CN1517789A

CN1517789A - Silver halides color photographic sensitive material and color image forming method

Info

Publication number: CN1517789A
Application number: CNA2004100029379A
Authority: CN
Inventors: 高田胜之; 生; 中村哲生
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2003-01-24
Filing date: 2004-01-20
Publication date: 2004-08-04
Anticipated expiration: 2024-01-20
Also published as: JP2004226783A; JP4068469B2; CN100447668C

Abstract

Provided is a silver halide color photographic sensitive material suitable for rapid processing, ensuring rapid progress of development even after digital exposure such as laser scanning exposure, and excellent in dependency on exposure temperature and resistant to variation of processing factors. In the silver halide color photographic sensitive material having, on a support, photographic constituent layers consisting of at least one yellow developing blue-sensitive silver halide emulsion layer, at least one magenta developing green-sensitive silver halide emulsion layer, at least one cyan developing red-sensitive silver halide emulsion layer, and at least one non-photosensitive hydrophilic colloidal layer, the yellow developing blue-sensitive silver halide emulsion layer includes a silver halide emulsion which comprises cubic or tetradecahedral grains having a silver chloride content of >=90 mol%, containing 0.02-1 mol% of silver iodide, and having {100} faces of <=0.51 [mu]m as cube side length, and has been spectrally sensitized with at least one sensitizing dye represented by formula (I).

Description

Silver halide colour photographic sensitive material and coloured image formation method

Technical field

The present invention relates to a kind of silver halide colour photographic sensitive material and coloured image formation method, more particularly, the present invention relates to a kind of fast processing, light sensitivity height, the temperature variation when exposing and treating fluid of being suitable for and change silver halide colour photographic sensitive material and the coloured image formation method little the influence of light sensitivity.

Background technology

As everyone knows, autochromy is by the main reagent that develops with primary aromatic amine system colour developing the photosensitive material that contains pigment on the support and be formed into toner (coupler) and silver emulsion to be carried out development treatment, oxide and pigment by the main reagent of development that generates are formed into the reaction of toner (hereinafter referred to as colour coupler) and obtain the method that pigment forms image, can obtain the photochrome of high image quality.

But in recent years as other colour printing modes, for example technology such as ink jet type, distillation formula, color static printing are also developed respectively, and admitted by people gradually as the colour printing mode of paying attention to the photograph image quality.Therefore, wish to improve high image quality, high productivity, and further improve the fastness of image, with high productivity more, with plain mode more, more economical provide more high-quality photo as the maximum feature of this silver halide colour photographic mode.

The existing photosensitive material that contains high silver chloride emulsion, normally with the development that develops the color of 45 second time, all the processing times approximately need 4 minutes (for example, the CP-45X colour printing machine made of Fuji Photo Film Co., Ltd. etc.).Compare with the processing time of other colour printing modes shown in top, high-silver chloride colour printing material handling system can satisfy the requirement to rapid property hardly.Rapidization of handling not only relates to the raising of throughput rate, and can also shorten the total processing time (super rapidization processing) of high-silver chloride colour printing material more, so people carried out many researchs to this.

As everyone knows, just can accelerate developing powder, but those skilled in the art know that also light sensitivity also can decrease by reducing the silver halide particle size.High sensitivity technology as silver halide particle, known has when adopting tabular silver emulsion particle in sensitive photographic material, compares with non-flat tabular silver halide particle, can reduce the ratio that incident ray passes photographic layer, can improve the efficient of supplying of light, improve light sensitivity.The ISO technology that in patent documentation 1～5, discloses dull and stereotyped particle formation method and followed it for example.And, also disclose many in recent years by in this high silver chloride emulsion, importing the technology that iodide are realized ISOization, and in patent documentation 6～10, all stress to have proposed in matrix (host) high silver chloride emulsion particle, to import the method for iodide, it is characterized in that on the inferior surface of emulsion grain, having maximum iodide ion concentration, and form the high-silver chloride phase that does not contain iodide containing going up mutually wittingly of iodide.

But, above-mentioned particle through ISOization, though can directly improve light sensitivity with small size, the rapid property of processing is good, but has the shortcoming of the influence that is subject to processing factors vary easily on the other hand.For example when actual colour development is handled, be made of dipper, photographic fixing bleaching cistern and rinsing bowl, wherein by replenishing the adjusting of liquid, the reagent treatment in developer solution and the photographic fixing bleaching liquid can keep uniform concentration usually.But in fact, reagent concentration also can change with the quantity of handled photosensitive material and the evaporation of moisture content, so from the angle of colour-printing paper that high reliability is provided, importantly this variation at reagent treatment concentration also can form the image with certain performance.And in fact also higher to the requirement that improves this Treatment Stability on the market, wish that the permanance (tolerance) of high silver chloride emulsion in the development treatment operation further improves.In addition, under the situation of the high illumination exposure of adopting laser scanning exposure and so on, cause the deep-seated problem that gray shade scale changes with the variation of the factor of processing easily in gray shade scale exposure portion.Image with certain performance described here is meant resulting image under the condition that sensitizing and gray shade scale do not change because of the variation of above-mentioned treating fluid.

Existing people has proposed the method that various inhibition photo performances change because of the change of photograph treating fluid.Disclose a kind of in the patent documentation 11 by containing the method that specific single methyl pigment and nitrogen heterocyclic ring sulfhydryl compound improve described treating fluid stability.Yet, the process inventor's etc. further investigation is found, under the situation that contains above-mentioned specific single methyl pigment and nitrogen heterocyclic ring sulfhydryl compound, though certain improvement is arranged, but contain the silver iodide particle because of what have a suitable property of rapid processing, it is bigger that the photo performance changes the variation that takes place with treating fluid, thereby produce the problem in the practicality.Find out in addition, this particle that contains silver iodide with the suitable property of rapid processing, under the situation that adopts the contour illumination exposure of laser scanning exposure and handle in the exposure back short time, particle size is more little responsive more to exposure environmental change (particularly variation of temperature).That is to say that when handling immediately after exposure for pursuing rapid processing, the picture photosensitive degree can change because of the environment temperature in when exposure, can not obtain the image of certain quality.For example, in the exposure device of small-scale test chamber, even set conditions of exposure when operation begins in the morning, because environment temperature changes in use thereafter, must carry out several on the 1st and calibrate revisal, thereby have the problem that production efficiency reduces, can not give full play to the advantage of rapid processing at all.

In the embodiment of patent documentation 12, disclose by making the particle that forms I section (band) contain specific compound in the moment that forms 93% particle, can obtain the temperature dependency and all good emulsion of pressure in reciprocity failure (reciprocitylaw failure), when exposure, but the temperature dependency the during exposure of the short time latent image of in these known technologies, but not touching upon and cause the instable improvement problem of the photo characteristic of concentration change with the processing factors vary in the photographic fog grade part easily.

In addition, in patent documentation 13～15, pass through at the top layer of silver halide particle doping iron compound, and in patent documentation 16～17 by selenium sensitizing, and in patent documentation 18, improve the temperature dependent method in when exposure by modes such as tellurium sensitizing, but wherein do not touch upon yet when when particle size diminishes, how to improve exposure temperature dependency and cause the instability of the photo characteristic of concentration change easily with the processing factors vary in the photographic fog grade part.

Usually know, in order under high illumination conditions, also to obtain the strong photographic fog grade of contrast, improve the method for the bad phenomenon of high silver chloride emulsion under high illumination by doping Ir coordination compound, disclose in the patent documentation 19 by the high localization phase of bromide sliver content is set, and the Ir coordination compound that mixes therein, can improve the reciprocity failure problem under the high illumination.The stability problem when but the processing factor of wherein not touching upon changes, and do not speak of the temperature dependency in when exposure.

The 5th, 320, No. 938 communiques of [patent documentation 1] United States Patent (USP)

The 5th, 264, No. 337 communiques of [patent documentation 2] United States Patent (USP)

The 4th, 400, No. 463 communiques of [patent documentation 3] United States Patent (USP)

The 5th, 185, No. 239 communiques of [patent documentation 4] United States Patent (USP)

The 5th, 176, No. 991 communiques of [patent documentation 5] United States Patent (USP)

[patent documentation 6] spy opens flat 8-220681 communique

[patent documentation 7] spy opens flat 8-234340 communique

[patent documentation 8] spy opens flat 8-220684 communique

[patent documentation 9] spy opens flat 8-240879 communique

[patent documentation 10] spy opens flat 8-234345 communique

[patent documentation 11] spy opens clear 62-153850 communique

[patent documentation 12] European patent the 0th, 928, the 988A communique

[patent documentation 13] spy opens flat 3-132647 communique

The 0th, 423, No. 765 communiques of [patent documentation 14] European patent

[patent documentation 15] spy opens flat 4-104136 communique

[patent documentation 16] spy opens flat 4-335337 communique

[patent documentation 17] spy opens flat 4-335347 communique

[patent documentation 18] spy opens flat 5-134345 communique

[patent documentation 19] spy opens flat 7-34103 communique

Summary of the invention

The object of the present invention is to provide and a kind ofly be suitable for handling rapidly and in digital exposures such as laser scanning exposure, develop and carry out also comparatively fast and the also good photosensitive silve halide material of performance of exposure temperature dependency and anti-processing factors vary.

The inventor etc. have finished problem of the present invention through further investigation by following (1)～(11).(1) a kind of silver halide colour photographic sensitive material, it is the silver halide emulsion layer that on support, has at least by each one deck displaing yellow sense indigo plant, the silver halide emulsion layer that shows the green property of pinkish red color sensation, the silver halide colour photographic sensitive material that shows the silver halide emulsion layer of the red property of cyan sense and the photo formation layer that non-photosensitive hydrophilic colloid layer constitutes, it is characterized in that, in the silver halide emulsion layer of this displaing yellow sense indigo plant, it is above and contain the silver emulsion of 0.02～1 mole of % silver iodide to contain silver chloride content and be 90 moles of %, this silver emulsion is that { cube of 100} face or 14 body crystal grain constitute having below 0.51 micron, and are used to down at least a sensitizing coloring matter enforcement optical sensibilization of general formula (I) expression by the cube length of side.

General formula (I)

[changing 5]

In the general formula (I), X ¹And X ²Independent separately expression oxygen atom, sulphur atom, selenium atom, tellurium atom, nitrogen-atoms, carbon atom.Y ¹Expression can be with other 5～6 Yuans carbocyclic rings or heterocycle condensation, also can have substituent furan nucleus, pyrrole ring, thiphene ring or phenyl ring.Y ²Expression forms phenyl ring or 5～6 Yuans atom groups that unsaturated heterocycle is required, and can with other 5～6 Yuans carbocyclic rings or heterocycle condensation, also can have substituting group.Y wherein ¹And Y ²Encircle key between two carbon atoms that contract, can be singly-bound or two key.R ¹And R ²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.L ¹, L ²And L ³Independent separately expression methine, n ¹Expression 0.M ¹The expression counterion, m ¹In the expression and molecule in the required numeral more than 0 of electric charge.

(2) according to the silver halide colour photographic sensitive material of (1) record, it is characterized in that, with the sensitizing coloring matter of described general formula (I) expression, can by under remember general formula (II) or (III) represent.

General formula (II)

[changing 6]

In the general formula (II), Y ¹¹Expression oxygen atom, sulphur atom or N-R ¹³, R ¹³Expression hydrogen atom or alkyl.V ¹⁵And V ¹⁶Independent separately expression hydrogen atom or monovalence substituting group.X ¹¹And X ¹²Independent separately expression oxygen atom or sulphur atom.R ¹¹And R ¹²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.V ¹¹, V ¹², V ¹³And V ¹⁴Independent separately expression hydrogen atom or monovalence substituting group.M ¹¹The expression counterion, m ¹¹In the expression and molecule in the required numeral more than 0 of electric charge.

General formula (III)

[changing 7]

In the general formula (III), Y ²¹Expression oxygen atom, sulphur atom or N-R ²³, R ²³Expression hydrogen atom or alkyl.V ²⁵And V ²⁶Independent separately expression hydrogen atom or monovalence substituting group.X ²¹And X ²²Independent separately expression oxygen atom or sulphur atom.R ²¹And R ²²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.V ²¹, V ²², V ²³And V ²⁴Independent separately expression hydrogen atom or monovalence substituting group.M ²¹The expression counterion, m ²¹In the expression and molecule in the required numeral more than 0 of electric charge.

(3) according to the silver halide colour photographic sensitive material of (1) record, it is characterized in that, with the sensitizing coloring matter of described general formula (I) expression, can by under remember that general formula (IV) represents.

General formula (IV)

[changing 8]

In the general formula (IV), X ³¹And X ³²Independent separately expression oxygen atom or sulphur atom.R ³¹With ³²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.V ³¹, V ³², V ³³, V ³⁴V ³⁵, V ³⁶, V ³⁷And V ³⁸Independent separately expression hydrogen atom or monovalence substituting group, two adjacent substituting groups also can be connected to each other the formation condensed ring.M ³¹The expression counterion, m ³¹In the expression and molecule in the required numeral more than 0 of electric charge.

(4) according to the silver halide colour photographic sensitive material of any one record in (1)～(3), it is characterized in that described displaing yellow sense indigo plant silver emulsion, its cube length of side is below 0.47 micron.

(5) according to the silver halide colour photographic sensitive material of any one record in (1)～(4), it is characterized in that the contained silver iodide phase that contains in the described displaing yellow sense indigo plant silver emulsion, its iodide concentration distributes and decays gradually to internal direction from ion surface.

(6), it is characterized in that in described displaing yellow sense indigo plant silver emulsion, containing the silver bromide of 0.5～5 mole of % according to the silver halide colour photographic sensitive material of any one record in (1)～(5).

(7), it is characterized in that the silver coating total amount is in 0.2g/m in the described photo formation layer according to the silver halide colour photographic sensitive material of any one record in (1)～(6) ²More than, 0.5g/m ²Below.

(8), it is characterized in that coating gelatin total amount is in 3g/m in the described photo formation layer according to the silver halide colour photographic sensitive material of any one record in (1)～(6) ²More than, 6g/m ²Below.

(9), it is characterized in that coating gelatin total amount is 3g/m in the described photo formation layer according to the silver halide colour photographic sensitive material of any one record in (1)～(6) ²More than, 6g/m ²Below, the silver coating total amount is 0.2g/m ²More than, 0.5g/m ²Below.

(10) a kind of coloured image formation method is characterized in that utilizing the light beam according to the image information modulation, each silver halide colour photographic sensitive material put down in writing in (1)～(9) is carried out scan exposure after, carry out development treatment.

(11) a kind of coloured image formation method, it is characterized in that with following time in 20 seconds to the development treatment that develops the color of each silver halide colour photographic sensitive material put down in writing in (1)～(9).

(12), it is characterized in that carrying out following colour developing development treatment in 20 seconds according to the coloured image formation method of (10) record.

Embodiment

Employed group among the present invention at first is described.

In the present invention, specific part is become under the situation of " group ", itself both can not be substituted this part, can be replaced by more than one (until the maximum number that may replace) substituting groups yet.For example, so-called " alkyl " is meant and replaces or unsubstituted alkyl.In addition, the operable substituting group of The compounds of this invention, have unsubstituted all can, and can contain any substituting group.

When this substituting group is called W; as the substituting group of being represented by W can be any substituting group; be not particularly limited; for example can enumerate halogen atom; alkyl [(comprising naphthenic base), and comprise thiazolinyl (comprising cycloalkenyl group); alkynyl]; aryl; heterocyclic group; cyano group; hydroxyl; nitro; carboxyl; alkoxy; aryloxy group; siloxy; heterocyclic oxy group; acyloxy; carbamoyloxy; alkyl oxy carbonyl oxygen; virtue oxygen carbonyl oxygen base; amino (comprising anilino-); nitrogen base (ammonio); amide group; amino carbonyl amino; alkoxycarbonyl amido; aryloxy carbonyl amino; the sulfonamide amido; the alkyl or aryl sulfoamido; sulfydryl; alkylthio group; arylthio; the heterocycle sulfenyl; sulfamoyl; sulfo group; the alkyl or aryl sulfinyl; the alkyl or aryl sulfonyl; acyl group; aryloxy carbonyl; alkoxy carbonyl group; carbamyl; aryl or heterocycle azo base; imide; phosphino-; phosphinyl (phosphinyl); phosphine oxide oxygen base; the phosphine oxide amido; phospho-(phospho) (also being called phosphono (phosphono)); silicyl; diazanyl; urea groups; boronate; phosphate-based; sulfate radical; with other known substituting groups.

More particularly, W represents halogen atom (for example fluorine atom, chlorine atom, bromine atoms and iodine atom), alkyl { [replacement or the unsubstituted alkyl of expression straight chain, side chain, ring-type.They are alkyl (preferred 1～30 carbon atom alkyls, for example methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, eicosyl, 2-chloro ethyl, 2-cyano ethyl, 2-ethylhexyl), naphthenic base (replacement of preferred 3～30 carbon atoms or unsubstituted naphthenic base, for example cyclohexyl, cyclopentyl, 4-dodecyl cyclohexyl), (replacement of preferred 5～30 carbon atoms or unsubstituted bicyclic alkyl are promptly removed the univalent perssad of a hydrogen atom to bicyclic alkyl from the bicyclic alkane of 5～30 carbon atoms.For example two ring (1.2.2) heptane-2-bases, two encircle (2.2.2) octane-3-yls), but also comprise that ring structure has the structure of three rings etc.Below the alkyl in Shuo Ming the substituting group (for example alkyl in the alkylthio group) though represent the alkyl of this conception of species, also comprises thiazolinyl and alkynyl];

Thiazolinyl [replacement or the unsubstituted thiazolinyl of expression straight chain, side chain, ring-type.They are thiazolinyl (replacement of preferred 2～30 carbon atoms or unsubstituted thiazolinyls, for example vinyl, allyl, isopentene group, geranyl, oleyl), (replacement of preferred 3～30 carbon atoms or unsubstituted cycloalkenyl group are promptly removed the univalent perssad of a hydrogen atom to cycloalkenyl group from the cycloolefin of 3～30 carbon atoms.For example 2-cyclopentene-1-base, 2-cyclohexene-1-yl), bicycloenyl (replaces or unsubstituted bicycloenyl, the replacement of preferred 5～30 carbon atoms or unsubstituted bicycloenyl are promptly removed the univalent perssad of a hydrogen atom from two cycloolefins with two keys.For example comprise two the ring (2.2.1) hept-2-ene"-1-bases, two the ring (2.2.2) oct-2-ene-4-yls)], alkynyl (replacement of preferred 2～30 carbon atoms or unsubstituted alkynyl, for example ethinyl, propargyl, trimethyl silyl ethinyl);

Aryl (replacement of preferred 6～30 carbon atoms or unsubstituted aryl, for example phenyl, p-methylphenyl, naphthyl, a chlorphenyl, adjacent palmityl amido phenyl), heterocyclic radical (preferably removes the univalent perssad of a hydrogen atom, more preferably five of 3～30 carbon atoms Yuans or six Yuans aromatic heterocyclic groups from five Yuans or six s' replacement or unsubstituted, aromatic series or non-aromatic heterogeneous ring compound.For example 2-furyl, 2-thienyl, 2-pyrimidine radicals, 2-[4-morpholinodithio base also can be cationic heterocyclic groups such as 1-methyl-2-pyridinio, 1-methyl-2-quinolinio);

Cyano group, hydroxyl, nitro, carboxyl, alkoxy (replacement of preferred 1～30 carbon atom or unsubstituted alkoxy, methoxyl for example, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, the 2-methoxyethoxy), aryloxy group (replacement of preferred 6～30 carbon atoms or unsubstituted aryloxy group, phenoxy group for example, the 2-methylphenoxy, 4-tert-butyl group phenoxy group, the 3-nitro-phenoxy, 2-myristamide phenoxyl), siloxy (the siloxy of preferred 3～20 carbon atoms, trimethylsiloxy for example, the t-butyldimethylsilyloxy base), heterocyclic oxy group (replacement of preferred 2～30 carbon atoms or unsubstituted heterocyclic oxy group, 1-phenyltetrazole-5-oxygen base for example, the 2-tetrahydro-pyran oxy), acyloxy (preferred formyloxy, the replacement of 2～30 carbon atoms or unsubstituted alkyl carbonyl oxygen base, the replacement of 6～30 carbon atoms or unsubstituted aryl-carbonyl oxygen, for example formyloxy, acetoxyl group, trimethyl acetoxyl, stearoyl-oxy, benzoyloxy, p-methoxyphenyl carbonyl oxygen base);

Carbamoyloxy (replacement of preferred 1～30 carbon atom or unsubstituted carbamoyloxy, N for example, N-dimethylamino formyloxy, N, N-diethylamino formyloxy, morpholino carbonyl oxygen base, N, the amino carbonyl oxygen of N-di-n-octyl base, N-n-octyl carbamoyloxy), alkyl oxy carbonyl oxygen (replacement of preferred 2～30 carbon atoms or unsubstituted alkyl oxy carbonyl oxygen, methoxy carbonyl oxygen base for example, ethoxy carbonyl oxygen base, tertiary butyloxycarbonyl oxygen base, n-octyl carbonyl oxygen base), virtue oxygen carbonyl oxygen base (replacement of preferred 7～30 carbon atoms or unsubstituted fragrant oxygen carbonyl oxygen base, carbonyl phenoxy oxygen base for example, to methoxyl carbonyl phenoxy oxygen base, to n-hexadecane oxygen base carbonyl phenoxy oxygen base), amino (preferred amino, the replacement of 1～30 carbon atom or unsubstituted alkyl amino, the replacement of 6～30 carbon atoms or unsubstituted anilino-, for example amino, methylamino, dimethylamino, anilino-, N-methyl-anilino-, diphenyl amino);

Nitrogen base (preferred nitrogen base, by the replacement of 1～30 carbon atom or unsubstituted alkyl, nitrogen base, for example trimethyl nitrogen base, triethyl nitrogen base, diphenyl methyl nitrogen base that aryl, heterocyclic group replaced), amide group (replacement of the replacement of preferred formamido, 1～30 carbon atom or unsubstituted alkyl carbonylamino, 6～30 carbon atoms or unsubstituted aryl-amino-carbonyl, for example formamido, acetamido, pivaloyl amido, lauroyl amido, benzamido, 3,4,5-three n-octyloxy phenylcarbonyl group amino);

Amino carbonyl amino (replacement of preferred 1～30 carbon atom or unsubstituted amino carbonyl amino, carbamido group for example, N, N-dimethylamino carbonylamino, N, N-diethylamino carbonylamino, morpholino carbonyl amino), alkoxycarbonyl amido (replacement of preferred 2～30 carbon atoms or unsubstituted alkoxycarbonyl amido, methoxycarbonyl group amino for example, ethoxy carbonyl amino base, t-butoxycarbonyl amino, n-octadecane oxygen base carbonylamino, N-methyl methoxy carbonylamino), aryloxy carbonyl amino (replacement of preferred 7～30 carbon atoms or unsubstituted aryloxy carbonyl amino, for example phenyloxycarbonyl amino, to the chlorophenoxy carbonylamino, between-(n-octyloxy) phenyloxycarbonyl amino);

Sulfonamide amido (replacement of preferred 0～30 carbon atom or unsubstituted sulfonamide amido, sulfonamide amido for example, N, N-dimethylamino sulfonamide amido, the just hot amino sulfonamide amido of N-), alkyl or aryl sulfoamido (replacement of preferred 1～30 carbon atom or unsubstituted alkyl sulfonamide base, the replacement of 6～30 carbon atoms or unsubstituted aryl-sulfonyl amino, sulfonyloxy methyl amido for example, the butyl sulfonamide base, the phenyl-sulfamide base, 2,3,5-trichlorophenyl sulfoamido, the p-methylphenyl sulfoamido), sulfydryl, alkylthio group (replacement of preferred 1～30 carbon atom or unsubstituted alkylthio group, for example methyl mercapto, ethylmercapto group, the n-hexadecane sulfenyl);

Arylthio (replacement of preferred 6～30 carbon atoms or unsubstituted arylthio, thiophenyl for example, to the chlorobenzene sulfenyl, the meta-methoxy thiophenyl), heterocycle sulfenyl (replacement of preferred 2～30 carbon atoms or unsubstituted heterocycle sulfenyl, 2-[4-morpholinodithio sulfenyl for example, 1-phenyltetrazole-5-sulfenyl), sulfamoyl (replacement of preferred 0～30 carbon atom or unsubstituted sulfamoyl, N-ethyl sulfamoyl for example, N-(3-dodecyloxy propyl group) sulfamoyl, N, N-dimethylamino sulfonyl, N-acetyl group sulfamoyl, N-benzoyl sulfamoyl, N-(N '-the phenyl amino formoxyl) sulfamoyl), sulfo group, alkyl or aryl sulfinyl (replacement of preferred 1～30 carbon atom or unsubstituted alkyl sulfinyl, the replacement of 6～30 carbon atoms or unsubstituted aryl sulfonyl kia, for example methylsulfinyl, the ethyl sulfinyl, the phenyl sulfinyl, the p-methylphenyl sulfinyl);

Alkyl or aryl sulfonyl (replacement of preferred 1～30 carbon atom or unsubstituted alkane sulfonyl, the replacement of 6～30 carbon atoms or unsubstituted aryl sulfonyl, methyl sulphonyl for example, ethylsulfonyl, phenyl sulfonyl, the p-methylphenyl sulfonyl), acyl group (preferred formoxyl, the replacement of 2～30 carbon atoms or unsubstituted alkyl carbonyl, the replacement of 7～30 carbon atoms or unsubstituted aryl carbonyl, replace or heterocycle carbonyl that unsubstituted carbon atom combines with carbonyl by 4～30, for example acetyl group, pivaloyl group, 2-chloro acetyl group, stearyl, benzoyl, align the octyloxyphenyl carbonyl, 2-pyridine radicals carbonyl, the 2-furyl carbonyl);

Aryloxycarbonyl (replacement of preferred 7～30 carbon atoms or unsubstituted aryloxycarbonyl, phenyloxycarbonyl for example, adjacent chlorophenoxy carbonyl, m-nitro oxygen base carbonyl, to tert-butyl group phenyloxycarbonyl), alkoxy carbonyl group (replacement of preferred 2～30 carbon atoms or unsubstituted alkoxy carbonyl, methoxycarbonyl for example, ethoxy carbonyl, tert-butoxycarbonyl, n-octadecane oxygen base carbonyl), carbamyl (replacement of preferred 1～30 carbon atom or unsubstituted carbamyl, carbamyl for example, N-methylamino formoxyl, N, the N-formyl-dimethylamino, N, N-di-n-octyl carbamyl, N-(methyl sulphonyl) carbamyl), aryl or heterocycle azo base (replacement of preferred 6～30 carbon atoms or unsubstituted arylazo base, the replacement of 3～30 carbon atoms or unsubstituted heterocycle azo base, phenylazo for example, the rubigan azo group, 5-ethylmercapto group-1,3,4-thiadiazoles-2-base azo group);

Imide (preferred N-succinimido, the N phlhalimide base), phosphino-(replacement of preferred 2～30 carbon atoms or unsubstituted phosphino-, dimethyl phosphino-for example, diphenylphosphino, the methylenedioxy phenoxy phosphino-), phosphinyl (replacement of preferred 2～30 carbon atoms or unsubstituted phosphinyl, phosphinyl for example, two octyloxy phosphinyls, the diethoxy phosphinyl), phosphine oxide oxygen base (replacement of preferred 2～30 carbon atoms or unsubstituted phosphine oxide oxygen base, two phenoxy group phosphine oxide oxygen bases for example, two octyloxy phosphine oxide oxygen bases), phosphine oxide amino (replacement of preferred 2～30 carbon atoms or unsubstituted phosphine oxide amino, for example dimethoxy phosphine oxide amino, dimethylamino phosphine oxide amino);

Phospho-, silicyl (replacement of preferred 3～30 carbon atoms or unsubstituted silicyl, for example trimethyl silyl, t-butyldimethylsilyl, phenyl dimetylsilyl), diazanyl (replacement of preferred 0～30 carbon atom or unsubstituted diazanyl, trimethyl diazanyl for example), urea groups (replacement of preferred 0～30 carbon atom or unsubstituted urea groups, N for example, N-dimethyl urea groups).

In addition, two W also can form condensed ring structure (aromatic series or non-aromatic hydrocarbon ring or heterocycle jointly.These rings can also further be combined to form polycyclic fused ring.For example can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, the quinoline ring, phenanthrene ring, the fluorenes ring, the Sanya phenyl ring, the naphthacene ring, cyclohexyl biphenyl, pyrrole ring, furan nucleus, thiphene ring, imidazole ring oxazole ring, thiazole ring, pyridine ring, the pyrazine ring, pyrimidine ring, the pyridazine ring, the indolizine ring, indole ring, the coumarone ring, the benzothiophene ring, between the coumarone ring, the quinolizine ring, the isoquinoline ring, the phthalazines ring, the naphthyridines ring, quinoxaline ring, the quinoxazoline ring, the carbazole ring, the azepine phenanthrene ring, the acridine ring, the phenanthroline ring, the thianthrene ring, the chromene ring, oxa-anthracene nucleus; phenoxthine ring, the phenothiazine ring, the azophenlyene ring).

Among the above-mentioned substituting group W, the group with hydrogen atom also can further be replaced by above-mentioned substituting group after losing hydrogen atom.As this substituting group, can enumerate-CONHSO ₂-Ji (sulfuryl amino formoxyl, carbonyl sulfamoyl) ,-CONHCO-base (carbonylamino formoxyl) ,-SO ₂NHSO ₂-Ji (Herbicidal sulphonylamino sulfonyl).

More specifically can enumerate alkyl-carbonyl-amino sulfonyl (for example acetamido sulfonyl), aryl-amino-carbonyl sulfonyl (for example benzamido sulfonyl), alkylsulfonamido carbonyl (for example sulfonyloxy methyl amido carbonyl), aryl-sulfonyl amino carbonyl (for example to Methyl benzenesulfonyl amido carbonyl).

Below describe the sensitizing coloring matter that uses among the present invention in detail.

Silver emulsion of the present invention is used the sensitizing coloring matter institute optical sensibilization of note general formula (I) expression down.

General formula (I)

[changing 9]

In the general formula (I), X ¹And X ²Independent separately expression oxygen atom, sulphur atom, selenium atom, tellurium atom, nitrogen-atoms or carbon atom.Y ¹Expression can also can have substituent furan nucleus, pyrrole ring, thiphene ring or phenyl ring with other 5～6 Yuans carbocyclic rings or heterocycle condensation.Y ²Expression forms phenyl ring or 5～6 Yuans atom groups that unsaturated heterocycle is required, can also can have substituting group with other 5～6 Yuans carbocyclic rings or heterocycle condensation.Y in addition ¹And Y ²Encircle key between two carbon atoms that contract, can be singly-bound or two key.R ¹And R ²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.L ¹, L ²And L ³Independent separately expression methine, n ¹Expression 0.M ¹The expression counterion, m ¹In the expression and molecule in the required numeral more than 0 of electric charge.

Below elaborate with regard to the sensitizing coloring matter by general formula (I) expression of the present invention.

X ¹And X ²Independent separately expression oxygen atom, sulphur atom, selenium atom, tellurium atom, nitrogen-atoms, carbon atom.Nitrogen-atoms is preferably used-N (Rx)-expression, carbon atom preferably uses-C (Ry) (Rz)-expression, and Rx, Ry and Rz independently are hydrogen atom or monovalence substituting group (as above-mentioned W) separately, and they are preferably alkyl, aryl or the heterocyclic group that illustrates among the above-mentioned W, more preferably alkyl.X ¹And X ²Preferred oxygen atom, sulphur atom, nitrogen-atoms, more preferably oxygen atom and sulphur atom.

Y ¹Expression can or have substituent furan nucleus, pyrrole ring, thiphene ring or phenyl ring with other 5～6 Yuans carbocyclic rings or heterocycle condensation.Y wherein ¹Key between two carbon atoms of condensation can be singly-bound or two key, but preferred two key.Y ¹Also can further form condensed ring (for example coumarone ring, indole ring, benzothiophene ring, naphthalene nucleus) with other 5～6 Yuans carbocyclic rings or heterocycle.Y ¹Preferred thiphene ring.Y ¹Substituting group can be any substituting group, for example can enumerate above-mentioned W.Preferred substituted is alkyl (for example methyl), aryl (for example phenyl), aromatic heterocyclic group (for example 1-pyrrole radicals), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom); more preferably methyl, methoxyl, cyano group, halogen atom; further preferred halogen atom; preferred especially fluorine atom, chlorine atom, bromine atoms, most preferably chlorine atom.The special Y that works as ¹Be under the situation of thiphene ring, preferably do not replace or have the substituent thiphene ring of halogen atom, and as preferred chlorine atom of substituting group or bromine atoms, most preferably the chlorine atom.

Y ²Expression forms phenyl ring or 5～6 Yuans atom groups that unsaturated heterocycle is required, and can also can have substituting group with other 5～6 Yuans carbocyclic rings or heterocycle condensation.Y wherein ²Key between two carbon atoms of condensation can be singly-bound or two key, but preferred two key.And conduct is by Y ²Five Yuans unsaturated heterocycles that form can be enumerated pyrrole ring, pyrazoles ring, imidazole ring, triazole ring, furan nucleus, oxazole ring, isoxazole ring, thiphene ring, thiazole ring, isothiazole ring, thiadiazoles ring, selenium phenol ring, selenazoles ring, different selenazoles ring, tellurium phenol ring, tellurium azoles ring, different tellurium azoles ring etc.; Can enumerate pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyranoid ring, thiapyran ring etc. as six Yuans unsaturated heterocycles, but also can be further and other five member～six carbocyclic rings or heterocycle condensation, form indole ring, coumarone ring, benzothiophene ring, thienothiophene ring etc., but the 3rd condensed ring does not exist preferably.

Y ¹Preferred phenyl ring, pyrrole ring, furan nucleus, thiphene ring, preferred especially phenyl ring, furan nucleus and pyrrole ring, most preferably phenyl ring.Y ²Substituting group can be any, for example can enumerate above-mentioned W.Preferred substituted is alkyl (for example methyl), aryl (for example phenyl), aromatic heterocyclic group (for example 1-pyrrole radicals), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom); more preferably methyl, methoxyl, cyano group, halogen atom; further preferred halogen atom; preferred especially fluorine atom, chlorine atom, bromine atoms, most preferably chlorine atom.

R ¹And R ²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.

Below describe with regard to acidic group.So-called acidic group is meant the group with dissociation property.

Specifically for example be sulfo group, carboxyl, sulfate radical ,-CONHSO ₂-Ji (sulfuryl amino formoxyl, carbonyl sulfamoyl) ,-CONHCO-base (carbonylamino formoxyl) ,-SO ₂NHSO ₂-Ji (Herbicidal sulphonylamino sulfonyl), sulfophenyl, sulfamoyl, phosphate radical, phosphono, boronate, phenol hydroxyl etc.According to the pKa of these groups and pH on every side, also may there be the group of the proton that dissociates, preferably include the proton disassociation property acidic-group more than 90% of can between pH5～11, dissociating of the group of above-mentioned particular instantiation.

In the sensitizing coloring matter of general formula (I) expression, use R ¹And R ²Preferred group in " alkyl that is replaced by acidic group " of expression can be represented with following form.

Preferred alkyl=-Qa-T ¹

Qa represents to form the linking group (preferred divalent linker) of the required necessity of alkyl.T ¹Expression-SO ₃-,-CO ₂H ,-CONHSO ₂Ra ,-SO ₂NHCORb ,-CONHCORc or-SO ₂NHSO ₂Rd.Wherein Ra, Rb, Rc and Rd independently represent alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclic oxy group, amino separately.

As long as can satisfy above-mentioned requirements, Qa can be any linking group, but preferably constitutes by containing atom at least a in carbon atom, nitrogen-atoms, sulphur atom and the oxygen atom or atomic group.One or more following radicals constituted in the expression combination; carbon number is more than 0 and below 10; preferred carbon number is more than 1 below 8; more preferably carbon number linking group below 5 more than 1: alkylene (methylene for example; ethylene; trimethylene; tetramethylene; penta-methylene; the methyl trimethoxy support); alkene support (vinylene for example; the propylene support); alkynes support (ethynylene for example; the propine support); amide group; ester group; sulfoamido; sulfonate group; urea groups; sulfonyl; sulfinyl; thioether group; ether; carbonyl;-N (Wa)-(Wa represents hydrogen atom or monovalence substituting group.Can enumerate above-mentioned W as the monovalence substituting group).

The substituting group that above-mentioned linking group both can useful above-mentioned W be represented, and can contain ring (aromatic series or non-aromatic hydrocarbon ring or heterocycle).

More preferably do not contain heteroatomic group in these linking groups.The group of the substituting group replacement of especially preferably not represented in addition, with above-mentioned W.

Preferred group is that Qa serves as reasons carbon number that following one or more moiety combinations form more than 1 and 5 following divalent linkers: carbon number 1 or more and 5 following alkylenes (for example methylene, ethylene, trimethylene, tetramethylene, penta-methylene, methyl trimethoxy support), carbon number 2 or more and 5 following alkene supports (for example vinylene, propylene support), carbon number 2 or more and the alkynes below 5 support (for example ethynylene, propine support).Particularly preferably be carbon number more than 1 and 5 following alkylenes (for example methylene, ethylene, trimethylene, tetramethylene).

Work as T ¹Be under the situation of sulfo group, as more preferably ethylene, trimethylene, tetramethylene, methyl trimethoxy support of Qa, preferred especially trimethylene.Xa is under the situation of carboxyl, as Qa more preferably methylene, ethylene, trimethylene, and preferred especially methylene.

Work as T ¹Be-CONHSO ₂Ra ,-SO ₂NHCORb ,-CONHCORc ,-SO ₂NHSO ₂Under the situation of Rd, as Qa more preferably methylene, ethylene, trimethylene, preferred especially methylene.

Ra, Rb, Rc and Rd represent alkyl, aryl, heterocyclic group, alkoxy, aryloxy group, heterocyclic oxy group or amino, and wherein preferred group can be listed below.

For example can enumerate: 1～18, preferred 1～10, the more preferably alkyl of 1～5 carbon atom (methyl for example, ethyl, propyl group, butyl), 1～18, preferred 1～10, the more preferably substituted alkyl of 1～5 carbon atom (methylol for example, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl group, acetamidomethyl, and substituted alkyl also comprises preferred 2～18 here, more preferably 3～10, the unsaturated alkyl of preferred especially 3～5 carbon atoms (vinyl for example, ethinyl, the 1-cyclohexenyl group, benzenyl, benzylidene))

6～20, preferred 6～15, the more preferably replacement of 6～10 carbon atoms or unsubstituted aryl (phenyl for example, naphthyl, to carboxyl phenyl, p-nitrophenyl, 3, the 5-dichlorophenyl, to cyano-phenyl, between the fluoro phenyl, p-methylphenyl), 1～20, preferred 2～10, more preferably 4～6 carbon atoms can substituted heterocyclic group (pyridine radicals for example, the 5-picolyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), 1～10, the alkoxy of preferred 1～8 carbon atom (methoxyl for example, ethoxy, the 2-methoxy ethoxy, the 2-hydroxyl-oxethyl, the 2-phenyl ethoxy), 6～20, preferred 6～12, the more preferably aryloxy group of 6～10 carbon atoms (phenoxy group for example, to methylphenoxy, to chlorophenoxy, naphthoxy), 1～20, preferred 3～12, more preferably the heterocyclic oxy group of 3～10 carbon atoms (refers to the oxygen base that replaced by heterocyclic group.For example 2-thianthrene oxygen base, 2-morpholino oxygen base), 0～20, preferred 0～12, the more preferably amino of 0～8 carbon atom (for example the morpholino base of amino, methylamino, dimethylamino, ethylamino, lignocaine, hydroxyethylamino, benzyl amino, anilino-, diphenyl amino, formation ring, pyrrolidino yl).In addition, these substituting groups can also be replaced by above-mentioned W.

Preferred group is methyl, ethyl, hydroxyethyl, special preferable methyl.

Wherein in acidic group, for example the nitrogen-atoms of carboxyl, disassociation property etc. both can also can be used disassociation form (COO with the form of not dissociating (COOH, NH) expression ^-, N ^-) expression.In fact according to environment such as the residing pH of pigment and can become the disassociation state or the state that do not dissociate.

Existing as counterion under the cationic situation, for example can be designated as (COO ^-Na ⁺), (N ^-Na ⁺).Can not be designated as (COOH), (NH) under the disassociation state, but be considered as proton, then can be designated as (COO yet as if cationic compound with counterion ^-H ⁺), (N ^-H ⁺).

In the sensitizing coloring matter of general formula (I) expression, R ¹And R ²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group is as the above-mentioned preferred 3-sulfo group of alkyl propyl group, 4-sulfo group butyl, 3-sulfo group butyl, 2-sulfo group ethyl, more preferably 3-sulfo group propyl group with sulfo group.As the alkyl that is replaced by the acidic group beyond the sulfo group, preferably by carboxyl ,-CONHSO ₂-Ji ,-SO ₂The NHCO-base ,-the CONHCO-base ,-SO ₂NHSO ₂The alkyl that-Ji replaces, preferred especially ethyloic, mesyl carbamyl ylmethyl.

As R ¹And R ²Combination; preferably one of them is ethyloic or mesyl carbamyl ylmethyl; and another is the situation of 3-sulfo group propyl group, 4-sulfo group butyl, 3-sulfo group butyl, 2-sulfo group ethyl; preferred combination is that one of them is ethyloic or mesyl carbamyl ylmethyl, and another is a 3-sulfo group propyl group.

L ¹, L ²And L ³Independent separately expression methine; can not be substituted; also can be substituted base (for example above-mentioned W) and replace, can enumerate aryl as preferred substituted; unsaturated alkyl; carboxyl; sulfo group; sulfate radical; cyano group; halogen atom (fluorine atom for example; the chlorine atom; bromine atoms; the iodine atom); hydroxyl; sulfydryl; alkoxy; aryloxy group; alkylthio group; arylthio; acyl group; alkoxy carbonyl group; aryloxy carbonyl; acyloxy; carbamyl; sulfamoyl; heterocyclic group; alkane sulfuryl amino formoxyl; the acyl amino formoxyl; the acyl group sulfamoyl; alkane Herbicidal sulphonylamino sulfonyl etc.

n ¹Expression 0.As L ¹Preferred unsubstituted methine.

M ¹The expression counterion in the time the ionic charge of pigment need being neutralized to neutrality, can be included in the formula with expression kation or anionic the existence.Certain pigment is kation or negative ion, perhaps whether has net charge, depends on the environment (pH etc.) in its substituting group and the solution.As typical kation, can enumerate hydrogen ion (H+), alkali metal ion (for example sodion, potassium ion, lithium ion), alkaline-earth metal ion inorganic cations such as (for example calcium ions), ammonium ion organic ions such as (for example ammonium ion, tetraalkyl ammonium ion, triethyl ammonium ion, pyridinium ion, ethylpyridine ion, 1,8-two azos two ring (5.4.0)-7-undecylene ions).Negative ion can be an inorganic anion, it also can be organic anion, can enumerate halide anions (fluoride ion for example, chloride ion, bromide ion, iodide ion), the aryl sulfonic acid ion that replaces (p-toluenesulfonic acid ion for example, the p-chlorobenzenesulfonic acid ion), aryl disulfonic ion (for example 1,3-benzene sulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkylsurfuric acid ion (for example methyl sulfate ion), sulfate ion, thiocyanate ion, the high chloro acid ion, the tetrafluoro boric acid ion, the picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion etc.In addition, also can use ionic polymers or have other pigment with the pigment opposite charges.

Preferred cation is sodion, potassium ion, triethyl ammonium ion, tetraethyl ammonium ion, pyridinium ion, ethylpyridine ion, picoline ion.Preferred anionic surfactants is high chloro acid ion, iodide ion, bromide ion, substituted aryl azochlorosulfonate acid ion (for example p-toluenesulfonic acid ion).

m ¹Expression makes the required numeral more than 0 of charge balance, is 0 under the situation that forms molecule inner salt.Preferred integer below 4 more than 0.

With the sensitizing coloring matter of above-mentioned general formula (I) expression, more preferably represent or represent by general formula (IV) by general formula (II) or general formula (III).

General formula (II)

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General formula (III)

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General formula (IV)

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In the general formula (IV), X ³¹And X ³²Independent separately expression oxygen atom or sulphur atom.R ³¹And R ³²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group.V ³¹, V ³², V ³³, V ³⁴V ³⁵, V ³⁶, V ³⁷And V ³⁸Independent separately expression hydrogen atom or monovalence substituting group, two adjacent substituting groups also can be connected to each other the formation condensed ring.M ³¹The expression counterion, m ³¹In the expression and molecule in the required numeral more than 0 of electric charge.

These preferred compounds below are described.

In the general formula (II), Y ¹¹Expression oxygen atom, sulphur atom or N-R ¹³, R ¹³The alkyl (for example alkyl that is replaced by above-mentioned W) of expression hydrogen atom, unsubstituted alkyl or replacement.As the substituting group on the substituted alkyl, the substituting group that preferred hydrophilic is stronger than iodine atom, more preferably identical or than its stronger substituting group with the water wettability of chlorine atom, particularly preferably be alkyl identical with fluorine atom or that replace than its stronger substituting group by water wettability.As R ¹³More preferably hydrogen atom or unsubstituted alkyl, preferred especially hydrogen atom or methyl.Y ¹¹Preferred especially sulphur atom.

X ¹¹And X ¹²Independent separately expression oxygen atom or sulphur atom, preferably one of them is that sulphur atom or the two are sulphur atom at least.

V ¹¹, V ¹², V ¹³, V ¹⁴, V ¹⁵And V ¹⁶Independent separately expression hydrogen atom or monovalence substituting group, V ¹¹, V ¹², V ¹³And V ¹⁴In adjacent two substituting groups or V ¹⁵And V ¹⁶Also can be connected to each other and form saturated or unsaturated condensed ring, but preferably not form condensed ring.The monovalence substituting group can be enumerated above-mentioned W, preferred alkyl (for example methyl), aryl (for example phenyl), aromatic heterocyclic group (for example 1-pyrrole radicals), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom).More preferably methyl, methoxyl, cyano group, halogen atom, further preferred halogen atom particularly preferably is fluorine atom, chlorine atom, bromine atoms, preferably the chlorine atom.V ¹¹, V ¹², and V ¹⁴Preferred hydrogen atom.

Y ¹¹Under the situation for sulphur atom, V ¹⁵And V ¹⁶Preferred the two be hydrogen atom or one of them is halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom), more preferably V ¹⁶Be hydrogen atom, and V ¹⁵Be hydrogen atom or chlorine atom.

R ¹¹And R ¹²In the alkyl that replaced by the group beyond the sulfo group (preferred carboxyl or alkane sulfuryl amino formoxyl) of expression, the alkyl that another expression is replaced by sulfo group.In addition, the concrete example and the preferred compositions thereof of the alkyl that these are replaced by acidic group are with above-mentioned R ¹Middle illustrate identical.In addition more preferably, R ¹¹And R ¹²In one be ethyloic or mesyl carbamyl ylmethyl, special preferable case is, wherein R ¹¹Be ethyloic or mesyl carbamyl ylmethyl, and R ¹²It is 3-sulfo group propyl group.

M ¹¹The expression counterion, m ¹¹In the expression and molecule in the required numeral more than 0 of electric charge, can enumerate and above-mentioned M ¹¹And m ¹¹Same content.As M ¹¹Special preferred cationic, and preferred cation is sodion, potassium ion, triethyl ammonium ion, pyridinium ion, N-ethylpyridine ion.

In the general formula (III), Y ²¹Expression oxygen atom, sulphur atom or N-R ²³, R ²³The alkyl (for example alkyl that is replaced by above-mentioned W) of expression hydrogen atom, unsubstituted alkyl or replacement.As the substituting group of substituted alkyl, the substituting group that preferred hydrophilic is stronger than iodine atom more preferably with the identical or stronger substituting group of chlorine atom water wettability, particularly preferably is the alkyl that is replaced by the water wettability substituting group identical or stronger with fluorine atom.As R ²³More preferably hydrogen atom or unsubstituted alkyl, preferred especially hydrogen atom or methyl.Y ²¹Preferred especially sulphur atom.

X ²¹And X ²²Independent separately expression oxygen atom or sulphur atom, preferably one of them is sulphur atom for sulphur atom or the two at least.

V ²¹, V ²², V ²³, V ²⁴, V ²⁵And V ²⁶Independent separately expression hydrogen atom or monovalence substituting group, V ²¹, V ²², V ²³And V ²⁴In adjacent two substituting groups or V ²⁵And V ²⁶Also can be connected to each other and form saturated or unsaturated condensed ring, but preferably not form condensed ring.Can enumerate above-mentioned W as the monovalence substituting group, but preferred alkyl (for example methyl), aryl (for example phenyl), aromatic heterocyclic group (for example 1-pyrrole radicals), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom).More preferably methyl, methoxyl, cyano group, halogen atom, further preferred halogen atom, preferred especially fluorine atom, chlorine atom, bromine atoms, preferably chlorine atom.V ²¹, V ²², and V ²⁴Preferred hydrogen atom.

Y ²¹Be under the situation of sulphur atom, V ²⁵And V ²⁶Preferred the two be hydrogen atom or one of them is halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom), more preferably V ²⁶Be hydrogen atom, and V ²⁵Be hydrogen atom or chlorine atom.

R ²¹And R ²²In the alkyl that replaced by the group beyond the sulfo group (preferred carboxyl or alkane sulfuryl amino formoxyl) of expression, the alkyl that another expression is replaced by sulfo group.And the concrete example and the preferred compositions thereof of these alkyl that replaced by acidic group, with above-mentioned R ¹Middle illustrate identical.In addition, more preferably, R ²¹And R ²²One of be ethyloic or mesyl carbamyl ylmethyl, preferred especially R ²¹Be ethyloic or mesyl carbamyl ylmethyl, and R ²²It is 3-sulfo group propyl group.

M ²¹The expression counterion, m ²¹In the expression and molecule in the required numeral more than 0 of electric charge, can enumerate and above-mentioned M ¹And m ¹Same content.As M ²¹Special preferred cationic, and preferred cation is sodion, potassium ion, triethyl ammonium ion, pyridinium ion, N-ethylpyridine ion.

In the general formula (IV), X ³¹And X ³²Independent separately expression oxygen atom or sulphur atom, preferably one of them is that sulphur atom or the two are sulphur atom at least.

R ³¹And R ³²In the alkyl that replaced by the group beyond the sulfo group (preferred carboxyl or alkane sulfuryl amino formoxyl) of expression, the alkyl that another expression is replaced by sulfo group.In addition, these are by the concrete example of acidic group substituted alkyl and preferred compositions thereof, with above-mentioned R ¹Middle illustrate identical.And then, preferred R ³¹And R ³²In have one to be ethyloic or mesyl carbamyl ylmethyl, preferred especially R ³¹Be ethyloic or mesyl carbamyl ylmethyl, and R ³²It is 3-sulfo group propyl group.

V ³¹, V ³², V ³³, V ³⁴, V ³⁵, V ³⁶V ³⁷And V ³⁸Independent separately expression hydrogen atom or monovalence substituting group, two adjacent substituting groups also can be connected to each other the formation condensed ring.Two adjacent substituting groups can be connected to each other and form saturated or unsaturated condensed ring, can enumerate by V as condensed ring ³³And V ³⁴The naphthalene nucleus that is connected to form.Can enumerate above-mentioned W as the monovalence substituting group, but preferred alkyl (for example methyl), aryl (for example phenyl), aromatic heterocyclic group (for example 1-pyrrole radicals), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom).More preferably methyl, methoxyl, cyano group, halogen atom, further preferred halogen atom, preferred especially fluorine atom, chlorine atom, bromine atoms, preferably chlorine atom.V ³¹, V ³², V ³⁴, V ³⁵, V ³⁶And V ³⁸Preferred hydrogen atom.

M ³¹The expression counterion, m ³¹In the expression and molecule in the required numeral more than 0 of electric charge, can enumerate and above-mentioned M ¹And m ¹Same content.As M ³¹Special preferred cationic, and preferred cation is sodion, potassium ion, triethyl ammonium ion, pyridinium ion, N-ethylpyridine ion.

Can in sense indigo plant emulsion layer, use the sensitizing coloring matter of general formula (I) expression among the present invention, preferably select from general formula (II), (III) or (IV), more preferably general formula (II) or (III) sensitizing coloring matter of expression, the sensitizing coloring matter of special preferred formula (II) expression.

Preferred X ¹¹, X ¹²And Y ¹¹(X ²¹, X ²²And Y ²¹) (X ³¹And X ³²) be sulphur atom, V ¹⁵(V ²⁵) be hydrogen atom or chlorine atom, V ¹⁶(V ²⁶) be hydrogen atom.V ¹¹, V ¹², V ¹⁴(V ²¹, V ²², V ²⁴) (V ³¹, V ³², V ³⁴, V ³⁵, V ³⁶And V ³⁸) preferred hydrogen atom, V ¹³(V ²³) (V ³³, V ³⁷) preferred alkyl (for example methyl), alkoxy (for example methoxyl), alkylthio group (for example methyl mercapto), cyano group, acyl group (for example acetyl group), alkoxy carbonyl group (for example methoxycarbonyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom); more preferably methyl, methoxyl, cyano group, acetyl group, methoxycarbonyl group, halogen atom; preferred especially halogen atom, preferably fluorine atom, chlorine atom.

Preferred R ¹¹And R ¹²(R ²¹And R ²²) (R ³¹And R ³²) in expression ethyloic or a mesyl carbamyl ylmethyl, another expression 3-sulfo group propyl group, preferred especially R ¹¹(R ²¹) (R ³¹) be ethyloic or mesyl carbamyl ylmethyl, R ¹²(R ²²) (R ³²) be the occasion of 3-sulfo group propyl group.

Preferred M ¹¹(M ²¹) (M ³¹) be the organic or inorganic monovalent cation, and m ¹¹(m ²¹) (m ³¹) be 0 or 1.

Below list the concrete example of using the sensitizing coloring matter of general formula (I), (II), (III), (IV) expression of the present invention, but the present invention is not limited.

[changing 13]

X???????R?????????????????M

S-1???????Cl??????CH ₂CONHSO ₂CH ₃??-

S-2???????Cl??????CH ₂CO ₂H?????????-

S-3???????Br??????CH ₂CO ₂H?????????-

[changing 14]

X????????Y????????Z ₁?????Z ₂????R?????????????????M

S-4??????Cl???????O????????S???????S????CH ₂CO ₂H???????????-

S-5??????Cl???????NH???????S???????S????CH ₂CONHSO ₂CH ₃????-

S-6??????Br???????O????????S???????S????CH ₂CO ₂H???????????-

X????????Y????????Z ₁?????Z ₂?????R????????????????M

S-7??????Cl???????S????????O???????S????CH ₂CO ₂H???????????-

S-8??????Cl???????NH???????S???????S????CH ₂SO ₂NHCOCH ₃????-

S-9??????Br???????O????????S???????S????CH ₂CO ₂H???????????-

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

[changing 21]

The sensitizing coloring matter by general formula (I), (II), (III), (IV) expression that uses among the present invention can be synthetic according to the method for following document record.

A) F.M.Hamer work " heterogeneous ring compound-cyanines pigment and related compound " (John Wiley﹠amp; Sons publishing house, published in 1964 in New York, London)

B) D.M.Sturmer work " the specific problem in heterogeneous ring compound-hydridization chemistry ", the 8th chapter, the 4th joint, 482～515 pages of (John Wiley﹠amp; Sons publishing house, published in 1977 in New York, London)

C) " Rodd ' the s chemistry of carbon compound ", the 2nd edition, the 4th volume, B part, the 15th chapter, 369～422 pages (published in 1977 years in Elsevir scientific publication company limited, New York).

In addition, as synthetic with the heterocycle of the raw material of the sensitizing coloring matter of general formula (I), (II), (III), (IV) expression among the present invention, for example can be with reference to " French Chemical Society meeting will " II-150 page or leaf (1980) and " heterocyclic chemistry magazine ", the record in 1563 pages of documents such as (1979) of 16 volumes.

Contain the methine pigment by general formula (I), (II), (III), (IV) expression of the present invention in the silver emulsion of the present invention for making, both can directly it be dispersed in the emulsion, also it can be dissolved in water, methyl alcohol, ethanol, propyl alcohol, acetone, methyl Cellosolve, 2,2,3,3,-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxyl-1-propyl alcohol, 3-methoxyl-1-butanols, 1-methoxyl-2-propyl alcohol, N are added in the emulsion after in single solvent such as dinethylformamide or its mixed solvent.

In addition, can adopt United States Patent (USP) the 3rd, 469, No. 987 records such as instructions be dissolved in pigment in the volatile organic solvent after, this solution is dispersed in water or the hydrophilic colloid, in emulsion, add the method for this dispersion liquid again; Special wait record water-insoluble pigment is dispersed in (rather than dissolving) in the water-soluble solvent for public clear 46-24185 number, again this dispersion liquid is added on the method in the emulsion; Special public clear 44-23389, same 44-27555, with records such as 57-22091 communique be dissolved in pigment in the acid after, again this solution is added on the method in the emulsion, the method that perhaps makes acid or alkali coexist and in emulsion, add with the aqueous solution form; United States Patent (USP) the 3822135th and with adding in emulsion under the coexistence of surfactant of record in No. 4006026 instructions etc. made aqueous solution or colloid disperses thing method; The spy open clear 53-102733, with 58-105141 equal sign communique record directly be dispersed in pigment in the hydrophilic colloid after, again this dispersion thing is added to the method in the emulsion; The compound dissolution pigment that the usefulness that the spy opens clear 51-74624 record makes it red shift adds this solution to the method in the emulsion again.Can adopt the method for ultrasound wave dissolving in addition.

The time that the sensitizing coloring matter that general formula of the present invention (I), (II), (III), (IV) are represented adds in silver emulsion of the present invention, can be in any operation of the emulsion preparation of thinking suitable so far.For example, according to No. the 2735766th, United States Patent (USP), with No. 3628960, with No. 4183756, with No. 4225666, spy open clear 58-184142 number, with open in the instructions such as 60-196749 number, period in the period before silver halide particle forms operation and/or desalination, the desalination operation and/or after the desalination before begin chemical slaking or as specially open being disclosed in of clear 58-113920 instructions and be about to begin before the chemical curing step or all can add any period before the coating emulsion to the coating and the operation in the operation, after chemical slaking.And open clear 58-7629 number etc. in the instructions open as No. the 4225666th, United States Patent (USP), spy, can be separately combine with same compound or with the compound of different structure, be divided into and form in the operation and in the chemical curing step or after chemical curing step finishes at particle, perhaps be divided into before chemical slaking or in the operation or after finishing etc. gradation add, also can after the kind that changes compound that gradation adds and compound combination, add.

The consumption of the sensitizing coloring matter by general formula (I), (II), (III), (IV) expression of the present invention is different because of the shape and size of silver halide particle, add 0.1 to 4 mM in preferred every mole of silver halide, more preferably add 0.2 to 2.5 mM, but also can and use with other sensitizing coloring matters.

Among the present invention, except that sensitizing coloring matter, also can use other sensitizing coloring matters by general formula (I), (II), (III), (IV) expression.Usually under the purpose of rich shade sensitizing, be used in combination sensitizing coloring matter.Its representative example is documented in United States Patent (USP) 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, with No. 1507803, special public clear 43-4936 number, with 53-12375 number, the spy opens clear 52-110618 number, with waiting for 52-109925 number among the instructions.

Below elaborate with regard to silver emulsion.

Among the present invention, the silver emulsion in the silver halide emulsion layer of displaing yellow sense indigo plant contains specific silver emulsion of the present invention (specific silver halide particle perhaps of the present invention).The shape of silver halide particle of the present invention must be to have { the crystal grain of the cube of 100} face or 14 bodies (these particle summits are rounded, and the high order face can be arranged again) in fact.What is called has in fact that { the cube particle of 100} face is meant that { particle that crystal boundary is arranged on the 100} crystal face can { not show beyond the 100} crystal face and can confirm crystal face at six because of slaking shows some circles in the bight of this particle and edge yet at six.And so-called 14 body crystal grain, be meant the relative direction and the interval of satisfying the cube particle, in that { 100} crystal face to small part defines the particle of crystal boundary, because of slaking can present some circles at the bight and the edge of particle, for example have three pairs of equally spaced parallel { 100} crystal face and eight { 111} crystal faces.Particle size is by the cube conversion length of side, must be in (preferred more than 0.1 micron and below 0.51 micron) below 0.51 micron, more preferably (preferred more than 0.2 micron and below 0.47 micron) below 0.47 micron preferably is in (preferred more than 0.2 micron and below 0.3 micron) below 0.3 micron.

Be formed into the silver halide emulsion layer of toner and contain silver emulsion in the silver halide emulsion layer that cyanine is formed into toner about containing pinkish red pigment, though there is no particular restriction to shape of particle, but preferably { cube of 100} face or 14 body crystal grain (these particle summits are rounded, and can have the high order face), octahedra lattice, first type surface are by { 100} face or { shape that the 111} face constitutes is in tabular particle formation 2 or more than (aspect) by having in fact.So-called shape is than the numerical value of the diameter of equivalent circle that is meant projected area divided by particle thickness.About first type surface by { 100} face or { the tabular particle that the 111} face constitutes can be opened record in the 0033rd～0040 section in the 2000-352794 communique with reference to the spy, can be introduced among this instructions.Particle size preferably is in (preferred more than 0.1 micron and below 0.4 micron) below 0.4 micron in the cube conversion length of side, more preferably (preferred more than 0.1 micron and below 0.3 micron) below 0.3 micron

In this instructions, the length of side when the so-called cube length of side is meant each particle volume is converted into the cube of equal volume, the cube conversion length of side also refers to identical meaning in this manual.Emulsion particles Size Distribution of the present invention preferably is made up of monodispersed particle.The variation factor of the cube conversion length of side of all particles of the present invention preferably is in below 20%, more preferably is in below 15%, especially preferably is in below 10%.The variation factor of the so-called cube conversion length of side is represented with respect to the percentage of length of side mean value with the standard deviation of an edge lengths of the cube conversion length of side of each particle.Also preferably with one deck mixing using above-mentioned list disperse emulsion or its double-layer be coated with use in order to obtain the tolerance of broadness this moment.

In the silver emulsion of the present invention, also can contain the silver halide particle outside the contained silver halide particle (being specific silver halide particle) in the silver emulsion of the present invention definition.Yet in the silver emulsion that defines among the present invention, the silver halide particle of the present invention's definition must account in all particles projected area

More than 50%, preferred more than 80%, more preferably more than 90%.

As the silver emulsion that uses among the present invention, can use the emulsion that contains silver halide particle with specific silver halide content, particularly ought contain under the situation of silver halide emulsion layer that xanthein is formed into toner, silver chloride content must be in 90 moles more than the %, from the property handled viewpoint rapidly, preferred silver chloride content is 93 moles more than the %, more preferably 95 moles more than the %.The angle that bromide sliver content is strong from contrast, latent image stability is good, preferred 0.1～7 mole of %, more preferably 0.5～5 mole of %.Among the present invention, agi content must be between 0.02～1 mole of %, considers exposure under the high illumination, ISO and high-contrast, preferred 0.05～0.5 mole of %, more preferably 0.07～0.40 mole of %.The preferred iodine bromine of specific silver halide particle of the present invention silver chloride particle more preferably has the iodine bromine silver chloride particle that above-mentioned halogen is formed.

On the other hand, contain pinkish red pigment and be formed into the silver halide emulsion layer of toner and contain in the silver halide emulsion layer that the cyan pigment is formed into toner, it also is comparatively desirable having same silver halide content.

Specific silver halide particle in the silver emulsion of the present invention preferably has the silver bromide of containing phase and/or contains the silver iodide phase.Described herely contain silver bromide mutually or contain the silver iodide phase, be meant and compare silver bromide or the high position of silver iodide concentration on every side.Contain the silver bromide phase or contain silver iodide and the composition of the silver halide around it, both can change continuously, also can sharply change.Thisly contain silver bromide mutually or contain the silver iodide phase, certain part concentration that both can be formed in the particle has the layer of certain width substantially, also can form the maximal point that does not have width.Contain the local bromide sliver content of silver bromide in mutually, preferably be in 5 moles more than the %, more preferably 10～80 moles of %, most preferably 15～50 moles of %.Contain the local agi content of silver iodide in mutually, preferably be in 0.3 mole more than the %, more preferably 0.5～8 mole of %, most preferably 1～5 mole of %.And thisly contain silver bromide mutually or contain the silver iodide phase, and can in particle, exist a plurality ofly respectively with the stratiform form, and the content of silver bromide separately or silver iodide also can be different, but it contains preferably the rarest one mutually.

Containing the silver bromide phase or containing the silver iodide phase of silver emulsion of the present invention preferably and importantly is in the stratiform state that respectively particle is surrounded.What form the stratiform of surrounding particle contains silver bromide mutually or contain the silver iodide phase, its preferred condition be separately mutually in around particle, have uniform CONCENTRATION DISTRIBUTION.But, form the stratiform of surrounding particle contain silver bromide mutually or contain silver iodide mutually in, around particle, also can have the maximal point or the minimal point of silver bromide or silver iodide concentration, and have CONCENTRATION DISTRIBUTION.For example, when containing silver bromide mutually or contain under the situation of silver iodide phase what have stratiform that particle is surrounded near the particle surface, on the particle angle or the silver bromide of edge or silver iodide concentration, often the concentration with first type surface is different.In addition, also can comprise be different from form the stratiform of surrounding particle contain silver bromide mutually or contain the silver iodide phase, and be present in the privileged site of particle surface fully isolatedly and do not surround containing the silver bromide phase or containing the silver iodide phase of particle.

Silver emulsion of the present invention contains under the situation of silver bromide phase, and this contains silver bromide and is preferably formed a kind of stratiform that has very big silver bromide concentration in particle inside mutually.In addition, silver emulsion of the present invention contains under the situation of silver iodide phase, and this contains silver iodide and is preferably formed a kind of stratiform that has very big silver iodide concentration at particle surface mutually.Thisly contain silver bromide mutually or contain the silver iodide phase, consider from the meaning that improves local concentration with less silver bromide or agi content, preferably by account for particle volume more than 3% and 30% following silver amount constitute, more preferably by account for particle volume 3% or more and the silver amount below 15% constitute.

Silver emulsion of the present invention preferably contains the silver bromide phase simultaneously and contains silver iodide mutually.In this case, contain the silver bromide phase and contain the same position that silver iodide both can be in particle mutually, also can be in diverse location, but the viewpoint that calm particle easy to control forms preferably is in diverse location.And both can contain silver iodide in mutually containing silver bromide, also can contain silver bromide in mutually containing silver iodide.Generally speaking, add iodide in the high-silver chloride particle forms, compare owing to easier with bromide and ooze out at particle surface, silver iodide are easier mutually to be formed near particle surface so contain.Therefore, contain silver bromide mutually and contain under the situation that silver iodide are in diverse location in the particle mutually, contain silver bromide mutually preferably than containing silver iodide more in the inner part position formation mutually.In this case, also can contain the silver bromide phase than on the silver iodide phase position more in the outer part other being set near the containing particle surface.

Show necessary bromide sliver content of effect of the present invention and agi contents such as ISO and strong contrast, along with containing silver bromide mutually or contain silver iodide and increase mutually, might make silver chloride content drop to the following and infringement of the aequum property handled rapidly inner formation of particle.Therefore, for these functions that make the control photographic effect concentrate near the particle surface, preferred adjacent setting contains silver bromide mutually and contain silver iodide mutually.From these viewpoints, from inboard meter, preferably make contain silver bromide particle volume 50%～100% between form on any position, contain silver iodide particle volume 85%～100% between form on any position.And more preferably make contain silver bromide particle volume 70%～95% between form on any position, contain silver iodide particle volume 90%～100% between form on any position.

Be used to make silver emulsion of the present invention to contain the introducing of the bromide or the iodide of silver bromide or silver iodide, can add the solution of bromide salt or iodide salt separately, add the solution of bromide salt or iodide salt when perhaps adding silver salt solution and perchloride salt solusion.Adopt under the latter's the situation, both can add bromide salt or iodide salt solution and perchloride salt solusion respectively, also can add the mixed solution of bromide salt or iodide salt and perchloride salt.Bromide salt or iodide salt can add with the form of the dissolubility salt of the bromide salt of alkaline metal or alkaline-earth metal or iodide salt and so on.That perhaps also can adopt No. 5389508 instructions record of United States Patent (USP) goes out the method that imports behind bromide ion or the iodide ion from the organic molecule cracking.In addition, as the source of other bromides or iodide ion, can also adopt small silver bromide particle or small silver iodide particle.

The interpolation of bromide salt or iodide salt solution both can have been concentrated in the period that particle forms and carried out, and the certain hour of also can being separated by carries out.In perchloride emulsion, import the position of iodide ion, obtained the restriction of the emulsion of ISO and low photographic fog.The importing of iodide ion, more little the closer to the increase of the inner light sensitivity of emulsion particles.Therefore the interpolation of iodide salt solution, preferably by the outside of particle volume 50%, more preferably 70% the outside is preferably undertaken by 85% the outside.And the interpolation of bromide salt solution, preferably in the inboard of particle volume 98%, more preferably stop in 96% inboard.The interpolation of iodide salt solution under situation about stopping than particle surface position slightly in the inner part, can obtain the more emulsion of ISO and lower fog.

The interpolation of bromide salt solution on the other hand preferably by the outside of particle volume 50%, is more preferably carried out from 70% the outside.

The bromide on particle internal depth direction or the CONCENTRATION DISTRIBUTION of iodide ion, can adopt etching/TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, the TRIFTII type TOS-SIMS that for example available Phi Evans company makes measures.About the TOF-SIMS method, specifically be documented in Japanese Surface Science and can write among " surface analysis technique book series secondary ion mass spectrometry " (ball is apt to Co., Ltd., distribution in 1999).If adopt etching/TOF-SIMS method to resolve emulsion particles, even, also can analyze the iodide ion that oozes out towards particle surface then in the inboard interpolation that stops iodide salt solution of particle.Emulsion of the present invention is in etching/TOF-SIMS method is analyzed, and it is very big that iodide ion preferably has concentration at particle surface, and iodide ion concentration decay gradually to the inside; Bromide ion preferably has concentration very big in particle inside.Arrive to a certain degree if bromide sliver content is high, the local concentration of silver bromide can also adopt the X-ray diffraction method to measure.

Silver emulsion of the present invention preferably contains iridium.Preferably have six ligands and be the hexa-coordinate compound of central metal as iridic compound with iridium, so that be accommodated among the silver halide crystal by homogeneous, a kind of preferred condition as the operable iridium of the present invention, preferably have Cl, Br or I as ligand and with the hexa-coordinate compound of Ir as central metal, more preferably whole six ligands are by Cl, Br or I constitutes and with the hexa-coordinate compound of Ir as central metal.In this case, Cl, Br or I can mix existence in the hexa-coordinate compound.Have Cl, Br or I and with the hexa-coordinate compound of Ir as ligand as central metal, preferably be contained in especially contain silver bromide mutually among, can under high illumination, obtain the strong gray shade scale of contrast like this.

Enumerate below that whole six ligands are formed by Cl, Br or I and with the instantiation of Ir, but the iridium among the present invention is not limited to these as the hexa-coordinate compound of central metal.

[IrCl ₆] ^2-

[IrCl ₆] ^3-

[IrBr ₆] ^2-

[IrBr ₆] ^3-

[IrI ₆] ^3-

As the different preferred condition of the iridium that can use in the present invention, preferably have at least ligand beyond a halogen or the cyano group with the hexa-coordinate compound of Ir, preferably with H as central metal ₂O, OH, O, OCN, thiazole or substituted thiazole are ligand and with the hexa-coordinate compound of Ir as central metal, more preferably have at least one H as ligand ₂The thiazole of O, OH, O, OCN, thiazole or replacement, all the other ligands are made up of Cl, Br or I, and with the hexa-coordinate compound of Ir as central metal.In addition, preferably with one or two 5-methylthiazol as ligand, all the other ligands are made of Cl, Br or I, and with the hexa-coordinate compound of Ir as central metal.

Below enumerate as ligand and have a H at least ₂The thiazole of O, OH, O, OCN, thiazole or replacement, all the other ligands are made up of Cl, Br or I, and with the hexa-coordinate compound of Ir as central metal, but the iridium among the present invention is not limited to these.

[IrCl ₅(H ₂O)] ^2-

[IrCl ₄(H ₂O) ₂] ^-

[IrCl ₅(H ₂O) ^-]

[IrCl ₄(H ₂O) ₂] ⁰

[IrCl ₅(OH)] ^3-

[IrCl ₄(OH) ₂] ^2-

[IrCl ₅(OH)] ^2-

[IrCl ₄(OH) ₂] ^2-

[IrCl ₅(O)] ^4-

[IrCl ₄(O) ₂] ^5-

[IrCl ₅(O)] ^3-

[IrCl ₄(O) ₂] ^4-

[IrBr ₅(H ₂O)] ^2-

[IrBr ₄(H ₂O) ₂] ^-

[IrBr ₅(H ₂O)] ^-

[IrBr ₄(H ₂O) ₂] ⁰

[IrBr ₅(OH)] ^3-

[IrBr ₄(OH) ₂] ^2-

[IrBr ₅(OH)] ^2-

[IrBr ₄(OH) ₂] ^2-

[IrBr ₅(O)] ^4-

[IrBr ₄(O) ₂] ^5-

[IrBr ₅(O)] ^3-

[IrBr ₄(O) ₂] ^4-

[IrCl ₅(OCN)] ^3-

[IrBr ₅(OCN)] ^3-

[IrCl ₅(thiazole)] ^2-

[IrCl ₄(thiazole) ₂] ^-

[IrCl ₃(thiazole) ₃] ⁰

[IrBr ₅(thiazole)] ^2-

[IrBr ₄(thiazole) ₂] ^-

[IrBr ₃(thiazole) ₃] ⁰

[IrCl ₅(5-methylthiazol)] ^2-

[IrCl ₄(5-methylthiazol) ₂] ^-

[IrBr ₅(5-methylthiazol)] ^2-

[IrBr ₄(5-methylthiazol) ₂] ^-

[IrCl ₅(5-diuril diazole)] ^2-

[IrCl ₄(5-diuril diazole) ₂] ^-

[IrBr ₅(5-diuril diazole)] ^2-

[IrBr ₄(5-diuril diazole) ₂] ^-

The metal complex of more than enumerating is a negative ion, during with salt forming cation, preferably is dissolved in structure in the water easily as its balance cation.Alkali metal ion, ammonium ion, alkyl phosphate ions such as specifically preferred sodion, potassium ion, rubidium ion, cesium ion and lithium ion.These metal complexes can be dissolved in it outside dewatering in the mixed solvent of the water and the suitable organic solvent (for example alcohols, ethers, glycols, ketone, ester class, amide-type etc.) that can mix with water and use.The preferably per 1 moles of silver interpolation 1 * 10 in particle forms of these iridium complex compounds ^-10Mole～1 * 10 ^-3Mole preferably adds 1 * 10 ^-8Mole～1 * 10 ^-5Mole.

Above-mentioned iridium complex compound among the present invention, can when forming silver halide particle, directly be added in the reaction solution or form silver halide particle, preferably be introduced in the silver halide particle by adding the method that particle forms in the reaction solution to in the halide solution or in the solution in addition.In addition, also preferred with the particulate enforcement physics slaking that in advance iridium complex compound is incorporated in the particle, be introduced in silver halide particle.Also these methods can be used in combination in addition, it is contained in the silver halide particle.

When these coordination compoundes are introduced silver halide particle, can make it in the inner evenly existence of particle, but preferably opening flat 4-208936 number, spy as the spy opens flat 2-125245 number, spy communique such as to open flat 3-188437 number disclosed, make it exist only in particle surface, also preferably make coordination compound exist only in particle inside, and on particle surface, add the layer that does not contain coordination compound.Disclosed as instructionss such as No. the 5252451st, United States Patent (USP) and No. 5256530 in addition, the also preferred particulate that coordination compound is introduced in the particle that utilizes is implemented the method that the physics slaking makes the modification of particle surface phase.These methods can be used in combination in addition, also several coordination compoundes can be introduced in a kind of silver halide particle.Form for the locational halogenide that contains above-mentioned coordination compound that there is no particular restriction, but preferably bromizate silver concentration greatly part contain that whole six ligands are formed by Cl, Br, I and be the hexa-coordinate compound of central metal with Ir.

Among the present invention, also can be on silver halide particle inside and/or surface except that iridium with other metal ion mixings.The preferred transition metal ion of employed metallic ion, wherein preferred iron, ruthenium, osmium, lead, cadmium or zinc.In addition, more preferably make these metallic ions follow ligand to use as hexa-coordinate octahedral build coordination compound.Adopt under the situation of mineral compound as ligand, preferred cyanide ion, halide ion, thiocyano, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion or the sulfo-nitrosyl ion of adopting, preferably make it with above-mentioned iron, ruthenium, osmium, lead, cadmium or zinc in arbitrary metal-complexing use, and preferably in a coordination compound molecule, use multiple ligand.

In addition, also preferably use organic compound as ligand, preferred organic compound can be enumerated the heterogeneous ring compound of backbone c atoms number at the chain compound below 5 and/or five Yuans or six membered ring.Preferred organic compound is the compound that uses as the coordination atom of metal with nitrogen-atoms, phosphorus atoms, oxygen atom or sulphur atom in the molecule, particularly preferably be furans, thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazoles, pyrazoles, triazole, furazan, pyrans, pyridine, pyridazine, pyrimidine, pyrazine, but also be that skeleton has imported substituent compound therein preferably with these compounds.

As the combination of metallic ion and ligand, the combination of preferred ferric ion and ruthenium ion and cyanide ion.Preferably among the present invention also use these compounds with iridium.In these compounds, cyanide ion preferably surpasses half in as the coordination number of the iron of central metal or ruthenium, and preferably by thiocyano, ammonia, water, nitrosyl ion, dimethyl sulfoxide (DMSO), pyridine, pyrazine or 4,4 '-Lian pyrazine occupies at remaining coordination position.Six coordination positions that are preferably in central metal are all occupied by cyanide ion, form six cyano group iron complex compounds or six cyano group ruthenium complexes.These are with the coordination compound of cyanide ion as ligand, and preferably per 1 moles of silver adds 1 * 10 in particle forms ^-8Mole～1 * 10 ^-2Mole preferably adds 1 * 10 ^-6Mole～5 * 10 ^-4Mole.

With ruthenium and osmium under the situation as central metal, also preferably as the shared nitrosyl ion of ligand, sulfo-nitrosyl ion or hydrone and chloride ion.More preferably form pentachloro-nitrosyl coordination compound, pentachloro-sulfo-nitrosyl coordination compound or pentachloro-aquo-complex, also be preferably formed the chlordene coordination compound.The preferably per 1 moles of silver interpolation 1 * 10 in particle forms of these coordination compoundes ^-10Mole～1 * 10 ^-6Mole preferably adds 1 * 10 ^-9Mole～1 * 10 ^-6Mole.

Employed silver emulsion among the present invention is preferably and has implemented the emulsion that golden sensitizing well known in the art is handled.This is because handle by golden sensitizing and can make the emulsion ISOization, when utilizing scan exposure such as laser the variation of photographic property is reduced.For implementing golden sensitizing, gold (I) compound that can utilize various inorganic gold compounds and have gold (I) coordination compound of inorganic ligand and have organic ligand.As inorganic gold compound, for example can use gold chloride or its salt, as the gold with inorganic ligand (I) coordination compound, for example can use compounds such as two thiosulfuric acid gold compounds such as two thiocyanic acid gold compounds such as two thiocyanic acid gold (I) potassium and two gold aurothiosulfates (I) trisodium.

As the gold with organic ligand (organic compound) (I) compound, two gold (I) mesoionic compound heterocyclic that can use the spy to open to put down in writing in the flat 4-267249 communique, for example two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborate; Organic sulfydryl gold (I) coordination compound of Te Kaiping 11-218870 communique record, for example two (1-[3-(2-sulfonate benzamide) phenyl]-5-mercapto-tetrazole sylvite) oleate (I) pentahydrate; The coordination of Te Kaiping 4-268550 communique record has the anionic gold of nitrogen compound (I) compound, for example two (1-methyl hydantoin hydrochlorate) gold (I) sodium salt tetrahydrate.Gold (I) compound with these organic ligands, except that can use in advance synthetic separate, can also generate by organic ligand is mixed with gold compound (for example gold chloride and salt thereof), and directly be added in the emulsion without separation.In addition, also can respectively organic ligand and gold compound (for example gold chloride and salt thereof) be added in the emulsion, in emulsion, form gold (I) compound with organic ligand.

In addition, can also use gold (I) thiol salinization compound, the spy of the record of No. the 3503749th, United States Patent (USP) open flat 8-69074 number, spy open No. 5620841, gold compound, United States Patent (USP) that flat 8-69075 number, spy record such as open flat 9-269554 number, with No. 5912112, with No. 5620841, with No. 5939245, with the compound of record such as No. 5912111.

The addition of these compounds can according to circumstances become, but every mole of silver halide preferably adds 5 * 10 ^-7Mole～5 * 10 ^-3Mole, more preferably 5 * 10 ^-6Mole～5 * 10 ^-4Mole.

Can use the colloidal aurosulfo in addition, its manufacture method is documented in " exploration discovery " (Reseach Di sclosure), the 79th volume, 60～66 pages, nineteen ninety-five publishes, and " Compt.Rend.Hebt.Seances Acad.Sci.Sect. " B, the 263rd volume, 1328 pages, among publication in 1966 waits.Though in above-mentioned " exploration discovery ", record the method that when making the colloidal aurosulfo, adopts thiocyanate ion, also can use sulfide compounds such as methionine and thiodiethanol to replace.

Can use the particle of various sizes as the colloidal aurosulfo, but preferred mean grain size is in the following particle of 50 nanometers, more preferably below 10 nanometers, mean grain size is preferably below 3 nanometers for mean grain size.This particle diameter can be measured with the TEM photographic process.In addition, the composition of colloidal aurosulfo both can be Au ₂S ₁, also can be Au ₂S ₁～Au ₂S ₂Deng composition, preferably has the excessive composition of sulphur, more preferably Au with excess of sulfur ₂S _1.1～Au ₂S _1.8

As the composition analysis of this colloidal aurosulfo, for example can after taking out the aurosulfo particle, utilize analytical approachs such as ICP and iodimetric titration to obtain gold content and sulfur content respectively.In a single day the gold ion, the sulphion (comprising sulfuretted hydrogen and salt thereof) that are dissolved in the liquid phase are present in the colloidal aurosulfo and will the composition analysis of colloidal aurosulfo particle be exerted an influence, so analyze after can utilizing ultrafiltration with the aurosulfo separate particles again.The addition of aurosulfo colloid according to circumstances can change on a large scale, but with respect to every mole of silver halide, gold atom is in 5 * 10 ^-7Mole～5 * 10 ^-3In the molar range, preferred 5 * 10 ^-6Mole～5 * 10 ^-4Mole.

Chalcogen sensitizing also can be carried out in a part with golden sensitizing, can use and can emit AuCh ^-Molecule.Au represents Au (I) in the formula, and Ch represents sulphur atom, selenium atom, tellurium atom.Can emit AuCh ^-Molecule, can enumerate the gold compound of for example representing by AuCh-L.L represents to combine the atomic group that constitutes molecule with AuCh in the formula.For Au, with the further more than one ligand of coordination of Ch-L.And have following feature by the gold compound that AuCh-L represents, promptly under the situation of silver ion coexistence in case in solvent, make it reaction, be to form AgAuS, AgAuSe and AgAuTe respectively easily under the situation of S, Se and Te at Ch.As these compounds, can enumerate L is acylated compound, can enumerate down the compound of note formula (AuCh1), formula (AuCh2) and formula (AuCh3) expression in addition.

Formula (AuCh1)

R ₁-X-M-ChAu

In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom or tellurium atom, and M represents to replace or unsubstituted methylene, and X represents oxygen atom, sulphur atom, selenium atom or NR ₂, R ₁Expression can combine the atomic group (for example organic groups such as alkyl, aryl, heterocyclic group) that constitutes molecule, R with X ₂Expression hydrogen atom or substituting group (for example organic groups such as alkyl, aryl, heterocyclic group).R ₁Also can interosculate with M and to form ring.

In the compound by formula (AuCh1) expression, Ch is preferably sulphur atom or selenium atom, and X is preferably oxygen atom or sulphur atom, R ₁Be preferably alkyl or aryl.Examples for compounds has more specifically, Au (I) salt of Au (I) salt of the Au of sulfo-sugar (I) salt (aurothioglucose such as α aurothioglucose, gold are crossed acetyl thio glucose, golden sulfo-mannose, golden sulfo-galactose, golden sulfo-arabinose etc.), seleno sugar (gold is crossed acetyl seleno glucose, gold is crossed acetyl seleno mannose etc.), telluro sugar etc.Sulfo-sugar described here, seleno sugar and telluro sugar, the compound that different head (anomer) locational hydroxyl of expression sugar is replaced by SH base, SeH base and TeH base respectively.

Formula (AuCh2)

W ₁(W ₂)C＝C(R ₃)ChAu

In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom or tellurium atom, R ₃And W ₂Independent separately expression hydrogen atom or substituting group (for example organic groups such as halogen atom or alkyl, aryl, heterocyclic group), W ₁The special substituent constant σ of expression Hamann _pThe value on the occasion of the electrophilic group.R ₃With W ₁, R ₃With W ₂And W ₁With W ₂Also can interosculate and form ring.

In compound by formula (AuCh2) expression, preferred sulphur atom of Ch or selenium atom, R ₃Preferred hydrogen atom or alkyl.W ₁With W ₂The special substituent constant σ of independent separately preferred Hamann _pValue is at the electrophilic group more than 0.2.Examples for compounds has more specifically, (NC) ₂C=CHSAu, (CH ₃OCO) ₂C=CHSAu, CH ₃CO (CH ₃OCO) C=CHSAu etc.

Formula (AuCh3)

W ₃-E-ChAu

In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom or tellurium atom, and E represents to replace or unsubstituted vinyl W ₃The special substituent constant σ of expression Hamann _pValue is positive electrophilic group.

In the compound of formula (AuCh3) expression, preferred sulphur atom of Ch or selenium atom, E preferably have the special substituent constant σ of Hamann _pValue on the occasion of the vinyl of electrophilic group.W ₃The special substituent constant σ of preferred Hamann _pValue is at the electrophilic group more than 0.2.

The addition of these compounds according to circumstances can change on a large scale, but with respect to every mole of silver halide, its addition should be in 5 * 10 ^-7Mole～5 * 10 ^-3In the molar range, preferred 3 * 10 ^-6Mole～3 * 10 ^-4Mole.

Among the present invention, above-mentioned golden sensitizing also can with other process for increasing sensitivity, for example sulphur sensitizing, selenium sensitizing, tellurium sensitizing, reduction sensitization or adopt the sensitizing etc. of noble metal beyond the gold compound to be used in combination.Preferred especially and sulphur sensitizing, selenium process for increasing sensitivity make up.

Produce photographic fog in order to prevent in the manufacturing process, preservation process at photosensitive material or to take a picture in handling, perhaps, can in silver emulsion of the present invention, add all cpds or their precursor in order to make the photographic property stabilization.The concrete example of these compounds, preferred spy opens the material of the 39th page～72 pages of records in the clear 62-215272 communique.Also can preferably adopt the 5-virtue amino-1,2,3 of EP0447647 number record, 4-thiatriazole compound (having an electrophilic group in this aromatic yl residue at least).

In addition, in the present invention, in order to improve the keeping quality of silver emulsion, the special hydroxamic acid derivant of putting down in writing in the flat 11-109576 communique of opening of also preferred use, having by the cyclic ketones class of two keys of amino or hydroxyl replacement with the carbonyl adjacent both ends of putting down in writing in the Te Kaiping 11-327094 communique (particularly used the material of general formula (S1) expression, the 0036th～0071 section can be introduced in this instructions), catechol that the sulfo group put down in writing in the Te Kaiping 11-143011 communique replaces and hydroquinone type (for example 4,5-dihydroxy-1, the 3-benzenedisulfonic acid, 2,5-dihydroxy-1, the 4-benzenedisulfonic acid, 3, the 4-dihydroxy benzenes sulfonic acid, 2, the 3-dihydroxy benzenes sulfonic acid, 2, the 5-dihydroxy benzenes sulfonic acid, 3,4,5-trihydroxy benzene sulfonic acid and salt thereof etc.), the azanol class by general formula (A) expression of No. 5556741 instructions record of United States Patent (USP) (record of the 56th row～the 11 hurdle, No. 5556741 instructions of United States Patent (USP) the 4th hurdle the 22nd row also is applicable to the present invention, its part as this instructions can be introduced), the water-soluble reductive agent of representing by general formula (I)～(III) in the Te Kaiping 11-102045 communique.

Silver halide colour photographic sensitive material of the present invention (following brief note is sometimes made " photosensitive material "), be on support, at least respectively to have one deck to contain silver halide emulsion layer that xanthein is formed into toner, contain pinkish red pigment and be formed into the silver halide emulsion layer of toner and contain the silver halide colour photographic sensitive material that the cyan pigment is formed into the silver halide emulsion layer of toner, it is characterized in that having at least in the described silver halide emulsion layer one deck to contain silver emulsion of the present invention.Among the present invention, describedly contain silver halide emulsion layer that xanthein is formed into toner, describedly contain pinkish red pigment and be formed into the silver halide emulsion layer of toner and describedly contain the effect that the silver halide emulsion layer that the cyan pigment is formed into toner can be brought into play the displaing yellow layer respectively, show magenta layer and apparent cyan layers.Contained separately silver emulsion in described displaing yellow layer, apparent magenta layer and the apparent cyan layers, preferably the light (for example blue region, green area and red area) for those mutual different wavelength regions has photonasty.

Photosensitive material of the present invention except that described displaing yellow layer, apparent magenta layer and apparent cyan layers, can also have hydrophilic colloid layer described later, anti-halo layer, middle layer and dyed layer as required.

Photosensitive material of the present invention can use over known photograph with material and adjuvant.

For example, can use transmission-type support and reflection-type support as the photograph support.And as the transmission-type support, the preferred clarity films such as cellulose nitrate film or pet film that use, and then preferably by 2, the polyester that 6-naphthalene dicarboxylic acids (NDCA) and the synthetic polyester that forms of ethylene glycol (EG) or synthesized by NDCA and terephthalic acid (TPA) and ethylene glycol forms etc. is provided with the film of information recording layer such as magnetosphere.As the reflection-type support, preferred especially laminated multilayer polyethylene layer and polyester layer forms and these water-resistant resin layers (laminate layers) in have at least one deck to contain the reflection-type support of Chinese white such as titanium dioxide.

As preferred reflection support, can enumerate the structure that on the paper substrate matrix that silver halide emulsion layer one side is set, has with the polyolefin layer of small emptying aperture among the present invention.Polyolefin layer also can be made of multilayer, does not have small emptying aperture in more preferably adjacent with the gelatin layer of silver halide emulsion layer one side in this case polyolefin (for example polypropylene, the tygon) layer and the support that is made of the polyolefin with small emptying aperture (for example polypropylene, tygon) near paper substrate matrix one side.These multilayers between paper substrate matrix and photograph formation layer or the density of one deck polyolefin layer, preferred 0.40～1.0 grams per milliliter, more preferably 0.50～0.70 grams per milliliter.And these multilayers between paper substrate matrix and photograph formation layer or the thickness of one deck polyolefin layer, preferred 10～100 microns, more preferably 15～70 microns.The thickness ratio of polyolefin layer and paper substrate matrix in addition, preferred 0.05～0.2, more preferably 0.1～0.15.

In addition, from improving the viewpoint of reflection-type support rigidity, also preferably polyolefin layer is set constituting on the opposite side (back side) of layer with the photo of above-mentioned paper substrate matrix, in this case, the polyolefin layer preferred surface at the back side is carried out tygon or the polypropylene that delustring is handled, more preferably polypropylene.Preferred 5～50 microns of the polyolefin layer thickness at the back side, more preferably 10～30 microns, and preferred 0.7～1.1 grams per milliliter of density.In the reflection-type support of the present invention, the relevant preferred condition that is arranged on the polyolefin layer on the paper substrate matrix, can enumerate the spy open flat 10-333277 communique, with the 10-333278 communique, with the 11-52513 communique, with the example of putting down in writing in 11-65024 equal sign communique, EP0880065 instructions and the EP0880066 instructions.

In addition, preferably contain fluorescer in the above-mentioned water-resistant resin layer.And can form the hydrophilic colloid layer that disperses to contain described fluorescer in addition.As described fluorescer, can use benzoxazole system, coumarin series, pyrazoline is fluorescer, and preferred fluorescer is that benzoxazolyl naphthalene system and benzoxazolyl stilbene are fluorescer.There is no particular restriction about its consumption, but preferred 1～100 milligram/square metre.Mixing ratio when mixing in water-resistant resin is preferably 0.0005～3 weight % with respect to resin, more preferably 0.001～0.5 weight %.

As the reflection-type support, also can be the structure that coating setting is contained the hydrophilic colloid layer of Chinese white on transmission-type support or above-mentioned reflection-type support.In addition, the reflection-type support can also be the support with specular reflective or the 2nd kind of scattered reflection matallic surface layer.

As the support that is used for photosensitive material of the present invention, can also use display to be provided with the support that contains the Chinese white layer with white polyester class support or support with silver halide emulsion layer one side.In order further to improve sharpness, preferably be coated with anti-halo layer at the coating silver halide emulsion layer side or the back side of support.Especially preferably the transmission density with support is set in 0.35～0.8 scope, so that can both view and admire display with reflection ray or transmitted light.

In the photosensitive material of the present invention, for improving image definition etc., can in the hydrophilic colloid floor, add the 27th～76 page of dyestuff above-mentioned year, that pass through to handle to decolour of European patent EP 0337490A2 instructions (wherein preferred oxonol class dyestuff), the optical reflection concentration of photosensitive material under 680nm can be reached more than 0.70, perhaps preferably make the surface of containing 12 weight % above (more preferably containing more than the 14 weight %) in the water-resistant resin layer of support wait the titanium dioxide of processing through binary～quaternary alcohols (for example trimethylolethane).

In the photosensitive material of the present invention, for preventing irradiation (irradiation) and halation, perhaps for the security that improves safety lamp (safelight) etc., preferably in the hydrophilic colloid floor, add the treated dyestuff (wherein preferred oxonol dyestuff, cyanine dyes) that can decolouring of above-mentioned year of the 27th～76 page in European patent EP 0337490A2 instructions.In addition, the also preferred in the present invention dyestuff of putting down in writing in No. 0819977 instructions of European patent EP that adds.In these water-soluble dyes, use amount is also arranged in case increase the dyestuff that tends to worsen look separation and safety lamp security.As can not worsening the dyestuff that use under the situation that look separates, preferred spy opens flat 5-127324 communique, with the 5-127325 communique, with the water-soluble dye of putting down in writing in the 5-216185 communique.

Can use the treated dyed layer that can decolour to replace water-soluble dye among the present invention or with it and use.The operable treated dyed layer that can decolour both can directly contact with emulsion, also can be configured to prevent that across processing such as containing gelatin and quinhydrones the middle layer of blending agent is in contact with it.This dyed layer preferably is arranged on lower floor's (support one side) of the emulsion layer that can demonstrate the primary colors identical with being colored color.Each corresponding with each primary colors respectively dyed layer both can be set one by one, and also can selecting wherein arbitrarily, a part is provided with.But also the dyed layer that is coloured to corresponding to most primary colors zone can be set.The optical reflection concentration of dyed layer, (in common printing exposure is the visible region of 400～700nm in the employed wavelength region may of exposure, be the wavelength of employed scan exposure light source under the scan exposure situation) in, optical concentration value under the highest wavelength of optical concentration preferably is in more than 0.2 with below 3.0, more preferably more than 0.5 and below 2.5, especially preferably be in more than 0.8 with below 2.0.

Form dyed layer and can adopt over known method.Open the dyestuff of the 3rd page of upper right hurdle～8 of flat 2-282244 communique page going up record and specially open the dyestuff of putting down in writing in page hurdle, lower-left, the 3rd page of upper right hurdle～11 of flat 3-7931 communique as the spy, under solia particle dispersion state, be contained in method in the hydrophilic colloid floor, with the method for anionic property pigment mordant dyeing on cationic polymer, make pigment be adsorbed on the particulate such as silver halide method etc. to be fixed on the method in the floor and to use the special collargol of opening flat 1-239544 communique record.As method with solid-state dispersion pigment micropowder, for example can adopt and open the method for putting down in writing on the 4-13 page or leaf of flat 2-308244 communique the spy, that is, contain at least in water insoluble in fact below the pH6 and the method for water-soluble in fact micropowder dyestuff more than pH8 at least.In addition, as with the method for anionic property pigment mordant dyeing on cationic polymer, be documented in the spy and open on the 18th～26 page of flat 2-84637 communique.About preparation method, be documented in No. 2688601 instructions of United States Patent (USP) and with in No. 3459563 instructionss as the collargol of light absorber.In these methods, preferred method that contains the micropowder dyestuff and the method for using collargol etc. used.

In the silver halide photographic sensitive material of the present invention, can use colour negative, colour positive, colour reversal film, colour reversal sensitized paper and color sensitive paper etc., but wherein preferred color sensitive paper.Color sensitive paper preferably at least respectively has one deck displaing yellow silver halide emulsion layer respectively, shows magenta silver halide emulsion layer and apparent cyan silver halide emulsion layer, and generally speaking these silver halide emulsion layers are according to from the nearer order of support being displaing yellow silver halide emulsion layer, apparent magenta silver halide emulsion layer and apparent cyan silver halide emulsion layer successively.

Yet also can adopt and above different layer structures.

Can on any position of support, dispose the silver halide emulsion layer that contains yellow colour former, but in this contains the layer of yellow colour former, contain under the situation of the dull and stereotyped particle of silver halide, preferably it is coated with and is located at than the silver halide emulsion layer that contains magenta colour coupler or contains one deck at least in the silver halide emulsion layer of cyan coupler on the position of support.In addition, the viewpoint that develops the color and develop, promote the desilverization and reduce the residual look that causes by sensitizing coloring matter from promotion, the silver halide layer that contains yellow colour former preferably is coated with and is located at than other silver halide emulsion layers on the position of support.In addition, from reducing the viewpoint that Blix fades, the silver halide emulsion layer that contains cyan coupler preferably is located at the central authorities of other silver halide emulsion layers, and from reducing the viewpoint of photofading, the silver halide emulsion layer that contains cyan coupler preferably is in orlop.Also have, color layers of all kinds such as yellow, magenta and cyan, also can by two-layer or three layers form.For example, according to the spy open flat 4-75055 communique, with the 9-114035 communique, with the record of 10-246940 communique, No. 5576159 instructions of United States Patent (USP) etc., the color former layer that also preferably will not contain silver emulsion is arranged to adjacent with silver halide emulsion layer, as color layer.

Use adjuvant as constituting layer (layer configuration etc.) and be used to handle the disposal route of this photosensitive material and handle applicable to silver emulsion of the present invention and other material (adjuvant etc.) and photo, preferred spy opens clear 62-215272 communique, the spy opens the material of putting down in writing in flat 2-33144 communique, the European patent EP 0355660A2 instructions, the material of putting down in writing in the preferred especially European patent EP 0355660A2 instructions.In addition, also preferred spy opens flat 5-34889 communique, discloses the silver halide colour photographic sensitive material and the disposal route thereof of record such as 0520457A2 instructions with the 4-359249 communique, with the 4-313753 communique, with the 4-270344 communique, with the 5-66527 communique, with the 4-34548 communique, with the 4-145433 communique, with the 2-854 communique, with the 1-158431 communique, with the 2-90145 communique, with the 3-194539 communique, with 2-93641 communique and European patent.

Especially about following item, be above-mentioned reflection-type support and silver emulsion among relevant the present invention, and can be entrained in dissimilar metal ionic species in the silver halide particle, the preserving stabilizer or the photographic fog of silver emulsion prevent agent, chemical sensitization method (sensitizer), optical sensibilization method (optical sensitizer), cyan, magenta and yellow colour former and emulsification process for dispersing thereof, colour retention improver (anti fouling agent and anti-decolourant), dyestuff (dyed layer), the layer structure of gelatin kind and photosensitive material and the pH of photosensitive material film etc., the content of being put down in writing in note table 1 patent under preferred especially the employing.

[table 1]

Key element	Te Kaiping 7-104448 number	Te Kaiping 7-77775 number	Te Kaiping 7-301895 number
Key element	Te Kaiping 7-104448 number	Te Kaiping 7-77775 number	Te Kaiping 7-301895 number	The reflection-type support	12 row～12 hurdles, the 7th hurdle, 19 row	43 row～44 hurdles, the 35th hurdle, 1 row	40 row～9 hurdles, the 5th hurdle, 26 row
Silver emulsion	29 row～74 hurdles, the 72nd hurdle, 18 row	36 row～46 hurdles, the 44th hurdle, 29 row	48 row～80 hurdles, the 77th hurdle, 28 row	The reflection-type support	12 row～12 hurdles, the 7th hurdle, 19 row	43 row～44 hurdles, the 35th hurdle, 1 row	40 row～9 hurdles, the 5th hurdle, 26 row
Silver emulsion	29 row～74 hurdles, the 72nd hurdle, 18 row	36 row～46 hurdles, the 44th hurdle, 29 row	48 row～80 hurdles, the 77th hurdle, 28 row	The dissimilar metal ionic species	The 74th hurdle 19 row～44 row	30 row～47 hurdles, the 46th hurdle, 5 row	29 row～81 hurdles, the 80th hurdle, 6 row
Preserving stabilizer or antifoggant	The 75th hurdle 9 row～18 row	The 47th hurdle 20 row～29 row	11 row～31 hurdles, the 18th hurdle, 37 row (particularly sulfhydryl heterocycle compound)	The dissimilar metal ionic species	The 74th hurdle 19 row～44 row	30 row～47 hurdles, the 46th hurdle, 5 row	29 row～81 hurdles, the 80th hurdle, 6 row
Preserving stabilizer or antifoggant	The 75th hurdle 9 row～18 row	The 47th hurdle 20 row～29 row		Chemical sensitization (chemical sensitizer)	45 row～75 hurdles, the 74th hurdle, 6 row	The 47th hurdle 7 row～17 row	The 81st hurdle 9 row～17 row
Optical sensibilization (optical sensitizer)	19 row～76 hurdles, the 75th hurdle, 45 row	30 row～49 hurdles, the 47th hurdle, 6 row	21 row～82 hurdles, the 81st hurdle, 48 row	Chemical sensitization (chemical sensitizer)	45 row～75 hurdles, the 74th hurdle, 6 row	The 47th hurdle 7 row～17 row	The 81st hurdle 9 row～17 row
Optical sensibilization (optical sensitizer)	19 row～76 hurdles, the 75th hurdle, 45 row	30 row～49 hurdles, the 47th hurdle, 6 row	21 row～82 hurdles, the 81st hurdle, 48 row	Cyan coupler	20 row～39 hurdles, the 12nd hurdle, 49 row	50 row～63 hurdles, the 62nd hurdle, 16 row	49 row～89 hurdles, the 88th hurdle, 16 row
Yellow colour former	40 row～88 hurdles, the 87th hurdle, 3 row	The 63rd hurdle 17 row～30 row	The 89th hurdle 17 row～30 row	Cyan coupler	20 row～39 hurdles, the 12nd hurdle, 49 row	50 row～63 hurdles, the 62nd hurdle, 16 row	49 row～89 hurdles, the 88th hurdle, 16 row
Yellow colour former	40 row～88 hurdles, the 87th hurdle, 3 row	The 63rd hurdle 17 row～30 row	The 89th hurdle 17 row～30 row	Red colour coupler	The 88th hurdle 4 row～18 row	3 row～64 hurdles, the 63rd hurdle, 11 row	The 31st hurdle 34 row～77 hurdles 44 row and 88 hurdles, 32 row～46 row
The emulsification dispersion method of colour coupler	3 row～72 hurdles, the 71st hurdle, 11 row	The 61st hurdle 36 row～49 row	The 87th hurdle 35 row～48 row	Red colour coupler	The 88th hurdle 4 row～18 row	3 row～64 hurdles, the 63rd hurdle, 11 row
The emulsification dispersion method of colour coupler	3 row～72 hurdles, the 71st hurdle, 11 row	The 61st hurdle 36 row～49 row	The 87th hurdle 35 row～48 row	Colour retention improver (anti fouling agent)	50 row～70 hurdles, the 39th hurdle, 9 row	50 row～62 hurdles, the 61st hurdle, 49 row	49 row～88 hurdles, the 87th hurdle, 48 row
Anti-decolourant	10 row～71 hurdles, the 70th hurdle, 2 row			Colour retention improver (anti fouling agent)	50 row～70 hurdles, the 39th hurdle, 9 row	50 row～62 hurdles, the 61st hurdle, 49 row	49 row～88 hurdles, the 87th hurdle, 48 row
Anti-decolourant	10 row～71 hurdles, the 70th hurdle, 2 row			Dyestuff (colorant)	42 row～78 hurdles, the 77th hurdle, 41 row	The 7th hurdle 14 row～19 hurdles 42 row and 3 row～51 hurdles, 50 hurdles, 14 row	27 row～18 hurdles, the 9th hurdle, 10 row
The gelatin kind	The 78th hurdle 42 row～48 row	The 51st hurdle 15 row～20 row	The 83rd hurdle 13 row～19 row	Dyestuff (colorant)	42 row～78 hurdles, the 77th hurdle, 41 row		27 row～18 hurdles, the 9th hurdle, 10 row
The gelatin kind	The 78th hurdle 42 row～48 row	The 51st hurdle 15 row～20 row	The 83rd hurdle 13 row～19 row	The layer structure of photosensitive material	The 39th hurdle 11 row～26 row	The 44th hurdle 2 row～35 row	38 row～32 hurdles, the 31st hurdle, 33 row
The pH of photosensitive material film	The 72nd hurdle 12 row～28 row			The layer structure of photosensitive material	The 39th hurdle 11 row～26 row	The 44th hurdle 2 row～35 row	38 row～32 hurdles, the 31st hurdle, 33 row

Scan exposure	6 row～77 hurdles, the 76th hurdle, 41 row	7 row～50 hurdles, the 49th hurdle, 2 row	49 row～83 hurdles, the 82nd hurdle, 12 row
Scan exposure	6 row～77 hurdles, the 76th hurdle, 41 row	7 row～50 hurdles, the 49th hurdle, 2 row	49 row～83 hurdles, the 82nd hurdle, 12 row	Antioxidant in the developer solution	19 row～89 hurdles, the 88th hurdle, 22 row

As can be used for cyan of the present invention, magenta and yellow colour former, the colour coupler that in addition also can use the spy and open that～121 pages of upper left hurdles of the 4th row, the upper right hurdle of the 91st page in clear 62-215272 communique the 6th row, spies open that the 4th page of 15 row～27 row of No. 144 communiques of flat 2-33 the 3rd page of upper right hurdle～18 pages of upper left hurdle footlines of the 14th row and the 30th page of upper right hurdle hurdle, the 6th～35 pages of bottom rights of row the 11st row and EP0355660A2 instructions ,～28 pages of footlines of the 5th page of 30 row, 45 page of 29 row～31 are gone, put down in writing in～63 page of 50 row of 47 page of 23 row.

In addition, also preferably among the present invention add by the general formula (II) of record in WO98/33760 number and (III) and specially open the compound that the general formula (D) put down in writing in the flat 10-221825 communique is represented.

Can be used in the colour coupler (simply being called " cyan coupler " sometimes) that the formation cyan pigment among the present invention is used, the preferred pyrrolo-triazole of using is tied to form toner, especially preferably uses the spy to open in the flat 5-313324 communique by illustrative colour coupler in the colour coupler of being represented by general formula (I) in general formula (I) or colour coupler of (II) representing and the flat 6-347960 communique of Te Kai and these patents.In addition, also preferred phenol is, the cyan coupler of naphthols system, and for example preferred spy opens the cyan coupler of being represented by general formula (ADF) in the flat 10-333297 communique.As the cyan coupler beyond above-mentioned; the pyrrolo-pyrrole type cyan coupler of putting down in writing in also preferred No. 0488248 instructions of European patent EP and the EP0491197A1 instructions; in No. the 5888716th, the United States Patent (USP) 2 of record; 5-diamides base phenol colour coupler; No. 4873183 instructions of United States Patent (USP); has the electrophilic group with what put down in writing in No. 4916051 instructions at 6; the pyrazolo pyrrole type cyan coupler of hydrogen bond group, preferred especially spy opens flat 8-171185 communique; with the 8-311360 communique and with put down in writing in the 8-339060 communique at 6 pyrazolo pyrrole type cyan couplers with carbamyl.

Also have, except the spy opens the diphenyl-imidazole of putting down in writing in the flat 2-33144 communique is the cyan coupler, and can also use the 3-pyridone of putting down in writing in the European patent EP 0333185A2 instructions is that cyan coupler (is given the dechlorination group on preferred especially wherein 4 equivalent colour couplers as the cited colour coupler of instantiation (42) and carried out 2 when the structure that quantizes, and colour coupler (6) and (9)), the ring-type active methylene group that the spy opens clear 64-32260 communique record is that cyan coupler is (preferred especially wherein as the cited colour coupler example 3 of instantiation, 8 and 34), the pyrrolo-imidazole type cyan coupler of putting down in writing in the pyrrolo-pyrazoles type cyan coupler of putting down in writing in the European patent EP 0456226A1 instructions and No. 0484909 instructions of European patent EP.

In these cyan couplers, preferred especially spy opens the pyrrolo-azole series cyan coupler by general formula (I) expression of flat 11-282138 communique record, the record that this patent is the 0012nd～0059 section comprises cyan coupler (1)～(4), can be directly used among the present invention, its part as this instructions can be incorporated into this paper.

The colour coupler of using as the formation magenta pigment that can use in the present invention (simply being called " magenta colour coupler " sometimes), though can use the 5-pyrazolone of known patent documentation record in the above-mentioned table is magenta colour coupler and pyrazolo azole series magenta colour coupler, but from the color harmony picture steadiness, viewpoints such as colour rendering consider that preferred use spy opens secondary alkyl or the tertiary alkyl put down in writing in the clear 61-65245 communique and directly is connected in 2 of Pyrazolotriazole ring, Pyrazolotriazole colour coupler on 3 or 6, the molecule that the spy opens the record of clear 61-65246 communique contains the pyrazolo azole series colour coupler of sulfoamido, the spy opens the pyrazolo azole series colour coupler with stable (ballast) group of alkoxyl phenyl sulfoamido of clear 61-147254 communique record, and 6 pyrazolo pyrrole colour couplers putting down in writing in European patent 226849A instructions and the same 294785A instructions with alkoxy or aryloxy group.As the magenta colour coupler, preferred especially spy opens the pyrazolo pyrrole colour coupler of putting down in writing in the flat 8-122984 communique by general formula (M-I) expression, the 0009th～0026 section of this patent can be directly used among the application, its part as this instructions can be incorporated herein.In addition, 3 and 6 the pyrazolo pyrrole colour couplers of putting down in writing in No. 854384 instructions of also preferred European patent, same No. 884640 instructions that sterically hindered base is all arranged.

In addition; form the colour coupler (following be called sometimes " yellow colour former ") of xanthein; the compound of in above-mentioned table, putting down in writing, the acyl group acetamide type yellow colour former of 3～5 ring structures is arranged on the acyl group of preferred especially European patent EP 0447969A1 instructions record; the malonyl with ring texture of European patent EP 0482552A1 instructions record is for diphenylamine type yellow colour former; Europe publication 953870A1 instructions; with the 953871A1 instructions; with the 953872A1 instructions; with the 953873A1 instructions; with the 953874A1 instructions; with the pyrroles-2-of record such as 953875A1 instructions or-3-base or indoles-2-or-the basic carbonyl acetanil of 3-is tied to form toner; the acyl group acetamide type yellow colour former with diox structure of No. 5118599 instructions record of United States Patent (USP).Wherein especially preferably acyl group is the acyl group acetamide type yellow colour former of 1-alkyl trimethylene-1-carbonyl, is made of the malonyl of dihydroindole ring the side in the anilid for diphenylamine type yellow colour former.These colour couplers can use separately also and can and use.

Preferably in the presence of the high boiling organic solvent of in above-mentioned table, putting down in writing (or not), the colour coupler that uses among the present invention is contained in (loadable) latex polymer (for example No. 4203716 instructions of United States Patent (USP)) that is immersed in loadable, perhaps with water-insoluble but the organic solvent soluble polymer dissolve and its emulsification be dispersed in the hydrophilic colloid aqueous solution.The water-insoluble that can preferably use but organic solvent soluble polymer can be enumerated in No. 4857449 instructions of United States Patent (USP) the homopolymer or the multipolymer of the 12nd page～30 pages of records in the 7th～15 hurdle and the open WO88/00723 instructions of international monopoly.More preferably methacrylate ester or acrylamide polymer from colour stability angle, especially preferably use acrylamide polymer.

Can use known anti-blending agent among the present invention, the compound of putting down in writing in the patent of enumerating below wherein preferred.

For example can use the spy to open the high molecular weight redox compound of flat 5-333501 communique record, 1-phenyl-3-the pyrazolidone or the hydrazine based compound of record such as WO98/33760 instructions, No. 4923787 instructions of United States Patent (USP), the spy opens flat 5-249637 communique, the spy opens the white colour coupler of records such as flat 10-282615 communique and Deutsche Bundespatent 19629142A1 instructions.In addition, improving developer solution pH value, and under the situation of developing rapidly, also especially preferably use the redox compound of records such as Deutsche Bundespatent 19618786A1 instructions, European patent 839623A1 instructions, European patent 842975A1 instructions, Deutsche Bundespatent 19806846A1 instructions and French Patent (FRP) 2760460A1 instructions.

The preferred high compound with triazine skeleton of molar extinction coefficient that uses for example can use the compound of putting down in writing in the following patent as ultraviolet light absorber among the present invention.Preferably these materials are added on photographic layer or/and in the non-photographic layer.For example can use the spy to open clear 46-3335 communique, with the 55-152776 communique, Te Kaiping 5-197074 communique, with the 5-232630 communique, with the 5-307232 communique, with the 6-211813 communique, with the 8-53427 communique, with the 8-234364 communique, with the 8-239368 communique, with the 9-31067 communique, with the 10-115898 communique, with the 10-147577 communique, with the 10-182621 communique, Deutsche Bundespatent 19739797A1 instructions, the compound of record in European patent 711804A instructions and the flat 8-501291 communique of Te Biao etc.

Bond or protecting colloid as using in photosensitive material of the present invention can use gelatin, but also can be separately or use in addition hydrophilic colloid with gelatin.As preferred gelatin, beavy metal impurities such as wherein contained iron, copper, zinc, manganese preferably are in below the 5ppm, more preferably are in below the 3ppm.And contained calcium amount in the photosensitive material, preferably be in 20mg/m ²Below, more preferably be in 10mg/m ²Below, preferably be in 5mg/m ²Below.

Among the present invention, make image deterioration in order to prevent various moulds and bacterium because of breeding in hydrophilic colloid, the special fungi-proofing mildewproof agent of putting down in writing in the clear 63-271247 communique of opening of preferred interpolation.The pH of photosensitive material film is preferably 4.0～7.0 in addition, and more preferably 4.0～6.5.

Among the present invention, photo constitutes total coating weight of gelatin in the layer, preferably is in 3g/m ²More than and 6g/m ²Below, more preferably be in 3g/m ²More than and 5g/m ²Below.In addition, in order also to satisfy the carrying out property of developing, photographic fixing bleaching property and residual look requirement under the situation about handling in hypervelocity, photo constitutes preferred 3～7.5 microns of the overall thickness of layer, more preferably 3～6.5 microns.The evaluation method of dry film thickness, the variation in thickness before and after can peeling off according to desciccator diaphragm is measured, and perhaps can measure by the method with optical microscope and electron microscope observation cross section.Among the present invention, for improving develop carrying out property and rate of drying, preferred 8～19 microns of swelling thickness, more preferably 9～18 microns simultaneously.As the assay method of swelling thickness, can adopt dried photosensitive material is immersed in 35 ℃ of aqueous solution to make it swelling, adopt the method for getting ready to measure under the state after reaching abundant balance.Silver coating amount among the present invention, preferred 0.2～0.5g/m ², more preferably 0.2～0.45g/m ², 0.2～0.40g/m preferably ²

Among the present invention, from the coating stability that improves photosensitive material, prevent viewpoints such as generation of static electricity and accommodation zone electric weight, can in photosensitive material, add surfactant.As surfactant anionic surface active agent, cationic surfactant, quaternary ammonium carboxylic acid inner salt (betaine) type surfactant, non-ionics are arranged, can enumerate for example special surfactant of putting down in writing in the flat 5-333492 communique of opening.As the surfactant that uses among the present invention, the surfactant of preferred contain fluorine atoms.Especially preferably use fluorochemical surfactant.These fluorochemical surfactants both can use separately, also can with known other surfactants and usefulness, but preferred with known other surfactants and use.Though the addition of these surfactants in photosensitive material is not particularly limited, and is generally 1 * 10 ^-5～1g/m ², preferred 1 * 10 ^-4～1 * 10 ^-1G/m ², more preferably 1 * 10 ^-3～1 * 10 ^-2G/m ²

Photosensitive material of the present invention by according to the exposure process of image information irradiation light with to the above-mentioned developing procedure that develops through light-struck photosensitive material, can form image.

Photosensitive material of the present invention except being used to adopt the printing system of common negative film photo print apparatus, also is applicable to the mode of the scan exposure that adopts cathode ray (CRT).Exposure apparatus for cathode-ray tube is compared with the device that adopts laser, and is simple and compact, and with low cost.Also adjust optical axis and color in addition easily.For cathode-ray tube (CRT), can adopt in case of necessity can be at the luminous various luminophors of SPECTRAL REGION for image exposure.For example, both can use in emitting red light body, green emitting body and the blue-light emitting body any, also can be two or more mixing use.Described SPECTRAL REGION is not limited to above-mentioned red, green, blue, also can use at yellow, orange, purple or the luminous fluorophor of region of ultra-red.What especially often use is the cathode-ray tube (CRT) that these luminophors mixing uses is sent white light.

When having the most photographic layers and the cathode-ray tube (CRT) that have different beam split light sensitivity distributions, photosensitive material also has under the situation of the luminous fluorophor of a plurality of spectral region, can the multiple color of disposable exposure, can import the picture signal of multiple color to cathode-ray tube (CRT), luminous from ray tube pipe face.After can also adopting the picture signal of importing each color successively to make shades of colour luminous successively, the method (face exposes successively) of exposing through the film that filters color beyond this kind color.Generally speaking, face exposes successively because of adopting high-resolution cathode-ray tube (CRT), and its image quality is good, and is therefore preferred.

Photosensitive material of the present invention, the preferred digital scanning Exposure mode that uses, this mode adopt gas laser, light emitting diode, semiconductor laser, with semiconductor laser or adopt solid state laser that semiconductor laser makes excitation source with the combination of non-linearity optical crystal the second higher harmonics illuminating source monochromatic high intensity light source such as (SGH) of formation.In order to make system compact, reduce price, so the second higher harmonics illuminating source (SGH) that preferably uses semiconductor laser, semiconductor laser or solid state laser and non-linearity optical crystal are combined.In order to design compactness, inexpensive and life-span length and the high device of stability, especially preferably adopt semiconductor laser, have at least a light source to use semiconductor laser in the preferred exposure light source.

Use under the situation of this scan exposure light source, the very big wavelength of beam split light sensitivity of photosensitive material of the present invention can be set arbitrarily with the wavelength of light source according to employed scan exposure.In the SGH light source that adopts semiconductor laser to do to obtain after the solid state laser of excitation source or semiconductor laser and the combination of non-linearity optical crystal, owing to the laser vibration wavelength being reduced by half, so can obtain blue light and green light.Therefore, can have the beam split light sensitivity maximum value of photosensitive material in common indigo plant, green and red three wavelength region may.Time shutter in this scan exposure is the time of the pixel size under the 400dpi situation if be defined as the exposure PEL (picture element) density, and the then preferred time shutter is 1 * 10 ^-4Below second, more preferably 1 * 10 ^-6Below second.

Silver halide colour photographic sensitive material of the present invention, preferably adopting emission wavelength is that the coherent light (coherent) of the blue laser of 420～460nm carries out image exposure.And especially preferably adopt blue semiconductor laser in the blue laser.

As the concrete preferred blue semiconductor laser that adopts wavelength 430～450nm of LASER Light Source (March calendar year 2001 by day inferior chemistry be published in the 48th Joining Report that relates to applied physics and can go up), utilize LiNbO with waveguide-shaped reversal zone structure ₃SGH crystal noise spectra of semiconductor lasers (resonance wave is about 940nm) carry out penetrating behind the wavelength conversion about 470nm light blue laser, utilize LiNbO with waveguide-shaped reversal zone structure ₃SGH crystal noise spectra of semiconductor lasers (resonance wave is about 1060nm) carry out penetrating behind the wavelength conversion green laser, the red laser diode (the type No.HL6738MG of Hitachi) of the about 685nm of wavelength and the red laser diode (the type No.HL6501MG of Hitachi) of the about 650nm of wavelength etc. of about 530nm light.

Silver halide colour photographic sensitive material of the present invention, preferably with following known data in the combined use of exposure, toning system put down in writing.As above-mentioned toning system, can enumerate automatic printing and toning system that the spy opens flat 10-333253 communique record, the spy opens the handling apparatus for photosensitive material of 2000-10206 communique record, the register system that comprises image read-out of Te Kaiping 11-215312 communique record, the exposure system that constitutes by the coloured image recording mode of the flat 10-202950 communique of Te Kaiping 11-88619 communique and Te Kai record, the digital light seal system of the telediagnosis mode that comprises of Te Kaiping 10-210206 communique record and special light seal (photoprint) system that comprises image recording structure that opens flat 10-159187 communique record.

About applicable to scan exposure mode of the present invention, be disclosed in detail among the patent of putting down in writing in the above-mentioned table.

When photosensitive material of the present invention is carried out the printing exposure, preferably adopt the rejection filter of putting down in writing in No. 4880726 instructions of United States Patent (USP).Can eliminate optical mixing like this, significantly improve the repeatability of color.

Among the present invention,, also can before giving image information, at first carry out the exposure in early stage, implement photocopying restriction (copy restraint) yellow particulate pattern as European patent EP 0789270A1 instructions and the record of EP0789480A1 instructions.

When handling photosensitive material of the present invention, preferably use special the 26th page of hurdle, bottom right of flat 2-207250 communique the 1st row～34 pages of upper right hurdles the 9th row and special processing material and the disposal route of opening the 5th page of upper left hurdle hurdle, the 17th～18 pages of bottom rights of row the 20th row record of flat 4-97355 communique opened.In addition, the antioxidant as this developer solution is used preferably uses the compound of putting down in writing on the patent in the above-mentioned table.

The present invention can be as the photosensitive material with rapid handling property.The colour developing development time was in below 28 seconds, and is preferred below 25 seconds more than 6 seconds, more preferably below 20 seconds more than 6 seconds.Equally, the blix time is preferably below 30 seconds, and is more preferably below 25 seconds more than 6 seconds, further preferred below 20 seconds more than 6 seconds.Washing or stabilizing take are preferred below 60 seconds in addition, more preferably below 40 seconds more than 6 seconds.

Wherein so-called colour developing development time is meant, photosensitive material is put into the time that begins behind the colour developing developer solution to the bleach-fixing liquid that enters next treatment process.For example under the situation about handling with automatic processing machine etc., the colour developing development time refers to be photosensitive material time (time in the so-called liquid) of in the colour developing developer solution, flooding with break away from developer solution from photosensitive material after in air, bathe total ascent time of the time (so-called in-flight time) of carrying to the blix of next treatment process.Equally, the so-called blix time is meant, photosensitive material is put into the washing or the stabilization that begin after putting into behind the bleach-fixing liquid bathe the time before.In addition, so-called washing or stabilizing take are meant photosensitive material are put into the time (so-called liquid time) that begins to be in liquid behind washing or the stabilization liquid to drying process.

Behind exposure photosensitive material of the present invention, as developing method, except can adopt with in the past contain alkaline reagent and the method for the developing liquid developing of the main reagent that develops or in photosensitive material the main reagent of built-in development and using the wet developing methods such as method of activator solutions such as the alkaline solution development that does not contain the main reagent that develops, can also adopt without the thermal development mode for the treatment of fluid etc.Because treating fluid does not contain the main reagent that develops in the activator method, the management for the treatment of fluid and operation be than being easier to, and bear little and help the viewpoint of environmental protection from liquid waste processing, also is particularly preferred method.

In the activator method, as the main reagent of development or its precursor in the interior plant photosensitive material, for example preferred spy opens flat 8-234388 communique, with the 9-152686 communique, with the 9-152693 communique, with the 9-211814 communique, with the hydrazine type compound of 9-160193 communique record.

In addition, also preferably reduced silver coating amount in the photosensitive material and adopt the developing method of the image processing and amplifying (thickening is handled) of hydrogen peroxide.Particularly preferably in adopting the method in the activator method.Specifically, the preferred employing specially opened flat 8-297354 communique and with the image forming method of putting down in writing in the 9-152695 communique, use the activator solution that contains hydrogen peroxide.In the above-mentioned activator method, after the activator solution processing, can carry out the desilverization usually and handle, but in the image processing and amplifying method that adopts low silver-colored amount photosensitive material, can omit the desilverization and handle, can implement simple and easy methods such as washing or stabilization processes.In addition, reading in the mode of image information in the photosensitive material,, also can adopt to need not the processing mode that the desilverization is handled even use is the photosensitive material of the contour silver amount of photographic photosensitive material with scanner.

The processing material and the disposal route of operable activator solution, desilverization liquid (bleaching/stop bath), washing and stabilization liquid can adopt technique known among the present invention.Preferred the 536th～541 page of " exploration discovery " Item 36544 (in September, 1994) and the special technology of opening flat 8-234388 communique record of adopting.

[embodiment]

Below by embodiment the present invention is specified, but the present invention is not subjected to the restriction of these embodiment.

Embodiment 1

Emulsion (preparations of B-11～14) reference examples: silver chloride cube, 0.46 micron of the length of side

In aqueous gelatin solution through stirring, add silver nitrate and sodium chloride and mixing simultaneously, utilize this conventional method to prepare high-silver chloride cube particle.Wherein, add potassium bromide in during adding silver nitrate 80% to 90%, its addition should make in every mole of silver halide of generation 2 moles of % silver bromides, during adding silver nitrate 80% to 90% in, interpolation K ₄[Ru (CN) ₆].And in during adding silver nitrate 83% to 88%, add K ₂[IrCl ₆], during adding silver nitrate 90% to 95% in, add K ₂[Ir (5-methylthiazol) Cl ₅].After the emulsion enforcement desalting processing that obtains, add gelatin and make it to disperse again.Parallel { the cube length of side that 110} bread encloses is 0.46 micron to the particle that obtains, and variation factor is 9.5% Cubic Emulsion by six.

Under 40 ℃,, add sensitizing coloring matter Dye-1 and thiosulfonic acid sodium, add the sodium thiosulfate pentahydrate as the sulphur sensitizer with this emulsion dissolving, as golden sensitizer with two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborate, advanced optimum cure.Add 1-phenyl-5-mercapto-tetrazole and 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole again, also add potassium bromide.The emulsion that obtains thus is decided to be emulsion B-11.

[changing 22]

(sensitizing coloring matter Dye-1)

The sensitizing coloring matter Dye-1 that adds when comparing different just post curing with emulsion B-11 becomes the emulsion of sensitizing coloring matter S-12, S-26 or S-32, is decided to be emulsion B-12, emulsion B-13 and emulsion B-14 respectively.

(preparations of emulsion B-21～24) reference examples: chlorine silver bromide, 0.61 micron of the length of side

In aqueous gelatin solution through stirring, add silver nitrate and sodium chloride simultaneously and mix, utilize this conventional method to prepare by six that parallel { the cube length of side that 100} bread encloses is that 0.61 micron, variation factor are 8.9% high-silver chloride Cubic Emulsion.Wherein, add potassium bromide in during adding silver nitrate 80% to 90%, its addition makes in every mole of silver halide of generation 2 moles of % silver bromides, during adding silver nitrate 80% to 90% in, interpolation K ₄[Ru (CN) ₆].And interpolation K in during adding silver nitrate 83% to 88% ₂[IrCl ₆], during adding silver nitrate 90% to 95% in, add K ₂[Ir (5-methylthiazol) Cl ₅].After the emulsion enforcement desalting processing that obtains, add gelatin and disperse again.

Under 40 ℃,, add sensitizing coloring matter Dye-1 and thiosulfonic acid sodium, use the sodium thiosulfate pentahydrate as the sulphur sensitizer with this emulsion dissolving, and as golden sensitizer use two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborate, carried out optimum cure.In addition, also add 1-phenyl-5-mercapto-tetrazole and 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, added potassium bromide again.The emulsion that obtains thus is decided to be emulsion B-21.

The sensitizing coloring matter Dye-1 that adds when comparing different just post curing with emulsion B-21 becomes the emulsion of sensitizing coloring matter S-12, S-26 or S-32, is decided to be emulsion B-22, emulsion B-23 and emulsion B-24 respectively.

(preparations of emulsion B-31～34) the present invention: chlorine iodine silver bromide, 0.46 micron of the length of side

For emulsion B-11, except add moment of 90% at silver nitrate, under violent condition of mixing, add a certain amount of potassium iodide aqueous solution, make and contain in every mole of silver halide of separating out outside 0.24 mole of % iodine, similarly prepare emulsion with emulsion B-11.The emulsion particles that obtains, parallel { the cube length of side that 100} bread encloses is that 0.46 micron, variation factor are 9.5% cube chlorine iodine silver bromide emulsion by six.The emulsion that obtains thus is decided to be emulsion B-31.In addition, the CONCENTRATION DISTRIBUTION of iodide ion on depth direction measured through etching/TOF-SIMS method, and iodide ion has at particle surface and oozes out, and have peak concentration slowly on outmost surface, and concentration decays gradually towards interior side direction.

The sensitizing coloring matter Dye-1 that adds when comparing different just post curing with emulsion B-31 becomes the emulsion of sensitizing coloring matter S-12, S-26 or S-32, is decided to be emulsion B-32, emulsion B-33 and emulsion B-34 respectively.

(preparations of emulsion B-41～44) reference examples: chlorine iodine silver bromide, 0.61 micron of the length of side

For emulsion B-21, except add moment of 90% at silver nitrate, under violent condition of mixing, add a certain amount of potassium iodide aqueous solution, make and contain in every mole of silver halide of separating out outside 0.24 mole of % iodine, similarly prepare emulsion with emulsion B-21.The emulsion particles that obtains, parallel { the cube length of side that 100} bread encloses is that 0.61 micron, variation factor are 8.7% cube chlorine iodine silver bromide emulsion by six.The emulsion that obtains thus is decided to be emulsion B-41.

The sensitizing coloring matter Dye-1 that adds when comparing different just post curing with emulsion B-41 becomes the emulsion of sensitizing coloring matter S-12, S-26 or S-32, is decided to be emulsion B-42, emulsion B-43 and emulsion B-44 respectively.

(preparations of emulsion B-51～54) reference examples: { 100} chlorine iodine silver bromide flat board, 0.46 micron of the length of side

Under 27 ℃ of constant temperature, on one side vigorous stirring in aqueous gelatin solution, add simultaneously silver nitrate and sodium chloride on one side through stirring, then under violent the mixing, add a certain amount of potassium bromide, make in every mole of silver halide of generation and contain 0.46 mole of % silver bromide.Add silver nitrate and sodium chloride then simultaneously.Be warmed up to 75 ℃ and carry out optimum cure, and then add silver nitrate and sodium chloride, make it to grow into required particle size as the growth operation.At this moment, when reaching the moment of adding 90% silver nitrate, under violent the mixing, add a certain amount of potassium iodide aqueous solution, make every mole of silver halide of generation contain 0.24 mole of % iodine, in during silver nitrate adds 80% to 90%, under violent the mixing, add a certain amount of potassium bromide, make every mole of silver halide of generation contain 2 moles of % silver bromides.

In addition, during adding silver nitrate 80% to 90% in, add K ₄[Ru (CN) ₆], during silver nitrate adds 83% to 88% in, add K ₂[IrCl ₆].In then during adding silver nitrate 90% to 95%, add K ₂[Ir (5-methylthiazol) Cl ₅].

Then the emulsion that obtains is implemented desalting processing, add gelatin again and disperse again.

Then get a part of emulsion and observe the electron micrograph (TEM picture) that duplicates with particle.So, all have 95.1% to be that principal plane is that { the tabular particle of 100}, its mean grain size are 0.90 micron in the silver halide particle projected area, averaged particles thickness is 0.15 micron, the average shape ratio is 6.1, and the ratio of average adjacent edge is 1.12, and the cube conversion length of side is 0.46 micron.

This emulsion 40 ℃ of dissolvings down, is added sensitizing coloring matter Dye-1 and thiosulfonic acid sodium, use the sodium thiosulfate pentahydrate as the sulphur sensitizer, with two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborate carries out optimum cure as golden sensitizer.In addition, also add 1-phenyl-5-mercapto-tetrazole and 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, added potassium bromide again.The emulsion that obtains thus is decided to be emulsion B-51.

The sensitizing coloring matter Dye-1 that adds when comparing different just post curing with emulsion B-51 becomes the emulsion of sensitizing coloring matter S-12, S-26 or S-32, is decided to be emulsion B-52, emulsion B-53 and emulsion B-54 respectively.

(preparation of emulsion G-1)

In aqueous gelatin solution through stirring, add silver nitrate and sodium chloride simultaneously and mix, utilizing this conventional method to prepare the equivalent bulb diameter is that 0.35 micron, variation factor are 10% cube high silver chloride emulsion.Wherein, during adding silver nitrate 80% to 90% in, add K ₄[Ru (CN) ₆].During adding silver nitrate 80% to 100%, add potassium bromide (addition should make in every mole of silver halide of generation 4 moles of % silver bromides).Add moment of 90% at silver nitrate, add potassium iodide (addition should make in every mole of silver halide of generation 0.2 mole of % silver iodide).During silver nitrate adds 92% to 95%, added K ₂[Ir (5-methylthiazol) Cl ₅].During silver nitrate adds 92% to 98%, added K ₂[Ir (H ₂O) Cl ₅].After the emulsion enforcement desalting processing that obtains, add gelatin and disperse again.In this emulsion, add sodium benzenethiosulfonate, use the sodium thiosulfate pentahydrate, carry out optimum cure as golden sensitizer with two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborates as the sulphur sensitizer.In addition, sensitizing coloring matter Dye-2,1-phenyl-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole and potassium bromide have been added.The emulsion that obtains thus is decided to be emulsion G-1.

[changing 23]

(sensitizing coloring matter Dye-2)

(preparation of emulsion R-1)

In aqueous gelatin solution through stirring, add silver nitrate and sodium chloride simultaneously and mix, utilizing this conventional method to prepare the equivalent bulb diameter is that 0.35 micron, variation factor are 10% cube high silver chloride emulsion.Wherein, during silver nitrate adds 80% to 90% in, add K ₄[Ru (CN) ₆].During silver nitrate adds 80% to 100%, added potassium bromide (addition should make in every mole of silver halide of generation 4.3 moles of % silver bromides).And added for 90% the moment at silver nitrate, add potassium iodide (addition should make in every mole of silver halide of generation 0.15 mole of % silver iodide).Add 92% to 95% silver nitrate during in, add K ₂[Ir (5-methylthiazol) Cl ₅].And then in during adding silver nitrate 92% to 98%, add K ₂[Ir (H ₂O) Cl ₅].After the emulsion enforcement desalting processing that obtains, add gelatin and disperse again.In this emulsion, add sodium benzenethiosulfonate, use the sodium thiosulfate pentahydrate, carry out optimum cure as golden sensitizer with two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptide) oleate (I) tetrafluoroborates as the sulphur sensitizer.In addition, sensitizing coloring matter Dye-3,1-phenyl-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, Compound I and potassium bromide have been added.The emulsion that obtains thus is decided to be emulsion R-1.

[changing 24]

(sensitizing coloring matter Dye-3)

(Compound I)

For the support surface of making after the two sides of paper substrate is coated with polyvinyl resin, after implementing Corona discharge Treatment, setting contains the gelatin undercoat of neopelex, and then coating is provided with first～layer 7 photo formation layer successively, has made the silver halide colour photographic sensitive material sample that has with understructure.The coating fluid that each photo constitutes layer usefulness is prepared as follows.

The preparation of ground floor coating fluid

57 gram yellow colour formers (ExY-1), 7 gram colour stabilizing agents (Cpd-1), 4 gram colour stabilizing agents (Cpd-2), 7 gram colour stabilizing agents (Cpd-3) and 2 gram colour stabilizing agents (Cpd-8) are dissolved in 21 to be restrained in solvents (Solv-1) and the 80 milliliters of ethyl acetate, with high-speed stirred mulser (dissolving machine) this emulsifying soln is dispersed in aqueous gelatin solution 220 grams of the 23.5 weight % that contain 4 gram neopelexes, adds entry and make 900 gram emulsifications dispersion thing A.

On the other hand, above-mentioned emulsification is disperseed thing A and emulsion B-1 mixed dissolution, make and form ground floor coating fluid as described later.The emulsion coating weight is represented silver amount conversion coating weight.

With preparing the coating fluid of the second layer～layer 7 with the same method of ground floor coating fluid.Gelatin hardening agent as each layer has used 1-oxo-3,5-two chloro-s-triazine sodium salts (H-1), (H-2) and (H-3).And added Ab-1, Ab-2, Ab-3 and Ab-4 in each layer, its separately total amount be respectively 15.0 milligrams/square metre, 60.0 milligrams/square metre, 5.0 milligrams/square metre and 10.0 milligrams/square metre.

[changing 25]

(H-1) hardener

(each gelatin is with 1.4 weight %

(H-2) hardener

(H-3) hardener

[changing 26]

Ab-1 antiseptic Ab-2 antiseptic

The Ab-3 antiseptic

The Ab-4 antiseptic

A, b, c, d 1: 1: 1: 1 potpourri (mol ratio)

In addition, respectively add 1-phenyl-5-mercapto-tetrazole for green property emulsion layer of sense and the red property emulsion layer of sense, its addition is to be respectively 1.0 * 10 with respect to every mole of silver halide ^-3With 5.9 * 10 ^-4Mole.In the second layer, the 4th layer and layer 6, also respectively add 1-phenyl-5-mercapto-tetrazole then, make each layer contain 0.2 milligram/square metre, 0.2 milligram/square metre and 0.6 milligram/square metre respectively.

In the red property emulsion layer of sense, add 0.05 gram/square metre methacrylic acid and the copolymer emulsion (weight ratio 1: 1, mean molecular weight are 200000～400000) of butyl acrylate.And in the second layer, the 4th layer and layer 6, respectively having added catechol-3,5-disulfonic acid disodium makes it to reach respectively 6 milligrams/square metre, 6 milligrams/square metre and 18 milligrams/square metre.In addition, in order to prevent irradiation, added following dyestuff (expression coating weight in the parantheses).

[changing 27]

(layer structure)

The structure of below representing each layer.The numeral coating weight (gram/square metre).Silver emulsion is represented silver-colored conversion coating weight.

Support

The polyvinyl resin laminated paper

[contain Chinese white (TiO in the polyvinyl resin of ground floor side ₂: content 16 weight %, ZnO: content 4 weight %) and fluorescer (4,4 '-two (5-Jia base benzoxazolyl) stilbene, content: 0.03 weight %), blue dyes (ultramarine)]

Ground floor (sense indigo plant emulsion layer)

Emulsion B-11 0.19

Gelatin 1.00

Yellow colour former (ExY-1) 0.46

Colour stabilizing agent (Cpd-1) 0.06

Colour stabilizing agent (Cpd-2) 0.03

Colour stabilizing agent (Cpd-3) 0.06

Colour stabilizing agent (Cpd-8) 0.02

Solvent (Solv-1) 0.17

The second layer (anti-colour mixture layer)

Gelatin 0.50

Prevent blending agent (Cpd-4) 0.05

Colour stabilizing agent (Cpd-5) 0.01

Colour stabilizing agent (Cpd-6) 0.06

Colour stabilizing agent (Cpd-7) 0.01

Solvent (Solv-1) 0.03

Solvent (Solv-2) 0.11

The 3rd layer (feeling green property emulsion layer)

Emulsion G-1 0.12

Gelatin 1.36

Magenta colour coupler (ExM) 0.15

Colour stabilizing agent (Cpd-2) 0.02

Colour stabilizing agent (Cpd-4) 0.002

Colour stabilizing agent (Cpd-6) 0.09

Colour stabilizing agent (Cpd-8) 0.02

Colour stabilizing agent (Cpd-9) 0.03

Colour stabilizing agent (Cpd-10) 0.01

Colour stabilizing agent (Cpd-11) 0.0001

Solvent (Solv-3) 0.11

Solvent (Solv-4) 0.22

Solvent (Solv-5) 0.20

The 4th layer (anti-colour mixture layer)

Gelatin 0.36

Prevent blending agent (Cpd-4) 0.03

Colour stabilizing agent (Cpd-5) 0.006

Colour stabilizing agent (Cpd-6) 0.05

Colour stabilizing agent (Cpd-7) 0.004

Solvent (Solv-1) 0.02

Solvent (Solv-2) 0.08

Layer 5 (feeling red property emulsion layer)

Emulsion R-1 0.10

Gelatin 1.11

Cyan coupler (ExC-2) 0.13

Cyan coupler (ExC-3) 0.03

Colour stabilizing agent (Cpd-1) 0.05

Colour stabilizing agent (Cpd-6) 0.06

Colour stabilizing agent (Cpd-7) 0.02

Colour stabilizing agent (Cpd-9) 0.04

Colour stabilizing agent (Cpd-10) 0.01

Colour stabilizing agent (Cpd-14) 0.01

Colour stabilizing agent (Cpd-15) 0.12

Colour stabilizing agent (Cpd-16) 0.03

Colour stabilizing agent (Cpd-17) 0.09

Colour stabilizing agent (Cpd-18) 0.07

Solvent (Solv-5) 0.15

Solvent (Solv-8) 0.05

Layer 6 (UV-absorbing layer)

Gelatin 0.46

Ultraviolet light absorber (UV-B) 0.45

Compound (S1-4) 0.0015

Solvent (Solv-7) 0.25

Layer 7 (protective seam)

Gelatin 1.00

The acrylic acid modified multipolymer of polyvinyl alcohol (PVA)

(modification degree 17%) 0.04

Whiteruss 0.02

Surfactant (Cpd-13) 0.01

[changing 28]

(ExY-1) yellow colour former

With

70: 30 potpourris (mol ratio)

[changing 29]

(ExM) magenta colour coupler

With

40: 20: 20 potpourris (mol ratio)

[changing 30]

(ExC-2) cyan coupler

(ExC-3) cyan coupler

With

50: 25: 25 potpourris (mol ratio)

[changing 31]

(Cpd-1) colour stabilizing agent

Number-average molecular weight 60,000

(Cpd-2) colour stabilizing agent

(Cpd-3) colour stabilizing agent

N=7-8 (mean value)

(Cpd-4) anti-blending agent

[changing 32]

(Cpd-5) colour stabilizing agent

(Cpd-6) colour stabilizing agent

Number-average molecular weight 600 m/n=10/90

(Cpd-7) colour stabilizing agent (Cpd-8) colour stabilizing agent

(Cpd-9) colour stabilizing agent (Cpd-10) colour stabilizing agent

[changing 33]

(Cpd-13) surfactant

With

7: 3 potpourris (mol ratio)

[changing 34]

(Cpd-19) anti-blending agent

[changing 35]

(UV-1) ultraviolet light absorber (UV-2) ultraviolet light absorber

(UV-3) ultraviolet light absorber (UV-4) ultraviolet light absorber

(UV-5) ultraviolet light absorber (UV-6) ultraviolet light absorber

(UV-7) ultraviolet light absorber

The potpourri of UV-A:UV-1/UV-2/UV-3/UV-4=4/2/2/3 (weight ratio)

The potpourri of UV-B:UV-1/UV-2/UV-3/UV-4/UV-5/UV-6=9/3/3/4/5/3 (weight ratio)

The potpourri of UV-C:UV-2/UV-3/UV-6/UV-7=1/1/1/2 (weight ratio)

[changing 36]

[changing 37]

The above sample that obtains is made sample B (111).For sample B (111), according to the emulsion of changing sense indigo plant emulsion layer shown in the table 2, made sample B (112)～sample B (144) equally respectively.

Table 2

The sample name	The emulsion name	Shape	Contain the silver iodide phase	The cube conversion length of side	The optical sensibilization pigment	Remarks
The sample name	The emulsion name	Shape	Contain the silver iodide phase	The cube conversion length of side	The optical sensibilization pigment	Remarks	B(111)	B-11	Cube	Do not have	0.46 micron	Dye-1	Reference examples
B(112)	B-12	Cube	Do not have	0.46 micron	S-12	Reference examples	B(111)	B-11	Cube	Do not have	0.46 micron	Dye-1	Reference examples
B(112)	B-12	Cube	Do not have	0.46 micron	S-12	Reference examples	B(113)	B-13	Cube	Do not have	0.46 micron	S-26	Reference examples
B(114)	B-14	Cube	Do not have	0.46 micron	S-32	Reference examples	B(113)	B-13	Cube	Do not have	0.46 micron	S-26	Reference examples
B(114)	B-14	Cube	Do not have	0.46 micron	S-32	Reference examples	B(121)	B-21	Cube	Do not have	0.61 micron	Dye-1	Reference examples
B(122)	B-22	Cube	Do not have	0.61 micron	S-12	Reference examples	B(121)	B-21	Cube	Do not have	0.61 micron	Dye-1	Reference examples
B(122)	B-22	Cube	Do not have	0.61 micron	S-12	Reference examples	B(123)	B-23	Cube	Do not have	0.61 micron	S-26	Reference examples
B(124)	B-24	Cube	Do not have	0.61 micron	S-32	Reference examples	B(123)	B-23	Cube	Do not have	0.61 micron	S-26	Reference examples
B(124)	B-24	Cube	Do not have	0.61 micron	S-32	Reference examples	B(131)	B-31	Cube	Have	0.46 micron	Dye-1	Reference examples
B(132)	B-32	Cube	Have	0.46 micron	S-12	The present invention	B(131)	B-31	Cube	Have	0.46 micron	Dye-1	Reference examples
B(132)	B-32	Cube	Have	0.46 micron	S-12	The present invention	B(133)	B-33	Cube	Have	0.46 micron	S-26	The present invention
B(134)	B-34	Cube	Have	0.46 micron	S-32	The present invention	B(133)	B-33	Cube	Have	0.46 micron	S-26	The present invention
B(134)	B-34	Cube	Have	0.46 micron	S-32	The present invention	B(141)	B-41	Cube	Have	0.61 micron	Dye-1	Reference examples
B(142)	B-42	Cube	Have	0.61 micron	S-12	Reference examples	B(141)	B-41	Cube	Have	0.61 micron	Dye-1	Reference examples
B(142)	B-42	Cube	Have	0.61 micron	S-12	Reference examples	B(143)	B-43	Cube	Have	0.61 micron	S-26	Reference examples
B(144)	B-44	Cube	Have	0.61 micron	S-32	Reference examples	B(143)	B-43	Cube	Have	0.61 micron	S-26	Reference examples
B(144)	B-44	Cube	Have	0.61 micron	S-32	Reference examples	B(151)	B-51	{ the dull and stereotyped particle of 100}	Have	0.46 micron	Dye-1	Reference examples
B(152)	B-52	??”	Have	0.46 micron	S-12	Reference examples	B(151)	B-51	{ the dull and stereotyped particle of 100}	Have	0.46 micron	Dye-1	Reference examples
B(152)	B-52	??”	Have	0.46 micron	S-12	Reference examples	B(153)	B-53	??”	Have	0.46 micron	S-26	Reference examples
B(154)	B-54	??”	Have	0.46 micron	S-32	Reference examples	B(153)	B-53	??”	Have	0.46 micron	S-26	Reference examples

(estimate 1: the temperature dependency of exposure environment)

For studying the photographic property of these samples, carried out following experiment.

Each coating sample is fully placed under 10 ℃, 30%RH atmosphere, directly under this environment with high illumination exposure with sensitometer (DENSO Corporation manufacturing HIE type under the mountain), the sensitometry that shows grey is with 10 ^-6High illumination gray shade scale exposure in second.Through the sample of overexposure, after 5 seconds of exposing, carry out colour developing development treatment a shown below.

Treatment process below is described.

[colour developing development treatment a]

Above-mentioned photosensitive material sample B (132) is processed into the web-like of 127 mm wides, use colour developing developer solution tankage size is 1 liter an experiment treating apparatus, the negative film that sees through average mean concentration carries out image exposure to the photosensitive material sample, handles (running test) continuously and reaches 0.5 times of colour developing developing tank capacity until the capacity of remembering the colour developing developer replenisher solution that uses in the treatment process down.The processing of using this continuous treating fluid is decided to be colour developing development treatment a.

Treatment process temperature-time magnitude of recruitment ^*

Colour developing develop 45.0 ℃ 16 seconds 45 milliliters

35 milliliters of 40.0 ℃ of blixs 16 seconds

Wash 1 40.0 ℃ 8 seconds-

Wash 2 40.0 ℃ 8 seconds-

40.0 ℃ of 3** of flushing 8 seconds-

Wash 4 38.0 ℃ 8 seconds 121 milliliters

Dry 80.0 ℃ 16 seconds

(notes) * is with respect to the magnitude of recruitment of 1 square metre of photosensitive material

The rinse-system RC50D that * makes Fuji Photo Film Co., Ltd. is installed in flushing 3 places, takes out washing fluid with being pumped to reverse osmosis module (RC50D) from washing 3.Supply with the use of flushing operation with the permeate water that groove is sent here, concentrate returns flushing 3.Adjust pump pressure and make the water yield that sees through of reverse osmosis module maintain 50～300 ml/min, the limit is regulated temperature and is made it to circulate one day 10 hours.Four jars of reflux types from 1 to 4 are adopted in flushing.

Various treating fluids composed as follows.

[colour developing developer solution] [jar liquid] [replenishing liquid]

800 milliliters 600 milliliters in water

Fluorescer (FL-1) 5.0 grams 8.5 grams

Triisopropanolamine 8.8 grams 8.8 grams

Paratoluenesulfonic acid sodium salt 20.0 grams 20.0 grams

Ethylenediamine tetraacetic acid 4.0 grams 4.0 grams

Sodium sulphite 0.10 gram 0.50 gram

Potassium chloride 10.0 grams-

4,5-dihydroxy benzenes-1,3-sodium disulfonate 0.50 gram 0.50 gram

Disodium N, two (sulfonic acid ethyl ester) azanol 8.5 grams of N-14.5 grams

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

(β-methylsulfonyl amido ethyl) aniline

3/2 sulfate, 1 hydrate, 10.0 grams, 22.0 grams

Sal tartari 26.3 grams 26.3 grams

Add entry to 1000 milliliters 1000 milliliters of total amounts

PH (25 ℃ are adjusted with sulfuric acid and KOH) 10.35 12.6

[bleach-fixing liquid] [jar liquid] [replenishing liquid]

800 milliliters 800 milliliters in water

107 milliliters 214 milliliters of ATS (Ammonium thiosulphate) (750 grams per liter)

Succinic acid 29.5 grams 59.0 grams

Ethylenediamine tetraacetic acid iron (III) ammonium 47.0 grams 94.0 grams

Ethylenediamine tetraacetic acid 1.4 grams 2.8 grams

Nitric acid (67%) 17.5 gram 35.0 grams

Imidazoles 14.6 grams 29.2 grams

Ammonium sulfite 16.0 grams 32.0 grams

Potassium metabisulfite 23.1 grams 46.2 restrain partially

Add entry to 1000 milliliters 1000 milliliters of full doses

PH (25 ℃) 6.00 6.00 with nitric acid and ammoniacal liquor adjustment

[washing fluid] [jar liquid] [replenishing liquid]

Chloro sodium isocyanate 0.02 gram 0.02 gram

1000 milliliters 1000 milliliters of deionized waters (conductivity 5 μ s/cm are following)

pH(25℃)?????????????????????6.5?????????6.5

[changing 38]

Equally, each coating sample is fully placed under 35 ℃, 30%RH atmosphere, directly under this environment with high illumination exposure with sensitometer (DENSO Corporation manufacturing HIE type under the mountain), the sensitometer that shows grey is with 10 ^-6High illumination gray shade scale exposure in second.Through the sample of overexposure, after exposure through the development treatment a that develops the color for 5 seconds.Measure the displaing yellow concentration of handling each sample of back, obtained 10 ^-6The family curve of high illumination exposure in second.Light sensitivity is defined with the inverse that shows the exposure more required than the colour developing concentration of minimum colour developing concentration high 1.0.

Sample B (111) is exposed under 10 ℃, 30%RH atmosphere, be made as 100, relative sensitivity=S separately through the light sensitivity under the colour developing development treatment a disposition _{10 ℃ of 30%RH}Be shown among the table 3.And then exposure when each sample is handled through colour developing development treatment a after the exposure under 10 ℃, 30%RH atmosphere and under 35 ℃, 30%RH atmosphere is after the light sensitivity difference Δ S of colour developing development treatment a when handling _{(35 ℃-10 ℃}, use than the logarithm of difference of the exposure inverse of the dense high 1.0 colour developing concentration of minimum colour developing and represent that these data are shown in Table 3.Δ S _{(35 ℃-10 ℃)}Numerical value more little, the variation (exposure temperature) of expression exposure environment is more little to the influence of photographic property.

Table 3

The sample name	????S _10℃30％RH	????ΔS _{(35℃-10℃)}	????Δγ	Remarks
The sample name	????S _10℃30％RH	????ΔS _{(35℃-10℃)}	????Δγ	Remarks	B(111)	????100	????0.15	????1.08	Reference examples
B(112)	????78	????0.10	????1.22	Reference examples	B(111)	????100	????0.15	????1.08	Reference examples
B(112)	????78	????0.10	????1.22	Reference examples	B(113)	????66	????0.11	????1.25	Reference examples
B(114)	????95	????0.10	????1.21	Reference examples	B(113)	????66	????0.11	????1.25	Reference examples
B(114)	????95	????0.10	????1.21	Reference examples	B(121)	????166	????0.16	????1.09	Reference examples
B(122)	????112	????0.11	????1.22	Reference examples	B(121)	????166	????0.16	????1.09	Reference examples
B(122)	????112	????0.11	????1.22	Reference examples	B(123)	????107	????0.12	????1.17	Reference examples
B(124)	????145	????0.08	????1.19	Reference examples	B(123)	????107	????0.12	????1.17	Reference examples
B(124)	????145	????0.08	????1.19	Reference examples	B(131)	????172	????0.09	????1.15	Reference examples
B(132)	????173	????0.02	????1.05	The present invention	B(131)	????172	????0.09	????1.15	Reference examples
B(132)	????173	????0.02	????1.05	The present invention	B(133)	????170	????0.03	????1.07	The present invention
B(134)	????170	????0.02	????1.05	The present invention	B(133)	????170	????0.03	????1.07	The present invention
B(134)	????170	????0.02	????1.05	The present invention	B(141)	????298	????0.04	????1.21	Reference examples
B(142)	????310	????0.03	????1.25	Reference examples	B(141)	????298	????0.04	????1.21	Reference examples
B(142)	????310	????0.03	????1.25	Reference examples	B(143)	????307	????0.03	????1.28	Reference examples
B(144)	????307	????0.02	????1.22	Reference examples	B(143)	????307	????0.03	????1.28	Reference examples
B(144)	????307	????0.02	????1.22	Reference examples	B(151)	????285	????0.05	????1.35	Reference examples
B(152)	????288	????0.05	????1.33	Reference examples	B(151)	????285	????0.05	????1.35	Reference examples
B(152)	????288	????0.05	????1.33	Reference examples	B(153)	????285	????0.06	????1.40	Reference examples
B(154)	????288	????0.04	????1.35	Reference examples	B(153)	????285	????0.06	????1.40	Reference examples

(estimate 2: the treating fluid vary stable)

And then, in order to study the treating fluid vary stable, carried out following test.The sample that under 25 ℃, 30%RH atmosphere, fully place, under this environment directly with high illumination exposure sensitometer (DENSO Corporation manufacturing HIE type under the mountain), the sensitometry that shows grey is with 10 ^-6High illumination gray shade scale exposure in second.Sample to exposure has carried out colour developing development treatment b and c shown below then.

Treatment process below is described.

[colour developing development treatment b]

In [colour developing development treatment b], the magnitude of recruitment of every square metre of photosensitive material in the working fluid preparation of the development treatment a that will develop the color has improved 15%, handle continuously under all identical condition of other condition, and with the processing of using the continuous treating fluid that obtains this moment as colour developing development treatment b.

Treatment formulations is as follows.

Treatment process temperature-time magnitude of recruitment ^*

Colour developing develop 45.0 ℃ 16 seconds 51.8 milliliters

35 milliliters of 40.0 ℃ of blixs 16 seconds

Wash 1 40.0 ℃ 8 seconds-

Wash 2 40.0 ℃ 8 seconds-

40.0 ℃ of 3** of flushing 8 seconds-

Wash 4 38.0 ℃ 8 seconds 121 milliliters

Dry 80.0 ℃ 16 seconds

[colour developing development treatment c]

Equally, in [colour developing development treatment c], the magnitude of recruitment of every square metre of photosensitive material in the working fluid preparation of the development treatment a that will develop the color has reduced 15%, handle continuously under all identical condition of other condition, and with the processing of using the continuous treating fluid that obtains this moment as colour developing development treatment c.

Treatment formulations is as follows.

Treatment process temperature-time magnitude of recruitment ^*

Colour developing develop 45.0 ℃ 16 seconds 38.3 milliliters

35 milliliters of 40.0 ℃ of blixs 16 seconds

Wash 1 40.0 ℃ 8 seconds-

Wash 2 40.0 ℃ 8 seconds-

40.0 ℃ of 3** of flushing 8 seconds-

Wash 4 38.0 ℃ 8 seconds 121 milliliters

Dry 80.0 ℃ 16 seconds

Measure the displaing yellow concentration of handling each sample of back through various, obtained family curve.Wherein gray shade scale (γ) is defined as the numerical value of representing with the point that shows minimum colour developing concentration+1.4 these colour developing concentration and the logarithm of the difference of these 2 the exposure inverses of point that show minimum colour developing concentration+2.0 these colour developing concentration.Gray shade scale variation factor Δ γ (γ (b)/γ (c)) between the gray shade scale (γ) when gray shade scale (γ) when adopting colour developing development treatment b to handle and employing colour developing development treatment c handle is shown among the table 3.Δ γ value is more near 1.0, and the influence of expression processing variation is more little.

As in the table 3 shown in the result, sample B of the present invention (132), B (133) and B (134), the light sensitivity height, the exposure variation of ambient temperature is shown stable, even and the also rare variation of gray shade scale in processing variation, can obtain stable printing.

Embodiment 2

For sample B (111), constitute layer according to following content changing photo, made the sample of thin layerization.

Ground floor (sense indigo plant emulsion layer)

Emulsion B-11 0.14

Gelatin 0.75

Yellow colour former (ExY-2) 0.34

Colour stabilizing agent (Cpd-1) 0.04

Colour stabilizing agent (Cpd-2) 0.02

Colour stabilizing agent (Cpd-3) 0.04

Colour stabilizing agent (Cpd-8) 0.01

Solvent (Solv-1) 0.13

The second layer (anti-colour mixture layer)

Gelatin 0.60

Anti-blending agent (Cpd-19) 0.09

Colour stabilizing agent (Cpd-5) 0.007

Colour stabilizing agent (Cpd-7) 0.007

Ultraviolet light absorber (UV-C) 0.05

Solvent (Solv-5) 0.11

The 3rd layer (feeling green property emulsion layer)

Emulsion G-1 0.12

Gelatin 0.73

Magenta colour coupler (ExM) 0.15

Ultraviolet light absorber (UV-A) 0.05

Colour stabilizing agent (Cpd-2) 0.02

Colour stabilizing agent (Cpd-7) 0.008

Colour stabilizing agent (Cpd-8) 0.07

Colour stabilizing agent (Cpd-9) 0.03

Colour stabilizing agent (Cpd-10) 0.009

Colour stabilizing agent (Cpd-11) 0.0001

Solvent (Solv-3) 0.06

Solvent (Solv-4) 0.11

Solvent (Solv-5) 0.06

The 4th layer (anti-colour mixture layer)

Gelatin 0.48

Anti-blending agent (Cpd-4) 0.07

Colour stabilizing agent (Cpd-5) 0.006

Colour stabilizing agent (Cpd-7) 0.006

Ultraviolet light absorber (UV-C) 0.04

Solvent (Solv-5) 0.09

Layer 5 (feeling red property emulsion layer)

Emulsion R-1 0.10

Gelatin 0.59

Cyan coupler (ExC-2) 0.13

Cyan coupler (ExC-3) 0.03

Colour stabilizing agent (Cpd-7) 0.01

Colour stabilizing agent (Cpd-9) 0.04

Colour stabilizing agent (Cpd-15) 0.19

Colour stabilizing agent (Cpd-18) 0.04

Ultraviolet light absorber (UV-7) 0.02

Solvent (Solv-5) 0.09

Layer 6 (UV-absorbing layer)

Gelatin 0.32

Ultraviolet light absorber (UV-C) 0.42

Solvent (Solv-7) 0.08

Layer 7 (protective seam)

Gelatin 0.70

The acrylic acid modified multipolymer of polyvinyl alcohol (PVA)

(modification degree 17%) 0.04

Whiteruss 0.01

Surfactant (Cpd-13) 0.01

Dimethyl silicone polymer 0.01

Silicon dioxide 0.003

[changing 39]

Be decided to be sample B (211) by the sample that obtains with upper type.For sample B (211), replace the emulsion of sense indigo plant emulsion layer respectively according to table 3, and prepare sample equally, be decided to be sample B (212)～B (254).

Table 4

The sample name	The emulsion name	Shape	Halogen is formed	The cube conversion length of side	The optical sensibilization pigment	Remarks
The sample name	The emulsion name	Shape	Halogen is formed	The cube conversion length of side	The optical sensibilization pigment	Remarks	B(211)	B-11	Cube	Do not have	0.46 micron	Dye-1	Reference examples
B(212)	B-12	Cube	Do not have	0.46 micron	S-12	Reference examples	B(211)	B-11	Cube	Do not have	0.46 micron	Dye-1	Reference examples
B(212)	B-12	Cube	Do not have	0.46 micron	S-12	Reference examples	B(213)	B-13	Cube	Do not have	0.46 micron	S-26	Reference examples
B(214)	B-14	Cube	Do not have	0.46 micron	S-32	Reference examples	B(213)	B-13	Cube	Do not have	0.46 micron	S-26	Reference examples
B(214)	B-14	Cube	Do not have	0.46 micron	S-32	Reference examples	B(221)	B-21	Cube	Do not have	0.61 micron	Dye-1	Reference examples
B(222)	B-22	Cube	Do not have	0.61 micron	S-12	Reference examples	B(221)	B-21	Cube	Do not have	0.61 micron	Dye-1	Reference examples
B(222)	B-22	Cube	Do not have	0.61 micron	S-12	Reference examples	B(223)	B-23	Cube	Do not have	0.61 micron	S-26	Reference examples
B(224)	B-24	Cube	Do not have	0.61 micron	S-32	Reference examples	B(223)	B-23	Cube	Do not have	0.61 micron	S-26	Reference examples
B(224)	B-24	Cube	Do not have	0.61 micron	S-32	Reference examples	B(231)	B-31	Cube	Have	0.46 micron	Dye-1	Reference examples
B(232)	B-32	Cube	Have	0.46 micron	S-12	The present invention	B(231)	B-31	Cube	Have	0.46 micron	Dye-1	Reference examples
B(232)	B-32	Cube	Have	0.46 micron	S-12	The present invention	B(233)	B-33	Cube	Have	0.46 micron	S-26	The present invention
B(234)	B-34	Cube	Have	0.46 micron	S-32	The present invention	B(233)	B-33	Cube	Have	0.46 micron	S-26	The present invention
B(234)	B-34	Cube	Have	0.46 micron	S-32	The present invention	B(241)	B-41	Cube	Have	0.61 micron	Dye-1	Reference examples
B(242)	B-42	Cube	Have	0.61 micron	S-12	Reference examples	B(241)	B-41	Cube	Have	0.61 micron	Dye-1	Reference examples
B(242)	B-42	Cube	Have	0.61 micron	S-12	Reference examples	B(243)	B-43	Cube	Have	0.61 micron	S-26	Reference examples
B(244)	B-44	Cube	Have	0.61 micron	S-32	Reference examples	B(243)	B-43	Cube	Have	0.61 micron	S-26	Reference examples
B(244)	B-44	Cube	Have	0.61 micron	S-32	Reference examples	B(251)	B-51	{ the dull and stereotyped particle of 100}	Have	0.46 micron	Dye-1	Reference examples
B(252)	B-52	”	Have	0.46 micron	S-12	Reference examples	B(251)	B-51	{ the dull and stereotyped particle of 100}	Have	0.46 micron	Dye-1	Reference examples
B(252)	B-52	”	Have	0.46 micron	S-12	Reference examples	B(253)	B-53	”	Have	0.46 micron	S-26	Reference examples
B(254)	B-54	”	Have	0.46 micron	S-32	Reference examples	B(253)	B-53	”	Have	0.46 micron	S-26	Reference examples

Carried out similarly to Example 1 estimating 1 and 2, the B light sensitivity of obtaining sample B (211) is relative sensitivity=S of 100 o'clock _{10 ℃ of 30%RH}, Δ S _{(35 ℃-10 ℃)}With gray shade scale variation factor Δ γ (γ (b)/γ (c)), be shown among the table 5.

As in the table 5 shown in the result, sample B of the present invention (232), B (233) and B (234), the light sensitivity height, the variation of exposure environment temperature is shown stable, even and the also rare variation of gray shade scale in processing variation, can obtain stable printing.

Table 5

The sample name	????S _10℃30％RH	????ΔS _{(35℃-10℃)}	????Δγ	Remarks
The sample name	????S _10℃30％RH	????ΔS _{(35℃-10℃)}	????Δγ	Remarks	B(211)	????100	????0.17	????1.05	Reference examples
B(212)	????75	????0.10	????1.25	Reference examples	B(211)	????100	????0.17	????1.05	Reference examples
B(212)	????75	????0.10	????1.25	Reference examples	B(213)	????60	????0.11	????1.15	Reference examples
B(214)	????92	????0.09	????1.20	Reference examples	B(213)	????60	????0.11	????1.15	Reference examples
B(214)	????92	????0.09	????1.20	Reference examples	B(221)	????170	????0.16	????1.05	Reference examples
B(222)	????120	????0.11	????1.28	Reference examples	B(221)	????170	????0.16	????1.05	Reference examples
B(222)	????120	????0.11	????1.28	Reference examples	B(223)	????110	????0.12	????1.22	Reference examples
B(224)	????150	????0.10	????1.25	Reference examples	B(223)	????110	????0.12	????1.22	Reference examples
B(224)	????150	????0.10	????1.25	Reference examples	B(231)	????175	????0.13	????1.28	Reference examples
B(232)	????180	????0.02	????1.02	The present invention	B(231)	????175	????0.13	????1.28	Reference examples
B(232)	????180	????0.02	????1.02	The present invention	B(233)	????175	????0.01	????1.03	The present invention
B(234)	????176	????0.02	????1.02	The present invention	B(233)	????175	????0.01	????1.03	The present invention
B(234)	????176	????0.02	????1.02	The present invention	B(241)	????303	????0.04	????1.28	Reference examples
B(242)	????315	????0.02	????1.32	Reference examples	B(241)	????303	????0.04	????1.28	Reference examples
B(242)	????315	????0.02	????1.32	Reference examples	B(243)	????310	????0.03	????1.30	Reference examples
B(244)	????310	????0.02	????1.28	Reference examples	B(243)	????310	????0.03	????1.30	Reference examples
B(244)	????310	????0.02	????1.28	Reference examples	B(251)	????290	????0.05	????1.33	Reference examples
B(252)	????293	????0.05	????1.43	Reference examples	B(251)	????290	????0.05	????1.33	Reference examples
B(252)	????293	????0.05	????1.43	Reference examples	B(253)	????290	????0.03	????1.45	Reference examples
B(254)	????292	????0.03	????1.38	Reference examples	B(253)	????290	????0.03	????1.45	Reference examples

Embodiment 3

Use sample B (111)～B (154) and B (211)～B (254), can cross laser scanning exposure and form image.

As LASER Light Source, used following light source: utilize LiNbO with reversal zone structure ₃The SHG crystal, to the YAG solid state laser (resonance wavelength 946nm) of semiconductor laser GaAlAs (resonance wavelength 808.5nm), carry out the 473nm light that penetrates behind the wavelength conversion as excitation source; Utilization has the LiNbO of reversal zone structure ₃The SHG crystal, to the YVO of semiconductor laser GaAlAs (resonance wavelength 808.7nm) as excitation source ₄Solid state laser (resonance wavelength 1064nm) carries out the 532nm light that penetrates behind the wavelength conversion; And AlGaInP (resonance wave is about 680nm, and Panasonic's electricity produces the No.LN9R20 type of making).Every kind of three kinds of color laser beam all by polygonal mirror with respect to the direction of scanning vertical moving, successively sample is carried out scan exposure.By utilizing the Pei Erdi element that temperature is remained on the certain value, the light quantity that can suppress to be taken place by the temperature of semiconductor laser changes.The diameter of efficient beam is 80 microns, and sweep span is 42.3 microns (600dpi), and the mean exposure time of each pixel is 1.7 * 10 ^-7Second.

Replace behind the above-mentioned laser scanning exposure with sensitometer and similarly to Example 1 coating sample B (111)～B (154) to be estimated, estimate similarly to Example 2 after sample B (211)～B (254) also replaces above-mentioned laser scanning exposure with sensitometer being coated with, found that and the coming to the same thing of embodiment 1 and 2, sample of the present invention is the emulsion of ISO, the dependence that temperature variation during for exposure and treating fluid change is little, also is suitable for adopting the image of laser scanning exposure to form operation.

According to the present invention, also can obtain stable photographic property usually under the situation about handling that exceeds the speed limit, can obtain a kind of silver halide colour photographic sensitive material that is particularly suitable for colour printing.

Claims

1. silver halide colour photographic sensitive material, be on support, to have by the silver halide emulsion layer of each one deck displaing yellow sense indigo plant at least, the silver halide emulsion layer that shows the green property of pinkish red color sensation, the silver halide colour photographic sensitive material that shows the silver halide emulsion layer of the red property of cyan sense and the photo formation layer that non-photosensitive hydrophilic colloid layer constitutes, it is characterized in that in the silver halide emulsion layer of this displaing yellow sense indigo plant, it is above and contain the silver emulsion of 0.02～1 mole of % silver iodide to contain silver chloride content and be 90 moles of %, this silver emulsion is that { cube of 100} face or 14 body crystal grain constitute having below 0.51 micron by the cube length of side, and implemented optical sensibilization by at least a sensitizing coloring matter of following general formula (I) expression

General formula (I)

[changing 1]

In the general formula (I), X ¹And X ²Independent separately expression oxygen atom, sulphur atom, selenium atom, tellurium atom, nitrogen-atoms, carbon atom; Y ¹Expression can also can have substituent furan nucleus, pyrrole ring, thiphene ring or phenyl ring with other 5～6 Yuans carbocyclic rings or heterocycle condensation; Y ²Expression forms phenyl ring or 5～6 Yuans atom groups that unsaturated heterocycle is required, can further also can have substituting group with other 5～6 Yuans carbocyclic rings or heterocycle condensation; Also has Y ¹And Y ²Key between two carbon atoms that ring contracts can be singly-bound or two key; R ¹And R ²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group; L ¹, L ²And L ³Independent separately expression methine, n ¹Expression 0; M ¹The expression counterion, m ¹In the expression and molecule in the required numeral more than 0 of electric charge.

2. according to the described silver halide colour photographic sensitive material of claim 1, it is characterized in that described sensitizing coloring matter by general formula (I) expression, by under remember general formula (II) or (III) expression,

General formula (II)

[changing 2]

In the general formula (II), Y ¹¹Expression oxygen atom, sulphur atom or N-R ¹³, R ¹³Expression hydrogen atom or alkyl; V ¹⁵And V ¹⁶Independent separately expression hydrogen atom or monovalence substituting group; X ¹¹And X ¹²Independent separately expression oxygen atom or sulphur atom; R ¹¹And R ¹²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group; V ¹¹, V ¹², V ¹³And V ¹⁴Independent separately expression hydrogen atom or monovalence substituting group; M ^11-The expression counterion, m ¹¹In the expression and molecule in the required numeral more than 0 of electric charge;

General formula (III)

[changing 3]

In the general formula (III), Y ²¹Expression oxygen atom, sulphur atom or N-R ²³, R ²³Expression hydrogen atom or alkyl; V ²⁵And V ²⁵Independent separately expression hydrogen atom or monovalence substituting group; X ²¹And X ²²Independent separately expression oxygen atom or sulphur atom; R ²¹And R ²²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group; V ²¹, V ²², V ²³And V ²⁴Independent separately expression hydrogen atom or monovalence substituting group; M ²¹The expression counterion, m ²¹In the expression and molecule in the required numeral more than 0 of electric charge.

3. according to the described silver halide colour photographic sensitive material of claim 1, it is characterized in that described sensitizing coloring matter by general formula (I) expression, by under remember general formula (IV) expression,

General formula (IV)

[changing 4]

In the general formula (IV), X ³¹And X ³²Independent separately expression oxygen atom or sulphur atom; R ³¹And R ³²In the alkyl that replaced by the acidic group beyond the sulfo group of expression, the alkyl that another expression is replaced by sulfo group; V ³¹, V ³², V ³³, V ³⁴, V ³⁵, V ³⁶, V ³⁷And V ³⁸Independent separately expression hydrogen atom or monovalence substituting group, two adjacent substituting groups also can be connected to each other the formation condensed ring; M ³¹The expression counterion, m ³¹In the expression and molecule in the required numeral more than 0 of electric charge.

4. according to any one described silver halide colour photographic sensitive material in the claim 1～3, it is characterized in that the silver coating total amount is in 0.2g/m in the described photo formation layer ²More than, 0.5g/m ²Below.

5. according to any one described silver halide colour photographic sensitive material in the claim 1～4, it is characterized in that coating gelatin total amount is in 3g/m in the described photo formation layer ²More than, 6g/m ²Below.

6. a coloured image formation method is characterized in that utilizing the light beam of modulating according to image information to after any one described silver halide colour photographic sensitive material enforcement scan exposure in the claim 1～5, carries out development treatment.

7. a coloured image formation method is characterized in that any one described silver halide colour photographic sensitive material in the claim 1～5, handles under colour developing is condition below 20 seconds the development treatment time.