression silver halide particles of the diameter of equivalent circle of averaged particles and thickness in the table 1, the diameter of equivalent circle of its particle is 7 with the ratio of thickness.Also identical in the following table 2)

2) supporter

The supporter that uses in the present embodiment is made as follows.

With 100 mass parts tygon-2,6-naphthalene dicarboxylic acids ester polymer and 2 mass parts are after P.326 (Ciba-Ceigy society system) carries out drying as the Tinuvin of ultraviolet light absorber, after 300 ℃ of following fusions, by T pattern tool extruding, 3.3 times of 140 ℃ of following longitudinal extensions are then under 130 ℃, 3.3 times of horizontal expansions, under 250 ℃, heat fixation 6 seconds obtains the PEN that thickness is 90 μ m (polyethylene naphthalenedicarboxylate dicarboxylic ester) film again.Can add an amount of cyan dye, rosaniline dyes and weld (open skill and technique: I-1, I-4, I-6, I-24, I-26, I-27, the II-5 of 94-6023 number record of public branch designation) in this pen film.And then be wound on the stainless steel core of diameter 20cm, 110 ℃ of thermal treatments, form the supporter that does not have the coiling defective through 48 hours.

3) be coated with and plant coating

After two faces enforcement Corona discharge Treatment, UV discharge process and then the glow discharges processing to above-mentioned supporter, coating gelatin 0.1g/m on each face ², ソ ウ ジ ウ system α-sulfo-two-ethylhexyl succinate 0.01g/m ², salicylic acid 0.04g/m ², parachlorophenol 0.2g/m ², (CH ₂=CHSO ₂CH ₂CH ₂NHCO) ₂CH ₂0.012g/m ², polyamide-chloropropylene oxide condensation product 0.02g/m ²Primary coat liquid (10mL/m ², use rod to be coated with machine), will descend coating to be located at high temperature face side when extending.Implement 6 minutes dryings (roller of dry section and conveying device all are 115 ℃) down for 115 ℃.

4) coating backing layer

On a face that is coated with the above-mentioned supporter after planting coating, as backing layer, be coated with antistatic backing, the magnetic recording layer of following composition, and then sliding layer.

4-1) coating antistatic backing

With mean grain size is that the ratio resistance of 0.005 μ m tin oxide, one antimony oxide compound is that the fine-particle powder of 5 Ω cm disperses thing (2 about 0.08 μ m of aggregated particle diameter) 0.2g/m ², with gelatin 0.05g/m ², (CH ₂=CHSO ₂CH ₂CH ₂NHCO) ₂CH ₂0.02g/m ², poly-(degree of polymerization 10) oxygen ethene-to nonyl phenol 0.005g/m ²And resorcinol is coated with together.

4-2) be coated with magnetic recording layer

Use acetone, butanone, cyclohexanone as solvent, be coated with cobalt-gamma-iron oxide (specific surface area 43m that the machine coating is covered and handles with poly-(degree of polymerization 15) oxygen ethene-third oxygen trimethoxy silane (15 quality %) of 3-with rod ²/ g, major axis 0.14 μ m, single shaft 0.03 μ m, saturated magnetization 89Am ²/ kg, Fe ^{+ 2}/ Fe ^{+ 3}=6/94, the surface with the aluminium oxide monox with 2 quality % iron oxide treatment) 0.06g/m ², diacetyl cellulose 1.2g/m ²(implementing iron oxide with open type mixer and sand mill disperses), and as hardening agent use 0.3g/m ²C ₂H ₅C (CH ₂OCONH-C ₆H ₃(CH ₃) NCO) ₃, obtain the magnetic recording layer that thickness is 1.2 μ m.As matting agent, add 10mg/m respectively ²Silicon oxide particle (0.3 μ m) and 10mg/m ²Lapping compound aluminium oxide (0.15 μ m) with poly-(degree of polymerization 15) oxygen ethene-third oxygen trimethoxy silane (the 15 weight %) lining of 3-processing.115 ℃ of down dry 6 minutes (roller of dry section and conveying device all are 115 ℃).The D of magnetic recording layer under X-light (blue color filter) ^BColour saturation increases share and is about 0.1, and the saturated magnetization square of magnetic recording layer is 4.2Am ²/ kg, coercive force are 7.3 * 10 ⁴A/m, squareness ratio are 65%.

4-3) modulation sliding layer

Coating diacetyl cellulose (25mg/m ²), C ₆H ₁₃CH (OH) C ₁₀H ₂₀COOC ₄₀H ₈₁(compound a, 6mg/m ²)/C ₅₀H ₁₀₁O (CH ₂CH ₂O) ₁₆H (compound b, 9mg/m ²) potpourri.This potpourri is that 105 ℃ dissolve in toluene/propylene monomethyl ether (1/1), joins then in the propylene monomethyl ether (10 times of amounts) of normal temperature, after disperseing to make, in acetone, form and disperse thing (mean grain size 0.01 μ m), and then add.Add silicon dioxide granule (0.3 μ m) as matting agent, and add the aluminium oxide (0.15 μ m) that is coated with poly-(degree of polymerization 15) the oxygen ethylene propylene oxygen trimethoxy silane (15 quality %) of 3-, make their content reach 15mg/m as lapping compound ²115 ℃ of down dry 6 minutes (roller of dry section and conveying device all are 115 ℃).Sliding layer has excellent characteristic, and kinetic friction coefficient is 0.06 (the stainless steel hard sphere of 5mm φ, load 100g, speed 6cm/ branch), coefficient of static friction 0.07 (clip method), and the kinetic friction coefficient of sliding layer and following emulsion side is 0.12, its excellent.

5) photosensitive coated layer

Then on the opposition side of above-mentioned gained backing layer, each layer of the following composition of overlapping coating has been made ISO sensitivity according to JIS K7614-1981 method mensuration and is 1600 colored negative photosensitive material, sample 101.According to sample 101, by each emulsion of replacing respectively shown in the following table 3 in the 5th, 6,8,9,10,11,13,14 layer, and add to outside the DIR colour coupler in the 8th, 9,10 layer and the 13rd layer, made sample 102-114 with sample 101 fully the samely.

At this moment, measure for emulsion to wait silver, and replace the DIR colour coupler with equimolar amounts.For the layer that has used form of mixtures emulsion, with etc. silver measure emulsion for same letter.(for example, the 5th layer of sample 105 is, by the 5th layer of sample 101 with etc. the silver amount emulsion K1 is substituted by K2, to wait silver to measure emulsion L1 is substituted by L2.)。

(composition of photographic layer)

The main material that uses in each layer is classified as follows:

ExC: cyan coupling agent UV: ultraviolet absorber

ExM: pinkish red coupling agent HBS: high boiling organic solvent

ExY: yellow coupler H: gelatin hardener (hard coat agent)

(concrete compound is the material of following record, has paid numerical value behind mark, thereafter also illustration chemical formula is arranged)

With the corresponding numeral of each composition with g/m ²The coating weight of unit representation, with regard to silver halide, the coating weight that expression converts with silver.

The 1st layer (the 1st anti-halo layer)

Black colloidal silver silver 0.07

Gelatin 0.660

ExM-1?????????????????????????????????????????0.048

Cpd-2?????????????????????????????????????????0.001

F-8???????????????????????????????????????????0.001

HBS-1?????????????????????????????????????????0.090

HBS-2?????????????????????????????????????????0.010

The 2nd layer (the 2nd anti-halo layer)

Black colloidal silver silver 0.09

Gelatin 0.830

ExM-1?????????????????????????????????????????0.057

ExF-1?????????????????????????????????????????0.002

F-8???????????????????????????????????????????0.001

HBS-1?????????????????????????????????????????0.090

HBS-2?????????????????????????????????????????0.010

The 3rd layer (middle layer)

ExC-2?????????????????????????????????????????0.010

Cpd-1?????????????????????????????????????????0.086

UV-2??????????????????????????????????????????0.029

UV-3??????????????????????????????????????????0.052

UV-4??????????????????????????????????????????0.011

HBS-1?????????????????????????????????????????0.100

Gelatin 0.580

The 4th layer (low sensitivity magenta-sensitive emulsion layer)

Em-M silver 0.40

Em-N silver 0.35

Em-O silver 0.18

ExC-1????????????????????????????????????????????0.222

ExC-2????????????????????????????????????????????0.010

ExC-3????????????????????????????????????????????0.072

ExC-4????????????????????????????????????????????0.148

ExC-5????????????????????????????????????????????0.005

ExC-6????????????????????????????????????????????0.008

ExC-8????????????????????????????????????????????0.071

ExC-9????????????????????????????????????????????0.010

UV-2?????????????????????????????????????????????0.036

UV-3?????????????????????????????????????????????0.067

UV-4?????????????????????????????????????????????0.014

Cpd-2????????????????????????????????????????????0.010

Cpd-4????????????????????????????????????????????0.012

HBS-1????????????????????????????????????????????0.240

HBS-5????????????????????????????????????????????0.010

Gelatin 1.630

The 5th layer (middle sensitivity magenta-sensitive emulsion layer)

Em-K1 silver 0.43

Em-L1 silver 0.23

ExC-1????????????????????????????????????????????0.121

ExC-2????????????????????????????????????????????0.042

ExC-3????????????????????????????????????????????0.018

ExC-4????????????????????????????????????????????0.074

ExC-5????????????????????????????????????????????0.019

ExC-6????????????????????????????????????????????0.024

ExC-8????????????????????????????????????????????0.010

ExC-9????????????????????????????????????????????0.021

Cpd-2????????????????????????????????????????????0.020

Cpd-4????????????????????????????????????????????0.021

HBS-1????????????????????????????????????????????0.129

Gelatin 0.900

The 6th layer (high sensitivity magenta-sensitive emulsion layer)

Em-J0????????????????????????????????????????????1.15

ExC-1????????????????????????????????????????????0.112

ExC-6????????????????????????????????????????????0.032

ExC-8????????????????????????????????????????????0.110

ExC-9????????????????????????????????????????????0.005

ExC-10???????????????????????????????????????????0.159

Cpd-2????????????????????????????????????????????0.068

Cpd-4????????????????????????????????????????????0.015

HBS-1?????????????????????????????????????????????0.440

Gelatin 1.710

The 7th layer (middle layer)

Cpd-1?????????????????????????????????????????????0.081

Cpd-6?????????????????????????????????????????????0.002

Solid disperse dye ExF-4 0.015

HBS-1?????????????????????????????????????????????0.049

Polyethyl acrylate latex 0.088

Gelatin 0.759

The 8th layer (double-layer effect donor layer (paying the layer of double-layer effect to the sense red beds))

Em-E1 silver 0.40

Cpd-4?????????????????????????????????????????????0.010

ExM-2?????????????????????????????????????????????0.082

ExM-3?????????????????????????????????????????????0.006

ExM-4?????????????????????????????????????????????0.026

ExY-1?????????????????????????????????????????????0.010

ExY-4?????????????????????????????????????????????0.051

ExC-7?????????????????????????????????????????????0.047

HBS-1?????????????????????????????????????????????0.203

HBS-3?????????????????????????????????????????????0.003

HBS-5?????????????????????????????????????????????0.010

Gelatin 0.570

The 9th layer (low sensitivity green-sensitive emulsion layer)

Em-G1 silver 0.15

Em-H silver 0.23

Em-1 silver 0.26

ExM-2?????????????????????????????????????????????0.388

ExM-3?????????????????????????????????????????????0.040

ExY-1?????????????????????????????????????????????0.003

ExY-3?????????????????????????????????????????????0.002

ExC-7?????????????????????????????????????????????0.006

HBS-1?????????????????????????????????????????????0.337

HBS-3?????????????????????????????????????????????0.018

HBS-4?????????????????????????????????????????????0.260

HBS-5?????????????????????????????????????????????0.110

Cpd-5?????????????????????????????????????????????0.010

Gelatin 1.470

The 10th layer (middle sensitivity green-sensitive emulsion layer)

Em-F1 silver 0.30

Em-G1 silver 0.12

ExM-2?????????????????????????????????????????????0.084

ExM-3?????????????????????????????????????????????0.012

ExM-4?????????????????????????????????????????????0.005

ExY-3?????????????????????????????????????????????0.002

ExC-6?????????????????????????????????????????????0.003

ExC-7?????????????????????????????????????????????0.004

ExC-8?????????????????????????????????????????????0.008

HBS-1?????????????????????????????????????????????0.096

HBS-3?????????????????????????????????????????????0.002

HBS-5?????????????????????????????????????????????0.002

Cpd-5?????????????????????????????????????????????0.004

Gelatin 0.382

11th layer (high sensitivity green-sensitive emulsion layer)

Em-P0 silver 1.200

ExC-6?????????????????????????????????????????????0.002

ExC-8?????????????????????????????????????????????0.010

ExM-1?????????????????????????????????????????????0.014

ExM-2?????????????????????????????????????????????0.023

ExM-3?????????????????????????????????????????????0.015

ExM-6?????????????????????????????????????????????0.010

ExM-4?????????????????????????????????????????????0.005

ExM-5?????????????????????????????????????????????0.040

ExY-3?????????????????????????????????????????????0.003

Cpd-3?????????????????????????????????????????????0.004

Cpd-4?????????????????????????????????????????????0.007

Cpd-5?????????????????????????????????????????????0.010

HBS-1?????????????????????????????????????????????0.259

HBS-5?????????????????????????????????????????????0.020

Polyethyl acrylate latex 0.099

Gelatin 1.110

The 12nd layer (filter buffy layer)

Cpd-1?????????????????????????????????????????????0.088

Solid disperse dye ExF-2 0.051

Solid disperse dye ExF-8 0.010

HBS-1?????????????????????????????????????????????0.049

Gelatin 0.593

The 13rd layer (low sensitivity blue-sensitive emulsion layer)

Em-B1 silver 0.50

Em-C silver 0.12

Em-D silver 0.09

ExC-1?????????????????????????????????????????????0.024

ExC-7?????????????????????????????????????????????0.008

ExY-1?????????????????????????????????????????????0.002

ExY-2?????????????????????????????????????????????0.956

ExY-4?????????????????????????????????????????????0.091

Cpd-2?????????????????????????????????????????????0.037

Cpd-3?????????????????????????????????????????????0.004

HBS-1?????????????????????????????????????????????0.372

HBS-5?????????????????????????????????????????????0.047

Gelatin 2.200

The 14th layer (high sensitivity blue-sensitive emulsion layer)

Em-A1 silver 1.22

ExY-2?????????????????????????????????????????????0.235

ExY-4?????????????????????????????????????????????0.018

Cpd-2?????????????????????????????????????????????0.075

Cpd-3?????????????????????????????????????????????0.001

HBS-1?????????????????????????????????????????????0.087

Gelatin 1.156

The 15th layer (the 1st protective seam)

The iodine silver bromide 0.28 of average particle size 0.07 μ m

Silver emulsion

UV-1??????????????????????????????????????????????0.358

UV-2??????????????????????????????????????????????0.179

UV-3??????????????????????????????????????????????0.254

UV-4??????????????????????????????????????????????0.025

F-11??????????????????????????????????????????????0.008

S-1???????????????????????????????????????????????0.078

ExF-5?????????????????????????????????????????????0.0024

ExF-6?????????????????????????????????????????????0.0012

ExF-7?????????????????????????????????????????????0.0010

HBS-1?????????????????????????????????????????????0.175

HBS-4?????????????????????????????????????????????0.050

Gelatin 2.231

The 16th layer (the 2nd protective seam)

H-1???????????????????????????????????????????????0.400

B-1 (diameter 1.7 μ m) 0.050

B-2 (diameter 1.7 μ m) 0.150

B-3???????????????????????????????????????????????0.050

S-1???????????????????????????????????????????????0.200

Gelatin 0.711

And then, in order to improve keeping quality, the property handled, compression resistance, the fungi-proofing property of mildew-resistant, static electricity resistance, to reach coating, can suit in each layer to contain W-1～W-6, B-4～B-6, F-1～F-17, and molysite, lead salt, golden salt, platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt.

(the dispersion thing modulation of organic solid disperse dyes)

The solid dispersion that disperses ExF-2 by the following method.

Add the 3% solution 376g of 4000g water and W-2 in 2800g contains the wet cake of ExF-2 of 18% water, stir, the concentration that forms ExF-2 is 32% slurries.Then, fill the zirconia ball of 1 700mL mean grain size 0.5mm in ア イ メ Star Network ス (strain) system ウ Le ト ラ PVC ス コ ミ Le (UVM-2), feed slurries, with linear velocity 10m/sec, discharge rate 0.5L/min pulverized 8 hours.Mean grain size is 0.45 μ m.

Similarly obtain the solid dispersion of ExF-4, ExF-8.The mean grain size of dyestuff particulate is respectively 0.28 μ m, 0.49 μ m.

Open Em-A～O emulsion modulation method of putting down in writing among the embodiment of Em-A～P of putting down in writing among 2001-92057 number the embodiment and Te Kai 2001-92059 number according to the spy, appropriate change particle formation condition has been modulated emulsion Em-B1～Em-O, and its characteristic is shown in table 2.

Table 2 (silver emulsion E _MThe particle properties of-B1～O)

Emulsion No.	Use layer	Average ball equivalent diameter μ m	The area diameter μ m of averaging projection	The ratio of the diameter of equivalent circle of averaged particles and thickness	Dislocation line (bar/particle)	Average silver iodide amount mol%	The sensitizing coloring matter kind
								Em-B1	The blue layer of low sensitivity sense	??0.9	??1.3	??4.3	Can not observe	??9.0	????ExS-1 ????ExS-2
Em-B2	The blue layer of low sensitivity sense	??1.0	??2.0	??12.2	Article 10, more than	??10.0	????ExS-1 ????ExS-2
								Em-C	The blue layer of low sensitivity sense	??0.7	??0.6	??1.0	Article 10, more than	??4.0	????ExS-1 ????ExS-2
Em-D	The blue layer of low sensitivity sense	??0.4	??0.5	??3.5	Article 10, more than	??4.1	????ExS-1 ????ExS-2
								Em-E1	The sense red beds is paid the layer of double-layer effect	??0.9	??2.0	??4.5	Article 10, more than	??6.0	????ExS-9 ????ExS-11
Em-E2	The sense red beds is paid the layer of double-layer effect	??1.1	??2.6	??20.6	Article 10, more than	??6.7	????ExS-9 ????ExS-11
								Em-P0	The high sensitivity green layer	??1.4	??1.8	??3.0	Can not observe	??5.0	????ExS-6 ????ExS-7 ????ExS-8
Em-F1	Middle sensitivity green layer	??0.9	??2.0	??3.0	Article 10, more than	??7.0	????ExS-6 ????ExS-7 ????ExS-8
								Em-F2	Middle sensitivity green layer	??1.2	??2.7	??18.0	Article 10, more than	??6.9	????ExS-6 ????ExS-7 ????ExS-8

Table 2 (continuing)

Emulsion No.	Use layer	Average ball equivalent diameter μ m	The area diameter μ m of averaging projection	The ratio of the diameter of equivalent circle of averaged particles and thickness	Dislocation line (bar/particle)	Average silver iodide amount mol%	The sensitizing coloring matter kind
								Em-G1	Sensitivity green layer in low	??0.8	??1.6	??4.5	Article 10, more than	??6.1	????ExS-6 ????ExS-7 ????ExS-8
Em-G2	Sensitivity green layer in low	??0.9	??2.0	??15.9	Article 10, more than	??6.1	????ExS-6 ????ExS-7 ????ExS-8
								Em-H	Low sensitivity green layer	??0.7	??1.2	??4.7	Article 10, more than	??6.0	????ExS-8 ????ExS-9 ????ExS-10
Em-I	Low sensitivity green layer	??0.7	??1.2	??4.7	Article 10, more than	??6.0	????ExS-8 ????ExS-9 ????ExS-10
								Em-J0	High sensitivity sense red beds	??1.4	??1.8	??3.0	Can not observe	??5.0	????ExS-3 ????ExS-4 ????ExS-5
Em-K1	Middle sensitivity sense red beds	??1.2	??2.0	??4.0	Article 10, more than	??4.5	????ExS-3 ????ExS-4 ????ExS-5
								Em-K2	Middle sensitivity sense red beds 0	??1.0	??2.4	??20.0	Article 10, more than	??4.5	????ExS-3 ????ExS-4 ????ExS-5

Table 2 (continuing)

Emulsion No.	Use layer	Average ball equivalent diameter μ m	The area diameter μ m of averaging projection	The ratio of the diameter of equivalent circle of averaged particles and thickness	Dislocation line (bar/particle)	Average silver iodide amount mol%	The sensitizing coloring matter kind
								??Em-L1	Middle sensitivity sense red beds	??0.8	??1.5	??4.5	Article 10, more than	??3.5	????ExS-3 ????ExS-4 ????ExS-5
??Em-L2	Middle sensitivity sense red beds	??0.8	??1.9	??19.0	Article 10, more than	??3.6	????ExS-3 ????ExS-4 ????ExS-5
								??Em-M	Low sensitivity sense red beds	??0.6	??1.1	??4.9	Article 10, more than	??2.9	????ExS-3 ????ExS-4 ????ExS-5
??Em-N	Low sensitivity sense red beds	??0.4	??0.6	??4.5	Article 10, more than	??2.0	????ExS-3 ????ExS-4 ????ExS-5
								??Em-O	Low sensitivity sense red beds	??0.3	??0.4	??3.0	Article 10, more than	??1.0	????ExS-3 ????ExS-4 ????ExS-5

The compound that uses in above-mentioned each layer formation as shown below.

Change 49

Change 50

Change 51

Change 52

Change 53

Change 54

Change 55

Change 56

Change 57

Change 58

Change 59

Change 60

Change 61

Change 62

Change 63

6) development treatment

Below by using the system automatic processing machine FP-360B of Fujiphoto society to develop.The overflowing liquid that is transformed into bleaching bath does not flow to the bath of back, and all enters in the waste liquid tank.This FP-360B has carried and has invented the evaporation servicing unit that association discloses record in skill and technique 94-4992 number.

Shown in processing procedure and treating fluid are composed as follows.

(processing procedure)

Process	Processing time	Treatment temperature	Magnitude of recruitment *	Tankage
					Color development develops	????3’5”	????37.8℃	????20mL	????11.5L
Bleaching	????50”	????38.0℃	????5mL	????5L
					Photographic fixing (1)	????50”	????38.0℃	????-	????5L
Photographic fixing (2)	????50”	????38.0℃	????8mL	????5L
					Washing	????30”	????38.0℃	????17mL	????3L
Stable (1)	????20”	????38.0℃	????-	????3L
					Stable (2)	????20”	????38.0℃	????15mL	????3L
Dry	????1’30”	????60.0℃

^*Magnitude of recruitment is, to wide 35mm, and the photosensitive material of 1.1m (being equivalent to the 24Ex.1 bar)

Stabilizing solution and stop bath are from (2) reflux type to (1), and the water overflowing liquid of washing all imports in the fixing bath (2).Developer solution is to the influx of bleaching process, the bleaching liquid influx to fixing, and stop bath is to the influx of water-washing process, and wide for 35mm, the photosensitive material of 1.1m is respectively 2.5mL, 2.0mL, 2.0mL.(cross over) time of leap all is 6 seconds, and this time was included in the processing time of preceding process.

The aperture area of above-mentioned processor is 100cm for the color development developer solution ², bleaching liquid is 120cm ², other treating fluids are 100cm ²

Treating fluid below is shown to be formed

(color development developer solution) tank liquor (g) replenishes liquid (g)

Diethylene-triamine pentaacetic acid 3.0 3.0

Catechol-3,5-disulfonic acid disodium 0.3 0.3

Sodium sulphite 3.9 5.3

Sal tartari 39.0 39.0

Disodium-N, two (the 2-sulphonic acid ester ethyl) hydramines 1.5 2.0 of N-

Potassium bromide 1.3 0.3

Sulfonation potassium 0.3mg-

4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-

テトラザインデン????????????????????0.05????????????-

Hydroxylamine sulfate 2.4 3.3

2-methyl-4-[N-ethyl-N-

(beta-hydroxyethyl) amino] aniline sulfate 4.5 65

Add 1.0 liters 1.0 liters in water

PH (with potassium hydroxide and sulfuric acid adjustment) 10.05 10.18

(bleaching liquid) tank liquor (g) replenishes liquid (g)

1,3-diaminopropanetetraacetic acid iron ammonium-water salt 113 170

Ammonium bromide 70 105

Ammonium nitrate 14 21

Succinic acid 34 51

Maleic acid 28 42

Add 1.0 liters 1.0 liters in water

PH (adjusting) 4.6 4.0 with ammoniacal liquor

(photographic fixing (1) tank liquor)

5: 95 (volume ratio) mixed liquors of above-mentioned bleaching tank liquor and following photographic fixing tank liquor

(photographic fixing (2)) tank liquor (g) replenishes liquid (g)

Thiosulfuric acid aqueous ammonium (750g/l) 240mL 720mL

Imidazoles 7 21

Methane thiosulfonic acid ammonium 5 15

Methane sulfinic acid ammonium 10 30

Ethylenediamine tetraacetic acid 13 39

Add water 1.0L 1.0L

PH (with ammoniacal liquor, acetic acid adjustment) 7.4 7.45

(washing water)

In the mixed bed formula post that is filled with H type storng-acid cation exchange resin (ロ-system ア Application De Ha-system ア of ス society Application バ-ラ イ De IR-120B) and OH type strong-base anion-exchange resin (with ア Application バ ラ イ De IR-400), feed tap water, calcium, magnesium ion concentration are handled below the 3mg/l, then added dichloride fulminuric acid sodium 20mg/l and sodium sulphate 150mg/l.The pH of this liquid is 6.5-7.5.

(stabilizing solution) tank liquor, additional liquid general (g of unit)

SPTS 0.03

The single nonylplenyl ether 0.2 of polyoxyethylene-p-

(average degree of polymerization 10)

1,2-benzisothiazole-3-ketone sodium 0.10

Disodium EDTA 0.05

1,2,4-triazole 1.3

1, two (1,2, the 4-triazol-1-yl methyl) piperazines 0.75 of 4-

Add water 1.0L

pH???????????????????????????????????????????????8.5

Photographic property is estimated

To the sample 101 of above-mentioned making, the ISO sensitivity of mensuration is 1600.

With white light the sample 101-114 of above-mentioned making is implemented image exposure, after carrying out above-mentioned colour development and handling, will pay the exposure inverse of pinkish red concentration (photographic fog+0.5) and obtain as sensitivity.The result is taken as 100 o'clock relative value with sample 101 to be shown in table 3.The RMS value of expression granularity (value of pinkish red concentration photographic fog+0.5 of obtaining with the aperture of diameter 48 μ m), represent that the measurement result of the mtf value of clarity is shown in table 3.

And then, with red light each sample is paid the uniform exposure of 0.05 lux second after, carry out image exposure with green light, the cyan concentration value that deducts pinkish red concentration and be photographic fog+1.5 concentration from the cyan concentration of pinkish red photographic fog concentration is shown in table 3 as the double-layer effect.

Be shown in table 3 as above-mentioned performance of trying to achieve sample 101-114.

Table 3-1

Sample No.	The DIR colour coupler		The emulsion change		Relative sensitivity	RMS value * 1000	MIF value circulation/mm	The double-layer effect	Remarks
										Layer	Compound	Layer	Emulsion
	??101	The 8th, 9,10,13 layers	ExC- 7	The 5th layer										??K1，L1	??100	????21.5	???0.76	??0.21	Comparative example
The 6th layer					??J0
				The 8th layer		??E1
The 9th layer					??G1，H，I
				The 10th layer		??G1，F1
11th layer					??P0
				The 13rd layer		??B1，C，D
The 14th layer					??A1
				??102		The 8th, 9,10,13 layers	(31)	The same	The same	??105	????22.0	???0.85	??0.33	Comparative example
??103	The 8th, 9,10,13 layers	(44)	The same		The same										??100	????21.6	???0.83	??0.30	Comparative example
				??104		The 8th, 9,10,13 layers	(54)	The same	The same	??102	????21.8	???0.92	??0.37	Comparative example
??105	The 8th, 9,10,13 layers	ExC- 7	The 5th layer		??K2，L2										??105	????19.0	???0.64	??0.15	Comparative example
				The 6th layer		??J1
			The 8th layer		??E2
				The 9th layer		??G2，H，I
			The 10th layer		??F2，G2
				11th layer		??P1
			The 13rd layer		??B2，C，D
				The 14th layer		??A1

Table 3-2

Test portion No.	The DIR colour coupler		The emulsion change		Relative sensitivity	RMS value * 1000	MIF value circulation/mm	The double-layer effect	Remarks
										Layer	Compound	Layer	Emulsion
	??106	The 8th, 9,10,13 layers	????(24)	The same										The same	????110	????19.2	???0.83	??0.31	The present invention
??107					The 8th, 9,10,13 layers	????(32)	The same	The same	????107	????19.0	???0.80	??0.29	The present invention
	??108	The 8th, 9,10,13 layers	????(37)	The same										The same	????110	????19.1	???0.88	??0.35	The present invention
??109					The 8th, 9,10,13 layers	????ExC- ????7	The 5th layer	????K2，L2	????107	????18.8	???0.66	??0.16	Comparative example
	The 6th layer	????J2
			The 8th layer	????E2
	The 9th layer	????G2，H，I
			The 10th layer	????F2，G2
	11th layer	????P2
			The 13rd layer	????B2，C，D
	The 14th layer	????A2
			??110	The 8th, 9,10,13 layers			????(24)	The same						The same	????115	????19.0	???0.87	??0.34	The present invention
??111	The 8th, 9,10,13 layers	????(32)			The same	The same			????110	????18.9	???0.85	??0.30	The present invention
			??112	The 8th, 9,10,13 layers			????(37)	The same						The same	????112	????18.9	???0.94	??0.38	The present invention
??113	The 8th, 9,10,13 layers	????(57)			The same	The same			????112	????18.9	???0.92	??0.37	The present invention
			??114	The 8th, 9,10,13 layers			????(61)	The same						The same	????111	????19.0	???0.88	??0.36	The present invention

As shown in Table 3, with respect to sample 101-104, the diameter of equivalent circle of use particle is the 105-108 of the emulsion more than 8 with the ratio of thickness, high sensitivity, graininess excellence, but the sample 105 of use DIR colour coupler in the past, the double-layer effect is less, and color and luster reproduces upward undesirable.The mtf value of expression clarity is also less.Use 106～108 samples of DIR colour coupler of the present invention fully to improve double-layer effect and clarity.

On the other hand, used the sample 109 of the tabular particle of the top layer of regulation of the present invention silver iodide containing ratio, high sensitivity and improved graininess, but because of having used relatively DIR colour coupler, so double-layer effect and clarity are still insufficient, but use the sample 110-114 of DIR colour coupler of the present invention, not only sensitivity, graininess is good but also can realize high-caliber double-layer effect.

And then high sensitivity, high image quality can be provided, so clarity, the photosensitive material that the color and luster repeatability is also good.

(embodiment 2)

The sample 101-114 that makes among the embodiment 1 is cut off processing, pack in the packaging unit that has camera function of Fujiphoto system single-use camera " ス-パ-ス リ system エ-ス ", the photographic article of dress photosensitive material in obtaining.

This photographic article has been carried out evaluation similarly to Example 1, and the result has obtained same result.

Claims (5)

1. silver halide colour photographic sensitive material, on supporter, has the unit sense indigo plant silver halide emulsion layer that the photosensitive emulsion layer constitutes more than 2 layers that sensitivity is different by various colour sensitivity are identical, unit sense green property silver halide emulsion layer and the red property of unit sense silver halide emulsion layer, it is characterized in that, this silver halide colour photographic sensitive material, at least contain a kind with the compound of remembering the expression of general formula (I) or general formula (II) down, and being occupied at the tabular particle more than 5.0 by the diameter of equivalent circle of the particle ratio with thickness of total projection area of contained silver halide particle at least 1 layer of this photosensitive emulsion layer;

[changing 1]

In the formula, R ₁Expression can substitute onto the substituting group on the naphthalene nucleus, and n represents the integer of 0-6, and n is 2 when above, each R ₁Can be the same or different; R ₂The expression alkyl or aryl; R ₂And R ₁Also can be in conjunction with forming ring; R ₃Be m the independent substituting group that closes with fragrant oxygen loops, all R ₃Hami special substituent constant σ p value summation more than 0.1, R ₃And R ₅Also can be in conjunction with forming ring; M represents the integer of 1-3; M is 2 or 3 o'clock, each R ₃Can be the same or different; R ₄And R ₅Represent hydrogen atom, alkyl (comprising naphthenic base), alkenyl (comprising cycloalkenyl), alkynyl or aryl respectively separately; INH represents mercapto-tetrazole derivant, mercapto-triazole derivant, dimercaptothiodiazole derivant, mercapto oxdiazole derivative, thyroidan derivant, Qiu oxazole derivatives, mercaptoimidazole derivant, sulfhydryl benzimidazole derivative, mercaptobenzothiazolderivative derivative, mercaptobenzoxazole derivant, terazole derivatives, 1,2,3-triazole derivative, 1,2, the residue of 4-triazole derivative or benzotriazole derivatives.

2, silver halide colour photographic sensitive material according to claim 1, it is characterized in that, in the above-mentioned silver-halide color photoelement, the full projected area of contained silver halide particle is to be occupied at the tabular particle more than 8.0 by the diameter of equivalent circle of the particle ratio with thickness more than 60% at least 1 layer of photosensitive emulsion layer.

3, silver halide colour photographic sensitive material according to claim 1 and 2 is characterized in that above-mentioned tabular silver halide particle, has 10 above dislocation lines in per 1 particle.

4, according to any described silver halide colour photographic sensitive material of claim 1～3, it is characterized in that contained emulsion at least 1 layer of the photosensitive emulsion layer of this silver halide colour photographic sensitive material, be with the tabular particle of (111) face as principal plane, the silver iodide containing ratio on the top layer of this tabular particle partly is I at principal plane ₁Mole % is I at lateral parts ₂During mole %, I ₂/ I ₁＜1 particle accounts for more than 50% of total silver halide particle projected area.

5, according to any described silver halide colour photographic sensitive material of claim 1～4, the ISO light sensitivity that it is characterized in that above-mentioned silver halide colour photographic sensitive material is more than 640.