CN1035571C - silver halide color photographic lightsensitive material - Google Patents
silver halide color photographic lightsensitive material Download PDFInfo
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- CN1035571C CN1035571C CN 85109626 CN85109626A CN1035571C CN 1035571 C CN1035571 C CN 1035571C CN 85109626 CN85109626 CN 85109626 CN 85109626 A CN85109626 A CN 85109626A CN 1035571 C CN1035571 C CN 1035571C
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- silver halide
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- 0 C#*C(C(C1)C1C(C1)C2C#CC2)=C1I Chemical compound C#*C(C(C1)C1C(C1)C2C#CC2)=C1I 0.000 description 4
- VVKFZFBGPIGOHG-UHFFFAOYSA-O C=Nc(cc1)ccc1[OH2+] Chemical compound C=Nc(cc1)ccc1[OH2+] VVKFZFBGPIGOHG-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/382—Heterocyclic compounds with two heterocyclic rings
- G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A silver halide color photographic material comprising a support having formed thereon at least one silver halide emulsion layer containing a pyrazoloazole series magenta coupler having at least one group expressed by the formula (1). The substituted group of arylsulfonyl amino group is alkoxy, aryloxy or heterocycle group, wherein R1, X, Za, Zb and Zc are defined in the description. The silver halide color photographic light-sensitive material has improved coloring properties.
Description
Content of the present invention relates to silver halide colour photographic sensitive material.Particularly relate to and have the silver halide colour photographic sensitive material that has improved colouristic properties.
More properly say, silver halide colour photographic sensitive material involved in the present invention includes pyrazolo pyrroles series magenta colour coupler, contains Arenesulfonyl amino in this colour coupler molecule, and have alkoxy on the ring of aryl, aryloxy group or heterocyclic oxy group group are as substituting group.
In silver halide colour photographic sensitive material, often use the silver emulsion and the so-called dye forming coupler that can generate dyestuff of energy sensitization.This colour coupler in developing process and the oxidation product of primary aromatic amine class developer react and just generate dyestuff.As everyone knows, these colour couplers are normally with yellow colour former, and the potpourri of cyan coupler and magenta colour coupler is used.
Wherein, usually the 5-pyrazolone series colour coupler as magenta colour coupler has serious problem on the performance of reproducing colour, this is owing to the azomethine dyes that wherein produces demonstrates in 430nm (millimicron) vicinity subsidiary absorption to be arranged, and this is absorbed in reduction suddenly of long-wavelength region.
In order to address these problems, up to the present, the patent of having delivered has more following: rosaniline dyes imaging colour coupler aspect, it is the BrP 1,047,612 of skeleton structure with the pyrazoles benzimidazole that narration is arranged, the United States Patent (USP) 3,725,065 of narration Pyrazolotriazole skeleton structure.In addition, early have Japanese patent application (OPI) No.162548/84, suggestion adopt the 1H-imidazo (1,2-b)-pyrazoles is a skeleton structure; United States Patent (USP) 4,540,654 propose to adopt 1H-pyrazolo (1,5-b) (1,2,4)-triazole is a skeleton structure, in Japanese patent application (OPI) No.33552/85, adopt 1H-pyrazoles (1,5-b)-tetrazolium is a skeleton structure, and in Japanese patent application (OPI) No.43659/85, adopt the 1H-pyrazoles (1,5-b)-pyrazoles is a skeleton structure.
These colour couplers of above-mentioned patent, though aspect tone, may solve some problems, another problem found.In silver halide emulsion layer since in the process of developing under the condition of a kind of oxidation product of the aromatic primary amine developer that forms capacity, the conversion ratio that colour coupler changes into azomethine dyes is but not high, (claiming that hereinafter this kind conversion ratio is for becoming colour efficiency).Thereby reduced maximum quality density value and (hereinafter be expressed as D
Max).
Have seeking to increase into the method that has adopted aspect the method for colour efficiency: introduce the method that can discharge group at the coupling activity site; The method that adds toner; Be the non-dispersive group to be changed become the method (for example, being published in the method for the No.42045/83 of Japanese patent application (OPI)) that is connected on the colour coupler skeleton structure in addition, etc.
First purpose of the present invention is to adopt to have the serial magenta colour coupler of the pyrazolo pyrroles who improves color performance to provide color performance (one-tenth colour efficiency) good silver halide colour photographic sensitive material.
Second purpose of the present invention is to adopt the pyrazolo pyrroles series magenta colour coupler with improvement color sensitive degree that a kind of novel silver halide colour photographic sensitive material with ISO is provided.
Result according to multiple linking group and non-dispersive group are studied has confirmed and can achieve the above object.Method is to adopt a kind of silver halide colour photographic sensitive material that contains pyrazolo pyrroles series magenta colour coupler, and this series colour coupler structurally contains with alkoxy, and aryloxy group or heterocyclic oxy group are its substituent aryl sulphonyl amino group.
With-NHSO
2-as the colour coupler of linking group, previous United States Patent (USP) 2,698,795 and 2,710,803 grades have had report.In recent years, employing-NHSO
2-group is published in United States Patent (USP) 3,894 as the linking group of acyl group-monoacetylaniline type yellow colour former, and 876 and 4,356,258, European patent (EP) No.17833A1 etc.; And adopt-NHSO
2-group is published in United States Patent (USP) 4,124 as the linking group of phenol and naphthol serial cyan coupler, and 396 and 4,334,011 etc.And be published in Japanese patent laid-open publication gazette No.7039/57 with its content as the linking group of 5-pyrazolone series magenta colour coupler, Japanese patent application (OPI) NOS.44927/76 and 146251/82, etc.Yet, for general-NHSO wherein
2-be applied to know little according to the example of pyrazolo pyrroles series of the present invention.And for skeleton with can be used for predicting that the relation owing to combining with it between the spacer group that tells on is unknown usually.And known be, up to the synthetic colour coupler of reality and the effect of so a kind of combination before being applied to silver halide colour photographic sensitive material do not display.Particularly when the skeleton that forms azomethine dyes with known to the routine those not simultaneously, the above-mentioned fact is just more obvious.Therefore, the color performance of pyrazolo pyrroles series magenta colour coupler, can roll into a ball the pyrazolo pyrroles series magenta colour coupler of introducing by formula (I) expression as a substituting group by the fragrant sulfonamido that will be replaced by alkoxy, aryloxy group or the heterocyclic oxy group of formula of the present invention (A) representative and be improved, this makes us very surprised.
The pyrazolo pyrroles colour coupler that can be used among the present invention can be represented with following structural formula (I):
In the formula, R
1Expression hydrogen atom or substituted radical.X represents that hydrogen atom or can discharge group, and this group can discharge when the oxidation product coupling reaction of colour coupler and primary aromatic amine developer.Za, Zb and Zc are expressed as methine separately, replace methine ,=N-or-NH-; Have one to be two keys in Za-Zb key and Zb-Zc key, another then is a singly-bound.When Zb-Zc was carbon-to-carbon double bond, it can be the part on the aromatic rings; R
1Or X can form dipolymer or superpolymer; When Za, Zb or Zc are when being substituted methine, this type of group also may form dipolymer or superpolymer.R
1, X and by in the represented substituted methine group of Za, Zb, Zc, have at least one to contain with the represented above-mentioned group of structural formula (A).
Applied noun " polymkeric substance " in structural formula (I) refers to the minimum compound that has by two parts of formula (I) representative in each molecule, and comprises two compounds and polymkeric substance colour coupler.The polymkeric substance colour coupler can be the homopolymer of being made up of a kind of monomer fully, the part that this monomer has by structural formula (I) expression (preferably has vinyl on the monomer, hereinafter be referred to as vinyl monomer), also can be the multipolymer of the ethylidene monomer of above-mentioned monomer and a kind of non-quality; Coupling reaction does not take place in the oxidation product of this ethylidene monomer and primary aromatic amine developer.
The represented compound of structural formula (I) is a kind of condensation azacyclo-colour coupler of 5-joint ring-5 joint rings.Its painted nuclear shows with naphthalene to have isoelectronic aromaticity, and has usually the chemical constitution that is referred to as " azepine pentalene ".With the colour coupler of structural formula (I) expression, reasonable have more following compounds, and its structural formula is followed successively by (II) (III) (IV) (V) (VI) and (VII), its title be followed successively by the 1H-imidazo (1,2-b) pyrazoles, 1H-pyrazolo (1,5-b) pyrazoles, 1H-pyrazolo (5,1-c) (1,2,4) triazole type, 1H-pyrazolo (1,5-b) (1,2,4) triazole type, 1H-pyrazolo (1,5-b) tetrazolium class and 1H-pyrazolo (1,5-a) benzimidazole.
Arrive in (VII) substituent R at structural formula (II)
2, R
3And R
4Can be expressed as following group separately: hydrogen atom; halogen atom; alkyl; aryl; heterocyclic group; cyano group; alkoxy; aryloxy group; heterocyclic oxy group group; acyloxy; carbamoyloxy; siloxy; sulfonyloxy; acylamino-; phenylamino; urea groups; imino group; aminosulfonyl amino; carbamyl amino; alkylthio group; arylthio; the heterocycle sulfenyl; alkoxy carbonyl amino; the aryloxy group carbon acylamino; sulfonamido; carbamyl; acyl group; sulfamoyl; sulfonyl; sulfinyl; alkoxy carbonyl base or aryloxy group carbonic acyl radical.X represents hydrogen atom, halogen atom, carboxyl or a releasable group when coupling, and it is to be connected on the carbon atom at coupling position place by an oxygen atom, also can play the connection effect by nitrogen-atoms, sulphur atom except that oxygen atom.
Work as R
2, R
3, R
4Or X is when being divalent group, and it can form two compounds.In addition, when appearing on the vinyl monomer with the represented component unit of structural formula (II) to (VII), R then
2, R
3Or R
4Expression key or linking group.Part with structural formula (II) to (VIII) expression couples together by them and vinyl group.
More precisely say R
2, R
3And R
4Can represent more following groups separately; hydrogen atom; halogen atom (routine chlorine atom; bromine source etc.); alkyl (for example; methyl; propyl group; the tert-butyl group; trifluoromethyl; tridecyl; 3-(2; 4-two tertiary pentyl phenoxy groups) propyl group; 2-dodecane oxygen ethyl; 3-benzene oxygen propyl group; 2-hexyl sulfonyl-ethyl; cyclopentyl; benzyl etc.); aryl (phenyl for example; 4-2-methyl-2-phenylpropane base; 2; 4-two uncles penta phenyl; 4-myristoyl aminophenyl etc.); heterocyclic group (for example; the 2-furyl; the 2-thienyl; the 2-pyrimidine radicals; 2-[4-morpholinodithio base etc.); cyano group; alkoxy (methoxyl for example; ethoxy; the 2-methoxyethoxy; 2-dodecyloxy ethoxy; 2-sulfonyloxy methyl ethoxy etc.); aryloxy group (phenoxy group for example; the 2-methylphenoxy; 4-tert-butyl group phenoxy group etc.); heterocyclic oxy group (for example 2-benzimidazole oxygen base etc.); acyloxy (acetoxyl group for example; 16 carbon acyloxy etc.); carbamoyloxy (N-phenyl amino formyloxy for example; N-ethylamino formyloxy etc.); siloxy (for example trimethyl silicane alcoxyl base etc.); sulfonyloxy (for example dodecyl sulfonyloxy etc.); acylamino-(acetylamino for example; benzamido; myristoyl amino; α-(2; 4-two tertiary pentyl phenoxy groups) butyrylamino; γ-(3-tertiary butyl-4-hydroxy phenoxy group) butyrylamino; α-[4-(4-hydroxyphenyl sulphonyl) phenoxy group] lauroyl amino etc.); phenylamino (phenyl amino for example; 2-chlorobenzene amino; 2-chloro-5-myristoyl amino phenyl amino; 2-chloro-5-dodecyloxy phosphinylidyne phenylamino; N-acetophenone amino; 2-chloro-5-[α-(3-tertiary butyl-4-hydroxy phenoxy group) lauroyl ammonia] phenylamino etc.); urea groups (for example phenyl urea groups etc.); imino group (N-succinimide base for example; 3-benzyl hydantoins base; 4-(2-ethyl hexanoyl amino) phthalimido etc.); aminosulfonyl amino (N for example; N-dipropyl aminosulfonyl amino; N-methyl-N-decyl sulfamoylamino group etc.); alkyl sulfenyl (methyl sulfenyl for example; the octyl group sulfenyl; the myristyl sulfenyl; 2-phenoxy group ethyl sulfenyl; 3-phenoxy propyl sulfenyl; 3-(4-tert-butyl group phenoxy group) propyl group sulfenyl etc.); arylthio (thiophenyl for example; 2-butoxy-uncle's 5-octyl group thiophenyl; 3-pentadecane phenyl sulfenyl; 2-carboxyl phenyl sulfenyl; 4-myristoyl aminobenzene sulfenyl etc.); heterocycle sulfenyl (for example 2-[4-morpholinodithio sulfenyl etc.); alkoxy carbonyl amino (methoxyl carbon acylamino for example; tetradecyloxyaniline carbon acylamino etc.); aryloxy group carbon acylamino (phenoxy group carbon acylamino for example; 2; 4-di-tert-butyl oxygen carbon acylamino etc.); sulfonamido (sulfonyloxy methyl amino for example; the cetyl sulfonamido; benzenesulfonamido-; tolysulfonyl amino; the octadecyl sulfonamido; 2-methoxyl-5-tert-butyl benzene sulfonamido etc.); carbamyl (N-ethylamino formoxyl for example; N; N-dibutylamino formoxyl; N-(2-dodecane oxygen ethyl) carbamyl; N-methyl-N-dodecyl carbamyl; N-[3-(2; 4-two tertiary pentyl phenoxy groups) propyl group] carbamyl etc.); acyl group (acetyl group for example; (2; 4-two tertiary pentyl phenoxy groups) acetyl group; benzoyl etc.); sulfamoyl (N-ethyl sulfamoyl for example; N; N-dipropyl sulfamoyl; N-(2-dodecane oxygen ethyl) amino-sulfonyl; N-ethyl-N-dodecane amino-sulfonyl; N; N-diethylamino sulfonyl etc.); sulfonyl (methyl sulphonyl for example; the octyl group sulfonyl; benzenesulfonyl; tosyl etc.); sulfinyl (octyl group sulfinyl for example; the dodecyl sulfinyl; phenylsulfinyl base etc.); alkoxy carbonyl base (methoxyl carbonic acyl radical for example; the butoxy carbonic acyl radical; the dodecyloxy carbonic acyl radical; octadecane oxygen base carbonic acyl radical etc.); or aryloxy group carbonic acyl radical (for example phenoxy group carbonic acyl radical, 3-pentadecyl phenoxy group carbonic acyl radical etc.).X represents hydrogen atom, halogen atom (chlorine atom for example, bromine atoms, iodine atom etc.), carboxyl, group (example by the oxygen atom connection, acetoxyl group, propionyloxy, benzoyloxy, 2,4-dichloro-benzoyl oxygen base, ethoxy ethane diacid acyloxy, pyruvic acid acyl ethyleneoxy, cinnamoyloxy group, phenoxy group, the 4-cyano-benzene oxygen, 4-sulfonyloxy methyl amino-benzene oxygen, 4-methylsulfonyl phenoxy group, the alpha-naphthoxy base, 3-pentadecyl phenoxy group, benzyloxy carbon acyloxy, ethoxy, 2-cyano group ethoxy, benzyloxy, 2-phenethyl oxygen base, 2-phenoxy group ethoxy, 5-phenyltetrazole oxygen base, 2-[4-morpholinodithio base oxygen base etc.).The group that connects by nitrogen-atoms (benzenesulfonamido-for example, N-ethyltoluene sulfonamido, five fluorine butyrylaminos, 2,3,4,5,6-phenyl-pentafluoride formamido group, the octyl group sulfonamido, right-the cyano group phenylcarbamido, N, N-diethyl amino sulfonamido, the 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazole alkyl, 1-benzyl-ethoxy-3-hydantoins base, 2N-1,1-dioxo-3 (2H)-oxo-1,2-benzisothiazole base, 2-oxo-1,2-dihydro-1-pyridine radicals, imidazole radicals, pyrazolyl, 3,5-diethyl-1,2, the 4-triazol-1-yl, 5 or 6-bromo-benzotriazole-1-base, the 5-methyl isophthalic acid, 2,3, the 4-triazol-1-yl, benzimidazolyl, 3-benzyl-1-hydantoins base, 1-benzyl-5-hexadecane oxygen base-3-hydantoins base, 5-methyl isophthalic acid-tetrazole radical, 4-methoxybenzene azo group, 4-pivaloyl aminobenzene azo group, 2-hydroxyl-4-propionyl phenylazo etc.), or the group that connects by sulphur atom (for example, thiophenyl, 2-carboxyl thiophenyl, 2-methoxyl-uncle's 5-octyl group thiophenyl, 4-sulfonyloxy methyl thiophenyl, 4-octyl group sulfonamido thiophenyl, 2-butyl phenyl ether sulfenyl, 2-(2-hexyl sulphonyl ethyl)-uncle's 5-octyl group thiophenyl, benzylthio, 2-cyano group ethylmercapto group, 1-ethoxy phosphinylidyne tridecane sulfenyl, 5-phenyl-2,3,4,5-tetrazolium sulfenyl, 2-[4-morpholinodithio base sulfenyl, 2-dodecane sulfenyl-5-sulfur phenenyl base, 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-sulfenyl etc.).
If the group of structural formula (A) expression is comprised in the X, this X group preferably is not directly connected on the ring structure of pyrazolo pyrroles series colour coupler.(in other words, X itself not merely is structural formula (A) group).
When selecting R in order to generate the dimorphism compound
2, R
3, R
4Or X is when being the group of divalence, and these bivalent radicals can include: substituted or unsubstituted alkylidene (for example, methylene, ethylidene, 1, the inferior decyl of 10-,-CH
2CH
2-O-CH
2CH
2-etc.), be substituted or unsubstituted phenylene, (example, 1,4-phenylene, 1, the 3-phenylene,
Deng).
And group-NHCO-R-CONH-, (R represents to be substituted or unsubstituted alkylidene or phenylene).
When if the group of structural formula (II) to (VII) appears among the vinyl monomer, R
2, R
3, R
4Represented linking group can comprise the group by the group be combined into of selecting in following-a little groups, as be selected from alkylidene (be substituted or unsubstituted alkylidene, for example methylene, ethylidene, 1, the inferior decyl of 10-,-CH
2-CH
2OCH
2CH
2-, etc.), phenylene (substituted or unsubstituted phenylene for example 1,4-phenylene, 1, the 3-phenylene,
Deng) ,-NHCO-,-CONH-,-O-,-OCO-and aryl alkylene are (for example
Deng),
In addition, the vinyl in vinyl monomer except structural formula (II) arrives those pointed vinyl of (VII), comprises having those vinyl of substituting group.Preferred substituted is hydrogen atom, chlorine atom and has 1 to 4 carbon atom (rudimentary) alkyl.
Not participating in the example that oxidation product with the primary aromatic amine developer carries out the non-quality ethylidene monomer of coupling reaction is acrylic acid, α-Lv Bingxisuan, alpha-alkyl acrylic acid (for example methacrylic acid etc.).Ester class that this class oleic series derives or amide-type (acrylamide for example, n-butyl acrylamide, tert-butyl group acrylamide, diacetone acrylamide, Methacrylamide, methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, the acrylic acid-2-ethyl hexyl ester, the acrylic acid n-octyl, lauryl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA and beta-hydroxy n-BMA), methylene two bisacrylamides, vinyl acetate (vinyl acetate for example, propionate and vinyl laurate), vinyl cyanide, methacrylonitrile, aromatic vinyl compound (for example styrene and derivant thereof, vinyltoluene, divinylbenzene, vinyl benzene ethyl ketone and sulfonated phenylethylene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (for example ethyl vinyl ether), maleic acid, maleic anhydride, maleate, N-vinyl-2-Pyrrolidone, the N-vinylpyridine, and 2-and 4-vinylpyridine.Also can get two or more when the unsaturated monomer of the band ethylidene of these non-quality uses and mix use.
Sulfonamido group with regard to structural formula (A) expression does detailed explanation below
Structural formula (A)
In structural formula (A), R
11Expression hydrogen atom, aliphatic group or acyl group; R
12Expression aliphatic group, aromatic group or heterocyclic group; N represents an integer in from 1 to 5; R
13Expression hydrogen atom or a substituting group, m are represented an integer of zero or from 1 to 4.
Being connected substituting group adjacent one another are on the phenyl ring can couple together and form 5 joints or 6 joint rings.
The sulfonamido of structural formula (A) expression is R wherein preferably
11Be hydrogen atom R
12The O-group is connected on the ortho position of the following group on the phenyl ring
R wherein more preferably in the sulfonamido group of structural formula (A) expression
11Be hydrogen atom, R
12The O-group is received on the ortho position of following group and R
12It is alkyl.
More specifically narrate aliphatic group, aromatic group, heterocyclic group and acyl group below.Aliphatic group be contain 1 to 36 carbon atom and comprise straight chained alkyl or branched alkyl, the aliphatic group of alkenyl, aralkyl, naphthenic base, alkynyl and ring-type thiazolinyl.Each these fatty groups can be used each R except hydrogen atom
2, R
3And R
4Group replaces.Aryl is represented phenyl or naphthyl that has 6 to 40 carbon atoms etc., and these aryl also can be with the above-mentioned R that does not comprise hydrogen atom
2, R
3And R
4Group replaces.Heterocyclic group represents that 5 save the group of 7 joint rings, and these groups contain 1 to 4 nitrogen-atoms, oxygen atom and sulphur atom, for example at least: furyl, thienyl, pyrimidine radicals, imidazole radicals, pyrazolyl, benzothiazolyl, piperidyl, morpholino base, benzimidazolyl, triazolyl, triazinyl or the like.These groups can not comprised each R of hydrogen
2, R
3, R
4Substituting group replaces.Acyl group comprises acetyl group, propiono, 2-methylpropionyl, benzoyl etc.
R
13The group of expression comprises at R
2, R
3, R
4Definition in those groups of being narrated.
Representative instance by the group of structural formula (A) expression is as follows, still, the group of structural formula (A) be not limited to following these:
What propose below is colour coupler exemplary with structural formula of the present invention (I) expression, but colour coupler kind of the present invention has more than and is limited to these.
This class colour coupler with structural formula of the present invention (I) expression can synthesize by the technology of the document of announcing below, and they are respectively:
The compound of structural formula (II) is published in Japanese patent application
(OPI) No.16248/84 etc.;
The compound of structural formula (III) is published in Japanese patent application
(OPI) No.43659/85 etc.;
It is open that the compound of structural formula (IV) is published in Jap.P.
No.27411/72 etc.;
The compound of structural formula (V) is published in United States Patent (USP) 4,540,654 Hes
Japanese patent application (OPI) No.172982/85;
The compound of structural formula (VI) is published in Japanese patent application
(OPI) No.33552/85 etc.;
The compound of structural formula (VIII) is published in United States Patent (USP) 3,061,432 etc.:
Can be applicable to the colour coupler with structural formula (I) expression of the present invention and preferably join in the silver halide photographic light-sensitivity layer, certainly, also can be added in the non-sensitization photograph layer as needs.
In silver halide colour photographic sensitive material, what the present invention can be employed comprises: colour paper, colour reversal photographic paper, colour negative, colour positive etc. and wherein be specially adapted to colour paper and colour reversal photographic paper.
Magenta colour coupler of the present invention and as the said colour coupler that is used hereinafter, can be blended in the photosensitive material by the process for dispersing of various routines and go.Have than typical method, solid dispersion method, alkali dispersion method, be preferably with emulsion method, be more preferably oil-in-water and drip method.It is to be dissolved in colour coupler in 175 ℃ of boiling points or the more high boiling high boiling organic solvent and/or to be dissolved in lower boiling being called in the secondary solvent that oil-in-water drips dispersion method, and then this solution is dispersed in aqueous medium that contains surfactant as water and aqueous gelatin solution subtly, the example of high boiling organic solvent is published in United States Patent (USP) 2,322, in 027, and in the content of being narrated below.Dispersion process can accompany by phase transition behavior.Need, secondary solvent can be by distillation, washing emulsion bar, and ultrafiltration or other method were removed before coating or reduced.
The object lesson of dowtherm has phthalic acid ester (dibatyl phithalate for example, phthalic acid two-3,7-dimethyl monooctyl ester, dicyclo-hexyl phthlate, phthalic acid two-2-ethylhexyl, phthalic acid two-dodecane ester etc.), phosphate or phosphonate ester (triphenyl phosphate for example, tricresyl phosphate, phosphoric acid 2-ethylhexyl-diphenyl, tricyclohexyl phosphate, tricresyl phosphate-2-ethylhexyl, tricresyl phosphate-dodecane ester, three butoxy ethyl ester of phosphoric acid, tricresyl phosphate chloropropyl ester, di(2-ethylhexyl)phosphate-2-ethylhexyl phenylester etc.), benzoic ether (benzoic acid-2-ethylhexyl for example, benzoic acid dodecane ester, P-hydroxybenzoic acid 2-ethylhexyl etc.), acid amides (diethyl dodecoic acid acid amides for example, N-myristyl pyrrolidone etc.), alcohols or phenols (isooctadecane alcohol for example, 2,4-di-tert-pentyl phenol etc.), aliphatic carboxylic acid esters,'s (dioctyl azelate for example, tributyrin, lactic acid isooctadecane ester, trioctyl lemon acid etc.), phenyl amines (for example N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline etc.), hydro carbons (paraffin oil for example, dodecyl benzene, diisopropyl naphthalene etc.), and other material.Applied secondary solvent comprise boiling point from about 30 ℃ to about 160 ℃ organic solvent, typical example has ethyl acetate, butyl acetate, ethyl propionate, MEK, cyclohexanone, acetic acid-2-ethoxy ethyl ester, dimethyl formamide etc.
Relevant latex process for dispersing and effect thereof, and the object lesson of dipping latex is published in United States Patent (USP) 4,199,363, Deutsches Reichs-Patent application 2,541,274 and 2,541,230 etc.
Technology of the present invention is mostly taked to allocate colour coupler in the photosensitive silver halide emulsion layer method, the colour coupler that is added, concerning the photograph color sensitive material, its addition is counted 0.003 to 0.5 mole with every mole of silver halide, preferably get 0.005 to 0.3 mole, and concerning colour paper, preferably get 0.1 to 0.3 mole.
Color sensitive material of the present invention can also contain conventional colour coupler and magenta colour coupler of the present invention again and cooperate use, suitable colour former agent exemplary includes naphthols or phenol series compound, pyrazolone or pyrazolo pyrroles series compound and open chain or heterocyclic ketone methylene compounds.The object lesson of the cyan that can use in the present invention, magenta, yellow colour former is published in " research is open " No.17643, in each patent that VII-D (in Dec, 1978) and same publication No.18717 (in November, 1979) are quoted.
Usually these colour couplers have the non-dispersive group, or polymerization, thereby right and wrong are diffusible.Preferably can be discharged base at the coupling position place replaces rather than hydrogen atom.Also operable colour coupler also comprises the colour coupler that can provide suitable diffusivity dyestuff; Coloured quality agent: colourless coupler or can when coupling reaction, discharge development restrainer or discharge colour coupler of development accelerant etc.
Can be used for yellow colour coupler exemplary of the present invention has the acyl group acetamide series colour coupler of oil guard type, and this class colour coupler specifically is published in more following patents, and for example United States Patent (USP) 2,407, and 210,2,875,057 and 3,265,506.Use twice normality yellow colour developing better in the present invention, its typical son is at United States Patent (USP) 3,408,194,3,447,928,3,933,501 and 4,401, the 752 oxygen atom release type yellow colour formers of delivering: also have nitrogen-atoms release type yellow colour former in addition, example is published in more following patents: the open No.10739/83 of Jap.P., United States Patent (USP) 4,022,620 and 4,326,024, " research is open " No.18053 (in April, 1979), BrP 1,425,020 and Deutsches Reichs-Patent application (OLS) No.2,219,917,2,261,361,2,329,587 and 2,433,812.Wherein comparatively outstanding is α-pivaloyl-monoacetylaniline series colour coupler, the dyestuff that generates after this colour coupler develops, and colour fastness is fine, and another kind of α-benzoyl acetanilide series colour coupler then has good color performance.
The magenta colour coupler that can be used comprises oil guard type indazolone series or cyano group acetyl group series colour coupler in the present invention.Be preferably 5-pyrazolone series colour coupler.Color harmony quality speed from developing dye is preferably in the colour coupler of 5-pyrazolone series, introduces fragrant amino or acylamino-on its 3-position.What the representative instance of these colour couplers had been delivered has, United States Patent (USP) 2,311,082,2,343,703,2,600,788,2,908,573,3,062,63,3,152,896 and 3,936,015 etc.Preferably adopt two equivalent 5-pyrazolones series colour coupler.Discuss with the releasable group, United States Patent (USP) 4,310,619 nitrogen-atoms release type group of delivering or United States Patent (USP)s 4,351, the 897 arylthio groups that deliver are better, in addition, European patent No.73, the 636 relevant 5-pyrazolone series colour couplers of delivering that have the non-dispersive group demonstrate very high quality activity.
The cyan coupler that can be used among the present invention comprises oil guard type naphthols and phenol series colour coupler.The exemplary of naphthol serial colour coupler is published in United States Patent (USP) 2,474,293.Chang Yong oxygen atom release type 2-equivalent naphthol type high activity colour coupler is published in United States Patent (USP) 4,052,212,4 especially, 146,396,4,228,233 and 4,296,200, the exemplary of phenol type colour coupler is published in United States Patent (USP) 2,369, and 929,2,423,730,2,772,162 and 2,895,826 etc.
The present invention has selected moisture-proof and heat-resisting cyan coupler for use, and the exemplary of these colour couplers is phenol type cyan couplers, is published in United States Patent (USP) 3,772,002; 2, the phenol series colour coupler that the 5-diamido replaces is published in United States Patent (USP) 2,772,162,3,758,308,4,126,396,4,334,011 and 4,327,173, Deutsches Reichs-Patent bulletin (OLS) No.3,329,729 and Japanese patent application No.42671/83 etc.Phenylcarbamido is arranged and have the phenol series colour coupler of acylamino-to be published in United States Patent (USP) 3,446 in the 5-position at 2, on 622,4,333,999,4,451,559 and 4,427,767 grades.
In order to satisfy the special requirement of some photosensitive material, can in same emulsion layer, use two or more colour coupler of the present invention, and more above-mentioned colour couplers can be added to in one deck, and perhaps a kind of colour coupler among them joins in the two-layer or two-layer above different emulsion layers and goes.
In order to proofread and correct unnecessary absorption, colour former agent need be blended in the colour photographic sensitive material and use at cyan coupler with the coloured dye of magenta of short wavelength region.The representative instance of colour former agent is to be published in United States Patent (USP) 4,163,670 and the open No.39413/72 of Jap.P. etc. in yellowy magenta colour coupler and be published in United States Patent (USP) 4,004,929 and 4,138,258, BrP 1,146, the cyan coupler of the band magenta in 368 grades.
Can make dipolymer or superpolymer as mixing the colour coupler that uses.The exemplary of the colour coupler of aggretion type is published in United States Patent (USP) 3,451, and 820 and 4,080,211.The object lesson of aggretion type magenta colour coupler is published in BrP 2,102, and 173 and United States Patent (USP) 4,367,282.
In order to improve graininess, the colour coupler that in prescription, can use some that diffusible dyestuff can be provided, the concrete instance of this class colour coupler, wherein magenta colour coupler is published in United States Patent (USP) 4,366,237 and BrP 2,125,570, and European patent No.96, that delivers in 873 and open (OLS) No.3 of Deutsches Reichs-Patent, 324,533 has yellow, magenta and a cyan coupler.
Be used as the bonding agent of photosensitive material emulsion layer or interlayer among the present invention or protect expansion property colloid, select for use gelatin more favourable, other hydrophilic colloid also can be used separately, perhaps mixes use with gelatin.
Can be used as the silver halide in the photographic emulsion layer of sensitive photographic material of the present invention, silver bromide, iodine silver bromide, iodine chlorine silver bromide, chlorine silver bromide and silver chloride are arranged.Preferred silver halide is the iodine silver bromide that agi content is not more than 15 moles of %, and more preferably, the content of silver iodide is 2 to 12 moles of % in the iodine silver bromide.
Mean size for silver halide particle in the photographic emulsion there is no special regulation, but preferably mean particle size is not more than 3 microns.(mean particle size is based on the mean value of particle projection area.When particle is a ball or when being approximately sphere, get its diameter mean value; Particle is got its length of side mean value during for cube).
Both can be narrow in the distribution of grain size also can be wide.
Silver halide crystal can be well-regulated crystallization shape in photographic emulsion, as the cube shaped or octahedral bodily form; Also can be irregular crystallization shape, as sphere or sheet shape; Or the mixing of these several crystallization shapes.The potpourri of the silver halide particle of the multiple often crystallization shape of silver halide particle.
Also can adopt a kind of emulsion, wherein contain and account for the more sheet silver halide particle of total projection area, the diameter of these platy shaped particles is more than five times or five times of its thickness.
Between the inside and superficial layer of silver halide particle, different phases can be arranged.Some particle latent image mainly is to form at superficial layer, and also some particle latent image mainly is that portion forms within it.
Being applied to photographic emulsion of the present invention can be prepared by the method that more following documents are introduced.
The photographic emulsion chemistry of the photograph chemistry of P.Glafkides work and physics (Chimie et physiquephotographique) Paul Montel (1979) G.F.Duffin work for example, (Photographic Emulsion Chemistry), The Focal press (1966) V.L.Zelikman et al preparation and coating photographic emulsion, (Making and CoatingPhotographic Emulsion), The Focal press (1964)
In detail, photographic emulsion can prepare with kinds of processes, and acid technology is arranged, neutral technology, ammonia process technology or the like.Reaction can occur between soluble silver salt and the solubility halogen to be passed through with single notes method, and double-jet method or both mixing methods are carried out.
Prepare silver halide particle and can also use a kind of method that is called the back mixing method, at this time, silver ion is excessive.Can also use to be called the method (a kind of pattern in the double-jet method) of controlling double-jet method, the concentration of silver ions PAg that this method will remain in the liquid phase that wherein forms silver halide is constant.
Can obtain having the crystal form rule according to the method, the uniform basically silver emulsion of grain size.
In the maturing process that generates silver halide particle or physics, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt with and complex salt, rhodium salt and complex salt, molysite and complex salt thereof etc. can exist.
Silver emulsion is often by chemical sensitization, the chemical sensitization method is published in " basic photograph technology and silver halide " (Die Grund Lagender PhotographischenProzesse mit silberhalogeniden Akademische Verlagsgesellschaft) book that H.Friese writes, and scientific publication company publishes 675-734 page or leaf (1968).
More particularly, can use can with active gelatin or the sulfocompound that reacts of silver, carry out chemical sensitization by the method for sulphur sensitizing.(for example vulcanizing sulfate, thiocarbamide, sulfhydryl compound, rhodanine (having another name called rhodanic acid) etc.); Use reducing substances to carry out reduction sensitization (for example tin salt, amine, hydrazine derivate, formamidine sulfinic acid, silane compound etc.); Use noble metal sensitizing (for example Jin complex salt and the complex salt that belongs to VIII family metal in the periodic table, for example platinum, iridium, palladium etc.) or its potpourri of precious metal chemical complex.
For photosensitive material is preparing, prevent during storage or the shooting process that fog from producing, or make photographic property stable that the photographic emulsion that can use in the present invention can contain some different compounds.These examples for compounds that can add comprise: azole such as benzothiazolium salt, nitrogen imidazoles, nitrobenzimidazole, chloro benzimidazole, bromobenzene and imidazoles, thyroidan, mercaptobenzothiazoler, mercaptobenzimidazole, dimercaptothiodiazole, aminotriazole(ATA), benzotriazole, nitrobenzene and triazolam, mercapto-tetrazole (particularly, 1-phenyl-5-mercapto-tetrazole) etc.; Mercaptopyrimidine, mercapto-triazine, thione compounds, Li such as oxazoline thioketones etc.; Azepine indenes class is benzotriazole, the purine (particularly (1,3,3a, 7) purine of 4-hydroxyl-replacement), pentaaza indenes etc. for example; Benzene thiosulfonic acid, benzenesulfinic acid, benzenesulfonamide etc. and the multiple known compound that can be used as anti-fog agent or stabilizing agent.
For super-sens and contrast or acceleration development, the photographic emulsion layer of sensitive photographic material of the present invention can comprise more following materials, polyoxygenated alkene or derivatives thereof for example, for example ether, ester, amine etc., sulfide compound, thiomorpholine, quarternary ammonium salt compound, urethane ester derivant, urea derivatives, imdazole derivatives, 3-pyrazolidone etc.
The present invention is in order to improve dimensional stability, can contain insoluble in the photographic emulsion layer of photosensitive material of the present invention or other hydrophilic colloid layer or is slightly soluble in the synthetic polymer dispersion of water.
Can adopt methine dyes and other dyestuff to come spectral sensitization in the photographic emulsion of the present invention, the dyestuff that is used for the spectral sensitization purpose has: cyanine dye, merocyanine dyes, cooperation cyanine dye, auxiliary section cyanine dye, full polarity cyanine dye, half cyanine dye, styryl dye and half oxygen alcohol dyestuff (hemioxonol dyes), what use always in these is cyanine dye, merocyanine dyes and auxiliary section cyanine dye, to all these dyestuffs, all can adopt as any nucleolus of cyanine dye usually as the nuclear of basic heterocycle.
These sensitizing dyes can be single uses, perhaps severally mix use.Mix and use sensitizing dye normally to be applied in the occasion that requires supersensitization.
Also can sneak into a class itself in the emulsion and not have the dyestuff of spectral sensitization ability, perhaps contain and a kind ofly do not absorb visible light basically, yet when mixing, but demonstrate the material of supersensitization effect with sensitizing dye.The example of this respect has: including with nitrogenous heterocyclic radical in emulsion is substituent aminobenzene vinyl compound, (as at United States Patent (USP) 2,933,390 and 3,635, described in 721) aromatic organic acid-(example is published in United States Patent (USP) to the formaldehyde condensation product.3,743,510), cadmium salt, azepine indene compound etc.The present invention can be applied in the multilayer broken colour photographic material, and this multilayer broken colour photographic material comprises a kind of base material and has the two-layer different photoreception of spectrum performance that has thereon at least.That is to say that multilayer natural color photographic material normally has a magenta-sensitive emulsion layer at least on base material, have a green-sensitive emulsion layer at least and have the blue emulsion layer of a sense at least.The order of these emulsion layers requires and can at random select according to purpose.In general the magenta-sensitive emulsion layer includes the formation cyan coupler, and the green-sensitive emulsion layer contains the formation magenta colour coupler, feels blue emulsion layer and contains the formation yellow colour former, but if needed, also other collocation mode can be arranged.
In the sensitive photographic material of the present invention; can contain organic or inorganic hardener in photographic emulsion layer or other hydrophilic colloid layer; the example of hardener has active vinyl-compound (for example 1; 3,5-three acryloyls six hydrogen-all=and triazine, 1; 3-vinylsulfonyl-2-propyl alcohol etc.); active halogen compound (for example 2,4-two chloro-6-hydroxyl-sym-triazines etc.), sticking hydracid (for example mucochloric acid, glue phenoxy chloric acid etc.), they can be present in the emulsion layer with mixing individually or.
Can also comprise colored anti-fog agent by photosensitive material of the present invention, quinhydrones (being reciprocity diphenol) derivant for example, aminophenol derivates with fungicidal property, gallic acid (having another name called tannic acid) derivant, ascorbic acid (having another name called vitamin C) derivant, or the like.
The hydrophilic colloid layer of photosensitive material of the present invention can also contain ultraviolet light absorber.The object lesson of operable ultraviolet light absorber has: the benzotriazole compound so that aryl replaces is published in United States Patent (USP) 3,533,794 and 4,236,013; Open No.6540/76 of Jap.P. and European patent No.57,160 etc.; Butadiene type is published in United States Patent (USP) 4,0450, and 229 and 4,295,999; Cinnamate derivative is published in United States Patent (USP) 3,705, and 805 and 3,707,375; Benzophenone is published in United States Patent (USP) 3,215, and 530 and BrP 1,321,355; The superpolymer that has the UVA group is published in United States Patent (USP) 3,761, and 272 and 4,431,726.Also can use to be published in United States Patent (USP) 3,499 762 and 3,700,455 UVA fluorescent bleaches.The typical object lesson of ultraviolet light absorber is published in " research is open " 24239 (in June, 1984) etc.
Photosensitive material by the present invention's preparation can also contain water-soluble dye, to use as the colour filter dyestuff or such as multiple other purposes such as radiation proofs.The example of these dyestuffs comprises oxygen alcohol dyestuff (oxonol dyes), half oxygen alcohol dyestuff, styryl dye, merocyanine dyes, cyanine dye and azo dyes, and wherein, oxygen alcohol dyestuff, half oxygen alcohol dyestuff and merocyanine dyes are particularly useful.
Can be used known fade inhibitor as follows when enforcement is of the present invention, the dyestuff video stabilizing agent that uses among the present invention can mix use more than 2 kinds or 2 kinds.Known fade inhibitor kind has: hydroquinone derivatives, gallic acid-derivate, palkoxy benzene phenols, para hydroxybenzene amphyl and bisphenols.
By the present invention, generate the cambial autochromy emulsion layer of dyestuff video, be coated on usually above the sensitive photographic material pliable and tough base material commonly used.Base material includes plastic sheeting, paper, cloth etc.Pliable and tough sheet base commonly used comprises the film of being made up of semi-synthetic or synthetic superpolymer, cellulose acetate for example, butyl acetate cellulose, polystyrene, polyphenyl dioctyl phthalate ethyl ester, polycarbonate etc.; And with the paper wood of baryta or alpha-olefine polymers (example, tygon, polypropylene) coating, or with they superimposed paper woods that gets on.The sheet base can be with dyestuff or pigment coloring.Sometimes the sheet base is dyed the effect that black can play shading.
The base material that uses for the reflection-type photosensitive material is preferably in above it or adds Chinese white on the overlapping layers.The kind of Chinese white has titania, barium sulphate, zinc paste, zinc sulphide, lime carbonate, antimony trioxide, silicon is white, aluminium is white, titanium phosphate etc., titania wherein, and barium sulphate and zinc paste are more comparatively commonly used.
Usually substrate surface is carried out gluing and handle, can improve bonding between photographic emulsion layer etc. and base material like this.Before or after the gluing processing, also can carry out Corona discharge Treatment, ultraviolet ray irradiation, flame treatment etc. to base material.
For the sheet base of reflection-type photosensitive material, the hydrophilic colloid layer of one deck high-load Chinese white can be applied between sheet base and the emulsion layer, to play the effect that improves video whiteness and sharpness.
The reflection-type photosensitive material that contains magenta colour coupler of the present invention, normal using polymer-lamination scraps of paper base is as its sheet base.Particularly preferred be to use mix through kneading Chinese white in the film of wherein synthetic resin as base material, thereby can obtain having improved flatness, glossiness, sharpness, and have good saturation degree and at the video of the repeatability that shows the dark space.Particularly preferred in this case film of synthetic resin is polyphenyl dioctyl phthalate ethyl ester and cellulose acetate, and Chang Yong Chinese white is barium sulphate and titania especially.
Colour photographic sensitive material of the present invention also can contain the auxiliary agent of once mentioning in the various documents as required except the top all cpds of speaking of, as stabilizing agent, and anti-fog agent, surfactant, antistatic agent, developer etc.The example of these auxiliary agents is published in " research is open " 17643.
In addition, depend upon circumstances, silver halide emulsion layer or other hydrophilic colloid layer can contain the particulate silver emulsion (for example containing mean particle size in 0.20 μ silver chloride, silver bromide or chlorine silver bromide emulsion) of essentially no photosensitive property.
The colour developing solution that can adopt among the present invention, what often select for use is to contain the alkaline aqueous solution of primary aromatic amine color developer as principal ingredient, the exemplary of colour developing solution has: 4-amino-N, the N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-Beta-methyl sulfonamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-'beta '-methoxy ethylaniline etc.
Can be added with the pH buffering agent in the colour developing solution, the alkali metal salt of sulphurous acid, carbonic acid, boric acid or phosphoric acid for example, or the like; Can also contain development restrainer or anti-fog agent in the colour developing solution, as bromide, iodide and organic anti-fog agent.Need, also can add for example azanol of water softener, antiseptic in the colour developing solution; Organic solvent, for example benzyl alcohol, diethylene glycol.Development accelerator, for example polyglycol, quaternary ammonium salt, amine; Dye forming coupler, competition colour coupler, the agent of fog screen, for example sodium borohydride; Auxiliary developer, for example 1-phenyl-3-pyrazolidone; Tackifier, at United States Patent (USP) 4,083,723 polycarboxylate chelating agents that deliver, at Deutsches Reichs-Patent bulletin (OLS) No.2,622,950 antioxidant of delivering, or the like.
Usually carry out the bleaching of photographic emulsion layer after the colour development, bleaching process can or separately carry out with the fixing while.The compound that the example of the bleaching agent that uses includes polyvalent metal is the compound of iron (II), cobalt (III), chromium (VI), copper (II) etc. for example.Also have peracid, quinones, nitroso compound or the like, the for example ferricyanide, dichromate, organic complex salt of iron (III) or cobalt (III), aminopolycanboxylic acid's complex salt for example, as, ethylene dinitrilotetra-acetic acid, triglycollamic acid, 1,3-diamido-2-propyl alcohol four acetic acid etc., perhaps complex salt of the above-mentioned metal of organic acid, for example citric acid, tartrate, malic acid etc. also can be used persulfate, manganate, nitrosophenol etc.In the middle of these chemicals, the potassium ferricyanide, ethylene dinitrilotetra-acetic acid iron (III) sodium and ethylene dinitrilotetra-acetic acid iron (III) ammonium are used always.Ethylene dinitrilotetra-acetic acid iron (III) complex salt can be used in single liquid lime chloride, also can be used for the blix solution of mono bath.
Photographic material washes with water after colour development or blix process.Carrying out the temperature of colour development can select arbitrarily between 18 ℃ and 55 ℃, selects 30 ℃ or higher slightly more suitable usually, specifically, selects better more than 35 ℃ or 35 ℃.Development time is approximately 1 minute to about 3.5 minutes, and the time, shorter effects can be quite a lot of.For continuous developing process process, preferably replenish fresh developer solution by technological requirement, additional amount is in every square metre of area photosensitive material, can replenish 330cc to 160cc but in fact comprehensive each side consideration would rather be selected 100cc or less usually.In developer solution, the content of benzyl alcohol is got 5 milliliters/liter or less usually.The temperature of blix technological process can choose at random between 55 ℃ at 18 ℃, is generally selected in 30 ℃ or higher slightly more suitable.Temperature is more than 35 ℃ or 35 ℃ the time, and the time of process can be reduced to 1 minute or less, replenishes fresh liquid measure simultaneously and also can reduce.The later wash time of colour development or blix process is generally in 3 minutes, if adopt the time of stabilizer bath, water-washing process can reduce to 1 minute or less.
The color and luster of back quality dyestuff of developing is not only exposed, heat and moist influence and worsen, and also can be subjected to the infringement of bacterial action in storage life.The cyan dye video is subjected to the effect of bacterium and the phenomenon that worsens is the most serious, therefore need be with addition of germifuge.Japanese patent application No.17244/82 has delivered the object lesson of the relevant 2-of containing thiabendazole series bactericidal agent.Germifuge may be combined in the photosensitive material in developing process, also can be added in the developer solution and use.Applying germifuge can carry out in any stage, as long as after technological process finishes, have germifuge in the photosensitive material just.Now with regard to following object lesson the present invention is done an explanation, what will clarify here a bit is that this is an example only, and the present invention is not limited thereto.
Example 1
Digesting compound (M-7) 8.3 adds in 16.6 milliliters of tri-2-ethylhexyl phosphates and the 25 milliliters of ethyl acetates, mixture heated is become solution, the colour coupler solution of gained be added to 100 milliliters contain 10 the gram gelatin and 1.0 the gram neopelexes aqueous solution in, then high speed machine stirs, make the particulate emulsified dispersed liquid of colour coupler, whole emulsified dispersed liquids are added in the chlorine silver bromide emulsion that contains 50 moles of % bromines (the silver amount is 6.5 grams), and the 2.4 2 chloro-6-hydroxyl-sym-triazines that add 10 milliliter 2% are simultaneously made hardener.Respectively be superimposed with on the poly paper wood sheet base on the two sides and be coated with emulsion, its coating weight is 200 milligrams/meter 2 of silver-colored topped amounts, is coated with gelatin layer more in the above, makes sample, is denoted as sample A.
Prepare emulsified dispersed liquid with top identical method, but digest compound (M-9) with 8.1 respectively, 8.3 the compound (M-7) of method in gram (M-33) or 8.8 gram (M-32) replacements, and adding the tri-2-ethylhexyl phosphate of 16.2 milliliters, 16.6 milliliters or 17.6 milliliters respectively, the amount of ethyl acetate still is 25 milliliters.By the equal number of the identical emulsion of last method, the potpourri of gained is applied on the of the same race base, its silver-colored topped amount is also constant.The sample that makes is denoted as B.C.D respectively.
For making comparisons, special preparation comparative sample, its preparation method is caught up with and is stated equally, only 17.8 milliliters or 20.6 milliliters of tri-2-ethylhexyl phosphates and 25 milliliters of ethyl acetates is added in " the comparative compounds 1 " or 10.3 grams " comparative compound 2 " of indication below 8.9 grams.The sample that makes like this is denoted as comparative sample 1 and comparative sample 2 respectively.
Comparative compound 1,
(colour coupler is published in Japanese patent application (OPI) 42045/83)
Each sample A, B, C and comparative sample 1 and 2 carry out each processing step with the process solutions of following indication then successively with the exposure of 1000C.M.S wedge shape.
Developer solution
15 milliliters of benzyl alcohols
Diethylene triamine five acetic acid 5 grams
KBr (potassium bromide) 0.4 gram
Na
2SO
3(sodium sulphite) 5 grams
Na
2CO
3(sodium carbonate) 30 grams
Hydroxylamine sulfate 2 grams
4-amino-3-methyl-N-β-(sulfonyloxy methyl amine) ethylaniline 3/2H
2SO
4H
2O 4.5 grams add water to totally 1000 milliliters
(pH10.1) 150 milliliters of Na of bleach-fixing liquid ATS (Ammonium thiosulphate) (70% weight concentration)
2SO
3(sodium sulphite) 5 gram Na[Fe (EDTA)] 40 gram EDTA, 4 gram water are added to totally 1000 milliliters
(pH6.8) 33 ℃ 3 of process steps temperature-time developer solution 33 ℃ 3 ' 30 " 33 ℃ 1 ' 30 of bleach-fixing liquid " washing '
The rosaniline dyes video of each sample that obtains like this has the high saturation degree of bright-coloured color harmony, measures the photographic property of these colored videos.Gained the results are shown in following table:
Table I
Photographic property sample number relative sensitivity * color gradation maximal density comparative sample 1 100 2.90 2.73 comparative samples 2 105 2.94 2.97 sample A (M-7) 88 3.35 3.05 sample B (M-9) 96 3.16 2.86 sample C (M-33) 92 3.28 3.02 sample D (M-32) 98 3.19 2.91 notes: * reach in fog density+0.5 o'clock light exposure under the relative value of gained speed, and
With the result of comparative sample 1 as standard (100).
The result of gained from table 1, colour coupler of the present invention, no matter from light sensitivity, aspects such as color gradation and maximal density have all shown excellent characteristic.Why can reach so good result, be owing to the cause of having introduced sulfonamido group among the present invention has improved quality activity and color effect.
Example 2
Both sides all are superimposed with on the poly paper wood sheet base and make colour photographic sensitive material E.F.G.H.I and J by being coated with ground floor (lowermost layer) shown in the Table II to layer 7 (the superiors).
In the preparation process, the coating composition that the 3rd layer of i.e. coating contains the emulsified dispersed liquid of magenta colour coupler and emulsion with and aforesaid example 1 same procedure prepare.
Each sample is except using colour filter orchid-green-red respectively from E to J, and other same quadrat methods by example 1 are carried out.
The photographic property data of gained are listed in Table III.
The Table II ground floor: (bottom) feels blue chlorine silver bromide emulsion (bromine: 80 moles of %; The topped amount of silver: 350
Milligram/rice
2), gelatin (topped amount: 1500 milligrams/meter
2) yellow colour former
-1)(multiple
Lid amount: 500 milligrams/meter
2).Solvent
-2)(topped amount: 400 milligrams/meter
2) second layer: gelatin (topped amount: 1100 milligrams/meter
2), colored mixed protective agent
-3)(topped amount:
200 milligrams/meter
2), solvent
-4)(topped amount: 100 milligrams/meter
2) the 3rd layer: feel green chlorine silver bromide emulsion (bromine: 50 moles of %; The topped amount of silver: 180 milligrams/meter
2)
Magenta colour coupler
-5)(topped amount: 3.4 * 10
-4Mole/rice
2), solvent
-6)(topped
Amount: be respectively, sample D is 440 milligrams/meter
2, sample E is 450 milligrams, sample
Product F is 380 milligrams/meter
2, sample G is 410 milligrams/meter
2) the 4th layer: gelatin (topped amount: 1600 milligrams/meter
2), ultraviolet light absorber
-7)(topped amount: 700
Milligram/rice
2), the color mix protective agent
-3)(topped amount: 200 milligrams/meter
2) solvent
-4)
(topped amount: 300 milligrams/meter
2) layer 5: feel red chlorine silver bromide emulsion (bromine: 50 moles of %, silver-colored topped amount: 300 milligrams/
Rice
2), gelatin (topped amount: 1200 milligrams/meter
2) cyan coupler
-8)(topped amount:
400 milligrams/meter
2), solvent
-4)(topped amount: 250 milligrams/meter
2) layer 6: gelatin (topped amount: 1000 milligrams/meter
2), ultraviolet light absorber
-7)(topped amount: 360
Milligram/rice
2) solvent
-4)(topped amount: 125 milligrams/meter
2) layer 7: (top layer) gelatin (topped amount: 1600 milligrams/meter
2) the sheet base on the two sides of paper wood superimposed poly base.* 1) yellow colour former: α-pivaloyl-α-(2,4-dioxo-5,5 '-dimethyl
Oxazolidine-3-yl)-2-chloro-5-[α-(2,4-two uncles
Amyl group-phenoxy group) butyramide] antifebrin.* 2) solvent: di(2-ethylhexyl)phosphate octyl group butyl ester.* 3) colored mixed protective agent: 2,5-dioctyl quinhydrones.* 4) solvent: dibatyl phithalate.* 5) magenta colour coupler: sample E (comparative compound 1)
Sample F (comparative compound 2).
Sample G (M-7)
Sample H (M-9)
Sample I (M-33)
Sample J (M-32).* 6) solvent: tri-2-ethylhexyl phosphate.* 7) ultraviolet light absorber: 2-(2-hydroxyl-3-sec-butyl-5-tert-butyl-phenyl) benzene
And triazole.* 8) cyan coupler: 2-[α-(2,4-two tertiary pentyl phenoxy groups)-butyramide]-4,
6-two chloro-5-methylphenols.
Table II
The speed relative value of photographic property sample number relative sensitivity * color gradation maximal density E (comparative sample 1) 100 2.88 2.75 F (comparative sample 2) 106 2.90 3.10 G (M-7) 90 3.21 3.15 H (M-9) 95 3.08 2.93 I (M-33) 91 3.18 3.11 J (M-32) 94 3.10 2.97 notes: * light exposure when fog density+0.5. With sample E (relatively
Sample 1) result of gained makes standard (100).
Listed presentation of results demonstrates good photographic property too by colour coupler of the present invention in the table in the multi layer colour print.
Example 3
Sample I is to the preparation process of L, except in each emulsified dispersed liquid, adding 7.3 grams light decolourizing inhibitor cited below other with example 2 in sample E the same to the preparation method of H.
Light decolourizing inhibitor:
Each sample E in the example 2 each sample I in H and the example 3 adopts corresponding orchid-green-red color filter to expose separately and processes by the method every trade of example 1 to L, and obtains colored video.
Expose each colored video to the open air under the light of a fluorescent lamp (decay-O-counter) (15,000 Lux) the four stars phase, carry out the test of rosaniline dyes video fastness to light then, Table IV has been listed the result of gained.
Table IV
The fastness to light of the video of dyestuff
Sample number (colour coupler) variable density *
E (relatively colour coupler 1) 0.63
F (relatively colour coupler 2) 0.59
G(M-7) 0.65
H(M-9) 0.64
I (relatively colour coupler 1+ light decolourizing inhibitor) 0.91
J (relatively colour coupler 2+ light decolourizing inhibitor) 0.87
K (M-7+ light decolourizing inhibitor) 0.93
L (M-9+ light decolourizing inhibitor) 0.93 annotates: * is 1.00 zone with initial density, the fuchsin density value that records behind color fading test.
Can find out that from above result colour coupler of the present invention has good light fastness for the dyestuff video, photostability can also further improve after using some light decolourizing inhibitor.Further confirm in addition, even the good performance of colour coupler also shows 100 ℃ high temperature or at temperature height to 60 ℃, carry out colored video light fastness test under the hot and humid condition of relative humidity height to 90%, the result is colour-fast basically, and finishes the back does not have residual colour coupler at uncoloured position stain formation in flushing.
From the result of example 1 and 2, no matter in single-layer system still was multilayer system, colour coupler of the present invention in light sensitivity, color gradation and color performance every indexs such as (maximal densities), all was good.
From the result of example 3, use the sensitization finish of colour coupler of the present invention, the light stability of its dyestuff video is good.And also showing in the example 3 to mix uses light decolourizing inhibitor can further improve the light stability of material.
Example 1 has the colour coupler nuclear of structural formula (V) and has wherein R among example 3 has all confirmed colour coupler series of the present invention
12The structure of the structural formula (A) when the O-group is connected to the ortho position of the sulfonamido group on this nuclear demonstrates good especially photographic property.
Also have, wherein R
12The group of the structural formula (A) when O-group the position of substitution is in the ortho position of sulfonamido group is than R wherein
12The group of the structural formula when O-is in contraposition (A) demonstrates more satisfied color performance usually.
Claims (1)
1. silver halide colour photographic sensitive material that on its sheet base, scribbles one deck silver halide emulsion layer at least, it is characterized in that containing in the emulsion layer magenta colour coupler with the pyrazolo pyrroles series of structural formula as follows (I) expression, its content is counted the 0.003-0.5 mole with per 1 mole of silver halide
Formula (II), formula (III), formula (IV), formula (V) or formula (VI) compound that this formula (I) compound is following specifically
In the formula:
R
2Be C
1-C
30Alkyl, C
6-C
22Arenesulfonyl amino or C
6-C
10Aryloxy group;
R
3And R
4Respectively be hydrogen atom or C
1-C
40Alkyl; And
X is a chlorine, the heterocyclic radical of five annular atomses, C
6-C
30Aryloxy group or C
2-C
5The perfluor alkyl amido,
In addition, the group that on the pyrazolo pyrrole ring of this colour coupler, contains a structural formula as follows (A) at least:
In the formula: R
11Be hydrogen; R
12Be C
1-C
25Alkyl; R
13Be chlorine, C
1-C
12Alkyl or C
1-C
12Alkoxy; And m is 0,1, or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26892484A JPS61147254A (en) | 1984-12-20 | 1984-12-20 | Silver halide color photographic sensitive material |
| JP268924/84 | 1984-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85109626A CN85109626A (en) | 1986-07-30 |
| CN1035571C true CN1035571C (en) | 1997-08-06 |
Family
ID=17465164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85109626 Expired - Lifetime CN1035571C (en) | 1984-12-20 | 1985-12-20 | silver halide color photographic lightsensitive material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS61147254A (en) |
| CN (1) | CN1035571C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354751C (en) * | 2001-11-22 | 2007-12-12 | 富士胶片株式会社 | Method for improving photosensitive rate of silver halide color photosensitive material |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH087405B2 (en) * | 1986-03-10 | 1996-01-29 | コニカ株式会社 | Silver halide photographic light-sensitive material containing novel magenta coupler |
| DE3624544C2 (en) * | 1986-07-19 | 1996-02-01 | Agfa Gevaert Ag | Color photographic recording material with a color coupler of the pyrazoloazole type |
| JPH0715573B2 (en) * | 1986-09-30 | 1995-02-22 | 富士写真フイルム株式会社 | Silver halide color photographic light-sensitive material |
| JPS63132237A (en) * | 1986-11-21 | 1988-06-04 | Konica Corp | Silver halide photographic sensitive material having excellent color formability even when subjected to quick processing |
| EP0285274B1 (en) * | 1987-03-09 | 1990-11-07 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic silver halide materials and process comprising new pyrazoloazole coupler |
| JPH0693105B2 (en) * | 1987-06-10 | 1994-11-16 | 富士写真フイルム株式会社 | Magenta dye forming coupler |
| JPH0675343A (en) | 1992-07-06 | 1994-03-18 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material and color image forming method |
| JPH09152696A (en) | 1995-11-30 | 1997-06-10 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JP3383499B2 (en) | 1995-11-30 | 2003-03-04 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| US7611829B2 (en) | 2004-01-30 | 2009-11-03 | Fujifilm Corporation | Silver halide color photographic light-sensitive material and color image-forming method |
| JP5326008B2 (en) | 2012-02-07 | 2013-10-30 | 株式会社エクセディ | Dynamic damper device and lock-up device for fluid power transmission device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113940A (en) * | 1981-12-26 | 1983-07-07 | Konishiroku Photo Ind Co Ltd | Blocked magenta dye forming coupler |
| JPS58113937A (en) * | 1981-12-26 | 1983-07-07 | Konishiroku Photo Ind Co Ltd | Blocked magenta dye forming coupler |
| JPS6098434A (en) * | 1983-11-02 | 1985-06-01 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
| JPS61144647A (en) * | 1984-12-18 | 1986-07-02 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
-
1984
- 1984-12-20 JP JP26892484A patent/JPS61147254A/en active Granted
-
1985
- 1985-12-20 CN CN 85109626 patent/CN1035571C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354751C (en) * | 2001-11-22 | 2007-12-12 | 富士胶片株式会社 | Method for improving photosensitive rate of silver halide color photosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH043860B2 (en) | 1992-01-24 |
| JPS61147254A (en) | 1986-07-04 |
| CN85109626A (en) | 1986-07-30 |
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