CN101023393A - Photosensitive material for silver halide color photograph - Google Patents

Abstract

The invention provides a silver halide chromophotograph sensitive material, which comprises at least a red sensitive silver halide emulsion layer, at least a green sensitive silver halide emulsion layer and at least a blue sensitive silver halide emulsion layer on a carrier. The silver halide chromophotograph sensitive material is characterized in that the silver halide emulsion layer comprises silver chloride accounting for 90 percent by mol or silver halide emulsion accounting for more. The silver halide emulsion comprises at least one selenium compound. The characteristic curve of the silver halide emulsion layer containing the silver halide emulsion satisfies the following condition (1): the relational expression (1) the ratio of Gamma H to Gamma L is less than or equal to 2.0 and more than or equal to 0.5. In the condition, Gamma indicates the slope of the characteristic curve; Gamma H indicates a slope under the exposure per 1*10<-6> second; Gamma L indicates a slope under the exposure of 100 seconds.

Description

Be used for silver halide color photographic photosensitive material

Technical field

The present invention relates to silver halide colour photographic sensitive material.Particularly, the present invention relates to the printing silver halide colour photographic sensitive material that when in the exposure of high intensity of illumination, can guarantee hard contrast and be suitable for the digit explosure system, and further relate to and be suitable for the printing silver halide colour photographic sensitive material that rapid processing also can provide the white background of high-quality.

In addition, the present invention relates to be particularly suitable for the silver halide colour photographic sensitive material of rapid processing, further relate to the silver halide colour photographic sensitive material that small performance change takes place owing to the processing conditions fluctuation.

Further, the present invention relates to be suitable for the silver halide colour photographic sensitive material of digit explosure and rapid processing, relate in particular to silver halide colour photographic sensitive material with ISO; This photosensitive material can reduce the color and high gray density of high saturation color, and guarantees inhomogeneous reduction.

In addition, the present invention relates in the rapid processing process, provide the silver halide colour photographic sensitive material of high quality graphic.

Background technology

Silver halide photographic sensitive material also refers to photographic silver halide material hereinafter, has been widely used as the cheap material that high quality graphic can be provided.In recent years, also popularized digitizing greatly in the colored printing field of using silver halide photographic sensitive material.For example,---print directly---with traditional analogue exposure that compare, the widespread use of the digit explosure by laser scanning exposure has had dramatic growth by the color negative film of color printer from processing.The characteristics of digit explosure are, obtain high-quality photos by carrying out image processing, and it has vital role for utilizing silver halide colour photographic sensitive material to improve photographic quality.In addition, because digital camera is popular, obtains high-quality photochrome easily from electric signal recording materials and also be considered to a key factor.Under this environment, digit explosure will be more universal.

On the other hand, printing technology comprises that ink jet printing, dye sublimation printing and electrophotographic color printer art have developed into the level that the photographic quality that is comparable to photograph is provided separately, and is recognized as the colored printing system.Compare with these competitive print systems, use the advantage of the print system of silver halide colour photographic sensitive material and digit explosure to be high image quality, high yield, and the high color fastness of image guarantees.Therefore, expectation further develops these advantages, and high quality printing service with low cost is provided at short notice.

For example, if one-stop (one-stop) of photochrome service becomes possibility, it is the recording medium that sales counter accepts to contain the Digital photographic machine data, finish the printing of recording medium in the very short turnaround time, in several minutes, return high-quality photo when client returns recording medium, like this, the advantage of the photochrome of use silver halide colour photographic sensitive material will the further increase than past.In addition, if further improve the rapid processing adaptability of silver halide colour photographic sensitive material, can dwindle the size of process equipment, thereby obtain the printing equipment of throughput rate height and while small inexpensive, the one-stop service of photochrome is expected to further expand like this.

In addition, shorten in recent years and the demand of accelerating process increases.The purpose of this demand is further to boost productivity, this just color photographic paper color photo paper carry out the photo printing system and be better than one of advantage of other colored printing system such as ink-jet and dye sublimation system.

Therefore, need study silver halide colour photographic sensitive material, comprise and shorten the time shutter, shorten time lapse (so-called latent image time), the drying time after shortening process time and shortening processing from end exposure to the beginning of developing from all angles.In order to shorten these time, various suggestions have been proposed so far.

The silver emulsion that is used for silver-halide color printing photographic material must satisfy above-mentioned various requirement.As the halogenation composition, use the silver emulsion (being also referred to as " being rich in silver chloride emulsion ") of high-silver chloride content to be used to adapt to the needs of rapid processing.In addition, the known emulsion grain size (being also referred to as " particle diameter ") that reduces in the silver emulsion can be accelerated developing powder, and relevant therewith technology open (referring to, the 2004 Autumn Convention of The Society of Photographic Science and Technology ofJapan abstracts of a thesis (20-21 page or leaf) for example).But the reducing of emulsion grain size also can make light sensitivity reduce, and causes reaching the problem of the required light sensitivity of digit explosure system.In this case, just need to increase the technology that is rich in photosensitivity of silver chloride emulsion.

In recent years, the technology of utilizing the chemical sensitization of selenium (Se) compound to be used for increasing photograph color sensitive material light sensitivity be widely known to and adopt.But therefore the well-known increase that is to use selenium compound easily to cause photographic fog is also studied the technology of improving this situation.

But when using color negative film as recording materials, the Maas gram density in the time of can passing through printing increases the increase calibration basically of misty grey too to some extent even work as silver emulsion photographic fog (fogging).On the other hand, when doing to observe material with colour reversal film, the photographic fog of silver emulsion can cause the reduction of maximal density (Dmax), owing to the image forming method that adopts, and makes minor alteration not obvious substantially herein.

Opposite with above-mentioned situation, the increase of silver emulsion photographic fog can cause the color contamination of white background area, with regard to colored printing photo material, is example with the colour paper, will become open defect.All can cause serious mass loss even the photographic fog increase is very little.In other words, need guarantee the high quality white background of colored printing photo material after making and after standing storage.Equally, in addition they when being carried out rapid processing, also need not increase photographic fog.Therefore when selenium compound when the rich silver chloride emulsion that is intended to be used for silver-halide color printing photographic material uses, just need antifog strongly.

Because iodine silver bromide emulsion is widely used in the photograph color sensitive material, therefore use the antifog technology of selenium compound also to be limited within those disclosed technology in emulsion field.In addition, these technical deficiencies are to satisfy aforesaid tight demand.

Recently, people study the compatibility of utilizing rich silver chloride emulsion and selenium compound to obtain between digit explosure and rapid processing.When carrying out high intensity of illumination exposure or laser scanning exposure, provide and guarantee ISO and hard contrast, even when rapid processing, the emulsion technology that the photographic fog of reduction and high quality white background are provided is at JP-A-2003-287838 (" JP-A " be meant unexamined disclosed Japanese patent application) in open.Though the document has been pointed out after making color silver halide photographic-material the improvement effect of sensitization photographic fog at once, after depositing, how to improve not mentioned hypothesis photosensitive material the problem of stability.In addition, the document has also been described exposure in 10 seconds and 10 ^-4The contrast (gradation) of exposure second, but represent with the relative value of standard sample.Therefore, this is described and is not had to the present invention with any enlightenment.

Though JP-A-4-335336 and JP-A-4-335338 have described exposure in 10 seconds and 10 ^-2The contrast of exposure second, its technology openly relate separately to improves pressure characteristic and latent image stability, but they do not relate to photographic fog.

JP-A-6-308652 relates to improvement stability, and discloses the technology that reduces with the aging sensitization photographic fog that occurs.Though it has described laser scanning exposure, do not illustrate with regard to its influence to contrast.In addition, mentioned rapid processing, but also unexposed among the embodiment.

The silver emulsion that uses in the autochromy printing paper is the silver emulsion of high-silver chloride content, to satisfy the needs of rapid processing.Though the photochromics of high-silver chloride content is particularly suitable for rapid processing, their shortcoming is that light sensitivity is low and be difficult to chemical sensitization and optical sensibilization, and the gained light sensitivity is unstable and form the sensitization photographic fog easily.In addition, knownly can further improve the rapid processing applicability by the silver emulsion that utilizes low particle size.But for spectral sensitization emulsion, the surface area of its light sensitivity and silver halide particle is proportional, and the particle size that therefore reduces silver halide will obviously reduce light sensitivity.Therefore, in order to improve the applicability of rapid processing, just need further to increase light sensitivity.

For the high illumination reciprocity rate of improving silver chloride emulsion lost efficacy and obtained hard contrast (hardgradation) under high illumination, known can be in emulsion admixture iridium.Yet, latent image sensitizing will take place in the short time in the known silver chloride emulsion that contains iridium after exposure, JP-B-7-34103 (" JP-B " be meant the open text of Jap.P. after the examination) the location phase by the high bromide sliver content of preparation is disclosed, and admixture iridium and latent image sensitizing problem is resolved.Though the silver emulsion by this method preparation possesses ISO and hard contrast, and even work as them and under high relatively intensity of illumination, expose a period of time as 1/100 second, latent image sensitizing problem can not take place yet, in case found to be intended to use in the digit explosure system of laser scanning exposure high when the exposure of 1 μ superelevation second intensity of illumination keeps ISO down, the trend that can cause their to form hard contrast reduces.

U.S. Patent number 5,783,373 and 5,783,378 disclose the method for intensifying, and it uses at least three kinds of adulterants to be used to reduce high illumination reciprocity rate inefficacy.But the acquisition of hard contrast is owing to used the adulterant that has the desensitization function and intensify function.Therefore, this method can not fundamentally improve light sensitivity.

As mentioned above, the autochromy printer paper also requires further to improve light sensitivity.For the light sensitivity of the emulsion that improves high-silver chloride content, chemical sensitization method and the method that forms the silver emulsion particle various improvement have been carried out.As the representative of chemical sensitization silver emulsion, developed various sensitization methods, comprise sulphur sensitizing, selenium sensitizing, tellurium sensitizing, noble metal sensitizing such as golden sensitizing, the combination of reduction sensitization and these process for increasing sensitivity.

Mention the selenium sensitizing in those process for increasing sensitivity especially, known seleno carboxylate, promptly the seleno ester can be used as the selenium sensitizer (as at U.S. Patent number 3,297,446 and 3,297,447 and JP-B-57-22090 in).Generally speaking, selenium sensitizing can produce the sensitizing effect bigger than sulphur sensitizing in the photograph industry, but selenium sensitizing tends to cause photographic fog and low contrast.Therefore, selenium sensitizing and be not suitable for the autochromy printer paper.

Though disclosed so far most of patents help to improve this defective, do not have to solve and the relevant photographic fog problem of processing factors variation.Enlarged color photograph shop on the market replenishes speed at soup sometimes not always under satisfied processing solution management, pH sets, and processing temperature and wash conditions depart under the condition of its right value separately carries out photo processing.Especially when carrying out selenium sensitizing, the variation of processing temperature and processing pH just becomes serious problem, when bleach-fixing liquid is sneaked into colour developing solution, can cause the variation of photographic fog, and the photographic quality that is processed into depends on this to a great extent.

Concerning the autochromy printer paper, guarantee that the needed key property of high-quality colour photo is the color that can not only reproduce high saturation and low dullness, and can reproduce higher gray scale.The high saturation of reproducing colors makes it may express fresh and alive tone, reproduces high gray density and makes it may express far-reaching fluoroscopy images.As long as the autochromy printer paper possesses the ability of the color that reproduces low dullness and high saturation, can process and finish by carrying out image on computers than the color of low saturation.On the contrary, if the autochromy printer paper does not possess the ability of reproducing the high saturation color, the color than high saturation just can not reproduce so.Because gray image is made by develop simultaneously yellow, magenta and cyan, therefore make the higher gray density of reproduction become possibility by the color density that improves each development.

We discover, can improve light sensitivity under the rapid processing really though implement selenium sensitizing, in some cases, can manifest inhomogeneous in the photograph that obtains, or color saturation reduces, or Fog density reduces.

In the autochromy printer paper, use the silver emulsion that least is easy to fogged to be suitable for expressing beautiful color white.Though selenium sensitizing can manifest according to the bigger sensitizing effect of the sulphur sensitizing of carrying out in the phase industry, selenium sensitizing is not suitable for the autochromy printer paper, because it can cause the photographic fog of certain degree and be easy to increase low contrast.In addition, be used in combination selenium sensitizing and golden sensitizing can significantly improve light sensitivity, but simultaneously, also can cause photographic fog significantly to improve and strengthen with low contrast.Therefore, strong expectation exploitation can be guaranteed the selenium sensitizing that photographic fog reduces and contrast strengthens.

In the faster processing of active demand in recent years, give rapid processing the adaptability of sensitive photographic material is tended to cause the color dimness of developing.The strong request of flexibility (adaptability) of operation is arranged in addition, always.Therefore, need further to improve these abilities strongly.

In the situation of many sensitive photographic materials of processing, require first print quality identical with last.On the other hand, sometimes, the problem that selenium sensitizing sensitive photographic material can cause printing repeatability or operation flexibility (adaptability) of operation takes place.Therefore, need to improve the operation flexibility (adaptability) of operation.

According to the type of used yellow colour former, the difference of the scale that emulsion is made (it is represented the amount of emulsion manufacturing and expresses with silver-colored molar content) may cause the situation of light sensitivity difference.Common sense can cause the difference of photo reductibility for the light sensitivity difference that is caused by emulsion manufacturing scale difference.

Of the present invention other will show from following description more fully with more feature and advantage.

Summary of the invention

According to the present invention, provide following manner:

(1) a kind of silver halide colour photographic sensitive material, it has at least one red sensing coppering silver emulsion layer, at least one green silver halide emulsion layer on carrier and at least one feels blue silver halide emulsion layer, be characterised in that wherein it is 90 moles of % or higher silver emulsion that at least one silver halide emulsion layer contains silver chloride content, this silver emulsion contains at least a selenium compound, and the family curve that contains the silver halide emulsion layer of silver emulsion satisfies following relational expression (1);

Relational expression (1) 2.0 〉=γ _H/ γ _L〉=0.5

γ characterization slope of a curve wherein, γ _HExpression 1 * 10 ^-6Slope and γ under exposure second _LRepresent 100 seconds slopes under the exposure.

(2) (1) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium-containing compound further comprises the metal complex of at least a following formula (D1) expression;

Formula (D1)

[M ^D1X ^D1 _n1L ^D1 _(6-n1)] ^m1

Wherein in formula (D1), M ^D1Expression Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt; X ^D1The expression halide ion; L ^D1Expression is different from X ^D1Part; n ₁Expression 3,4,5, or 6; And m ₁Be the electric charge and the expression 4-of metal complex, 3-, 2-, 1-, 0, or 1+; A plurality of X ^D1Can be identical or different; As a plurality of L ^D1When existing, a plurality of L ^D1Can be identical or different; Condition is not contain or only contain a cyano group (CN as part by the metal complex that formula (D1) is represented ^-) ion.

(3) (1) or (2) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium-containing compound further comprises the metal complex of at least a following formula (D2) expression;

Formula (D2)

[IrX ^D2 _n2L ^D2 _(6-n2)] ^m2

Wherein in formula (D2), X ^D2Expression halide ion or except cyanic acid ion OCN ^-Pseudohalogen in addition (pseudohalogen) ion; L ^D2Expression is different from X ^D2Part; n ₂Expression 3,4, or 5; m ₂Be the electric charge and the expression 4-of metal complex, 3-, 2-, 1-, 0, or 1+; A plurality of X ^D2Can be identical or different; And as a plurality of L ^D2When existing, a plurality of L ^D2Can be identical or different.

(4) any one described silver halide colour photographic sensitive material in above-mentioned (1) to (3), the wherein said silver emulsion that contains selenium compound comprise that average ball equivalent particle size is 0.65 μ m or following silver halide particle.

(5) any one described silver halide colour photographic sensitive material in above-mentioned (1) to (4), wherein the total coating weight of silver is 0.2g/m ²To 0.5g/m ²

(6) any one described silver halide colour photographic sensitive material in above-mentioned (1) to (5), wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

(7) a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye forms (cyan-dye-forming) colour coupler, at least one contains the silver halide emulsion layer that rosaniline dyes forms (magenta-dye-forming) colour coupler, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld forms (yellow-dye-forming) colour coupler, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer contains selenium sensitizing is 90 moles of % or higher silver emulsion, and at least one contains the colour coupler that silver halide emulsion layer that weld is formed into toner contains at least a following formula (Y) expression;

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl; R ₂The expression alkyl, naphthenic base, acyl group or aryl; R ₃The expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, the alkane sulfonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl, or imino group; M represents 0 or 1 to 4 integer; Z ₁Expression-O-or-NR _A-; Z ₂Expression-NR _B-or-C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _DRepresent hydrogen atom or substituting group independently of one another.

(8) a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld is formed into toner, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer comprises (1) the selenium sensitizing crown ether that to be 90 moles of % or higher silver emulsion and (2) condense with at least a aromatic rings.

(9) a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld is formed into toner, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer comprises (1) selenium sensitizing is 90 moles of % or higher silver emulsion, (2) crown ether that condenses with at least a aromatic rings, in addition, at least one contain silver halide emulsion layer that weld is formed into toner contain at least a before the colour coupler of formula (Y) expression.

(10) any one described silver halide colour photographic sensitive material in above-mentioned (7) to (9), wherein the silver emulsion of selenium sensitizing further comprises at least two kinds of compounds that the argent cocooning tool had oxidation.

(11) any one described silver halide colour photographic sensitive material in above-mentioned (7) to (10), wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

(12) any one described silver halide colour photographic sensitive material in above-mentioned (7) to (11), wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

(13) a kind of silver halide colour photographic sensitive material, it has at least one and contains the silver halide emulsion layer that cyan dye is formed into toner on the reflection carrier, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that weld is formed into toner, is characterised in that the silver chloride content that at least one silver halide emulsion layer that contains dye forming coupler comprises selenium sensitizing is 90 moles of % or higher silver emulsion; By only will contain weld be formed into toner the layer in silver emulsion carry out 1 * 10 ^-4Processing is developed in second exposure then and the maximal density (DYmax) of the yellow of the development that obtains is 1.90-2.30; By only will contain rosaniline dyes be formed into toner the layer in silver emulsion carry out 1 * 10 ^-4Processing is developed in second exposure then and the maximal density (DMmax) of the magenta of the development that obtains is 1.95-2.30; By only will contain cyan dye be formed into toner the layer in silver emulsion carry out 1 * 10 ^-4Processing is developed in second exposure then and the maximal density (DCmax) of the cyan of the development that obtains is 1.85-2.40; By with all silver halide emulsion layers that contains dye forming coupler in 1 * 10 ^-4Exposure under second, the maximal density (DGYmax) of the yellow of the development of developing processing then and obtaining, the maximal density (DGCmax) of the cyan of the maximal density (DGMmax) of the magenta of developing and development is respectively 2.10-2.40,2.30-2.70 and 2.10-2.45; And at 25 ℃, during relative humidity 20% time, the sensitive photographic material crimpness is-15 to+15.

(14) (13) described silver halide colour photographic sensitive material, wherein cyan dye is formed into toner, and rosaniline dyes is formed into toner and weld is formed into the total amount of toner and is 1.1g/m ²Or below.

(15) (13) or (14) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE1) is represented;

Formula (SE1)

Wherein in formula (SE1), M ¹And M ²Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl or carbamyl; Q represents alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OM ³, or NM ⁴M ⁵M ³, M ⁴, and M ⁵Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; M ¹, M ²Can be combined together to form ring structure with any two groups among the Q.

(16) (13) or (14) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE2) is represented;

Formula (SE2)

X wherein ¹, X ²And X ³Represent alkyl independently of one another, alkenyl, alkynyl, aryl, heterocyclic radical, OJ ¹, or NJ ²J ³J ¹, J ²And J ³Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical.

(17) (13) or (14) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE3) is represented;

Formula (SE3)

E ¹-Se-E ²

E wherein ¹And E ²Can be identical or different, represent alkyl independently of one another, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, alkoxy carbonyl group, aryloxycarbonyl or carbamyl.

(18) (13) or (14) described silver halide colour photographic sensitive material, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (PF1) to (PF6) is represented.

Formula (PF1)

Formula (PF2)

Formula (PF4) formula (PF3)

Formula (PF5) formula (PF6)

[Q ²¹……Au…(Q ²²) _n ²³]J ²¹

Wherein, in formula (PF1), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²¹Expression O, S or NR ²⁴R ²¹To R ²⁴Represent hydrogen atom or substituting group separately; And R ²³Can with R ²¹Or R ²²Form 5 to 7 yuan of rings;

Wherein, in formula (PF2), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; X ²¹Expression O, S or NR ²⁵Y ²¹The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹R ²⁵To R ²⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; And X ²¹And Y ²¹Can interosculate and form ring;

Wherein, in formula (PF3), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; R ²¹⁰, R ²¹¹And R ²¹²Represent hydrogen atom or substituting group independently of one another, R ²¹⁰And R ²¹¹At least one represents electron withdraw group;

Wherein, in formula (PF4), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; W ²¹The expression electron withdraw group; R ²¹³To R ²¹⁵Represent hydrogen atom or substituting group separately; W ²¹And R ²¹³Formation ring texture alternatively mutually combines;

Wherein, in formula (PF5), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²²Expression O, S, Se or NR ²¹⁹R ²¹⁶The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical or acyl group; R ²¹⁷To R ²¹⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; Z ²¹The expression substituting group; n ²²The integer of expression 0 to 4; And work as n ²²Be 2 or when bigger, Z ²¹Can be mutually the same or different;

Wherein, in formula (PF6), Q ²¹And Q ²²Expression is selected from the selenium sensitizer compound of formula (SE1) to (SE3), Q ²¹And Q ²²In selenium atom and Au form coordination bond; n ²³Expression 0 or 1; And J ²¹The expression balance anion; Work as n ²³Be 1 o'clock, Q ²¹And Q ²²Can be identical or different; Condition is arbitrary compound that the compound of formula (PF6) expression does not comprise formula (PF1) to (PF5) expression.

(19) each described silver halide colour photographic sensitive material in above-mentioned (13) to (18), wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

(20) each described silver halide colour photographic sensitive material in above-mentioned (13) to (19), wherein the total coating weight of silver is 0.2g/m ²To 0.5g/m ²

(21) a kind of silver halide colour photographic sensitive material, it has at least one and contains the silver halide emulsion layer that cyan dye is formed into toner on carrier, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that weld is formed into toner, be characterised in that at least one contains the silver halide emulsion layer that weld is formed into toner and comprises that (1) contains the silver chloride content of selenium sensitizing is 90 moles of % or higher, the average ball equivalent diameter of silver halide particle is 0.75 μ m or following silver emulsion, (2) at least a weld of following formula (Y) expression is formed into toner, and silver halide colour photographic sensitive material satisfy condition (a).

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl; R ₂The expression alkyl, naphthenic base, acyl group or aryl; R ₃The expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, alkane sulfonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl or imino group; M represents 0 or 1 to 4 integer; Z1 represents-O-or-NR _A-; Z ₂Expression-NR _B-or-C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _DRepresent hydrogen atom or substituting group independently of one another;

Condition (a): in spectral sensitivity distributes, have a peak at least in the 450-490nm scope, and provide 70% long wave of crest light sensitivity that spectral sensitivity distributes and the exposure wavelength difference between the shortwave at 20nm-100nm.

(22) (21) described silver halide colour photographic sensitive material wherein adds the sensitizing dye that at least a following formula (II) is represented;

Formula (II)

Wherein α 1, and α 2 and β 1 to β 4 represent hydrogen atom separately, alkyl, and alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl or carbamyl, and these groups can be substituted.

(23) (21) or (22) described silver halide colour photographic sensitive material, it is 25 ℃ of temperature, and the crimpness under the humidity 20% is-15 to+15.

(24) each described silver halide colour photographic sensitive material in above-mentioned (21) to (23), wherein at least one contains the silver halide emulsion layer that cyan dye is formed into toner, and/or at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner and comprises that the silver chloride content of selenium sensitizing is 90 moles of % or higher, and the average ball equivalent diameter of silver halide particle is 0.50 μ m or following silver emulsion.

Hereinafter, the first embodiment of the present invention comprises above-mentioned (1) to (6) described silver halide colour photographic sensitive material.

The second embodiment of the present invention comprises above-mentioned (7) to (12) described silver halide colour photographic sensitive material.

The third embodiment of the present invention comprises above-mentioned (13) to (20) described silver halide colour photographic sensitive material.

The fourth embodiment of the present invention comprises above-mentioned (21) to (24) described silver halide colour photographic sensitive material.

At this, unless otherwise indicated, the present invention includes all above-mentioned the first, the second, third and fourth embodiment.

Embodiment

Describe the present invention below.

In the present invention, as in the first embodiment of the present invention, γ representing characteristic slope of a curve, it is defined as follows.With conventional method, the silver halide emulsion layer of sensitization of all kinds is carried out its exposure respectively of color separately, after 30 minutes, carry out colour development processing.Then, with the corresponding spectral range of developing color tone of each layer in carry out density measure, thereby draw family curve.

For conventional colour paper, use the SP-1 wave filter, respectively to the blue-sensitive emulsion layer, green-sensitive emulsion layer or magenta-sensitive emulsion layer expose for SP-2 wave filter or SP-3 wave filter (trade name, photograph company of Fuji makes).In other words, exactly colour paper is carried out so-called blue independent exposure respectively, green independent exposure and red independent exposure.The exposure colour paper of gained was placed the processing of developing then 30 minutes.The yellow that forms on it with the optics densimeter measurement, the reflection density separately of magenta and cyan image, with reflection density (D) is ordinate, and the exposure of expressing with logarithmically calibrated scale (logE) is a horizontal ordinate, and the density data of gained is mapped and obtained the family curve of each color image.Wherein, yellow image is relevant with the family curve of blue-sensitive emulsion layer, and pinkish red image is relevant with the family curve of green-sensitive emulsion layer, and cyan image is relevant with the family curve of magenta-sensitive emulsion layer.

In each family curve of drawing, be defined as the sensitization photographic fog corresponding to the minimum density (Dmin) of unexposed portion.In addition, be that the inverse of the exposure of 0.5 some A is defined as light sensitivity S with density.In addition, be that 1.5 point is set at B with density, the slope of the straight line of tie point A and B is defined as slope γ.For exposure, carry out exposure in 100 seconds and 1 * 10 ^-6Exposure second, γ and S value defined that the conditions of exposure of front is measured down are γ _LAnd S _L, and γ and S value defined that the conditions of exposure of back is measured down are γ _HAnd S _H

In each silver halide colour photographic sensitive material of the present invention, preferably in first embodiment of the present invention, preferably need at least one silver halide emulsion layer to comprise that silver chloride content is 90 moles of % or higher silver emulsion, and need this silver emulsion to comprise at least a selenium compound, and the family curve that contains the silver halide emulsion layer of aforementioned silver emulsion satisfies following relational expression (1):

Relational expression (1) 2.0 〉=γ _H/ γ _L〉=0.5

Work as γ _H/ γ _LIn the time of not in this scope, the sensitization photographic fog will occur increases, and light sensitivity descends, and low contrast increases or stability reduces, so this just may be the situation that the present invention can not realize its effect.γ _H/ γ _LValue be preferably 0.75 or more than, more preferably 0.95 or more than, preferred especially 1.05 or more than.In addition, γ _H/ γ _LValue be preferably 1.8 or below, more preferably 1.6 or below.

In first embodiment of the present invention, the silver emulsion that uses in the photographic material contains specific silver halide particle, and the shape of this silver halide particle is not specifically limited.Yet, preferred particulates by have basically the 100} face cube ten four sides crystal grain (its summit can be rounded, and the high order face can be arranged), octahedral crystal particles or have by the 100} face or 111} face interarea, the aspect ratio formed be 3 or bigger plate-like particles form.Term used herein " aspect ratio " is meant the value that the diameter of a circle that equates with the particle projection area obtains divided by thickness.

In first embodiment of the present invention, the structure of preferred silver halide particle be have basically the 100} face cube or ten four sides crystal grains.

The photographic silver halide material of first embodiment of the invention requires to contain specific emulsion in its at least one silver halide emulsion layer.The specific emulsion of term be meant the silver chloride content of silver emulsion be 90 moles of % or more than, and comprise at least a selenium compound.

In first embodiment of the present invention, the silver chloride content of specific silver emulsion require be 90 moles of % or more than, from the rapid processing adaptable angle, preferred 94 moles of % or more than.From ISO and hard contrast angle, bromide sliver content is preferably 0.1 to 8 mole of %, more preferably 0.5 to 6 mole of %.Obtain the angle of ISO and hard contrast under the high illumination, agi content is preferably 0.02 to 1 mole of %, more preferably 0.05 to 0.50 mole of %, most preferably 0.07 to 0.40 mole of %.In first embodiment of the present invention, specific silver halide particle is preferably iodine bromine silver chloride particle, especially preferably has the iodine bromine silver chloride particle of above-mentioned halide compositions.

The silver halide particle that is used for the specific silver emulsion of first embodiment of the invention preferably has phase that contains silver bromide and/or the phase that contains silver iodide separately.At this, the meaning of term " phase that contains silver bromide " or " phase that contains silver iodide " is the content in the projecting zone of content of silver bromide or silver iodide wherein.The halogen that contains the phase of silver bromide or contain the phase of silver iodide is formed and the halogen of peripheral region (periphery) form can be continuously or rapid variation.What this contained the phase of silver bromide or contained silver iodide can be formed on the layer that has approximately constant concentration in the specific width of a certain position of particle mutually, and perhaps it can form the maximum point that does not have diffusion.Contain silver bromide mutually in local bromide sliver content be preferably 5 moles of % or bigger, more preferably 10 to 80 moles of %, most preferably 15 to 50 moles of %.Contain silver iodide mutually in local agi content be preferably 0.3 mole of % or bigger, more preferably 0.5 to 8 mole of %, most preferably 1 to 5 mole of %.This contain silver bromide or silver iodide mutually can a plurality of layers form be present in the particle, these can have silver bromide or the agi content that differs from one another mutually, comprise at least one phase that contains silver bromide and contain silver iodide mutually with at least one but be used for silver halide particle requirement of the present invention.

Be used for that the phase that contains silver bromide of silver halide particle of specific silver emulsion of first embodiment of the invention or the phase that contains silver iodide form with the form of layer separately and around the particle center, this point is very important.Preferred embodiment is that the form with layer forms around the phase that contains silver bromide of particle or the phase that contains silver iodide in each phase and circumferentially to have a uniform CONCENTRATION DISTRIBUTION at particle.Yet, form with the form of layer around the phase that contains silver bromide of particle or contain silver iodide mutually in, in the maximum point that silver bromide or silver iodide concentration circumferentially can be arranged of particle or smallest point to have CONCENTRATION DISTRIBUTION.For example, form phase that contains silver bromide that centers on particle or the phase time that contains silver iodide when emulsion grain has in the form with layer near particle surface, the silver bromide of grain edges angle part or silver iodide concentration can be different from the interarea of particle.In addition, except forming around the phase that contains silver bromide of particle with the form of layer or containing the phase of silver iodide, in addition not around the phase that contains silver bromide of particle or contain silver iodide can isolate the specific part that is present in particle surface mutually.

Include in the situation of phase of silver bromide at the silver halide particle of the specific silver emulsion that is used for first embodiment of the invention, the preferred described form with layer that contains silver bromide forms so that have the silver bromide of Cmax in granule interior.Equally, include the situation of the phase of silver iodide at the silver emulsion that is used for first embodiment of the invention, the preferred described form with layer that contains silver iodide forms so that have the silver iodide of Cmax on particle surface.From improving the littler silver bromide or the local concentration angle of agi content, represent with particle volume, this contain the phase of silver bromide or contain silver iodide mutually preferably by 3% to 30% silver amount, more preferably 3% to 15% silver amount is formed.

The phase that the silver halide particle that is used for the silver emulsion of first embodiment of the invention preferably includes silver bromide with contain silver iodide mutually.In this case, the phase that contains silver bromide with contain silver iodide mutually can the same position in particle on or on its diverse location, exist.Preferred these are present in diverse location mutually, and the preparation of this particle is controlled easily.What in addition, contain silver bromide can contain silver iodide mutually.What similarly, contain silver iodide can contain silver bromide mutually.Usually, the iodide that add during the high-silver chloride particle forms are easier to ooze out into particle surface than bromide, thus contain silver iodide be easier to mutually near particle surface, form.Therefore, when the phase that contains silver bromide with contain silver iodide be present in the diverse location of particle mutually the time, preferably contain comparing of silver bromide contain silver iodide in more inner formation.In this case, the near surface at particle can further provide the phase that contains silver bromide in addition in the phase outside of containing silver iodide.

Show effect of the present invention as obtaining ISO and realize required bromide sliver content or the agi content of hard contrast, separately along with in the phase that contains silver bromide of the more inner formation of particle or contain the phase of silver iodide and increase.This makes silver chloride content more than required reduction, causes damaging rapid processing adaptability.Therefore, come the sense of control light action, preferably contain the phase and the placement mutually located adjacent one another that contains silver iodide of silver bromide for the function of integrating near these phases the particle surface.From these viewpoints, the any position in 50% to 100% scope that begins to measure from particle volume inside of preferably containing silver bromide forms, and any position in 85% to 100% scope that begins to measure from particle volume inside of containing silver iodide forms.In addition, any position in 70% to 100% scope that begins to measure from particle volume inside of more preferably containing silver bromide forms, and any position in 90% to 100% scope that begins to measure from particle volume inside of containing silver iodide forms.

In order to introduce bromide ion or iodide ion are used for first embodiment of the invention with preparation the specific silver emulsion that comprises silver bromide or silver iodide, bromide salt or iodide salt solution can add separately, perhaps can add in conjunction with silver salt solution and perchloride salt solusion.Under latter event, bromide or iodide salt solution and perchloride salt solusion can separately add, and perhaps the mixture solution as these bromides or iodide and perchloride salt adds.Bromide or iodide salt add with the form of soluble-salt such as alkaline metal or alkaline earth metal bromide or iodide salt usually.Alternatively, as U.S. Patent number 5,389,508 is described, can introduce bromide or iodide ion by cracking bromide or iodide ion from organic molecule.As another kind of bromide or iodide ion source, can use meticulous silver bromide grain or meticulous silver iodide particle.

Silver emulsion in the color silver halide photographic-material of the second, the three or the 4th embodiment of the present invention contains silver halide particle, and the shape of this silver halide particle is not specifically limited.Yet, preferred particulates by have basically the 100} face cube ten four sides crystal grain (its summit can be rounded, and the high order face can be arranged), octahedral crystal particles or have by the 100} face or 111} face interarea, the aspect ratio formed be 3 or bigger plate-like particles form.Term used herein " aspect ratio " is meant the value that the diameter of a circle that equates with the particle projection area obtains divided by thickness.

In silver halide colour photographic sensitive material of the present invention, further preferred cube or ten four sides crystal grains.

Silver emulsion in second embodiment of the invention comprises silver chloride, silver chloride content be 90 moles of % or more than, the silver halide total content in the emulsion is decided to be 100 moles of %.From the rapid processing adaptable angle, silver chloride content be preferably 93 moles of % or more than, more preferably 95 moles of % or more than.In addition, the silver chloride of the preferred selenium sensitizing of silver chloride, selenium sensitizer are suc as formula the selenium compound of (SE1) to (SE3) expression, or the gold-selenium compound of formula (PF1) to (PF6) expression.In addition, the silver chloride that preferably is contained at least one silver halide emulsion layer is the silver chloride of selenium sensitizing, and the silver chloride that further preferably is contained in all silver halide emulsion layers is the silver chloride of selenium sensitizing.

In second embodiment of the present invention, preferred silver emulsion comprises silver bromide and/or silver iodide.From the angle of hard contrast with the latent image stability of excellence, bromide sliver content is preferably 0.1 to 7 mole of %, further preferred 0.5 to 5 mole of %.With regard to ISO and hard contrast under the high illumination exposure, agi content is preferably 0.02 to 1 mole of %, further preferred 0.05 to 0.50 mole of %, preferred especially 0.07 to 0.40 mole of %.

Further, preferred silver emulsion is an iodine bromine silver chloride emulsion, further preferably has the iodine bromine silver chloride emulsion that above-mentioned particular halide is formed.

In the silver emulsion in the color silver halide photographic-material of third embodiment of the invention, silver chloride content require be 90 moles of % or more than, guaranteeing rapid processing adaptability, preferred 93 moles of % or more than, further preferred 95 moles of % or more than.Bromide sliver content is preferably 0.1 to 7 mole of %, further preferred 0.5 to 5 mole of %.With regard to ISO and hard contrast under the high illumination exposure, agi content is preferably 0.02 to 1 mole of %, further preferred 0.05 to 0.50 mole of %, preferred especially 0.07 to 0.40 mole of %.Specific silver halide particle in the 3rd embodiment of the present invention is preferably iodine bromine silver chloride particle, further preferably has the iodine bromine silver chloride particle that above-mentioned particular halide is formed.

In the color silver halide photographic-material of four embodiment of the invention, from the adaptive angle of rapid processing, when the silver halide total content is decided to be 100 moles of %, the silver chloride content of silver emulsion require be 90 moles of % or more than, preferred 93 moles of % or more than, preferred especially 95 moles of % or more than.Though it can be pure silver chloride that silver halide is formed, and preferably includes more a spot of different halogenide, promptly more a spot of silver bromide and/or silver iodide.

In the color silver halide photographic-material of four embodiment of the invention, preferred silver emulsion has phase that contains silver bromide and/or the phase that contains silver iodide.When silver emulsion has the phase time that contains silver bromide, bromide sliver content is preferably 0.1 to 6 mole of %, further preferred 0.5-5 mole %, preferred especially 1-4 mole %.When silver emulsion has the phase time that contains silver iodide, agi content is preferably 0.01 to 1 mole of %, further preferred 0.05-0.5 mole %, preferred especially 0.1-0.4 mole %

In the present invention, silver halide particle preferably has phase that contains silver bromide and/or the phase that contains silver iodide.At this, the meaning of term " phase that contains silver bromide " or " phase that contains silver iodide " is the content in the projecting zone of content of silver bromide or silver iodide wherein.The halogen that contains the phase of silver bromide or contain the phase of silver iodide is formed and the halogen of peripheral region (periphery) form can be continuously or rapid variation.What this contained the phase of silver bromide or contained silver iodide can be formed on the layer that has approximately constant concentration in the specific width of a certain position of particle mutually, and perhaps it can form the maximum point that does not have diffusion.Contain silver bromide mutually in local bromide sliver content be preferably 5 moles of % or bigger, more preferably 10 to 80 moles of %, most preferably 15 to 50 moles of %.Contain silver iodide mutually in local agi content be preferably 0.3 mole of % or bigger, more preferably 0.5 to 8 mole of %, most preferably 1 to 5 mole of %.This contain silver bromide or silver iodide mutually can a plurality of layers form be present in the particle, these can have silver bromide or the agi content that differs from one another mutually, comprise at least a phase that contains silver bromide and contain silver iodide mutually with at least a but be used for silver halide particle requirement of the present invention.

In the present invention, when the phase that will contain silver bromide or contain silver iodide be added in the silver emulsion time, preferably should form with form of layer, center on each particle.Preferred embodiment is that the form with layer forms around the phase that contains silver bromide of particle or the phase that contains silver iodide in each phase and circumferentially to have a uniform CONCENTRATION DISTRIBUTION at particle.Yet, form with the form of layer around the phase that contains silver bromide of particle or contain silver iodide mutually in, in the maximum point that silver bromide or silver iodide concentration circumferentially can be arranged of particle or smallest point to have CONCENTRATION DISTRIBUTION.For example, form phase that contains silver bromide that centers on particle or the phase time that contains silver iodide when emulsion grain has in the form with layer near particle surface, the silver bromide of grain edges angle part or silver iodide concentration can be different from the interarea of particle.In addition, except forming around the phase that contains silver bromide of particle with the form of layer or contain the phase of silver iodide, other not around the phase that contains silver bromide of particle or contain silver iodide can isolate the specific part that is present in particle surface mutually.

In the present invention, comprise in the situation of the phase that contains silver bromide at silver emulsion, the preferred described form with layer that contains silver bromide forms so that have the silver bromide of Cmax in granule interior.Equally, include in the situation of phase of silver iodide at silver emulsion of the present invention, the preferred described form with layer that contains silver iodide forms so that have the silver iodide of Cmax on particle surface.From improve the angle of local concentration with littler silver bromide or agi content, represent with particle volume, this contain the phase of silver bromide or contain silver iodide mutually preferably by 3% to 30% silver amount, more preferably 3% to 15% silver amount is formed.

In the present invention, the preferred silver emulsion phase that includes silver bromide with contain silver iodide mutually.In this case, the phase that contains silver bromide with contain silver iodide mutually can the same position in particle on or on its diverse location, exist.Preferred these are present in diverse location mutually, and it is easy that granuloplastic control becomes.What in addition, contain silver bromide can contain silver iodide mutually.What alternatively, contain silver iodide can contain silver bromide mutually.Usually, the iodide that add during the high-silver chloride particle forms are easier to ooze out into particle surface than bromide, thus contain silver iodide be easier to mutually near particle surface, form.Therefore, when the phase that contains silver bromide with contain silver iodide be present in the diverse location of particle mutually the time, preferably contain comparing of silver bromide contain silver iodide in more inner formation.In this case, in the outside of the phase that contains silver iodide, the near surface of particle, can further provide another one to contain the phase of silver bromide.

Show effect of the present invention as obtaining ISO and realize required bromide sliver content or the agi content of hard contrast, separately along with particle more inner contain the phase of silver bromide or contain silver iodide phase formation and increase.This makes silver chloride content more than required reduction, causes damaging rapid processing adaptability.Therefore, come the sense of control light action, preferably contain the phase of silver bromide in order to integrate the function that near the particle surface these contain silver bromide or contain the phase of silver iodide.Therefore, the phase and the placement mutually located adjacent one another that contains silver bromide that preferably contain silver iodide.From these viewpoints, the any position in 50% to 100% scope that begins to measure from particle volume inside of preferably containing silver bromide forms, and any position in 85% to 100% scope that begins to measure from particle volume inside of containing silver iodide forms.In addition, any position in 70% to 95% scope that begins to measure from particle volume inside of more preferably containing silver bromide forms, and any position in 90% to 100% scope that begins to measure from particle volume inside of containing silver iodide forms.

In silver halide colour photographic sensitive material of the present invention, when silver emulsion has the phase time that contains silver bromide, another optimal way with silver emulsion of the phase that contains silver bromide is that wherein silver emulsion has the zone that bromide sliver content is 0.5 to 20 mole of % on the 20nm under the emulsion grain surface or the degree of depth still less.Here, preferably contain silver bromide be positioned on the 10nm under the emulsion grain surface or the degree of depth still less mutually and the content of silver bromide is 0.5-10 mole %, more preferably 0.5-5 mole %.In this case, not necessarily require to contain the form of taking layer mutually of silver bromide.Yet, come around emulsion grain in order to maximize the effect of silver halide colour photographic sensitive material of the present invention, be preferably formed the form of taking layer mutually that contains silver bromide.

In the present invention, so that silver emulsion comprises silver bromide or silver iodide, bromide salt or iodide salt solution can add separately in order to introduce bromide ion or iodide ion, perhaps can add in conjunction with silver salt solution and perchloride salt solusion.Under latter event, bromide or iodide salt solution and perchloride salt solusion can separately add, and perhaps the mixture solution as these bromides or iodide and perchloride salt adds.Bromide or iodide salt are usually with soluble-salt, as the form adding of alkaline metal or alkaline earth metal bromide or iodide salt.Alternatively, as U.S. Patent number 5,389,508 is described, can introduce bromide or iodide ion by cracking bromide or iodide ion from organic molecule.As another kind of bromide or iodide ion source, can use meticulous silver bromide grain or meticulous silver iodide particle.

The adding of bromide salt or iodide salt solution can concentrate in the primary particle forming process or can be during certain in carry out.In order to obtain to have the emulsion of ISO and low photographic fog, can limit the position that iodide ion is introduced perchloride emulsion.The particle iodide ion is introduced deeply more in the emulsion, and the light sensitivity increase is more little.Therefore, iodide salt solution is preferably introduced in 50% place or its outside of particle volume, more preferably introduces in 70% place or its outside of particle volume, most preferably introduces at 85% place or outside it.In addition, the adding of iodide salt solution is preferably in 98% place or its inboard of particle volume, and more preferably introduce 96% place or its inboard.When being added in particle surface inside and little by little finishing of iodide salt solution, can obtain to have the more emulsion of ISO and lower photographic fog.

On the other hand, the adding of bromide salt solution is preferably from 50% or the outside of particle volume, more preferably 70% or the outside begin.

By for example TRIFT II type TOF-SIMS equipment (trade name, by Phi Evans Co. preparation), according to etching/TOF-SIMS (flight time-secondary ion mass spectrometry) method, can measure the distribution of the bromide ion concentration and the iodide ion concentration of particle depth direction.The TOF-SIMS method is edited at NipponHyomen Kagakukai particularly, Hyomen Bunseki Gijutsu Sensho Niji Ion Shitsuryo Bunsekiho (Surface Analysis Technique Selection-Secondary Ion Mass Analytical Method), describe among the Maruzen Co., Ltd. (1999).When by etching/TOF-SIMS methods analyst emulsion grain, can analyze the iodide ion that oozes out to particle surface, although finish the inside that is added in particle of iodide salt solution.In the analysis of using etching/TOF-SIMS method, be preferred for emulsion of the present invention has Cmax on the surface of particle iodide ion, iodide ion concentration is inwardly successively decreased in particle, and bromide ion has Cmax in granule interior.Use the X-ray diffraction method can also measure the local concentration of silver bromide, as long as bromide sliver content is high extremely to a certain degree.

Silver emulsion in the preferred silver halide colour photographic sensitive material of the present invention is made up of the particle with monodisperse particles Size Distribution.In the silver emulsion that silver halide colour photographic sensitive material of the present invention comprises, the coefficient of alteration of the ball equivalent diameter of all emulsion grains be preferably 20% or below, more preferably 15% or below, preferred especially 10% or below.At this, the coefficient of alteration of ball equivalent diameter is expressed as the percent of the ball equivalent diameter standard deviation of single particle divided by the mean value of ball equivalent diameter.In order to obtain wide tolerance, preferably in one deck, use the potpourri of two or more above-mentioned single dispersion emulsions or in multilayer, be coated with two or more single emulsions that disperse and carry out.

Below, will the size of silver halide particle be described.

In the present invention, unless otherwise indicated, the particle diameter of silver halide particle is meant average ball equivalent diameter.Term ball equivalent diameter used herein is meant that each particle has the diameter of the ball of equal volume.

In first embodiment of the present invention, particle size length (length of side) expression that has the cubical limit of equal volume with this particle perhaps uses the diameter that has a ball of equal volume with this particle to represent.Be used for the preferably so-called single emulsion that disperses of emulsion of the color photographic material of first embodiment of the invention, promptly emulsion is made up of the single particle that disperses to distribute of particle size.The coefficient of alteration of the particle size of all particles in each silver emulsion be preferably 20% or below, more preferably 15% or below, further preferred 10% or below.The coefficient of alteration of particle size is expressed as the percent of the standard deviation of the length of side of single particle or ball equivalent diameter divided by the mean value of the length of side or ball equivalent diameter.In order to obtain wide tolerance, preferably in one deck, will singly disperse emulsion to use use with, or the single emulsion that disperses of coating carry out in having a plurality of layers of same color light sensitivity.

In first embodiment of the present invention, the ball equivalent diameter of the particle in the silver emulsion of selenium-containing compound is preferably 0.65 μ m or following, more preferably 0.6 μ m or following, further preferred 0.5 μ m or following, preferred especially 0.4 μ m or following.In addition, the lower limit of the ball equivalent diameter of silver halide particle is preferably 0.05 μ m, more preferably 0.1 μ m.Particle with ball equivalent diameter of 0.6 μ m is equivalent to the cubic granules that the length of side is about 0.48 μ m, particle with ball equivalent diameter of 0.5 μ m is equivalent to the cubic granules that the length of side is about 0.4 μ m, and the particle with ball equivalent diameter of 0.4 μ m is equivalent to the cubic granules that the length of side is about 0.32 μ m.

In second embodiment of the present invention, the ball equivalent diameter of the particle in the silver emulsion is preferably 0.6 μ m or following, more preferably 0.5 μ m or following, preferred especially 0.4 μ m or following.In addition, the lower limit of the ball equivalent diameter of silver halide particle is preferably 0.05 μ m, more preferably 0.1 μ m.

In the 3rd embodiment of the present invention, the ball equivalent diameter that contains the emulsion grain in the silver emulsion in the silver halide emulsion layer that weld is formed into toner is preferably 0.6 μ m or following, more preferably 0.5 μ m or following, preferred especially 0.4 μ m or following.The lower limit that is included in the ball equivalent diameter of the silver halide particle in arbitrary silver emulsion be preferably 0.05 μ m or more than, more preferably 0.1 μ m, further preferred 0.2 μ m.

Silver halide colour photographic sensitive material in the four embodiment of the invention has at least one and contains the silver halide emulsion layer that weld is formed into toner, and at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that cyan dye is formed into toner.The ball equivalent diameter that contains the silver halide particle in the silver halide emulsion layer that weld is formed into toner is 0.75 μ m (upper limit) or lower, preferred 0.68 μ m or lower, further preferred 0.60 μ m or lower, preferred especially 0.56 μ m or lower.Contain preferably 0.50 μ m (upper limit) or lower of ball equivalent diameter that rosaniline dyes is formed into the silver halide emulsion layer of toner or contains the silver halide particle in the silver halide emulsion layer that cyan dye is formed into toner, further preferred 0.40 μ m or lower, preferred especially 0.32 μ m or lower.In arbitrary silver emulsion, the lower limit of average ball equivalent diameter is 0.05 μ m, further preferred 0.1 μ m.

Particle with ball equivalent diameter of 0.6 μ m is equivalent to the cubic granules that the length of side is about 0.48 μ m, particle with ball equivalent diameter of 0.50 μ m is equivalent to the cubic granules that the length of side is about 0.40 μ m, particle with ball equivalent diameter of 0.40 μ m is equivalent to the cubic granules that the length of side is about 0.32 μ m, and the particle with ball equivalent diameter of 0.30 μ m is equivalent to the cubic granules that the length of side is about 0.24 μ m.

Silver emulsion in the silver halide colour photographic sensitive material of the present invention can comprise the silver halide particle that the ball equivalent diameter is the upper limit greater than its place layer respectively.Yet, in each layer, the silver halide particle of preferred spheres equivalent diameter between upper and lower bound (being generally 0.05 μ m) henceforth also is referred to as " at the last silver halide particle that is limited in the lower range ", account for the summation that constitutes all particle projection areas 50% or more.Further, preferably the last silver halide particle that is limited in the lower range account for the summation that constitutes all particle projection areas 80% or more, particularly 90% or more.The ball equivalent diameter of silver halide particle can be measured from the electron micrograph of silver halide particle, and calculates the ball equivalent diameter of silver halide particle from the cube length of side that has an equal volume with this silver halide particle.It is very many to measure quantity, and even the length of side of the silver halide particle of the remarkable quantity of statistics (as 600 or more), and its mean value is decided to be average ball equivalent diameter.

Below, the selenium compound that is used for silver halide colour photographic sensitive material of the present invention is described.

As selenium compound, preferably use following formula (SE1), (SE2) or (SE3) compound of expression.

Formula (SE1) formula (SE2) formula (SE3)

E ¹-Se-E ²

In formula (SE1), M ¹And M ²The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl, or carbamyl; Q represents alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OM ³, or NM ⁴M ⁵, M here ³, M ⁴, and M ⁵The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.M ¹, M ²Can combine with Q, form ring structure.

In formula (SE2), X ¹, X ², and X ³The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OJ ¹, or NJ ²J ³, J here ¹, J ², and J ³The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.

In formula (SE3), E ¹And E ²The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, alkoxy carbonyl group, aryloxycarbonyl, or carbamyl.E ¹And E ²Can be identical or different.

Below, will explain the selenium compound that formula (SE1) is represented in detail.

In formula (SE1), by M ¹To M ⁵" alkyl " represented with Q is meant the replacement or the unsubstituted alkyl of straight chain, side chain or ring-type.Its preferred examples comprises the replacement of straight or branched or the alkyl of the unsubstituted 1-30 of a containing carbon atom (methyl for example, ethyl, isopropyl, n-pro-pyl, normal-butyl, the tert-butyl group, the 2-amyl group, n-hexyl, n-octyl, uncle's octyl group, 2-ethylhexyl, 1,5-dimethyl hexyl, positive decyl, dodecyl, the n-tetradecane base, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2, the 3-dihydroxypropyl, ethyloic, carboxyethyl, thio-ethyl sodium group, the diethylamino ethyl, diethylamino propyl group, butoxy propyl group, ethoxy ethoxy ethyl and just own oxygen base propyl group); Replace or the unsubstituted naphthenic base that contains 3-18 carbon atom (cyclohexyl encircles octyl group, adamantyl (adamanthyl), and cyclo-dodecyl for cyclopropyl for example, cyclopentyl); The bicyclic alkyl of a replacement or the unsubstituted 5-30 of a containing carbon atom (promptly by removing the univalent perssad that a hydrogen atom forms from the bicyclic alkane that contains 5-30 carbon atom, for example two encircles [1,2,2] heptane-2-base group, two ring [2,2,2] octanes-3-base group); With tricyclic alkyl etc., it can have more ring structure.The non-limiting examples of alkenyls of being represented by M1 to M5 and Q comprises the alkenyl that contains 2-16 carbon atom (for example allyl, 2-butenyl group and 3-pentenyl).The example of the alkynyl of being represented by M1 to M5 and Q comprises the alkynyl (for example propargyl and 3-pentynyl) that contains 2-10 carbon atom.

The aryl of being represented by M1 to M5 and Q comprises and replacing or the phenyl or naphthyl (as unsubstituted phenyl, unsubstituted naphthyl, 3,5-3,5-dimethylphenyl, 4-butoxy phenyl and 4-dimethylaminophenyl) of the unsubstituted 6-20 of a containing carbon atom.The example of heterocyclic radical comprises pyridine radicals, furyl, imidazole radicals, piperidyl and morpholinyl.

In formula (SE1), by M ¹And M ²The acyl group example of expression comprises acetyl group, formoxyl, benzoyl, uncle's valeryl, caproyl and positive pelargonyl group; Amino example comprises unsubstituted amino, methylamino, hydroxyethylamino, n-octyl amino, dibenzyl amino, dimethylamino, and diethylamino; The alkoxy example comprises methoxyl, ethoxy, n-butoxy, cyclohexyloxy, n-octyloxy, and n-decyloxy; The carbamyl example comprises unsubstituted carbamyl, N, N-diethylamino formoxyl and N-carbanilino.

In formula (SE1), M ¹And M ², Q and M ¹, or Q and M ²Can be combined together to form ring structure.In addition, represent NM as Q ⁴M ⁵The time, M ⁴And M ⁵Can be combined together to form ring structure.

M in the formula (SE1) ¹To M ⁵Can have substituting group as much as possible with Q.Substituent example comprises halogen atom (fluorine, chlorine, bromine; or iodine), alkyl (any straight chain; side chain or cyclic alkyl comprise bicyclic alkyl and active methylene); alkenyl, alkynyl, aryl; heterocyclic radical (not probing into the position of substitution), acyl group, alkoxy carbonyl group; aryloxy carbonyl, heterocyclyloxy base carbonyl, carbamyl; N-hydroxyl amino formoxyl, N-acyl amino formoxyl, N-sulfuryl amino formoxyl; N-carbamyl carbamyl, thiocarbamoyl, N-sulfamoyl carbamyl; carbazyl, carboxyl or its salt, oxalyl group; the oxamoyl base, cyano group, carbon imino group; formoxyl; hydroxyl, alkoxy (comprise and contain ethyleneoxy or propenyloxy group unit group), aryloxy group as repetitive; the heterocyclyloxy base; acyloxy, alkoxy or aryloxy group-ketonic oxygen base, carbamyl oxygen base; sulfonyloxy; amino, alkyl-, aryl-or heterocyclic radical-amino; acylamino-; sulfonamido, urea groups, sulfo-urea groups; N-hydroxyl urea groups; imino group, alkoxy-or aryloxy group-carbonylamino, sulfamoyl amino; the semicarbazides group; the sulfo-amino urea groups, diazanyl, the molten base of ammonia (ammonio); oxamoyl base amino; the N-alkyl-or N-aryl-sulfonyl urea groups, N-acyl group urea groups, N-acyl group sulfamoyl amino; hydroxyl amino; nitro contains heterocyclic radical (pyrido for example, the imidazo of quaternary nitrogen atoms; quino; or isoquinoline is also), isocyano group, imino group; sulfydryl; alkyl-, virtue very-, or heterocyclic radical-sulfenyl; alkyl-; aryl-, or heterocyclic radical-disulfide group, alkyl-or aryl-sulfonyl; alkyl-or aryl-sulfinyl; sulfo group or its salt, sulfamoyl, N-acyl group sulfamoyl; N-Herbicidal sulphonylamino sulfonyl or its salt; phosphino-, phosphinyl, phosphinyl oxygen base; phosphinyl amino, and silicyl.Here, active methylene is meant the methine that is replaced by two electron withdraw groups, and electron withdraw group is meant acyl group, alkoxy carbonyl group, aryloxy carbonyl; carbamyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl; trifluoromethyl, cyano group, nitro and carbon imino group.These two electron withdraw groups formation ring structure that can be bonded to each other.In addition, term used herein " salt " is intended to comprise kation and organic cation such as the ammonium ion and the phosphonium ion of alkaline metal, earth alkali metal and heavy metal.Those substituting groups can be further by any replacement the in those substituting groups.

As the compound shown in the formula (SE1), more preferably following state: M ¹And M ²Represent hydrogen atom independently of one another, replace or do not replace, the alkyl that contains 1-6 carbon atom of straight or branched, replace or the unsubstituted naphthenic base that contains 3-6 carbon atom, the alkenyl that contains 2-6 carbon atom, replace or the unsubstituted aryl that contains 6-10 carbon atom, heterocyclic radical, or acyl group; Q represents to replace or the alkyl that contains 1-6 carbon atom unsubstituted, straight or branched, replaces or the last naphthenic base that contains 3-6 carbon atom that replaces, and contains the alkenyl of 2-6 carbon atom, replace or the unsubstituted aryl that contains 6-10 carbon atom, or NM ⁴M ⁵, M wherein ⁴And M ⁵The expression hydrogen atom, replace or do not replace, the alkyl that contains 1-6 carbon atom of straight or branched, replacement or the unsubstituted naphthenic base that contains 3-6 carbon atom contain the alkenyl of 2-6 carbon atom, replace or the unsubstituted aryl that contains 6-10 carbon atom, or heterocyclic radical.

As the compound by formula (SE1) expression, more preferably following state: M ¹And M ²Represent hydrogen atom independently of one another, replace or do not replace, the alkyl that contains 1-6 carbon atom of straight or branched, contain the alkenyl of 2-6 carbon atom, or replacement or the unsubstituted aryl that contains 6-10 carbon atom; Q represents to replace or does not replace, the alkyl that contains 1-6 carbon atom of straight or branched, replacement or the unsubstituted aryl that contains 6-10 carbon atom, or NM ⁴M ⁵, M wherein ⁴And M ⁵The expression hydrogen atom replaces or does not replace, the alkyl that contains 1-6 carbon atom of straight or branched, contains the alkenyl of 2-6 carbon atom, or replacement or the unsubstituted aryl that contains 6-10 carbon atom.

As the compound by formula (SE1) expression, more preferably following state: Q represents NM ⁴M ⁵, M wherein ⁴And M ⁵The expression hydrogen atom replaces or does not replace, the alkyl that contains 1-6 carbon atom of straight or branched, contains the alkenyl of 2-6 carbon atom, or replacement or the unsubstituted aryl that contains 6-10 carbon atom.

With reference to as at Chem.Rev., 55,181-228 (1955); J.Org.Chem., 24,470-473 (1959); J.Heterocycl.Chem., 4,605-609 (1967); J.Dmg (Yakushi), 82,36-45 (1962); JP-B-39-26203, JP-A-63-229449, and OLS-2, the compound that the method for describing in 043,944 can synthesis type (SE1) expression.

To describe the compound of formula (SE2) expression in detail.

In formula (SE2), by X ¹To X ³And J ¹To J ³The expression alkyl, alkenyl, alkynyl, aryl and heterocyclic radical have with formula (SE1) in by M ¹To M ⁵Those identical implications of representing with Q.X ¹To X ³And J ¹To J ³Can have substituting group as much as possible separately, substituent example comprises with the front mentions the example that example is identical.

As the compound of formula (SE2) expression, preferred following state: X ¹To X ³Expression independently of one another replaces or does not replace, the alkyl that contains 1-6 carbon atom of straight or branched, replace or the unsubstituted aryl that contains 6-10 carbon atom, or heterocyclic radical.As the compound of formula (SE2) expression, more preferably following state: X ¹To X ³Expression independently of one another replaces or the unsubstituted aryl that contains 6-10 carbon atom.

With reference to as at Organic Phosphorus Compounds, vol.4, pp.1-73; J.Chem.Soc.B, p.1416 (1968); J.Org.Chem., vol.32, p.1717 (1967); J.Org.Chem., vol.32, p.2999 (1967); Tetrahedron, vol.20, p.449 (1964); And J.Am.Chem.Soc., vol.91, the p.2915 compound that method of describing in (1969) can synthesis type (SE2) expression.

To explain the compound of formula (SE3) expression.

In formula (SE3), by E ¹And E ²The expression alkyl, alkenyl, alkynyl, aryl and heterocyclic radical have with formula (SE1) in by M ¹To M ⁵Those identical implications of representing with Q.By E ¹And E ²The acyl group example of expression comprises acetyl group, formoxyl, benzoyl, uncle's valeryl, caproyl and positive pelargonyl group; By E ¹And E ²The alkoxy carbonyl group example of expression comprises methoxycarbonyl group, carbethoxyl group, positive butoxy carbonyl, hexamethylene oxygen carbonyl, positive hot oxygen carbonyl and positive last of the ten Heavenly stems the oxygen carbonyl; By E ¹And E ²The aryloxycarbonyl example of expression comprises phenyloxycarbonyl and naphthoxy carbonyl; And by E ¹And E ²The carbamyl example of expression comprises unsubstituted carbamyl, N, N-diethylamino formoxyl and N-phenyl amino formoxyl.E ¹And E ²Can further contain substituting group as much as possible separately.This substituent example comprises above-mentioned substituent same instance.

Among those of formula (SE3) expression in preferred compound, E ¹And E ²Select the group of free style (T1) to (T4) expression.In these cases, E ¹And E ²Can be identical or different.

Formula (T1) formula (T2) formula (T3) (formula T4)

-L ¹¹-EWG

In formula (T1), Y ¹¹The expression alkyl, alkenyl, alkynyl, aryl, heteroaryl, OR ¹¹, or NR ¹²R ¹³, R wherein ¹¹, R ¹², and R ¹³The expression alkyl, alkenyl, alkynyl, aryl, or heteroaryl.In formula (T2), L ¹¹The expression divalent linker, EWG represents electron withdraw group.In formula (T3), A ¹¹The expression oxygen atom, sulphur atom, or NR ¹⁷R ¹⁴, R ¹⁵, R ¹⁶And R ¹⁷The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.In formula (T4), A ¹²The expression oxygen atom, sulphur atom, or NR ¹¹¹R ¹⁸The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, or acyl group; R ¹⁹, R ¹¹⁰, and R ¹¹¹The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.Z ¹¹The expression substituting group; n ¹¹It is the integer of 0-4.Work as n ¹¹Be 2 or when bigger, Z ¹¹Can be identical or different.

In formula (T1), Y ¹¹The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical ,-OR ¹¹, or-NR ¹²R ¹³, R wherein ¹¹, R ¹², and R ¹³The expression alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.When relating to alkyl, it has and the middle M of formula (SE1) ¹To M ⁵With those identical implications that Q represents, their preferable range is also identical.Equally, alkenyl, alkynyl, aryl and heterocyclic radical have respectively and the middle M of formula (SE1) ¹To M ⁵With Q alkenyl separately, alkynyl, aryl,, also identical about these groups preferable range separately with the identical implication that heterocyclic radical is represented.

In formula (T1), Y ¹¹Be preferably alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical; More preferably alkyl or aryl.

In formula (T2), by L ¹¹The divalent linker of expression represents to contain the alkylidene of 2-20 carbon atom, alkylene group or alkynylene; Preferred expression contains straight chain, side chain or the cyclic alkylidene (for example, ethylidene, propylidene, cyclopentylene and cyclohexylidene) of 2-10 carbon atom, alkylene group (for example ethenylidene), or alkynylene (for example inferior propinyl).L ¹¹Preferably by following formula (L1) or (L2) expression group.

Formula (L1) formula (L2)

In formula (L1) with (L2), G ¹, G ², G ³, and G ⁴Represent hydrogen atom, contain the alkyl of 1-10 carbon atom, contain the aryl of 6-20 carbon atom, or contain the heterocyclic radical of 1-10 carbon atom.G ¹, G ², and G ³Can combine into ring.G ¹, G ², G ³, and G ⁴Be preferably hydrogen atom separately, alkyl, or aryl, more preferably hydrogen atom or alkyl.

In formula (T2), EWG represents electron withdraw group.Here so-called term " electron withdraw group " is meant to have positive Hammett substituent constant σ _mValue (or σ _pValue) group, preferred 0.12 or bigger σ _mValue (or 0.2 or bigger σ _pValue), be limited to 1.0 or littler on it.Has positive σ _mValue (or 0.2 or bigger σ _pThe instantiation of electron withdraw group value) comprises alkoxy (the preferably alkoxy that is replaced by two or more at least halogen atoms), aryloxy group (the preferably aryloxy group that is replaced by two or more at least halogen atoms), alkylthio group (the preferably alkylthio group that is replaced by two or more at least halogen atoms); arylthio, acyl group, formoxyl; acyloxy, acyl mercapto, carbamyl; alkoxy carbonyl group, aryloxycarbonyl, cyano group; nitro, dialkyl phosphine acyl group, diaryl phosphono; the dialkyl group phosphinyl, diaryl phosphinyl, phosphoryl; the alkyl sulfinyl; the aryl sulfinyl, alkyl sulphonyl, aryl sulfonyl; sulfonyloxy; the acyl sulfenyl, sulfamoyl, thiocyanate group; thiocarbonyl; imino group, by the imino group that the N atom replaces, carboxyl (or its salt); by the alkyl of two or more at least halogen atoms replacements; acylamino-is by the alkylamino of two or more at least halogen atoms replacements, by other positive σ _mValue (or σ _pValue is 0.2 or bigger) the electron withdraw group aryl, heterocyclic radical, halogen atom, azo group and the selenocyanate group that replace.EWG is preferably alkoxy, acyl group, formoxyl, carbamyl, alkoxy carbonyl group, aryloxycarbonyl, cyano group, nitro, the dialkyl phosphine acyl group, diaryl phosphono, dialkyl group phosphinyl, the diaryl phosphinyl, alkyl sulfinyl, aryl sulfinyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl, thiocarbonyl, imino group, the imino group that is replaced by the N atom; Phosphoryl, carboxyl (or its salt) is by the alkyl of two or more at least halogen atoms replacements, by other positive σ _mValue (or σ _pValue is 0.2 or bigger) the aryl that replaces of electron withdraw group, heterocyclic radical, or halogen atom; More preferably alkoxy, acyl group, formoxyl, carbamyl, alkoxy carbonyl group, aryloxycarbonyl, cyano group, nitro, alkyl sulphonyl, aryl sulfonyl, carboxyl, or the alkyl that is replaced by two or more at least halogen atoms; Further preferred alkoxy, acyl group, formoxyl, cyano group, nitro, alkyl sulphonyl, aryl sulfonyl, or by the alkyl of two or more at least halogen atoms replacements.

Hammett's rule is the quantitative description substituting group that the proposes L.P.Hammett nineteen thirty-five thumb rule to the influence of benzene derivative reaction or balance.σ _pAnd σ _mAs the substituent constant that obtains according to Hammett's rule, many general books are described these values.For example, " Lange ' s Handbook of Chemistry ", J.A.Dean edits, and the 12nd edition, 1979 (McGraw-Hill); " Extra issue of Kagakuno Ryoiki ", No.122, the 96-103 page or leaf, 1979 (Nankodo Publishing Co., Ltd.); " ChemicalReviews ", Vol.91, the 165-195 page or leaf is described these values in detail in 1991.In the present invention, substituting group utilizes the Hammett substituent constant to define and explain.Yet, must be noted that substituting group is not limited to known and disclosed substituting group with Hammett constant in the document.Therefore, much less, even do not describe substituent Hammett constant in the document, the substituting group that the Hammett constant drops in the scope of measuring based on Hammett's rule comprises within the scope of the present invention.

In formula (T2), preferred following situation: L ¹¹Preferably by formula (L1) expression, G ¹To G ³Represent hydrogen atom or alkyl separately, EWG represents alkoxy, acyl group, formoxyl, carbamyl, alkoxy carbonyl group, aryloxycarbonyl, cyano group, nitro, alkyl sulphonyl, aryl sulfonyl, carboxyl or the alkyl that is replaced by at least two halogen atoms.More preferably following situation: L ¹¹Preferably by formula (L1) expression, G ¹To G ³Represent hydrogen atom or alkyl separately, EWG represents alkoxy, acyl group, formoxyl, cyano group, nitro, alkyl sulphonyl, aryl sulfonyl or the alkyl that is replaced by at least two halogen atoms.

In formula (T3), R ¹⁴To R ¹⁷The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic radical.Here so-called alkyl have with above-mentioned formula (SE1) in by M ¹To M ⁵The identical implication of alkyl of expression, preferable range is also identical.Equally, alkenyl, alkynyl, aryl and heterocyclic radical have respectively and the middle M of above-mentioned formula (SE1) ¹To M ⁵With the alkenyl that Q represents, alkynyl, aryl, the implication identical with heterocyclic radical, preferable range are also identical.

R ¹⁴Be preferably alkyl.R ¹⁵And R ¹⁶Be preferably hydrogen atom separately, alkyl, or aryl, more preferably hydrogen atom, or alkyl.More preferably R wherein also ¹⁵And R ¹⁶One of be hydrogen atom and another situation for hydrogen atom or alkyl.R ¹⁷Be preferably hydrogen atom, alkyl, or aryl, more preferably hydrogen atom or alkyl, also more preferably alkyl.

In formula (T3), A ¹¹The expression oxygen atom, sulphur atom, or NR ¹⁷A ¹¹Be preferably oxygen atom or sulphur atom, more preferably oxygen atom.

In formula (T3), preferred A wherein ¹¹Be oxygen atom or sulphur atom, R ¹⁴Be alkyl, R ¹⁵And R ¹⁶The hydrogen atom of respectively doing for oneself, the situation of alkyl or aryl.More preferably A wherein ¹¹Be oxygen atom, R ¹⁴Be alkyl, R ¹⁵And R ¹⁶Respectively the do for oneself situation of hydrogen atom or alkyl.

Next, will explain formula (T4).

In formula (T4), by R ¹⁸, R ¹⁹, R ¹¹⁰And R ¹¹¹The expression alkyl have with above-mentioned formula (SE1) in by M ¹To M ⁵With the identical implication of alkyl that Q represents, preferable range is also identical.Equally, alkenyl, alkynyl, aryl and heterocyclic radical have respectively and the middle M of above-mentioned formula (SE1) ¹To M ⁵With the alkenyl that Q represents, alkynyl, aryl, the implication identical with heterocyclic radical, preferable range are also identical.By R ¹⁸The example of the acyl group of expression comprises acetyl group, formoxyl, benzoyl, valeryl, caproyl and positive pelargonyl group.

Z in the formula (T4) ¹¹The expression substituting group, the example comprises substituting group same as described above.

Z ¹¹Preferred embodiment comprise halogen atom, alkyl, aryl; heterocyclic radical, acyl group, alkoxy carbonyl group; aryloxycarbonyl, carbamyl, N-acyl amino formoxyl; N-sulfuryl amino formoxyl, N-carbamyl carbamyl, thiocarbamoyl; N-sulfamoyl carbamyl, carbazyl, carboxyl (comprising its salt); cyano group, formoxyl, hydroxyl; alkoxy, aryloxy group, heterocyclyloxy base; acyloxy, nitro, amino; alkyl; aryl-or heterocyclic radical-amino, acylamino-, sulfonamido; urea groups, sulfo-urea groups, alkylthio group; arylthio, the heterocyclic radical sulfenyl, alkyl-or aryl-sulfonyl; alkyl-or aryl-sulfinyl, sulfo group (comprising its salt), and sulfamoyl.Its preferred example comprises halogen atom, alkyl, aryl, heterocyclic radical, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, heterocyclyloxy base, acyloxy, amino, alkyl-, aryl-or heterocyclic radical-amino, acylamino-, urea groups, sulfo-urea groups, alkylthio group, arylthio, heterocyclic radical sulfenyl, and sulfo group (comprising its salt).Its further preferred example comprises alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, alkyl-, aryl, or heterocyclic radical-amino, urea groups, alkylthio group, arylthio, and sulfo group (comprising its salt).

In formula (T4), n ¹¹The integer of expression 0-4.n ¹¹Be preferably the integer of 0-2, more preferably integer 0 or 1.

In formula (T4), A ¹²The expression oxygen atom, sulphur atom, or NR ¹¹¹A ¹²Preferred expression oxygen atom or sulphur atom, more preferably oxygen atom.

In formula (T4), preferred following situation: A wherein ¹²Be oxygen atom or sulphur atom, R ¹⁸Be hydrogen atom, alkyl or acyl group, R ¹⁹And R ¹¹⁰Each is hydrogen atom naturally, alkyl or aryl, n ¹¹Be 0-2, Z ¹¹Be alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, alkyl-, aryl-or heterocyclic radical-amino, urea groups, alkylthio group, arylthio or sulfo group (comprising its salt).More preferably following situation: A wherein ¹²Be oxygen atom, R ¹⁸Be hydrogen atom or alkyl, R ¹⁹And R ¹¹⁰Each is hydrogen atom or alkyl naturally, n ¹¹Be 0-2, Z ¹¹Be alkyl, aryl, carboxyl (comprising its salt), hydroxyl, urea groups or sulfo group (comprising its salt).Further more preferably following situation: A wherein ¹²Be oxygen atom, R ¹⁸Be alkyl, R ¹⁹And R ¹¹⁰Each is hydrogen atom naturally, n ¹¹Be 0-2, Z ¹¹Be alkyl, carboxyl (comprising its salt), hydroxyl or sulfo group (comprising its salt).

In the compound of formula (SE3) expression, preferred compound corresponds respectively to wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T1), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T2), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T2) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T2) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T3) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T3) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T4) ²It is the situation of the group of formula (T4).In these cases, with respect to more preferably E wherein of other situation ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T1), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T2), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T2) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T3) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T4) ²It is the situation of the group of formula (T4); Especially preferred E wherein ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T2), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T1) ²Be the situation of the group of formula (T4), wherein E ¹Be the group and the E of formula (T2) ²Be the situation of the group of formula (T3), wherein E ¹Be the group and the E of formula (T3) ²It is the situation of the group of formula (T4).Among these situations, E wherein most preferably ¹The group and the E of formula (T1) ²Be the situation of the group of formula (T2), wherein E ¹Be the group and the E of formula (T1) ²Be the situation and the E wherein of the group of formula (T3) ¹Be the group and the E of formula (T2) ²It is the situation of the group of formula (T3).

In addition, in the compound of formula (SE3) expression, preferred compound is corresponding to E wherein ¹Or E ²Be the group that is selected from formula (T1), or arbitrary in them is the situation that is selected from the group of formula (T4) at least.More preferably E wherein ¹Or E ²Be the group that is selected from formula (T1), and another is to be selected from formula (T1), (T2) or the situation of group (T4), or E wherein ¹Or E ²Be the group that is selected from formula (T4), and another is the situation that is selected from formula (T3) or group (T4).Further preferred E wherein ¹Or E ²Be the group that is selected from formula (T1), and another is to be selected from formula (T2) or group (T4), or E wherein ¹And E ²All be selected from the situation of the group of formula (T4).The best is E wherein ¹Or E ²Be the group that is selected from formula (T1), and another is the group that is selected from formula (T2), or E wherein ¹And E ²All be selected from the situation of the group of formula (T4).

According to the method for in following known document, describing can synthesis type (SE3) expression compound: by the The Chemistry of Organic Selenium and TelluriumCompounds that S.Patai and Z.Rappoport edit, Vol.1 (1986) and ibid.Vol.2 (1987); The OrganoseleniumChemistry (1987) that edits with D.Liotta.

Below with the instantiation of the compound of arbitrary expression in the display type (SE1) to (SE3), but the compound that is used for color silver halide photographic-material of the present invention is not limited to these.In addition, about having the compound of a plurality of steric isomers, their spatial structure is not limited to these.

Except above-claimed cpd, at JP-B-43-13489, JP-B-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341, JP-A-5-40324, JP-A-5-11385, JP-A-6-51415, JP-A-6-175258, JP-A-6-180478, JP-A-6-208186, JP-A-6-208184, JP-A-6-317867, JP-A-7-92599, JP-A-7-98483, JP-A-7-140579, JP-A-7-301879, JP-A-7-301880, JP-A-8-114882, JP-A-9-138475, JP-A-9-197603, with the selenium compound of describing among the JP-A-10-10666, colloidal metal selenium particularly, seleno skeleton (for example seleno benzophenone), different selenocyanate and seleno carboxylic acid compound can be used for color silver halide photographic-material of the present invention.In addition, can also use selenium compound, comprise the selenous acid compound, selenocyanic acid compound (as selenocyanic acid potassium), selenazoles, and selenide as JP-B-46-4553 and the described non-volatility of JP-B-52-34492.In these compounds, with respect to the preferred selenocyanic acid compound of other compound.

The structure of above-described selenium compound not will be understood that it is the selenium compound that restriction is used for silver halide colour photographic sensitive material of the present invention.From the angle that hard contrast strengthens and photographic fog reduces, the 3d-orbital electron that is preferred for the selenium atom in the selenium compound in the color silver halide photographic-material of the present invention has the binding energy of 54.0eV to 65.0eV, and this uses the sub-spectroscope of X-ray photoelectric to measure.

The amount that is used for the selenium sensitizer of silver halide colour photographic sensitive material of the present invention changes according to used selenium compound, the silver halide particle that is used in combination with it and the chemical slaking condition that adopted, is generally every mole of silver halide about 1 * 10 ^-8To about 1 * 10 ^-4Mole, preferred about 1 * 10 ^-7To about 1 * 10 ^-5Mole.The present invention is not particularly limited the condition of chemical sensitization, but pC1 is preferably 0-7, more preferably 0-5, and preferred especially 1-3, temperature is preferably 40-95 ℃, more preferably 50-85 ℃.In addition, temperature is preferably 40 ℃-80 ℃, more preferably 50 ℃-70 ℃.Compound for formula (SE1) to (SE3) expression can be used alone, or use two or more with form of mixtures.In addition, they can make up with other selenium sensitizer simultaneously.

According to the selenium compound of color silver halide photographic-material of the present invention can form from particle before being near completion to chemical sensitization at once during any stage add.The preferred joining day is after desalination is finished at once and during comprising between the chemical sensitization process.

Can be in one deck or a plurality of layer the compound of use formula (SE1) to (SE3) expression separately, or mix and use in them two or more.In addition, they can add other selenium sensitizer simultaneously.

Below, will the gold-selenium compound that be preferred for second of the present invention or the 3rd embodiment be described.

For can be used for gold-selenium compound of the present invention, the compound of arbitrary expression all is fit in the following formula (PF1) to (PF6).

Formula (PF1) formula (PF2)

Formula (PF4) formula (PF3)

Formula (PF5) formula (PF6)

[Q ²¹……Au…(Q ²²) _n ²³]J ²¹

In formula (PF1), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²¹Expression O, S or NR ²⁴R ²¹To R ²⁴Represent hydrogen atom or substituting group separately; And R ²³Can with R ²¹Or R ²²Form 5-to 7-unit ring;

In formula (PF2), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; X ²¹Expression O, S or NR ²⁵Y ²¹The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹R ²⁵To R ²⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; And X ²¹And Y ²¹Can interosculate and form ring;

In formula (PF3), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; R ²¹⁰, R ²¹¹And R ²¹²Represent hydrogen atom or substituting group independently of one another, simultaneously R ²¹⁰And R ²¹¹In at least one the expression electron withdraw group;

In formula (PF4), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; W ²¹The expression electron withdraw group; And R ²¹³To R ²¹⁵Represent hydrogen atom or substituting group separately, simultaneously W ²¹And R ²¹³Formation ring texture alternatively mutually combines;

In formula (PF5), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²²Expression O, S, Se or NR ²¹⁹R ²¹⁶The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical or acyl group; R ²¹⁷To R ²¹⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; Z ²¹The expression substituting group; n ²²Expression 0 to 4 integer; And work as n ²²Be 2 or when bigger, Z ²¹Can be mutually the same or different;

In formula (PF6), Q ²¹And Q ²²Expression is selected from the selenium sensitizer compound of formula (SE1) to (SE3), Q ²¹And Q ²²In selenium atom and Au form coordination bond; n ²³Expression 0 or 1; And J ²¹The expression balance anion.Work as n ²³Be 1 o'clock, Q ²¹And Q ²²Can be identical or different, condition is the compound that the compound of formula (PF6) expression does not comprise arbitrary expression in the formula (PF1) to (PF5).

Next, the gold-selenium compound that will represent formula (PF1) below is described.

In formula (PF1), R ²¹And R ²²Preferably represent hydrogen atom separately, alkyl, aryl, heterocyclic radical, hydroxyl, alkoxy, aryloxy group, heterocyclyloxy base, amino, sulfydryl, alkylthio group, arylthio or heterocycle sulfenyl, more preferably hydrogen atom, alkyl, aryl or heterocyclic radical, most preferably hydrogen atom or alkyl.

R ²³Preferred expression hydrogen atom, alkyl, aryl or heterocyclic radical; More preferably alkyl, aryl or heterocyclic radical; Alkyl or aryl most preferably.R ²⁴Preferred expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, amino, acylamino-, alkyl-or aryl-sulfuryl amino, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl; Further preferred hydrogen atom, alkyl, aryl or heterocyclic radical.

R ²³Can with R ²¹Or R ²²Form 5-to 7-ring structure.Formed ring structure is a non-aromatic ring, contain oxygen-, sulphur-or nitrogen-heterocycle.And this ring structure can form condensed ring with fragrance or non-aromatic carbocyclic or heterocycle.In the present invention, more preferably R ²³With R ²¹Or R ²²Form 5-to 7-ring structure.

In the present invention, in the compound of formula (PF1) expression, preferred A wherein ²¹Expression O, S or NR ²⁴R ²¹And R ²²Represent hydrogen atom separately, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclyloxy base, alkylthio group, arylthio or heterocycle sulfenyl; R ²³The expression hydrogen atom, alkyl, aryl or heterocyclic radical; R ²⁴The expression hydrogen atom, alkyl, aryl, heterocyclic radical, amino, acylamino-, alkyl-or aryl-sulfuryl amino, alkyl-or aryl-sulfonyl or acylated compound.Preferred compound is A wherein ²¹Expression O or S; R ²¹And R ²²Represent hydrogen atom separately, alkyl, aryl or heterocyclic radical; And R ²³Expression alkyl, aryl or heterocyclic radical.Even preferred compound is A wherein ²¹Expression O or S; R ²¹And R ²²Represent hydrogen atom separately, alkyl or aryl; And R ²³The expression alkyl or aryl.Particularly preferred compound is R wherein ²³With R ²¹Or R ²²Form sugar derivatives ring structure such as glucose, mannose, galactose, wood sugar, lyxose, arabinose, ribose, fucose, idose, talose, allose, altrose, rhamnose, sorbose, digitoxose, 2-deoxyglucose, 2-deoxy-galactose, fructose, aminoglucose, galactosamine or the glucuronic acid (A in its Chinese style (PF1) ²¹The situation of expression O) and its sulfur analogs (A in its Chinese style (PF1) ²¹The situation of expression S).Term used herein " sugar derivatives " is meant with alkoxy (comprise and contain ethyleneoxy or the propenyloxy group unit group as repetitive), aryloxy group, heterocyclyloxy base; acyloxy, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base; carbamyl oxygen base, sulfonyloxy, silicyl oxygen base; alkyl; aryl-or heterocyclic radical-amino, acylamino-, sulfonamido; urea groups, sulfo-urea groups, N-hydroxyl urea groups; alkoxy-carbonylamino, aryloxy group-carbonylamino, sulfamoyl amino; the semicarbazides group, sulfo-amino urea groups, oxamoyl base amino; N-(alkyl or aryl) sulfonyl urea groups; N-acyl group urea groups, N-acyl group sulfamoyl amino, hydroxyl amino; acyl group; alkoxy carbonyl, aryloxycarbonyl, heterocyclyloxy base carbonyl; carbamyl; N-hydroxyl amino formoxyl, N-acyl amino formoxyl, N-sulfonyl carbamyl; N-carbamyl carbamyl or N-ammonia sulfonyl carbamyl replace the hydroxyl in the sugared structure, amino or carboxyl and the compound that makes.In these sugared structures, there be mutually different alpha-isomer and β-isomeride of 1 bit space structure, with the D-isomeride of mirror and L-isomeride each other mutually.Yet, not difference of these isomeride in the present invention.Under these situations, preferred examples of compounds comprises golden selenium glucose, golden selenium mannose, golden selenium-galactose, golden selenium lyxose and its sugar derivatives.

Next, the compound that will represent formula (PF2) below is described.

In formula (PF2), X ²¹Preferred O or S, more preferably O.Y ²¹Preferred expression has the alkyl of 1-30 carbon atom, alkenyl, and alkynyl, aryl contains in N atom, O atom and the S atom at least one 5-to 7-heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹Preferred alkyl, aryl, heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹More preferably alkyl, aryl, heterocyclic radical or N (R ²⁸) R ²⁹Even more preferably alkyl, aryl or heterocyclic radical.

R ²⁵To R ²⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; Preferred hydrogen atom, alkyl, aryl or heterocyclic radical; More preferably alkyl or aryl.

In formula (PF2), X ²¹And Y ²¹Can mutually combine and form ring.In this case, ring is the nitrogen heterocyclic ring of 3-to 7-unit, and the example comprises the pyrroles, indoles, imidazoles, benzimidazole, thiazine, benzothiazine ， isoxazole ， oxazole, benzoxazole, indazole, purine, pyridine, pyrazine, pyrimidine, quinoline and quinazoline.

In the compound of formula (PF2) expression, preferred compound is X wherein ²¹Expression O or S; Y ²¹The expression alkyl, aryl, heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹And R ²⁶To R ²⁹Represent alkyl separately, the compound of aryl or heterocyclic radical.Preferred compound is X wherein ²¹Expression O; And Y ²¹Expression alkyl, aryl or heterocyclic radical.Most preferred is X wherein ²¹Expression O; And Y ²¹Expression alkyl, aryl or heterocyclic radical.

Next, the compound that will represent formula (PF3) below is described.

In formula (PF3), R ²¹⁰And R ²¹¹In at least one the expression electron withdraw group.Term used herein " electron withdraw group " is meant to have positive Hammett substituent constant σ _pValue, preferred 0.2 or bigger σ _pThe substituting group of value (on be limited to 1.0).Have 0.2 or bigger σ _pThe instantiation of the electron withdraw group of value comprises acyl group, formoxyl, acyloxy; acyl mercapto, carbamyl, alkoxy carbonyl group; aryloxycarbonyl, cyano group, nitro; the dialkyl phosphine acyl group, diaryl phosphono, dialkyl group phosphinyl; the diaryl phosphinyl, phosphoryl, alkyl sulfinyl; the aryl sulfinyl, alkyl sulphonyl, aryl sulfonyl; sulfonyloxy, acyl sulfenyl, sulfamoyl; the thiocyanate group, thiocarbonyl, imino group; by the imino group that the N atom replaces, carboxyl (or its salt) is by the alkyl of at least two halogen atoms replacements; by the alkoxy of at least two halogen atoms replacements; by the aryloxy group that at least two halogen atoms replace, acylamino-is by the alkylamino of at least two halogen atoms replacements; by the alkylthio group of at least two halogen atoms replacements, by other σ _pValue is 0.2 or bigger the electron withdraw group aryl, heterocyclic radical, halogen atom, azo group and the selenocyanate group that replace.In the present invention, preferred acyl group, formoxyl, carbamyl; alkoxy carbonyl group, aryloxycarbonyl, cyano group, dialkyl phosphine acyl group; the diaryl phosphono, dialkyl group phosphinyl, diaryl phosphinyl, alkyl sulfinyl; the aryl sulfinyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl; thiocarbonyl, imino group, the imino group that is replaced by the N atom; carboxyl (or its salt) is by the alkyl of at least two halogen atoms replacements, by other σ _pValue is 0.2 or the aryl that replaces of bigger electron withdraw group, heterocyclic radical, or halogen atom; More preferably acyl group, carbamyl, alkoxy carbonyl group, aryloxycarbonyl, cyano group, carboxyl, the alkyl that is replaced by at least two halogen atoms is by other σ _pValue is 0.2 or bigger the electron withdraw group aryl or the heterocyclic radical that replace.

In formula (PF3), preferred R ²¹⁰And R ²¹¹All represent electron withdraw group.R ²¹²Preferred expression hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, the heterocyclyloxy base, amino, acylamino-, alkylthio group, arylthio, the heterocycle sulfenyl, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbonyl; More preferably hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclyloxy base, amino or acylamino-.

In formula (PF3), also preferred R ²¹⁰, R ²¹¹And R ²¹²Mutually combine and form ring.Formed ring is non-aromatic carbocyclic or heterocycle, the first ring of preferred 5-to 7-.Form the R of ring ²¹⁰Acyl group preferably, carbamyl, oxygen base carbonyl, thiocarbonyl or sulfonyl, and R ²¹¹Acyl group preferably, carbamyl, oxygen base carbonyl, thiocarbonyl, sulfonyl, imino group, by the imino group that the N atom replaces, acylamino-or carbonyl sulfenyl.

In the compound of formula (PF3) expression, preferred compound is R wherein ²¹⁰And R ²¹¹The expression electron withdraw group; And R ²¹²The expression hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclyloxy base, amino or acylamino-.Preferred compound is R wherein ²¹⁰And R ²¹¹The expression electron withdraw group; And R ²¹²Expression hydrogen atom, alkyl, aryl or heterocyclic radical.Most preferred is R wherein ²¹⁰And R ¹¹The expression electron withdraw group; And R ²¹²Expression hydrogen atom, alkyl, aryl or heterocyclic radical.

And in the compound of formula (PF3) expression, also preferred compound is R wherein ²¹⁰And R ²¹¹Form 5-to 7-unit non-aromatic ring.In this case, R ²¹²The expression hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclyloxy base, amino or acylamino-.Preferred compound is R wherein ²¹⁰And R ²¹¹Form 5-to 7-unit non-aromatic ring; And R ²¹²Expression hydrogen atom, alkyl, aryl or heterocyclic radical.Optimum compound is to select wherein R ²¹⁰And R ²¹¹Form 5-to 7-unit non-aromatic ring; And R ²¹²Expression hydrogen atom, alkyl, aryl or heterocyclic radical.

Next, the compound that will represent formula (PF4) below is described.

In formula (PF4), W ²¹The electron withdraw group and the aforementioned R of expression ²¹⁰And R ²¹¹The electron withdraw group of expression is identical and its preferable range is also identical.

In formula (PF4), R ²¹³To R ²¹⁵Preferred embodiment comprise hydrogen atom, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfamoyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl and carbamyl.Its preferred example comprises hydrogen atom, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl and carbamyl.

W ²¹And R ²¹³Can mutually combine and form ring.The hydrocarbon ring or the heterocycle of the ring right and wrong fragrance that forms, the first ring of preferred 5-to 7-.Form the W of ring ²¹Acyl group preferably, carbamyl, oxygen base carbonyl, thiocarbonyl or sulfonyl, and R ²¹³Preferably alkyl, alkenyl, aryl or heterocyclic radical.

In the compound of formula (PF4) expression, preferred compound is W wherein ²¹The expression electron withdraw group; And R ²¹³To R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.More excellent compound is to select wherein W ²¹The expression electron withdraw group; And R ²¹³To R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.Most preferred is W wherein ²¹The expression electron withdraw group; And R ²¹³To R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.

And in the compound of formula (PF4) expression, also preferred compound is W wherein ²¹And R ²¹³5-to the 7-unit ring that mutually combines and form non-fragrance.In this case, R ²¹³The expression alkyl, alkenyl, aryl, heterocyclic radical or analog, and R ²¹⁴And R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.Preferred compound is W wherein ²¹And R ²¹³5-to the 7-unit ring that mutually combines and form non-fragrance; And R ²¹⁴And R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.Most preferred is W wherein ²¹And R ²¹³5-to the 7-unit ring that mutually combines and form non-fragrance; And R ²¹⁴And R ²¹⁵Represent hydrogen atom separately, halogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.

Next, the compound that will represent formula (PF5) below is described.

In formula (PF5), R ²¹⁶Preferred expression hydrogen atom, alkyl, aryl or acyl group, more preferably hydrogen atom, alkyl or acyl group, special preferred alkyl.R ²¹⁷And R ²¹⁸Be preferably hydrogen atom separately, alkyl or aryl, more preferably hydrogen atom or alkyl, particularly preferred situation is R wherein ²¹⁷And R ²¹⁸In one be hydrogen atom, another is hydrogen atom or alkyl.R ²¹⁹Hydrogen atom preferably, alkyl or aryl, more preferably hydrogen atom or alkyl, special preferred alkyl.

In formula (PF5), though A ²²Expression O, S, Se, Te or NR ²¹⁹, but preferred A wherein in the present invention ²²Be O, S or NR ²¹⁹Situation, more preferably A wherein ²²Be the situation of O or S, especially preferred A wherein ²²It is the situation of O.

In formula (PF5), Z ²¹The expression substituting group.This substituting group example comprises the substituting group identical with above-mentioned substituting group.In the present invention preferably as Z ²¹Substituting group be halogen atom, alkyl, aryl; heterocyclic radical, acyl group, alkoxy carbonyl; aryloxycarbonyl, carbamyl, N-acyl amino formoxyl; N-sulfuryl amino formoxyl, N-carbamyl carbamyl, thiocarbamoyl; N-sulfamoyl carbamyl, carbazyl, carboxyl (comprising its salt); cyano group, formoxyl, hydroxyl; alkoxy, aryloxy group, heterocyclyloxy base; acyloxy, nitro, amino; alkyl; aryl or heterocyclic radical amino, acyl amino, sulfonamido; urea groups, sulfo-urea groups, alkyl sulfenyl; artyl sulfo, heterocyclic radical sulfenyl, (alkyl or aryl) sulfonyl; (alkyl or aryl) sulfinyl, sulfo group (comprising its salt) or sulfamoyl are as Z ²¹More preferred substituents be halogen atom, alkyl, aryl, heterocyclic radical; carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group; the heterocyclyloxy base, acyloxy, amino; (alkyl, aryl or heterocyclic radical) amino, acyl amino, urea groups; the sulfo-urea groups, alkyl sulfenyl, artyl sulfo; heterocyclic radical sulfenyl, or sulfo group (comprising its salt) are as Z ²¹Further preferred substituted be alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl, aryl or heterocyclic radical) amino, urea groups, alkyl sulfenyl, artyl sulfo, heterocyclic radical sulfenyl or sulfo group (comprising its salt).

In formula (PF5), n ²²The integer of expression 0-4, but the preferred n of the present invention ²²The situation of the integer of expression 0-2, more preferably n ²²The situation of expression 0 or 1.

In formula (PF5), preferred A wherein ²²Expression O, S or NR ²¹⁹, R ²¹⁶The expression hydrogen atom, alkyl, aryl or acyl group, R ²¹⁷And R ²¹⁸Represent hydrogen atom separately, alkyl or aryl, R ²¹⁹The expression hydrogen atom, alkyl or aryl, n ²²Expression 0-2, and Z ²¹The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl, aryl or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).More preferably A wherein ²²Expression O, S or NR ²¹⁹, R ²¹⁶The expression alkyl, R ²¹⁷And R ²¹⁸Represent hydrogen atom or alkyl separately, R ²¹⁹The expression alkyl or aryl, n ²²Expression 0-2, and Z ²¹The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl, aryl or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).Further preferred A wherein ²²Expression O, S or NR ²¹⁹, R ²¹⁶The expression alkyl, R ²¹⁷And R ²¹⁸Represent hydrogen atom or alkyl separately, R ²¹⁹The expression alkyl, n ²²Expression 0-2, and Z ²¹The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl, aryl or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).Especially preferred A wherein ²²Expression O, R ²¹⁶The expression alkyl, R ²¹⁷Or R ²¹⁸The expression hydrogen atom, remaining expression hydrogen atom or alkyl, n ²²Expression 0 or 1 and Z ²¹The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl, aryl or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).

At (PF1) in (PF5), n ²¹Expression 0 or 1, and work as n ²¹Be 1 o'clock, L ²¹Expression can be passed through N, S, Se, the compound of Te or P atom and golden coordination.Described examples for compounds comprises and replacing or the unsubstituted amines (one-level that preferably has 1-30 carbon atom, secondary or three grades of arylamine or alkanamine), 5-or 6-member heterocyclic ring containing nitrogen (refer to by N O, any 5-that constitutes or 6-member heterocyclic ring containing nitrogen can contain substituting group among S and the C; Described heterocycle can pass through N atom or substituting group and golden coordination, the example comprises benzotriazole, triazole, tetrazolium, indazole, benzimidazole, imidazoles, the pyrroles, pyrrolidine, imidazolidine and morpholine), (term used herein " meso-ionic compound " is meant 5-or the 6-membered heterocyclic compound that can't represent with arbitrary covalency or the satisfaction of polar structure formula to meso-ionic compound, but this compound has with all and forms the sixfold pi-electron that the atom of ring associates, the identical negative charge amount balance on wherein this endless belt has part positive charge and this electric charge and encircles outer atom or group; The example of Jie-ion ring comprises imidazole ring, pyrazoles ring oxazole ring, thiazole ring, triazole ring, tetrazole ring, thiadiazoles Huan ， oxadiazole ring, thiatriazole Huan is with the oxatriazole ring), mercaptan compound (alkyl sulfhydryl that preferably has 1-30 carbon atom has the aryl mercaptan of 6-30 carbon atom or contains at least one N, 5-to the 7-unit ring heterocyclic thiol of O or S atom), sulfide compound (preferably contains the S atom and is selected from the alkyl with 1-30 carbon atom, aryl or contain at least one N, O or S atom are as separately the heteroatomic 5-or the compound of the arbitrary group combination in the 7-unit ring heterocyclic group, and this compound can be a symmetry or asymmetric; Example comprises dialkyl sulfide, diaryl sulfide, two heterocyclic radical thioethers, the alkylaryl thioether, alkyl heterocyclic thioether and aryl-heterocyclic base thioether), the disulfide (compound that preferably contains two S atoms, described two S atoms respectively be selected from alkyl with 1-30 carbon atom, aryl or contain at least one N, O or S atom are as any two the group combinations in heteroatomic 5-to the 7-unit ring heterocycle separately, and this compound can be a symmetry or asymmetric; Example comprises dialkyl disulphides, diaryl disulfide, two heterocyclic radical disulfide, alkylaryl disulfide, alkyl heterocycle based bisulfide and aryl-heterocyclic based bisulfide, preferred dialkyl disulphides, diaryl disulfide and alkylaryl disulfide), (thioamides can partly be a ring structure to thioamide compound, or the thioamides of non-ring structure; The optional U.S. Patent number freely 4,030,925,4,031 of available thioamides, 127,4,080,207,4,245,037,4,255,511,4,266,031 and 4, the 276,364 and Research Disclosure, the 151st volume, the 15162nd (Nov., 1976) and the 176th the volume, disclosed compound in the 17626th (Dec., 1978); They especially comprise thiocarbamide, thioxanthamide, dithiocar-bamate, 4-thiazoline-2-thioketones, thiazoline-2-thioketones, 4-oxazoline-2-thioketones oxazoline-2-thioketones, 2-pyrazoline-5-thioketones, the 4-imidazoline-2-sulfur-one, the 2-2-thiohydantoin, rhodanine, different rhodanine, 2-sulphur-2,4-Zuo oxane diketone, bathyran, tetrazolium quinoline-5-thioketones, 1,2,4-triazoline-3-thioketones, 1,3,4-Thiadiazoline-2-thioketones, 1,3,4-oxadiazole quinoline-2-thioketones, benzo imidazoline-2-thioketone benzoxazole quinoline-2-thioketones and benzothiazole quinoline-2-thioketones, it can be substituted separately), selenol compound (the alkyl selenol that preferably has 1-30 carbon atom, aryl selenol or contain at least one N, 5-to the 7-unit heterocycle selenol of O or S atom), the selenide compound (preferably contains Se atom and the alkyl with 1-30 carbon atom, the selenide compound of aryl or heterocyclic radical combination, this compound can be a symmetry or asymmetric with respect to the Se atom, example comprises the dialkyl group selenide, the diaryl selenide, two heterocyclic radical selenides, the alkylaryl selenide, alkyl heterocyclic selenide and aryl-heterocyclic base selenide, preferred dialkyl group selenide, diaryl selenide and alkylaryl selenide), two selenium compounds (preferably contain two Se atoms respectively be selected from alkyl with 1-30 carbon atom, two selenium compounds of any two the group combinations in aryl or the heterocyclic radical, and this compound can be a symmetry or asymmetric with respect to seleno group, example comprises the dialkyl group diselenide, the diaryl diselenide, two heterocyclic radical diselenides, the alkylaryl diselenide, alkyl heterocyclic diselenide and aryl-heterocyclic base diselenide, preferred dialkyl group diselenide, diaryl diselenide and alkylaryl diselenide), selenium substituted acid amide compound (example comprises the compound that replaces with the Se atom corresponding to the S atom in the aforesaid thioamide compound), telluromercaptan compound (example comprises the compound that replaces with the Te atom corresponding to the Se atom in the aforesaid selenol compound), telluride compound (example comprises the compound that replaces with the Te atom corresponding to the Se atom in the aforesaid selenide compound), two tellurides (example comprises the compound that replaces with the Te atom corresponding to the Se atom in the aforesaid diselenide), telluro amide compound (example comprises the compound that replaces with the Te atom corresponding to the Se atom in the aforesaid selenium substituted acid amide compound), alkylphosphines compound (the one-level that preferably has 1-20 carbon atom, secondary or three grades of alkylphosphines) and aromatic yl phosphine compound (one-level that preferably has 1-20 carbon atom, secondary or three grades of aryl phosphines).

L ²¹Preferably 5-or 6-member heterocyclic ring containing nitrogen compound, meso-ionic compound, mercaptan compound, sulfide compound, sulphamide compound, selenol compound, selenide compound, selenium substituted acid amide compound, alkylphosphines compound or aromatic yl phosphine compound; More preferably 5-or 6-member heterocyclic ring containing nitrogen compound, meso-ionic compound, mercaptan compound, sulfide compound, sulphamide compound, selenol compound, alkylphosphines compound or aromatic yl phosphine compound; Meso-ionic compound most preferably, mercaptan compound, sulfide compound, sulphamide compound, selenol compound, alkylphosphines compound or aromatic yl phosphine compound.The compound of arbitrary expression is as L in the special preferred formula (PL1) to (PL5) ²¹

Formula (PL1) formula (PL2) formula (PL3)

Formula (PL4) formula (PL5)

In (PL5), Ch represents S in formula (PL1), Se or Te; And M ²¹The balance cation of expression hydrogen atom or each compound electric charge that neutralizes.In formula (PL1), A ²³Expression O, S or NR ²²³And R ²²⁰, R ²²¹, R ²²²And R ²²³Have respectively and aforementioned R ²¹, R ²², R ²³And R ²⁴Identical implication, and preferable range separately is identical.

In formula (PL2), X ²²Expression O, S or NR ²²⁴And Y ²²Expression H, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OR ²²⁵, SR ²²⁶Or N (R ²²⁷) R ²²⁸R ²²⁴, R ²²⁵, R ²²⁶, R ²²⁷And R ²²⁸Have respectively and aforementioned R ²⁵, R ²⁶, R ²⁷, R ²⁸And R ²⁹Identical implication, and preferable range separately is identical.

In formula (PL3), R ²²⁹, R ²³⁰And R ²³¹Have respectively and aforementioned R ²¹⁰, R ²¹¹And R ²¹²Identical implication, and preferable range separately is identical.

In formula (PL4), W ²², R ²³², R ²³³And R ²³⁴Have respectively and aforementioned W ²¹, R ²¹³, R ²¹⁴And R ²¹⁵Identical implication, and preferable range separately is identical.

In (PL5), A ₂₄Expression O, S, Se, Te or NR ²³⁸R ²³⁵, R ²³⁶, R ²³⁷, R ²³⁸, Z ²²And n ²³Have respectively and aforementioned R ²¹⁶, R ²¹⁷, R ²¹⁸, R ²¹⁹, Z ²¹And n ²²Identical implication, and preferable range separately is identical.

Work as L ²¹When being selected from the compound of formula (PL1) arbitrary expression in (PL5), the compound of arbitrary expression can become symmetrical complex compound or the asymmetric complex compound of relative Au (I) in the formula (PF1) to (PF5).In the present invention, symmetrical complex compound or asymmetric complex compound all are fit to, but the more preferably relative symmetrical complex compound of Au (I).

In (PL5), Ch represents S in formula (PL1), Se or Te, but preferably S or Se are as Ch in the present invention, and more preferably S is as Ch.

In formula (PL1) in (PL5), M ²¹The balance cation of expression hydrogen atom or each compound electric charge that neutralizes.Work as M ²¹Expression is during balance cation, be preferably inorganic cation such as alkaline metal (as Li, Na, K, Rb, Cs) or earth alkali metal (as Mg, Ca, Ba), or organic cation is as replacing or unsubstituted ammonium ion or phosphonium ion.Yet, work as M in the present invention ²¹When being inorganic cation, it neither represents Ag ⁺, do not represent Au yet ⁺In the present invention, M ²¹Hydrogen atom preferably, alkali metal cation, alkaline earth metal cation or replacement or unsubstituted ammonium ion, more preferably alkali metal cation or replacement or unsubstituted ammonium ion, even further preferred as alkali kation or replacement or unsubstituted ammonium ion.

In the compound of formula (PL1) expression, preferred M wherein in invention ²¹Be alkali metal cation, Ch is S or Se, A ²³Be O or S, R ²²⁰And R ²²¹Each is hydrogen atom naturally, alkyl or aryl and R ²²²It is the situation of alkyl or aryl.More preferably M wherein ²¹Be alkali metal cation, Ch is S, A ²³Be O or S, R ²²⁰And R ²²¹Each is hydrogen atom naturally, alkyl or aryl and R ²²²It is the situation of alkyl or aryl.Particularly preferred situation is R wherein ²²²By with R ²²⁰Or and R ²²¹In conjunction with the ring structure that forms is glucose, mannose, galactose, wood sugar, lyxose, arabinose, ribose, fucose, idose, talose, allose, altrose, rhamnose, sorbose, digitoxose, 2-deoxyglucose, the 2-deoxy-galactose, fructose, aminoglucose, galactosamine, glucuronic acid, its any sugar derivatives is (corresponding to the A in wherein (PL1) ²³Be oxygen (O)) situation of atom), or its any sulfur analogs is (corresponding to the A in wherein (PL1) ²³Be the situation of sulphur (S) atom).For various sugared structures, all exist the different α of 1-position conformation-and β-isomeride and the mutually D-and L-body of mirror image, but the present invention's as broad as long these isomeride fully.Be suitable as L ²¹Examples of compounds comprise thioglucose, sulfo-mannose, sulfo-galactose, the sulfo-wood sugar, sulfo-lyxose, sulfo-arabinose, seleno glucose, seleno mannose, seleno galactose, the seleno wood sugar, seleno lyxose, seleno arabinose, telluro glucose, its alkali metal salt, its sulfur analogs and its derivant.

In the compound of formula (PL2) expression, preferred M wherein ²¹The expression alkali metal cation, Ch is S or Se, X ²²Be O or S, Y ²²Be H, alkyl, aryl, heterocyclic radical, OR ²²⁵, SR ²²⁶Or N (R ²²⁷) R ²²⁸, and R ²²⁴To R ²²⁸Each is alkyl naturally, the situation of aryl or heterocyclic radical.More preferably M wherein ²¹The expression alkali metal cation, Ch is S or Se, X ²²Be O, Y ²²Be alkyl, the situation of aryl or heterocyclic radical.Best circumstance is M wherein ²¹The expression alkali metal cation, Ch is S, X ²²Be O, and Y ²²Be alkyl, aryl or heterocyclic radical.

In the compound of formula (PL3) expression, preferred M wherein ²¹The expression alkali metal cation, Ch is S or Se, R ²²⁹And R ²³⁰Each is electron withdraw group naturally, and R ²³¹Be hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclic oxy group, the situation of amino or acylamino-.More preferably M wherein ²¹The expression alkali metal cation, Ch is S or Se, R ²²⁹And R ²³⁰Each is electron withdraw group naturally, and R ²³¹Be hydrogen atom, alkyl, the situation of aryl or heterocyclic radical.Best circumstance is M wherein ²¹The expression alkali metal cation, Ch is S, R ²²⁹And R ²³⁰Each is electron withdraw group naturally, and R ²³¹Be hydrogen atom, alkyl, aryl or heterocyclic radical.

In the compound of formula (PL3) expression, also preferably by R ²²⁹And R ²³⁰In conjunction with and the compound of nonaromatic 5-to the 7-unit ring that forms.At this, M ²¹Be alkali metal cation, Ch is S or Se, R ²³¹Be hydrogen atom, alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group, heterocyclic oxy group, amino or acylamino-.In representing more preferably the formula of compound (PL3), R ²²⁹And R ²³⁰In conjunction with forming the first ring of nonaromatic 5-to 7-, M ²¹Be alkali metal cation, Ch is S or Se, and R ²³¹Be hydrogen atom, alkyl, aryl or heterocyclic radical.Under the situation of optimization compound, M ²¹Be alkali metal cation, Ch is S, R ²²⁹And R ²³⁰Nonaromatic 5-to 7-is first to be encircled in conjunction with forming, and R ²³¹Be hydrogen atom, alkyl, aryl or heterocyclic radical.

In the compound of formula (PL4) expression, preferred M wherein ²¹Be alkali metal cation, Ch is S or Se, W ²²Be electron withdraw group, and R ²³²To R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, the situation of alkoxy carbonyl or carbamyl.More preferably M wherein ²¹Be alkali metal cation, Ch is S or Se, W ²²Be electron withdraw group, and R ²³²To R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, the situation of alkoxy carbonyl or carbamyl.Best circumstance is M wherein ²¹Be alkali metal cation, Ch is S, W ²²Be electron withdraw group, and R ²³²To R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.

In the compound of formula (PL4) expression, also preferably by W ²²And R ²³²In conjunction with and the compound of nonaromatic 5-to the 7-unit ring that forms.At this, M ²¹Be alkali metal cation, Ch is S or Se, R ²⁶Be alkyl, alkenyl, aryl or heterocyclic radical, and R ²³³And R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.More preferably M wherein ²¹Be alkali metal cation, Ch is S or Se, W ²²And R ²³²Mutually combining forms the first ring of nonaromatic 5-to 7-, and R ²³³And R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, the situation of alkoxy carbonyl or carbamyl.Best circumstance is that wherein M21 is an alkali metal cation, and Ch is S, W ²²And R ²³²Mutually combining forms the first ring of nonaromatic 5-to 7-, and R ²³³And R ²³⁴Each is hydrogen atom naturally, halogen atom, and alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, cyano group, carboxyl, sulfo group, alkyl-or aryl-sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl or carbamyl.

In the compound of formula (PL5) expression, preferably wherein Ch is S or Se, A ₂₄Expression O, S or NR ²³⁸, R ²³⁵Be hydrogen atom, alkyl, aryl or acyl group, R ²³⁶And R ²³⁷Represent hydrogen atom separately, alkyl or aryl, R ²³⁸The expression hydrogen atom, alkyl or aryl, n ²³Expression 0 to 2, and Z ²²The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl-, aryl-or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).More preferably wherein Ch is S or Se, A ₂₄Expression O, S or NR ²³⁸, R ²³⁵Be alkyl, R ²³⁶And R ²³⁷Represent hydrogen atom or alkyl separately, R ²³⁸The expression alkyl or aryl, n ²³Expression 0 to 2, and Z ²²The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl-, aryl-or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).Further preferred A wherein ₂₄Expression O, S or NR ²³⁸, R ²³⁵Be alkyl, R ²³⁶And R ²³⁷Represent hydrogen atom or alkyl separately, R ²³⁸The expression alkyl, n ²³Expression 0 to 2, and Z ²²The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl-, aryl-or heterocyclic radical) amino, urea groups, alkyl sulfenyl, the situation of artyl sulfo or sulfo group (comprising its salt).Best circumstance is that wherein Ch is S, A ₂₄Expression O, R ²³⁵Be alkyl, R ²³⁶Or R ²³⁷Expression hydrogen atom and all the other expression hydrogen atom or alkyl, n ²³Expression 0 to 1, and Z ²²The expression alkyl, aryl, carboxyl (comprising its salt), hydroxyl, alkoxy, aryloxy group, (alkyl-, aryl-or heterocyclic radical) amino, urea groups, alkyl sulfenyl, artyl sulfo or sulfo group (comprising its salt).

Can the middle arbitrary compound represented of synthesis type (PL1) to (PL5) according to disclosed method among the JP-A-2004-4446.

In formula (PL1) to (PL5) in the compound of arbitrary expression, preferably with formula (PL1), (PL2) and arbitrary compound of expression (PL5) as L ²¹, more preferably with formula (PL1) or (PL5) expression compound as L ²¹, especially preferably the compound that formula (PL1) is represented is as L ²¹

The compound of formula (PF6) expression then, will be described.

In formula (PF6), J ²¹The expression balance anion.The example of described balance anion comprises halide ion (for example, F ^-, Cl ^-, Br ^-, I ^-), tetrafluoro boric acid salt ion (BF ₄ ^-), hexafluorophosphoric acid salt ion (PF ₆ ^-), hexafluoro-antimonic acid salt ion (SbF ₆ ^-), aryl sulfonic acid salt ion (for example, the p-toluenesulfonic acid salt ion), alkyl sulfonic acid salt ion (for example, methane sulfonate ion, trifluoro-methanyl sulfonate ion) and carboxylate ion (for example, acetate ion, trifluoracetic acid salt ion, benzoic acid salt ion).In addition, preferably these balance anions do not comprise can ADSORPTION OF GOLD group, typically as sulfydryl (SH), thioether group (S-), the selenide base (Se-) and the telluride base (Te-).

In the present invention, J ²¹Halide ion preferably, tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion, aryl sulfonic acid salt ion or alkyl sulfonic acid salt ion, more preferably halide ion, tetrafluoro boric acid salt ion or hexafluorophosphoric acid salt ion, further preferred halide ion.In halide ion, preferred Cl ^-, Br ^-Or I ^-, more preferably Cl ^-Or Br ^-, further preferred Cl ^-

In formula (PF6), Q ²¹And Q ²²Be selected from the compound of arbitrary expression in aforementioned (SE1) to (SE3).

Work as Q ²¹Or Q ²²When being the compound of (SE1) expression, preferred M ¹And M ²Each is hydrogen atom naturally, alkyl, and alkenyl, aryl, heterocyclic radical or acyl group, Q are alkyl, alkenyl, aryl or NM ⁴M ⁵, and M ⁴And M ⁵Be hydrogen atom, alkyl, alkenyl, aryl or heterocyclic radical.More preferably M wherein ¹And M ²Each is hydrogen atom naturally, alkyl, and alkenyl or aryl, Q are alkyl, aryl or NM ⁴M ⁵, and M ⁴And M ⁵Be hydrogen atom, alkyl, the situation of alkenyl or aryl.Further preferred M wherein ¹And M ²Each is hydrogen atom naturally, and alkyl or aryl, Q are NM ⁴M ⁵, and M ⁴And M ⁵Be hydrogen atom, the situation of alkyl or aryl.

Work as Q ²¹Or Q ²²When being the compound of (SE2) expression, preferred X ¹To X ³Represent alkyl separately, aryl or heterocyclic radical, more preferably X ¹To X ³Represent alkyl separately.

Work as Q ²¹Or Q ²²When being the compound of (SE3) expression, preferred E ¹And E ²Be selected from formula (T2) separately to (T4), more preferably E ¹Or E ²Be selected from formula (T4), and all the other are selected from (T2), (T3) or (T4), further preferred E ¹Or E ²Be selected from formula (T4), and all the other are selected from (T3) or (T4), preferred especially E ¹And E ²All be selected from formula (T4).

In the compound of formula of the present invention (PF6) expression, preferred J wherein ²¹Be halide ion, tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion, aryl sulfonic acid salt ion or alkyl sulfonic acid salt ion, n ²³Be 0 or 1, and Q ²¹And Q ²²Be selected from the situation of compound of formula (SE1) or formula (SE3) expression separately, more preferably J wherein ²¹Be halide ion, tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion, n ²³Be 0 and Q ²¹Be the situation that is selected from the compound of formula (SE3) expression, further preferred J wherein ²¹Be halide ion, n ²³Be 0 and Q ²¹It is the situation that is selected from the compound of formula (SE3) expression.

In formula (PF1) to (PF6) in the compound of arbitrary expression, preferred compound is (PF1), (PF5) and the compound of arbitrary expression (PF6), and more preferably formula (PF1) or (PF6) compound of expression, the most preferably compound of formula (PF6) expression.

Next, will be below the instantiation of the compound of arbitrary expression in the display type (PF1) to (PE6), but the present invention is not limited to this.And about having the compound of a plurality of steric isomers, their space structure is not limited to these.In addition, the Et in the above-mentioned exemplary compounds, Me, i-Pr, Ph, Bn and Ac represent ethyl respectively, methyl, isopropyl, phenyl, benzyl and acetyl group.

In the present invention, the addition of the compound of arbitrary expression can change use according to situation in the formula (PF1) to (PF6) in broad range, but is generally 1 * 10 ^-7To 5 * 10 ^-3The moles/mole silver halide is preferably 5 * 10 ^-6To 5 * 10 ^-4The moles/mole silver halide.

Can be with the compound dissolution of arbitrary expression in the formula (PF1) to (PF6) at water, alcohol (as methyl alcohol or ethanol), ketone (as acetone) and acid amides (as dimethyl formamide), in dibasic alcohol (as the metering system ethyl glycol) or the ester (as ethyl acetate), or it is added as the solid dispersion that makes with known dispersion method (fine crystals spreading agent).

The The compounds of this invention of arbitrary expression can add in any stage of preparation emulsion in the formula (PF1) to (PF6), but preferably after silver halide particle forms and chemical sensitization finish before adding.Compound about formula (PF1) to (PF6) expression can be used alone in one deck or two-layer or multilayer, or mixes and use its two or more.In addition, they can be used in combination with other selenium sensitizer simultaneously.

According to disclosed method among the JP-A-2004-280026 can synthesis type (PF1) to (PF6) in the compound of arbitrary expression.

Selenium sensitizer as using in the present invention is preferably SE1-2, SE2-1, SE2-12, SE3-16 and SE3-31, SE3-4 more preferably, SE3-9, SE3-17, SE3-29 and SE3-37, further preferred PF2-5, PF3-6, PF4-3 and PF5-7 are preferably PF1-1 and PF6-1 especially.

The selenium compound that is used as the selenium sensitizer in color silver halide photographic-material of the present invention is preferably compound (SE1-2), (SE2-1), and (SE2-12), (SE3-16), (SE3-31), (SE3-4), (SE3-17) or (SE3-37), and gold-selenium compound is preferably compound (PF2-5), (PF3-6), and (PF4-3), (PF5-7), (PF3-9), (PF3-29), (PF1-1) or (PF6-1).

Generally speaking, silver emulsion is a chemical sensitization.

In the present invention, silver halide particle can carry out selenium sensitizing with other chemical sensitizer combination.For chemical sensitization, can be used alone or in combination sulphur sensitizing (particularly by adding the sensitizing of unsettled sulphur compound), noble metal sensitizing (particularly golden sensitizing), or reduction sensitization.For chemical sensitization, preferably use JP-A-62-215272, disclosed compound in 22 pages of right hurdles of downside to the, the 18th page of right hurdle upside.In silver emulsion, compare other preferred those silver emulsions with gold compound sensitizing.

In the present invention, except sulphur sensitizing and tellurium sensitizing, can also be used in combination golden sensitizing and other noble metal sensitizing.The golden sensitizer that preferred compositions is used is colloidal gold sulfide or stability constant log β ₂Gold complex for 21-35.Except these golden sensitizers, can also use the conventional gold compound that uses (for example gold chloride, potassium chloroaurate, gold trichloride, sulphur auric potassium cyanide, Potassium Tetraiodoaurate, four auric cyanide acids, sulphur ammonium aurocyanide, pyridine radicals trichlorine gold).

In addition, can be used in combination the reduction sensitization agent with above-mentioned sensitizer.The example of reduction sensitization agent comprises stannous chloride, amino imino methyl-sulfinic acid, hydrazine derivate, borane compound, silane compound, and polyamine compounds.

In addition, preferably in the presence of ag halide solvent, use the chemical sensitization of above-mentioned selenium compound in the present invention.Here the example of operable ag halide solvent comprises thiocyanate (as potassium rhodanide), sulfide compound is (as at U.S. Patent number 3,021,215 and 3,271,157, the compound of describing among JP-B-58-30571 and the JP-A-60-136736, particularly 3,6-two sulfo-s-1,8-octane glycol), quaternary thiourea compound is (as at JP-B-59-11892 and U.S. Patent number 4, the compound, particularly tetramethyl thiocarbamide described in 221,863), the thione compounds of in JP-B-60-11341, describing, the sulfhydryl compound of in JP-B-63-29727, describing, the meso-ionic compound of describing in JP-A-60-163042 is at U.S. Patent number 4,782, the seleno ether compound of describing in 013, the telluro ether compound of in Japanese patent application No. 63-17474, describing, and sulphite.In these solvents, more preferably thiocyanate, sulfide compound, quaternary thiourea compound and thione compounds.The consumption of ag halide solvent is about 1 * 10 ^-5To 1 * 10 ^-2The moles/mole silver halide.

Below, use description to the metal (complex compound) in the color silver halide photographic-material of the present invention.

Silver emulsion preferably contains iridium.Preferred iridium is under the state that forms iridium complex, and be central metal with iridium, six coordinate complex with six parts is fit to be introduced in the silver halide particle equably.The suitable embodiment that is used for the iridium of this color silver halide photographic-material is the 6-co-ordination complex, its central metal is iridium (Ir) atom, some part is chlorine (Cl), bromine (Br) or iodine (I) atom, preferred its central metal is that iridium (Ir) atom and all six parts are chlorine (Cl), the 6-co-ordination complex of bromine (Br) or iodine (I) atom.In this case, the chlorine atom, bromine atoms and iodine atom can be mixed in the 6-co-ordination complex.In order under high illumination exposure, to obtain hard contrast, especially preferably will have iridium (Ir) atom as central metal and chlorine (Cl), bromine (Br) or iodine (I) atom are introduced the phase that contains silver bromide as the 6-co-ordination complex of some parts.

Central metal is that iridium (Ir) atom and all six parts are chlorine (Cl), and the example of the 6-co-ordination complex of bromine (Br) or iodine (I) atom comprises [IrCl ₆] ^2-, [IrCl ₆] ^3-, [IrBr ₆] ^2-, [IrBr ₆] ^3-[IrI ₆] ^3-, but be not limited to these complex ions.

Another suitable method that contains the compound of iridium preferably has the six coordinate complex of iridium atom as central metal and at least one part except halogen atom and cyanogen part, preferably has Ir as central metal and hydrone (H ₂O), OH, oxygen atom (O), OCN, replacement or unsubstituted thiazole or replacement or unsubstituted thiadiazoles are as the six coordinate complex of a part, and more preferably wherein central metal is that Ir and at least one part are hydrone (H ₂O), OH, oxygen atom (O), OCN replaces or unsubstituted thiazole is chlorine (Cl) with all the other parts, the six coordinate complex of bromine (Br) or iodine (I) atom.Particularly preferred six coordinate complex has Ir as central metal, the 5-methylthiazol, and 2-chloro-5-fluorine thiadiazoles or 2-bromo-5-fluorine thiadiazoles are as one or two part and Cl, and Br or atom are as all the other parts.

Has iridium (Ir) atom as central metal, at least one hydrone (H ₂O), OH, oxygen atom (O), OCN, or replacement or unsubstituted thiazole be as its part, and chlorine (Cl), bromine (Br) or iodine (I) atom comprise [Ir (H as the example of the six coordinate complex of all the other parts ₂O) Cl ₅] ^2-, [Ir (OH) Br ₅] ^3-, [Ir (OCN) Cl ₅] ^3-, [Ir (thiazole) Cl ₅] ^2-, [Ir (5-methylthiazol) Cl ₅] ^2-, [Ir (2-chlorine 5-fluorine thiadiazoles) Cl ₅] ^2-[Ir (2-bromo-5-fluorine thiadiazoles) Cl ₅] ^2-But it does not limit the present invention.

Except the complex compound that comprises above-mentioned iridium, silver emulsion preferably includes has CN part and iron, ruthenium, and rhenium or osmium are as its 6-co-ordination complex of central metal separately, as [Fe (CN) ₆] ^4-, [Fe (CN) ₆] ^3-, [Ru (CN) ₆] ^4-, [Re (CN) ₆] ^4-[Os (CN) ₆] ^4-The silver emulsion that is preferred for this color silver halide photographic-material further comprises having ruthenium; rhenium and osmium atom are as its pentachloro-nitrosyl radical and the pentachloro-sulfo-nitrosyl radical complex compound of central metal separately; with have rhodium atom as central metal and chlorine, bromine or iodine is as the six coordinate complex of its part.These parts can be partially hydrated.

Above-mentioned metal complex is a negative ion.When they and salt forming cation, balance cation is preferably and is dissolved in the water those easily.Its preferred embodiment comprises alkali metal ion, as sodion, and potassium ion, rubidium ion, cesium ion, and lithium ion; Ammonium ion, and alkyl phosphate ion.These metal complexs can be dissolved in the water or in the mixed solvent of water and suitable water-miscible organic solvent (as alcohol, ether, dibasic alcohol, ketone, ester, and acid amides) and use.The addition of these metal complexs is preferably 1 * 10 in the particle forming process ^-10Mole is to 1 * 10 ^-3Moles/mole silver, preferred especially 1 * 10 ^-9Mole is to 1 * 10 ^-5Moles/mole silver, but optimised quantity is determined by kind.

When forming, silver halide particle preferably these metal complexs are directly added reaction solution, or add the reaction solution that forms particle indirectly by halide solution or other solution that add to form silver halide particle, so that they mix the inside of silver halide particle.In addition, the method for also preferably using metal complex wherein to mix silver halide particle is mixed the fine granular of complex compound in advance and is added fine granular by preparation and carries out physical ripening.In addition, also preferably can make up the inside that these methods are mixed complex compound silver halide particle.

These metal complexs are impregnated in the situation of silver halide particle inside therein, and they preferably are evenly distributed on the inside of particle.On the other hand, as " JP-A-4-208936, JP-A-2-125245 and JP-A-3-188437 are disclosed, and they also preferably only are distributed in the top layer of particle.Alternatively, they also preferably only are distributed in the inside of particle and particle surface covers with the layer that does not contain complex compound.In addition, as U.S. Patent number 5,252,451 and 5,256,530 is disclosed, and also preferred silver halide particle carries out physical ripening in the presence of the fine granular that has mixed metal complex, to modify the particle surface phase.In addition, these methods can be used in combination.Two or more complex compounds can mix the inside of single silver halide particle.The halogen composition that above-mentioned metal complex is mixed the site is not particularly limited, but the preferred center metal is that iridium (Ir) atom and six parts all are chlorine (Cl), and the six coordinate complex of bromine (Br) or iodine (I) atom is impregnated in maximum silver bromide concentration range.

The specific silver emulsion that is preferred for first embodiment of the invention comprises the compound of following formula (D1) expression.

Formula (D1)

[M ^D1X ^D1 _n1L ^D1 _(6-n1)] ^m1

In formula (D1), M ^D1Expression Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt; X ^D1The expression halide ion; L ^D1Expression is different from X ^D1Part; N1 represents integer 3,4,5, or 6; And m1 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.Here, a plurality of X ^D1Can be identical or different.As a plurality of L ^D1When existing, a plurality of L ^D1Can be identical or different.Yet, in the part of each metal complex of formula (D1) expression, do not have or only have one to be cyanogen (CN-) part.

In the metal complex of formula (D1) expression, preferably by the metal complex of formula (D1A) expression.

Formula (D1A)

[M ^D1AX ^D1A _n3L ^D1A _(6-n3)] ^m3

In formula (D1A), M ^D1AExpression Re, Ru, Os, or Rh; X ^D1AThe expression halide ion; Work as M ^D1ABe Re, Ru, or L during Os ^D1AExpression NO or NS, and work as M ^D1AWhen being Rh, L ^D1AExpression H ₂O, OH, or O; N3 represents integer 3,4,5, or 6; M3 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.X ^D1AHave and the middle X of formula (D1) ^D1Identical implication, and preferable range is also identical.

Here, 3 to 6 X ^D1ACan be identical or different mutually.As a plurality of L ^D1AWhen existing, a plurality of L ^D1ACan be identical or different mutually.

These metal complexs can pass through reference as Shogen Nakahara, Muki Kagobutsu Sakutai Jiten(Dictionary of Inorganic Compounds and Complexes) finished by Kodansha Scientific, and Kodansha Ltd. publishes in June 10,1997; Jikken Kagaku Koza(Lectures onExperimental Chemistry), 4th Ed., Vol.17, Maruzen Co., Ltd.; Gmelin Handbook of Inorganic and Organometallic Chemistry; Comprehensive Coordination Chemistry, Volume 4, Middle Transition Elements, Pergamon Press; With Kagehei Ueno (editor), Chelate Kagaku (1) to (6), Nankodo Co., Ltd synthesizes.Except these books, can also be with reference to U.S. Patent number 5,360,712, JP-A-2001-302558, JP-A-2002-155055, JP-A-2002-274855, JP-A-2002-357879 and JP-A-2003-95661 are used to synthesize.

Below show preferred embodiment by the metal complex of formula (D1) expression.Yet, the invention is not restricted to these complex compounds.

[ReCl ₆] ^2-

[ReCl ₅(NO)] ^2-

[RuCl ₆] ^2-

[RuCl ₆] ^3-

[RuCl ₅(NO)] ^2-

[RuCl ₅(NS)] ^2-

[RuBr ₅(NS)] ^2-

[OsCl ₆] ^3-

[OsCl ₆] ^2-

[OsCl ₅(NO)] ^2-

[OsBr ₅(NS)] ^2-

[RhCl ₆] ^3-

[RhCl ₅(H ₂O)] ^2-

[RhCl ₄(H ₂O) ₂] ^-

[RhBr ₆] ^3-，

[RhBr ₅(H ₂O)] ^2-

[RhBr ₄(H ₂O) ₂] ^-

[PdCl ₆] ^2-

[PtCl ₆] ^2-

Among them, preferred especially [RuCl ₅(NO)] ^2-, [OsCl ₅(NO)] ^2-, [RhBr ₆] ^3-[RhCl ₆] ^3-, preferred especially [RuCl ₅(NO)] ^2-

The specific silver emulsion that also is preferred for second embodiment of the invention comprises the compound of following formula (D2) expression.

Formula (D2)

[IrX ^D2 _n2L ^D2 _(6-n2)] ^m2

In formula (D2), X ^D2Expression halide ion or pseudohalogen ion (except cyanic acid ion OCN); L ^D2Expression is different from X ^D2Part; N2 represents integer 3,4, or 5; M2 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.Here, a plurality of X ^D2Can be identical or different mutually.As a plurality of L ^D2When existing, these a plurality of L ^D2Can be identical or different mutually.

In above, pseudohalogen (class halogen) ion is meant that character is similar to the ion of halide ion, and the example comprises cyanide ion (CN ^-), thiocyanate ion (SCN ^-), selenocyanic acid radical ion (SeCN ^-), telluro cyanic acid ion (TeCN ^-), nitrine dithiocarbonic acids salt ion (SCSN ₃ ^-), fulminate ion (ONC ^-) and azide ion (N ₃ ^-), but do not comprise cyanic acid ion (OCN ^-).

X ^D2Be preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyano ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion.Among these, preferred especially chloride ion and bromide ion.Specifically do not limit L ^D2, it can be can be with or can uncharged organic or inorganic compound, preferred uncharged organic or inorganic compound.

In the metal complex of formula (D2) expression, the metal complex of preferred following formula (D2A) expression.

Formula (D2A)

[IrX ^D2A _n4L ^D2A _(6-n4)] ^m4

In formula (D2A), X ^D2AExpression halide ion or the pseudohalogen ion except cyanic acid ion.L ^D2AExpression is different from X ^D2AInorganic part.N4 represents integer 3,4, or 5.M4 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.In formula (D2A), X ^D2AHave and the middle X of formula (D2) ^D2Identical implication and preferable range are also identical.L ^D2ABe preferably water (H ₂O), OCN, ammonia (NH ₃), phosphine (PH ₃) and carbonyl (CO), special preferred water (H ₂O).

At this, 3 to 5 X ^D2ACan be mutual or different.As a plurality of L ^D2AWhen existing, these a plurality of L ^D2ACan be mutual or different.

In the metal complex of formula (D2) expression, further preferably by the metal complex of following formula (D2B) expression.

Formula (D2B)

[IrX ^D2B _n5L ^D2B _(6-n5)] ^m5

In formula (D2B), X ^D2BExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^D2BExpression contains chain hydrocarbon or the cyclic hydrocarbon part as basic structure, or the part that replaced by other atom or atomic group of the part carbon atom of basic structure or hydrogen atom wherein; N5 represents integer 3,4 or 5; M5 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.X ^D2BHave and the middle X of formula (D2) ^D2Identical implication and preferable range are also identical.L ^D2BExpression contains chain hydrocarbon or the cyclic hydrocarbon part as basic structure, or the part that replaced by other atom or atomic group of the part carbon atom of basic structure or hydrogen atom wherein, but is not cyanide ion.L ^D2BBe preferably heterogeneous ring compound, more preferably 5-membered heterocyclic compound part.In the 5-membered heterocyclic compound, further preferably in its 5-unit ring skeleton, contain the compound of at least one nitrogen-atoms and at least one sulphur atom.

Here, 3 to 5 X ^D2BCan be identical or different.As a plurality of L ^D2BWhen existing, these a plurality of L ^D2BCan be identical or different.

In the metal complex of formula (D2B) expression, more preferably by the metal complex of formula (D2C) expression.

Formula (D2C)

[IrX ^D2C _n6L ^D2C _(6-n6)] ^m6

In formula (D2C), X ^D2CExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^D2CBe illustrated in the 5-unit ring part that contains at least one nitrogen-atoms and at least one sulphur atom in its ring skeleton, on the carbon atom of described ring skeleton, can have substituting group; N6 represents integer 3,4, or 5; M6 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.

X ^D2CHave and the middle X of formula (D2) ^D2Identical implication and preferable range are also identical.L ^D2CDescribed in substituting group on the carbon atom of ring skeleton be preferably and have than the n-pro-pyl substituting group of small size more.Substituent preferred embodiment comprises methyl, ethyl, methoxyl, ethoxy, cyano group; isocyano group, cyanate radical (cyanate) group, isocyano group, thiocyanate radical (thiocyanate) group, different thiocyanate radical group; formoxyl, thioformyl, hydroxyl, sulfydryl; amino, diazanyl, azido, nitro; nitroso-, hydroxyl amino, carboxyl, carbamyl; fluorine, chlorine, bromine, and iodine.

At this, 3 to 5 X ^D2CCan be identical or different.As a plurality of L ^D2CWhen existing, these a plurality of L ^D2CCan be identical or different.

In the metal complex of formula (D2C) expression, more preferably by the metal complex of formula (D2D) expression.

Formula (D2D)

[IrX ^D2D _n7L ^D2D _(6-n7)] ^m7

In formula (D2D), X ^D2DExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^D2DBe illustrated in the 5-unit ring part that contains at least two nitrogen-atoms and at least one sulphur atom in its ring skeleton, on the carbon atom of described ring skeleton, can have substituting group; N7 represents integer 3,4, or 5; M7 represents the electric charge of metal complex and is 4-, 3-, and 2-, 1-, 0, or 1+.

X ^D2DHave and the middle X of formula (D2) ^D2Identical implication and preferable range are also identical.L ^D2DBe preferably and contain the compound of thiadiazoles, and the substituting group except hydrogen preferably combines with carbon atom in this compound as skeleton.Substituent preferred embodiment comprises halogen atom (as fluorine, chlorine, bromine, iodine), methoxyl, ethoxy, carboxyl, methoxyl carboxyl, acyl group, acetyl group, chloroformyl, sulfydryl, methyl mercapto, thioformyl, thiocarboxyl group, two thiocarboxyl groups, sulfino, sulfo group, sulfamoyl, methylamino, cyano group, isocyano group, cyanate radical (cyanato) group, isocyano group, thiocyanate radical (isocyanato) group, hydroxyl amino, oxyimino, carbamyl, nitroso-, nitro, diazanyl, hydrazono-, azido; Preferred example comprises halogen atom (fluorine, chlorine, bromine, iodine), chloroformyl, sulfino, sulfo group, sulfamoyl, isocyano group, cyanate radical group, isocyano group, thiocyanate radical group, oxyimino, nitroso-, nitro, and azido.Among them, preferred especially chlorine, bromine, chloroformyl, isocyano group, cyanate radical group, isocyano group, thiocyanate radical group.N7 preferably represents 4 or 5, and m7 preferably represents 2-or 1-.

At this, 3 to 5 X ^D2DCan be identical or different.As a plurality of L ^D2DWhen existing, these a plurality of L ^D2DCan be identical or different.

Below show preferred embodiment by the metal complex of formula (D2) expression.Yet, the invention is not restricted to these complex compounds.

[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] ^3-

[IrCl ₅(OH)] ^2-

[IrCl ₄(OH) ₂] ^2-

[IrCl ₅(O)] ^4-

[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] ^3-

[IrBr ₅(OH)] ^2-

[IrBr ₄(OH) ₂] ^2-

[IrBr ₅(O)] ^4-

[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] ^-

Among them, preferred especially [IrCl ₅(H ₂O)] ^2-, [IrCl ₅(thiazole)] ^2-And [IrCl ₅(5-methylthiazol)] ^2-

Formula (D1) or the above-mentioned metal complex of (D2) representing are negative ion, or electroneutral.When negative ion combines with kation when forming salt, balance cation is high those of dissolubility in water preferably.Its preferred embodiment comprises alkali metal ion, as sodion, and potassium ion, rubidium ion, cesium ion, and lithium ion; Ammonium ion, and alkyl phosphate ion.These metal complexs can be dissolved in the water or in the mixed solvent of water and the organic solvent (as alcohol, ether, dibasic alcohol, ketone, ester, and acid amides) that is suitable for dissolving each other with water and use.In the particle forming process, the addition of the metal complex of formula (D1) is preferably 1 * 10 ^-11Mole is to 1 * 10 ^-6The moles/mole silver atoms, preferred especially 1 * 10 ^-10Mole is to 1 * 10 ^-7The moles/mole silver atoms.In the particle forming process, the addition of the metal complex of formula (D2) is preferably every moles of silver atom 1 * 10 ^-10Mole is to 1 * 10 ^-3The moles/mole silver atoms, preferred especially 1 * 10 ^-8Mole is to 1 * 10 ^-5The moles/mole silver atoms.

In the present invention, preferably when silver halide particle forms, above-mentioned metal complex is directly added reaction solution, or add the reaction solution that forms particle indirectly by halide solution or other solution that add to form silver halide particle, so that they mix the inside of silver halide particle.In addition, the method for also preferably using metal complex wherein to mix silver halide particle is mixed the fine granular of complex compound in advance and is added fine granular by preparation and carries out physical ripening.In addition, also preferably can make up the inside that these methods are mixed complex compound silver halide particle.

These metal complexs are impregnated in the situation of silver halide particle inside therein, and they preferably are evenly distributed on the inside of particle.On the other hand, as JP-A-4-208936, JP-A-2-125245 and JP-A-3-188437 are disclosed, and they also preferably only are distributed in the top layer of particle.Alternatively, they also preferably only are distributed in the inside of particle and particle surface covers with the layer that does not contain complex compound.In addition, as U.S. Patent number 5,252,451 and 5,256,530 is disclosed, and also preferred silver halide particle carries out the physics slaking in the presence of the fine granular that has mixed metal complex, to modify the particle surface phase.In addition, these methods can be used in combination.Two or more complex compounds can mix the inside of single silver halide particle.

In the present invention, preferably use two or more, preferred three kinds or multiple iridium complex.

In first embodiment of the present invention, specific silver halide particle can not only contain the aforementioned iridic compound by formula (D2) expression, but also comprises the other iridium complex with 6 parts, and all these parts are Cl, Br or I.In this case, Cl, among Br and the I any two or three can mix and be present in the 6-co-ordination complex.Especially preferably wherein part is Cl, Br, or the iridium complex of I mixes the phase that contains silver bromide, so that obtain the hard contrast under the high illuminance exposure.

Show that below wherein all 6 parts are by Cl, Br, or the instantiation of the iridium complex of I composition.Yet, the invention is not restricted to these complex compounds.

[IrCl ₆] ^2-

[IrCl ₆] ^3-

[IrBr ₆] ^2-

[IrBr ₆] ^3-

[IrI ₆] ^3-

In the 3rd or the 4th embodiment of the present invention, carry out an optimal way of the present invention and be silver halide particle in the silver emulsion and comprise and have the 6-co-ordination complex that Ir is central metal and at least two different ligands.Be that wherein iridium is the 6-co-ordination complex that central metal and halogen and organic ligand all exist especially preferably as described 6-co-ordination complex, wherein iridium is central metal, not only has halogen ligands and also have the 6-co-ordination complex of inorganic part except halogen.More preferably each combination that includes the hexa-coordinate iridium complex of halogen ligands and organic ligand and contain the hexa-coordinate iridium complex of halogen ligands and the inorganic part except halogen ligands in the specific silver halide particle of the present invention.

The six coordinate complex that is suitable for wherein iridium among the 3rd of the present invention and the 4th embodiment and is central metal is the metal complex of following formula (I) expression.

Formula (I)

[IrX ^I _nL ^I _(6-n)] ^m

In formula (I), X ^IExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^IExpression is different from X ^IAny part, n represents 3,4 or 5; And m represents 4-, 3-, 2-, 1-, 0 or 1+.

At this, 3 to 5 X ^ICan be same to each other or different to each other mutually.As a plurality of L ^IWhen existing, these a plurality of L ^ICan be same to each other or different to each other.

In above, pseudohalogen (class halogen) ion is meant that character is similar to the ion of halide ion, and the example comprises cyanide ion (CN ^-), thiocyanate ion (SCN ^-), selenocyanic acid radical ion (SeCN ^-), telluro cyanic acid ion (TeCN ^-), nitrine dithiocarbonic acids salt ion (SCSN ₃ ^-), cyanic acid ion (OCN ^-), fulminate ion (ONC ^-) and azide ion (N ₃ ^-).

X ^IBe preferably fluorine ion, chlorion, bromide ion, iodide ion, cyanide ion, isocyano ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion.Among these, preferred especially chlorion and bromide ion.Specifically do not limit L ^I, it can be can be with or can uncharged organic or inorganic compound, preferred uncharged organic or inorganic compound.

In the metal complex of formula (I) expression, preferably by the metal complex of following formula (IA) expression.

Formula (IA)

[IrX ^IA _nL ^IA _(6-n)] ^m

In formula (IA), X ^IAExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^IAExpression is different from X ^IAInorganic part.N represents integer 3,4 or 5.M represents 4-, 3-, 2-, 1-, 0 or 1+.

In formula (IA), X ^IAHave and the middle X of formula (I) ^IIdentical implication and preferable range are also identical.L ^IAWater preferably, OCN, ammonia, phosphine and carbonyl, special preferred water.

At this, 3 to 5 X ^IACan be identical or different.As a plurality of L ^IAWhen existing, these a plurality of L ^IACan be identical or different.

In the metal complex of formula (I) expression, further preferably by the metal complex of following formula (IB) expression.

Formula (IB)

[IrX ^IB _nL ^IB _(6-n)] ^m

In formula (IB), X ^IBExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^IBExpression contains chain hydrocarbon or the cyclic hydrocarbon part as basic structure, or the part that replaced by other atom or atomic group of the part carbon atom of basic structure or hydrogen atom wherein; N represents integer 3,4 or 5; M represents 4-, 3-, 2-, 1-, 0 or 1+.

X ^IBHave and the middle X of formula (I) ^IIdentical implication and preferable range are also identical.L ^IBExpression contains chain hydrocarbon or the cyclic hydrocarbon part as basic structure, or the part that replaced by other atom or atomic group of the part carbon atom of basic structure or hydrogen atom wherein, but is not cyanide ion.L ^IBBe preferably heterogeneous ring compound, more preferably 5-membered heterocyclic compound part.In the 5-membered heterocyclic compound, further preferably in its 5-unit ring skeleton, contain the compound of at least one nitrogen-atoms and at least one sulphur atom.

At this, 3 to 5 X ^IBCan be identical or different.As a plurality of L ^IBWhen existing, these a plurality of L ^IBCan be identical or different.

In the metal complex of formula (IB) expression, more preferably by the metal complex of following formula (IC) expression.

Formula (IC)

[IrX ^IC _nL ^IC _(6-n)] ^m

In formula (IC), X ^ICExpression halide ion or the pseudohalogen ion except cyanic acid ion; L ^ICBe illustrated in the 5-unit ring part that contains at least one nitrogen-atoms and at least one sulphur atom in its ring skeleton, on the carbon atom of described ring skeleton, can have substituting group; N represents integer 3,4, or 5; And m represents 4-, 3-, and 2-, 1-, 0, or 1+.

X ^ICHave and the middle X of formula (I) ^IIdentical implication and preferable range are also identical.L ^ICDescribed in substituting group on the carbon atom of ring skeleton be preferably and have than the n-pro-pyl substituting group of small size more.Substituent preferred embodiment comprises methyl, ethyl, methoxyl, ethoxy, cyano group; isocyano group, cyanate radical group, isocyano group, thiocyanate radical group, different thiocyanate radical group; formoxyl, thioformyl, hydroxyl, sulfydryl; amino, diazanyl, azido, nitro; nitroso-, hydroxyl amino, carboxyl, carbamyl; fluorine, chlorine, bromine, and iodine.

At this, 3 to 5 X ^ICCan be identical or different.As a plurality of L ^ICWhen existing, these a plurality of L ^ICCan be identical or different.

The preferred embodiment of the metal complex of following display type (I) expression.Yet, the invention is not restricted to these complex compounds.

[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] ^3-

[IrCl ₅(OH)] ^2-

[IrCl ₄(OH) ₂] ^2-

[IrCl ₅(O)] ^4-

[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] ^3-

[IrBr ₅(OH)] ^2-

[IrBr ₄(OH) ₂] ^2-

[IrBr ₅(O)] ^4-

[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] ^-

In the 3rd and the 4th embodiment of the present invention, the specific silver halide particle in the silver emulsion preferably further contains and has 6 parts and as 6 co-ordination complexs of the iridium of central metal, all these parts are Cl, Br or I.In this case, Cl in the 6-co-ordination complex, Br, or I can be their mixing.Especially preferably will have Cl, Br, or I is as part, iridium as the six coordinate complex of central metal mix contain silver bromide mutually in, to obtain the hard contrast under the high illuminance exposure.

Below show to have Ir as central metal, all 6 parts are by Cl, Br, or the instantiation of the six coordinate complex of I composition.Yet, the invention is not restricted to these complex compounds.

[IrCl ₆] ^2-

[IrCl ₆] ^3-

[IrBr ₆] ^2-

[IrBr ₆] ^3-

[IrI ₆] ^3-

Above-mentioned metal complex is a negative ion.When these ions and salt forming cation, preferred balance cation is soluble in water.Wherein preferred examples comprises alkali metal ion, as sodion, and potassium ion, rubidium ion, cesium ion and lithium ion; Ammonium ion, and alkyl phosphate ion.These metal complexs be dissolvable in water in the water or the mixed solvent of the organic solvent (as ethanol, ethers, glycols, ketone, ester class and amide-type) that water and Yi Yushui mix in use.When forming, particle adds Se metal complex, the preferred every moles of silver atom 1 * 10 of its addition ^-10Mole is to 1 * 10 ^-3The moles/mole silver atoms, preferred especially 1 * 10 ^-8Mole is to 1 * 10 ^-5The moles/mole silver atoms.

In the present invention; above-mentioned iridium metals complex compound preferably directly joins in the reaction solution when silver halide particle forms; or join particle indirectly and form in the reaction solution forming silver halide particle or other solution, thereby they are applied to the inside of silver halide particle by being added to water-based halogen solution.Further, also preferably use the iridium metals complex compound is applied to method on the silver halide particle, be coated with the particulate of complex compound in advance and add particulate to carry out physical ripening by preparation.Further, also these methods of preferred combination make complex compound be attached to silver halide particle inside.

Be incorporated at these complex compounds under the situation of silver halide particle inside, they preferably are distributed in the inside of particle equably, on the other hand, as disclosed among JP-A-4-208936, JP-A-2-125245 and the JP-A-3-188437, they also preferably only are distributed in the top layer of crystal grain.Selectively, when particle surface applied the layer that does not contain complex compound, they also preferably only were distributed in the inside of particle.And as United States Patent(USP) Nos. 5,252, disclosed in 451 and 5,256,530, also preferred silver halide particle carries out physical ripening in the presence of the fine granular that has mixed metal complex, to improve the surperficial phase of particle.Further, these methods can be used in combination.Can be in each silver halide particle in conjunction with two or more complex compound.In the present invention, be favourable with two or more iridium complexs, preferred three kinds or more kinds of.

Though above-mentioned complex compound has no particular limits for the halide compositions of binding site, contain Ir as their central metal and Cl, Br and the I zone of going into to have maximum bromide sliver content as the 6-co-ordination complex preferred combination of all six parts separately.

In the present invention, can be coated on the inside and/or the surface of silver halide particle except the metallic ion of above-mentioned metal complex beyond the region of objective existence.The preferred transition metal of used metallic ion.The example of preferred transition metal is iron, ruthenium, osmium, lead, cadmium and zinc.More have and select these metals to use with the form of the octahedral build 6-co-ordination complex that contains part.When using mineral compound, preferably use cyanide ion, halide ion, thiocyanate ion, hydroxide ion, hydrogen peroxide ions, azides ion, nitrite ion, water, ammonia, nitrosyl radical ion or sulfo-nitrosyl radical ion as part.This part preferably with any metallic ion coordination that is selected from above-mentioned iron, ruthenium, osmium, lead, cadmium and zinc ion.Two or more these parts also preferably use in a kind of complex molecules.Further, a kind of organic compound of also preferred use is as part.The example of preferred organic compound comprises 5 or less than the chain compound of 5 carbon atoms and/or the heterogeneous ring compound of 5 yuan or 6 yuan rings on the main chain.The example of preferred organic compound in molecule, have at least nitrogen, phosphorus, oxygen or sulphur atom as can with the atom of metal-complexing.Most preferred organic compound is furans, thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazoles, pyrazoles, triazole, furan (furazane), pyrans, pyridine, pyridazine, pyrimidine and pyrazine.In addition, also preferably have organic compound on the basic framework that substituting group is incorporated into above-claimed cpd.

As the combination of metallic ion and part, preferred ferric ion and the combination of cyano group part and the combination of ruthenium ion and cyano group part.In the present invention, preferably use these compounds to combine with iridium ion.In the present invention, the preferred cyanide ion of these compounds is to accounting for most of quantity as the iron of central metal or the coordination number (position) of ruthenium coordination.Remaining position is preferably by thiocyanic acid, ammonia, hydrated ion, nitrosyl radical ion, dimethyl sulfoxide, pyridine, pyrazine or 4, and 4 '-dipyridine is coordination with it.Most preferably each of six of central metal coordination positions all by the cyanide ion coordination to form six cyano group iron complexs or six cyano group ruthenium complexs.This metal complex of being made up of these cyanide ion parts preferably adds during particle forms, and its addition is 1 * 10 ^-8Mole is to 1 * 10 ^-2The moles/mole silver atoms, most preferably 1 * 10 ^-6Mole is to 5 * 10 ^-4The moles/mole silver atoms.Under the situation of ruthenium complex and osmium complex, also preferably when combining, use nitrosyl radical ion, sulfo-nitrosyl radical or hydrone as part with chlorion.More preferably these parts form pentachloro-nitrosyl complex, pentachloro-sulfo-nitrosyl complex, or pentachloro-hydration complex compound.Also be preferably formed the chlordene complex compound.These complex compounds preferably add when particle forms, and its addition is 1 * 10 ^-10Mole is to 1 * 10 ^-6The moles/mole silver atoms, more preferably 1 * 10 ^-9Mole is to 1 * 10 ^-6The moles/mole silver atoms.

The present invention's used silver emulsion of material of taking pictures is preferably and contains the emulsion that has passed through golden sensitizing well known in the art.This emulsion can improve light sensitivity by golden sensitizing, thereby the fluctuation that forms photographic property when with laser scanning exposure will reduce.For reaching effective golden sensitizing, can use various inorganic gold compounds, have gold (I) complex compound of inorganic part and have gold (I) complex compound of organic ligand.For example, gold chloride and salt thereof can be used as inorganic gold compound use; Two sulphur auric cyanide acid compounds as two sulphur auric potassium cyanides (I) and two thiosulfuric acid gold compounds, can be used as gold (I) complex compound with inorganic part as two thiosulfuric acid auric acid trisodiums (I).

As the gold with organic ligand (organic compound) (I) compound, can be with two gold medals (I) intermediate ions (mesoionic) heterocycle of describing among the JP-A-4-267249, as two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) auric acid (I) tetrafluoroborate; With organic sulfydryl gold (I) complex compound of describing among the JP-A-11-218870, as two (1-[3-(2-sulfonic acid benzamide) phenyl]-5-s-based tetrazolium sylvite) auric acid (I) potassium pentahydrate; With combine the anionic gold of nitrogen compound (I) compound, as two (1-methylhydantoinato) that describe among JP-A-4-268550 gold (I) sodium salt tetrahydrate, be prepared.These gold (I) compounds with organic ligand can be prepared by those first synthetic separation again, and those that perhaps first mixing organic ligand and gold compound (as gold chloride or its salt) are made join in the emulsion under the situation of the gold compound that does not separate gained.And organic ligand and gold compound (as gold chloride or salt) can join respectively in the emulsion of gained, thereby form gold (I) compound with organic ligand in emulsion.

Can also use U.S. Patent No. 3,503, mercaptan gold (I) compound of describing in 749, gold compound of describing among JP-A-8-69074, JP-A-8-69075 and the JP-A-9-269554 and United States Patent(USP) Nos. 5,620,841,5,912,112,5,620,841,5,939, the compound of describing in 245 and 5,912,111.

The addition of above-claimed cpd can according to circumstances change in a very wide scope, and its scope is 5 * 10 usually ^-7Mole is to 5 * 10 ^-3The moles/mole silver halide, preferred 5 * 10 ^-6Mole is to 5 * 10 ^-4The moles/mole silver halide.

Further, also can carry out golden sensitizing with the colloid aurosulfo.The method for preparing colloidal gold sulfide is as Research Disclosure No.37154; Solid State Ionics, Vol.79, pp.60-66 (1995); With Compt.Rend.Hebt.Seances Acad.Sci.Sect.B, Vol.263, p.1328 describe in (1996).In above-mentioned Research Disclosure, a kind of method for preparing the colloid aurosulfo with thiocyanate ion has been described.Also can replace with sulfide compound as methionine or sulphur diethanol (thiodiethanol).

Can be 50nm or littler preferably with the colloid aurosulfo that the variable grain size is arranged with average particulate diameter, more preferably 10nm or littler, more preferably 3nm or littler.The diameter of particle can record from the TEM photo.Same colloid aurosulfo composition can be Au ₂S ₁Or the over cure composition, as preferred Au ₂S ₁To Au ₂S ₂More preferably Au ₂S _1.1To Au ₂S _1.8

The colloid aurosulfo can be analyzed with following mode: as, remove the aurosulfo particle to obtain the golden content and the content of sulphur by utilizing respectively as icp analysis method and iodometry.If the gold ion and the sulphion (comprising sulfuretted hydrogen and salt thereof) that are dissolved in the liquid phase are present in the aurosulfo colloid, this can influence the analysis of aurosulfo colloidal solid composition.Therefore, performing an analysis after by ultrafiltration etc. the aurosulfo particle separation.The addition of colloid aurosulfo can according to circumstances change in a very wide scope, and its scope adds 5 * 10 in every mole of silver halide of gold atom usually ^-7Mole is to 5 * 10 ^-3Mole, preferred 5 * 10 ^-6Mole is to 5 * 10 ^-4Mole.

The sulfur family sensitized performance of (just the sulphur sensitizing except that above-mentioned selenium sensitizing, tellurium sensitizing and selenium sensitizing) can be by using molecule acquisition a kind of and of the same race except the selenium sensitizing that above-mentioned and golden sensitizing combines.This molecule is a kind ofly can discharge AuCh ^-Molecule.Here, Au represents Au (I), and Ch represents sulphur atom, selenium atom or tellurium atom.Can discharge AuCh ^-The example of molecule comprise the gold compound of representing with AuCh-L.Here, L represents by combine the atomic group of formation molecule with AuCh.Other or more part further combine with Ch-L and Au simultaneously.In addition, the gold compound of representing with AuCh-L has following characteristics, reacts in the solution that has silver ion to exist, and is that they are easy to produce AgAuS under the situation of S as Ch, being to be easy to produce AgAuSe under the situation of Se as Ch, is to be easy to produce AgAuTe under the situation of Te as Ch.These gold compounds comprise that not only Ls is an acylated compound, also comprises following formula: (AuCh1), (AuCh2) or (AuCh3) expression compound

Formula (AuCh1)

R ₁-X-M-ChAu

In the formula (AuCh1), Au represents Au (I); Ch represents sulphur atom, selenium atom or tellurium atom; M represents to replace or unsubstituted methylene; X represents oxygen atom, sulphur atom, selenium atom or NR ₂R ₁Expression and X bonding form the atomic group (as organic group, as alkyl, aryl or heterocyclic radical) of molecule; R ₂Expression hydrogen atom or substituting group (as organic group, as alkyl, aryl or heterocyclic radical); R ₁Encircle in conjunction with forming with M.

According to the compound of formula (AuCh1) expression, preferred sulphur atom of Ch or selenium atom; X preferred oxygen atom or sulphur atom; R ₁Preferred alkyl or aryl.Examples of compounds comprises that Au (I) salt of thiosugar is (as gold thioglucose (as α-gold thioglucose) more specifically, cross the acetyl gold thioglucose, sulphur mannose gold, sulphur galactose gold, sulphur pectinose gold), the Au of selenium sugar (I) salt (as, acetyl selenium glucose gold crossed, cross acetyl selenium mannose gold) and Au (I) salt of tellurium sugar.Here, " thiosugar ", " selenium sugar " and " tellurium sugar " mean the compound that the hydrogen base in the end group isomery position of sugar is replaced by SH base, SeH base and TeH base respectively.

Formula (AuCh2)

W ₁W ₂C＝CR ₃ChAu

In formula (AuCh2), Au represents Au (I); Ch represents sulphur atom, selenium atom or tellurium atom; R ₃And W ₂Represent substituting group (as hydrogen atom, halogen atom or organic group, as alkyl, aryl or heterocyclic radical) respectively; W ₁The special substituent constant σ in expression Hami _pThe value on the occasion of electron withdraw group; R ₃And W ₁, R ₃And W ₂, W ₁And W ₂Can be combined together to form ring.

In the compound of formula (AuCh2) expression, preferred sulphur atom of Ch or selenium atom; R ₃Preferred hydrogen atom or alkyl; W ₁And W ₂The special substituent constant σ in respectively preferred Hami _pValue is 0.2 or bigger electron withdraw group.The example of concrete compound comprises (NC) ₂C=CHSAu, (CH ₃OCO) ₂C=CHSAu and CH ₃CO (CH ₃OCO) C=CHSAu.

Formula (AuCh3)

W ₃-E-ChAu

In formula (AuCh3), Au represents Au (I); Ch represents sulphur atom, selenium atom or tellurium atom; E represents to replace or unsubstituted vinyl; W ₃The special substituent constant σ in expression Hami _pThe value on the occasion of electron withdraw group.

In the compound of formula (AuCh3) expression, preferred sulphur atom of Ch or selenium atom; E preferably has the special substituent constant σ in Hami _pValue on the occasion of the vinyl of electron withdraw group; W ₃The special substituent constant σ in preferred Hami _pValue is 0.2 or bigger electron withdraw group.

The addition of these compounds can according to circumstances change in a very wide scope, and its content range is 5 * 10 usually ^-7Mole is to 5 * 10 ^-3The moles/mole silver halide, preferred 3 * 10 ^-6Mole is to 3 * 10 ^-4The moles/mole silver halide.

In silver emulsion, above-mentioned golden sensitizing can with the combination of other sensitizing, as sulphur sensitizing, selenium sensitizing, tellurium sensitizing, reduction sensitization with use the noble metal sensitizing of the noble metal except that gold compound.Especially, golden sensitizing preferably with sulphur sensitizing and/or the combination of selenium sensitizing.

All cpds or its precursor can be used in the silver emulsion of the present invention, thereby make photographic material prevent to produce photographic fog in production, preservation or photograph process, or stable photographic property.JP-A-62-215272 39-72 page or leaf discloses and has reached the concrete example of the useful compound of above-mentioned order, and they can preferably use.In addition, also can preferably use disclosed 5-virtue amino-1,2,3 in european patent number 0447647,4-thiatriazole compound (having at least one electron withdraw group on the residual base of aryl).

And in the present invention, in order to improve the storage stability of silver emulsion, the present invention also preferably uses disclosed hydroxamic acid derivs in JP-A-11-109576; Cyclic ketones with two keys adjacent with acyl group, the end of described pair of key is all replaced by amino or hydroxyl, as (compound of formula (S1) expression particularly, in the 0036th to 0071 section of JP-A-11-327094 be described in that this is incorporated herein by reference) described among the JP-A-11-327094; Catechol (catecols) that the sulphur of describing in JP-A-11-143011 replaces or p-dihydroxy-benzene (as, 4,5-dihydroxy-1, the 3-benzenedisulfonic acid, 2,5-dihydroxy-1, the 4-benzenedisulfonic acid, 3,4-dihydroxy benzenes disulfonic acid, 2,3-dihydroxy benzenes sulfonic acid, 2, the 5-dihydroxy benzenes sulfonic acid, 3,4, this sulfonic acid of 5-trihydroxy and these sour salt); U.S. Patent number 5,556, the azanol of the formula of describing in 741 (A) expression (advantageous applications U.S. Patent number 5,556 of the present invention, 741 the 4th hurdles the 56th walk to and describe in the 11st hurdle the 22nd row, are incorporated herein this paper as a reference); With formula (I), (II) among the JP-A-11-102045 or the water-soluble reductive agent of (III) representing.

Can be implemented in spectral sensitization and give the present invention's purpose of used silver emulsion spectral sensitivity in the required optical wavelength zone.The example of sensitizing dye that is used for the spectral sensitization of blueness, green and region of red light comprises that for example F.M.Harmer exists Heterocyclic Compounds-Cyanine Dyes and Relate Compounds, John Wiley﹠amp; Sons, New York, disclosed among the London (1964).Preferred special examples of compounds of using and spectral sensitization process comprise in 38 pages on the 22nd page of upper right hurdle to the of JP-A-62-215272 disclosed among the present invention.In addition, consider that the sensitizing dye of describing among the preferred JP-A-3-123340 is used for the high silver emulsion particle of silver chloride content as the red sensitizing dye of sense from the temperature dependent angle of stability, absorption intensity, exposure.

In the use of digit explosure, spectral sensitization can be used to realize giving according to the wavelength of used light source the purpose of any spectral sensitivity, in addition, and preferably as the required infrared spectrum sensitizing of carrying out.For utilizing digit explosure, disclosed method is as the spectral sensitization method among the preferred JP-A-5-142712, and wherein disclosed compound is suitable as the infrared spectrum sensitizing dye and uses.

In photographic silver halide material of the present invention, as mentioned above, any known spectral sensitizing dye can use.The example of these dyestuffs includes the merocyanine dyes of two alkaline parent nucleus, it passes through thiazole, selenazoles, oxazole and imidazoles and benzene or naphthalene nucleus and acid parent nucleus arbitrarily, as rhodanine acid nuclear, 2-thiohydantoin nuclear, 2-sulphur selenazoles alkane (thioselenazolidine)-2,4-diketone nuclear and barbiturates nuclear fusion form, with the three nuclear complex compound merocyanine dyes that three parent nucleus are arranged, but the preferred cyan dye that uses, because they can be given ISO and reduce color stain effectively.In addition, two or more combinations in these dyestuffs can be distributed to reach required spectral sensitivity.

For spectral sensitizing dye is mixed in the silver emulsion, dyestuff can directly be dispersed in the emulsion, perhaps earlier they are dissolved in the single solvent, as water, methyl alcohol, ethanol, propyl alcohol, methylcellulose or 2,2,3, the 3-tetrafluoropropanol, or the mixing of two or more these solvents, join in the emulsion then.Another kind method, the aqueous solution that can in the presence of acid or alkali, prepare those dyestuffs, as JP-B-44-23389, disclosed among JP-B-44-27555 and the JP-B-57-22089, or as U.S. Patent No. 3,822, disclosed in 135 and 4,006,025, can in the presence of surfactant, prepare the aqueous solution or the colloidal dispersion of those dyestuffs, then they be joined in the emulsion.In another approach, those dyestuffs can be dissolved in fully with the immiscible solvent of water in, as Phenoxyethanol, be distributed to then in water or the hydrophilic colloid, join in the emulsion again.Selectively, as disclosed among JP-A-53-102733 and the JP-A-58-105141, those dyestuffs can directly be distributed in the hydrophilic colloid, and then join in the emulsion.The opportunity in the emulsion of being added to can be emulsion preparatory phase useful known to so far whenever.More preferably, before forming the silver emulsion particle, in the process that emulsion grain forms, form from particle and to finish during the washing beginning, before the chemical sensitization, during the chemical sensitization, chemical sensitization finishes during the cooled and solidified emulsion, or adds during the coating solution preparation.In the present invention, the interpolation of sensitizing dye is to carry out before coating after chemical sensitization is finished usually.Yet sensitizing dye can add simultaneously with chemical sensitizer, thereby finishes spectral sensitization and chemical sensitization simultaneously, as U.S. Patent number 3,628, describes in 969 and 4,225,666.In addition, as describing among the JP-A-58-113928, sensitizing dye added before chemical sensitization, or selectable, and sensitizing dye can add to start spectral sensitization before the silver halide particle precipitation forms.And as U.S. Patent number 4,225,666 kinds described, and sensitizing dye can add separately, and just a part of sensitizing dye added before chemical sensitization, and remaining sensitizing dye adds after chemical sensitization.Sensitizing dye can add in any stage during silver halide particle forms, as U.S. Patent number 4,183, and disclosed method institute example in 756.Sensitizing dye is particularly preferably in adding before emulsion washing process or the chemical sensitization.

The addition of these spectral sensitizing dyes according to circumstances can change in a very wide scope, and preferred range is 0.5 * 10 ^-6Mole is to 1.0 * 10 ^-2The moles/mole silver halide, more preferably 1.0 * 10 ^-6Mole is to 5.0 * 10 ^-3The moles/mole silver halide.

The silver halide of first embodiment of the present invention sensitizing dye (following also be called for short " photosensitive material ") of taking pictures has at least one red sensing coppering silver emulsion layer on carrier, at least one green silver halide emulsion layer and at least one are felt blue silver halide layer, the one deck at least that it is characterized in that these silver halide emulsion layers contains the silver emulsion of representing in the first embodiment of the invention, and satisfies aforementioned relation (1).

The sensitive photographic material of first embodiment of the invention has at least one and contains the silver halide emulsion layer that weld is formed into toner on carrier, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that cyan dye is formed into toner.In the present invention, contain silver halide emulsion layer that weld is formed into toner as yellow cambium layer, the silver halide emulsion layer that contains the rosaniline dyes colour coupler is as the magenta cambium layer, and the silver halide emulsion layer that contains the cyan dye colour coupler is as the cyan cambium layer.The sensitization of silver emulsion in the wavelength coverage that differs from one another in preferred yellow cambium layer, magenta cambium layer and the cyan cambium layer.Wherein suitable example is that the silver halide color photographic material contains in yellow cambium layer the emulsion to blue region sensitization, in pinkish red cambium layer to the emulsion of green area sensitization, in the cyan cambium layer to the emulsion of red area sensitization, but be not limited to this class material of taking pictures.

Has the composition of photograph layer as the photosensitive material on the carrier in the second embodiment of the invention, this photograph is formed layer and is comprised that at least one contains the photosensitive silver halide emulsion layer that weld is formed into toner, at least one contains the photosensitive silver halide emulsion layer that rosaniline dyes is formed into toner, and at least one contains photosensitive silver halide emulsion layer and at least one photostable hydrophilic colloid layer that cyan dye is formed into toner.Contain weld and be formed into the silver halide emulsion layer of toner as yellow cambium layer (Y), contain silver halide emulsion layer that rosaniline dyes is formed into toner as magenta cambium layer (M), containing the silver halide that cyan dye is formed into toner is cyan cambium layer (C) as emulsion layer.

Preferably respectively at colour-forming layer (Y), (M) and the silver emulsion (C) to three wavelength region may differing from one another (as described in sequential layer, the blue light from Y to C, green glow and ruddiness) light their light sensitivity are separately arranged.

In the digit explosure system applies as the light source of above-mentioned sensitization, can select three kinds of different spectral sensitivities arbitrarily with semiconductor laser or LEDs.Here, consider that the maximal value distance of adjacent spectral sensitivity is at least 30nm from the angle that look separates.Colour coupler (Y, M and C) adds the photographic layer of corresponding three different spectral sensitivity maximal values (λ 1, λ 2 and λ 3) respectively.Further, also can also, make the response infrared laser exposure become possibility with the wavelength coverage except that blue light, green glow and ruddiness preferably by giving the infrared spectrum light sensitivity to any those photographic layers.

Except that yellow cambium layer, pinkish red cambium layer and cyan cambium layer, the photosensitive material of second embodiment of the invention can contain antihalation layer, intermediate layer and dyed layer if desired as the non-photosensitive hydrophilic colloid layer of hereinafter describing.

The color silver halide photographic-material of third embodiment of the invention comprises that at least one contains the silver halide emulsion layer that weld is formed into toner, and at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that cyan dye is formed into toner.

In the present invention, cyan dye is formed into toner, rosaniline dyes and is formed into the coating total amount that toner and yellow dye be formed into toner and is preferably 1.1g/m ²Or below, more preferably from 0.4g/m ²To 1.0g/m ²

The silver emulsion that is present in respectively in the silver halide emulsion layer that contains different colour couplers needs different separately color sense luminosity.For example, a kind of preferred pattern can be, feeling blue silver emulsion is combined in and contains in the silver halide emulsion layer that weld is formed into toner, green silver halide emulsion is combined in and contains in the silver halide emulsion layer that rosaniline dyes is formed into toner, and red sensing coppering silver emulsion is combined in and contains in the silver halide emulsion layer that cyan dye is formed into toner.Under this pattern, the highest spectral sensitivity of blue-sensitive emulsion is preferably in the zone of 400nm to 500nm, more preferably in the zone of 420nm to 480nm, green-sensitive emulsion preferred in the zone of 510nm to 590nm, more preferably in the zone of 520nm to 580nm, magenta-sensitive emulsion preferred in the zone of 600nm to 800nm, more preferably in the zone of 620nm to 720nm.Further, the wavelength difference of the spectral sensitivity peak value between any two photosensitive silver halide emulsions be preferably 30nm or more than, more preferably 50nm or more than.By as mentioned above to the setting of color light sensitivity, photosensitive material of the present invention the develop less dead color of image restoring obtain and of back that under the light beam of at least three kinds of different wavelength region may, exposes than high colour saturation.

In the digit explosure system applies as the light source of above-mentioned sensitization, can select three kinds of different spectral sensitivities arbitrarily with semiconductor laser or LEDs.Under this selection, consider that from the angle that look separates the most adjacent preferred spectral sensitivity maximal value is at least 30nm apart.With the photosensitive layer unanimity that contains at least three different spectral sensitivity maximal values (λ 1, λ 2 and λ 3), color be formed into toner (Y, M and C) can mix arbitrarily mix those the layer.Further, also can be with wavelength region may except that blue light, green glow and ruddiness, also preferably by giving the infrared spectrum light sensitivity, thereby make this layer be easy to infrared laser exposure to any those photographic layers.

Except that having yellow cambium layer, magenta cambium layer and cyan cambium layer, photosensitive material of the present invention can contain antihalation layer, intermediate layer and dyed layer if desired as the non-photosensitive hydrophilic colloid layer of hereinafter describing.

Color silver halide photographic-material among the 4th embodiment of the present invention has a layer structure, have on the carrier and comprise that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that cyan dye is formed into toner.

Preferably the silver emulsion of combination has light sensitivity separately to the light (as the light of blue region, the light of green area and the light of red area) of the wavelength region may that differs from one another in those layers.Be used for the amount of each colour coupler of silver, 1 equivalent is desirable, but 0.6 equivalent or above be suitable, preferred especially 0.7 equivalent or more than.The term here " 1 equivalent " is meant and is used for the colour coupler and the amount of used silver-colored total overall reaction that color forms, and term " 0.5 equivalent " is meant the amount of the colour coupler that is used for color formation and used silver one half-reaction.

In the present invention, preferably having different light sensitivity and silver chloride is 90 moles of % or above at least two kinds of silver emulsions combination in silver halide emulsion layer.The quantity of the silver emulsion that light sensitivity is different can have two or more, but considers that from the angle of design photographic material its suitable quantity is in two or three kinds.Consider from the angle of the type of grain size, halide compositions, grain pattern and sensitizing dye, chemical sensitizer and antifoggant and addition, in two or two or more silver emulsions can be identical or different.

Though light sensitivity is different and silver chloride content is that 90 moles of % or at least two kinds of higher silver emulsions preferably mix in a kind of silver halide emulsion layer, can be coated with respectively to form different emulsion layers.But these layers need color light sensitivity much at one and produce tone color much at one here.Statement " color light sensitivity is much at one arranged " is under the situation of color photographic material, the meaning for every layer to the light sensation light in the same color scope, as the light of blue scope, light in the green scope or the light in the red scope, and need only spectral sensitivity in identical color gamut, the spectral sensitivity of described layer can be different.In addition, statement " produces tone color much at one " under the situation of color photographic material, the meaning produces color for described layer in identical tone range, as yellow, magenta or cyan, and as long as these different tones drop in the same tone range, described layer produces different tones.

As needs, photosensitive material of the present invention also provides hydrophilic colloid layer, antihalation layer, intermediate layer and dyed layer except that the above-mentioned yellow cambium layer of mentioning, pinkish red cambium layer and cyan cambium layer.

The yellow pigment by formula (Y) expression that describes below is formed into toner (below abbreviate " yellow colour former " as) and is used for color silver halide photographic-material of the present invention, is preferred for the present invention second or the 4th embodiment.

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl, R ₂Expression alkyl, naphthenic base, acyl group or aryl, R ₃Expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, alkyl sulphonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl or imino group; m represents integer 0 or 1-4, Z ₁Expression-O-or-NR _A-, Z ₂Expression-NR _B-or C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _D-each independently represents hydrogen atom or substituting group naturally.

R ₁The example of the alkyl of expression comprises methyl, ethyl, isopropyl, the tert-butyl group and dodecyl.R ₁The example of the alkyl of expression can further comprise substituting group.This substituent example comprises that halogen atom (as chlorine atom, bromine atoms), aryl (as phenyl, to this base of uncle's octyl group), alkoxy (as methoxyl), aryloxy group are (as 2; 4-two-tertiary pentyl phenoxy group), sulfonyl (as; methyl sulphonyl), acylamino-(as; acetyl group, benzoyl group), sulfonamido (as, n-dodecane sulfonyl) and hydroxyl.

The example of the naphthenic base that R1 represents comprises the aryl (as phenyl, 1-naphthyl, 9-anthryl) with 6 to 14 carbon atoms.R ₁The example of the naphthenic base of expression can further comprise substituting group.This substituent example comprises nitro, cyano group, amino (as dimethylamino, anilino-) and alkylthio group (as methyl mercapto).

R ₁Preferred alkyl, more preferably branched alkyl, preferred tertiary butyl especially.

R ₂The alkyl of expression and the example of naphthenic base comprise and R ₁The identical group of expression.R ₂The example of the acyl group of expression comprises acetyl group, propiono, bytyry, caproyl and benzoyl group.R ₂The aryl of expression comprises phenyl.These R ₂Alkyl, naphthenic base and the aryl of expression also further comprise and R ₁Identical substituting group.

R ₂Preferred alkyl or aryl, special preferred alkyl.

R ₃Expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, alkyl sulphonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl or imino group.

R ₃Preferred halogen atom, preferred especially chlorine atom.

M represents 0 or 1 to 4 integer, and is preferred 0,1,2 or 3, more preferably 0,1,2, preferred especially 1.

Z ₁Expression-O-, or-NR _A-(R wherein _AExpression halogen atom or substituting group, substituting group preferred alkyl, naphthenic base, aryl or heterocyclic radical).

Z ₂Expression-NR _B-(R wherein _BExpression halogen atom or substituting group, substituting group preferred alkyl, naphthenic base, aryl or heterocyclic radical), or-C (R _C) R _D-(R wherein _CAnd R _DRepresent hydrogen atom or substituting group respectively; the example that this substituting group is fit to comprises halogen atom (as chlorine atom, bromine atoms), aryl (as phenyl, to uncle's octyl phenyl), alkoxy (as methoxyl), aryloxy group (as 2,4-two tertiary pentyl phenoxy groups), sulfonyl (as methyl sulphonyl), acylamino-(as acetyl group, benzoyl group), sulfonamido (as the n-dodecane sulfonyl), hydroxyl, nitro, cyano group, amino (as dimethylamino) and alkylthio group (as the methyl sulfenyl).

In formula (Y) the expression yellow colour former, the yellow colour former of preferred following formula (Y-I) expression.

Formula (Y-I)

In formula (Y-I), R ₁To R ₃, Z ₁And Z ₂Respectively with formula (Y) in the expression implication identical, preferred range also respectively with formula (Y) in identical.

It is as follows that the present invention is used for the exemplary by the yellow colour former of formula (Y) expression of color silver halide photographic-material, but the present invention is not subjected to the restriction of these embodiment.

Be applicable to of the present inventionly, the yellow colour former that preferably is applicable to formula (Y) expression in the color silver halide photographic-material of of the present invention second and the 4th embodiment is by being easy to synthesize with JP-A-63-123047, JP-A-3-125141 disclosed method or its method afterwards.

The yellow colour former of formula (Y) expression can use separately in color silver halide photographic-material of the present invention, or two or more mixing in them is used.Further, they can mix use with other yellow colour formers.In color silver halide photographic-material of the present invention, the use amount scope of yellow colour former is about 1 * 10 usually ^-3Mole is to about 1 moles/mole silver halide, preferred 1 * 10 ^-2Mole is to 8 * 10 ^-1The moles/mole silver halide.

Further, the colour coupler of preferred formula (Y) expression adds it with high boiling solvent described below usually under the state of emulsification and dispersion.In addition, the colour coupler of formula (Y) expression can use separately or wherein two or more mixes use, or mixes with other colour couplers (colour coupler as described below).

Can be used for the present invention, details are as follows to be preferred for the crown ether of color silver halide photographic-material of second embodiment of the present invention.

Each of these crown ethers and at least one replacement or the fusion of unsubstituted aromatic ring.The substituent exemplary of aromatic ring comprises alkyl, aryl, anilino-, acylamino-, sulfonamido, alkylthio group, arylthio, thiazolinyl and naphthenic base.Except that these groups, aromatic ring can be replaced by halogen atom, cycloalkenyl group, alkynyl, heterocyclic radical, sulfonyl, sulfinyl, phosphono (phosphonyl), acyl group, carbamyl, sulfamoyl, cyano group or alkoxy.In addition, the heteroatoms of composition crown ether also can be replaced by nitrogen-atoms, sulphur atom or selenium atom except that oxygen atom.At synthetic its initial crown ethers in 1967 and since reporting its particular performances, a large amount of typical crown ethers are synthetic from Pedersen.The detailed description of these compounds can be as C.J.Pedersen, Journal of American Chemical Society, vol.86 (2495), 7017-7036 (1967); G W.Gokel﹠amp; S.H.Korzeniowski, Macrocyclic Polyether Synthesis, Springer-Veriag. (1982); Oda, Shono﹠amp; Tabuse (editors), Crown Ether no Kagaku(Chemistry of Crown Ether), Kagaku Dojin (1978); Tabuse etc., Host-Guest, Kyoritsu Shuppan (1979); And Sasaki﹠amp; Koga, Yuki Gosei Kagaku(Organic Synthesis Chemistry), vol.45 (6), 571-582 finds in (1987).

The example of crown ether that is preferred for color silver halide photographic-material of the present invention is as follows, but the crown ether that is used for color silver halide photographic-material of the present invention is not subjected to the restriction of these examples.

These compounds are described in the above-mentioned list of references of quoting, maybe can easily prepare by the method in the above-mentioned incorporated by reference document, or by following method preparation.

Of the present invention, used crown ether can be dissolved in water or the hydrophilic organic solvent in the color silver halide photographic-material in the preferred second embodiment of the invention, as methyl alcohol, ethanol with fluoridize ethanol, then it is joined in the hydrophilic colloid that contains silver halide particle, thereby form silver halide emulsion layer.The opportunity that their add can be before the emulsion coating whenever, before preferred chemical sensitization is finished.In addition, crown ether joins in one deck at least in the silver halide emulsion layer, preferably joins to contain the silver halide emulsion layer that cyan dye is formed into toner.

In color silver halide photographic-material of the present invention, in the preferred second embodiment of the invention, the consumption of crown ether depends on the kind of used crown ether, used silver halide particle and the chemical ripening condition of employing, but consumption is 1 * 10 usually ^-6Mole is to 1 * 10 ^-1The moles/mole silver halide, preferred 1 * 10 ^-5Mole is to 1 * 10 ^-2The moles/mole silver halide.Use the condition of crown compound to have no particular limits, but pC1 preferably from 0 to 7, more preferably from 0 to 5, more preferably from 1 to 3, temperature is preferably from 40 ℃ to 95 ℃, more preferably from 50 ℃ to 85 ℃.In the present invention, the crown ether in the color silver halide photographic-material in the preferred second embodiment of the invention is preferably as the hypersensitizer of feeling red sensitizing dye.About their addition sequence, any one in them can add earlier, or can add simultaneously, or can be used as the mixed solution adding.They can add many parts.Crown ether can use separately, or two or more can be added to in one deck, or their mixing can join in two-layer or the multilayer.

Of the present invention, in the color silver halide photographic-material in the preferred second embodiment of the invention used to argent bunch have the compound of oxidation be defined as to suppress development process in the compound of Photographic fog, described process is: contain in the composition described as follows gold sensitizer 3 minutes when coated sample is immersed under 20 ℃ in the development first being processed, wash 1 minute then with water, carry out common colour development again.Described coated sample is by being coated with preparation with silver emulsion with the gelatin film of protection.These compounds have no particular limits, but oxygenant and thiosulfonic acid compound usually can use, and example comprises hydrogen peroxide, nitric acid, nitrous acid, the halogen element as bromine and iodine, oxysalt, as permanganate (as KMnO ₄) and chromate (as K ₂CrO), high halogen (as potassium metaperiodate) and high-valency metal salt (as the potassium ferricyanide).

The preferred example of gold sensitizer composition is as follows:

0.1％H[AuCl ₄] 4ml

H ₂O 88ml

1.0％KSCN 5ml

1.2％NaCl 3ml

For reducing the darkness of development color, available known blend of colors inhibitor among the present invention.Term " blend of colors inhibitor " expression can prevent the compound that is distributed to other layers and prevented to react with wherein colour coupler by the oxidized developing agent that reaction between silver emulsion and the color developers produces.In these blend of colors inhibitor, disclosed in the preferred following patent documentation.For example, use disclosed oxidation polymer reducing compound among the JP-A-5-333501, WO98/33760 and U.S. Patent number 4,923, disclosed phenidone series and hydrazine series in 787, and JP-A-5-249637, disclosed white colour coupler is favourable among JP-A-10-282615 and the German patent 19629142A1.For the special circumstances of quickening by the pH value that improves developer to develop, also favourable with disclosed redox compound among German patent 19618786A1, european patent number 839623A1, european patent number 842975A1, German patent 19806846A1 and the French Patent (FRP) 2760460A1.

This blend of colors inhibitor can be mixed into to take a picture arbitrarily to be formed in the layer, but the preferred colors mixed inhibitor is sneaked into the middle layer between the adjacent silver halide emulsion layer, thereby reduces the darkness of development color.Because the developer of blend of colors inhibitor and oxidation reacts when color development, the increase of the amount of blend of colors inhibitor reduces the density of development color sometimes.Therefore the amount of blend of colors inhibitor can influence photographic property, the darkness of the color of just developing and density.Though the amount of blend of colors inhibitor is according to halogenation photosensitive material that they added and difference is generally 0.01g to 10g/m ²The light-sensitive silver halide phase material, preferred 0.04g to 1g/m ²The light-sensitive silver halide phase material.

Of the present invention, in the photographic silver halide material in the preferred third embodiment of the invention, preferably, undertaken 1 * 10 by the silver emulsion that only will contain in the layer that weld is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DYmax) of the yellow of the development that obtains is 1.90 to 2.30, is undertaken 1 * 10 by the silver emulsion that only will contain in the layer that rosaniline dyes is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DMmax) of the magenta of the development that obtains is 1.95 to 2.30, is undertaken 1 * 10 by the silver emulsion that only will contain in the layer that cyan dye is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DCmax) of the cyan of the development that obtains is 1.8 to 2.40, by with all silver halide emulsion layers that contains dye forming coupler in 1 * 10 ^-4Exposure under second, the maximal density (DGCmax) of the maximal density (DGMmax) of the maximal density (DGYmax) of the yellow that the sensitization of carrying out colour development processing then and obtaining is developed, the magenta of developing and the cyan of developing is respectively 2.10 to 2.40,2.30 to 2.70 and 2.10 to 2.45.More preferably (DYmax) is 1.95 to 2.25, (DMmax) is 2.00 to 2.25, (DCmax) be 1.90 and (DGYmax) to 2.35, (DGMmax) and (DGCmax) be respectively 2.15 to 2.35,2.25 to 2.65,2.15 to 2.40.

Of the present invention, the color silver halide photographic-material among preferred the 3rd embodiment makes its setting with above-mentioned scope through adjustment, even also can reduce low darkness and higher gray density in the color of developing by rapid processing.

When above-mentioned density is lower than the scope that the present invention lists, the density of gained image is lower, so they become the image of light-colored image or degree of depth deficiency sometimes.When above-mentioned density surpasses the scope that the present invention lists, the combination of digit explosure and rapid processing make development gray density decline but not rise, the darkness of color increases, and it is unbalanced to occur spot sometimes.

Describe the method for determining DYmax, DMmax, DCmax, DGYmax, DGMmax and DGCmax below in detail.

By only will contain weld be formed into toner the layer in silver emulsion carry out 1 * 10 ^-4Second exposure, then as followingly carry out colour development processing sensitization.Measure the density of the image of gained, thereby draw family curve.In this performance diagram, can read the maximal density (DYmax) of the yellow of development.

[processing]

Procedure of processing	Temperature	Time
			Colour development	38.5℃	45 seconds
Bleaching is fixing	38.0℃	45 seconds
			Flushing (1)	38.0℃	20 seconds
Flushing (2)	38.0℃	20 seconds
			Flushing (3)	38.0℃	20 seconds
Flushing (4)	38.0℃	30 seconds

(wash (1) to (4) with groove counter current method.)

Each process solutions composed as follows described:

[colour developing solution] [groove solution]

Water 800ml

Dimethyl polysiloxane surfactant 0.1g

(by Shin-Etsu Chemical Co., Ltd produces

Commodity are called silicones KF351A)

Three (isopropyl alcohol) amine 8.8g

Ethylenediamine tetraacetic acid 4.0g

Polyglycol (molecular weight: 300) 10.0g

4,5-dihydroxy benzenes-1,3-sodium disulfonate 0.5g

Potassium chloride 10.0g

Potassium bromide 0.040g

Triazine radical amido diphenyl ethylene brightener 2.5g

(commodity that Showa Chemial produces Hakkol FWA-SF by name)

Sodium sulphite 0.1g

Disodium-N, N-two (sulfonic acid ethyl) azanol 8.5g

N-ethane-N-(β-methane sulphur aminoethyl)-3-methyl 5.0g

4-amino-4-aminobenzene 3/2 sulfate 1 hydrate

Sal tartari 26.3g

Add water to 1,000ml

PH is (under 25 ℃, with KOH and H ₂SO ₄Regulate) 10.15

[bleaching fixed solution] [groove solution]

Water 700ml

Ammonium salt (III) 47.0g of (ethylenediamine tetraacetic acid) iron

Ethylenediamine tetraacetic acid 1.4g

Between carboxyl benzenesulfinic acid 8.3g

Nitric acid (67%) 16.5g

Imidazoles 14.6g

ATS (Ammonium thiosulphate) (750g/l) 107.0ml

Ammonium sulfite 16.0g

Ammonium bisulfite 56to 70 23.1g

Add water to 1,000ml

PH (under 25 ℃, regulating) 6.0 with acetic acid and ammonia

[rinse solution] [groove solution]

Chloro isocyanide urine sodium 0.02g

Go mineral water (conductivity: 5 μ S/cm or following) 1,000ml

pH 6.5

For only will contain yellow dye be formed into toner the layer in silver emulsion carry out sensitizing, the wavelength of need selecting is to join the light that the silver emulsion of other layers has minimum spectral sensitivity, and this is because the spectral sensitivity of each silver emulsion is distributed in a wavelength coverage.In addition, the light wavelength scope of selection needs narrower.This light can obtain by the light source of band filtrator.When definite DYmax value, form required peaked exposure by using greater than yellow, to the silver emulsion sensitization quality of other layers, be out of question.Reach under the maximum exposure the silver emulsion sensitization in other layers by density in the yellow of developing, even exposure is what to carry out under the light of wavelength outside the spectrum sensitivity zone, also the density of the yellow that will develop under the maximum exposure amount that other layers do not have color to form is decided to be DYmax.

Can read the maximal density (DMmax) of the magenta of development with the method identical, unless the light that is used for exposing changes and causes at this wavelength to only containing the silver emulsion sensitization that rosaniline dyes is formed into the layer of toner with definite DYmax.Further, can read the maximal density (DCmax) of the cyan of development, cause the silver emulsion sensitization of the layer that under this wavelength, only contains blue or green dye forming coupler unless the light that is used for exposing changes with the method identical with definite DYmax.

Further, image that all develops corresponding to all colours wherein or the family curve of grey figure can be with drawing with the identical method of definite DYmax curve, its sensitization simultaneously contains the silver emulsion that pigment is formed into all layers of toner unless the light that is used for exposing changes, and on this curve, read the maximal density (DGYmax) of the yellow of development, the maximal density (DGCmax) of the maximal density of the magenta of development (DGMmax) and the cyan of developing.

In addition, unbalanced for benefiting reduction, of the present invention, the color silver halide photographic-material among preferred the present invention the 3rd or four embodiment temperature be 25 ℃, relative humidity be 20% (relative humidity is hereinafter represented with RH sometimes) down crimpness be-15 to+15, preferably-10 to+10.

Can determine " crimpness " of the present invention with following process.

To be in not under environment temperature is 25 ℃, 55%RH that the photosensitive silve halide material of deformation state cuts into the thin slice that 10cm takes advantage of 10cm, be that 25 ℃, the dark place of 20%RH left standstill 24 hours in environment temperature.Under being 25 ℃, 20%RH, environment temperature records crimp radius (the R) (unit: m) of the distortion that photosensitive material occurs then.The 1/R reciprocal of this radius is defined as crimpness." under environment temperature is 25 ℃, 55%RH, be in not deformation state " among the present invention and mean environment temperature be under 25 ℃, 55%RH crimp radius be 1m or more than.

Because photosensitive material normally stores with the form that is rolled into volume, so carrier has curling test in the preservation of remaining untouched.So crimpness of the above-mentioned definition of energy measurement the present invention not.Make that to be in the method that the photosensitive material of deformation state not has this curling test under environment temperature is 25 ℃, 55%RH be photosensitive material to be placed on the material of plane, keep equably with about 1kg/100cm ²Pressure place.Remove in the curly course with pressure, need to have on the photosensitive material scratch that folding line can not be arranged.

When crimpness be positive (on the occasion of) time represent that the photosensitive material surface is recessed attitude at the photographic layer coated face, and represent that when crimpness is (negative value) born the photosensitive material surface is protruding attitude at the photographic layer coated face.

In the present invention, the crimpness of photographic silver halide material changes according to multiple factor.For example, these factors comprise the kind and the consumption of gelatin used in the photographic layer, and gelatin dissolves ratio shared in the compound at used oil, the concentration of used salt, the duration behind the type of used gelatin hardener and consumption and the preparation photographic material.In addition, crimpness also changes with the performance and the consumption of coating used on the performance of used carrier and thickness and the carrier.

Gelatin can be provided by the face at the uncoated photographic layer of carrier in the present invention or adjust crimpness-15 to+15 by the amount that changes the coating on the carrier.In these methods, one of preferred mode is that the amount of the coating that provides on the face of the uncoated photographic layer of carrier is done suitable change.

Of the present invention, color silver halide photographic-material in the preferred four embodiment of the invention preferably is adjusted at the silver emulsion that contains combination in one deck at least that color is formed into colorant layer, thereby by selection and its adding method of sensitizing dye type spectral sensitivity is distributed in the following scope.

Especially, of the present invention, a peak of the spectral sensitivity of the color silver halide photographic-material among preferred the 4th embodiment of the present invention is suitable in the zone of 450nm to 490nm, provide between 70% long wavelength of sensitivity maximum in the spectral sensitivity peak and the short wavelength side the exposure wavelength difference at 20nm to 100nm, preferred 20nm to 80nm, preferred especially 30nm to 80nm.Here, above-mentioned " exposure wavelength is poor " is illustrated in the difference of the exposure wavelength that 70% the light sensitivity that is equivalent to spectral sensitivity is provided on the short wavelength side at exposure wavelength that 70% the light sensitivity that is equivalent to spectral sensitivity is provided on the long wavelength side at the spectral sensitivity peak that 450 to 490nm long wavelength zone occurs and spectral sensitivity peak, and the absolute value of suggestion difference is preferably in the scope of 20nm to 100nm.

The distribution of the spectral sensitivity of silver-halide color material of the present invention changes according to different factors.For example be used for silver emulsion when two kinds or above spectral sensitizing dye, the distribute pH and the temperature of the emulsion that time interval of adding according to the order of joining day, speed and dyestuff material, dyestuff and stirring condition, dyestuff add of the photoreception of spectrum of emulsion alters a great deal.Above-mentioned definite for obtaining the present invention, especially the spectral sensitivity in the photographic silver halide material among the 4th embodiment distributes, and to add sensitizing dye in maturing process be suitable by remove emulsion after the salt with flocculation.Further, preferably when the chemical sensitization that begins from the emulsion maturation to being not later than maturation, add sensitizing dye.Under the situation that adds two or more dyestuffs, preferred a kind of mode is to prepare solution that contains dye mixture and the solution that adds preparation in advance.Also can add two or more dyestuffs continuously.Here, add the preferably at least 30 seconds time interval of different dyes, more preferably at least 1 minute.During adding sensitizing dye, preferably stir (so that it is preferred 20,000 to 130,000 to obtain Reynolds quantity, more preferably 20,000 to 120,000, more preferably 20,000 to 100,000) consumingly and carry out the temperature and the pH of suitable regulator solution.Term " Reynolds quantity " is represented in the present invention by the definite quantity of the viscosity of the solution of the diameter of the rotating speed that stirs blade, blade and stirring.Bigger quantitaes be stirred under the stronger condition and carry out (referring to Kagaku Daijiten(Encyclopedia Dictionaryof Chemistry), lst ed.6th printing, page 2537, Tokyo Kagaku Dojin Co., Ltd. (2001)).Dyestuff adds respectively and adds simultaneously but is not that form with mixed dye solution adds, further carry out suitable stirring, the distribution of the condition of absorbing dye in the silver halide can occur, spectral sensitivity distributes and has a broad peak (peak that the difference between the exposure wavelength is very big) or narrow peak (peak that the difference between the exposure wavelength is very little).

Of the present invention, in the color silver halide photographic-material in the preferred four embodiment of the invention, preferably use the sensitizing dye of following formula (II) expression.

Formula (II)

Wherein α 1, and α 2 and β 1 to β 4 represent hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl or carbamyl respectively, and each of these groups can be substituted.

Below the sensitizing dye of detailed description formula (II) expression.

In formula (II), α 1 and α 2 represent hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl or carbamyl respectively, and each of these groups can be substituted.Alkyl in the formula is the replacement or the unsubstituted alkyl of straight chain, side chain or ring-type.The example that these alkyl are suitable comprises that replacement or the unsubstituted straight or branched alkyl of 1 to 30 carbon atom that contains are (as methyl, ethyl, isopropyl, n-pro-pyl, normal-butyl, the tert-butyl group, the 2-phenyl, n-hexyl, n-octyl, uncle's octyl group, the 2-ethyl group, 1,5-dimethyl hexyl, positive decyl, dodecyl, the n-tetradecane base, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2, the 3-dihydroxypropyl, ethyloic, carboxyethyl, thio-ethyl, the sulfo-propyl group, the sulfo-butyl, diethyllaminoethyl, the lignocaine propyl group, fourth oxygen propyl group, ethoxy ethoxyethyl and just own oxygen propyl group) and replacement or the unsubstituted naphthenic base of 3 to 18 carbon atoms that contains (as cyclopropyl, the ring phenyl, cyclohexyl, the ring octyl group, adamantyl and cyclo-dodecyl).Further, comprising replace or replace contain 5 to 30 carbon atoms bicyclic alkyl (that is, by from each two cycloalkanes, removing the unit price base that a hydrogen atom forms, encircle [2 as two rings [1,2,2] heptan-2-base and two, 2,2] oct-3-yl) and have the alkyl of multiring structure, as tricyclic structure.The thiazolinyl of α 1 and α 2 expressions comprises the thiazolinyl (as propenyl, 2-butenyl group and 3-pentenyl) that contains 2 to 16 carbon atoms respectively, and the alkynyl of α 1 and α 2 expressions comprises the alkynyl (as propinyl and 3-pentynyl) that contains 2 to 10 carbon atoms respectively.

The example of the aryl of α 1 and α 2 expressions comprise respectively replace or the unsubstituted phenyl or naphthyl of 6 to 20 carbon atoms that contains (as the naphthyl, 3 of unsubstituted phenyl, replacement, 5-3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl and 4-dimethylaminophenyl), the example of heterocyclic radical comprises pyridine radicals, furyl, imidazole radicals, piperidyl and morpholinyl.

In formula (II); the acyl group of α 1 and α 2 expressions comprises acetyl group, formoxyl, benzoyl group, valeryl (pivaroyl), capryl and positive pelargonyl group respectively; the example of the amino of α 1 and α 2 expressions comprises unsubstituted amino, methylamino, hydroxyethylamino, positive hot amino, diphenylamino, dimethylamino and lignocaine.The example of alkoxy comprises methoxyl, ethoxy, n-butoxy, cyclohexyloxy, n-octyloxy and n-decyloxy, and the example of carbamyl comprises unsubstituted carbamyl, N, N-diethylamino formoxyl and N-phenyl amino formoxyl.

In addition; α 1 and α 2 in the formula (II) have substituting group as much as possible; these substituent examples comprise that halogen atom is (as fluorine; chlorine; bromine and iodine atom); alkyl (straight chain; the alkyl of side chain and ring-type comprises bicyclic alkyl and active methylene); thiazolinyl; alkynyl; aryl; heterocyclic radical (not considering to replace a little); acyl group; alkoxy carbonyl group; aryloxy carbonyl; heterocycle oxygen carbonyl; carbamyl; N-hydroxyl amino formoxyl; N-acyl amino formoxyl; N-sulfuryl amino formoxyl; N-carbamyl carbamyl; the sulfo-aminomethyl; N-sulfamoyl carbamyl; carbazyl (carbazoyl); carboxyl or its salt; oxalyl group; the oxamoyl base; cyano group; the alkoxy acylimino; formyl; hydroxyl; alkoxy (recurring group that comprises ethylene oxy or propylene oxygen unit); aryloxy group; heterocyclic oxy group; acyloxy; alcoxyl or fragrant oxygen carbonyl oxygen base; carbamoyloxy; sulfonyloxy; amino; alkyl-; aryl-or heterocyclic amino group; acylamino-; sulfonamido; urea groups; ghiourea group; N-hydroxyl urea groups; acylimino; alcoxyl-or fragrant oxygen-carbonyl amino; sulfamoylamino group; Semicarbazido; thiourea amino; diazanyl; amido; oxamoyl amino; the N-alkyl-or N-aryl-sulfonyl urea groups; N-acyl group urea groups; N-acyl group sulfamoylamino group; hydroxylamino; nitro; the heterocyclic radical that contains four-nitrogen is (as pyridine; imidazoline and isoquinolyl); isocyano group; imino group; sulfydryl; alkyl-; aryl-or the heterocyclic radical sulfenyl; alkyl-; aryl-or the heterocyclic radical sulfenyl; alkyl-or aryl-sulfonyl; alkyl-or aryl-sulfinyl; sulfo group or its salt; sulfonamide; N-acyl group sulfamoyl; N-Herbicidal sulphonylamino sulfonyl and salt thereof; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino and silicyl.In addition; above the methine that replaces of two electron attracting groups of used term " active methylene " expression, terminology used here " electron-withdrawing group " is meant and comprises acyl group, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl, trifluoromethyl, cyano group, nitro and alkoxy acylimino.Here, two electron-withdrawing groups formation ring texture that can mutually combine.Above-mentioned used term " salt " means inorganic cation, as alkaline metal, earth alkali metal and heavy metal ion, or organic cation, as ammonia and phosphine ion.Above-mentioned substituting group can further be replaced by above-mentioned any substituting group.

Define β 1 to β 4 respectively as α 1 and α 2.In addition, when two or more β 1, can be identical or different.β 2, β 3 and β 4 also are same.

Compound about formula (II) expression; preferred α 1; α 2 and β 1 to β 4 represent alkyl, thiazolinyl, aryl, heterocyclic radical or the acyl group of hydrogen atom, replacement respectively; more preferably α 1; α 2 and β 1 to β 4 represent alkyl, thiazolinyl or the aryl of hydrogen atom, replacement respectively; preferred especially α 1, α 2 and β 1 to β 4 represent the alkyl or aryl of hydrogen atom, replacement respectively.

Of the present invention, in the compound of formula (II) expression that the color silver halide photographic-material compound among preferred the 4th embodiment is used, more preferably use the compound of formula (IIA) expression.

α 1 in following formula (IIA) and α 2 respectively with formula (II) in identical, the implication with β 2 is identical respectively with γ 2 for γ 1 simultaneously, the implication with β 4 is identical respectively with γ 4 for γ 3, their suitable scopes are identical with β 2 and β 4 respectively.The exemplary of this compound is as follows, but the present invention is not subjected to the qualification of these examples.

The sensitizing dye sequence number	α1	α2	γ1	γ2	γ3	γ4
							BS-1	-(CH 2) 2-COO-	-(CH 2) 2-COOH	-H	-H	-H	-H
BS-2	-(CH 2) 3-SO 3 -	-(CH 2) 3-SO 3HN(C 2H5) 3	-H	-H	-H	-H
							BS-3	-CH 2-COOH	-(CH 2) 3-SO 3 -	-OCH 3	-OCH 3	-H	-H
BS-4	-(CH 2) 3-SO 3 -	-(CH 2) 3-SO 3HN(C 2H 5) 3	-OCH 3	-OCH 3	-OCH 3	-OCH 3
							BS-5	-(CH 2) 3-SO 3 -	-C 2H 5	-H	-H	-H	-H
BS-6	-(CH 2) 4-SO 3 -	-(CH 2) 4-SO 3HN(C 2H 5) 3	-H	-H	-OCH 3	-OCH 3
							BS-7	-(CH 2) 2-SO 3 -	-(CH 2) 3-SO 3HN(C 2H 5) 3	-H	-H	-OCH 3	-H
BS-8	-CH 2-SO 3 -	-(CH 2) 3-SO 3HN(C 2H 5) 3	-H	-H	-Cl	-H

Formula (IIA)

Of the present invention, the compound of formula (II) expression that the color silver halide photographic-material in the preferred four embodiment of the invention is used, can use and British Patent No. 660,408, U.S. Patent number 3,149,105 and JP-A-50-4127 in disclosed same procedure synthetic, or use F.M.Hamer, The Cyanine Dyes and Related Compounds, Interscience Publishers, New York, page32-75 (1969) disclosed method is synthetic, or synthetic by these following methods.

Following more detailed description photosensitive material of the present invention.

In photosensitive material of the present invention, can be with known photographic material or adjuvant (odditives).

For example, as photograph carrier (substrate), can use the carrier of transmission-type or the carrier of reflection-type.The carrier of transmission-type is preferably used hyaline membrane, as tri cellulose acetate membrane, nitrocellulose filter and polyethylene terephthalate film; Or 2,6-naphthalene dicarboxylic acids (NDCA) and 1,2 ethylene glycol (EG) polyester, or NDCA, terephthalic acids and EG polyester provide information recording layer, as magnetosphere on it.As the carrier of reflection-type, the preferred especially reflection-type carrier with the substrate that has is laminated with a plurality of polyethylene layers or polyester layer in substrate, and at least one waterproof resin bed (layer laminate) contains Chinese white, as titanium dioxide.In the present invention, preferably use the carrier (or reflection carrier) of reflection-type.

Preferred reflection carrier is the carrier that has paper substrates in the silver halide emulsion layer identical faces, and this paper substrates provides the polyolefin layer that contains micropore.Polyolefin layer can be made up of multilayer.In this case, carrier more preferably by do not contain micropore with form with the adjacent polyolefin of gelatin layer (as polypropylene, the tygon) layer of one side and the polyolefin that contain micropore (as polypropylene, the tygon) layer adjacent at silver halide emulsion layer with paper substrate.At paper substrate with take a picture to form multilayer between the layer or the density preferable range of the polyolefin layer of individual layer is 0.40 to 1.0g/ml, more preferably scope is 0.50 to 0.70g/ml.Further, the thickness preferable range of the polyolefin layer of multilayer between paper substrate and photograph composition layer or individual layer is that the preferred scope of 10 to 100 μ m is 15 to 70 μ m.Further, the thickness ratio of polyolefin layer and paper substrate is preferably in 0.05 to 0.2 scope, more preferably in 0.1 to 0.15 scope.

Further, be to strengthen the hardness of reflection carrier, also preferably on the above-mentioned paper substrate layer of the reverse side of forming layer of taking a picture, polyolefin layer is arranged, as the back side at paper substrate.In this case, preferred polyolefin layer overleaf is tygon or polypropylene, and it is rough, more preferably polypropylene.The thickness of the polyolefin layer at the back side preferably in the scope of 5 to 50 μ m, more preferably in the scope of 10 to 30 μ m, further, its density preferably 0.7 to 1.1g/ml.For the used reflection carrier of the present invention, preferably on paper substrate, there is the embodiment of polyolefin layer to comprise JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, JP-A-11-65024, european patent number 0880065 and 0880066 kind of description.

Further, preferred above-mentioned fluid-tight resin bed contains fluorescer.Fluorescer can further disperse and be included in the hydrophilic colloid layer, and it forms respectively in above-mentioned photosensitive material layer.Used preferred fluorescer comprises benzothiazole series, cumarin series and pyrazoles series compound.Further, more preferably use benzothiazole naphthalene series and benzoxazole stilbene fluorescer.The special example that is contained in the fluorescer in the water-fast resin bed comprises, as, 4,4 '-two (benzoxazolyl) stilbene, 4,4 '-two (5-methylbenzoxazole base) stilbene, and composition thereof.There is no particular limitation for the consumption of fluorescer, preferably 1 to 100mg/m ²Scope in.When fluorescer mixed with fluid-tight resin bed, the fluorescer in waterproof resin bed and the composite rate of resin were preferably in the scope of 0.0005 to 3% quality, more preferably in the scope of 0.001 to 0.5% quality.

Further, the transmission-type carrier or respectively the coating carrier of above-mentioned reflection-type that contains the hydrophilic colloid layer of pigments for whitening can be used as the reflection-type carrier.And the reflection-type carrier with direct reflection metal surface and second scattered reflection metal surface can be used as the reflection-type carrier.

As the carrier that is used for photosensitive material of the present invention, white polyester-type carrier or provide the carrier that contains the white pigments layer in the same one side of silver halide emulsion layer and can make developing and use.Further, for promoting clearness, preferably the dizzy layer that disappears is arranged at the face of silver halide emulsion layer or the back side of carrier.Especially, the transmission density of preferred vector (transmission density) is in 0.35 to 0.8 scope, so that all satisfactory by the result of transmission and catoptrical method.

In photosensitive material of the present invention, for improving as image definition, that describes among the 27th to 76 page of the available european patent number 0.337.490A2 pass through the dyestuff (particularly oxonole series dyes) that processing is decoloured, preferably be added to hydrophilic colloid layer, make under 680nm that optical reflection density is 0.70 or bigger in photosensitive material.The titanium dioxide that also preferably adds 12% quality or more (more preferably 14% quality or more) is exactly with to tetratomic alcohol (as trimethylolethane) the waterproof resin bed of carrier being carried out surface working as dihydroxy.

Photosensitive material of the present invention preferably includes in hydrophilic layer, and the processing decolouring of describing among the 27th to 76 page of the available european patent number 0337490A2 of dyestuff (particularly oxonole dyestuff and cyanine dye) is with the security etc. that prevents irradiation or halation or improve safety lamp.Further, the dyestuff of describing in the european patent number 0819977 also preferably is added in the photosensitive material of the present invention.In these water-soluble dyes, some can damage when increasing use amount, and look separates or the security of safety lamp.These can with and can not damage the preferred dyestuff example that look separates and comprise the water-soluble dye of describing among JP-A-5-127324, JP-A-5-127325 and the JP-A-5-216185.

In the present invention, the dyed layer that decolours in process of available energy replaces water-soluble dye or is used in combination with water-soluble dye.The used dyed layer that can decolour in process can directly contact with emulsion layer, or by containing the middle layer of the reagent that prevents blend of colors, as p-dihydroxy-benzene or gelatin, with the emulsion layer indirect contact.Dyed layer preferably relatively with the low layer of emulsion layer the layer of carrier (promptly near), emulsion layer develops the color and the dyed layer identical priming color that develops the color.Dyed layer can be provided separately, and priming color is corresponding respectively with separately.But alternative ground also can provide some layers in them.In addition, can provide the dyed layer of easy coloring, to match with most priming colors zone.In the wavelength coverage (visible-range that is used for common printing exposure is from 400nm to 700nm) of exposure, provide under the wavelength of highest optical density, the optical reflection density of preferred dyed layer is 0.2 or bigger, but less than 3.0, more preferably 0.5 or bigger, but less than 2.5, preferred especially 0.8 or bigger, but less than 2.0.

Available known method forms dyed layer.As describing in 8 pages on the 3rd page of upper right hurdle to the of JP-A-2-282244 and 11 pages of upper left hurdles, the 3rd page of upper right hurdle to the of JP-A-3-7931, the dyestuff that the solid fine particle is in dispersed is incorporated into the method in the hydrophilic colloid layer; In cationic polymer, anionic dye is carried out the mordant dyeing method for processing; Make dyestuff be adsorbed on silver halide fine granular etc. and be fixed on method in the layer; As the method for describing among the JP-A-1-239544 with collargol.For method at solid-state down disperse dyes fine granular, as describe among the 4th to 13 page of, the JP-A-2-308244 will be at least be 6 or littler not water-soluble in fact down but be 8 or be essentially the method that water-soluble dyestuff fine granular mixes down greatlyyer at pH at pH.The method of mordant dyeing anionic dye is as describing among the 18th to 26 page of the JP-A-2-84637 in cationic polymer.U.S. Patent number 2,688,601 and 3,459,563 disclose the preparation method as the collargol of light absorber.In these methods, preferably mix the method for dyestuff fine granular and with the method for collargol.

The silver halide of the present invention material of taking pictures can be used as colour negative, colour positive, colour reversal film, material counter-rotating photopaper, color photographic paper, developing photosensitive material, color digital proof, film colour positive or film colour negative etc.The silver halide of the present invention material of taking pictures is preferably used as developing photosensitive material, color digital proof, film colour positive, colour reversal photopaper and color photographic paper in these photosensitive materials, is preferably used as color photographic paper especially.

Silver halide color photographic photochromics of the present invention (for example color photographic paper color photo paper) preferably has at least one yellow sense blue silver halide emulsion layer (containing the silver halide emulsion layer that weld is formed into toner) that forms on carrier, at least one pinkish red formation green silver halide emulsion layer (containing the silver emulsion that rosaniline dyes is formed into toner) and at least one cyan form green silver halide emulsion layer (containing the silver emulsion that cyan dye is formed into toner).Usually, these silver halide emulsion layers are being the yellow silver halide emulsion layer that forms away from the order on the carrier direction, and magenta forms silver halide emulsion layer and cyan forms silver halide emulsion layer.

But also can adopt layer arrangement mode with above-mentioned different other.

In photosensitive material, consider negative film the yellow cover or when exposure halogen light source dichroism, the silver emulsion of feeling in the blue silver halide emulsion layer preferably has relative high light sensitivity than green silver halide emulsion and red sensing coppering silver emulsion.The length of side of the particle of particle side ratio in other layers of the emulsion in the blue-sensitive emulsion will be grown for this reason.Further, the molar extinction coefficient of the illuminating colour that is formed by yellow colour former is lower than the illuminating colour that is formed by magenta colour coupler and cyan colour coupler, so increases the coating weight of yellow colour former along with the increase of blue-sensitive emulsion coating weight.When considering opposing from the pressure of the material surface of taking pictures, as cut, yellow to form the blue silver halide emulsion layer of sense unfavorable than other layers, preferably places the one side that is close to carrier.

The silver halide emulsion layer that contains yellow colour former can place the optional position of carrier.If contain in the layer of yellow colour former for silver halide flaky grain, preferably will contain yellow colour former and be placed on from the carrier distance than at least one silver halide emulsion layer position far away that contains the silver halide emulsion layer of magenta colour coupler and contain cyan colour coupler.Further, from promoting colour development, promoting the angle of the residual look of the desilverization and reduction sensitizing dye to consider that the layer that preferably contains yellow colour former is all far away than the distance of other silver emulsion leafing carriers.Further, from reducing the angle consideration that blix declines and takes off, the silver emulsion that preferably will contain cyan colour coupler is placed on the centre of other silver halide emulsion layers.On the other hand, from reducing the angle consideration that light decay takes off, the silver halide emulsion layer that preferably contains cyan colour coupler is the bottom.Further, each yellow cambium layer, magenta cambium layer and cyan cambium layer by two-layer or three layers form.Also preferably provide the layer that does not contain silver emulsion that contains colour coupler to form colour-forming layer by adjoiner at silver halide emulsion layer, as at JP-A-4-75055, JP-A-9-114035, JP-A-10-246940 and U.S. Patent number 5,576, described in 159.

Can be used for silver emulsion of the present invention and other materials (adjuvant etc.), the preferred example of forming layer (arrangement of layer etc.) and processing the process of take pictures material and adjuvant of taking pictures is disclosed among JP-A-62-215272, JP-A-2-33144 and the european patent number 0355660A2.Especially, preferably use among the european patent number 0355660A2 disclosed.Further, also preferred using as disclosed silver halide color photographic light-sensitive material and wherein disclosed process among JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854, JP-A-1-158431 JP-A-2-90145 JP-A-3-194539 JP-A-2-93641 and the European Patent Publication No 0520457A2.

Particularly, the different kinds of metals ion that adopts in above-mentioned reflection carrier and silver emulsion and the silver halide particle, the preserving stabilizer of silver emulsion and antifoggant, the method of chemical sensitization (sensitizer), the method of spectral sensitization (spectral sensitizer), cyan, magenta and yellow colour former and emulsification and process for dispersing, dye image stability improver (anti-staining agent and anti-stripping agent), dyestuff (dyed layer), the gelatin kind, the layer structure of photosensitive material and the film pH of photosensitive material, these especially preferably use the present invention or are used in combination described in the patent disclosure shown in the following table 1.

Table 1

Composition	JP-A-7-104448	JP-A-7-77775	JP-A-7-301895
				The reflectivity carrier	The 7th hurdle the 12nd walks to the 12nd hurdle the 19th row	The 35th hurdle the 43rd walks to the 44th hurdle the 1st row	The 5th hurdle the 40th walks to the 9th hurdle the 26th row
Silver emulsion	The 72nd hurdle the 29th walks to the 74th hurdle the 18th row	The 44th hurdle the 36th walks to the 46th hurdle the 29th row	The 77th hurdle the 48th walks to the 80th hurdle the 28th row
				The different metal ionization series	The 74th hurdle the 19th to 44 row	The 46th hurdle the 30th walks to the 47th hurdle the 5th row	The 80th hurdle the 29th walks to the 81st hurdle the 6th row
Storage stability or antifoggant	The 75th hurdle the 9th to 18 row	The 47th hurdle the 20th to 29 row	The 18th hurdle the 11st walks to the 31st hurdle the 37th row (particularly sulfhydryl heterocycle compound)
				Chemical sensitization method (chemical sensitizer)	The 74th hurdle the 45th walks to the 75th hurdle the 6th row	The 47th hurdle the 7th to 17 row	The 81st hurdle the 9th to 17 row
Spectral sensitization method (spectral sensitizer)	The 75th hurdle the 19th walks to the 76th hurdle the 45th row	The 47th hurdle the 30th walks to the 49th hurdle the 6th row	The 21st row the 82nd hurdle, the 81st hurdle the 48th row
				Cyan colour coupler	The 12nd hurdle the 20th walks to the 39th hurdle the 49th row	The 62nd hurdle the 50th walks to the 63rd hurdle the 16th row	The 88th hurdle the 49th walks to the 89th hurdle the 16th row
Yellow colour former	The 87th hurdle the 40th walks to the 88th hurdle the 3rd row	The the 17th to 30 page on the 63rd hurdle	The 89th hurdle the 17th to 30 row
				Magenta colour coupler	The 88th hurdle the 4th to 18 row	The 63rd hurdle the 3rd walks to the 64th	The 31st hurdle the 34th walks to the 77th

		Hurdle the 11st row	Hurdle the 44th row and the 88th hurdle the 32nd to 46 row
				The emulsification of colour coupler and process for dispersing	The 71st hurdle the 3rd walks to the 72nd hurdle the 11st row	The 61st hurdle the 36th to 49 row	The 87th hurdle the 35th to 48 row

Table 1 (continuing)

Composition	JP-A-7-104448	JP-A-7-77775	JP-A-7-301895
				Dye image stabilizing agent improver (anti-staining agent)	The 39th hurdle the 50th walks to the 70th hurdle the 9th row	The 61st hurdle the 50th contains to the 62nd hurdle the 49th row	The 87th hurdle the 49th walks to the 88th hurdle the 48th row
Anti-fading agent	The 70th hurdle the 10th walks to the 71st hurdle the 2nd row
				Dyestuff (colorant)	The 77th hurdle the 42nd walks to the 78th hurdle the 41st row	The 7th hurdle the 14th walks to the 19th hurdle the 42nd row and the 50th hurdle the 3rd walks to the 51st hurdle the 14th row	The 9th hurdle the 27th walks to the 18th hurdle the 10th row
Gelatin	The 78th hurdle the 42nd to 48 row	The 51st hurdle the 15th to 20 row	The 83rd hurdle the 13rd to 19 row
				The layer structure of photosensitive material	The 39th hurdle the 11st to 26 row	The 44th hurdle the 2nd to 35 row	The 31st hurdle the 38th walks to the 32nd hurdle the 33rd row
The film pH of photosensitive material	The 72nd hurdle the 12nd to 28 row
				Scan exposure	The 76th hurdle the 6th walks to the 77th hurdle the 41st row	The 49th hurdle the 7th walks to the 50th hurdle the 2nd row	The 82nd hurdle the 49th walks to the 83rd hurdle the 12nd row
Antiseptic in the developer	The 88th hurdle the 19th walks to the 89th hurdle the 22nd row

Can use or mix cyan, magenta and the yellow colour former of use among the present invention, except that above-mentioned mention, JP-A-62-215272 walks on the 91st page of upper right hurdle the 4th the 121st page of upper left hurdle the 6th row, the 3rd page of upper right hurdle 14 of JP-A-2-33144 walks to 18 pages of upper left hurdle last columns and the 30th page of upper right hurdle the 6th walks to 35 pages of upper right hurdles the 11st row, european patent numbers 0355,660 (A2) the 4th page of the 15th to 27 row, the 5th page of the 30th to 28 page of last column, the 45th page of the 29th to 31 row, the 47th page the 23rd is walked to and disclosedly in the 63rd page of the 50th row also preferably uses.

Further, photosensitive material of the present invention preferably adds the compound of usefulness formula (D) expression of describing among WO98/33760 Chinese style (II) or compound of (III) representing and the JP-A-10-221825.

Can be used for cyan dye of the present invention is formed into toner (abbreviating " cyan coupler " here as) and preferably uses pyrrolo-triazole series, more preferably with the colour coupler of using formula (I) or (II) representing among the JP-A-5-313324, the colour coupler of representing with formula (I) among the JP-A-6-347960, the colour coupler of enumerating in preferred especially these open texts.Further, phenol series or naphthol serial cyan colour coupler are also preferred.For example, the cyan colour coupler of usefulness formula (ADF) expression of describing among the preferred JP-A-10-333297.Except that the above-mentioned cyan colour coupler of mentioning, the example of preferred cyan coupler comprises the pyrrolo-azoles type cyan coupler of describing in the european patent number 0488248 and 0491197 (A1); U.S. Patent number 5,888, describe in 716 2,5-diamido phenol colour coupler; Have electron-withdrawing group and the strong pyrazoloazole coupler type cyan coupler by alive 6 bondings of hydrogen, as U.S. Patent number 4873,183 and 4,916, described in 051; Particularly, JP-A-8-171185, describe among JP-A-8-311360 and the JP-A-8-339060 at 6 pyrazoloazole coupler type cyan couplers that contain carbamyl.

Further, also can be with the cyan coupler of the biphenyl imidazoles series of describing among the JP-A-2-33144; With the 3-hydroxy pyrimidine described among european patent number 0333185A2 series cyan coupler (colour coupler that particularly has 2 equivalents that the chlorine split-radix forms, and colour coupler (6) and (9) conduct exemplify and preferred especially especially) by 4 equivalent colour couplers that make colour coupler (42); The cyan coupler of the ring-type active methylene group series of describing among the JP-A-64-32260 (particularly colour coupler 3,8 and 34 as exemplifying especially and preferred especially); The pyrrolo-pyrazoles type cyan coupler of describing among european patent number 0456226 A1; With the pyrrolo-imidazole type cyan coupler of describing in the european patent number 0484909.

In these cyan couplers, the pyrrolo-azoles series cyan coupler of usefulness formula (I) expression of describing among the preferred especially JP-A-11-282138.The description of the 0012nd to 0059 section the cyan colour coupler that comprises illustration (1) to (47) can be applied among the present invention fully among the above-mentioned JP-A-11-282138, so they preferably incorporate the part of this instructions as a reference at this.

Being used for rosaniline dyes of the present invention, to be formed into toner (abbreviating " magenta colour coupler " here as) can be 5-pyrazolone series magenta colour coupler and pyrazoloazole coupler series magenta colour coupler, as above describes in the patent disclosure that table is mentioned.In the middle of these, preferably with Pyrazolotriazole colour coupler as describing among the JP-A-61-65245, wherein second and tertiary alkyl is direct and 2-, 3-or the 6-position bonding of Pyrazolotriazole ring; Pyrazoloazole coupler (pyrazoloazole) colour coupler that sulfonamido is arranged in molecule is described in JP-A-61-65246; Pyrazoloazole coupler with alkoxyphenyl radical sulfonamido ballast group (ballasting group), for example those that describe among the JP-A-61-147254; And from wherein the color of the image of formation and the angle of stability and colour coupler color formation performance are considered the pyrazoloazole coupler colour coupler that preferably has alkoxy or aryloxy group in the 6-position, for example those of european patent number 226849A and 294785A description.Especially preferably the pyrazoloazole coupler colour coupler of formula (M-I) expression that is described in JP-A-8-122984 is as magenta colour coupler.The 0009th section to the 0026th section the description of patent disclosure JP-A-8-122984 can all be used for the present invention and be hereby incorporated by, as the part of the application's instructions.In addition, also can preferably use the pyrazoloazole coupler colour coupler that all has space steric hindrance group in 3-and 6-position that is described in european patent number 854384 and 884640.

Further, yellow uitramarine is formed into toner (abbreviating " yellow colour former " here as), the preferred acyl group acetyl ammonia type yellow colour former that uses among the present invention, and wherein acyl group has 3 yuan of rings or 5 ring structures, those as describing among the european patent number 0447969A1; Be described in malonyl aniline (malondianilide) yellow colour former among the european patent number 0482552A1 with ring texture; As be described in the pyrroles-2 of european patent number (open) 953870A1,953871A1,953872A1,953873A1,953874A1 and 953875A1 or 3-base or indoles-2 or 3-base carbonyl acetanil series colour coupler; Have the acetanil yellow colour former of diox structure, for example U.S. Patent number 5,118, described in 599; The compound of in last table, describing, the heterocyclically substituted acetanil type of acyl group yellow colour former wherein, those as describing among the JP-A-2003-173007.In these colour couplers, use preferably that carboxyl groups wherein is the acetanil type yellow colour former of 1-alkyl trimethylene-1-carbonyl, wherein arbitrary aniline forms the yellow colour former and the heterocyclically substituted acetanil type of the acyl group yellow colour former of the malonyl aniline (malondianilide) of an anilid ring.These colour couplers can be used alone or in combination.

In photosensitive material, dye forming coupler is added in the photography useful matrix or high boiling organic solvent, with matrix or solvent emulsification and dispersion, the dispersion that obtains is then mixed in the photosensitive material.With known equipment, as ultrasonic equipment, colloid mill, homogenizer, Manton-Gaulin and high speed dissolver with this solution (dispersion) with the form emulsification of fine granular and with as show that the spreading agent of activating agent is distributed in the hydrophilic colloid, preferably to containing in the aqueous gelatin solution, thus the dispersion of obtaining.

There is no particular limitation to be used for high boiling organic material of the present invention, and common just can use.Example comprises U.S. Patent number 2,322,027 and JP-A-7-152129 in describe those.

Further, secondary solvent can use with high boiling organic solvent, and the example of these secondary solvents comprises the acetate of low alcohol, as ethyl acetate, and butyl acetate; Ethyl propionate, secondary butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, s-ethoxyethyl acetate, methyl acetic acid cellosolve, methyl carbitol acetate and cyclohexanone.

Further, if desired, can use the organic solvent that mixes fully with water a part in addition as secondary solvent, as methyl alcohol, ethanol, acetone, tetrahydrofuran and dimethyl formamide.These organic solvents can two or more mix use.

As in order to improve the stability of emulsification dispersion under long-time the storage, with improve the fluctuation of the performance of taking pictures that is mixed for being coated with the final component of (application) along with the stability of time lapse and inhibition and emulsion, in case of necessity, all or part secondary solvent can be removed from the dispersion of emulsification by for example decompression distillation, hydro-peening (noodle washing), ultrafiltration etc.

The average particle size of the oleophylic fine granular dispersion that this method obtains is preferably 0.04-0.50 μ m, more preferably 0.05-0.30 μ m, most preferably 0.06-0.20 μ m.This average particle size can be with measurement mechanism Coulter Submicron Particle Analyzer Model N4 mensuration such as (trade name, Coulter Electronics company limited systems) for example.

And, be used for painted pigment can one emulsification to the emulsion of silver halide material photographic light-sensitive material of the present invention, thereby adjust the painted of white background, or co-exist in the organic solvent that dissolves take pictures useful compound such as colour coupler, be used for photosensitive material of the present invention and emulsification altogether, therefore prepare emulsion.

In existing under (or not existing) of aforementioned high boiling organic solvent, but preferably will be used for colour coupler of the present invention puts into the latex polymer of load (for example U.S. Patent number 4,203, described in 716) in, perhaps having water insoluble but be dissolved in the existing under (or not existing) of aforementioned high boiling organic solvent of the polymkeric substance of organic solvent, then with its emulsification and be distributed in the hydrophilic colloid aqueous solution they dissolvings.The water that can preferably use is soluble but the example organic solvent soluble polymkeric substance comprises as U.S. Patent number 4,857 15 hurdles, 449 the 7th hurdles to the and WO 88/00723 the 12nd page to the 30th page disclosed homopolymer and multipolymer.Consider from coloured image stability equal angles, more preferably use methacrylate ester row or acrylamide series polymkeric substance, particularly acrylamide series polymkeric substance.

In the present invention, can use known color mix inhibitor.In these compounds, those that describe in the preferred following patent disclosure.

For example, can use the high molecular weight redox compound of describing among the JP-A-5-333501; Phenidone or the hydrazine series compound of describing in WO 98/33760 and the U.S. Patent number 4,923,787 for example; And use for example is described in the white colour coupler among JP-A-5-249637, JP-A-10-282615 and the German patent 19629142A1.Particularly in order to promote developing powder by the pH value that increases developing solution, preferably use for example German patent 19,618,786 A1, european patent number 839,623 A1 and 842,975 A1, German patent 19,806, the redox compound of describing among 846 A1 and French Patent (FRP) number 2,760,460 A1.

In the present invention, the preferred use has the compound of high molar extinction coefficient and triazine skeleton as a kind of ultraviolet light absorber.For example can use the compound that is described in the following patented claim, these compounds preferably join photographic layer or/and in the non-sensitization.In these compounds, can use, for example, JP-A-46-3335, JP-A-55-152776, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427, JP-A-8-234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898, JP-A-10-147577, JP-A-10-182621, German patent 19,739,797A, european patent number 0,711,804A and JP-T-8-501291 (" JP-T " be meant retrieval with disclosed international patent application) etc.

The bonding agent (hydrophile adhesive mass) or the protective colloid that can be used for photosensitive material of the present invention; the preferred gelatin that uses; but also can also can be used in combination separately or with gelatin as homopolymerization or multipolymer with other gelatine derivative hydrophilic colloids, gelatin copolymer and other superpolymer, outer protein, sugar derivatives, cellulose derivative or the synthetic high molecular weight hydrophilic compound of gelatin.The gelatin that is used for silver halide color photographic material of the present invention can be alkali processing or acid processing gelatin or the gelatin of being made as raw material by ox bone, ox-hide, pigskin etc., and the ox bone or the pigskin of preferred bases processing are the gelatin that raw material is made.Preferably, the heavy metal that the is used for gelatin of the present invention for example content of Fe, Cu, Zn and Mn (comprising impurity) can be reduced to 5ppm or lower, more preferably 3ppm or lower.In addition, the calcium content in the photosensitive material is preferably 20mg/m ²Or lower, more preferably 10mg/m ²Or lower, 5mg/m most preferably ²Or it is lower.

Among the present invention,, preferably add as (antimycotic) agent of the described antibacterium of JP-A-63-271247 and antimycotic agent in order to destroy various moulds and the bacterium that grows in the hydrophilic colloid layer and make image degradation.In addition, the pH of the film of photosensitive material is preferably 4.0-7.0, more preferably 4.0-6.5.

Gelatin total amount in the composition layer of taking pictures of photosensitive material of the present invention is preferably from 3.0g/m ²To 7.0g/m ², more preferably 3.0g/m ²To 6.5g/m ², more preferably 3.0g/m ²To 6.0g/m ², preferred especially 3.0g/m ²To 5.0g/m ²Statement " the gelatin total amount in the composition layer of taking pictures of photosensitive material " is illustrated in the total amount of the hydrophilic adhesive in all hydrophilic colloid layers, all hydrophilic colloid layers are coated with between the carrier hydrophilic colloid layer farthest of a side at carrier with from the silver emulsion of carrier, comprise Photoactive silver-halide emulsion layer and non-photosensitive hydrophilic colloid layer.The amount of hydrophilic adhesive reduces effect of the present invention too greatly sometimes, and this is owing to the rapid property of having damaged colour developing processing, has aggravated the rapid processing performance (comprising washing and/or stabilizing step) that blix fades and destroyed washing processing.On the other hand, the amount of hydrophilic adhesive too little through regular meeting produce the not enough relevant harmful effect of film strength and, the striped that causes as pressure is fuzzy.Satisfied in order to ensure develop processing, photograph bleachability and residual color ream people, or even carrying out under the superfast technology preferred 3 μ m to the 7.5 μ m of the cambial thickness of taking pictures, more preferably 3 μ m to 6.5 μ m.The assessment of build can be by measuring the film of dry film before and after layering thickness difference or with the side of optical microscope or electron microscope observation film.In the present invention, carry out and increase rate of drying rapidly for what reach development, the thickness of preferred swelling film is at 8 μ m to 19 μ m, more preferably 9 μ m to 18 μ m.The thickness of swelling film can be by recording the photosensitive material dot method, and this photosensitive material is to be immersed in by the photosensitive material with drying to reach the swelling equilibrium condition in 35 ℃ the aqueous solution and obtain.The preferred 0.5g/m of the total amount of the silver that is coated with among the present invention ²Or below, more preferably 0.2g/m ²To 0.5g/m ², more preferably 0.2g/m ²To 0.45g/m ², preferred especially 0.2g/m ²To 0.40g/m ²Terminology used here " total amount of the silver of coating " is illustrated in taking pictures of all photosensitive materials of the present invention and forms the summation of silver coating amount in the layer.

In the present invention, from improving coating stability, preventing that static from occurring and adjustment quantity of electric charge equal angles is considered, can in photosensitive material, add surfactant.Surfactant can be the surfactant that is formed by negative ion, kation, betaine and nonionic.Example comprises to be described among the JP-A-5-333492.The preferred fluorine-containing surfactant of the surfactant that the present invention can use.Fluorine-containing surfactant can use separately, or is used in combination with other known surfactants.Fluorine-containing surfactant preferably is used in combination with other known surfactants.There is no particular limitation to be added to the amount of the surfactant in the photosensitive material, but usually 1 * 10 ^-5To 1g/m ²Scope in, preferably 1 * 10 ^-4To 1 * 10 ^-1G/m ²Scope in, more preferably 1 * 10 ^-3To 1 * 10 ^-2G/m ²Scope in.

Through using light-struck step of exposure according to the picture information photosensitive material and through the developing step of the developing photosensitive material of illumination, photosensitive material of the present invention can form image.

Except the print system that is used for common negativity printer (negative printer), photosensitive material of the present invention also can be used for adopting in the scan exposure system of cathode ray tube (CRT).Compare with laser beam emitting device, exposure apparatus for cathode-ray tube is simpler, compacter, therefore also more cheap.In addition, optic axis and color (colourity) are easy to regulate.Be used for to use the various luminescent materials of the light that sends spectral region according to actual needs along the cathode-ray tube (CRT) of image direction exposure.For example, can use two or more potpourri in any one or these luminescent material of red emission material, green emission material, blue light emitting material.SPECTRAL REGION is not limited to above-mentioned redness, green and blue, can use the fluorescence that can send yellow, orange, purple or infrared light district.Especially, often use the cathode-ray tube (CRT) of launching white light by means of the potpourri of these luminescent materials.

Under following situation, promptly photosensitive material has a plurality of photographic layers, and each layer has the spectral sensitivity that differs from one another and distribute, and cathode-ray tube (CRT) also has under the situation of the luminous fluorescent material of a plurality of spectral region, can expose to a plurality of colors simultaneously.That is, can be with a plurality of colour picture signals input cathode-ray tube (CRT)s, thus make the light can be from the surface emitting of this pipe.But alternative ground, can utilize method as described below, wherein import the picture signal of various colors successively, and launch the light of each color in order, be different from the film of launching color and expose by cutting then, be i.e. zone (or surface) continuous exposure.Usually, in these methods, consider the increase of high picture quality, the favored area continuous exposure, this is to have high-resolution cathode-ray tube (CRT) because can use.

Photosensitive material of the present invention preferably can be used for utilizing the digital scanning exposure system of monochromatic high density light, as gas laser, light emitting diode, semiconductor laser, comprise the assembly of nonlinear optical crystal and semiconductor laser or solid-state laser, with semiconductor laser as the second harmonic generation light source (SHG) of excitation source.Preferably utilize semiconductor laser, or comprise the second harmonic generation light source (SHG) of the assembly of nonlinear optical crystal and solid-state laser or semiconductor laser, so that make system more compact and cheap.Particularly, have long life and high stability, preferably utilize semiconductor laser in order to design; And preferably, at least a exposure light source is a semiconductor laser.

When using above-mentioned scan exposure light source, the maximum spectral sensitivity wavelength of photosensitive material of the present invention can at random be provided with according to the wavelength of used scan exposure light source.Because semiconductor as excitation source, is utilized by the obtainable SHG light source of the assembly of nonlinear optical crystal and semiconductor laser or solid-state laser, can get half to the oscillation wavelength of laser, therefore, can obtain blue light and green glow.Therefore, photosensitive material might have the spectral sensitivity maximal value in three green and red standard wavelength's scopes in indigo plant.Time shutter in above-mentioned scan exposure, when picture element density is 400dpi (or 300dpi), the size of picture element (pixel) required time of exposing is determined that the preferred time shutter is 1 * 10 ^-4Second or lower, more preferably 1 * 10 ^-6Second or lower.

When the present invention being used for silver-halide color when the photosensitive material, be that the coherent light of the blue laser instrument of 420nm to 460nm is carried out to image (image-wise) and exposes preferably with emission wavelength.Blue laser instrument is especially preferably used blue semiconductor laser.

The example of the preferred LASER Light Source of using comprises that wavelength is 430 to 450nm blue-light semiconductor laser (being proposed March calendar year 2001 by Nichia Corporation) on 48th Applied Physics Related Joint Meeting; Use LiNbO by semiconductor laser (vibration wave is about 940nm) ₃The blue laser of about 470nm of obtaining of SHG crystal wavelength adjustment, this LiNbO ₃The SHG crystal with the form of wave guide the reverse domain structure is arranged; (vibration wave is about 1,060nm) uses LiNbO by semiconductor laser ₃The green laser of about 530nm of obtaining of SHG crystal wavelength adjustment, this LiNbO ₃The SHG crystal with the form of wave guide the reverse domain structure is arranged; Wavelength is about the red light semiconductor laser (Type No.HL6738MG (trade name) is by Hitachi, and Ltd produces) of 685nm; Be about the red light semiconductor laser (Type No.HL6501MG (trade name) by Hitachi, Ltd produce) of 650nm with wavelength.

Silver halide colour photographic sensitive material of the present invention preferably can with for example below exposure and the toning system described in the known document be used in combination.The example of toning system comprises: be described in automatic printing and toning system among the JP-A-10-333253, be described in the photoelement transfer appts among the JP-A-2000-10206, as be described among the JP-A-11-215312, the register system that comprises image read-out, as be described among JP-A-11-88619 and the JP-A-10-202950, the exposure system that has the coloured image recording method, as be described among the JP-A-10-210206, the digital photos print system that comprises remote diagnosis method, and as being described among the JP-A-2000-310822, the photographic printing system that comprises image recording structure.

Describe in detail in the open text of last table and can be used in scanning exposure method of the present invention, preferred.

When photographic material of the present invention prints the exposure of machine, preferably utilize as U.S. Patent number 4,880 rejection filter of describing in 726 (band stop filter).By above-mentioned means, can get rid of the color mixture of light, and obviously improve colorrendering quality.

In the present invention, in order to form the copy restriction, described in european patent number 0789270A1 and 0789480A1, can be pre-formed yellow little dot pattern by before providing image information, carrying out pre-exposure.

For photosensitive material of the present invention is processed, preferably can use rapidoprint and the job operation described in the following document: JP-A-2-207250, the 26th page of hurdle, bottom right the 1st walks to the 34th page of upper right hurdle the 9th row, and JP-A-4-97355, the 5th page of upper left hurdle the 17th walks to the 18th page of hurdle, bottom right the 20th row.In addition, as the antiseptic that can be used for this developer solution, the preferred use gone up the compound of describing in the patent disclosure text of listing in the table.

First embodiment of the invention can be used for having the photosensitive material of rapid processing adaptability.The color development time is 28 seconds or lower, preferred 25 seconds to 6 seconds, and more preferably 20 seconds to 6 seconds.Similarly, the blix time is preferably 30 seconds or lower, and more preferably 25 seconds to 6 seconds, and more preferred 20 seconds to 6 seconds.In addition, the washing or be preferably 60 seconds or lower stabilization time, more preferably 40 seconds to 6 seconds.

The silver halide color photographic light-sensitive material of second embodiment of the invention also is preferred for having the photosensitive material of rapid processing adaptability.Under the situation of rapid processing, the color development time is preferably 60 seconds or lower, and more preferably 50 seconds to 6 seconds, more preferred 30 seconds to 6 seconds, most preferably 20 seconds to 6 seconds.Equally, the blix time is preferably 60 seconds or still less, and more preferably 50 seconds to 6 seconds, more preferably 30 seconds to 6 seconds and most preferably be 20 seconds to 6 seconds.In addition, the washing or be preferably 150 seconds or lower stabilization time, more preferably from 130 seconds to 6 seconds.

The silver halide color photographic light-sensitive material of third embodiment of the invention also is preferred for having the photosensitive material of rapid processing adaptability.Under the situation of rapid processing, the color development time is preferably 40 seconds or lower, more preferably 30 seconds to 6 seconds, selects 20 seconds to 6 seconds most.Similarly, the blix time is preferably 40 seconds or lower, and more preferably 30 seconds to 6 seconds, and more preferred 20 seconds to 6 seconds.In addition, the washing or be preferably 100 seconds or lower stabilization time, more preferably 80 seconds to 6 seconds.

The photosensitive material of four embodiment of the invention also is preferred for having the photosensitive material of rapid processing adaptability.Under the situation of rapid processing, the color development time is preferably 30 seconds or lower, and more preferably 25 seconds to 6 seconds, more preferably 25 seconds to 6 seconds.Similarly, the blix time is preferably 30 seconds or lower, and more preferably 25 seconds to 6 seconds, preferred especially 20 seconds to 6 seconds.In addition, the washing or be preferably 60 seconds or lower stabilization time, more preferably 40 seconds to 6 seconds.

Term used herein " color development time " is meant from beginning that photosensitive material is immersed colour development solution and is dipped into the time required in the blix solution until photosensitive material procedure of processing subsequently.For example, add man-hour adding multiplexer etc. automatically, the color development time is photosensitive material T.T. (so-called " time in solution ") of immersing colour development solution wherein, and the wherein photosensitive material in the step after color develops is admitted to the time (so-called " airborne time ") in the bleaching immobile liquid from air.Similarly, term used herein " blix time " is meant from beginning that photosensitive material is immersed blix solution and is dipped into the time required in washing lotion or the stabilizing solution until photosensitive material procedure of processing subsequently.In addition, the term that uses among the present invention " washing or stabilization time " is meant from beginning that photosensitive material is immersed washing or stabilizing solution required time (so-called " time solution ") when dipping turns to drying steps latter stage.

Be used for that the example of developing method comprises wet method after the exposure of photographic material of the present invention, for example adopt the conventional developing method of the developer solution that contains alkaline reagent and developer (particularly p-phenylenediamine (PPD) series colour developing solution), and wherein developer is introduced into the developing method of photographic material and activator solution, for example, the alkaline solution that does not contain developer is used for developing, and the heat developing method that does not use process solutions.Compare with additive method, especially preferably adopt the activator method, this is because process solutions does not contain developer, thereby can be manageable and handle process solutions, reduces the processing or the relevant load of processing of waste liquid, is beneficial to environmental protection.

In addition, the present invention preferably uses the developing method of the developer solution that contains alkaline reagent and developer (particularly p-phenylenediamine (PPD) series colour developing solution).

Under the situation that adopts the activator method, preferred developer in the introducing photographic material or their precursor comprise, as, the hydrazine compound of describing among JP-A-8-234388, JP-A-9-152686, JP-A-9-152693, JP-A-9-211814 and the JP-A-9-160193.

In addition, can preferably adopt such developing method, wherein, the photographic material that the silver content of use reduces adopts hydrogen peroxide to carry out image amplification processing (strengthening processing).Particularly, this developing method is preferred for the activator method.Specifically, can preferably adopt the formation method of the activator solution of describing as JP-A-8-297354 and JP-A-9-152695 that contains hydrogen peroxide.Although in the activator method, carrying out desilverization step with after the activator solution processing usually, under the situation of image being amplified the photographic material that job operation is applied to the silver content with minimizing, can save desilverization step.In this case, after washing or the stable processing, can then process to simplify job operation with activator solution.On the other hand, when adopting by scanner etc.,, for example be used to the photographic material of photographing, also can adopt the described form processing that need not desilverization step even photographic material has high silver content from the system of photographic material reading images information.

The activator solution that uses among the present invention, desilverization solution (bleaching/fixed solution), wash solution and stabilizing solution can contain well-known components and can use in a usual manner.Preferably, Research Disclosure, Item 36544, and those that describe among pp.536-541 (in September, 1994) and the JP-A-8-234388 can be used for the present invention.

The silver halide color photographic light-sensitive material of the present invention even white background of excellent quality can be provided under rapid processing.And being used for the laser scanning exposure is that the digit explosure of representative has high adaptability.In addition, even use after this photosensitive material is storing for a long time, they also can provide the white background of excellent quality.

Even occurring under the situation that processing conditions changes, silver-halide color material photographic light-sensitive material of the present invention has ISO, low photographic fog, even and processing conditions change, the variation of its performance such as photographic fog is also very little.

In rapid processing, silver-halide color material photographic light-sensitive material of the present invention can obtain fabulous effect, guarantees ISO and high color saturation, reduces high grey color density and reduce unbalanced generation.

Even in the processing of the rapid processing behind digit explosure, silver halide color photographic light-sensitive material of the present invention can be guaranteed ISO and low photographic fog and produce the color image that darkness reduces.And silver halide color photographic light-sensitive material of the present invention reduces the dependence of the light sensitivity on the emulsion preparative-scale and has a superior processing adaptability.

And silver halide color photographic light-sensitive material of the present invention can be guaranteed ISO in the emulsion preparation process, low atomizing, the performance change in fabulous contrast characteristic and the minimizing emulsion preparation process.

To on the embodiment basis that provides, be described in more detail below, but the present invention is not subjected to the restriction of these embodiment the present invention.

Embodiment

Embodiment 1-1

(preparation of emulsion B-1)

Adopt the method that in the deionized-distilled water that contains deionized gelatin that stirs, adds silver nitrate aqueous solution and sodium-chloride water solution simultaneously and mix, make the high-silver chloride cubic granules.In preparation process, it is the time that nucleus forms part that 3% silver nitrate adds the time of finishing.During the stage, the interpolation speed of silver nitrate aqueous solution and sodium-chloride water solution increases with the linear function of time in 3% to 80% interpolation of silver nitrate total amount.During the stage, add potassium bromide (4.0 moles of silver halides that %/mole is final) in 80% to 100% interpolation of silver nitrate total amount.After 90% interpolation of silver nitrate total amount is finished, under strong agitation, add potassium iodide (0.3 mole of silver halide that %/mole is final).In interpolation stage of 92% to 97% of silver nitrate total amount, add K ₄[Ru (CN) ₆].The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, and by measuring to such an extent that its length of side is 0.50 μ m with transmission electron micrograph (direct method) observation and transmission electron micrograph, coefficient of alteration is 9.0%.After precipitation desalination processing, in the emulsion of gained, add following substances: deionized water, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, and then disperse emulsion.

(preparation of emulsion B-2)

The method identical with preparing emulsion B-1 prepares emulsion B-2, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (1 * 10 ^-7Mole %/mole final silver halide) and K[IrCl ₄(H ₂O) ₂] (1 * 10 ^-8The final silver halide of mole %/mole).

(preparation of emulsion B-3)

The method identical with preparing emulsion B-2 prepares emulsion B-3, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (3.4 * 10 ^-8The final silver halide of mole %/mole).

(preparation of emulsion B-4)

The method identical with preparing emulsion B-3 prepares emulsion B-4, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-5)

The method identical with preparing emulsion B-3 prepares emulsion B-5, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase ten times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-6)

The method identical with preparing emulsion B-3 prepares emulsion B-6, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase the thirtyfold of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-7)

The method identical with preparing emulsion B-3 prepares emulsion B-7, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase 100 times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-8 to B-14)

The method identical with preparing emulsion B-1 to B-7 prepares emulsion B-8 to B-14, and difference is to add K in the time that 0 to 3% silver nitrate adds ₂[RuCl ₅(NO)] (3.4 * 10 ^-9The final silver halide of mole %/mole).

(preparation of emulsion B-1a)

The emulsion of Fen Saning is 40 ℃ of dissolvings down again, add sodium benzenethiosulfonate, 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole (1/10 addition after chemical sensitization is finished), triethyl thiocarbamide as the sulphur sensitizer, as golden sensitizer two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate.Gained emulsion is in slaking under most preferred Chemical Sensitization under 60 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Thereafter, the temperature with emulsion is cooled to 40 ℃, adding 1-phenyl-5-mercapto-tetrazole; 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Principal ingredient is by the potpourri of compound-3 expression, and the repetitive of compound-3 is 2 or 3 (terminal X ₁And X ₂All be respectively hydroxyl); Compound-4 and potassium bromide (0.30 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-1, S-2, S-3 and S-9 are to carry out spectral sensitization.Obtain emulsion B-1a thus.

(preparation of emulsion B-2a to B-7a)

The method identical with preparing emulsion B-1a prepares emulsion B-2a to B-7a respectively, and difference is with the emulsion B-1 of emulsion B-2 to B-7 replacement in emulsion B-1a preparation.

(preparation of emulsion B-1b)

The emulsion of Fen Saning is 40 ℃ of dissolvings down again, add sodium benzenethiosulfonate, 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole (1/10 addition after chemical sensitization is finished), illustration compound (SE3-29) as the selenium sensitizer, as golden sensitizer two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate.Gained emulsion is in slaking under most preferred Chemical Sensitization under 60 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Thereafter, the temperature with emulsion is cooled to 40 ℃, adding 1-phenyl-5-mercapto-tetrazole; 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Principal ingredient in the potpourri is by compound-3 expression compound, and the repetitive of compound-3 is 2 or 3 (terminal X ₁And X ₂All be respectively hydroxyl); Compound-4 and potassium bromide (0.30 mole of (finished) silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-1, S-2 and S-3 are to carry out spectral sensitization.Obtain emulsion B-1b thus.

(preparation of emulsion B-2b to B-7b)

The method identical with preparing emulsion B-1b prepares emulsion B-2b to B-7b respectively, and difference is with the emulsion B-1 of emulsion B-2 to B-7 replacement in emulsion B-1b preparation.

(preparation of emulsion B-8b to B-14b)

The method identical with preparing emulsion B-1b prepares emulsion B-8b to B-14b respectively, and difference is with the emulsion B-1 of emulsion B-8 to B-14 replacement in emulsion B-1b preparation.

(preparation of emulsion G-1)

In the preparation of emulsion B-1, formed the adding rapid change of part at nucleus.The addition of potassium iodide becomes 0.2 mole of silver halide that %/mole is final.Method identical with emulsion B-1 except that change above-mentioned prepares emulsion G-1.The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, and by measuring to such an extent that its length of side is 0.40 μ m with transmission electron micrograph (direct method) observation and transmission electron micrograph, coefficient of alteration is 9.5%.After precipitation desalination processing, add following substances in the emulsion of gained: deionized gelatin, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, emulsion disperses again then.

(preparation of emulsion G-2)

The method identical with preparing emulsion G-1 prepares emulsion G-2, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (2.0 * 10 ^-8Mole %/mole final silver halide) and K[IrCl ₄(H ₂O) ₂] (2.0 * 10 ^-7The final silver halide of mole %/mole).

(preparation of emulsion G-3)

The method identical with preparing emulsion G-2 prepares emulsion G-3, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (6.6 * 10 ^-8The final silver halide of mole %/mole).

(preparation of emulsion)

The method identical with preparing emulsion B-3 prepares emulsion G-4 to G-7, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times, ten times of the remaining unaltered relative scale of these complex compounds, thirtyfold and 100 times respectively.

(preparation of emulsion G-8 to G-14)

The method identical with preparing emulsion G-1 to G-7 prepares emulsion G-8 to G-14, and difference is to add K in the time that 0 to 3% silver nitrate adds ₂[RuCl ₅(NO)] (6.6 * 10 ^-9The final silver halide of mole %/mole).

(preparation of emulsion G-1a)

The emulsion of Fen Saning adds sodium benzenethiosulfonate 40 ℃ of down dissolvings again, to the glutaramide diphenyl disulfide, as the sodium thiosulfate of sulphur sensitizer, as two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate of golden sensitizer.Gained emulsion is in slaking under most preferred Chemical Sensitization under 65 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Thereafter, 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.35 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-4, S-5, S-6 and S-7 are to carry out spectral sensitization.Obtain emulsion G-1a thus.

(preparation of emulsion G-2a to G-7a)

The method identical with preparing emulsion G-1a prepares emulsion G-2a to G-7a respectively, and difference is to replace the emulsion G-1 that uses with emulsion G-2 to G-7 in emulsion G-1a prepares.

(preparation of emulsion G-1b)

The emulsion of Fen Saning adds sodium benzenethiosulfonate, to the glutaramide diphenyl disulfide 40 ℃ of dissolvings down again, as the illustration compound (SE3-29) of selenium sensitizer, as two (1,4 of golden sensitizer, 5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate.Gained emulsion is in slaking under most preferred Chemical Sensitization under 65 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Add 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole thereafter; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.35 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-4, S-5, S-6 and S-7 are to carry out spectral sensitization.Obtain emulsion G-1b thus.

(preparation of emulsion G-2b to G-7b)

The method identical with preparing emulsion G-1b prepares emulsion G-2b to G-7b respectively, and difference is with the emulsion G-1 of emulsion G-2 to G-7 replacement in emulsion G-1b preparation.

(preparation of emulsion G-8b to G-14b)

The method identical with preparing emulsion G-1b prepares emulsion G-8b to G-14b respectively, and difference is with the emulsion G-1 of emulsion G-8 to G-14 replacement in emulsion G-1b preparation.

(preparation of emulsion R-1)

In the preparation of emulsion B-1, changed the adding speed that forms part at nucleus.The addition of potassium iodide becomes 0.1 mole of silver halide that %/mole is final.K ₄[Ru (CN) ₆] addition increased by three times.Method identical with emulsion B-1 except that change above-mentioned prepares emulsion R-1.The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, and by observing with transmission electron micrograph (direct method) and measuring to such an extent that its length of side is 0.40 μ m, coefficient of alteration is 9.5%.After precipitation desalination processing, in the emulsion of gained, add following substances: deionized gelatin, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, and then disperse emulsion.

(preparation of emulsion R-2)

The method identical with preparing emulsion R-1 prepares emulsion R-2, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (6.0 * 10 ^-8Mole %/mole final silver halide) and K[IrCl ₄(H ₂O) ₂] (6.0 * 10 ^-7The final silver halide of mole %/mole)

(preparation of emulsion R-3)

The method identical with preparing emulsion R-2 prepares emulsion R-3, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (1.0 * 10 ^-7The final silver halide of mole %/mole).

(preparation of emulsion R-4 to R-7)

The method identical with preparing emulsion R-3 prepares emulsion R-4 to R-7, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times, ten times of the remaining unaltered relative scale of these complex compounds, thirtyfold and 100 times respectively.

(preparation of emulsion R-8 to R-14)

The method identical with preparing emulsion R-1 to R-7 prepares emulsion R-8 to R-14, and difference is to add K in the time that 0 to 3% silver nitrate adds ₂[RuCl ₅(NO)] (3.3 * 10 ^-9The final silver halide of mole %/mole).

(preparation of emulsion R-1a)

The emulsion of Fen Saning adds sodium benzenethiosulfonate, as sulphur sensitizer and golden sensitizer compound-1 40 ℃ of dissolvings down again.Gained emulsion is in slaking under most preferred Chemical Sensitization under 55 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Thereafter, 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.35 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-8 and compound-5 is to carry out spectral sensitization.Obtain emulsion R-1a thus.

(preparation of emulsion R-2a to R-7a)

The method identical with preparing emulsion R-1a prepares emulsion R-2a to R-7a respectively, and difference is with the emulsion R-1 of emulsion R-2 to R-7 replacement in emulsion R-1a preparation.

(preparation of emulsion R-1b)

The emulsion of Fen Saning adds sodium benzenethiosulfonate, as the illustration compound (SE3-9) of selenium sensitizer, as two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate of golden sensitizer 40 ℃ of dissolvings down again.Gained emulsion is in slaking under most preferred Chemical Sensitization under 55 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Add 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole thereafter; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.35 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-8 and compound-5 is to carry out spectral sensitization.Obtain emulsion R-1b thus.

(preparation of emulsion R-2b to R-7b)

The method identical with preparing emulsion R-1b prepares emulsion R-2b to R-7b respectively, and difference is with the emulsion R-1 of emulsion R-2 to R-7 replacement in emulsion R-1b preparation.

(preparation of emulsion R-8b to R-14b)

The method identical with preparing emulsion R-1b prepares emulsion R-8b to R-14b respectively, and difference is with the emulsion R-1 of emulsion R-8 to R-14 replacement in emulsion R-1b preparation.

Sensitizing dye S-1

Sensitizing dye S-2

Sensitizing dye S-3

Compound-1 compound-2

Compound-3 compound-4

Sensitizing dye S-4

Sensitizing dye S-5

Sensitizing dye S-6

Sensitizing dye S-7

Sensitizing dye S-8

Sensitizing dye S-9

Sensitization compound-5

(preparation of the coating solution of ground floor)

At 17g solvent (Solv-4), 3g solvent (Solv-6), dissolving 24g yellow colour former (Ex-Y) in 17g solvent (Solv-9) and the 45ml ethyl acetate, 6g color image stabilizing agent (Cpd-8), 1g color image stabilizing agent (Cpd-16), 1g color image stabilizing agent (Cpd-17), 11g color image stabilizing agent (Cpd-18), 1g color image stabilizing agent (Cpd-19), 11g color image stabilizing agent (Cpd-21), 0.1g adjuvant (ExC-3) and 1g color image stabilizing agent (UV-A).With this solution with (dissolver) emulsification of high-speed stirred mulser be dispersed in the containing in the 3g neopelex aqueous gelatin solution of 20 quality % of 205g.To wherein adding entry, the dispersion liquid A of preparation 700g emulsification.

On the other hand, with the dispersion liquid A of above-mentioned emulsification and shown in emulsion B-1a mix and dissolving, make the ground floor coating solution, it contains composition as follows.According to silver convert the expression emulsion coating weight.

Coating solution with second to seven layer of the method preparation identical with preparing the ground floor coating solution.(H-1), (H-2) and (H-3) as every layer gelatin hardener.And every layer adds Ab-1, Ab-2, Ab-3 and Ab-4, and total amount is respectively 10.0mg/m ², 43.0mg/m ², 3.5mg/m ², and 7.0mg/m ²

Further, respectively to the second layer, the 3rd layer and layer 5 adding 1.20mg/m ², 0.36mg/m ², 0.44mg/m ²1-(3-methyl urea groups benzene)-5-mercapto-tetrazole.Further, add 1.5 * 10 to ground floor and layer 5 respectively ^-4Mole and 1.8 * 10 ^-44-hydroxyl-6-the methyl 1,3 of mole, 3a, 7-four benzazoles (tetrazaindene).Further, in the magenta-sensitive emulsion layer, add methacrylic acid and butyl acrylate (1: 1 mass ratio; Mean molecular weight is 200,000 to 400,000) copolymer latex, addition is 0.05g/m ²With Catecol-3, the disodium salt of 5-disulfonic acid is added in the second layer, the 3rd layer and the layer 5, makes coating weight be respectively 25mg/m ², 11mg/m ²And 14mg/m ²Further, if desired, in every layer, add kayexalate to adjust the viscosity of coating solution.And, in order to prevent radiation, the water-soluble dye Dye-1 to Dye-4 (coating weight is as shown in bracket) below adding.

(dyestuff-1)

(dyestuff-2)

(dyestuff-3)

(Ab-1) antiseptic (Ab-2) antiseptic

(Ab-3) antiseptic

(Ab-4) antiseptic

A, b, c, d was with 1: 1: 1: 1 mixes (mol ratio)

(H-1) hardener (H-2) hardener (H-3) hardener

(layer is formed)

Every layer combination is as follows.Numeral coating weight (g/m ²).Using under the situation of silver emulsion, coating weight is represented with silver.

The total coating weight of the gelatin of sample 101 is 4.44g/m ², the total coating weight of silver is 0.33g/m ², thickness is 6.2 μ m, the swelling thickness is 16.7 μ m.

Carrier

{ ground floor contains Chinese white (TiO to the stacked paper of polyvinyl resin ₂, content 16 quality %, ZnO; Content 4 quality %), fluorescer (4,4 '-two (benzoxazolyls)-1,2-talan and 4,4 '-two (5-Jia base benzoxazolyl) stilbene, content is 0.03 quality %) and the amount of the polyvinyl resin of a side of blue dyes (ultramarine, content are 0.33 quality %) be 29.2g/m ²}

Ground floor (blue-sensitive emulsion layer)

Emulsion (B-1a) 0.14

Gelatin 1.00

Yellow colour former (Ex-Y) 0.250

Coloured image stabilizing agent (Cpd-8) 0.063

Coloured image stabilizing agent (Cpd-16) 0.010

Coloured image stabilizing agent (Cpd-17) 0.010

Coloured image stabilizing agent (Cpd-18) 0.115

Coloured image stabilizing agent (Cpd-19) 0.010

Coloured image stabilizing agent (Cpd-21) 0.115

Adjuvant (ExC-3) 0.001

Coloured image stabilizing agent (UV-A) 0.010

Solvent (Solv-4) 0.177

Solvent (Solv-6) 0.031

Solvent (Solv-9) 0.177

The second layer (employed intermediate color cambium layer)

Gelatin 0.34

Yellow colour former (Ex-Y) 0.085

Coloured image stabilizing agent (Cpd-8) 0.021

Coloured image stabilizing agent (Cpd-16) 0.004

Coloured image stabilizing agent (Cpd-17) 0.004

Coloured image stabilizing agent (Cpd-18) 0.039

Coloured image stabilizing agent (Cpd-19) 0.004

Coloured image stabilizing agent (Cpd-21) 0.039

Adjuvant (ExC-3) 0.0004

Coloured image stabilizing agent (UV-A) 0.004

Solvent (Solv-4) 0.060

Solvent (Solv-6) 0.011

Solvent (Solv-9) 0.060

The 3rd layer (anti-colour mixture layer)

Gelatin 0.32

Mixed color inhibitor (Cpd-4) 0.020

Mixed color inhibitor (Cpd-12) 0.004

Coloured image stabilizing agent (Cpd-3) 0.004

Coloured image stabilizing agent (Cpd-5) 0.004

Coloured image stabilizing agent (Cpd-6) 0.020

Coloured image stabilizing agent (UV-A) 0.020

Coloured image stabilizing agent (Cpd-7) 0.002

Solvent (Solv-1) 0.024

Solvent (Solv-2) 0.024

Solvent (Solv-5) 0.028

Solvent (Solv-8) 0.028

The 4th layer (magenta-sensitive emulsion layer)

Emulsion (R-1a) 0.10

Gelatin 0.80

Cyan coupler (ExC-1) 0.175

Cyan coupler (ExC-2) 0.005

Cyan coupler (ExC-3) 0.015

Coloured image stabilizing agent (Cpd-1) 0.011

Coloured image stabilizing agent (Cpd-7) 0.011

Coloured image stabilizing agent (Cpd-9) 0.033

Coloured image stabilizing agent (Cpd-10) 0.001

Coloured image stabilizing agent (Cpd-14) 0.001

Coloured image stabilizing agent (Cpd-15) 0.165

Coloured image stabilizing agent (Cpd-16) 0.035

Coloured image stabilizing agent (Cpd-17) 0.022

Coloured image stabilizing agent (UV-5) 0.077

Solvent (Solv-5) 0.077

Layer 5 (anti-colour mixture layer)

Gelatin 0.38

Mixed color inhibitor (Cpd-4) 0.024

Mixed color inhibitor (Cpd-12) 0.005

Coloured image stabilizing agent (Cpd-3) 0.005

Coloured image stabilizing agent (Cpd-5) 0.005

Coloured image stabilizing agent (Cpd-6) 0.024

Coloured image stabilizing agent (UV-A) 0.024

Coloured image stabilizing agent (Cpd-7) 0.002

Solvent (Solv-1) 0.029

Solvent (Solv-2) 0.029

Solvent (Solv-5) 0.033

Solvent (Solv-8) 0.033

Layer 6 (green-sensitive emulsion layer)

Emulsion (G-1a) 0.09

Gelatin 1.10

Magenta colour coupler (Ex-M) 0.14

Coloured image stabilizing agent (Cpd-2) 0.01

Coloured image stabilizing agent (Cpd-8) 0.01

Coloured image stabilizing agent (Cpd-9) 0.005

Coloured image stabilizing agent (Cpd-10) 0.005

Coloured image stabilizing agent (Cpd-11) 0.0001

Coloured image stabilizing agent (Cpd-18) 0.01

Ultraviolet absorber (UV-B) 0.26

Solvent (Solv-3) 0.04

Solvent (Solv-4) 0.08

Solvent (Solv-6) 0.05

Solvent (Solv-9) 0.12

Solvent (Solv-7) 0.11

Compound (S1-4) 0.0015

Layer 7 (protective seam)

Gelatin 0.50

Adjuvant (Cpd-20)

0.015

Whiteruss 0.01

Surfactant (Cpd-13) 0.01

(Ex-Y) yellow colour former

(Ex-M) potpourri of magenta colour coupler 40: 40: 20 (mol ratio)

(ExC-1) cyan coupler

(ExC-2) cyan coupler

(ExC-3) cyan coupler

(Cpd-1) color image stabilizing agent

Quantity-mean molecular weight 60,000

(Cpd-2) color image stabilizing agent

(Cpd-3) color image stabilizing agent

(mean value)

(Cpd-4) color image stabilizing agent

(Cpd-5) color image stabilizing agent

(Cpd-6) color image stabilizing agent

Quantity-mean molecular weight

600，m/n＝10/90

(Cpd-7) color image stabilizing agent (Cpd-8) color image stabilizing agent

(Cpd-9) color image stabilizing agent (Cpd-10) color image stabilizing agent

(Cpd-13) with (a)/(b)/(c) potpourri of 6: 2: 2 (mol ratio)

(mol ratio)

(Cpd-21)

KAYARAD DPCA-30 (trade name is produced by Nippon Kayaku Co.Ltd)

(solvent-1) (solvent-2)

(solvent-3) (solvent-4)

O＝POC ₆H ₁₃(n)) ₃

(solvent-5)

(solvent-6) (solvent-7)

C ₈H ₁₇CH＝CHC ₈H ₁₆OH

(solvent-8) (solvent-9)

UV-A:(UV-1)/(UV-4) potpourri of (mass ratio)/(UV-5)=1/7/2

UV-B:(UV-1)/(UV-2) potpourri of (mass ratio)/(UV-3)/(UV-4)/(UV-5)=1/1/2/3/3

Be defined as sample 101 as the above-mentioned sample that makes.Other photosensitive materials can by replace in the sample 101 first respectively with the above-mentioned emulsion that contains identical silver-colored composition, the 4th and layer 6 in photosensitive emulsion prepare.The composition of sample number and every kind of photosensitive material is as shown in table 2.

Table 2

Sample number	Emulsion for the first time	The 4th layer of emulsion	Layer 6 emulsion
				101	B-1a	R-1a	G-1a
102	B-2a	R-2a	G-2a
				103	B-3a	R-3a	G-3a
104	B-4a	R-4a	G-4a
				105	B-5a	R-5a	G-5a

106	B-6a	R-6a	G-6a
				107	B-7a	R-7a	G-7b
108	B-1b	R-1b	G-1b
				109	B-2b	R-2b	G-2b
110	B-3b	R-3b	G-3b
				111	B-4b	R-4b	G-4b
112	B-5b	R-5b	G-5b
				113	B-6b	R-6b	G-6b
114	B-7b	R-7b	G-7b
				115	B-8b	R-8b	G-8b
116	B-9b	R-9b	G-9b
				117	B-10b	R-10b	G-10b
118	B-11b	R-11b	G-11b
				119	B-12b	R-12b	G-12b
120	B-13b	R-13b	G-13b
				121	B-14b	R-14b	G-14b

Each sample after the coating under the environment of 25 ℃ and 55%RH aging 10 days makes post bake wherein react completely.The sample that obtains thus is used for assessment.

(assessment 1: under high intensity of illumination exposure, characteristic measurement and assessment)

For each sample, carry out 1 * 10 with the exposure meter of high intensity of illumination (by YamashitaDenso Co., Ltd produces for Model HIE, trade name) ^-6The wedge exposure of second.

For exposure, use worry light device SP-1, the SP-2 or the SP-3 (trade name) that produce by Fuji Photo Film Co.Ltd to carry out so-called blue separate exposure, so-called green separate exposure and so-called red separate exposure respectively.This exposed sample can leave standstill 30 minutes, then according to the following technology A processing of developing.Measure the reflection density of yellow, magenta or the cyan of formation thus with the optical density (OD) device, with the family curve of every kind of color image of gained density data drafting, the longitudinal axis is reflection density (D), and transverse axis is the exposure of logarithm (logE) expression.In each sample, yellow image is relevant with the family curve of blue-sensitive emulsion layer, and pinkish red image is relevant with the family curve of green-sensitive emulsion layer, and cyan image is relevant with the family curve of magenta-sensitive emulsion layer.

In each family curve of painting, the least density (Dmin) that is equivalent to unexposed portion is defined as photographic fog.In addition, reflection density is that the inverse of 0.5 the A exposure of ordering is defined as light sensitivity S _HS _HBe worth greatly more, light sensitivity is just high more, also favourable more.Further, reflection density is that 1.5 point is called B, is defined as gradient γ with the skew lines that is connected of 2 of A and B _HGradient γ _HBe worth greatly more, contrast is strong more.

(assessment 2: under low light exposes according to intensity, characteristic measurement and assessment)

For each sample, carry out 100 seconds wedge exposure with exposure meter (Model FWH, trade name are produced by Fuji Photo Film Co.Ltd).For exposure, use the worry light device SP-1 that produces by Fuji Photo Film Co.Ltd,, SP-2 or SP-3 (trade name) carry out so-called blue separate exposure, so-called green separate exposure and so-called red separate exposure respectively.This exposed sample can leave standstill 30 minutes, carried out color development processing according to following technology A then.With measure 1 identical method, prepare the family curve of every kind of color image, and defines light sensitivity S _LWith gradient γ _LBy the way, photographic fog is irrelevant with conditions of exposure, its value with assess identical in 1.

(assessment 3: the retention assessment)

Each sample was preserved 30 days under the environment of 40 ℃ and 55%RH, and then carried out then as assessing exposure identical in 1, and develop processing and density measure prepare its family curve thus.Δ Fog and Δ S are used in the photographic fog of each sample and the variation of light sensitivity respectively _HExpression is calculated according to assessment 1 data that obtain.Because Δ Fog is the variation of Fog density, the not variation of ± 0 expression is preferred.Δ S _HLight sensitivity in the expression assessment 1 is 100 relative value.So Δ S _HNear 100, the variation of light sensitivity is just more little, just has bigger advantage more.

Technology A

By in Digital Minilab Frontier 350 (trade names, by Fuji Photo Film Co., Ltd produces) the middle printer of installing, be used for the EVER-BEAUTYPAPER TYPE II (trade name of laser, by Fuji Photo Film Co., Ltd. produces) the wide film sample of 127mm on the formation standard image of taking pictures.After this, the sample of exposure is processed (operation test) continuously with following processing step, replenishes the twice that liquid measure reaches color developing trough volume up to the accumulation of color developing solution.Use the technology called after technology A of this running process solutions.

Used LASER Light Source such as following, (vibration wavelength: about 940nm) wavelength of Chan Shenging is the blue laser of 470nm, and this wavelength is by having the LiNbO of waveguide reversal zone structure by semiconductor laser ₃The SHG crystal transition, (vibration wavelength: about 1,060nm) wavelength of Chan Shenging is the green laser of 530nm, and this wavelength is by having the LiNbO of waveguide reversal zone structure by semiconductor laser ₃The SHG crystal transition and be the red laser of about 650nm by the wavelength that semiconductor laser produces.With polygon mirror the LASER Light Source of these three kinds of colors is vertically moved into the direction of scanning, so that its scan exposure and then on sample.Each semiconductor laser keeps constant temperature with the Peltier element, to eliminate owing to temperature variation produces the strong variation of light intensity.The effective diameter of laser beam is 80 μ m, and sweep span is 42.3 μ m (600dpi), and the mean exposure time of each image point is 1.7 * 10 ^-7Second.The temperature of semiconductor laser keeps constant temperature with the Peltier device, to prevent that light quantity is owing to temperature changes.

The procedure of processing temperature-time replenishes liquid measure

38.5 ℃ of 45 seconds 45mL of colour development

38.0 ℃ of 45 seconds additional liquid A17.5mL are fixed in bleaching

Replenish liquid B17.5mL

1 38.0 ℃ of rinsings 20 seconds-

2 38.0 ℃ of rinsings 20 seconds-

3 38.0 ℃ of rinsings 20 seconds-

4 38.0 ℃ of 20 seconds 121mL of rinsing

Dry 80 ℃

(notes)

* every m ²Need the additional liquid measure of the photosensitive material of processing

* installs rinsing cleaning systems RC50D (Ltd. produces for trade name, Fuji Photo Film Co.) in rinsing (3), take out rinsing solution also with being pumped into inverse osmosis film module (RC50D) from rinsing (3).The infiltration water that obtains in that jar is delivered to rinsing (4), and condensed water is turned back to rinsing (3).The control pump pressure makes the water that will permeate in the inverse osmosis module remain on the amount of 50-300ml/min, every day circulation rinsing solution 10 hours under controlled temperature.In four jars of convection systems, carry out (1)-rinsing of (4).

Every kind of process solutions composed as follows:

(colour developing solution) (groove solution) (replenishing liquid)

Water 800mL 800mL

Fluorescer (FL-1) 2.2g 5.1g

Fluorescer (FL-2) 0.35g 1.75g

Triisopropanolamine 8.8g 8.8g

Poly-second vinylcarbinol

(mean molecular weight: 300) 10.0g 10.0g

Ethylenediamine tetraacetic acid 4.0g 4.0g

Sodium sulphite 0.10g 0.20g

Potassium chloride 10.0g-

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

Disodium-N, two sulfonation ethyl (sulfonatoethyl) the azanol 8.5g 14.0g of N-

4-amino-3-methyl-N-ethyl-N-(β-Methanesulfomide ethyl) aniline

-3/2 sulfuric acid 1 hydration sal tartari 4.8g 14.0g

Sal tartari 26.3g 26.3g

Water adds to 1000mL 1000mL

PH (25 ℃ are regulated with sulfuric acid and potassium hydroxide) 10.15 12.40

(bleaching-photographic fixing solution) (jar solution) (replenishing liquid A) (replenishing liquid B)

Water 800mL 500mL 300mL

ATS (Ammonium thiosulphate) (750g/l) 107mL-386mL

Bisulfite ammonia (65%) 30.0g-190g

Iron ammonium (III)

Edetate 47.0g 133g-

Ethylenediamine tetraacetic acid 1.4g 5g 6g

Nitric acid (67%) 16.5g 66.0g-

Imidazoles 14.6g 50.0g-

Between carboxyl methylbenzene sulfinic acid 8.3g 33.0g-

Water adds to 1000mL 1000mL 1000mL

PH (25 ℃ are regulated with nitric acid and ammoniacal liquor) 6.5 6.0 6.0

(rinsing solution) (groove solution) (replenishing liquid)

Chlorinated isocyanuric acid sodium 0.02g 0.02g

Deionized water (conductance: 1000mL 1000mL 5 μ S/cm or lower)

pH(25℃) 6.5 6.5

The result on yellow image who obtains thus is as shown in table 3.Light sensitivity S _LAnd S _HBe expressed as 100 o'clock the relative value of getting of sample 101 respectively, so, be worth greatly more, light sensitivity is just high more.

Table 3

Sample number	Photographic fog	Light sensitivity S L	Light sensitivity S H	γ H/γ L	Storage stability		Remarks
								ΔFog	Light sensitivity Δ S H
					101	0.085				100	100	0.25	+0.010	117	The comparative example
102	0.083	93	178	0.30			+0.008	112	The comparative example
					103	0.081				100	251	0.55	+0.007	110	The comparative example
104	0.080	95	282	0.80			+0.006	105	The comparative example
					105	0.080				91	316	1.00	+0.006	100	The comparative example
106	0.079	85	295	1.35			+0.005	95	The comparative example
					107	0.079				79	234	1.70	+0.005	87	The comparative example
108	0.090	141	158	0.30			+0.025	126	The comparative example
					109	0.086				141	282	0.40	+0.020	120	The comparative example
110	0.083	158	407	0.70			+0.010	110	The present invention
					111	0.080				158	447	1.00	+0.007	105	The present invention
112	0.079	158	501	1.25			+0.005	100	The present invention
					113	0.079				148	468	1.70	+0.005	95	The present invention

114	0.079	138	372	2.10	+0.005	89	The comparative example
								115	0.089	126	141	0.30	+0.024	129	The comparative example
116	0.084	126	251	0.40	+0.018	123	The comparative example
								117	0.080	141	363	0.65	+0.008	112	The present invention
118	0.077	141	398	0.95	+0.005	107	The present invention
								119	0.075	141	447	1.20	+0.003	102	The present invention
120	0.075	132	417	1.65	+0.003	98	The present invention
								121	0.075	123	331	2.05	+0.003	91	The comparative example

As shown in table 3, to compare with the sample of contrast, sample according to the present invention has reached good effect, and their gray scale density has reduced, and has kept ISO, and storge quality is also very good simultaneously.Sample according to the present invention has ISO and strong contrast, particularly under the situation of high intensity of illumination exposure, so they are very high to the adaptability of digit explosure.Also can increase photographic fog outward and destroy retention though use selenium compound can improve light sensitivity, the present invention can keep low photographic fog when obtaining ISO.Further, the present invention can keep low photographic fog even after long-time the storage, can also guarantee to be used for the suitable performance of colour print material.

Achievement of the present invention is to find and γ _H/ γ _LThese relevant premium properties.More especially, under the situation of digit explosure, use selenium compound, find γ _H/ γ _LThere is particularly preferred scope, to obtain ISO, strong contrast, low photographic fog and fabulous retention.

In addition, prepare the family curve of pinkish red and cyan image respectively, carry out the assessment of light sensitivity, photographic fog and storge quality with method same as described above.For yellow image, with the sample of contrast relatively, sample of the present invention is the same with cyan with magenta to have obtained fabulous result.

And, by the method for in Digital Minilab Frontier 350 (trade name, by Fuji Photo Film Co., Ltd produces), exposure device being installed, each sample is carried out imaging exposure by data, carry out following technology A then.As a result, find that each sample of the present invention can provide ISO, strong contrast and the good white background of effect.

Embodiment-2

(preparation of emulsion B-15)

In the preparation of emulsion B-15, nucleus has formed the interpolation rapid change of part.K ₄[RuCl ₅(NO)] addition has increased twice.Except that above-mentioned mention, the method identical with preparing emulsion B-8 makes emulsion B-15.The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, is 0.40 μ m by observing and record its length of side with (direct method) with transmission electron micrograph, and coefficient of alteration is 9.5%.After precipitation desalination processing, in the emulsion of gained, add following substances: deionized water, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, and then disperse emulsion.

(preparation of emulsion B-16)

The method identical with preparing emulsion B-15 prepares emulsion B-16, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (2.0 * 10 ^-7Mole %/mole final silver halide) and K[IrCl ₄(H ₂O) ₂] (2.0 * 10 ^-8The final silver halide of mole %/mole).

(preparation of emulsion B-17)

The method identical with preparing emulsion B-16 prepares emulsion B-17, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (6.7 * 10 ^-8The final silver halide of mole %/mole).

(preparation of emulsion B-18)

The method identical with preparing emulsion B-17 prepares emulsion B-18, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-19)

The method identical with preparing emulsion B-17 prepares emulsion B-19, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase ten times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-20)

The method identical with preparing emulsion B-17 prepares emulsion B-20, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase the thirtyfold of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-21)

The method identical with preparing emulsion B-17 prepares emulsion B-21, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase 100 times of the remaining unaltered relative scale of these complex compounds respectively.

(preparation of emulsion B-15b)

The emulsion of Fen Saning is 40 ℃ of dissolvings down again, add sodium benzenethiosulfonate, 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole (1/10 addition after chemical sensitization is finished), illustration compound (SE3-29) as the selenium sensitizer, as golden sensitizer two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoroborate.Gained emulsion is in slaking under most preferred Chemical Sensitization under 60 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Thereafter, the temperature with emulsion is cooled to 40 ℃, adding 1-phenyl 5-mercapto-tetrazole; 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Principal ingredient is by the potpourri of compound-3 expression, and the repetitive of compound-3 is 2 or 3 (terminal X ₁And X ₂All be respectively hydroxyl); Compound-4 and potassium bromide (0.38 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-1, S-2 and S-3 are to carry out spectral sensitization.Obtain emulsion B-15b thus.

(preparation of emulsion B-16b to B-21b)

The method identical with preparing emulsion B-15b prepares emulsion B-16b to B-21b respectively, and difference is with the emulsion B-15 of emulsion B-16 to B-21 replacement in emulsion B-15b preparation.

(preparation of emulsion G-15)

In the preparation of emulsion B-8, changed the adding speed that forms part at nucleus.K ₄[RuCl ₅(NO)] addition has increased by 2.4 times.Except that change above-mentioned, the method identical, preparation emulsion G-15 with emulsion B-8.The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, and by observing with transmission electron micrograph (direct method) and measuring to such an extent that its length of side is 0.30 μ m, coefficient of alteration is 9.9%.After precipitation desalination processing, in the emulsion of gained, add following substances: deionized gelatin, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, and then disperse emulsion.

(preparation of emulsion G-16)

The method identical with preparing emulsion G-15 prepares emulsion G-16, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (4.8 * 10 ^-8Mole %/mole final silver halide) and K[IrCl ₄(H ₂O) ₂] (4.8 * 10 ^-7The final silver halide of mole %/mole)

(preparation of emulsion G-17)

The method identical with preparing emulsion G-16 prepares emulsion G-17, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (1.6 * 10 ^-7The final silver halide of mole %/mole).

(preparation of emulsion G-18 to G-21)

The method identical with preparing emulsion G-17 prepares emulsion G-18 to G-21, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times, ten times of the remaining unaltered relative scale of these complex compounds, thirtyfold and 100 times respectively.

(preparation of emulsion G-15b)

The emulsion of Fen Saning adds sodium benzenethiosulfonate, to the glutaramide diphenyl disulfide 40 ℃ of dissolvings down again, as the illustration compound (SE3-29) of selenium sensitizer, as two (1,4 of golden sensitizer, 5-trimethyl-1,2,4-triazole -3-mercaptan root) aurate (I) tetrafluoroborate.Gained emulsion is in slaking under most preferred Chemical Sensitization under 65 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Add 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole thereafter; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.47 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-4, S-5, S-6 and S-7 are to carry out spectral sensitization.Obtain emulsion G-15b thus.

(preparation of emulsion G-16b to G-21b)

The method identical with preparing emulsion G-15b prepares emulsion G-16b to G-21b respectively, and difference is with the emulsion G-15 of emulsion G-16 to G-21 replacement in emulsion G-15b preparation.

(preparation of emulsion R-15)

In the preparation of emulsion R-8, formed the adding rapid change of part at nucleus.K ₂[RuCl ₅(NO)] addition has increased by 2.4 times.Method with emulsion R-8 except that change above-mentioned is identical, preparation emulsion R-15.The emulsion grain that obtains thus is a monodispersion cubic iodine bromine silver chloride, and by observing with transmission electron micrograph (direct method) and measuring to such an extent that its length of side is 0.30 μ m, coefficient of alteration is 9.9%.After precipitation desalination processing, in the emulsion of gained, add following substances: deionized gelatin, compd A b-1, Ab-2 and Ab-3 and calcium nitrate, and then disperse emulsion.

(preparation of emulsion R-16)

The method identical with preparing emulsion R-15 prepares emulsion R-16, and difference is interpolation stage of 92% to 97% in the silver nitrate total amount, adds K ₂[IrCl ₅(H ₂O)] (1.4 * 10 ^-7The silver halide that moles/mole is final) and K[IrCl ₄(H ₂O) ₂] (1.4 * 10 ^-8The silver halide that moles/mole is final)

(preparation of emulsion R-17)

The method identical with preparing emulsion R-16 prepares emulsion R-17, and difference is interpolation stage of 82% to 88% in the silver nitrate total amount, adds K ₂[IrCl ₅(5-methylthiazol)] (2.4 * 10 ^-7The silver halide that moles/mole is final).

(preparation of emulsion R-18 to R-21)

The method identical with preparing emulsion R-17 prepares emulsion R-18 to R-21, and difference is to add K ₂[IrCl ₅(H ₂O)], K[IrCl ₄(H ₂O) ₂] and K ₂[IrCl ₅(5-methylthiazol)] addition increase three times, ten times of the remaining unaltered relative scale of these complex compounds, thirtyfold and 100 times respectively.

(preparation of emulsion R-15b)

The emulsion of Fen Saning adds sodium benzenethiosulfonate, as the illustration compound (SE3-9) of selenium sensitizer, as two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan root) aurate (I) tetrafluoroborate of golden sensitizer 40 ℃ of dissolvings down again.Gained emulsion is in slaking under most preferred Chemical Sensitization under 55 ℃, to obtain 1 * 10 ^-6Under the exposure of second the strongest contrast is arranged.Add 1-(3-acetyl amino phenyl)-5-mercapto-tetrazole thereafter; 1-(5-methyl urea groups benzene)-5-mercapto-tetrazole; Compound-2; Compound-4 and potassium bromide (0.47 mole of silver halide that %/mole is final).Further, add sensitizer in advance, sensitizing dye S-8 and compound-5 is to carry out spectral sensitization.Obtain emulsion R-15b thus.

(preparation of emulsion R-16b to R-21b)

The method identical with preparing emulsion R-15b prepares emulsion R-16b to R-21b respectively, and difference is with the emulsion R-15 of emulsion R-16 to R-21 replacement in emulsion R-15b preparation.

Other photosensitive materials can by replace in the sample 101 first respectively with the above-mentioned emulsion that contains identical silver-colored composition, the 4th and layer 6 in photosensitive emulsion prepare.Sample number and every kind of photosensitive material composition as shown in table 4.

Table 4

Sample number	Ground floor emulsion	The 4th layer of emulsion	Layer 6 emulsion
				201	B-15b	R-15b	G-15b
202	B-16b	R-16b	G-16b
				203	B-17b	R-17b	G-17b
204	B-18b	R-18b	G-18b
				205	B-19b	R-19b	G-19b
206	B-20b	R-20b	G-20b
				207	B-21b	R-21b	G-21b

Each sample after the coating under the environment of 25 ℃ and 55%RH aging 10 days makes post bake wherein react completely.Then it is assessed.Respectively sample 201 to 207 is carried out test identical among the embodiment 1-1, compare with the result of sample 101 to 107, the result of the yellow image of gained is as shown in table 5.

Table 5

Sample number	Photographic fog	Light sensitivity S L	Light sensitivity S H	γ H/γ L	Storage stability		Remarks
								ΔFog	Light sensitivity Δ SH
					101	0.085				100	100	0.25	+0.010	117	The comparative example
102	0.083	93	178	0.30			+0.008	112	The comparative example
					103	0.081				100	251	0.55	+0.007	110	The comparative example
104	0.080	95	282	0.80			+0.006	105	The comparative example
					105	0.080				91	316	1.00	+0.006	100	The comparative example
106	0.079	85	295	1.35			+0.005	95	The comparative example
					107	0.079				79	234	1.70	+0.005	87	The comparative example
201	0.080	89	105	0.35			+0.022	132	The comparative example
					202	0.078				89	186	0.45	+0.017	123	The comparative example
203	0.075	100	269	0.70			+0.007	110	The present invention
					204	0.072				100	295	1.00	+0.005	105	The present invention
205	0.071	100	324	1.25			+0.003	100	The present invention
					206	0.071				93	295	1.75	+0.003	95	The present invention
207	0.070	87	229	2.15			+0.003	83	The comparative example

As shown in table 5, to compare with the sample of contrast, sample of the present invention has ISO under the situation of high intensity of illumination exposure, and low light is according to the exposure light sensitivity of intensity and equating of comparative sample simultaneously, and in addition, their photographic fog is low and have a fabulous retention.In addition, the present invention can be provided for the color photographic light-sensitive material of high intensity of illumination exposure, and good white background effect can be provided.

Further, the method by in Digital Minilab Frontier 350 (trade name, by Fuji Photo FilmCo., Ltd produces) exposure device being installed is carried out to exposure map by data to each sample, carries out following technology A then.As a result, find that each sample of the present invention can provide ISO, strong contrast and good white background effect.

Embodiment 1-3

With assessing, except replace the technology A among the embodiment 1-2 with following technology B according to the identical appraisal procedure of embodiment 1-2.The result of the yellow image of gained is as shown in table 6.

By following exposure method formation standard on the wide EVER-BEAUTY PAPER TYPEII that is used for laser of 127mm (trade name, by Fuji Photo Film Co., Ltd. produces) film sample image of taking pictures.After this use Digita Minilab Frontier 340 (trade names, by Fuji Photo Film Co., Ltd produces) sample of exposure is processed (running test) continuously with following processing step, reach 2 twices of color developing trough volume up to the amount of the additional liquid of the accumulation of color developing solution.Use the processing called after technology B that is using process solutions herein.In addition, in order in processing machine, to obtain following process time, change transmission speed by changing handling frame.

(technology B)

The procedure of processing temperature-time replenishes liquid measure

45.0 ℃ of 12 seconds 35mL of colour development

40.0 ℃ of 12 seconds additional liquid A 15mL are fixed in bleaching

Replenish liquid B 15mL

1 45.0 ℃ of rinsings 4 seconds-

2 45.0 ℃ of rinsings 2 seconds-

3 45.0 ℃ of rinsings 2 seconds-

4 45.0 ℃ of 3 seconds 175mL of rinsing

Dry 80 ℃ 15 seconds

(attention)

* every m ²Need the additional liquid measure of the photosensitive material of processing

Available following light source is as LASER Light Source, wavelength is the blue-light semiconductor laser (being proposed on 48th Applied Physics Related Joint Meeting March calendar year 2001 by NichiaCorporation) of 440nm, (vibration wave is about 1,060nm) uses LiNbO by semiconductor laser ₃The green laser of about 530nm of obtaining of SHG crystal wavelength adjustment, this LiNbO ₃The SHG crystal have anti-domain structure and wavelength to be about the red light semiconductor laser (Type No.HL6501MG (trade name) is by Hitachi, and Ltd produces) of 650nm with the form of wave guide.With polygon mirror each LASER Light Source of these three kinds of color laser is vertically moved into the direction of scanning, so that its scan exposure and then on sample.Each semiconductor laser keeps constant temperature with the Peltier element, to eliminate the intensity variation that produces owing to temperature variation.The effective diameter of laser beam is 80 μ m, and sweep span is 42.3 μ m (600dpi), and the mean exposure time of each image point is 1.7 * 10 ^-7Second.The temperature of semiconductor laser keeps constant temperature with the Peltier device, to prevent that light quantity is owing to temperature changes.

Every kind of process solutions composed as follows:

(color developer) (groove solution) (replenishing liquid)

Water 800mL 800mL

Fluorescer (FL-3) 4.0g 10.0g

Residue color reductive agent (SR-1) 3.0g 3.0g

Between carboxyl methylbenzene sulfinic acid 2.0g 4.0g

Paratoluenesulfonic acid sodium salt 10.0 10.0

Ethylenediamine tetraacetic acid 4.0g 4.0g

Sodium sulphite 0.10g 0.10g

Potassium chloride 10.0g-

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

Disodium-N, two sulfonation ethyl (sulfonatoethyl) the azanol 8.5g 14.0g of N-

4-amino-3-methyl-N-ethyl-N-(β-Methanesulfomide ethyl) aniline

3/2 sulfate, 1 hydrate 7.0g 19.0g

Sal tartari 26.3g 26.3g

Water adds to 1000mL 1000mL

PH (25 ℃ are regulated with sulfuric acid and KOH) 10.25 12.8

(bleaching-photographic fixing solution) (jar solution) (replenishing liquid A) (replenishing liquid B)

Water 700mL 300mL 300mL

ATS (Ammonium thiosulphate) (750g/l) 107mL-400mL

Bisulfite ammonia 30.0g--

Ferric ammonium ethylene diamine tetraacetate (III) 47.0g 200g-

Ethylenediamine tetraacetic acid 1.4g 0.5g 10.0g

Nitric acid (67%) 7.0g 30.0g-

Between carboxyl methylbenzene sulfinic acid 3.0g 13.0g-

Bisulfite ammonia (65%)--200g

Succinic acid 7.0g 30.0g-

Water adds to 1000mL 1000mL 1000mL

PH (25 ℃ are regulated with nitric acid and ammoniacal liquor) 6.0 2.0 5.6

(rinsing solution) (groove solution) (replenishing liquid)

Chlorinated isocyanuric acid sodium 0.02g 0.02g

Deionized water (conductance: 1000mL 1000mL 5 μ S/cm or lower)

pH(25℃) 6.5 6.5

Table 6

Sample number	Photographic fog	Light sensitivity S L	Light sensitivity S H	γ H/γ L	Storage stability		Remarks
								The Δ fog density	Light sensitivity Δ S H
					101	0.087				100	100	0.25	+0.012	120	The comparative example
102	0.085	95	182	0.30			+0.010	115	The comparative example
					103	0.083				102	257	0.55	+0.009	110	The comparative example
104	0.082	95	288	0.80			+0.008	105	The comparative example
					105	0.082				91	316	1.00	+0.008	102	The comparative example
106	0.081	83	288	1.35			+0.008	98	The comparative example
					107	0.081				76	224	1.70	+0.007	91	The comparative example
201	0.091	91	110	0.35			+0.026	135	The comparative example
					202	0.087				93	195	0.45	+0.020	123	The comparative example
203	0.082	100	282	0.70			+0.011	110	The present invention
					204	0.079				102	302	1.00	+0.008	102	The present invention
205	0.077	105	339	1.25			+0.006	98	The present invention

206	0.077	100	295	1.75	+0.006	95	The present invention
								207	0.076	91	224	2.15	+0.006	89	The comparative example

As shown in table 6, sample of the present invention is compared with control sample, has ISO under high illumination intensity, has the light sensitivity under the identical low illumination intensity simultaneously, in addition, has low photographic fog and excellent storage stability.Compare clearly with the result who obtains among the embodiment 1-2 and to have shown that although use the sample of selenium compound to have the tendency of high photographic fog under rapid processing, the present invention has controlled this defective, and has produced better result.In addition, on pinkish red and cyan image, all obtained similar result.Therefore the present invention can provide the colour photographic sensitive material that is suitable under the rapid processing, and can transmit good white background.

And the laser explosure element when moving process solutions (running processing solutions) by being applied to preparation is used for each sample with the imaging exposure (image-wise exposure) of numerical data, then processes B.As a result, find that each sample of the present invention can transmit ISO, hard contrast and good white background.

Embodiment 2-1

(preparation blue-sensitive emulsion layer (yellow cambium layer) BH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains deionized gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 10%-20%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 70%-85%, add potassium bromide (the final silver halide of 3mol%/mole adds) and K ₄[Fe (CN) ₆].In the step of adding silver nitrate total amount 75%-80%, add K ₂[IrCl ₆].Further, K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 88%-98%, add.When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (the final silver halide of 0.3mol%/mole adds).The emulsion grain of Huo Deing is the length of side 0.43 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.After the processing of precipitation desalination, following substances is joined the emulsion that obtains: gelatin, compd A b-1, Ab-2, and Ab-3, and calcium nitrate, and then disperse emulsion.

With the emulsion that disperses again 40 ℃ of dissolvings, and with oxygenant 1 as compound with the silver-colored bunch function in oxidized metal, the triethyl thiocarbamide is as the sulphur sensitizer, compound-1 adds as golden sensitizer.With the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole; Compound-2; With repetitive wherein is 2 or 3 (two end group X ₁And X ₂All be respectively a hydroxyl) the compound of compound-3 expression as the potpourri of principal ingredient; Compound-4, and potassium bromide.Further, add sensitizing dye S-1 in the emulsion preparation, S-2 and S-10 control spectral sensitization.The emulsion of Huo Deing is as emulsion BH-1 (wherein silver halide content accounts for 96.3 moles of % in the emulsion that forms) by this way.

Sensitizing dye S-10

Oxygenant 1 oxygenant 2

(preparation blue-sensitive emulsion layer (yellow cambium layer) BH-2)

The preparation method of emulsion BH-2 is identical with emulsion BH-1, just add selenium sensitizer SE3-9 and replace sulphur sensitizer triethyl thiocarbamide, tetrafluoro boric acid two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) gold (I) replaces golden sulphur sensitizer compound-1 as golden sensitizer, and replaces (wherein silver halide content accounts for 96.3 moles of % in the emulsion of finishing) according to the amount that adds compound.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BH-3)

The preparation method of emulsion BH-3 is identical with emulsion BH-2, just add selenium sensitizer SE3-29 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.3 moles of % in the emulsion that forms) of compound among the BH-2.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BH-4)

The preparation method of emulsion BH-4 is identical with emulsion BH-2, just add PF1-1 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.3 moles of % in the emulsion that forms) of compound among the BH-2.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BH-5)

The preparation method of emulsion BH-5 is identical with emulsion BH-4, just adds 1.0 * 10 ^-5The oxygenant 2 of moles/mole silver is as the compound with oxidized metal silver family (wherein silver halide content accounts for 96.3 moles of % in the emulsion that forms).

(preparation green-sensitive emulsion layer (magenta cambium layer) GH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains deionized gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 70%-85%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 70%-85%, add potassium bromide (whenever add the 1mol silver halide and add 1 mole of %).Further, in the step of adding silver nitrate total amount 70%-85%, add K ₂[IrCl ₆And K ₂[RhBr ₅(H ₂O)].When adding the step of silver nitrate total amount 90%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.1 mole of %).K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 87%-98%, add.The emulsion grain of Huo Deing is the length of side 0.31 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with the same procedure of foregoing description.

To disperse emulsion 40 ℃ of dissolvings again, and with oxygenant 1 as compound with oxidized metal silver bunch function, compound-1 is as golden sulphur sensitizer, the triethyl thiocarbamide is as the sulphur sensitizer, and two (1,4,5-trimethyl 1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoro boric acid adds as golden sensitizer, then with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4, and potassium bromide.Further, in the process of preparation emulsion, add sensitizing dye S4, S-5, S-6 and S-7 carry out spectral sensitization.The emulsion of Huo Deing is as emulsion GH-1 by this way.(wherein silver halide content accounts for 98.3 moles of % in the emulsion that forms)

(preparation green-sensitive emulsion layer (magenta cambium layer) GH-2)

The preparation method of emulsion GH-2 is identical with emulsion GH-1, just add selenium sensitizer SE3-9 and replace sulphur sensitizer triethyl thiocarbamide, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 98.3 moles of % in the emulsion that forms) of compound among the GH-1.

(preparation green-sensitive emulsion layer (magenta cambium layer) GH-3)

The preparation method of emulsion GH-3 is identical with emulsion GH-2, just add selenium sensitizer SE3-29 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 98.3 moles of % in the emulsion that forms) of compound among the GH-2.

(preparation green-sensitive emulsion layer (magenta cambium layer) GH-4)

The preparation method of emulsion GH-4 is identical with emulsion GH-2, just add selenium sensitizer PF1-1 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 98.3 moles of % in the emulsion that forms) of compound among the GH-2.

(preparation green-sensitive emulsion layer (magenta cambium layer) GH-5)

The preparation method of emulsion GH-5 is identical with emulsion GH-4, just adds 1.5 * 10 ^-5The oxygenant 2 of moles/mole silver is as the compound with oxidized metal silver family (wherein silver halide content accounts for 98.3 moles of % in the emulsion that forms).

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains deionized gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 60%-80%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 93%-98%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 85%-100%, add potassium bromide (whenever add the 1mol silver halide and add 3 moles of %).Further, in the step of adding silver nitrate total amount 88%-93%, add K ₂[IrCl ₅(5-methylthiazol)].When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.1 mole of %).Further, K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 93%-98%, add.The emulsion grain of Huo Deing is the length of side 0.32 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with same procedure described above.

To disperse emulsion 40 ℃ of dissolvings again, and with sensitizing dye S-8, compound-5, oxygenant 1 is as the compound with oxidized metal silver bunch function, the triethyl thiocarbamide is as the sulphur sensitizer, and compound-1 adds as golden sulphur sensitizer, then with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4, and potassium bromide.The emulsion of Huo Deing is as emulsion RH-1 by this way.(wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms)

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-2)

The preparation method of emulsion RH-2 is identical with emulsion RH-1, just add selenium sensitizer SE3-9 and replace sulphur sensitizer triethyl thiocarbamide, two (1,4,5-trimethyl 1,2,4-triazole-3-mercaptan) aurate (I) tetrafluoro boric acid replaces compound-1 as golden sensitizer, replaces (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) according to the amount that adds compound.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-3)

The preparation method of emulsion RH-3 is identical with emulsion RH-2, just add selenium sensitizer SE3-29 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) of compound among the RH-2.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-4)

The preparation method of emulsion RH-4 is identical with emulsion RH-2, just add selenium sensitizer PF1-1 and replace selenium sensitizer SE3-9, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) of compound among the RH-2.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-5)

The preparation method of emulsion RH-5 is identical with emulsion RH-1, just add SS-7 and replace compound-5, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) of compound among the RH-1.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-6)

The preparation method of emulsion RH-6 is identical with emulsion RH-3, just add SS-7 and replace compound-5, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) of compound among the RH-3.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-7)

The preparation method of emulsion RH-7 is identical with emulsion RH-4, just add SS-7 and replace compound-5, and the amount of the compound that will add is according to the quantitative changeization (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms) of compound among the RH-4.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RH-8)

The preparation method of emulsion RH-8 is identical with emulsion RH-7, just adds 9.0 * 10 ^-6The oxygenant 2 of moles/mole silver is as the compound with oxidized metal silver family (wherein silver halide content accounts for 96.6 moles of % in the emulsion that forms).

Preparation ground floor coating fluid

To 17g solvent (Solv-4), 5g solvent (Solv-6), 17g solvent (Solv-9) and be dissolved in the 24g yellow colour former (Ex-Y) of 45ml ethyl acetate, 7g coloured image stabilizing agent (Cpd-8), 1g coloured image stabilizing agent (Cpd-16), 1g coloured image stabilizing agent (Cpd-17), with 10g coloured image stabilizing agent (Cpd-18), 1g coloured image stabilizing agent (Cpd-19), 11g coloured image stabilizing agent (Cpd-21), 0.1g adjuvant (ExC-2), 1g coloured image stabilizing agent (UV-A).Be scattered in the gelatin solution of 20 quality % that 205g contains the 3g neopelex with this emulsifying soln and with high-speed stirred emulsifier (dissolver).Water is added to wherein, thereby prepares 700g emulsified dispersed liquid 2A.

On the other hand, with above-mentioned emulsified dispersed liquid 2A and described emulsion BH-1 mixing and dissolving, thereby prepare ground floor coating fluid with composition as follows.The emulsion coating weight is come in silver.

The second layer to layer 7 coating fluid prepares with the preparation method who is similar to the ground floor coating fluid.With (H-1), (H-2) and (H-3) as every layer gelatin hardener.Further, to every layer of interpolation Ab-1, Ab-2, Ab-3 and Ab-4, total amount is respectively 7.0mg/m ², 43.0mg/m ², 3.5mg/m ²And 10.0mg/m ²

Further, to the 3rd layer, layer 5 and layer 6 add 0.2mg/m respectively ², 0.2mg/m ², and 0.6mg/m ²1-(3-methyl urea groups the phenyl)-5-mercapto-tetrazole of amount.Further, add 1 * 10 respectively to blue-sensitive emulsion layer and green-sensitive emulsion layer ^-4Mole and 2 * 10 ^-4The 4-hydroxyl 6-methyl 1,3 of mole, 3a, the 7-purine/mole silver halide.Further, add 0.05g/m to the magenta-sensitive emulsion layer ²Methacrylic acid and copolymer latex (1: 1 mass ratio of butyl acrylate; Mean molecular weight, 200,000 to 400,000).To the 3rd layer, it is 6mg/m that layer 5 and layer 6 add coating weight respectively ², 7mg/m ²And 18mg/m ²Catechol-3, the perlate salt of 5-disulfonic acid.Further, if necessary, add kayexalate to regulate the stickiness of coating solution to every layer.Further, in order to prevent radiation, add following dyestuff (coating weight is as shown in parenthesis).

(layer structure)

Single formation layer forms following composition, and uses their preparation silver halide colour photographic sensitive materials.Numeric representation coating weight (g/m ²).Under the situation of silver emulsion, coating weight is in silver.

Carrier

{ polyvinyl resin on the ground floor side comprises Chinese white (TiO to the stacked paper of polyvinyl resin ₂Content, 16 quality %, ZnO content, 4 quality %), brightener (4,4 '-two (5-methylbenzoxazole base) talan content, 0.03 quality %) and the dyestuff that turns blue (ultramarine content, 0.33 quality %) and the amount of polyvinyl resin be 29.2g/m ²}

Ground floor (blue-sensitive emulsion layer/comprise the silver halide emulsion layer that weld is formed into toner)

Emulsion (BH-1) 0.26

Gelatin 1.30

Yellow colour former (Ex-Y) 0.48

Coloured image stabilizing agent (Cpd-8) 0.14

Coloured image stabilizing agent (Cpd-16) 0.02

Coloured image stabilizing agent (Cpd-17) 0.02

Coloured image stabilizing agent (Cpd-18) 0.21

Coloured image stabilizing agent (Cpd-19) 0.02

Coloured image stabilizing agent (Cpd-21) 0.22

Adjuvant (ExC-2) 0.002

Coloured image stabilizing agent (UV-A) 0.02

Solvent (Solv-4) 0.34

Solvent (Solv-6) 0.10

Solvent (Solv-9) 0.34

The second layer (anti-colour mixture layer)

Gelatin 0.99

Mixed color inhibitor (Cpd-4) 0.05

Mixed color inhibitor (Cpd-12) 0.01

Coloured image stabilizing agent (Cpd-3) 0.01

Coloured image stabilizing agent (Cpd-5) 0.006

Coloured image stabilizing agent (Cpd-6) 0.06

Coloured image stabilizing agent (UV-A) 0.07

Coloured image stabilizing agent (Cpd-7) 0.007

Solvent (Solv-1) 0.07

Solvent (Solv-2) 0.18

Solvent (Solv-5) 0.07

Solvent (Solv-8) 0.07

The 3rd layer (green-sensitive emulsion layer/comprise the silver halide emulsion layer that magenta dye is formed into toner)

Emulsion (GH-1) 0.15

Gelatin 1.35

Magenta colour coupler (Ex-M) 0.15

Ultraviolet light absorber (UV-A) 0.04

Coloured image stabilizing agent (Cpd-2) 0.01

Coloured image stabilizing agent (Cpd-6) 0.10

Coloured image stabilizing agent (Cpd-7) 0.007

Coloured image stabilizing agent (Cpd-8) 0.01

Coloured image stabilizing agent (Cpd-9) 0.01

Coloured image stabilizing agent (Cpd-10) 0.007

Coloured image stabilizing agent (Cpd-11) 0.0002

Coloured image stabilizing agent (Cpd-18) 0.01

Solvent (Solv-3) 0.08

Solvent (Solv-4) 0.16

Solvent (Solv-6) 0.07

Solvent (Solv-9) 0.18

The 4th layer (anti-colour mixture layer)

Gelatin 0.71

Mixed color inhibitor (Cpd-4) 0.06

Mixed color inhibitor (Cpd-12) 0.01

Coloured image stabilizing agent (Cpd-3) 0.01

Coloured image stabilizing agent (Cpd-5) 0.005

Coloured image stabilizing agent (Cpd-6) 0.04

Coloured image stabilizing agent (UV-A) 0.05

Coloured image stabilizing agent (Cpd-7) 0.005

Solvent (Solv-1) 0.05

Solvent (Solv-2) 0.05

Solvent (Solv-5) 0.06

Solvent (Solv-8) 0.06

Layer 5 (magenta-sensitive emulsion layer/comprise the silver halide emulsion layer that cyan dye is formed into toner)

Emulsion (RH-1) 0.13

Gelatin 1.11

Cyan coupler (ExC-1) 0.14

Cyan coupler (ExC-3) 0.01

Cyan coupler (ExC-2) 0.05

Coloured image stabilizing agent (Cpd-1) 0.04

Coloured image stabilizing agent (Cpd-7) 0.01

Coloured image stabilizing agent (Cpd-9) 0.05

Coloured image stabilizing agent (Cpd-10) 0.001

Coloured image stabilizing agent (Cpd-14) 0.002

Coloured image stabilizing agent (Cpd-15) 0.023

Coloured image stabilizing agent (Cpd-16) 0.06

Coloured image stabilizing agent (Cpd-17) 0.06

Coloured image stabilizing agent (UV-5) 0.13

Solvent (Solv-5) 0.24

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

Adjuvant (Cpd-20) 0.04

Liquid paraffin 0.02

Surfactant (Cpd-13) 0.02

Zhi Bei sample is as sample 2-101 like this.Further, other sample, prepares with the preparation method identical with sample 2-101 respectively to sample 2-106 as sample 2-102, is the emulsion of those blue-sensitive emulsion layers shown in difference in the table 7, the emulsion of magenta-sensitive emulsion layer and yellow colour former.Here the addition of every kind of yellow colour former makes the ratio between silver content and the colour coupler volumetric molar concentration remain unchanged.

In addition, the preparation method of silver halide colour photographic sensitive material is identical with sample 2-101, and just the total amount of silver coating is owing to changed different variation of component generation that photograph as follows constitutes layer.

Ground floor (blue-sensitive emulsion layer/comprise the silver halide emulsion layer that weld is formed into toner)

Emulsion (BH-1) 0.16

Gelatin 0.75

Yellow colour former (Ex-Y) 0.31

Coloured image stabilizing agent (Cpd-8) 0.07

Coloured image stabilizing agent (Cpd-16) 0.01

Coloured image stabilizing agent (Cpd-17) 0.01

Coloured image stabilizing agent (Cpd-18) 0.17

Coloured image stabilizing agent (Cpd-19) 0.01

Coloured image stabilizing agent (Cpd-21) 0.14

Adjuvant (ExC-2) 0.001

Coloured image stabilizing agent (UV-A) 0.01

Solvent (Solv-4) 0.21

Solvent (Solv-6) 0.06

Solvent (Solv-9) 0.21

The second layer (anti-colour mixture layer)

Gelatin 0.60

Mixed color inhibitor (Cpd-17) 0.09

Coloured image stabilizing agent (Cpd-5) 0.007

Coloured image stabilizing agent (Cpd-7) 0.007

Ultraviolet light absorber (UV-B) 0.05

Solvent (Solv-5) 0.11

The 3rd layer (green-sensitive emulsion layer/comprise the silver halide emulsion layer that magenta dye is formed into toner)

Emulsion (GH-1) 0.14

Gelatin 0.73

Magenta colour coupler (Ex-M) 0.15

Ultraviolet light absorber (UV-A) 0.05

Coloured image stabilizing agent (Cpd-2) 0.02

Coloured image stabilizing agent (Cpd-8) 0.07

Coloured image stabilizing agent (Cpd-9) 0.03

Coloured image stabilizing agent (Cpd-10) 0.009

Coloured image stabilizing agent (Cpd-11) 0.0001

Solvent (Solv-6) 0.05

Solvent (Solv-9) 0.12

Solvent (Solv-7) 0.11

Compound (S1-4) 0.0015

The 4th layer (anti-colour mixture layer)

Gelatin 0.48

Mixed color inhibitor (Cpd-4) 0.07

Coloured image stabilizing agent (Cpd-5) 0.006

Coloured image stabilizing agent (Cpd-7) 0.006

Ultraviolet light absorber (UV-B) 0.04

Solvent (Solv-5) 0.09

Layer 5 (magenta-sensitive emulsion layer/comprise the silver halide emulsion layer that cyan dye is formed into toner)

Emulsion (RH-1) 0.12

Gelatin 0.59

Cyan coupler (ExC-1) 0.16

Cyan coupler (ExC-3) 0.016

Coloured image stabilizing agent (Cpd-1) 0.01

Coloured image stabilizing agent (Cpd-7) 0.01

Coloured image stabilizing agent (Cpd-9) 0.03

Coloured image stabilizing agent (Cpd-10) 0.001

Coloured image stabilizing agent (Cpd-14) 0.001

Coloured image stabilizing agent (Cpd-15) 0.16

Coloured image stabilizing agent (Cpd-16) 0.04

Coloured image stabilizing agent (Cpd-17) 0.02

Coloured image stabilizing agent (UV-5) 0.07

Solvent (Solv-5) 0.07

Layer 6 (UV-absorbing layer)

Gelatin 0.32

Ultraviolet light absorber (UV-B) 0.42

Solvent (Solv-7) 0.08

Layer 7 (protective seam)

Gelatin 0.70

Adjuvant (Cpd-20) 0.015

The propenyl modified copolymer 0.04 of polyvinyl alcohol (PVA)

(modification degree: 17%)

Liquid paraffin 0.01

Surfactant (Cpd-13) 0.01

Dimethyl silicone polymer 0.01

Silicon dioxide 0.003

Zhi Bei sample is progressive as sample 2-111 like this, other sample as sample 2-112 to sample 2-118, preparing with the preparation method identical with sample 2-111 respectively, is the emulsion of those blue-sensitive emulsion layers shown in difference in the table 7, the emulsion of magenta-sensitive emulsion layer and yellow colour former.Here the addition of every kind of yellow colour former makes the ratio between silver content and the colour coupler volumetric molar concentration remain unchanged.

Table 7

Sample number	Silver coating total amount (g/m 2)	Gelatin coating total amount (g/m 2)	Blue-sensitive emulsion layer emulsion	Green-sensitive emulsion layer emulsion	Magenta-sensitive emulsion layer emulsion	Yellow colour former	Remarks
								2-101	0.54	6.92	BH-1	GH-1	RH-1	Ex-Y	The comparative example
2-102	0.54	6.92	BH-1	GH-1	RH-5	Y-19	The comparative example
								2-103	0.54	6.92	BH-2	GH-2	RH-2	Ex-Y	The comparative example
2-104	0.54	6.92	BH-3	GH-3	RH-6	Ex-Y	The comparative example
								2-105	0.54	6.92	BH-3	GH-3	RH-3	Y-11	The comparative example
2-106	0.54	6.92	BH-3	GH-3	RH-6	Y-11	The comparative example
								2-111	0.42	4.17	BH-1	GH-1	RH-1	Ex-Y	The comparative example
2-112	0.42	4.17	BH-1	GH-1	RH-5	Y-19	The comparative example
								2-113	0.42	4.17	BH-2	GH-2	RH-2	Ex-Y	The comparative example
2-114	0.42	4.17	BH-3	GH-3	RH-6	Ex-Y	The present invention
								2-115	0.42	4.17	BH-3	GH-3	RH-3	Y-11	The present invention
2-116	0.42	4.17	BH-3	GH-3	RH-6	Y-19	The present invention
								2-117	0.42	4.17	BH-4	GH-4	RH-7	Y-11	The present invention
2-118	0.42	4.17	BH-5	GH-5	RH-8	Y-11	The present invention

As shown in table 7, silver halide colour photographic sensitive material of the present invention is preparation method's preparation of 2-114 to 2-118 (embodiment of the invention) per sample.On the other hand, as the silver halide colour photographic sensitive material that contrasts preparation method's preparation of 2-101 to 2-113 (comparative example) per sample.

(experimental example 1)

In order to check the photographic property of these samples, carry out following test.

Processing 2A

Aforementioned sample 2-101 is made the volume of wide 127mm, use Digital Minilab Frontier 340 (trade name, by Fuji Photo Film Co., Ltd. produces) through the decent exposure of standard drawing; Afterwards, process (operation test) these samples continuously according to following procedure of processing, the additional liquid measure of the solution in being formed into the colour development groove reaches the twice of groove volume.In addition, in order to obtain to add the following process time in the multiplexer, change transfer rate according to the variation that adds the movements and postures of actors.The processing called after processing 2A of this operation process solutions will be used.

The procedure of processing temperature-time replenishes liquid measure ^*

45.0 ℃ of 13sec 35mL of colour development

45.0 ℃ of 13sed of bleaching-photographic fixing replenish liquid A 15mL

Replenish liquid B 15mL

1 45.0 ℃ of 4sec of rinsing-

2 45.0 ℃ of 2sec of rinsing-

3 45.0 ℃ of 2sec of rinsing-

4 45.0 ℃ of 3sec 175mL of rinsing

Dry 80 ℃ of 15sec

(notes) ^*Replenish liquid measure/m ²The processing photosensitive material

Shown in each process solutions composed as follows

(colour developing solution A) (groove solution) (replenishing liquid)

Water 800mL 800mL

Brightener (FL-3) 4.0g 10.0g

Remaining colour reproduction agent (SR-1) 3.0g 3.0g

Between carboxyl benzene sulfonic acid 2.0g 4.0g

Paratoluenesulfonic acid sodium salt 10.0g 10.0g

Ethylenediamine tetraacetic acid 4.0g 4.0g

Sodium sulphite 0.10g 0.10g

Potassium chloride 10.0g-

4,5-dihydroxy benzenes-1,3-two sulphur 0.50g 0.50g

Acid sodium

N, N-two (sulfonic acid ethyl) hydroxyl 8.5g 14.0g

Amine sodium

The amino 3-methyl of 4--N-ethyl-N-7.0g 19.0g

(β-methanesulfonamido ethyl) benzene

1 hydration of amine 3/2 sulfuric ester

Thing

Sal tartari 26.3g 26.3g

Add and add water to 1000mL 1000mL

PH (25 ℃, by sulfuric acid and 10.25g 12.8g

KOH regulates)

(bleaching-photographic fixing solution (groove solution) (replenishing liquid A) (replenishing liquid B)

A)

Water 700mL 300mL 300mL

ATS (Ammonium thiosulphate) 107mL-400mL

(750g/l)

Ammonium sulfite 30.0g--

Ethylenediamine tetraacetic acid ammonium 47.0g 200g-

Iron (III)

Ethylenediamine tetraacetic acid 1.4g 0.5g 10.0g

Nitric acid (67%) 7.0g 30.0g-

Between carboxyl benzene sulfonic acid 3.0g 13.0g-

Ammonium bisulfite (65% 200g

)

Succinic acid 7.0g 30.0g

Add and add water to 1000mL 1000mL 1000mL

PH (25 ℃, by nitre 6.0 2.0 5.6

Acid and ammoniacal liquor are regulated)

(rinsing liquid) (groove solution) (replenishing liquid)

Symclosene sodium 0.02g 0.02g

Deionized water (conductivity: 5 μ 1000mL 1000mL

S/cm or lower)

pH(25℃) 6.5 6.5

Thereby each sample is carried out the gradient exposure in colour development processing 2A subsequently, transmit grey with following exposure device; Then, 5 seconds the time, sample carries out colour development processing by processing 2A after exposure is finished.Used LASER Light Source is: from the LiNbO with transferring structure domain structure ₃The wavelength of SHG crystallization be about the blue laser of 470nm, this structure use semiconductor laser (vibration wavelength: about 940nm), from LiNbO with transferring structure domain structure ₃The wavelength of SHG crystallization be about the green (light) laser of 530nm, about 1060nm) and have the red light semiconductor laser (model HL6501MG, by Hitachi, Ltd. production) of the about 650nm of wavelength this structure is used semiconductor laser (vibration wavelength:.By polygon reflective mirror mirror these three color laser are moved with the direction vertical with the direction of scanning separately, so that can continuous sweep expose this sample.By utilizing the Peltier element to keep constant inhibition to change temperature because of the light quantity that the temperature of semiconductor laser causes.Beam effective diameter is 80 μ m, and scanning pitch is 42.3 μ m (600dpi), and the mean exposure time of each pixel is 1.7 * 10 ^-7Second.

The development yellow density of each sample, pinkish red development density and cyan development density are measured after machining, and obtain their family curve subsequently.Light sensitivity (S) is defined as under the situation that the density of giving colour development is higher than unexposed area 0.7, the inverse logarithm of the inverse of exposure; As 100, the light sensitivity of associated sample is represented with the relative value to it with the light sensitivity of sample 2-101.The numerical value that sample shows is big more, and its light sensitivity is just high more.Fog density (Dmin) is defined as: deduct the numerical value that basic density obtains from unexposed area in the colour density of each development.Therefore, the numerical value that obtains is more little, and white background is just beautiful more, so this numerical value is the smaller the better.

Table 8

Sample	Yellow cambium layer		The magenta cambium layer		The cyan cambium layer		Remarks
								S	Dmin	S	Dmin	S	Dmin
	2-101	100	0.03	100	0.07	100								0.05	The comparative example
2-102							101	0.03	99	0.07	101	0.05	The comparative example
	2-103	159	0.09	151	0.09	171								0.09	The comparative example
2-104							162	0.10	153	0.10	167	0.10	The comparative example
	2-105	165	0.09	155	0.08	150								0.10	The comparative example
2-106							165	0.09	154	0.09	167	0.09	The comparative example
	2-111	100	0.02	101	0.05	99								0.04	The comparative example
2-112							100	0.02	100	0.06	101	0.03	The comparative example
	2-113	159	0.07	152	0.09	173								0.08	The comparative example
2-114							165	0.04	153	0.06	171	0.04	The present invention
	2-115	166	0.03	152	0.06	161								0.04	The present invention
2-116							169	0.02	155	0.05	173	0.03	The present invention
	2-117	178	0.02	161	0.05	178								0.03	The present invention
2-118							178	0.02	161	0.04	178	0.03	The present invention

As can be seen from Table 8, all 2-114 to 2-118 samples of the present invention all have the advantage of ISO and low Fog density.

(experimental example 2)

The simulation test that bleaching-photographic fixing solution is mixed in the colour developing solution adopts aforesaid colour developing solution A and bleaching-photographic fixing solution A to finish.

Colour developing solution B prepares by adding 1ml bleaching-photographic fixing solution A among every liter of aforesaid colour developing solution A.The processing of developing is carried out in the mode identical with processing 2A.Just replace colour developing solution A with colour developing solution B.

The development yellow density of each sample is measured after machining, and obtains family curve by drawing these measurement numerical value subsequently.From unexposed area, deduct the yellow density in the unexposed area obtains behind the processing 2A numerical value after the simulation test in the yellow density as Fog density (DminY1).Because numerical value is the smaller the better hereto, because this numerical value is more little, Fog density is just low more, thereby white background is just beautiful more.Similarly, measured the cyan density of the magenta density of developing and development after, Fog density (DminM1) and (DminC1) also just definite respectively.

Table 9

Sample	DminY1	DminM1	DminC1	Remarks
					2-101	0.05	0.07	0.08	The comparative example
2-102	0.05	0.07	0.07	The comparative example
					2-103	0.13	0.14	0.12	The comparative example
2-104	0.15	0.12	0.13	The comparative example
					2-105	0.14	0.13	0.14	The comparative example
2-106	0.12	0.13	0.13	The comparative example
					2-111	0.04	0.06	0.07	The comparative example
2-112	0.03	0.06	0.05	The comparative example
					2-113	0.12	0.11	0.12	The comparative example
2-114	0.07	0.07	0.07	The present invention
					2-115	0.05	0.07	0.07	The present invention
2-116	0.03	0.06	0.05	The present invention
					2-117	0.02	0.06	0.05	The present invention
2-118	0.02	0.03	0.03	The present invention

As can be seen from Table 9, all 2-114 to 2-118 samples of the present invention owing to will bleach-that photographic fixing solution is sneaked into the variation of generation Fog density in the colour developing solution is little and all favourable sensuously.In addition, from table 9, it can also be seen that, use under the situation of two kinds of compounds with oxidized metal silver bunch function and can produce better effect.

(experimental example 3)

Detected the stability of sample when colour developing solution pH changes.Colour developing solution C and the D pH by the colour developing solution A that will be in the experimental example 1 uses is adjusted to 10.0 and 10.7 respectively and prepares, and the processing of developing uses each colour developing solution to carry out in the mode identical with processing 2A.

The development yellow density of each sample is measured after machining, and obtains family curve by drawing these measurement numerical value subsequently.From the numerical value that obtains with the yellow density that deducts in the yellow density the unexposed area after the colour developing solution D processing in the unexposed area of colour developing solution C processing back as Fog density (Δ DY2).This numerical value is more little, and is stable more, and the sample of Jian Ceing is just good more simultaneously.Similarly, measured the cyan density of the magenta density of developing and development after, from these numerical value, obtain Fog density (Δ DM2) and (Δ DC2) respectively.

Table 10

Sample	ΔDY2	ΔDM2	ΔDC2	Remarks
					2-103	0.04	0.02	0.03	The comparative example
2-104	0.03	0.01	0.02	The comparative example
					2-105	0.02	0.02	0.03	The comparative example
2-106	0.03	0.02	0.02	The comparative example
					2-113	0.03	0.02	0.02	The comparative example
2-114	0.01	0.005	0.01	The present invention
					2-115	0.02	0.005	0.01	The present invention
2-116	0.005	0.00	0.01	The present invention
					2-117	0.005	0.00	0.005	The present invention

As can be seen from Table 10, all 2-114 to 2-117 samples of the present invention owing to will bleach-photographic fixing solution is sneaked into the Fog density that produces in the colour developing solution and is changed for a short time, so all is favourable.

(experimental example 4)

Further, checked the photographic fog when 38 ℃ change to 48 ℃ of temperature in the colour development processing to change, it is little that the result shows that the photographic fog of the sample that the present invention is all changes, and all is favourable therefore.

From these embodiment and comparative example's result photosensitive material of the present invention as can be seen have ISO and when processing conditions changes photographic fog change less and they are favourable.

Embodiment 3-1

(preparation blue light emulsion B-31 to B-33)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 25%-30%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 60%-70%, add potassium bromide (whenever add the 1mol silver halide and add 3.0 moles of %) and K ₄[Fe (CN) ₆].Further, K ₂[IrCl ₆], K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 70%-75%, add.When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.35 mole of %).The emulsion grain of Huo Deing is the length of side 0.38 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.8%.After precipitation desalination processing, following substances is joined the emulsion that obtains: gelatin, compound (Ab-1), (Ab-2), (Ab-3) and (Ab-4), and calcium nitrate, then emulsion is disperseed again.

The emulsion that disperses again 40 ℃ of dissolvings, and is added benzene sodium thiosulfate, and to the glutaramide diphenyl disulfide, the triethyl thiocarbamide is as the sulphur sensitizer, and compound-1 is as golden sulphur sensitizer, with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole compound-2; With repetitive wherein is 2 or 3 (two end group X ₁And X ₂All be respectively a hydroxyl) the compound of compound-3 expression be the potpourri of principal ingredient; Compound-4, and potassium bromide.Further, in the process of preparation emulsion, add sensitizing dye S-1, sensitizing dye S-2 and sensitizing dye S-10 carry out spectral sensitization.The emulsion of Huo Deing is as emulsion B-31 by this way.

Emulsion B-32 prepares in the mode identical with emulsion B-31, just adds the temperature of mixed nitrate silver and sodium chloride simultaneously and add speed change has taken place.The emulsion grain of Huo Deing is the length of side 0.55 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.3%.

Emulsion B-33 prepares in the mode identical with emulsion B-31, and just selenium sensitizer compound (SE1-8) and tetrafluoro boric acid two (1,4,5-trimethyl-1,2, the 4-triazole-3-mercaptan) gold (I) with example replaces sulphur sensitizer and golden sulphur sensitizer respectively.The particle of emulsion B-33 is the length of side 0.38 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.7%.

(preparation of green-sensitive emulsion G-31 to G-33)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 75%-80%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 80%-90%, add potassium bromide (whenever add the 1mol silver halide and add 1.5 moles of %).Further, K ₂[IrCl ₆] and K ₂[IrBr ₅(H ₂O)] in the step of adding silver nitrate total amount 75%-90%, add.When adding the step of silver nitrate total amount 95%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.15 mole of %).K ₂[IrCl ₅(H ₂And K O)] ₂[IrCl ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 87%-98%, add.The emulsion grain of Huo Deing is the length of side 0.35 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.0%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with same procedure described above.

To disperse emulsion 40 ℃ of dissolvings again, and add benzene sodium thiosulfate, to the glutaramide diphenyl disulfide, sodium thiosulfate is as the sulphur sensitizer, and gold chloride (chlroauric acid) is as golden sulphur sensitizer, with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4 and potassium bromide.Further, in the process of preparation emulsion, add sensitizing dye S-14, sensitizing dye S-5, sensitizing dye S-6 and sensitizing dye S-7 control spectral sensitization.The emulsion of Huo Deing is as emulsion GH-31 by this way.

Sensitizing dye S-14

Emulsion G-32 prepares in the mode identical with emulsion G-31, just adds the temperature of mixed nitrate silver and sodium chloride simultaneously and add speed change has taken place.The emulsion grain of Huo Deing is the length of side 0.44 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.3%.

Emulsion G-33 prepares in the mode identical with emulsion G-31, and just except the sulphur sensitizer, the selenium sensitizer compound (SE2-12) that adds example makes that the selenium and the ratio of sulphur are 1: 3, and the emulsion that obtains is carried out chemical sensitization under best sensitization condition.The particle of emulsion G-33 is the length of side 0.35 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.7%.

(preparation of magenta-sensitive emulsion R-31 to R-33)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 40%-80%, add K ₂[RuCl ₅(NO)].In the step of adding silver nitrate total amount 93%-98%, add K ₄[Fe (CN) ₆].In the step of adding silver nitrate total amount 85%-100%, add potassium bromide (whenever add the 1mol silver halide and add 3.5 moles of %).Further, in the step of adding silver nitrate total amount 88%-93%, add K ₂[IrCl ₅(5-methylthiazol)].When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.10 mole of %).Further, K ₂[IrCl ₅(H ₂And K O)] ₂[IrCl ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 93%-98%, add.The emulsion grain of Huo Deing is the length of side 0.40 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with same procedure described above.

To disperse emulsion 40 ℃ of dissolvings again, and adding sensitizing dye S-8, compound-5, benzene sodium thiosulfate, to the glutaramide diphenyl disulfide, sodium thiosulfate is made tetrafluoro boric acid two (1,4 as the sulphur sensitizer, 5-trimethyl 1,2,4-triazole -3-mercaptan) gold (I) is golden sulphur sensitizer, with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4 and potassium bromide.The emulsion of Huo Deing is as emulsion R-31 by this way.

Emulsion R-32 prepares in the mode identical with emulsion R-31, just adds the temperature of mixed nitrate silver and sodium chloride simultaneously and add speed change has taken place.The emulsion grain of Huo Deing is the length of side 0.50 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.0%.

Emulsion R-33 prepares in the mode identical with emulsion R-31, and just except the sulphur sensitizer, the selenium sensitizer compound (SE2-12) that adds example makes that the selenium and the ratio of sulphur are 1: 3, and the emulsion that obtains is carried out chemical sensitization under the best.The particle of emulsion R-33 is the length of side 0.35 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.4%.

(coating solution of preparation ground floor)

Dissolving 57g yellow colour former (Ex-Y) in 21g solvent (Solv-1) and 80ml ethyl acetate, 7g coloured image stabilizing agent (Cpd-1), 4g coloured image stabilizing agent (Cpd-2), 7g coloured image stabilizing agent (Cpd-3) and 2g coloured image stabilizing agent (Cpd-8).This solution of emulsification, and with high-speed stirred emulsifier (dissolver) it is scattered in the 23.5 quality % gelatin solutions that 220g contains the 4g neopelex.Water is added to wherein, thereby prepares 900g emulsified dispersed liquid 3A.

On the other hand, with above-mentioned emulsified dispersed liquid 3A and described emulsion B-31 mixing and dissolving, thereby prepare ground floor coating fluid with composition as follows.The emulsion coating weight is come in silver.

The second layer to layer 7 coating fluid prepares with the preparation method who is similar to the ground floor coating fluid.With (H-1), (H-2) and (H-3) as every layer gelatin hardener.Further, to every layer of interpolation (Ab-1), (Ab-2), (Ab-3) and (Ab-4), total amount is respectively 14.0mg/m ², 62.0mg/m ², 5.0mg/m ²And 10.0mg/m ²

Further, to the second layer, the 4th layer and layer 6 add 0.2mg/m respectively ², 0.2mg/m ², and 0.6mg/m ²1-(3-methyl urea groups the phenyl)-5-mercapto-tetrazole of amount.Further, add every mole of silver halide 1 * 10 respectively to blue-sensitive emulsion layer and green-sensitive emulsion layer ^-4Mole and 2 * 10 ^-44-hydroxyl-6-the methyl isophthalic acid of molar weight, 3,3a, the 7-purine.Further, add 0.05g/m to the magenta-sensitive emulsion layer ²Methacrylic acid and copolymer latex (1: 1 mass ratio of butyl acrylate; Mean molecular weight, 200,000 to 400,000).

To the second layer, the 4th layer adds coating weight respectively with layer 6 is 6mg/m ², 6mg/m ²And 18mg/m ²Catechol-3, the perlate salt of 5-disulfonic acid.Further, if necessary, add kayexalate to regulate the stickiness of coating solution to every layer.Further, in order to prevent radiation, add following dyestuff (coating weight is as shown in parenthesis).

(layer structure)

Every layer composed as follows shown in.Numeric representation coating weight (g/m ²).Under the situation of silver emulsion, coating weight is in silver.

Carrier

{ polyvinyl resin on the ground floor side comprises Chinese white (TiO to the stacked paper of polyvinyl resin ₂Content, 18 quality %, ZnO content, 2 quality %), brightener (4,4 '-two (5-methylbenzoxazole base) talan content, 0.04 quality %) and the dyestuff that turns blue (ultramarine content, 0.28 quality %) and the amount of polyvinyl resin are 25.0g/m ²}

Ground floor (blue-sensitive emulsion layer)

Emulsion (B-31) 0.24

Gelatin 1.25

Yellow colour former (ExY) 0.57

Coloured image stabilizing agent (Cpd-1) 0.07

Coloured image stabilizing agent (Cpd-2) 0.04

Coloured image stabilizing agent (Cpd-3) 0.07

Coloured image stabilizing agent (Cpd-8) 0.02

Solvent (Solv-1) 0.21

The second layer (anti-colour mixture layer)

Gelatin 0.99

Mixed color inhibitor (Cpd-12) 0.09

Coloured image stabilizing agent (Cpd-5) 0.018

Coloured image stabilizing agent (Cpd-6) 0.13

Coloured image stabilizing agent (Cpd-7) 0.01

Mixed color inhibitor (Cpd-4) 0.005

Solvent (Solv-1) 0.06

Solvent (Solv-32) 0.22

The 3rd layer (green-sensitive emulsion layer)

Emulsion (G-31) 0.14

Gelatin 1.36

Magenta colour coupler (ExM) 0.15

Ultraviolet light absorber (UV-1A) 0.14

Coloured image stabilizing agent (Cpd-2) 0.02

Coloured image stabilizing agent (Cpd-12) 0.002

Coloured image stabilizing agent (Cpd-6) 0.09

Coloured image stabilizing agent (Cpd-8) 0.02

Coloured image stabilizing agent (Cpd-9) 0.03

Coloured image stabilizing agent (Cpd-10) 0.01

Coloured image stabilizing agent (Cpd-31) 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 0.71

Mixed color inhibitor (Cpd-12) 0.06

Coloured image stabilizing agent (Cpd-5) 0.013

Coloured image stabilizing agent (Cpd-6) 0.10

Coloured image stabilizing agent (Cpd-7) 0.007

Mixed color inhibitor (Cpd-4) 0.003

Solvent (Solv-1) 0.04

Molten system (Solv-32) 0.16

Layer 5 (magenta-sensitive emulsion layer)

Emulsion (R-31) 0.12

Gelatin 1.11

Cyan coupler (ExC-32) 0.13

Cyan coupler (ExC-33) 0.03

Coloured image stabilizing agent (Cpd-1) 0.05

Coloured image stabilizing agent (Cpd-6) 0.06

Coloured image stabilizing agent (Cpd-7) 0.02

Coloured image stabilizing agent (Cpd-9) 0.04

Coloured image stabilizing agent (Cpd-10) 0.01

Coloured image stabilizing agent (Cpd-14) 0.01

Coloured image stabilizing agent (Cpd-15) 0.12

Coloured image stabilizing agent (Cpd-36) 0.03

Coloured image stabilizing agent (Cpd-37) 0.09

Coloured image stabilizing agent (Cpd-16) 0.07

Solvent (Solv-5) 0.15

Solvent (Solv-7) 0.05

Layer 6 (UV-absorbing layer)

Gelatin 0.46

Ultraviolet light absorber (UV-1B) 0.45

Compound (S1-4) 0.0015

Solvent (Solv-37) 0.25

Layer 7 (protective seam)

Gelatin 1.00

The propylene modified copolymer of polyvinyl alcohol (PVA) (changes 0.04

Property degree: 17%)

Liquid paraffin 0.02

Surfactant (Cpd-33) 0.01

(ExY) the yellowly agent is with the potpourri of 70: 30 (mol ratio) mixing

With

(ExM) potpourri that becomes the purple toner to mix with 40: 40: 20 (mol ratio)

With

(Exc-32) yellow colour former

(Exc-33) cyan coupler is with the potpourri of 50: 25: 25 (mol ratio) mixing

With

(Cpd-33) surfactant is with the potpourri of 7: 3 (mol ratio) mixing

With

(UV-14) ultraviolet light absorber (UV-15) ultraviolet light absorber

(UV-16) ultraviolet light absorber

The potpourri of UV-1A:UV-4/UV-1/UV-2/UV-14=4/2/2/3 (mass ratio)

The potpourri of UV-1B:UV-4/UV-1/UV-2/UV-14/UV-15/UV-16=9/3/3/4/5/3 (mass ratio)

The potpourri of UV-1C:UV-4/UV-14/UV-15=1/7/2 (mass ratio)

The potpourri of UV-1D:UV-4/UV-1/UV-2/UV-14/UV-15=1/1/2/3/3 (mass ratio)

(solvent-32) (solvent-37)

The photosensitive material that permission will prepare was in the above described manner placed 6 days under the dark surrounds of 25 ℃ and 55%RH, with the material that so obtains as sample 3-101.

Sample 3-102 prepares in the mode identical with sample 3-101, and the stored fate of the photosensitive material that just prepares becomes 21 from 6.Sample 3-103 prepares in the mode identical with sample 3-102 with sample 104, it is ground floor, emulsifying agent B-31 in the 3rd layer and the 5th layer, G-31 and R-31 use emulsifying agent B-32 respectively, G-32 and R-32 replace, and the poly amount that is layered on the carrier side that does not have photosensitive coated layer has been done further change.Sample 3-105 prepares in the mode identical with sample 3-102 with sample 3-101 to sample 3-108, just under the situation that does not change each layer component ratio, has improved or reduced the coating weight of ground floor to layer 5.Sample 3-109 prepares in the mode identical with sample 3-102 with sample 3-101 with sample 3-110, the emulsifying agent B-31 in the ground floor just, the 3rd layer and layer 5, and G-31 and R-31 use emulsifying agent B-33 respectively, and G-33 and R-33 replace.Sample 3-111 prepares in the mode identical with sample 3-110 with sample 3-109 to sample 3-114, just under the situation that does not change each layer component ratio, has improved or reduced the coating weight of ground floor to layer 5.Sample 3-115 prepares in the mode identical with sample 3-110 with sample 3-109 to sample 3-119, just the poly amount that is layered on the carrier side that does not have photosensitive coated layer has been done change.Sample 3-120 prepares in the mode identical with sample 3-110 with sample 3-121, just under the situation that does not change each layer component ratio, improved ground floor, the coating weight of the 3rd layer and layer 5 and the poly amount that is layered on the carrier side that does not have photosensitive coated layer done further change.

Measured the crimpness of these samples under 25 ℃ and 20%RH environment.

With these samples by have the transmission peak wavelength peak be 470nm (half-peak breadth: 10nm) and the pass filter of wedge be exposed under the monochromatic light 1 * 10 ^-4Second, carry out following processing then.

[processing 3A]

The procedure of processing temperature-time

38.5 ℃ of 45sec of colour development

38.0 ℃ of 45sec of bleaching-photographic fixing

(1) 38.0 ℃ of 20sec of rinsing

(2) 38.0 ℃ of 20sec of rinsing

(3) 38.0 ℃ of 20sec of rinsing

(4) 38.0 ℃ of 30sec of rinsing

(rinse step is used four trough counter-currents (counter-current) system from (1)-(4))

Shown in each process solutions composed as follows.

(colour developing solution) (groove solution)

Water 800ml

Dimethylpolysiloxane--based surfactant 0.1g

(trade name Silicone KF351A is by Shinetsu

Kagaku Kogyo Co produces)

Three (isopropyl alcohol) amine 8.8g

Ethylenediamine tetraacetic acid 4.0g

Polyglycol (molecular weight: 300) 10.0g

4,5-dihydroxy-benzene-1,3-sodium disulfonate 0.5g

Potassium chloride 10.0g

Potassium bromide 0.040g

Triazine radical amido diphenyl ethylene base brightener 2.5g

(trade name Hacchol FWA-SF; By Showa

Chemical Industry Co., Ltd. produces)

Sodium sulphite 0.1g

N, N-two (sulfonic acid ethyl) azanol sodium 8.5g

N-ethyl-N-(β-methanesulfonamido ethyl)-3-5.0g

Methyl-4-amino-4-amino aniline 3/2 sulfuric ester

1 hydrate

Sal tartari 26.3g

Add water to 1000ml

PH (25 ℃ are regulated by sulfuric acid and potassium hydroxide) 10.15

(bleaching-stop bath) (groove solution)

Water 700ml

Ethylenediamine tetraacetic acid ammonium iron (III) 47.0g

Ethylenediamine tetraacetic acid 1.4g

Between carboxyl benzenesulfinic acid 8.3g

Nitric acid (67%) 16.5g

Imidazoles 14.6g

ATS (Ammonium thiosulphate) (750g/l) 107.0ml

Ammonium sulfite 16.0g

Ammonium bisulfite 23.1g

Add water to 1000ml

PH (25 ℃ are regulated by nitric acid and ammoniacal liquor) 6.0

(rinsing liquid) (groove solution)

Symclosene sodium 0.02g

Deionized water (conductivity: 1000ml 5 μ S/cm or lower)

pH 6.5

The sample of processing like this Fuji Photo Film Co., Ltd. the HPD type densitometer of Sheng Chaning has detected the color density of colour development respectively, and drawn corresponding to the family curve of they colored gradients that contains the yellow colour former layer separately with above-mentioned same way as and drawn family curve corresponding to they colored contrasts that contains the cyan coupler layer separately, the transmission peak wavelength peak of the pass filter that uses when just exposing changes to 550nm and 700nm from 470nm respectively.On these family curves, can read the maximal value (DYmax) of yellow density of developing, the maximal value (DCmax) of the density that the maximal value (DMmax) of the density that magenta is developed and cyan are developed.

In addition, to have drawn the family curve that corresponding grey forms with above-mentioned family curve same way as, just by being used for color printer (by Fuji Photo Film Co., Ltd. colour production) is corrected light filter and is exposed rather than expose by bandpass filter, make simultaneously to comprise yellow, magenta and cyan layers form color.From these family curves, determine grey and form the density maximal value (DGYmax) that middle yellow is developed, the maximal value (DGMmax) of the density that magenta was developed during grey formed and grey form the maximal value (DGCmax) of the density of middle cyan development.

The layer structure of these samples, crimpness and density are as shown in table 11.

Table 11

Sample number	Layer structure	From extremely processing of specimen preparation	Individual layer forms (singal layer generation)			Grey forms (Gray generation)			Curl	Remarks
											DYmax	DMmax	DCmax	DGYmax	DGMmax	DGCmax
			3-101	Sulphur sensitizing emulsion.	6 days	2.02	2.11	2.08									2.18	2.48	2.23	-22	The comparative example
3-102	21 days	2.01							2.10	2.07	2.15	2.46	2.20	-18	The comparative example
			3-103		Sulphur sensitizing emulsion.Further improve light sensitivity by improving the emulsion grain size.Change the coating weight of laminated polyethylene.	21 days	2.01	2.11								2.07	2.16	2.44	2.22	-6	The comparative example
3-104	21 days	2.01		2.11					2.07	2.16	2.44	2.22	+ 5	The comparative example
			3-105			Sulphur sensitizing emulsion.With ground floor, the 3rd layer of coating weight with layer 5 improves 20% respectively.	6 days	2.24							2.24	2.33	2.38	2.66	2.41	-25	The comparative example
3-106	21 days	2.23		2.26	2.33				2.35	2.64	2.40	-19	The comparative example
			3-107				Sulphur sensitizing emulsion.Coating weight with the second layer and the 4th layer improves 30% respectively.	6 days						2.03	2.12	2.07	2.28	2.51	2.22	-19	The comparative example
3-108	21 days	2.01		2.09	2.06	2.26			2.49	2.20	-13	The comparative example
			3-109					Selenium sensitizing emulsion.					6 days	2.01	2.12	2.07	2.19	2.47	2.20	-23	The comparative example
3-110	21 days	2.02		2.11	2.07	2.14	2.44		2.20	-18	The comparative example
			3-111									Selenium sensitizing emulsion.With ground floor, the 3rd layer of coating weight with layer 5 improves 20% respectively.	6 days	2.25	2.26	2.36	2.37	2.66	2.40	-24	The comparative example
3-112	21 days	2.24		2.25	2.35	2.33	2.65	2.39	-20	The comparative example
			3-113								Selenium sensitizing emulsion.Coating weight with the second layer and the 4th layer improves 30% respectively.		6 days	2.03	2.13	2.05	2.28	2.50	2.21	-18	The comparative example
3-114	21 days	2.01		2.11	2.06	2.27	2.49	2.20	-14	The present invention
			3-115									Selenium sensitizing emulsion.Change the coating weight of laminated polyethylene.With ground floor, the 3rd layer of coating weight with layer 5 improves 20% respectively.Change the coating weight of laminated polyethylene.	21 days	2.26	2.26	2.38	2.38	2.68	2.42	-5	The present invention

Each sample is exposed to blue light respectively individually by following digit explosure system, under green glow and the ruddiness.Kind was finished after the exposure in 5 seconds, according to processing 3B described below these samples was carried out rapid processing.

[digit explosure system]

What be used as LASER Light Source is: from the LiNbO with class waveguide (waveguide-like) conversion domain structure ₃About 470nm blue laser of SHG crystallization, this structure use semiconductor laser (vibration wavelength: about 940nm), from LiNbO with class waveguide (waveguide-like) conversion domain structure ₃About 530nm green (light) laser of SHG crystallization, about 1060nm) and about 650nm red light semiconductor laser (model HL6501MG is by Hitachi production) this structure is used semiconductor laser (vibration wavelength:.By the polygon catoptron these three color laser are moved with the direction vertical with the direction of scanning separately, simultaneously the exposure of each laser instrument is controlled by outside regulating device, so that can continuous sweep expose this sample.By utilizing the Peltier element to keep constant inhibition to change temperature because of the light quantity that the temperature of semiconductor laser causes.Beam effective diameter is 80 μ m, and scanning pitch is 42.3 μ m (600dpi), and the mean exposure time of each pixel is 1.7 * 10 ^-7Second.

Processing 3B

Sample 3-101

Sample 3-101 is made the volume of wide 127mm, use above-mentioned digital exposure apparatus through the decent exposure of standard drawing; Afterwards, process (operation test) these samples continuously according to following procedure of processing, the additional liquid measure of the solution in being accumulated to the colour development groove reaches the twice of groove volume.The processing called after processing 3B of this operation liquid will be used.

The procedure of processing temperature-time replenishes liquid measure *

45.0 ℃ of 25sec 35mL of colour development

45.0 ℃ of 25sec 30mL of bleaching-photographic fixing

1 45.0 ℃ of 4sec of rinsing-

2 45.0 ℃ of 4sec of rinsing-

3 45.0 ℃ of 3sec of rinsing-

4 45.0 ℃ of 5sec 121mL of rinsing

Dry 80 ℃ of 15sec

(notes) ^*Replenish liquid measure/m ²The processing photosensitive material

^*Rinse step (3) is used by Fuji Photo Film Co., the rinsing cleaning systems RC50D that Ltd. produces.Rinsing liquid is extracted into reverse osmosis membrane module (RC50D) from rinse step (3) by pump.Thus obtained infiltration water is delivered to rinse step (4), and condensed water turns back in the rinse step (3).Adjust pump pressure, make that the amount from the infiltration water of reverse osmosis membrane remains on 50-300ml/min.Circulated 10 hours following every day in the control temperature.During rinsing, rinse step uses four trough counter-current systems to finish from groove (1) to (4).

Shown in each process solutions is composed as follows.

(colour developing solution A) (groove solution) (replenishing liquid)

Water 800mL 800mL

Brightener (FL-3) 4.0g 8.0g

Remaining colour reproduction agent (SR-1) 3.0g 5.5g

Three (isopropyl alcohol) amine 8.8g 8.8g

Paratoluenesulfonic acid sodium salt 10.0g 10.0g

Ethylenediamine tetraacetic acid 4.0g 4.0g

Sodium sulphite 0.10g 0.10g

Potassium chloride 10.0g-

4,5-dihydroxy-benzene-1,3-two sulphur 0.50g 0.50g

Acid sodium

N, N-two (sulfonic acid ethyl) hydroxyl 8.5g 14.0g

Amine sodium

4-amino-3-methyl-N-ethyl-N-7.0g 19.0g

(β-methanesulfonamido ethyl) benzene

One hydration of amine 3/2 sulfuric ester

Thing

Sal tartari 26.3g 26.3g

Add and add water to 1000mL 1000mL

PH (25 ℃, by sulfuric acid and 10.25g 12.6g

KOH regulates)

(bleaching-photographic fixing solution A) (groove solution) (replenishing liquid)

Water 800mL 800mL

ATS (Ammonium thiosulphate) (750g/l) 107mL 214mL

Succinic acid 29.5g 59.0g

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

Ethylenediamine tetraacetic acid 1.4g 2.8g

Nitric acid (67%) 17.5g 35.0g

Imidazoles 14.6g 29.2g

Ammonium sulfite 16.0g 32.0g

Potassium metabisulfite 23.1g 46.2g

Add and add water to 1000mL 1000mL

PH (25 ℃, by nitric acid and 6.00 6.00

Ammoniacal liquor is regulated)

(rinsing liquid) (groove solution) (replenishing liquid)

Symclosene sodium 0.02g 0.02g

Deionized water (conductivity: 5 μ 1000mL 1000mL

S/cm or lower)

pH(25℃) 6.5 6.5

The density that the yellow of each sample is developed, the density that density that magenta is developed and cyan are developed is measured after processing, and draws out family curve then.Be exposed to sample after the processing behind the blue light from each, measured and comprise the corresponding colored family curve that forms in the yellow colour former layer.Be exposed to sample after the processing behind the green glow from each, measured and comprise the corresponding colored family curve that forms in the magenta colour coupler layer.Be exposed to sample after the processing behind the ruddiness from each, measured and comprise the corresponding colored family curve that forms in the cyan coupler layer.Light sensitivity is defined as gives the reciprocal of the exposure of development density than unexposed area density high 0.3 and represents as 100 relative value with the light sensitivity of processing back sample 3-101.Therefore, the big more light sensitivity of this value is high more.Comprise the corresponding colored family curve that forms the yellow colour former layer from each, magenta density when having measured yellow density 1.7 (M is in Y), magenta density when yellow density and cyan density and cyan density 1.7 (M is in C) is expressed as the variation of their respective value among the sample 3-101 during magenta density 1.7 (Y in M and C in M).These numerical value are as the index of color darkness (dullness of colors).These numerical value are more little, and darkness is few more, and the color of development is thought with regard to unreasonable.

Further, when the density of giving colour development is 1.7 (E0.7), determine exposure from each family curve that comprises corresponding colored formation the color former layer.Each sample is with the identical time, and identical exposure (E0.7) is exposed to blue light equably, green glow and ruddiness.In 5 seconds after exposure is finished, 3B carries out rapid processing according to processing.After processing, measure the density of each sample, and the middle yellow density (DGY) of developing of the gray image (grayimage) of having measured each sample, the density (DGC) that the middle cyan of density (DGM) that magenta is developed in the gray image (gray image) and gray image (gray image) is developed.The big more then grey color density of this numerical value is high more.

Further, with laser instrument each sample is carried out the homogeneous exposure, wherein exposure intensity is adjusted to yellow development density, and magenta development density and cyan development density reach 0.3.5 seconds after exposure is finished, thus carry out the gray image that aforesaid processing 3B obtains homogeneous.Be the photo with described gray image (prints) of ten 2L sizes of each specimen preparation, the striped unevenness (streaky unevenness) that wherein shows by the visual observation evaluation according to following standard.

[evaluation criterion of striped unevenness]

◎: at all can't see striped.

Zero: almost do not manifest striped.

△: manifest a small amount of striped, but still can accept.

*: manifest suitable striped, unacceptable.

* *: manifests a lot of stripeds, can't accept far away.

Gained the results are shown in the table 12.

Table 12

Sample	Light sensitivity			The color darkness is estimated				Grey forms density			Striped in the photo	Remarks
													Yellow cambium layer	The magenta cambium layer	The cyan cambium layer	M is in Y	Y is in M	C is in M	M is in C	DGY	DGM	DGC
	3-101	100	100	100	0	0	0	0	1.79	2.01													1.85	△	The comparative example
3-102											99	100	101	-0.01	-0.01	-0.01	0	1.55	1.65	1.65	△	The comparative example
	3-103	179	155	161	0.12	0.05	0.08	0.02	1.48	1.95													1.75	×	The comparative example
3-104											178	155	160	0.10	0.03	0.07	0.02	1.46	1.93	1.76	×	The comparative example
	3-105	104	103	103	0.05	0.03	0.04	0.02	1.66	2.03													1.95	△	The comparative example
3-106											102	102	102	0.04	0.02	0.03	0.01	1.54	1.98	1.93	△	The comparative example
	3-107	101	101	100	0.11	0.07	0.10	0.05	1.79	2.00													1.83	×	The comparative example
3-108											100	100	101	0.08	0.06	0.09	0.03	1.73	1.98	1.83	×	The comparative example
	3-109	180	155	161	-0.01	-0.02	-0.01	-0.01	1.87	2.06													1.88	×	The comparative example
3-110											180	156	161	-0.04	-0.02	-0.03	-0.02	1.85	2.01	1.86	×	The comparative example
	3-111	183	157	165	0	0	0	0	1.9	2.04													1.96	××	The comparative example
3-112											182	157	164	-0.01	-0.01	-0.01	0	1.88	2.01	1.93	××	The comparative example
	3-113	179	154	160	0.01	0	0.01	0	1.91	2.02													1.95	×	The comparative example
3-114											179	155	161	-0.01	-0.02	-0.01	0	1.89	2.01	1.94	△	The present invention
	3-115	181	156	162	0	-0.01	-0.01	-0.01	1.87	2.05													1.89	△	The present invention
3-116											180	156	161	-0.03	-0.02	-0.03	-0.03	1.86	2.03	1.86	○	The present invention
	3-117	180	155	162	-0.04	-0.03	-0.03	-0.04	1.86	2.03													1.86	○	The present invention
3-118											180	154	162	-0.04	-0.03	-0.03	-0.04	1.86	2.03	1.86	△	The present invention
	3-119	181	156	161	-0.04	-0.03	-0.03	-0.04	1.86	2.03													1.86	××	The comparative example
3-120											185	157	164	0	0	0	-0.01	1.89	2.00	1.92	○	The present invention
	3-121	187	160	167	0.033	0.008	0.035	0.019	1.71	1.90													1.85	×	The comparative example

Following content can be found out from table 11 and table 12.

Table 11 has shown as long as sample has identical layer structure, no matter wherein employed emulsion is sulphur sensitizing emulsion or selenium sensitizing emulsion, and sample is almost as broad as long by the maximum grey color density that processing 3A develops after too high illumination intensity exposure.On the other hand, table 12 has shown, utilize the combination of scanning and rapid processing, can be clear and definite see and has the identical layer structure, identical process time, but the sample that does not comprise selenium sensitizing emulsion is compared, use the sample of selenium sensitizing emulsion to have ISO, reduced darkness and high grey color density, the especially DGY of development color.Further, can notice that the particle by improving sulphur sensitizing emulsion can improve light sensitivity, but also improve the darkness of colour development, and therefore reduce grey color density.In addition, it is evident that, but for not comprising the sample of appointing selenium sensitizing emulsion, by changing darkness and the grey color density that the coating weight of forming layer can change colour development, even but the sample that therefore changes is gone up relatively poor with respect to the sample that comprises selenium sensitizing emulsion in grey color density (especially DGY).

The grey color density that comprises the sample of selenium sensitizing emulsion is better than those these phenomenons of sample that comprise sulphur sensitizing emulsion and only appears in the table 12 that wherein combines scan exposure and rapid processing, and this does not reckon with, and is surprising effect.

For the sample that comprises selenium sensitizing emulsion, as can be seen,, and, can improve this problem by crimpness to the framework of the present definition of regulating sample as a practical problems proposition although manifested the striped unevenness.Only in the sample that has comprised selenium sensitizing emulsion, observe thereby improve this phenomenon of striped unevenness, and this does not reckon with, and be surprising effect by the crimpness of regulating sample.Further, although the crimpness that has been found that the sample that comprises selenium sensitizing emulsion changes with the variation of sample process time, also can when being adjusted to the framework of the present definition, crimpness reduce the striped unevenness process time even shorten sample.The adjusting of described crimpness has also proved its profitability from the angle that is delivered to the photosensitive material marketability.In addition, obviously need only DYmax, DMmax, DCmax, DGYmax, DGMmax and DGCmax value in the framework of the present definition, are improved this effect of striped unevenness thereby just can produce the crimpness of regulating sample respectively.

Advantage of the present invention as can be seen is conspicuous from The above results.

Embodiment 3-2

(preparation blue-sensitive emulsion B-34 and B-35)

The preparation method of emulsion B-34 and B-35 is identical with emulsion B-31, has just changed to mix temperature and the speed that adds silver nitrate and sodium chloride simultaneously, and has replaced sensitizing dye S-2 with the combination of sensitizing dye S-10 and S-12.The emulsion B-34 that obtains in this mode is the length of side 0.42 μ m, and the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.1%, emulsion B-35 are the length of side 0.35 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.8%.

Sensitizing dye S-19

(preparation green-sensitive emulsion layer G-34 and G-35)

The preparation method of emulsion G-34 and G-35 is identical with emulsion G-31, has just changed to mix temperature and the speed that adds silver nitrate and sodium chloride simultaneously, and has replaced sensitizing dye S-14, S-5, S-6, and S-7 with sensitizing dye S-4.The emulsion G-34 that obtains in this mode is the length of side 0.33 μ m, and the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%, emulsion G-35 are the length of side 0.27 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.8%.

(preparation magenta-sensitive emulsion layer R-34 and R-35)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 40%-80%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 93%-98%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 85%-100%, add potassium bromide (whenever add the 1mol silver halide and add 3.5 moles of %).Further, in the step of adding silver nitrate total amount 88%-93%, add K ₂[IrCl ₅(5-methylthiazol)].When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.20 mole of %).Further, K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 93%-98%, add.The emulsion grain of Huo Deing is the length of side 0.38 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with same procedure described above.

To disperse emulsion 40 ℃ of dissolvings again, and with sensitizing dye S-11, sensitizing dye S-12, compound-6, benzene sodium thiosulfate, to the glutaramide diphenyl disulfide, sodium thiosulfate is as the sulphur sensitizer, tetrafluoro boric acid two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) gold (I) adds as golden sulphur sensitizer, with the emulsion slaking that obtains to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole, 1-phenyl-5-mercapto-tetrazole, 1-(4-ethoxyphenyl)-5-mercapto-tetrazole, compound-4 and potassium bromide.The emulsion of Huo Deing is as emulsion R-34 by this way.

Emulsion R-35 prepares in the mode identical with emulsion R-34, just adds the temperature of mixed nitrate silver and sodium chloride simultaneously and add speed change has taken place.The emulsion R-35 particle of Huo Deing is the length of side 0.29 μ m by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.8%.

Sensitizing dye S-11

Sensitizing dye S-12

Compound 6

Ground floor is identical with the preparation of coating fluid among the embodiment 3-1 to the preparation of layer 7 coating fluid.Use 1-oxygen base-3,5-two chloro-s-triazine sodium salts (H-1) are (H-2) and (H-3) as every layer gelatin hardener.Further, add 10.0mg/m respectively to every layer ², 60.0mg/m ², 10.0mg/m ²And 8.0mg/m ²(Ab-1), (Ab-2), (Ab-3) and (Ab-4).

Further, to the second layer, the 4th layer and layer 6 add 0.3mg/m respectively ², 0.2mg/m ², and 0.7mg/m ²1-(3-methyl urea groups the phenyl)-5-mercapto-tetrazole of amount.Further, add every mole of silver halide 1 * 10 respectively to blue-sensitive emulsion layer and green-sensitive emulsion layer ^-4Mole and 1 * 10 ^-4The 4-hydroxyl 6-methyl 1,3 of mole, 3a, the 7-purine.Further, add 0.03g/m to the magenta-sensitive emulsion layer ²Methacrylic acid and copolymer latex (1: 1 mass ratio of butyl acrylate; Mean molecular weight, 200,000 to 400,000).To the second layer, the 4th layer adds coating weight respectively with layer 6 is 4mg/m ², 8mg/m ²And 12mg/m ²Catechol-3, the perlate salt of 5-disulfonic acid.Further, if necessary, add kayexalate to regulate the stickiness of coating solution to every layer.Further, in order to prevent radiation, add following dyestuff (coating weight is as shown in parenthesis) with embodiment 3-1 same way as.

(layer structure)

Every layer composed as follows shown in.Numeric representation coating weight (g/m ²).Under the situation of silver emulsion, coating weight is in silver.

Carrier

{ polyvinyl resin on the ground floor side comprises Chinese white (TiO to the stacked paper of polyvinyl resin ₂Content, 20 quality %, ZnO content, 1 quality %), brightener (4,4 '-two (5-methylbenzoxazole base) talan content, 0.03 quality %) and the dyestuff that turns blue (ultramarine content, 0.28 quality %) and polyvinyl resin ground amount are 28.0g/m ²}

Ground floor (blue-sensitive emulsion layer)

(B-34 and B-35 were with 5: 5 (moles 0.16 of silver for emulsion

Ratio) potpourri)

Gelatin 1.32

Yellow colour former (Ex-Y) 0.34

Coloured image stabilizing agent (Cpd-1) 0.01

Coloured image stabilizing agent (Cpd-2) 0.01

Coloured image stabilizing agent (Cpd-8) 0.08

Coloured image stabilizing agent (Cpd-16) 0.01

Coloured image stabilizing agent (Cpd-18) 0.15

Coloured image stabilizing agent (Cpd-19) 0.01

Coloured image stabilizing agent (Cpd-21) 0.15

Coloured image stabilizing agent (Cpd-17) 0.02

Adjuvant (ExC-31) 0.001

Coloured image stabilizing agent (UV-1C) 0.01

Solvent (Solv-4) 0.23

Solvent (Solv-6) 0.04

Solvent (Solv-9) 0.23

The second layer (anti-colour mixture layer)

Gelatin 0.78

Mixed color inhibitor (Cpd-12) 0.05

Mixed color inhibitor (Cpd-12) 0.01

Coloured image stabilizing agent (Cpd-5) 0.006

Coloured image stabilizing agent (Cpd-6) 0.05

Coloured image stabilizing agent (UV-1C) 0.06

Coloured image stabilizing agent (Cpd-7) 0.006

Antiseptic (Ab-2) 0.006

Solvent (Solv-1) 0.06

Solvent (Solv-5) 0.07

Solvent (Solv-2) 0.06

Solvent (Solv-8) 0.07

The 3rd layer (green-sensitive emulsion layer)

(G-34 and G-35 were with 3: 7 (moles 0.12 of silver for emulsion

Ratio) potpourri)

Gelatin 0.95

Magenta colour coupler (ExM) 0.12

Ultraviolet light absorber (UV-1C) 0.03

Coloured image stabilizing agent (Cpd-2) 0.01

Coloured image stabilizing agent (Cpd-6) 0.08

Coloured image stabilizing agent (Cpd-7) 0.005

Coloured image stabilizing agent (Cpd-8) 0.01

Coloured image stabilizing agent (Cpd-9) 0.01

Coloured image stabilizing agent (Cpd-10) 0.005

Coloured image stabilizing agent (Cpd-31) 0.000

Coloured image stabilizing agent (Cpd-18) 0.01

Solvent (Solv-3) 0.06

Solvent (Solv-4) 0.12

Solvent (Solv-6) 0.05

Solvent (Solv-9) 0.16

The 4th layer (anti-colour mixture layer)

Gelatin 0.65

Mixed color inhibitor (Cpd-12) 0.04

Mixed color inhibitor (Cpd-12) 0.01

Coloured image stabilizing agent (Cpd-5) 0.005

Coloured image stabilizing agent (Cpd-6) 0.04

Coloured image stabilizing agent (UV-1C) 0.05

Coloured image stabilizing agent (Cpd-7) 0.005

Antiseptic (Ab-2) 0.005

Solvent (Solv-1) 0.05

Solvent (Solv-5) 0.06

Solvent (Solv-2) 0.05

Solvent (Solv-8) 0.06

Layer 5 (magenta-sensitive emulsion layer)

(R-34 and R-35 were with 7: 3 (moles 0.10 of silver for emulsion

Ratio) potpourri)

Gelatin 1.11

Cyan coupler (ExC-34) 0.16

Coloured image stabilizing agent (Cpd-1) 0.03

Coloured image stabilizing agent (Cpd-7) 0.01

Coloured image stabilizing agent (Cpd-9) 0.04

Coloured image stabilizing agent (Cpd-10) 0.001

Coloured image stabilizing agent (Cpd-14) 0.001

Coloured image stabilizing agent (Cpd-15) 0.18

Coloured image stabilizing agent (Cpd-36) 0.002

Coloured image stabilizing agent (Cpd-37) 0.001

Coloured image stabilizing agent (Cpd-16) 0.05

Coloured image stabilizing agent (Cpd-4) 0.04

Coloured image stabilizing agent (UV-15) 0.10

Solvent (Solv-5) 0.19

Layer 6 (UV-absorbing layer)

Gelatin 0.34

Ultraviolet light absorber (UV-1D) 0.24

Compound (S1-4) 0.0015

Solvent (Solv-7) 0.11

Layer 7 (protective seam)

Gelatin 0.82

Adjuvant (Cpd-20) 0.03

Liquid paraffin 0.02

Surfactant (Cpd-13) 0.02

(ExC-34) cyan colour coupler

62.5: 12.5: 2.5 potpourri (quality)

With

The photosensitive material that permission will prepare was in the above described manner placed 14 days under the dark surrounds of 25 ℃ and 55%RH, with the material that so obtains as sample 3-201.Other sample 3-202 prepares in the mode identical with sample 3-201 to sample 3-205, just be used to prepare ground floor emulsion B-34 and B-35, the 3rd layer of emulsion G-34 and G-35, the sulphur sensitizer of using when layer 5 emulsion R-34 and R-35 replaces with the selenium sensitizer shown in the table 13.In addition sample 3-206 to sample 3-210 respectively to prepare to the identical mode of sample 3-205 with sample 3-201, just the poly amount that is layered on the carrier side that does not have photosensitive coated layer has been done change.

Sample 3-201 is carried out exposure same among the embodiment 3-1 and processing respectively to sample 3-210.[processing 3B] yet that will be used for embodiment 3-1 here, use except process time different other all identical [processing 3C] with [processing 3B] replace.With the finished like this sample of the identical method evaluation of embodiment 3-1, just the darkness in sensitivity value and the colour development is that the relative value of benchmark is represented in order to embodiment 3-201.

The result who obtains is summarised in table 13 and 14.

[processing 3C]

Sample 3-101 is made the volume of wide 127mm, use above-mentioned digital exposure apparatus that it is carried out the decent exposure of standard drawing then; Afterwards, process (operation test) sample continuously according to following procedure of processing, the additional liquid measure of the solution in being formed into the colour development groove reaches the twice of groove volume.The processing called after processing 3C of this operation liquid will be used.

The procedure of processing temperature-time replenishes liquid measure ^*

45 ℃ of 15sec 35mL of colour development

40 ℃ of 15sec 30mL of bleaching-photographic fixing

(1) 45 ℃ of 3sec of rinsing-

(2) 45 ℃ of 3sec of rinsing-

(3) 45 ℃ of 3sec of rinsing-

(4) 45 ℃ of 4sec 121mL of rinsing

Dry 80 ℃ of 12sec

^*To be shorter than [processing 3B] in order making process time, photosensitive material have been carried out frame adjustment (rackmodifications) and altered transfer rate.

Table 13

Sample number	Emulsion	Individual layer forms			Grey forms			Curl	Remarks
										DYmax	DMmax	DCmax	DGY max	DGMma x	DGCma x
		3-201	Sulphur sensitizing emulsion	2.02	2.11	2.08	2.18									2.48	2.23	-17	The comparative example
3-202	Selenium sensitizer SE2-12							2.01	2.1	2.07	2.15	2.46	2.2	-18	The comparative example
		3-203	Selenium sensitizer SE3-9	2.24	2.24	2.33	2.38									2.66	2.41	-17	The comparative example
3-204	Selenium sensitizer SE3-29							2.23	2.26	2.33	2.35	2.64	2.4	-17	The comparative example
		3-205	Selenium sensitizer PFI-1	2.03	2.12	2.07	2.28									2.51	2.22	-18	The comparative example
3-206	Sulphur sensitizing emulsion							2.02	2.11	2.08	2.18	2.48	2.23	-4	The comparative example
		3-207	Selenium sensitizer SE2-12	2.01	2.1	2.07	2.15									2.46	2.2	-5	The present invention
3-208	Selenium sensitizer SE3-9							2.24	2.24	2.33	2.38	2.66	2.41	-4	The present invention
		3-209	Selenium sensitizer SE3-29	2.23	2.26	2.33	2.35									2.64	2.4	-4	The present invention
3-210	Selenium sensitizer PF1-1							2.03	2.12	2.07	2.28	2.51	2.22	-5	The present invention

^*Sample 3-206 is different on the poly amount that is layered on the carrier side that does not have photosensitive coated layer to sample 3-205 with sample 3-201 respectively to sample 3-210.

Table 14

Sample number	Light sensitivity			The evaluation of color darkness				Grey forms density			Striped in the photo	Remarks
													Yellow cambium layer	The magenta cambium layer	The cyan cambium layer	M is in Y	Y is in M	C is in M	M is in C	DGY	DGM	DGC
	3-201	100	100	100	0	0	0	0	1.33	1.58													1.61	△	The comparative example
3-202											178	170	161	-0.02	-0.01	-0.01	-0.02	1.72	1.99	1.98	×	The comparative example
	3-203	185	177	170	-0.04	-0.02	-0.03	-0.02	1.86	2.04													2.01	×	The comparative example
3-204											199	195	201	-0.07	-0.04	-0.04	-0.04	1.86	2.08	2.01	×	The comparative example
	3-205	210	210	215	-0.07	-0.03	-0.05	-0.04	1.89	2.06													2.03	××	The comparative example
3-206											99	100	99	0	0.01	0	0	1.33	1.58	1.61	△	The comparative example
	3-207	175	172	161	-0.01	-0.01	-0.01	-0.02	1.72	1.99													1.98	△	The present invention
3-208											186	177	171	-0.03	-0.02	-0.02	-0.02	1.86	2.04	2.01	○	The present invention
	3-209	199	195	202	-0.06	-0.04	-0.04	-0.04	1.86	2.08													2.01	◎	The present invention
3-210											210	211	214	-0.07	-0.04	-0.05	-0.04	1.89	2.06	2.03	◎	The present invention

Can find out obviously that from watch 13 and watch 14 effect of the present invention can also be in having changed embodiment 3-1 obtains among the structure of each photosensitive material and the process velocity embodiment 3-2 faster than embodiment 3-1.

Embodiment 4-1

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 10%-20%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 70%-85%, add potassium bromide (whenever add the 1mol silver halide and add 3.0 moles of %) and K ₄[Fe (CN) ₆].In the step of adding silver nitrate total amount 75%-80%, add K ₂[IrCl ₆].Further, K ₂[IrCl ₅(H ₂And K[IrCl O)] ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 88%-98%, add.When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.30 mole of %).The emulsion grain of Huo Deing is the length of side 0.64 μ m (corresponding average particle diameter such as ball (sphere-quivalent) such as grade is 0.80 μ m) by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.After the processing of precipitation desalination, following substances is joined the emulsion that obtains: gelatin, compd A b-1, Ab-2 and Ab-3, and calcium nitrate disperse emulsion then again.

Add sensitizing dye S-1 to disperseing not have the compartment of terrain in the emulsion simultaneously respectively again, the independent solution of S-2 and S-10 stirs under the situation of Reynolds number 6000 simultaneously, carries out spectral sensitization subsequently.Afterwards, emulsion is mixed with benzene sodium thiosulfate with to the glutaramide diphenyl disulfide, and slaking 15 minutes.Further add triethyl thiocarbamide and sodium thiosulfate as the sulphur sensitizer, then, add tetrafluoro boric acid two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) gold (I) as golden sensitizer.Then, the temperature of raising emulsion and slaking are to carry out optimum chemical sensitizing.In described chemical sensitization emulsion, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole; 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole; Compound-2 is with (the end group X wherein that is 2 or 3 of repetitive wherein ₁And X ₂Be hydroxyl) the compound of compound-3 expression be the potpourri of principal ingredient, compound-4, and potassium bromide.Comprise 96.7% chloride, 3.00% bromide and 0.3% iodide in the emulsion that obtains in the halide compositions of silver halide.The emulsion of Huo Deing is as emulsion BmH-1 by this way.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-2)

Accept precipitation desalination first being processed at emulsion grain, with with emulsion BmH-1 in the emulsion grain of those particle same way as preparation be the length of side 0.55 μ m (is 0.69 μ m corresponding to averaging projection's area (projected-area) diameter), the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that will comprise these emulsion grains precipitates desalination processing, then by the adding gelatin, and compd A b-1, Ab-2 and Ab-3 and calcium nitrate disperse it once more.

The emulsion that disperses is once more carried out chemical sensitization and spectral sensitization in the mode identical with emulsion BmH-1.The emulsion of Huo Deing is as emulsion BmH-2 by this way.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-3)

Emulsion BmH-3 prepares in the mode identical with emulsion BmH-1, just adds the method for spectral sensitizing dye and has done following change.

Under with the emulsion vigorous stirring (rotating speed reach Reynolds number 20,000 or more than), will comprise sensitizing dye S-1, the mixed solution of S-2 and S-10 joins in the emulsion that disperses again.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-4)

Emulsion BmH-4 prepares in the mode identical with emulsion BmH-1, just adds selenium sensitizer SE3-9 and replaces sulphur sensitizer in the emulsion BmH-1 preparation.

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-5)

Emulsion BmH-5 prepares in the mode identical with emulsion BmH-2, only is to use the method that adds sensitizing dye among the BmH-3, and replaces the sulphur sensitizer with selenium sensitizer SE3-9.

Preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-6)

Emulsion BmH-6 prepares in the mode identical with emulsion BmH-2, just adds selenium sensitizer SE3-9 and replaces sulphur sensitizer in the emulsion BmH-2 preparation.

Preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-7)

Emulsion BmH-7 prepares in the mode identical with emulsion BmH-2, just adds selenium sensitizer SE3-29 and replaces sulphur sensitizer in the emulsion BmH-2 preparation.

Preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-8)

Accept precipitation desalination first being processed at emulsion grain, with emulsion BmH-6 in the emulsion grain of those particle same way as preparations are the length of side 0.38 μ m, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.7%.The emulsion that will comprise these emulsion grains precipitates desalination processing, then by the adding gelatin, and compd A b-1, Ab-2 and Ab-3 and calcium nitrate disperse it once more.

The emulsion that disperses is once more carried out chemical sensitization and spectral sensitization in the mode identical with emulsion BmH-6.The emulsion of Huo Deing is as emulsion BmH-8 by this way.

(preparation green-sensitive emulsion layer (magenta cambium layer) GmH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 70%-85%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 70%-85%, add potassium bromide (whenever add the 1mol silver halide and add 1 mole of %).Further, K ₂[IrCl ₆] and K ₂[IrBr ₅(H ₂O)] in the step of adding silver nitrate total amount 70%-85%, add.When adding the step of silver nitrate total amount 90%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.1 mole of %).K ₂[IrCl ₅(H ₂And K O)] ₂[IrCl ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 87%-98%, add.The emulsion grain of Huo Deing is the length of side 0.25 μ m (is 0.31 μ m corresponding to averaging projection's area (projected-area) diameter) by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains is precipitated desalination processing and dispersion processing again with same procedure described above.

In this emulsion, add benzene sodium thiosulfate, to the glutaramide diphenyl disulfide, the combination of triethyl thiocarbamide/sodium thiosulfate as sulphur sensitizer and tetrafluoro boric acid two (1,4,5-trimethyl-1,2,4-triazole-3-mercaptan) gold (I) as golden sensitizer.Then improve the emulsion temperature, and slaking is to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole in the emulsion after slaking, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4 and potassium bromide.In the process of preparation emulsion, add sensitizing dye S-4, S-5, S-6 and S-7 carry out spectral sensitization.Comprise 96.8% chloride, 3.00% bromide and 0.2% iodide in the emulsion that obtains in the halide compositions of silver halide.The emulsion of Huo Deing is as emulsion GmH-1 by this way.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RmH-1)

Use a kind of silver nitrate and sodium chloride method to the deionized-distilled water that contains the deionization gelatin that stirs that mix to add simultaneously, prepare the high-silver chloride cubic granules.In this preparation, in the step of adding silver nitrate total amount 60%-80%, add Cs ₂[OsCl ₅(NO)].In the step of adding silver nitrate total amount 93%-98%, add K ₄[Ru (CN) ₆].In the step of adding silver nitrate total amount 85%-100%, add potassium bromide (whenever add the 1mol silver halide and add 3 moles of %).Further, in the step of adding silver nitrate total amount 88%-93%, add K ₂[IrCl ₅(5-methylthiazol)].When adding the step of silver nitrate total amount 93%, under vigorous stirring, add potassium iodide (whenever add the 1mol silver halide and add 0.1 mole of %).Further, K ₂[IrCl ₅(H ₂And K O)] ₂[IrCl ₄(H ₂O) ₂] in the step of adding silver nitrate total amount 93%-98%, add.The emulsion grain of Huo Deing is the length of side 0.25 μ m (is 0.31 μ m corresponding to averaging projection's area (projected-area) diameter) by this way, the monodispersion cubic iodine bromine silver chloride particle of coefficient of alteration 9.5%.The emulsion that obtains same procedure described above is precipitated desalination processing and dispersion processing again.

In this emulsion, add sensitizing dye S-8, compound-5, benzene sodium thiosulfate, to the glutaramide diphenyl disulfide, compound-1 as the combination of golden sensitizer and triethyl thiocarbamide/sodium thiosulfate as the sulphur sensitizer.Then improve the emulsion temperature, and slaking is to optimum chemical sensitizing.Then, add 1-(3-acetylamino phenyl)-5-mercapto-tetrazole in the emulsion after slaking, 1-(5-methyl urea groups phenyl)-5-mercapto-tetrazole, compound-2, compound-4 and potassium bromide.In the process of preparation emulsion, add sensitizing dye S-4, S-5, S-6 and S-7 carry out spectral sensitization.Comprise 96.9% chloride, 3.00% bromide and 0.1% iodide in the emulsion that obtains behind the spectral sensitization in the halide compositions of silver halide.The emulsion of Huo Deing is as emulsion RmH-1 by this way.

(coating solution of preparation ground floor)

To 17g solvent (Solv-4), 3g solvent (Solv-6), dissolving 24g yellow colour former (Ex-Y1) in 17g solvent (Solv-9) and the 45ml ethyl acetate, 6g coloured image stabilizing agent (Cpd-8), 1g coloured image stabilizing agent (Cpd-16), 1g coloured image stabilizing agent (Cpd-17), with 11g coloured image stabilizing agent (Cpd-18), 1g coloured image stabilizing agent (Cpd-19), 11g coloured image stabilizing agent (Cpd-21), 0.1g adjuvant (ExC-2) and 1g coloured image stabilizing agent (UV-A).This solution of emulsification, and with high-speed stirred emulsifier (dissolver) it is scattered in the 20 quality % gelatin solutions that 205g contains the 3g neopelex.Water is added to wherein, thereby prepares 700g emulsified dispersed liquid 4A.

On the other hand, with above-mentioned emulsified dispersed liquid 4A and described emulsion BmH-1 mixing and dissolving, thereby prepare ground floor coating fluid with composition as follows.The emulsion coating weight is come in silver.

The second layer to layer 7 coating fluid prepares with the preparation method who is similar to the ground floor coating fluid.With (H-1), (H-2) and (H-3) as every layer gelatin hardener.Further, to every layer of interpolation (Ab-1), (Ab-2), (Ab-3) and (Ab-4), total amount is respectively 10.0mg/m ², 43.0mg/m ², 3.5mg/m ²And 7.0mg/m ²

Further, to the second layer, the 4th layer and layer 6 add 0.2mg/m respectively ², 0.2mg/m ², and 0.6mg/m ²1-(3-methyl urea groups the phenyl)-5-mercapto-tetrazole of amount.Further, add every mole of silver halide 1 * 10 respectively to blue-sensitive emulsion layer and green-sensitive emulsion layer ^-4Mole and 2 * 10 ^-4The 4-hydroxyl 6-methyl isophthalic acid of molar weight, 3,3a, the 7-purine.Further, add 0.05g/m to the magenta-sensitive emulsion layer ²Methacrylic acid and copolymer latex (1: 1 mass ratio of butyl acrylate; Mean molecular weight, 200,000 to 400,000).For the layer structure that the distribution of green-sensitive emulsion layer and magenta-sensitive emulsion layer changes, the compound of above-mentioned adding has also been done suitable variation.To the second layer, the 4th layer adds coating weight respectively with layer 6 is 6mg/m ², 6mg/m ²And 18mg/m ²Catechol-3, the perlate salt of 5-disulfonic acid.Further, addition is 1.5mg/m ²Compound S 1-4, if necessary, add kayexalate to regulate the stickiness of coating solution to every layer.Further, in order to prevent radiation, add following dyestuff (coating weight is as shown in parenthesis).

(layer structure)

Every layer composed as follows shown in.Numeric representation coating weight (g/m ²).Under the situation of silver emulsion, coating weight is in silver.

Carrier

{ polyvinyl resin on the ground floor side comprises Chinese white (TiO to the stacked paper of polyvinyl resin ₂Content, 16 quality %, ZnO content, 4 quality %), the amount 29.2g/m of brightener (4,4 '-two (5-methylbenzoxazole base) talan content, 0.03 quality %) and dyestuff that turns blue (ultramarine content, 0.33 quality %) and polyvinyl resin ²}

All samples all have identical carrier

Ground floor (blue-sensitive emulsion layer/comprise the silver halide emulsion layer that weld is formed into toner): BL-1

Emulsion (BmH-1) 0.13

Gelatin 1.33

Yellow colour former (Ex-Y1) 0.32

Coloured image stabilizing agent (Cpd-8) 0.08

Coloured image stabilizing agent (Cpd-16) 0.01

Coloured image stabilizing agent (Cpd-17) 0.01

Coloured image stabilizing agent (Cpd-18) 0.14

Coloured image stabilizing agent (Cpd-19) 0.01

Coloured image stabilizing agent (Cpd-21) 0.14

Adjuvant (ExC-2) 0.001

Coloured image stabilizing agent (UV-A) 0.01

Solvent (Solv-4) 0.22

Solvent (Solv-6) 0.04

Solvent (Solv-9) 0.22

The second layer (anti-colour mixture layer): MCS1-1

Gelatin 0.39

Mixed color inhibitor (Cpd-4) 0.025

Mixed color inhibitor (Cpd-12) 0.005

Coloured image stabilizing agent (Cpd-3) 0.004

Coloured image stabilizing agent (Cpd-5) 0.004

Coloured image stabilizing agent (Cpd-6) 0.020

Coloured image stabilizing agent (UV-A) 0.020

Coloured image stabilizing agent (Cpd-7) 0.002

Solvent (Solv-1) 0.024

Solvent (Solv-2) 0.024

Solvent (Solv-5) 0.028

Solvent (Solv-8) 0.028

The 3rd layer (magenta-sensitive emulsion layer/comprise the silver halide emulsion layer that cyan dye is formed into toner): RL-1

Emulsion (RmH-1) 0.07

Gelatin 0.77

Cyan coupler (ExC-1) 0.16

Cyan coupler (ExC-3) 0.015

Coloured image stabilizing agent (Cpd-1) 0.01

Coloured image stabilizing agent (Cpd-7) 0.01

Coloured image stabilizing agent (Cpd-9) 0.03

Coloured image stabilizing agent (Cpd-10) 0.001

Coloured image stabilizing agent (Cpd-14) 0.001

Coloured image stabilizing agent (Cpd-15) 0.05

Coloured image stabilizing agent (Cpd-16) 0.08

Coloured image stabilizing agent (Cpd-17) 0.07

Solvent (Solv-5) 0.15

The 4th layer of (anti-colour mixture layer): MCS2-1

Gelatin 0.47

Mixed color inhibitor (Cpd-4) 0.030

Mixed color inhibitor (Cpd-12) 0.006

Coloured image stabilizing agent (Cpd-3) 0.005

Coloured image stabilizing agent (Cpd-5) 0.005

Coloured image stabilizing agent (Cpd-6) 0.025

Coloured image stabilizing agent (UV-A) 0.025

Coloured image stabilizing agent (Cpd-7) 0.002

Solvent (Solv-1) 0.030

Solvent (Solv-2) 0.030

Solvent (Solv-5) 0.035

Solvent (Solv-8) 0.035

Layer 5 (green-sensitive emulsion layer/comprise the silver halide emulsion layer that magenta dye is formed into toner): GL-1

Emulsion (GmH-1) 0.11

Gelatin 0.75

Magenta colour coupler (Ex-M) 0.12

Coloured image stabilizing agent (Cpd-2) 0.01

Coloured image stabilizing agent (Cpd-8) 0.01

Coloured image stabilizing agent (Cpd-9) 0.005

Coloured image stabilizing agent (Cpd-10) 0.005

Coloured image stabilizing agent (Cpd-11) 0.0001

Coloured image stabilizing agent (Cpd-18) 0.01

Ultraviolet light absorber (UV-B) 0.02

Solvent (Solv-3) 0.04

Solvent (Solv-4) 0.08

Solvent (Solv-6) 0.05

Solvent (Solv-9) 0.12

Layer 6 (UV-absorbing layer): UV-1

Gelatin 0.34

Ultraviolet light absorber (UV-B) 0.24

Solvent (Solv-7) 0.11

Layer 7 (protective seam): PC-1

Gelatin 0.44

Adjuvant (Cpd-20) 0.015

Liquid paraffin 0.01

Surfactant (Cpd-13) 0.01

(Ex-Y1 yellow colour former)

Sample with said structure layer is as sample 4-101 (comparative example)

Silver halide photographic sensitive material (embodiment of the invention) sample 4-108 to 4-110 prepares in the mode identical with sample 4-101, and change as shown in Table 15 has taken place for the emulsion and the colour coupler that only are included in ground floor.

In addition, sample 4-102 to 4-107 (comparative example) prepares in the mode identical with sample 4-101, and change as shown in Table 15 has taken place for the emulsion and the colour coupler that only are included in ground floor.

(processing)

Thereby with following exposure device each sample is carried out the gradient exposure and in colour development processing 4B subsequently, transmit grey; Then, 5 seconds the time, sample carries out colour development processing by processing 4A or 4B after exposure is finished.Used LASER Light Source is: from the LiNbO with transferring structure domain structure ₃The wavelength of SHG crystallization be about the blue laser of 470nm, this structure is used semiconductor laser (vibration wavelength: about 940nm); From LiNbO with class waveguide transferring structure domain structure ₃The wavelength of SHG crystallization be about the green (light) laser of 530nm, this structure is used semiconductor laser (vibration wavelength: about 1060nm); With the red light semiconductor laser with the about 650nm of wavelength (model HL6501MG, by Hitachi, Ltd. produces).By the polygon mirror these three color laser are moved with the direction vertical with the direction of scanning separately, so that can continuous sweep expose this sample.By utilizing the Peltier element to keep constant inhibition to change temperature because of the light quantity that the temperature of semiconductor laser causes.Beam effective diameter is 80 μ m, and scanning pitch is 42.3 μ m (600dpi), and the mean exposure time of each pixel is 1.7 * 10 ^-7Second.Keep the constant light quantity that prevents that the temperature because of semiconductor laser from causing to change temperature with the Peltier element.

The condition of the colour development processing of silver halide colour photographic sensitive material of the present invention is as follows.

Processing 4A

Aforementioned sample 4-101 is made the volume of wide 127mm, use Digital Minilab Frontier350 (trade name, by Fuji Photo Film Co., Ltd. produces) through the decent exposure of standard drawing; Afterwards, process (operation test) these samples continuously according to following procedure of processing, the additional liquid measure of the solution in being formed into the colour development groove reaches the twice of groove volume.The processing called after processing 4A of this operation liquid will be used.

The procedure of processing temperature-time replenishes liquid measure ^*

38.5 ℃ of 45sec 45mL of colour development

38.0 ℃ of 45sec of bleaching-photographic fixing replenish liquid A 17.5mL

Replenish liquid B 17.5mL

1 38.0 ℃ of 20sec of rinsing-

2 38.0 ℃ of 20sec of rinsing-

3 38.0 ℃ of 20sec of rinsing-

4 38.0 ℃ of 20sec 121mL of rinsing

Dry 80 ℃

(notes) ^*Replenish liquid measure/m ²The processing photosensitive material

^*Rinse step (3) is used by Fuji Photo Film Co., the rinsing cleaning systems RC50D that Ltd. produces.Rinsing liquid is extracted into reverse osmosis membrane module (RC50D) from rinse step (3) by pump.Thus obtained infiltration water is delivered to rinse step (4), and condensed water turns back in the rinse step (3).Adjust pump pressure, make that the amount from the infiltration water of reverse osmosis membrane remains on 50-300mL/min.Circulated 10 hours following every day in the control temperature.During rinsing, rinse step uses four trough counter-current systems to finish from groove (1) to (4).

The composition of used working fluid respectively with embodiment 1-1 in identical.

Processing 4B

Aforementioned sample 4-101 is made the volume of wide 127mm, use Digital Minilab Frontier 340 (trade name, by Fuji Photo Film Co., Ltd. produces) through the decent exposure of standard drawing; Afterwards, process (operation test) these samples continuously according to following procedure of processing, the additional liquid measure of the solution in being formed into the colour development groove reaches the twice of groove volume.In addition, in order to obtain to add the following process time in the multiplexer, change transfer rate according to the variation that adds the movements and postures of actors.The processing called after processing 4B of this operation liquid will be used.

The procedure of processing temperature-time replenishes liquid measure *

45.0 ℃ of 12sec 35mL of colour development

40.0 ℃ of 12sec of bleaching-photographic fixing replenish liquid A 15mL

Replenish liquid B 15mL

1 45.0 ℃ of 4sec of rinsing-

2 45.0 ℃ of 2sec of rinsing-

3 45.0 ℃ of 2sec of rinsing-

4 45.0 ℃ of 3sec 175mL of rinsing

Dry 80 ℃ of 15sec

(notes) ^*Replenish liquid measure/m ²The processing photosensitive material

The composition of used working fluid respectively with embodiment 1-3 in identical.

The yellow density of the development of each sample is measured after machining, and draws family curve then.Light sensitivity (S) is defined as the density of giving colour development and is higher than under unexposed area 1.0 situations, and the inverse logarithm of the inverse of exposure, is represented with the relative value to it as 100 with the light sensitivity of processing sample 4-101 behind the 4A.Therefore, the numerical value that sample shows is big more, and its light sensitivity is just high more.Fog density (fog densityDmin) is defined as: deduct the numerical value that base density obtains from unexposed area in the yellow density.Therefore, the numerical value that obtains is more little, and white background is thought with regard to unreasonable.Further, draw yellow gradient corresponding characteristics curve, just replace the light source that uses in the aforementioned exposure, and the blue layer of each sense is carried out the gray scale exposure with single blue laser light source with above-mentioned same way as.From the family curve that obtains, determine yellow density 2.1 (M is in Y) and locate magenta density, show with the analog value of sample 4-101 different.This numerical value is as the index of color darkness (dullness of colors).This numerical value is more little, and darkness is few more, and the chromaticity of development is just good more.For the variation of different performance between the more different emulsion preparative-scales, emulsion is prepared into the emulsion of 1 moles of silver amount and 20 moles of silver amounts respectively.Sample is carried out above-mentioned identical exposure, processing and measurement, the emulsion that is coated with in the described sample replaces with the preparative scale emulsion of these different emulsions.Measured the light sensitivity of using 1 moles of silver amount emulsion sample and those use the light sensitivity of 20 moles of silver amount emulsion samples with above-mentioned same way as, the sample that calculates every group of different emulsion amounts between the light sensitivity difference, and as " light sensitivity difference ".The more for a short time photographic property that means of light sensitivity difference is stable more to the variation of emulsion preparation amount.In addition, the spectral sensitization of measuring each sample distributes, appear at about 400nm extremely the wavelength (nm) at the light sensitivity peak between about 500nm and shortwave to and the long wave light sensitivity that makes progress be difference between place, the 70% light sensitivity peak wavelength.

The result who obtains is shown in table 15 and 16.

Table 15

Sample number	Ground floor emulsion					Remarks
							Emulsion number	Grain size (μ m)	Sensitizer	Peak spectral sensitization degree/wavelength difference (nm)	Yellow colour former
	4-101	BmH-1	0.64	S	494/105							Ex-Y1	The comparative example
4-102						BmH-2	0.55	S	494/106	Ex-Y1	The comparative example
	4-103	BmH-2	0.55	S	493/103							Y-11	The comparative example
4-104						BmH-3	0.64	S	474/61	Y-11	The comparative example
	4-105	BmH-4	0.64	Se	494/104							Ex-Y1	The comparative example
4-106						BmH-5	0.55	Se	494/103	Ex-Y1	The comparative example
	4-107	BmH-5	0.55	Se	494/103							Y-11	The comparative example
4-108						BmH-6	0.55	Se	473/60	Y-11	The present invention
	4-109	BmH-7	0.55	Se	473/60							Y-11	The present invention
4-110						BmH-8	0.38	Se	473/62	Y-11	The present invention

Table 16

Sample number	Processing A				Processing B				Remarks
										Light sensitivity	Photographic fog	Colored darkness (M is in Y)	The light sensitivity difference	Light sensitivity	Photographic fog	Colored darkness (M is in Y)	The light sensitivity difference
	4-101	100	0.04	0.00	12	100	0.04	0.00										13	The comparative example
4-102									75	0.02	-0.01	10	95	0.02	0.00	10	The comparative example
	4-103	77	0.02	-0.06	11	85	0.02	-0.06										12	The comparative example
4-104									76	0.02	-0.05	10	83	0.02	-0.06	10	The comparative example
	4-105	183	0.09	0.02	12	135	0.09	0.03										19	The comparative example
4-106									166	0.03	0.02	13	165	0.03	0.03	21	The comparative example
	4-107	167	0.03	-0.01	19	160	0.03	-0.03										35	The comparative example
4-108									195	0.02	-0.06	8	220	0.02	-0.08	9	The present invention
	4-109	201	0.02	-0.06	8	228	0.02	-0.08										5	The present invention
4-110									102	0.02	-0.07	8	115	0.02	-0.08	8	The present invention

Following result as can be seen from table 15 and 16.

Being used in combination of selenium sensitizing emulsion and formula (Y) yellow colour former can bring the low darkness of ISO and colour development to photosensitive material, but the performance difference that causes the emulsion preparation amount to produce increases.On the other hand, the performance difference that the emulsion preparation amount produces can distribute by the spectral sensitization of regulating photosensitive material of the present invention and be minimized, and in addition, this adjusting can make light sensitivity improve and reduce Fog density.These effects only can be found apparently in having the photosensitive material of structure of the present invention, and be unpredictable consequences.

Sample prepares in the mode identical with sample 4-101 to 4-110 respectively, and the layer of just accepting above-mentioned replacement becomes the 3rd layer or layer 5 from ground floor.These samples are also carried out above-mentioned identical mensuration, can therefrom pick out above-mentioned identical trend.

Embodiment 4-2

(preparation blue-sensitive emulsion layer (yellow cambium layer) BmH-9)

Emulsion BmH-9 prepares in the mode identical with emulsion BmH-6, and just the combination with the sensitizing dye S-2 and the compd B S-2 that gives an example is used for replacing sensitizing dye S-1, the combination of S-2 and S-10.

Sample 4-201 prepares in the mode identical with sample 4-108, just replaces emulsion BmH-6 with emulsion BmH-9.

According to method identical among the embodiment 4-1, comparative sample 4-101 and silver halide photographic sensitive material sample 4-108 of the present invention and 4-201 have been done evaluation.The result who obtains is shown in table 17.

Table 17

Sample number	Processing A			Processing B			Peak spectral sensitization degree/wavelength difference (nm)	Remarks
									Light sensitivity	Photographic fog	The light sensitivity difference	Light sensitivity	Photographic fog	The light sensitivity difference
	4-101	100	0.04	12	100	0.04									13	495/106	The comparative example
4-108							219	0.02	9	211	0.02	9	471/60	The present invention
	4-201	234	0.02	8	226	0.02									4	470/58	The present invention

The sample 4-108 and the sample 4-201 that comprise sensitizing dye BS-2 as can be seen from Table 17 in embodiment 4-1 in the ground floor silver emulsion are better, because they have higher light sensitivity and have reduced the performance difference that the difference of emulsion preparation amount causes to a greater degree.

Sample respectively with sample 4-101, the mode that 4-108 is identical with 4-201 prepares, and has just replaced the 3rd layer and layer 5 in each sample.These samples are also carried out aforesaid same measured, can therefrom pick out above-mentioned identical trend.

Embodiment 4-3

Sample 4-301 prepares in the mode identical with 4-201 with sample 4-101 respectively with 4-302, just the poly amount that is layered on the carrier side that does not have photosensitive coated layer has been done change.

Measure the crimpness of comparative sample 4-101 and 4-301 and silver halide colour photographic sensitive material sample 4-201 of the present invention and 4-302.Further, the laser instrument controlled with exposure intensity carries out uniform exposure to aforementioned each sample, so that 0.3 yellow density is provided respectively, and 0.3 magenta density and 0.3 cyan density.After 5 seconds, carry out aforementioned processing 4B or following processing 4C, thereby produce uniform gray image after exposure is finished.

Processing 4C

Except having changed the movements and postures of actors that add among the processing 4B, changed transfer rate, colour development is adjusted to 9 seconds process time, bleaching-photographic fixing bath temperature is adjusted to 45 ℃, and bleaching-photographic fixing is adjusted to 9 seconds process time, and other condition is identical with processing 4B's.

In order to estimate the operation suitability, 300 in each sample is carried out the grey exposure, subsequently they are processed 4B or 4C.Measure respectively the density of developing from the 1st and the 300th 's yellow, with the difference of these density as the index of moving suitability.This difference is more little, and the operation suitability is good more.The result who obtains is shown in table 18.

Table 18

Sample number	Crimpness	The operation suitability		Remarks
					Processing B density difference	Processing C density difference
		4-101	+17				0.08	0.12	The comparative example
4-201	+17			0.03	0.07	The present invention
		4-301	+18				0.09	0.11	The comparative example
4-302	+8			0.02	0.02	The present invention

Table 18 shows that when photosensitive material of the present invention is carried out rapid processing the crimpness that needs only them is adjusted to particular range, just can go up to obtain to improve significantly at operation suitability (running suitability), thus the big benefit of acquisition.Carry out more rapid processing, find that photosensitive material of the present invention also can improve the operation suitability.

In addition, find that the sample 4-302 different with the crimpness of sample 4-201 can further improve operation adaptability in rapid processing.

Respectively with sample 4-101,4-201, the mode that 4-301 is identical with 4-302 prepares sample, has just replaced the 3rd layer and layer 5 in each sample.These samples are also carried out aforesaid same measured, can therefrom pick out above-mentioned identical trend.

Embodiment 4-4

(preparation green-sensitive emulsion layer (magenta cambium layer) GmH-2)

Emulsion GmH-2 prepares in the mode identical with emulsion GmH-1, just adds the sulphur sensitizer in the selenium sensitizer SE3-9 replacement emulsion GmH-1 preparation.

(preparation magenta-sensitive emulsion layer (cyan cambium layer) RmH-2)

Emulsion RmH-2 prepares in the mode identical with emulsion RmH-1, just adds the sulphur sensitizer in the selenium sensitizer SE3-9 replacement emulsion RmH-1 preparation.

Sample 4-401 prepares in the mode identical with sample 4-201, just replaces emulsion GmH-1 at layer 5 with emulsion GmH-2.Sample 4-402 prepares in the mode identical with sample 4-201, just replaces emulsion RmH-1 at the 3rd layer with emulsion RmH-2.Sample 4-403 prepares in the mode identical with sample 4-201, just replaces emulsion GmH-1 at layer 5 with emulsion GmH-2, replaces emulsion RmH-1 at the 3rd layer with emulsion RmH-2.

According to method identical among the embodiment 4-3, to contrast comparative sample 4-101 and silver halide photographic sensitive material sample 4-201 of the present invention, 4-401, the operation suitability of 4-402 and 4-403 has been done evaluation.The result who obtains is shown in table 19.

Table 19

Sample number	The operation suitability		Remarks
				Processing B density difference	Processing C density difference
	4-101	0.09				0.13	The comparative example
4-201			0.03	0.08	The present invention
	4-401	0.03				0.05	The present invention
4-402			0.03	0.06	The present invention
	4-403	0.02				0.03	The present invention

Table 19 has shown under rapid processing, not only also use selenium sensitizing emulsion can further improve operation adaptability at yellow cambium layer but also at other layer, so this is preferable.

Respectively with sample 4-101,4-201,4-401, the mode that 4-402 is identical with 4-403 prepares sample, has just replaced the 3rd layer and layer 5 in each sample.These samples are also carried out aforesaid same measured, can therefrom pick out above-mentioned identical trend.

Embodiment 4-5

Prepared sample with following structure with reference to sample 4-501.Digitized representation coating weight (g/m ²).For each silver emulsion, described numeral is based on the coating weight of silver.The preparation method of sample 4-502 is identical with sample 4-501, and the yellow colour former that only is to use becomes example colour coupler Y-11 from colour coupler Ex-Y1.

Ground floor (blue-sensitive emulsion layer/contain the silver halide emulsion layer that weld is formed into toner): BL-2

Emulsion (BmH-7) 0.24

Gelatin 1.10

Yellow colour former (Ex-Y1) 0.46

Coloured image stabilizing agent (ST-1) 0.04

Coloured image stabilizing agent (ST-2) 0.06

Coloured image stabilizing agent (ST-5) 0.10

Antistain agent (HQ-1) 0.005

Coloured image stabilizing agent A 0.07

Coloured image stabilizing agent B 0.05

Dinonyl phthalate 0.06

Dibutyl phthalate 0.14

The second layer (anti-colour mixture layer): MCS1-2

Gelatin 1.20

Antistain agent (HQ-1) 0.02

Antistain agent (HQ-2) 0.03

Antistain agent (HQ-3) 0.055

Antistain agent (HQ-4) 0.035

Antistain agent (HQ-5) 0.03

Diisooctyl phthalate 0.038

Dibutyl phthalate 0.022

The 3rd layer (magenta-sensitive emulsion layer/comprise the silver halide emulsion layer that cyan dye is formed into toner): RL-2

Emulsion (RmH-1) 0.17

Gelatin 1.00

Cyan coupler (C-1) 0.22

Cyan coupler (C-2) 0.06

Coloured image stabilizing agent (ST-1) 0.055

Antistain agent (HQ-1) 0.03

Dioctyl phthalate 0.20

Dibutyl phthalate 0.10

The 4th layer of (anti-colour mixture layer): MCS2-2

Gelatin 0.94

Ultraviolet light absorber (UV-A1) 0.28

Ultraviolet light absorber (UV-4) 0.16

Antistain agent (HQ-5) 0.06

Layer 5 (green-sensitive emulsion layer/comprise the silver halide emulsion layer that magenta dye is formed into toner)

Emulsion (GmH-1) 0.12

Gelatin 1.30

Magenta colour coupler (M-1) 0.05

Magenta colour coupler (M-2) 0.15

Coloured image stabilizing agent (ST-3) 0.10

Coloured image stabilizing agent (ST-4) 0.02

Diisooctyl phthalate 0.095

Dibutyl phthalate 0.105

Layer 6 (UV-absorbing layer): UV-2

Gelatin 0.40

Ultraviolet light absorber (UV-A1) 0.12

Ultraviolet light absorber (UV-4) 0.068

Antistain agent (HQ-5) 0.02

Layer 7 (protective seam): PC-2

Gelatin 0.69

Diisooctyl phthalate 0.0018

Dibutyl phthalate 0.0018

Silicon dioxide 0.003

The details of adjuvant that is used to prepare sample 4-501 and 4-502 is as follows:

HQ-1:2,5-two-uncle-octyl group p-dihydroxy-benzene

HQ-2:2, two-second month in a season of 5--dodecyl p-dihydroxy-benzene

HQ-3:2, the 5-two-second month in a season-four decyl p-dihydroxy-benzene

HQ-4:2-second month in a season-dodecyl 5-the second month in a season-four decyl p-dihydroxy-benzene

HQ-5:2,5-two [(1, the own oxygen carbonyl of 1-dimethyl-4-) butyl] p-dihydroxy-benzene

Image stabilizing agent A: right-uncle-octyl phenol

Image stabilizing agent B: poly-(tert-butyl acrylamide)

Magenta colour coupler

Cyan coupler

The coloured image stabilizing agent

In addition, the preparation method of sample 4-503 is with sample 4-501, and just layer 5 adds emulsion GL-2 and replaces the 3rd layer, and the 3rd layer adds emulsion RL-2 and replace layer 5, and proofreaies and correct the colour density of development by changing silver amount in each layer.The preparation method of sample 4-504 just replaces yellow colour former ExY1 with example colour coupler Y-11 with sample 4-503 in emulsion BL-2.

According to method assess sample 4-501, sample 4-502, sample 4-503 and sample 4-504 identical among the embodiment 4-1.

Evaluation result shows that the sample 4-502 of photosensitive material of the present invention among the embodiment 4-1 compares with 4-503 with sample 4-501 with 4-504 and has good effect.

Industrial applicibility

Silver halide colour photographic sensitive material of the present invention is preferably used as, for example, colour negative, colour positive, the colour reversal film, colour reversal photographic paper, color photographic paper color photo paper shows photosensitive material, color digital proof (proof), film colour positive and film colour negative.

Described our invention in conjunction with embodiments of the invention, unless otherwise noted, we are intended to the present invention and not limited by any details of instructions, and think and belong to widely in its spirit and scope that appended claim illustrates.

The claim of this non-provisional application is enjoyed the number of patent application 2004-068408 that submits in Japan on March 11st, 2004 under 35U.S.C. § 119 (a) regulation, the number of patent application 2005-056468 that on March 25th, 2004 submitted in Japan, the number of patent application 2005-056705 that on March 1st, 2005 submitted in Japan, the number of patent application 2005-056707 that on March 1st, 2005 submitted in Japan, the right of priority of the number of patent application 2005-056712 that on March 1st, 2005 submitted in Japan, and above-mentioned application is all incorporated by reference at this.

Claims (30)

1, a kind of silver halide colour photographic sensitive material, it has at least one red sensing coppering silver emulsion layer, at least one green silver halide emulsion layer on carrier and at least one feels blue silver halide emulsion layer, be characterised in that wherein it is 90 moles of % or higher silver emulsion that at least one silver halide emulsion layer contains silver chloride content, this silver emulsion contains at least a selenium compound, and the family curve that contains the silver halide emulsion layer of silver emulsion satisfies following relational expression (1);

Relational expression (1) 2.0 〉=γ _H/ γ _L〉=0.5

γ characterization slope of a curve wherein, γ _HExpression 1 * 10 ^-6Slope and γ under exposure second _LRepresent 100 seconds slopes under the exposure.

2, silver halide colour photographic sensitive material according to claim 1, wherein the silver emulsion of selenium-containing compound further comprises the metal complex of at least a following formula (D1) expression;

Formula (D1)

[M ^D1X ^D1 _n1L ^D1 _(6-n1)] ^m1

Wherein in formula (D1), M ^D1Expression Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt; X ^D1The expression halide ion; L ^D1Expression is different from X ^D1Part; n ₁Expression 3,4,5, or 6; And m ₁Be the electric charge and the expression 4-of metal complex, 3-, 2-, 1-, 0, or 1+; A plurality of X ^D1Identical or different; And as a plurality of L ^D1When existing, a plurality of L ^D1Identical or different; Condition is not contain or only contain the cyano group as part (CN) ion by the metal complex that formula (D1) is represented.

3, silver halide colour photographic sensitive material according to claim 1, wherein the silver emulsion of selenium-containing compound further comprises the metal complex of at least a following formula (D2) expression;

Formula (D2)

[IrX ^D2 _n2L ^D2 _(6-n2)] ^m2

Wherein in formula (D2), X ^D2Expression halide ion or except cyanic acid ion OCN ^-Pseudohalogen ion in addition; L ^D2Expression is different from X ^D2Part; n ₂Expression 3,4, or 5; m ₂Be the electric charge and the expression 4-of metal complex, 3-, 2-, 1-, 0, or 1+; A plurality of X ^D2Identical or different; And as a plurality of L ^D2When existing, a plurality of L ^D2Identical or different.

4, silver halide colour photographic sensitive material according to claim 1, the silver emulsion of wherein said selenium-containing compound comprise that average ball equivalent particle size is 0.65 μ m or following silver halide particle.

5, silver halide colour photographic sensitive material according to claim 1, wherein the total coating weight of silver is 0.2g/m ²To 0.5g/m ²

6, silver halide colour photographic sensitive material according to claim 1, wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

7, a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld is formed into toner, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer contains selenium sensitizing is 90 moles of % or higher silver emulsion, and at least one contains the colour coupler that silver halide emulsion layer that weld is formed into toner contains at least a following formula (Y) expression;

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl; R ₂The expression alkyl, naphthenic base, acyl group or aryl; R ₃The expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, the alkane sulfonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl, or imino group; M represents 0 or 1 to 4 integer; Z ₁Expression-O-or-NR _A-; Z ₂Expression-NR _B-or-C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _DRepresent hydrogen atom or substituting group independently of one another.

8, silver halide colour photographic sensitive material according to claim 7, wherein the silver emulsion of selenium sensitizing further comprises at least two kinds of compounds that the argent cocooning tool had oxidation.

9, silver halide colour photographic sensitive material according to claim 7, wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

10, silver halide colour photographic sensitive material according to claim 7, wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

11, a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld is formed into toner, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer comprises (1) the selenium sensitizing crown ether that to be 90 moles of % or higher silver emulsion and (2) condense with at least a aromatic rings.

12, silver halide colour photographic sensitive material according to claim 11, wherein the silver emulsion of selenium sensitizing further comprises at least two kinds of compounds that the argent cocooning tool had oxidation.

13, silver halide colour photographic sensitive material according to claim 11, wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

14, silver halide colour photographic sensitive material according to claim 11, wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

15, a kind of silver halide colour photographic sensitive material, the photograph that has on its carrier is formed layer and is comprised that at least one contains the silver halide emulsion layer that cyan dye is formed into toner, at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner, at least one contains silver halide emulsion layer and at least one not sensitization hydrophilic colloid layer that weld is formed into toner, and the total coating weight of silver that being characterised in that takes a picture forms in the layer is 0.5g/m ²Or below, the silver chloride content that at least one silver halide emulsion layer comprises (1) selenium sensitizing is 90 moles of % or higher silver emulsion, (2) crown ether that condenses with at least one aromatic rings, and in addition, at least one contains the colour coupler that silver halide emulsion layer that weld is formed into toner contains at least a following formula (Y) expression;

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl; R ₂The expression alkyl, naphthenic base, acyl group or aryl; R ₃The expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, the alkane sulfonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl, or imino group; M represents 0 or 1 to 4 integer; Z ₁Expression-O-or-NR _A-; Z ₂Expression-NR _B-or-C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _DRepresent hydrogen atom or substituting group independently of one another.

16, silver halide colour photographic sensitive material according to claim 15, wherein the silver emulsion of selenium sensitizing further comprises at least two kinds of compounds that the argent cocooning tool had oxidation.

17, silver halide colour photographic sensitive material according to claim 15, wherein the total coating weight of gelatin is 3g/m ²To 6g/m ²

18, silver halide colour photographic sensitive material according to claim 15, wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

19, a kind of silver halide colour photographic sensitive material, it has at least one and contains the silver halide emulsion layer that cyan dye is formed into toner on the reflection carrier, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that weld is formed into toner, is characterised in that the silver chloride content that at least one silver halide emulsion layer that contains dye forming coupler comprises selenium sensitizing is 90 moles of % or higher silver emulsion; Undertaken 1 * 10 by the silver emulsion that only will contain in the coating that weld is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DYmax) of the yellow of the development that obtains is 1.90-2.30; Undertaken 1 * 10 by the silver emulsion that only will contain in the coating that rosaniline dyes is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DMmax) of the magenta of the development that obtains is 1.95-2.30; Undertaken 1 * 10 by the silver emulsion that only will contain in the coating that cyan dye is formed into toner ^-4Colour development processing is carried out in second exposure then and the maximal density (DCmax) of the cyan of the development that obtains is 1.85-2.40; By with all silver halide emulsion layers that contains dye forming coupler in 1 * 10 ^-4Exposure under second, the maximal density (DGYmax) of the yellow of the development of carrying out colour development processing then and obtaining, the maximal density (DGCmax) of the cyan of the maximal density (DGMmax) of the magenta of developing and development is respectively 2.10-2.40,2.30-2.70 and 2.10-2.45; And at 25 ℃, during relative humidity 20% time, the sensitive photographic material crimpness is-15 to+15.

20, silver halide colour photographic sensitive material according to claim 19, wherein cyan dye is formed into toner, and it is 1.1g/m that rosaniline dyes is formed into the summation that toner and weld be formed into the toner amount ²Or below.

21, silver halide colour photographic sensitive material according to claim 19, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE1) is represented;

Formula (SE1)

Wherein in formula (SE1), M ¹And M ²Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl or carbamyl; Q represents alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OM ³, or NM ⁴M ⁵M ³, M ⁴, and M ⁵Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; M ¹, M ²Combine with any two groups among the Q, form ring structure.

22, silver halide colour photographic sensitive material according to claim 19, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE2) is represented;

Formula (SE2)

X wherein ¹, X ²And X ³Represent alkyl independently of one another, alkenyl, alkynyl, aryl, heterocyclic radical, OJ ¹, or NJ ²J ³J ¹, J ²And J ³Represent hydrogen atom independently of one another, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical.

23, silver halide colour photographic sensitive material according to claim 19, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (SE3) is represented;

Formula (SE3)

E ¹-Se-E ²

E wherein ¹And E ²Identical or different, represent alkyl independently of one another, alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, alkoxy carbonyl group, aryloxycarbonyl or carbamyl.

24, silver halide colour photographic sensitive material according to claim 19, wherein the silver emulsion of selenium sensitizing is to carry out chemical sensitization with the selenium sensitizer that following formula (PF1) to (PF6) is represented.

Wherein, in formula (PF1), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²¹Expression O, S or NR ²⁴R ²¹To R ²⁴Represent hydrogen atom or substituting group separately; And R ²³Can with R ²¹Or R ²²Form 5 to 7 yuan of rings;

Wherein, in formula (PF2), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; X ²¹Expression O, S or NR ²⁵Y ²¹The expression alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, OR ²⁶, SR ²⁷Or N (R ²⁸) R ²⁹R ²⁵To R ²⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; And X ²¹And Y ²¹Can interosculate and form ring;

Wherein, in formula (PF3), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; R ²¹⁰, R ²¹¹And R ²¹²Represent hydrogen atom or substituting group independently of one another, simultaneously R ²¹⁰And R ²¹¹In at least one the expression electron withdraw group;

Wherein, in formula (PF4), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; W ²¹The expression electron withdraw group; R ²¹³To R ²¹⁵Represent hydrogen atom or substituting group separately; While W ²¹And R ²¹³The formation ring texture can preferably mutually combine;

Wherein, in formula (PF5), L ²¹Expression can be passed through N atom, S atom, Se atom, the compound of Te atom or P atom and golden coordination; n ²¹Expression 0 or 1; A ²²Expression O, S, Se or NR ²¹⁹R ²¹⁶The expression hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical or acyl group; R ²¹⁷To R ²¹⁹Represent hydrogen atom separately, alkyl, alkenyl, alkynyl, aryl or heterocyclic radical; Z ²¹The expression substituting group; n ²²The integer of expression 0 to 4; And work as n ²²Be 2 or when bigger, Z ²¹Mutually the same or different;

Wherein, in formula (PF6), Q ²¹And Q ²²Expression is selected from the selenium sensitizer compound of formula (SE1) to (SE3), Q ²¹And Q ²²In selenium atom and Au form coordination bond; n ²³Expression 0 or 1; And J ²¹The expression balance anion; Work as n ²³Be 1 o'clock, Q ²¹And Q ²²Identical or different; Condition is arbitrary compound that the compound of formula (PF6) expression does not comprise formula (PF1) to (PF5) expression.

25, silver halide colour photographic sensitive material according to claim 19, wherein the average ball equivalent diameter of the silver halide particle of the silver emulsion of selenium sensitizing is 0.60 μ m or following.

26, silver halide colour photographic sensitive material according to claim 19, wherein the total coating weight of silver is 0.2g/m ²To 0.5g/m ²

27, a kind of silver halide colour photographic sensitive material, it has at least one and contains the silver halide emulsion layer that cyan dye is formed into toner on carrier, at least one contains, and rosaniline dyes is formed into the silver halide emulsion layer of toner and at least one contains the silver halide emulsion layer that weld is formed into toner, be characterised in that at least one contains the silver halide emulsion layer that weld is formed into toner and comprises that (1) contains the silver chloride content of selenium sensitizing is 90 moles of % or higher, with the average ball equivalent diameter of silver halide particle be 0.75 μ m or following silver emulsion, (2) at least a weld of following formula (Y) expression is formed into toner, and silver halide colour photographic sensitive material satisfy condition (a).

Formula (Y)

R wherein ₁The expression alkyl or cycloalkyl; R ₂The expression alkyl, naphthenic base, acyl group or aryl; R ₃The expression hydrogen atom, halogen atom, alkyl, alkoxy, aryloxy group, alkoxy carbonyl group, alkane sulfonyl, alkyl-carbamoyl, aryl-amino-carbonyl, alkylsulfamoyl group, ammonia aryl sulfonyl, the inferior acylamino-of alkyl, amino-alkyl sulfinyl, aromatic yl sodium sulfonamido, sulfamoyl or imino group; M represents 0 or 1 to 4 integer; Z ₁Expression-O-or-NR _A-; Z ₂Expression-NR _B-or-C (R _C) R _D-, R wherein _A, R _B, R _CAnd R _DRepresent hydrogen atom or substituting group independently of one another;

Condition (a): in spectral sensitivity distributes, have a peak at least in the 450-490nm scope, and provide 70% long wave of crest light sensitivity that spectral sensitivity distributes and the exposure wavelength difference between the shortwave at 20nm-100nm.

28, silver halide colour photographic sensitive material according to claim 27 wherein adds the sensitizing dye that at least a following formula (II) is represented;

Formula (II)

Wherein α 1, and α 2 and β 1 to β 4 represent hydrogen atom separately, alkyl, and alkenyl, alkynyl, aryl, heterocyclic radical, acyl group, amino, alkoxy, hydroxyl oxygen base or carbamyl, and in these groups each all can be substituted.

29, silver halide colour photographic sensitive material according to claim 27, it is 25 ℃ of temperature, and the crimpness under the humidity 20% is-15 to+15.

30, silver halide colour photographic sensitive material according to claim 27, wherein at least one contains the silver halide emulsion layer that cyan dye is formed into toner, and/or at least one contains the silver halide emulsion layer that rosaniline dyes is formed into toner and comprises that the silver chloride content of selenium sensitizing is 90 moles of % or higher, and the average ball equivalent diameter of silver halide particle is 0.50 μ m or following silver emulsion.