CN1346072A - Silver halide photographic photosensitive material and colour image formation method - Google Patents

Abstract

The present invention relates to a silver halide colour photographic photosensitive material which possesses silver halide emulsion layers containing colour former for forming black colouring matter, colour former for forming red colouring matter and colour former for forming yellow colouring matter on the reflection support body, in which at least one layer of silver halide emulsion layers contains at least one kind of spectrosensitizing silver halide emulsion granules. Besides, it also relates to an image forming method by means of processing the above-mentioned silver halide colour photographic photosensitive material and its total processing time is below 75 sec.

Description

Silver halide photographic sensitive material and color image forming method

The present invention relates to silver halide colour photographic sensitive material and image forming method thereof, particularly relate to the photochrome sensitive photographic material. In more detail, the present invention relates to improve light splitting sensitizing, rapid treatability and carrying out property of development, reduce photographic fog and occur, { silver halide { silver halide colour photographic sensitive material and the image forming method thereof of 100} tabular grain emulsion that the change of 100} tabular granular sensation luminosity is few during use is modulated to coating from full milk.

The autochromy of knowing has according to being that colour development host development processing has the photosensitive material that forms pigment colour coupler and silver emulsion at support with primary aromatic amine, because the reaction of the oxide of the development host that generates and formation pigment colour coupler (hereinafter referred to as colour coupler) obtains forming the method for pigment image.

This silver halide colour photographic sensitive material, because speed is high, gray scale is superior etc., at present use in vogue. Particularly colour-printing paper is processed rapid property owing to develop, and using the photosensitive material of the high silver halide particle of silver chloride content is main flow. To significantly strengthen ISO more, the requirement of processing the performances such as stabilisation, high-qualityization of image, rapidization of development treatment process from now on. As the method for processing rapidization, for example disclose in the world and point out in W087-04534 number that it is desirable using high silver chloride emulsion as photographic emulsion. But if the silver chloride content of employed silver emulsion is high, developing powder can improve by leaps and bounds, and on the other hand, known silver chloride emulsion generally has the low shortcoming of speed. For practical, overcoming its shortcoming is a problem. Also have, in this manual, will process beginning (contacting with developer solution) and be called the processing time to dry (Dry to Dry).

On the other hand, in the occasion that tabular silver emulsion particle is used for sensitive photographic material, compare with non-flat tabular silver halide particle, known incident light does not enter the photosensitive layer ratio to be reduced, the additional efficient of light improves, and improves image quality (covering power, definition, graininess), carrying out property of development, light splitting sensitizing characteristic etc. For this reason, have twin plane parallel to each other, and multiplex principal plane is { the dull and stereotyped particle of 111} face. Usually the high silver chloride emulsion particle is easy to form and has { the cube crystal structure of 100} outer surface, but JP 63-2043 number, put down in writing in the United States Patent (USP) No. 4400463, No. 4783398 to exist particle to form controlling agent and obtain to keep { the method for the dull and stereotyped particle of 111} face at principal plane. But { the 111} face is that the high-silver chloride tabular particle of principal plane almost is (hereinafter referred to as X by the halogen ion^-) face that consists of, and with Ag⁺With X^-For the mutual face of arranging the 100} face be principal plane the dull and stereotyped Particle Phase of 100} relatively, a little less than the absorption of sensitizing coloring matter, follow this moment when making after the coating fluid adjustment during exist photographic property to change large problem.

The lower high-silver chloride particle of usually creating conditions have take the tendency that the 100} face consists of as the particle of outer surface, in recent years, about { the 100} face is that the research of tabular silver halide particle of principal plane is in vogue.

On the other hand, compare with cube, the part that the ratio of dull and stereotyped granule surface area/volume increases is desirable but a bit obtain light splitting sensitizing with volume absorption sensitizing coloring matter, therefore, the problem by the residual look generation photographic fog of following the light splitting sensitizing coloring matter to increase is deep.

Photochrome particularly, about 180 seconds processing time becomes main flow now, because developing time wherein is 45 seconds, the residual look of following pigment to increase usually becomes deep problem. For this reason, the exploitation of light splitting sensibilization technology, as ISO, the emulsion that the rapid superior colour-printing paper of treatability is used is practical to be the important point. In No. the 5674674th, the United States Patent (USP) about { the 100} face is the improving technology that the cubic granules of principal plane discloses the coloring agent of the residual look of following the light splitting sensitizing coloring matter, but is not provided as the practical dull and stereotyped emulsion that colour-printing paper is used.

No. the 5320938th, United States Patent (USP), No. 5264337, in No. 5292632 grade { 100} tabular silver halide particle is disclosed. These methods that all relate to according to main use iodide ion form dull and stereotyped particle, and the light splitting sensibilization technology of dull and stereotyped particle is not provided.

In addition, about the light splitting sensibilization technology of dull and stereotyped particle, in Unexamined Patent 6-289517 number, be disclosed. According to this record, according to the regulation of particle surface agi content, can improve the light splitting sensitizing mainly as the emulsion used of photography photosensitive material, but the practical emulsion of using as colour-printing paper is not provided.

In addition, in Unexamined Patent 6-337489 number, about { the dull and stereotyped particle of 100} discloses according between the storage life make in batches sensitive photographic material with the light splitting sensitizing coloring matter during, after the manufacturing, the improving one's methods of the deviation of preservation condition speed. But, about according between the storage life after making, preservation condition, the variation of contrast, insufficient in practical as the emulsion that colour-printing paper is used.

On the other hand, about photo chromatic material, wish to shorten the processing time again. Shorten the processing time and follow the photographic fog problem of sensitizing coloring matter remaining (residual look) more deep. And maintenance and the interchangeability of usually processing are important problems.

Thereby it is superior that first purpose of the present invention provides light splitting sensitizing characteristic, and use when modulate from full milk the silver halide colour photographic sensitive material of the few ISO high silver chloride emulsion of the change of speed during be coated with, photographic fog, contrast.

Second purpose of the present invention provides has rapid processing adaptability, keeps changing with the contrast of usually processing the silver halide colour photographic sensitive material of few interchangeability.

And the 3rd purpose of the present invention provides with rapid processing and can obtain good image, reduces the color image forming method that produces photographic fog.

Above-mentioned and other objects, features and advantages of the present invention can be clearer from following record.

The result that the inventor attentively studies repeatedly, above-mentioned purpose reaches with following invention. (1) has the silver halide emulsion layer that contains formation cyanine colour coupler at the reflection support, contain the silver halide emulsion layer that forms the haematochrome colour coupler and the silver halide colour photographic sensitive material that contains the silver halide emulsion layer that forms the uranidin colour coupler, at least one deck of this silver halide emulsion layer contains the silver emulsion particle with at least a light splitting sensitizing of the pigment of following general expression (I) expression, this silver emulsion particle is to have full projected area more than 50%, average { the tabular particle of 100} interarea of length-width ratio more than 2, contain the silver chlorate more than 80 % by mole, and the silver iodide that contain more than 0.1 % by mole for Quan Yinliang are the silver halide colour photographic sensitive material of feature.

General expression (I)(in the formula, Z₁And Z₂Expression sulphur atom, selenium atom or oxygen atom. V₁And V₂The sub stituent of expression monovalence. But V₁And V₂Without the aromatic series base, in addition, the formation condensed ring that do not interosculate more than two of adjacency. R₁、R ₂Independently represent separately alkyl, M₁Expression equalizing charge ion pair, m₁The number more than 0 of expression neutralization minute charge of the electron necessity. L₁、L ₂And L₃The expression methine, n₁Expression 0,1 or 2, n₂Represent 0～4 integer with n3. )

(2) have this tabular particle of 100} principal plane be have the polyvinyl alcohol compound of gelatin and following general expression (II) or following general expression (III) expression lower form { the tabular particle of 100} principal plane is silver halide colour photographic sensitive material that (1) item of feature is put down in writing.

General expression (II)

(in the formula, R₃The alkyl of expression hydrogen atom or carbon number 1-6, R₄The alkyl of expression hydrogen atom or carbon number 1-20, but D represents the ethylene unsaturated monomer of copolymerization. A, b and c represent each repetitive (comonomer) content (% by mole), a is not 0. )

General expression (III)

(in the formula, X₁The polymer of expression in the expression general expression (II).-S-represents thioether group. X₂Expression has the homopolymers of the acrylic monomer of ionic base, or has the acrylic monomer of ionic base and the copolymer of non-ionic monomer unit. M, n represent the content (X of each block₁Or X₂Weight/full weight amount))

(3) contain silver emulsion particle by at least a light splitting sensitizing of the pigment of above-mentioned general expression (I) expression, this silver halide particle is to have full projected area more than 50%, average { the tabular particle of 100} interarea of length-width ratio more than 2, contain silver chlorate more than 80 % by mole, and to be positioned at apart from reflection support emulsion layer farthest for the silver halide emulsion layer that Quan Yinliang contains silver iodide more than 0.1 % by mole be silver halide colour photographic sensitive material of (1) or (2) record of feature.

(4) process the silver halide colour photographic sensitive material of each record of (1)～(3) below 75 seconds as the color image forming method of feature take the full processing time.

(5) silver halide colour photographic sensitive material scanning is being exposed, thereafter in the image forming method that colour development is processed, this silver halide colour photographic sensitive material is that the silver halide colour photographic sensitive material that (1)～(3) are put down in writing in each is the image forming method of feature.

The present invention below is described.

At least one deck that silver halide colour photographic sensitive material of the present invention contains silver halide emulsion layer is { the silver emulsion particle of the tabular particle of 100} interarea with at least a light splitting sensitizing of the pigment that represents with above-mentioned general expression (I).

This silver emulsion particle is that the projected area of perhalogenation silver particle adds up to 50-100 %, preferably 80-100%, better 90-100%, preferably the principal plane of 95-100% is { 100} face, length-width ratio is 2.0-100, preferably 2.0-50, more preferably 4.0-50, be preferably the tabular particle of 6.0-50, thickness is 0.01-0.30 μ m preferably, and more preferably 0.02-0.20 μ m is preferably 0.05-0.15 μ m, diameter projected is 0.1-10 μ m preferably, more preferably 0.2-5.0 μ m. The variation coefficient of diameter projected and thickness (standard deviation of distribution/averaging projection's diameter or average thickness) is 0-0.4 preferably, and more preferably 0-0.3 is preferably 0.01-0.2. At this, so-called length-width ratio is exactly to remove the value of the diameter of a circle that is equivalent to projected area with the thickness of particle. Length-width ratio is larger, and grain thickness is thinner, and is more flat. Among the present invention so-called tabular particle be exactly length-width ratio be 1.2 above particles, so-called average length-width ratio means the mean value of the length-width ratio of the whole tabular particles in the emulsion. In addition, so-called diameter projected refers to the diameter of a circle that has with particle projection area phase homalographic, and thickness refers to the distance between the principal plane of 2 dull and stereotyped particles. The diameter projected of dull and stereotyped particle refers to that to put principal plane parallel with real estate, has the diameter of a circle of the area that the projected area with from its vertical direction observation the time equates.

As with principal plane for { the dull and stereotyped particle of 100} face is classified with shape, can enumerate following 6 kinds. (1) the principal plane shape is the right angle parallelogram, and aspect ratio in a dull and stereotyped particle (length of the length/minor face on long limit) is 1-10, preferably 1-3, the more preferably particle of 1-2. (2) in 4 angles of this right angle parallelogram, have more than 1, more preferably 1-3 non-equivalence shortcoming particle. I.e. [(area of the area of maximum shortcoming part/minimum shortcoming part)=K1 is the particle of 2-∞]; (3) particle (this K1 is than 2 little particles) of this 4 angles shortcoming of equal value; (4) 5-100% of the area of the faceted pebble of this shortcoming part, preferably 20-100% is the { particle of 111} face; (5) consist of the particle that 2 relative at least limits in 4 seamed edges of profile of projection shape of dull and stereotyped particle are curves protruding in the outside; (6) in 4 of this right angle parallelogram angles more than 1, better 1-3 particle that is short of in right angle parallelogram shape.

In addition, can enumerate the 1-100% of area of the faceted pebble of this flat board particle, preferably 5-50 % is the particle of [n10] face. At this, n=1-5, preferably 1.

In the present invention the particle of (this aspect ratio 〉=7) and/or like that shape particle meet at right angles more than at least 2 or the crystal grain of parallel joint is that the 0-20 % by weight of whole silver halides is desirable, better is 0%.

{ the formation method of the tabular silver emulsion particle of 100} principal plane is added silver salt solution and the halide salts aqueous solution in the decentralized medium of aqueous gelatin solution sample to while stirring as having. And mix, at this moment, for example, silver iodide or iodide ion are disclosed in Unexamined Patent 6-301129 number, 6-347929 number, 9-34045 number, 9-96881 number, or under silver bromide or the bromide ion existence, owing to the difference generation center distortion of silver chlorate lattice size, import the method for the crystal defect of the long property of anisotrophy of paying spiral dislocation sample. As imported this spiral dislocation, and because 2 karyomorphisms of its face become without speed law under low supersaturated condition, carry out crystallization at this face, form the tabular particle by importing the spiral dislocation. At this, better below 35% when so-called low supersaturated condition represents critical interpolation, better 2-20%. Consider not only and to determine that this crystal defect is the spiral dislocation, and because the importing direction of dislocation or to pay each in particle be that the possibility of spiral dislocation is very high to different growth.

But this occasion forms clearance plane owing to have discontinuous or continuous silver halide in dull and stereotyped granule interior, is easy to import without intention galactic nucleus and electron trap, about speed, contrast etc., has the occasion of the reason that becomes manufacture deviation.

In order to solve such problem, use polyvinyl alcohol (PVA) class etc., { the 100} face forms promoter formation, and { the dull and stereotyped particle of 100} is developed the granule interior silver halide and is formed uniform dull and stereotyped formation method in interpolation. The present invention is in this unqualified meaning, and it is desirable particularly using the flat board formation method of polyvinyl alcohol. Plate shaped established law can be with reference to Unexamined Patent 8-339044 number.

So-called high-silver chloride particle is the particle of silver chloride content more than 80 % by mole among the present invention. Preferably 90-99.99 % by mole of silver chloride content, is preferably 98-99.9 % by mole by more preferably 95-99.9 % by mole.

Silver iodide in the silver halide particle of the present invention can import in the silver halide particle equably. It is desirable importing heart section and containing the shell section (top layer) that silver iodide Duo than heart section. Shell section is that full particle volume is desirable below 50%. Desirable especially below 20%. Heart section silver halide forms also and can be made of different parts more than two. The present invention contains silver iodide more than 0.1 % by mole, and better iodide ion content is 0.1-1 % by mole.

Bromide sliver content shell section is desirable than heart section height also. Bromide sliver content is desirable below 20 % by mole, is desirable especially below 5 % by mole.

The silver emulsion that the present invention uses can import various polyvalent metal ion impurity in emulsion grain formation or physics maturing process. As the example of the compound that uses can with and and with iron, iridium, ruthenium, starve, salt or the complex salt of the periodic table group VIII metals such as rhenium, rhodium, cadmium, zinc, lead, copper, thallium. In the present invention, have at least 4 cyano group dentates iron, ruthenium, starve, the metallic compound of rhenium etc. improves high illumination speed more, is being desirable especially suppressing aspect the sub-image sensitizing. The addition of these compounds corresponding to the wide region of purpose is: for 1 mole of silver halide 10^-9～10 ^-2Mole is desirable. Illustrate in greater detail with regard to these metal ions, but these are not to limit.

Containing the iridium ion compound is salt or the complex salt of 3 valencys or 4 valencys, and complex salt is desirable. For example, to close halogen, amine, oxalic acid complex salt class that the sour sodium of iridium (III), chlordene closes the sour potassium of iridium (IV), six ammino iridium (IV) salt, three oxalic acid iridium (III) salt, three oxalic acid iridium (IV) salt etc. be desirable for protochloride iridium (III), protobromide iridium (III), iridium chloride (IV), chlordene. Contain the platinum ion compound, be divalent or 4 valency salt or complex salts, complex salt is desirable. Such as using platinum chloride (IV), chlordene to close that the sour potassium of platinum (IV), tetrachloro close platinum (II) acid, tetrabromo closes platinum (II) acid, the sour sodium of four (thiocyanogen) platinum (IV), six ammino platinum (IV) chlorides etc.

Contain the palladium ion compound, be generally divalent or 4 valency salt or complex salts, particularly complex salt are desirable. Close the sour sodium of palladium (IV), chlordene and close the sour potassium of palladium (IV), four ammino palladium (II) chlorides, four cyanogen and close the sour potassium of palladium (II) etc. such as using tetrachloro to close the sour sodium of palladium (II), tetrachloro. Contain the nickel ion compound, close the sour sodium of nickel (II) etc. such as using nickel chloride, nickelous bromide, tetrachloro to close the sour potassium of nickel (II), hexamine nickel (II) chloride, four cyanogen.

It is desirable containing the common 3 valency salt of rhodium ion compound or complex salt. Such as using chlordene to close that rhodium acid potassium, hexabromo close rhodium acid sodium, chlordene closes rhodium acid ammonium etc. Containing the iron ion compound, contain 2 valencys or 3 valency iron ion compounds, better is to have water miscible molysite or iron complex salt in the working concentration scope. Particularly preferred is the iron complex salt that easily contains in silver halide particle. Frerrous chloride, iron chloride, ferrous hydroxide, iron hydroxide, thiocyanation ferrous iron, thiocyanation iron, six cyanogen close iron (II) complex salt, six cyanogen close iron (III) complex salt, ferrous rhodanate complex salt and ferric rhodanate complex salt etc. such as having. In addition, the desirable 6 coordination metal complex bodies with at least 4 cyanogen dentates that also can use record in European patent 336426A number.

Provide the compound of above-mentioned metal ion when silver halide particle forms, this particulate can be used in the aqueous gelatin solution that is dissolved in the formation decentralized medium, in the halide solution, add in the silver salt solution or in other aqueous solution or with the form of the silver halide grains that contains in advance metal ion and equal means and make and be contained in the silver halide particle of the present invention. In addition, for the metal ion that the present invention is used is contained in can be before particle forms in this particle, during particle formed, particle formed successor's one-phase and carries out. This can change according to which position that metal ion is contained in particle.

(better more than 80 % by mole) localization is desirable on the silver halide particle surface to being equivalent in the superficial layer of particle volume below 45% more than 50 % by mole in the compound that uses metal ion is provided. The volume of this superficial layer is preferably below 30%, more preferably below 20%. Such as superficial layer volume as much as possible little (thin), can suppress inner speed and rise, be favourable to obtaining ISO. For the superficial layer that concentrates on such silver halide particle and make and contain the compound that metal ion is provided, after the silver halide grain nucleus of removing surface layer part forms, can cooperate and add water-soluble silver salt solution and halide solution and supply with the compound that metal ion is provided for forming superficial layer.

The modulating process of silver emulsion of the present invention, as know like that, consisted of by the operation, desalination operation and the chemical slaking operation that form silver halide particle by water soluble silver salt and water-soluble halide reaction.

The below describes the light splitting sensitizing coloring matter of used general expression (I) expression of the present invention in detail.

Z in general expression (I)₁And Z₂Expression sulphur atom, selenium atom or oxygen atom. It is desirable to Z₁And Z₂At least one be sulphur atom. V₁And V₂The sub stituent of expression monovalence. But, V₁And V₂Not aryl, in addition, two formation condensed ring that do not interosculate of adjacency. n₂And n₃Expression 0,1,2,3 or 4. R₁And R₂The expression alkyl. L₁、L ₂And L₃The expression methine. n₁Expression 0,1 or 2. M₁Expression equalizing charge ion pair, m₁In the expression and the number more than 0 of electric charge necessity.

Below describe the compound that the present invention uses in detail.

Z ₁And Z₂Expression sulphur atom, selenium atom or oxygen atom. n₁Be 0 o'clock, better Z₁And Z₂In at least 1 be sulphur atom, better Z₁And Z₂It all is sulphur atom. n₁Be 1 o'clock, better Z₁And Z₂In at least 1 be oxygen atom, better Z₁And Z₂It all is oxygen atom. n₁Be 2 o'clock, better Z₁And Z₂It all is sulphur atom.

As V₁And V₂, if not the aromatic series base, 2 mutual condensations of adjacency form condensed ring, and the sub stituent of any monovalence can. Be the sub stituent of monovalence such as V; halogen atom is for example arranged for example (such as chlorine; bromine; iodine; fluorine); sulfydryl; cyano group; carboxyl; phosphate; sulfo group; hydroxyl; carbon number 1-10; better 2-8; the carbamoyl of better 2-5 is (such as the methylamino formyl; the ethylamino formyl; the morpholino phosphinylidyne); carbon number 0-10; better 2-8; the sulfamoyl of better 2-5 is (such as the first sulfonamides; the second sulfonamides); nitro; carbon number 1-20; better 1-10; the alkoxyl of better 1-8 is (such as methoxyl group; ethyoxyl; the 2-methoxy ethoxy; 2-benzene ethyoxyl); carbon number 1-20; better 2-12; the acyl group of better 2-8 is (such as acetyl group; benzoyl group; the tribromo-acetyl base); carbon number 1-20; than 2-12; the acyloxy (such as acetoxyl group) of better 2-8; carbon number 1-20; better 2-12; the amide groups (such as acetamide) of better 2-8; carbon number 1-20; better 1-10; the sulfonyl of better 1-8 is (such as methylsulfonyl; the second sulphonyl; benzene sulfonyl etc.); carbon number 1-20; better 1-10; the sulfenyl of better 1-8 is (such as the first sulfenyl; phenylsulfinyl); carbon number 1-20; better 1-10; the sulfoamido of better 1-8 is (such as the methylsulfonyl amido; ethanesulfonamide group etc.); amino; carbon number 1-20; better 1-12; the displacement of better 1-8 is amino (such as methylamino; dimethylamino; benzamido group; anilino-); carbon number 0-15; better 3-10; the ammonium of better 3-6 is (such as the front three ammonium; three second ammoniums); carbon number 0-15; better 1-10; the diazanyl (such as the front three diazanyl) of better 1-6; carbon number 1-15; better 1-10; the urea groups of better 1-6 is (such as urea groups; N; N-diformazan urea groups); carbon number 1-15; better 1-10; the imido grpup (such as succinimido) of better 1-6; carbon number 1-20; better 1-12; the alkyl or aryl sulfenyl of better 1-8 is (such as methyl mercapto; ethylmercapto group; the carboxylic ethylmercapto group; sulfo group butylthio etc.); carbon number 2-20; better 2-12; the alkoxy carbonyl group of better 2-8 is (such as methoxycarbonyl group; carbethoxyl group), carbon number 1-18, better 1-10; the nothing displacement alkyl of better 1-5 is (such as methyl; ethyl; propyl group; butyl); carbon number 1-18, better 1-10, the displacement alkyl of better 1-5 is (such as methylol; trifluoromethyl; benzyl; carboxyethyl; ethoxy carbonyl methyl; the acetamide methyl; in addition; at this better carbon number 2-18, better 3-10, the unsaturated hydrocarbons of special good 3-5 is (such as vinyl; acetenyl; the 1-cyclohexenyl group) is also contained in the displacement alkyl. ), carbon number 1-20, better 2-10, the also replaceable heterocyclic radical (such as pyridine radicals, 5-picolyl, thienyl, furyl, morpholino, tetrahydrochysene furfuryl group) of better 4-6. Also have, also the replaceable base of lifting is re-used as V on these sub stituents₁And V₂。

As V₁And V₂, preferably above-mentioned alkyl, alkoxyl, halogen atom, acyl group, cyano group, more preferably alkyl, alkoxyl, halogen atom, particularly preferably methyl, methoxyl group, fluorine atom, chlorine atom, bromine atoms, iodine atom.

Be preferably fluorine atom, chlorine atom.

n ₂And n₃Be 0,1,2,3,4, preferably 0,1,2, more preferably 1,2, particularly preferably 1. n₂、n ₃Be 2 when above, V₁And V₂There is no need identical repetition.

For making the pigment ion electric charge be neutral essential M₁The time, can be contained in the formula of expression cation or anion existence. As typical cation hydrogen ion (H is arranged for example⁺), the inorganic cation such as alkali metal ion (such as sodium ion, potassium ion, lithium ion), alkaline-earth metal ion (such as calcium ion), the organic ion of ammonium ion (such as ammonium ion, tetraalkyl ammonium ion, pyridinium ion, ethylpyridine ion) etc. Anion can be any of inorganic anion or organic anion, and halide anion (such as fluorine ion, chlorion, iodide ion) is arranged for example. Displacement aryl sulfonic acid radical ion (such as p-methyl benzenesulfonic acid radical ion, p-chlorobenzenesulfonic acid radical ion), aryl disulfonic radical ion are (such as 1,3-benzene sulfonic acid radical ion, 1,5 naphthalenedisulfonic acid radical ions, 2,6-naphthalenedisulfonic acid radical ion), alkyl sulfate ion (such as the methylsulfuric acid radical ion), sulfate ion, thiocyanate ion, cross chloranion, tetrafluoroborate ion, picratol ion, acetate ion, TFMS radical ion. Also have, also can use other pigment that has with ionic polymers or pigment opposite charges. In addition, CO₂ ^-、 SO ₃ ^-Also can be denoted as CO when keeping hydrogen ion as ion pair₂H、SO ₃H。

m ₁Expression makes the number of equalizing charge necessity, and the occasion that forms salt in molecule is 0. 0-10 preferably, 0-4 more preferably, particularly preferably 0 or 1.

R ₁And R₂Represent respectively alkyl, carbon number 1-18 is for example arranged for example, better 1-7, the nothing displacement alkyl (such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, hexyl, octyl group, dodecyl, octadecyl) of special good 1-4, carbon number 1-18, better 1-7, special good 1-4 displacement alkyl is { such as above-mentioned V₁Displacement alkyl for example. Aralkyl is better arranged (such as benzyl; the 2-phenethyl); unsaturated hydrocarbons (such as pi-allyl); hydroxyalkyl is (such as the 2-ethoxy; 3-hydroxypropyl); carboxyalkyl is (such as the 2-carboxyethyl; 3-carboxylic propyl group; 4-carboxylic butyl; carboxymethyl); the alcoxyl alkyl is (such as the 2-methoxy ethyl; 2-(2-methoxy ethoxy) ethyl); acyloxy alkyl (such as 2-acetoxyl group ethyl); acyl group alkyl (such as 2-acetyl group ethyl); carbamyl alkyl (such as 2-morpholino phosphinylidyne ethyl); sulfonamides alkyl (N; N-dimethylamino formyl methyl); the sulfo group alkyl is (such as the 2-sulfoethyl; the 3-sulfopropyl; 3-sulphur butyl; 4-sulphur butyl; 2-[3-sulphur propoxyl group] ethyl; 2-hydroxyl-3-sulfopropyl; 3-sulphur propoxyl group ethoxyethyl group); the sulfo group alkenyl; the sulfate radical alkyl is (such as 2-sulfate radical ethyl; 3-sulfate radical propyl group; 4-sulfate radical butyl); heterocycle displacement alkyl is (such as 2-(pyrrolidinyl-2-ketone-1-yl) ethyl; the tetrahydrochysene furfuryl group), the amino formyl methyl (such as methanesulfonamido formyl methyl) of alkyl sulfonyl }.

As R₁And R₂Alkyl preferably above-mentioned carboxyl alkyl, sulfo group alkyl, without displacement alkyl, sulfo group alkyl more preferably.

L ₁、L ₂And L₃The expression methine. L₁、L ₂And L₃The methine of expression also can have sub stituent, as sub stituent have for example the displacement or without the displacement carbon number 1-15, better 1-10, the alkyl (such as methyl, ethyl, 2-carboxyethyl) of better 1-5, the displacement or without the displacement carbon number 3-20, better 4-15, the heterocyclic radical of better 6-10 is (such as N, N-diethyl barbituric acid base), halogen atom (such as chlorine, bromine, fluorine, iodine), carbon number 1-15, better 1-10, the alkoxyl (such as methoxyl group, ethyoxyl) of better 1-5, carbon number 1-15, better 1-10, the alkyl sulfenyl (such as methyl mercapto, ethylmercapto group) of better 1-5, carbon number 0-15, better 2-10, the cyano group (such as the N methyl piperazine base) of better 4-10 etc. In addition, R₁、R ₂Also can together form ring. It better is the methine without displacement.

When n1 is 0, as L₁It better is the methine without displacement.

Work as n₁It is 1 o'clock, as L₁、L ₃Better be the methine without displacement, as L₂The methine of preferably replacing with the nothing displacement alkyl of carbon number 1-4, the methine of more preferably replacing with ethyl.

Work as n₁Being 2 o'clock, consisting of five methine cyanines, better is the crosslinked occasion of methine chain.

In addition, work as n₁Be 2 o'clock, L₂、L ₃There is no need to repeat identical.

For the emulsion layer with general expression of the present invention (I) compound light splitting sensitizing is desirable, more preferably be apart from reflecting support emulsion layer farthest from least one deck of selecting apart from reflection support emulsion layer farthest and emulsion layer that next is far away. On the other hand, from containing the emulsion layer of colour coupler, from contain the silver halide emulsion layer that forms the uranidin colour coupler and contain at least one deck that the silver halide emulsion layer that forms the haematochrome colour coupler selects contain this general expression (I) expression compound be desirable, more preferably contain the silver halide emulsion layer that forms the uranidin colour coupler. It is desirable using the compound of general expression (I) among above-mentioned in distance support emulsion layer farthest, uses apart from support farthest and to contain the silver halide emulsion layer that forms the uranidin colour coupler be optimal.

The object lesson of general expression of the present invention (I) compound below is shown, but does not limit the meaning of the present invention with this.

No.	V
		(1) (2) (3) (4) (5) (6) (7) (8) (9)	Cl     Br     I     F     H     CH 3     OCH 3     CO 2H     CO 2C 2H 5

No.	R
		(10) (11) (12) (13) (14) (15) (16) (17)	(CH 2) 3SO 3 -   (CH 2) 2CH(CH 3)SO 3 -     CH 2CO 2 -     (CH 2) 2SO 3 -     (CH 2) 2CO 2 -     (CH 2) 3OSO 3 -     (CH 2) 2OSO 3 -     (CH 2) 3PO 3 -

No.	V	R
			(51) (52) (53) (54)	Br     ″       Cl     ″	(CH 2) 4SO 3 -   CH 2CO 2 -   CH 2CO 2 -   (CH 2) 4SO 3 -

No.	V
		(59)   (60)   (61)   (62)	5，6-Cl 2     5-CN，6-Cl     5-CF 3     5-CN

The compound of general expression of the present invention (I) expression can be according to エ Off エ system Ha one マ one (F.M.Harmer) work " ヘ テ ロ サ イ Network リ Star Network コ Application パ ウ Application ズ one シ ア ニ Application ダ イ ズ ア Application De リ レ イ テ イ De コ Application パ ウ Application ズ (Heterocyclic Compounds-Cyanine Dyes and Related Compounds) ", ジ ヨ Application ウ イ リ one ア Application De サ Application ズ (John Wiley ﹠ Sons) one ニ ユ, one ヨ of society one Network, ロ Application De Application, 1964 annuals; デ one エ system ス one マ one (D.M.Sturmer) work " ヘ テ ロ サ イ Network リ Star Network コ Application パ ウ Application ズ one ス ペ シ ヤ Le ト ピ Star Network ス イ Application ヘ テ ロ サ イ Network リ Star Network ケ ミ ス ト リ one (Heterocyclic Compounds-Special topics in heterocyclic chemistry) ", the 18th chapter, the 14th joint, the 482-515 page or leaf, ジ ヨ Application ウ イ リ one one ニ ユ, one ヨ of ア Application De サ Application ズ (John Wiley﹠Sons) society one Network, ロ Application De Application, 1977 annuals; " ロ Star ズ ケ ミ ス ト リ one オ Block カ one ボ Application コ Application パ ウ Application ズ (Rodd ' s Chemistry of Carbon Compounds) " 2nd.Ed.vol. IV, partB, 1977 annuals, the method of record is synthetic in the 15th chapter, 369-422 page or leaf, エ Le ヤ PVC ア サ イ エ Application ス パ Block リ Star Network カ Application パ ニ one イ Application Network (Elsevier Science Publishing Company Inc.) society periodical, ニ ユ one ヨ one Network etc.

In silver halide, contain the sensitizing coloring matter that the present invention uses for making, can directly be dispersed in sensitizing coloring matter in the emulsion, or also may be dissolved in water, methyl alcohol, ethanol, propyl alcohol, acetone, methyl Cellosolve, 2,2,3,3 ,-tetrafluoropropanol, 2,2, add in the single solvents such as 2-trifluoroethanol, 3-MP, 3-methoxyl group-n-butyl alcohol, 1-methoxy-2-propanol, acetonitrile, oxolane, DMF or the mixed solvent.

In addition, can use as record in No. 3469987 specification of United States Patent (USP) etc., pigment is dissolved in the volatile organic solvent, with this Solution Dispersion in water or hydrophilic colloid, the method that this dispersion is added in the emulsion; In examined patent publication 46-24185 grade, put down in writing, water-insoluble pigment is dispersed in the water-soluble solvent not dissolve, the method that this dispersion is added in the emulsion; As record in No. the 3822135th, United States Patent (USP), No. 4006025 specification of United States Patent (USP) etc., the method that the aqueous solution that coexists with surfactant or colloid dispersion are added in the emulsion; As record in JP 53-102733 number, JP 58-105141 number, pigment directly is dispersed in the hydrophilic colloid method that its dispersion is added in the emulsion; Record in JP 51-74624 number uses the red shift compound to dissolve pigment, the method that this solution is added in the emulsion etc.

In addition, also can use ultrasonic wave during dissolving.

It is that this pigment is dissolved in the aqueous solution in water or the hydrophilic colloid that the pigment that the present invention is used is contained in better method in the silver halide of the present invention, is 1.5 * 10 at pigment 25 ℃ of solubility^-2Occasion below mole/liter is dispersed in water or the hydrophilic colloid with the fine grained below the 1 μ m, as the method for its dispersion interpolation. Dissolving or be dispersed in the method for adding in water-miscible organic solvent or the water-miscible organic solvent aqueous solution and also can use well, is more preferably below the 5 capacity % of the amount of the organic solvent of interpolation for the silver halide emulsion dosage of modulation.

Moreover the pigment of using in the present invention is 5 * 10 25 ℃ solubility^-4Occasion more than mole/liter, the method that the individual former state that these cyanine fine powders are broken directly is added in the silver emulsion also is desirable.

Also can so far think in the operation how useful emulsion is modulated the period that the sensitizing coloring matter that the present invention is used adds in the silver emulsion of the present invention. For example, in No. the 2735766th, United States Patent (USP), No. the 3628960th, United States Patent (USP), No. 4183756, United States Patent (USP), No. the 4225666th, United States Patent (USP), JP 58-184142 number, JP 60-196749 number etc. the specification disclosed like that, form operation or/and the period before the desalination at silver halide particle, begin front period to chemical slaking in the desalination operation and/or after the desalination, wait for JP 58-113920 number in the specification disclosed such, the chemistry slaking before or operation in period, in period before the coating emulsion that arrives the period till being coated with after the chemistry slaking, also can in operation, add. In addition, in the specifications such as No. the 4225666th, United States Patent (USP), JP 58-7629 number disclosed like that, same compound is independent, or heteroid compound combination, as in same operation, or form in the operation and in the chemical slaking operation or after chemical slaking finishes at particle, also can be before chemical slaking or the different operations that wait after finishing of operation neutralization in separately add, also the kind of the combination of the compound of separately interpolation and compound can be changed to add.

In addition, also can add at short notice ormal weight, also can be for a long time, finish more than half etc. with chemical slaking operation to particle formation after forming karyomorphism in the operation and become such as particle, continuous interpolation in operation arbitrarily. But the interpolation speed flow constant speed of occasion also can be accelerated flow, the deceleration flow like this.

The temperature that sensitizing coloring matter is added in the silver emulsion is had no particular limits, be generally 35-70 ℃, also can change and add temperature and curing temperature. Temperature rises after adding below 45 ℃, and the method for slaking is more preferably.

As the total addition level of the present invention with pigment, according to shape, the change in size of silver halide particle, per 1 mole of silver halide can use 5.5 * 10^-6-1.2×10 ^-2Mole. For example, silver halide particle is of a size of the occasion of 0.2-2.0 μ m, every 1m²The surface area of silver halide particle, 4.0 * 10^-7-6.5×10 ^-6The addition of mole is desirable, 1.0 * 10^-6-4.2×10 ^-6The addition of mole is more preferably.

Illustrate that the present invention uses the PVA compound of good general expression (II) or general expression (III) expression.

The PVA compound of general expression (II) expression at first is described.

General expression (II)

R in the general expression (II)³The alkyl of expression hydrogen atom or carbon number 1-6. Specifically, hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, n-hexyl etc. are arranged for example, preferably hydrogen atom, methyl are managed and are hydrogen atom. As the vinyl alcohol comonomer in the general expression (II) vinyl alcohol, Alpha-Methyl vinyl alcohol, α-ethylethylene alcohol, α-propyl ethylene alcohol, α-butylethylene alcohol, α-hexyl vinyl alcohol etc. are arranged for example. Therein ethylene alcohol is optimal.

R ⁴The alkyl of expression hydrogen atom or carbon number 1-20. Specifically, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-hexyl, 2-ethylhexyl, dodecyl, octadecyl etc. are arranged for example, preferably methyl, ethyl, n-pro-pyl, more preferably methyl. As the ethene ester comonomer in the general expression (II) vinyl acetate, formic acid ethene, vinyl propionate, laurate ethene and α displacement body thereof are arranged for example. Wherein vinyl acetate is optimal.

But D represents the olefinic unsaturated monomer of copolymerization. Specifically, ethene, propylene, 1-butylene, isobutene, styrene, styrene derivative (styrene, vinyltoluene, p-tert-butylstyrene, to methoxy styrene, to tert-butoxy styrene, to acetoxyl group styrene etc.), acrylic acid, methacrylic acid, methacrylate, ethylacrylic acid ester, normal-butyl acrylate, methyl acrylate, normal-butyl methacrylate, 2-ethylhexyl methacrylate, acrylonitrile, maleic anhydride, acrylamide, MAAm, ethyl vinyl ether, butyl vinyl ether, NVP, vinyl chloride, bromine ethene, PVF, vinylidene chloride, partially PVF, tetrafluoroethene etc. are arranged for example, and acrylic acid, acrylamide are desirable. Also can select olefinic unsaturated monomer more than 2 kinds as D.

A, b, c represent each repetitive (comonomer) content (% by mole), a is not 0, preferably 50-100 % by mole, more preferably 70-100 % by mole, 90-100 % by mole is optimal. Content about b and c is respectively 0-100-a) % by mole. The average degree of polymerization of the polymer of general expression (II) is 30-50000 preferably, and more preferably 30-25000 is preferably 30-10000.

The following describes general expression (III)

General expression (III)

General expression (III) is with X₁The polymer of expression is as 1 block and X₂The block copolymer that the polymer of expression links with thioether group as another block. X in the general expression (III)₁The polymer of expression in the expression general expression (II).-S-represents thioether group. X₂For having the acrylic monomer (a of ionic base₁) homopolymers or have acrylic monomer and the non-ionic monomer unit (a of ionic base₂) the copolymer principal component. Represent X in this so-called principal component₂In its ratio account for 30-100 % by mole, better 60-100 % by mole, better 80-100 % by mole form.

a ₁The acrylic monomer with ionic base, such as acrylic acid, methacrylic acid, propyloic acrylic ester and slaine thereof and ammonium salt. a₂The expression non-ionic monomer is such as acrylamide, Methacrylamide, vinyl pyrrolidone etc. The monomer that contains acrylic acid and salt thereof in this ionic monomer is desirable especially, and in addition, particularly acrylamide is desirable in this non-ionic monomer.

At this X₂By the occasion that the copolymer of the acrylic monomer with ionic base and non-ionic monomer consists of, a₁Content to be 1.0-100 % by mole be desirable, 30-100% is more preferably, 70-100% is optimal.

In addition, m, n represent the content (X of each block₁Or X₂Weight/full weight amount), be desirable for weight ratio (n/m) 0.001-3.00 of n and m, 0.01-1.50 is more preferably, 0.02-1.00 is optimal. This block copolymer is water-soluble or aqueous dispersion is desirable. Take the ratio of the ionic base of X2 as 50-100 % by mole, better 75-100 % by mole of Component units that consists of polyacrylic acid or its salt is desirable especially. X₂Average degree of polymerization can be according to X₁The degree of polymerization and X₁With X₂Weight ratio change arbitrarily.

The PVA compound of general expression (II) expression is can known radical polymerization incompatible synthetic.

The PVA compound (block copolymer) of general expression (III) expression can be synthetic by following known method. That is to say to have endways end that the polyvinyl ester saponification of thiolic acid ester group obtains and have under the existence of polyvinyl alcohol of sulfydryl, can be desirable with the incompatible manufacturing of the radical polymerizations such as monomer, particularly redox polymerization manufacturing with ionic base. Polyvinyl alcohol can be in the presence of thiolic acid be that the polyvinyl ester that the vinyl monomer polymerization of main body obtains obtains by the well-established law saponification with the vinyl esters monomer. About the polymerization of polyvinyl ester, the thiolic acid of use be have-organic thiolic acid of COSH base is desirable, can enumerate thiol acetic acid, thiolpropionic acid, thiol butyric acid, thiol valeric acid as concrete example, but thiol acetic acid is desirable especially. The addition of this thiolic acid, interpolation method have no particular limits, and can select in right amount according to purpose.

Also have, the end of the compound of general expression (II), general expression (III) expression is hydrogen atom, alkyl etc., is not particularly limited.

About these synthetic methods, characteristic can be with reference to the great first-class work of Nagano, Port バ one Le (polyvinyl alcohol, trade name), the meeting (1970) of macromolecule publication; The work such as Pu, mountain and man, Port リ PVC ニ Le ア Le コ one Le (polyvinyl alcohol), the meeting (1991 years) of macromolecule publication; Port バ one Le can be compiled, the PVA world, the meeting (1992) of macromolecule publication; Finch compiles, Polyvinyl Alcohol Development, John Wiley﹠Sons (1992); No. 189113, Unexamined Patent 8-339044 number, No. 109539,3-, 4-226449 number, 6-19029 number, JP 59-187003 number, 59-; New experimental chemistry lecture 19, polymer chemistry (I), ball kind (1978); The 4th edition experimental chemistry lecture 28,29, the record of ball kind (1992).

Can enumerate vinyl formate, vinyl acetate, propionate, branched paraffin carboxylic acid's (acid of バ one サ テ イ Star Network) ethene ester, vinyl laurate, stearic acid vinyl ester as the object lesson of vinyl esters, but vinyl acetate is more preferably. This polymerization can be carried out with any method of mass polymerization, polymerisation in solution method, bead polymerization method, emulsion polymerization method etc. in the presence of the radical polymerization initator. Methyl alcohol is that the polymerisation in solution method of solvent is desirable especially. Can use the known methods such as batch (-type), semi continuous, continous way as polymerization methods.

As initator can use 2,2 '-the known radical polymerization initator such as azodiisobutyronitrile, benzoperoxide, peroxycarbonates, but 2,2 '-azo of azodiisobutyronitrile etc. is that initator is more preferably. In addition, also can use radioactive ray, electron ray.

Polyvinyl ester can be obtained polyvinyl alcohol by the well-established law saponification. Saponification solution is that alcoholic solution is desirable, and methanol solution is more preferably. It is desirable that saponification temperature is 5-80 ℃. As the saponification catalyst, the base catalysts such as NaOH, KOH, methyl alcohol Na methyl alcohol K are desirable. Be that 0.001-0.3 is desirable for ethene ester unit addition mol ratio, 0.002-0.2 is more preferably.

Be sulfydryl according to this saponification polymer ends, main chain is vinyl alcohol. Can select the ratio of a and b according to the selection of saponification degree. The polymer that saponification is separated out is removed foreign material with known method refining (as with methanol cleaning etc.), and drying can obtain white powder.

The monomer etc. that will have ionic base in the presence of polyvinyl alcohol carries out initiated polymerization (particularly redox polymerization) with free radical, can obtain the PVA compound (block copolymer) of general expression (III) expression. It is desirable that potassium peroxydisulfate, ammonium persulfate, potassium bromate etc. are used in this polymerization. Potassium bromate does not produce separately free radical under common polymerizing condition, only because decomposing with the redox reaction of the sulfydryl of PVA end, produces free radical, is desirable especially therefore.

Be the occasion of alkalescence in this paradigmatic system, because this sulfydryl carries out ion addition to two keys of monomer, disappearance speed is large, and aggregate rate reduces greatly. For this reason, making this paradigmatic system is desirable for acidity, and the pH value is desirable below 5 in the water system, and 1-3 is more preferably. More detailed description relevant for this can be with reference to JP 60-240763 number, 59-187003 number, 59-189113 number record.

The scope (below 3) that the distribution (weight average molecular weight/number-average molecular weight) of the molecular weight of the PVA compound of general expression (II) or general expression (III) expression obtains for common free radical polymerization. Preferably more than 1.5, below 2.5. Particularly the PVA compound (block copolymer) of general expression (III) expression is not if limit the interpolation method of the thiolic acid that works as chain-transferring agent during the synthesizing polyethylene ester then become wide molecular weight distribution, and effect of the present invention weakens.

The PVA compound of general expression (II) or general expression (III) expression can contrast purposes, the feature of the emulsion that will make and select. The object lesson of the representation compound that uses in the emulsion of the present invention below is shown, but does not limit thus the present invention.

PVA compound N o.	Average degree of polymerization	Ratio of components a/b (mol ratio)
			1	200	9.8/0.2
2	300	9.8/0.2
			3	500	9.8/0.2
4	1000	9.8/0.2
			5	1700	9.8/0.2
6	2000	9.8/0.2
			7	2200	9.8/0.2

PVA compound N o.	Weight average molecular weight	Ratio of components a/b/c (mol ratio)
			8	25000	9.8/0.2/1
9	38000	9.8/0.2/1
			10	41000	9.8/0.2/0.5
11	68000	9.8/0.2/1
			12	71000	9.8/0.2/2
13	74000	9.8/0.2/3

PVA compound N o.	Weight average molecular weight	Ratio of components a/b/c (mol ratio)
			14	24500	9.8/0.2/1
15	36600	9.8/0.2/1
			16	40000	9.8/0.2/0.5
17	66700	9.8/0.2/1
			18	69800	9.8/0.2/2
19	73300	9.8/0.2/3

PVA compound N o	Block (X1) average degree of polymerization	Ratio of components a/b (mol ratio)	Ratio of components m/n (weight ratio)
				20	300	9.6/0.4	10/1
21	300	9.6/0.4	20/1
				22	300	9.6/0.4	30/1
23	500	9.6/0.4	10/1
				24	500	9.6/0.4	20/1
25	500	9.6/0.4	30/1
				26	1000	9.6/0.4	10/1
27	1000	9.6/0.4	20/1

28	1000	9.6/0.4	30/1
				29	1500	9.6/0.4	10/1
30	1500	9.6/0.4	20/1
				31	1500	9.6/0.4	30/1

PVA compound N o.	Block (X1) average degree of polymerization	Ratio of components a/b (mol ratio)	Ratio of components e/f (weight ratio)	Ratio of components m/n (weight ratio)
					32	500	9.6/0.4	90/10	10/1
33	500	9.6/0.4	50/50	10/1
					34	500	9.6/0.4	10/90	10/1
35	500	9.6/0.4	90/10	10/2
					36	500	9.6/0.4	50/50	10/2
37	500	9.6/0.4	10/90	10/2
					38	500	9.6/0.4	90/10	10/0.5
39	500	9.6/0.4	50/50	10/0.5
					40	500	9.6/0.4	10/90	10/0.5
41	1500	9.6/0.4	90/10	10/1
					42	1500	9.6/0.4	50/50	10/1
43	1500	9.6/0.4	10/90	10/1
					44	1500	9.6/0.4	90/10	10/2
45	1500	9.6/0.4	50/50	10/2
					46	1500	9.6/0.4	10/90	10/2
47	1500	9.6/0.4	90/10	10/0.5
					48	1500	9.6/0.4	50/50	10/0.5
49	1500	9.6/0.4	10/90	10/0.5

PVA compound N o.	Block (X1) average degree of polymerization	Ratio of components a/b (mol ratio)	Ratio of components m/n (weight ratio)
				29	1500	9.6/0.4	10/1

It is desirable that the silver emulsion that the present invention uses is implemented golden sensitizing known in the art. Owing to implement golden sensitizing, the change of photographic property can be less during with scanning exposures such as laser. In order to implement golden sensitizing, can use the compounds such as gold chloride or its salt, thiocyanic acid gold salt, gold aurothiosulfate class. The addition of these compounds can according to circumstances change, per 1 mole of silver halide 5 * 10^-7-5×10 ^{- 2}Mole, better 1 * 10^-6-1×10 ^-3Mole. In the interpolation period of these compounds, carry out the chemical sensitization that the present invention uses until end.

For the present invention, with golden sensitizing and other sensitizing method, such as sulphur sensitizing, selenium sensitizing, tellurium sensitizing, reduction sensitization or use the noble metal sensitizing combination beyond the full compound also can carry out well.

In the silver emulsion that the present invention uses for prevent in the manufacturing process of photosensitive material, preserve in or take a picture in processing photographic fog or make the stable purpose of photographic property can add various compounds or its precursor. The object lesson of these compounds that can fine use is documented in the JP 62-215272 number 39-72 page or leaf. The emulsion that the present invention uses mainly forms sub-image at particle surface, and so-called surperficial sub-image type emulsion is desirable.

The support of the silver halide colour photographic sensitive material of using as the present invention is with many polyethylene layers and the special lamination of polyester layer, and the reflection support that contains coloured pigment of the look pigment of titanium oxide etc. and/or ultramarine etc. at least one deck of such water-resistant resin layer (laminate layers) is desirable.

Moreover it is desirable containing fluorescent whitening agent in above-mentioned water-resistant resin layer. In addition, fluorescent whitening agent also can be dispersed in the hydrophilic colloid layer in the photosensitive material. As fluorescent whitening agent, better can use benzoxazole system, tonka-bean prime system, pyrazoline system, be more preferably the fluorescent whitening agent of benzoxazolyl naphthalene system and benzoxazolyl stilbene system. Use amount is not particularly limited, preferably 1-100mg/m² The mixing ratio of mixing occasion in water-resistant resin is for resin preferably 0.0005-3 % by weight, more preferably 0.001-0.5 % by weight.

The transparent membranes such as cellulosic triacetate film and PETG, and then 2, the film of the information recording layer of magnetosphere etc. is set in the polyester of 6-naphthalene dicarboxylic acids (NDCA) and ethylene glycol (EG) and the polyester of NDCA and terephthalic acid (TPA) and EG etc., or be coated with the hydrophilic colloid layer that contains Chinese white and coloured pigment at reflection support as described above also can be used as the reflector use.

Can by the 680nm optical reflection concentration 0.50 of this photosensitive material to add European patent EP0337490A2 number 27-76 page or leaf record, take a picture and process the dyestuff (wherein also aerobic alcohol is dyestuff) that can decolour in the hydrophilic colloid floor take the definition of improving image etc. as purpose in the photosensitive material of the present invention.

Substitute or the water-soluble dye of water-soluble dye can be and used in the present invention, the dyed layer that can decolour can be used in the processing. The dyed layer that can decolour in the processing also can directly contact emulsion layer, also can intermediary's configuration contain the intermediate layer that the processing such as gelatin and quinhydrones prevent blending agent. It is desirable with lower floor's (support one side) with the emulsion layer of primary colors of the same race colour developing that this dyed layer is arranged on painted color. Can each and every one dyed layer be set all corresponding to each primary colors, also can only selecting arbitrarily wherein, a part arranges. In addition, it is possible carrying out the painted dyed layer that arranges corresponding to many primary colors zone. The optical reflection concentration of dyed layer, the optical concentration value of the highest wavelength of the wavelength optical concentration of the light source colour that uses take scanning exposure is desirable below 3.0 as more than 0.2. Better is more than 0.5, below 2.5, more than 0.8, is desirable especially below 2.0.

Can use in the past known method in order to form dyed layer. For example, be contained in method in the hydrophilic colloid with the such solia particle dispersion state of dyestuff of the dyestuff of No. 282244 the 3rd page of 8 pages of records in upper right hurdle to the of Unexamined Patent 2-and the record of hurdle, 11 pages of lower-lefts, Unexamined Patent 3-7931 number the 3rd page of upper right hurdle to the, with the method for anionic property pigment to the cationic polymer mordant dyeing, pigment is adsorbed on the particulate such as silver halide and is fixed on method in the layer, use the method for the such collargol of No. 239544 records of Unexamined Patent 1-etc. As the method that the pigment fine powder is dispersed on the solid, for example the record of Unexamined Patent 2-308244 number 4-13 page or leaf contains that the pH value is water-insoluble in fact below 6 at least, the method for pH value water miscible in fact fine powder dyestuff more than 8 at least. Be shown in United States Patent (USP) No. 2688601, No. 3459563 about the modulator approach as the collargol of light absorber. It is desirable containing the method for fine powder dyestuff, the method for use collargol etc. in these methods.

As adhesive available in the photosensitive material of the present invention or protecting colloid, it is favourable using gelatin. Also can use separately in addition hydrophilic colloid or use simultaneously with gelatin. As gelatin preferably, calcium content is below the 800ppm, and more preferably below the 200ppm, it is desirable using low calcium gelatin. In addition, for the various moulds and the bacterium that prevent from breeding and image being worsened in hydrophilic colloid, it is desirable adding mould inhibitor as record in JP 63-271247 number.

The photosensitive material that exposed is implemented colour development commonly used process, in the occasion of photosensitive material of the present invention, according to the purpose of rapid processing, after the colour development, it is desirable carrying out the blix processing. Particularly promote the purposes such as the desilverization, the pH value of blix liquid for about be desirable below 6.5, about is more preferably below 6.

As the silver emulsion that is applicable to photosensitive material of the present invention and other raw materials (additive etc.) and photograph constituting layer (layer configuration etc.), with the processing method and the additive of processing usefulness that are applicable to process this photosensitive material, use the patent shown in the following table 1-5, record is desirable in particularly European patent EP0355660A2 number (Unexamined Patent 2-139544 number).

Photograph inscape etc.	JP 62-215272 number	Unexamined Patent 2-33144 number	EPO.355660A2 number
				Silver emulsion ag halide solvent chemical sensitizer divides light sensitizer (light splitting sensitizing method emulsion stabilizing agent development promoter	10 pages of upper right hurdle 6 row～hurdle, 12 pages of lower-lefts 5 row and hurdle, 12 pages of bottom rights 4 row reciprocal～hurdle, 12 pages of lower-lefts of 17 row, 13 pages of upper left hurdles 6 row～14 row and 13 pages of upper left hurdle 3 row reciprocal～hurdle, 12 pages of lower-lefts of footline, hurdle, 18 pages of lower-lefts 3 row reciprocal～hurdle, bottom right 5 row reciprocal and hurdle, 18 pages of bottom rights 1 row～22 pages of upper right hurdles of 9 row reciprocal, 22 pages of upper right hurdles, 8 row reciprocal～39 pages of upper left hurdles of 38 pages of footlines, 1 row～hurdle, 72 pages of lower-lefts of footline, 72 pages of upper right hurdles 1 row～91 pages of upper right hurdle 3 row	28 pages of upper right hurdle 16 row～hurdle, 29 pages of bottom rights 11 row and 30 page of 2 row～5 row _ _ _ 29 page hurdle, bottom right 12 row～30 pages of upper left hurdles of footline, 1 row～30 pages of upper left hurdles of 13 row, 14 row～upper right hurdle 1 row _ _ _	45 page of 53 row～47 page 3 row and 47 page of 20 row～22 row _ _ _ 47 page 4 row～47 page of 10 row of 9 row～47 page of 16 row of 15 row～19 row _ _ _

Photograph inscape etc.	JP 62-215272 number	Unexamined Patent 2-33144 number	EPO.355660A2 number
				Colour former agent (take a picture with the process for dispersing of additive by cyan, redness, anti-stripping agent (image stability agent) higher boiling of yellow colour former colour developing reinforcing agent ultra-violet absorber and/or low boiling point organic solvent	91 pages of upper right hurdle 4 row～121 pages of upper left hurdles of 6 row, 121 pages of upper left hurdles, 7 row～125 pages of upper right hurdles of 1 row, 125 pages of upper right hurdles, 2 row～hurdle, 127 pages of bottom rights of footline, hurdle, 127 pages of lower-lefts 1 row～hurdle, 137 pages of lower-lefts of 8 row, hurdle, 137 pages of lower-lefts 9 row～hurdle, 144 pages of lower-lefts of footline, 144 pages of upper right hurdles 1 row～146 pages of upper right hurdle 7 row	3 pages of upper right hurdle 14 row～18 pages of upper left hurdle footlines and 30 pages of upper right hurdle 6 row～hurdle, 35 pages of bottom rights 11 row _ _ _ 37 pages of hurdle, bottom right 14 row～36 pages of upper right hurdles of 11 row, 38 pages of upper left hurdles, 12 row～hurdle, 35 pages of bottom rights of 19 row, 37 pages of upper left hurdles 14 row～hurdle, 27 pages of bottom rights of 4 row reciprocal, 36 pages of upper left hurdles 10 row～28 pages of upper left hurdle footlines and hurdle, 35 pages of bottom rights 12 row～36 pages of upper right hurdle 7 row	4 page of 15 row～27 row, 5 page of 30 row～28 page footline, 45 page of 29 row～31 row, 47 page of 23 row～63 page 50 row _ _ _ 65 pages of 22 row～4 page of 30 row～5 of 31 row page 23 row, 29 page of 1 row～45 page 25 row, 45 page of 33 row～40 row, 65 page of 2 row～64 page of 1 row of 21 row～63 page of 51 row～64 of 51 row page 56 row

Photograph inscape etc.	JP 62-215272 number	Unexamined Patent 2-33144 number	EPO 355660A2 number
				Dura mater agent developer precursor development restrainer is emitted compound support photosensitive material layer and is consisted of the anti-blending agent gray scale conditioning agent of dyestuff	146 pages of upper right hurdle 8 row～hurdle, 155 pages of lower-lefts of 4 row, hurdle, 155 pages of lower-lefts 5 row～hurdle, 155 pages of bottom rights of 2 row, hurdle, 155 pages of bottom rights 3 row～hurdle, 155 pages of bottom rights of 9 row 19 row～156 pages of upper left hurdles of 14 row, 156 pages of upper left hurdles, 15 row～hurdle, 156 pages of bottom rights of 14 row, hurdle, 156 pages of bottom rights 15 row～185 pages of upper left hurdles of footline, hurdle, 184 pages of bottom rights, 1 row～hurdle, 188 pages of bottom rights of 3 row, hurdle, 188 pages of bottom rights 4 row～8 row	_ _ _ _ _ _ _ _ _ 38 page upper right hurdle 18 row～28 pages of upper right hurdles of 3 row, 39 pages of upper left hurdles, 1 row～38 pages of upper left hurdles of 15 row, 12 row～36 pages of upper right hurdles of 7 row, upper right hurdle, 8 row～11 row---	_ _ _ _ _ _ _ _ _ 66 page 29 row～67 page 45 page of 41 row of 13 row～66 page of 18 row of 52 row～64 page of 57 row～65 of 22 row page 1 row _ _ _

Photograph inscape etc.	JP 62-215272 number	Unexamined Patent 2-33144 number	EPO.355660A2 number
				Anti-coloring agent surfactant fluorochemical (anti-live agent, help smears, lubricant, antitack agent etc.) adhesive (hydrophilic colloid) tackifier anti-live agent	Hurdle, 201 pages of lower-lefts of 10 row, hurdle, 193 pages of bottom rights of 9 row, hurdle, 188 pages of bottom rights 1 row～hurdle, 210 pages of lower-lefts of footline, 210 pages of upper right hurdles 1 row～hurdle, 222 pages of lower-lefts of 5 row, hurdle, 222 pages of lower-lefts 6 row～225 pages of upper right hurdles of 225 pages of upper left hurdle footlines, 1 row～227 pages of upper right hurdles of 2 row, 227 pages of upper right hurdles, 3 row～230 upper left hurdles, 1 row	37 pages of upper left hurdle footline～hurdle, bottom right 13 row 18 pages of upper right hurdles, 1 row, 24 pages of bottom rights hurdle footlines and hurdle, 27 pages of lower-lefts 10 row reciprocal～25 pages of upper left hurdles of 9 row, hurdle, bottom right, 1 row～38 pages of upper right hurdles of 9 row, hurdle, 27 pages of bottom rights, 8 row～18 row _ _ _ _ _ _	65 page of 32 row～66 page 17 row _ _ _ _ _ _ 66 page 23 row～28 row------

Photograph inscape etc.	JP 62-215272 number	Unexamined Patent 2-33144 number	EPO.355660A2 number
				Polymer emulsion flatting agent photograph processing method (treatment process and additive etc.)	230 pages of upper left hurdle 2 row～240 pages of upper left hurdles of 239 pages of footlines, 1 row～3 pages of upper right hurdles of 240 pages of upper right hurdle footlines, 7 row～10 pages of upper right hurdle 5 row	_ _ _ _ _ _ 39 page upper left hurdle 4 row～42 pages of upper left hurdle footlines	Page 14 row～69, _ _ _ _ _ _ 67 page 28 row
The place of notes) quoting for JP 62-215272 number also comprises the content of the clear and formality documents of correction revisal that on March 16th, 62 is attached of publishing at this communique end. In addition, in the above-mentioned colour former agent, as yellow colour former, it is desirable using the so-called shortwave type yellow colour former of record in JP 63-231451 number, 63-123047 number, 63-241547 number and No. 173499, Unexamined Patent 1-, 1-213648 number, 1-250944 number. The acyl group acetanil that particularly uses in Unexamined Patent 4-116643 number the loop chain alkane element of record is that the dihydroindole of record is that acetanil type yellow colour former is desirable in yellow colour former and the special 2-286341 of Yuanping City number.

Cyan, redness or yellow colour former, (or not) can be immersed in the Nuo Danlan latex polymer (ロ one ダ Block Le ラ テ Star Network ス polymer) (such as No. the 4203716th, United States Patent (USP)) in the presence of the high boiling organic solvent of putting down in writing in above-mentioned table, or be dissolved in water-insoluble, but in the polymer of organic solvent solubility, emulsion dispersion is desirable in hydrophilic colloid aqueous solution simultaneously. Water-insoluble that can fine use, but the polymer of organic solvent solubility has homopolymers or the copolymer of No. 4857449 7-15 hurdle of United States Patent (USP) and international open WO88/00723 number 12-30 page or leaf record for example. Be more preferably methacrylate ester or acrylamide polymer, particularly using acrylamide polymer is desirable at aspects such as colour stability.

In the photosensitive material of the present invention with colour coupler use simultaneously in European patent EP0277589A2 number to put down in writing such conservatory compound of improvement colour be desirable. Desirable with ピ ラ ゾ ロ ア ゾ one Le (pyrazoline azoles) colour coupler, pyrrolo-triazole colour coupler, acyl group acetamide type yellow colour former also particularly.

Namely, processing rear remaining aromatic amine with colour development is development host chemical bonding, remaining aromatic amine is the oxide chemistry bonding of colour development host after processing with compound in the above-mentioned European patent specification that generates chemical torpescence and colourless in fact compound and/or colour development, use simultaneously or separately the compound in the above-mentioned European patent specification that generates chemical torpescence and colourless in fact compound, preventing from for example processing in the film of rear preservation remaining colour development host or its oxide, to produce other side effect aspect with the colored pigment colouring agent of colour coupler reaction generation be desirable.

In addition, as cyan coupler, using the diphenylimidazol of record in Unexamined Patent 2-33144 number is cyan coupler, the 3-pyridone of record is that the active methene of ring-type of record in cyan coupler and JP 64-32260 number is cyan coupler in European patent EP0333185A2 number, the pyrrolo-pyrazoles type cyan coupler of record in European patent EP0456226A1 number, the pyrrolo-imidazoles type cyan coupler of record in European patent EP0484909 number, European patent EP0488248 number is desirable with the pyrrolo-triazole type cyan coupler of EP0491197A1 number record. It is desirable especially wherein using the pyrrolo-triazole type cyan coupler of record in Unexamined Patent 9-189988 number.

As red colour coupler the pyrazolin-5-one of the known document record in the above-mentioned table being arranged for example is red colour coupler. Be red colour coupler as pyrazolin-5-one, the pyrazolin-5-one that the aryl thiolysis of record is inhaled in international publication WO92/No. 18901, WO92/18902 number and WO92/18903 number be red colour coupler the image keeping quality with process that to change few this respect be desirable.

In addition; the present invention uses known ピ ラ ゾ ロ ア ゾ one Le to be tied to form toner; wherein at aspects such as color and picture steadiness, colour renderings; use as put down in writing for JP 61-65246 number 2 grades or 3 grades of alkyl at the ピ ラ ゾ ロ ア ゾ of 2,3 or 6 direct combinations of ピ ラ ゾ ロ ア ゾ one Le ring one Le colour coupler; the such molecule of record includes the ピ ラ ゾ ロ ア ゾ one Le colour coupler of sulfamoyl in JP 61-65246 number, in JP 61-147254 number in the ピ ラ ゾ ロ ア ゾ one Le colour coupler of the such maintenance alkoxyl benzene sulfonamide base バ ラ ス ト base of record and the European patent 226849A number and 294785A number the such ピ ラ ゾ ロ ア ゾ one Le colour coupler at 6 maintenance alkoxyls and aryloxy group of record be desirable.

As yellow colour former; better use known acyl group acetanil type colour coupler; wherein use the pivaloyl acetanil type colour coupler that keeps halogen atom or alkoxyl at the ortho position of anilid ring; the acyl group of record is the carbonylic acyl group acetanil of the ring acyl group type colour coupler that 1 position is changed in European patent 0447969A number, Unexamined Patent 5-107701 number, 5-113642 number etc., in European patent 0482552A number, 0524540A number etc. the malonyl of record for diphenylamines type colour coupler and Unexamined Patent 5-11416 number with 5-307250 number in the indoles base system yellow colour former put down in writing be desirable.

In the present invention, on each support, can be coated with at least one deck formation color sensitive material of yellow colour rendering silver halide emulsion layer, red colour rendering silver halide emulsion layer, cyan colour rendering silver halide emulsion layer. In general colour-printing paper, become the colour coupler of the pigment of complementary color relation can carry out the color reproduction of subtractive process to contain formation with the light of the sensitization of silver emulsion.

In the present invention, the same with general colour-printing paper, by the blue or green photonasty of future color layer order, green photonasty, red photosensitive light splitting sensitizing coloring matter difference light splitting sensitizing, in addition, the order that can go out first on support is coated with to consist of. But from the viewpoint of rapid processing, containing silver emulsion photosensitive layer of the present invention is desirable in the superiors, the addition of the per 1 mole of silver of pigment of the present invention with what sequentially be positioned at away from the reflection support emulsion layer be desirable. In this patent, the so-called the superiors refer to apart from reflection support silver halide emulsion layer farthest.

Processing method as photosensitive material of the present invention, beyond the method for putting down in writing in the above-mentioned table, processing raw material and the processing method put down in writing in Unexamined Patent 2-207250 number the 26th page of hurdle, bottom right 1 row-34 page upper right hurdle 9 row and No. 97,355 5 pages of upper left hurdle 7 row-18 page hurdle, bottom right 20 row of Unexamined Patent 4-are desirable.

So-called the present invention processes rapidization and means the developing photosensitive material processing that will expose, and the drying operation is to the time shorten that obtains the image needs. Specifically, the more than one activity time shortening with colour development operation, desilverization operation, washing and/or stabilisation operation and drying process makes whole treatment process below 90 seconds, more fortunately below 75 seconds, better below 70 seconds, more than 30 seconds. In addition, throughout in the science and engineering order, the processing time of developing procedure and desilverization operation each 30 seconds with interior be desirable, better is 5-25 second, is desirably 5-20 second most. In addition, at this moment, the processing time (Tw) of washing and/or stabilisation operation is to be desirable below 1.3 with the ratio (Tw/Tbf) in the processing time (Tbf) of blix operation simultaneously. So-called in this manual super rapid type processing means to be processed the whole treatment process that contain the photosensitive material of the silver emulsion of silver chloride content more than 95 % by mole within the above-mentioned time.

The so-called colour development time means from photosensitive material being put into colour developing solution to the time of the blix liquid of putting into next treatment process in the present invention. For example, the occasion of processing in automatic video picture machine etc. is immersed in time (time in the so-called liquid) in the colour developing solution and photosensitive material with photosensitive material and breaks away from colour developing solution and be called colour development time to both sums of time (what is called in-flight time) of carrying during the blix of next treatment process is bathed in the air. Equally, so-called blix time means from photosensitive material being put into blix liquid to the time of then putting into washing or stabilizer bath. In addition, so-called washing or stabilizing take mean from photosensitive material is put into washing or stabilizing solution to drying process in time (so-called liquid time) that liquid exists.

About the rapid processing of the object of the invention, the colour development time below 30 seconds, below 25 seconds, is well below 20 seconds, to be preferably below 15 seconds, more than 6 seconds more preferably more preferably. Equally, the blix time below 30 seconds, below 25 seconds, is well below 20 seconds, to be preferably below 15 seconds, more than 6 seconds more preferably more preferably. In addition, washing or stabilizing take below 45 seconds, below 40 seconds, are well below 30 seconds, to be preferably below 20 seconds, more than 6 seconds more preferably more preferably.

In addition, be below 20 seconds drying time, preferably below 15 seconds, more than 5 seconds, is preferably below 10 seconds, more than 5 seconds.

In the present invention, development host is ensconced in the photosensitive material beyond above-mentioned, the mode of developing in the activator liquid of the alkali lye that does not contain development host etc. is desirable.

As the wet type development mode of photosensitive material, there is the method for using common developer solution and activator liquid. Particularly the Treatment with activating agent mode is not used development host owing to do not contain in the treatment fluid to develop the color, and the management for the treatment of fluid and processing are easy, and in addition, the burden of liquid waste processing is little, sees it is desirable method from the environmental protection aspect.

The Treatment with activating agent mode uses built-in colour developing with the photosensitive material of developer or its precursor, in for example Unexamined Patent 8-234388 number, 9-152686 number, 9-152693 number, 9-160193 number, the flat 8-287288 of Patent number record like that, be desirable as colour developing with the photosensitive material that development host contains hydrazine type compound. In addition, use the photosensitive material of low silver content. The method that thickens image (strengthen process) with hydrogen peroxide is desirable, and the image forming method that contains the activator liquid of hydrogen peroxide such as the use of record in Unexamined Patent 8-297354 number, 9-152695 number is desirable.

Usually carry out the desilverization after the Treatment with activating agent and process, but use the image of the photosensitive material of low silver content to thicken processing, do not need the desilverization to process, wash after the Treatment with activating agent or simple and easy processing that stabilisation is processed is desirable. In addition, read the mode of pictorial information as photographic material with scanner etc., use the occasion of the photosensitive material of high silver content, the processing form processed of the desilverization is not possible.

The method that the activator liquid that the present invention uses, desilverization liquid, washing and stabilizing solution are processed raw material at length is documented in Unexamined Patent 8-234388 リ サ one チ デ イ ス Network ロ one ジ ヤ, one Item 36544 (in September, 1994) 536-541 page or leaf.

Photosensitive material of the present invention not only can expose by colored negative film face, and can use well the scanning exposure.

Use the light of semiconductor laser as the visible light modulation of light source according to image information. Can not get the occasion of visible light at independent semiconductor laser, the 2nd higher hamonic wave generating device (SHG element) that the nonlinear optics crystallization is consisted of is used in combination with semiconductor laser.

The beam diameter of scanning exposure is generally below the 150 μ m, preferably 10-120 μ m, more preferably 20-100 μ m. So-called beam diameter is that light beam vertical cross section strength decreased is to the 1/e of central shaft intensity²The diameter of the peripheral part of (e is the end of natural logrithm).

The beam shape of scanning exposure is not particularly limited, and it is desirable being essentially circle. " in fact " of this occasion refer to the sub scanning direction diameter to the main scanning direction diameter ratio in the scope of 97-103 %.

Effective beam diameter of the light beam of scanning exposure uses the method for putting down in writing complete phase with hurdle, Unexamined Patent 5-19423 number 4 pages of lower-left to ask. Namely for photosensitive material to give and to form line segment of laser beam lithography that the highest colour developing concentration in the image is used 50% output of enough laser intensities, implement colour development and process and obtain the wire color images. The concentration of measuring this wire color images in the vertical direction of this line segment with little densimeter distributes. Delineation is beam effective diameter corresponding to the live width of 1/5 the concentration D1/5 of the highest colour developing concentration Dmax of this distribution.

The beam effective diameter of scanning exposure is below the 300 μ m, preferably 10-240 μ m, more preferably 20-200 μ m.

The sweep span of scanning exposure defines with the interval of grating (ラ ス Network) (track of light beam), is circular occasion at light beam, with the time interval of beam center. Effectively beam diameter is greatly desirable than scanning of image spacing. Specifically, overlapping wide between grating, scanning of image spacing and beam effective diameter satisfy following mathematical expression:

L＝d-p

L: overlapping wide, d: beam effective diameter, p: sweep span

In satisfying the scope of above-mentioned mathematical expression, sweep span 0.25-190 μ m is better, and 2-80 μ m is best.

In addition, there is no particular limitation for grating overlapping wide, and by preventing not even cutting marks (seal defect) etc. of image, beam effective diameter is in the 5-95% scope, and better 15-85% is better in the scope of 20-80%.

Beam flying about the scanning exposure, can the drum scanning mode carry out, the minute surface (polygon prism) that incides the polyhedral of High Rotation Speed with light beam carries out main scanning, and the method for carrying out subscan with mobile photosensitive material on perpendicular direction is more preferably. The face number of polygon prism has no particular limits, and 2-36 face is desirable, and wherein 6-14 face is better. Scope as the stable rotation number 4000-36000rpm of polygon prism is desirable. The face number that multiply by minute surface such as this rotation number can be calculated the scanning number of unit interval.

About time for exposure of per 1 pixel of scanning exposure be that the occasion of 400dpi is 10 at PEL density^-4Below second, more preferably 10^-6Below second.

Silver halide colour photographic sensitive material light splitting sensitizing characteristic of the present invention is superior, and for use speed in period, photographic fog, contrast performance to coating when modulating from full milk changes little emulsion, be coated with the silver halide colour photographic sensitive material that can obtain superior function after the full milk modulation.

In addition, according to this silver halide colour photographic sensitive material and image forming method of the present invention, can super rapid processing, and also because the contrast change of usually processing and processing rapidly is little, it is possible keeping usually processing with the interchangeability of processing rapidly.

According to the such image processing method of the present invention, it is possible using the super rapid processing mode of processing based on formation development after the beam flying exposure of image information modulation silver halide colour photographic sensitive material.

Below specify the present invention with embodiment, but the invention is not restricted to this.

Embodiment synthesis example 1

(the modulation of emulsion A: { the dull and stereotyped grain emulsion of 100} the high-silver chloride, [AgCl that use the PVA compound to form with flat board₁₀₀])

In reaction vessel, add H₂O 1200ml, gelatin (the sub-choline of the disengaging of about 40 micromoles of methionine content/g is processed bone gelatin) 25g, sodium chloride 0.4g, nitric acid 1N liquid 4.5ml (pH value 4.5) is at 40 ℃ of constant temperature. Then Ag-1 liquid (silver nitrate 0.2g/cc) and x-1 liquid (sodium chloride 0.069g/cc) are divided inner edge high degree of agitation limit interpolation mixing in 4 minutes with 48cc/. Add polyvinyl alcohol water solution [(containing PVA compound-29) 6.7g, H after 15 seconds₂The O1 liter] 150ml.

And add nitric acid 1N liquid 12.3ml, adjust to pH value 3.5. Be warmed up to 75 ℃ in 15 minutes, it is 6.5 that interpolation NaOH 1N liquid 23ml makes the pH value, adds 1-(5-methylurea base phenyl)-5-mercapto-tetrazole (0.05%) 4.0ml, N, N-(methylimidazole base-2-sulphur (1% aqueous solution 4.0ml. Add sodium chloride 4g, adjust silver-colored current potential [a pair of room temperature saturated calomel electrode] to 100mv, assign to sideline property increase in 63cc/ minute as developmental process flow velocity in 11 minutes from 60cc/ and add simultaneously Ag-1 liquid and x-2 liquid (sodium chloride-containing 69g, 6 iridium chlorides 3.3 * 10 1 liter^-8The aqueous solution of mole) limit keeps silver-colored current potential 100mv. Adding nitric acid 1N liquid 12.5ml, to make the pH value be 4.0 again. Add sodium chloride 28.8g, making silver-colored current potential is 60mv.

Then, per 1 mole of silver 9.59 * 10^-4After the sensitizing coloring matter of mole interpolation table 6 (the emulsion A-F of last letter representation in the emulsion in the table 6) record is finished, with flow velocity 50cc/ divide in 4 minutes add Ag-2 liquid (silver nitrate 0.1g/cc) and x-3 liquid (aqueous solution of sodium chloride-containing 34.5g in 1 liter) after, 75 ℃ of placements 10 minutes.

Table 6

Emulsion No.	Grain shape	Add polyvinyl alcohol	Add KI	Sensitizing coloring matter	Remarks
						101-A	{ 100} is dull and stereotyped	Have	Nothing	2	Relatively
102-B	{ 100} is dull and stereotyped	Have	Have	1	Relatively
						103-B	{ 100} is dull and stereotyped	Have	Have	2	The present invention
104-C	{ 100} is dull and stereotyped	Nothing	Nothing	2	Relatively
						105-D	{ 100} is dull and stereotyped	Nothing	Have	1	Relatively
106-D	{ 100} is dull and stereotyped	Nothing	Have	2	The present invention
						107-E	{ 111} is dull and stereotyped	Nothing	Have	2	Relatively
108-F	Cube	Nothing	Have	2	Relatively
						109-F	Cube	Nothing	Have	1	Relatively
110-A	{ 100} is dull and stereotyped	Have	Nothing	4	Relatively
						11 1-B	{ 100} is dull and stereotyped	Have	Have	3	Relatively
112-B	{ 100} is dull and stereotyped	Have	Have	4	The present invention
						113-C	{ 100} is dull and stereotyped	Nothing	Nothing	4	Relatively
114-D	{ 100} is dull and stereotyped	Nothing	Have	3	Relatively
						115-D	{ 100} is dull and stereotyped	Nothing	Have	4	The present invention
116-E	{ 111} is dull and stereotyped	Nothing	Have	4	Relatively
						117-F	Cube	Nothing	Have	4	Relatively
118-F	Cube	Nothing	Have	3	Relatively

Sensitizing coloring matter 1Sensitizing coloring matter 2

Sensitizing coloring matter 3

Sensitizing coloring matter 4

At 40 ℃ precipitate washing, implement desalination thereafter. Add gelatin 100g, emulsion is disperseed again, making the pH value is that 6.0, pAg is 7.3. Then get a part of emulsion, observe the electron micrograph (TEM photo) of particle replication sample. Thus, all the projected area meter 98% of AgX particles be principal plane the tabular particle of 100} face, its average particulate diameter are 0.80 μ m, and average particle thickness is 0.10 μ m, average length-width ratio 7.8, on average the adjacent side is than 1.2. Synthesis example 2

(the modulation of emulsion B: { the dull and stereotyped grain emulsion of 100} the high-silver chloride, [AgCl that use the PVA compound to form with flat board_99.6I _0.4])

Take as total silver amount 0.4 % by mole of the addition of iodine, add in 1 liter and contain sodium chloride 33g in above-mentioned synthesis example 1, the aqueous solution of KI 1.95g (X-4) replaces (X-3) in addition, the same emulsion B that modulates with above-mentioned emulsion A. Get a part of emulsion, observe the electron micrograph (TEM photo) of particle replication sample. Thus, all AgX particle projection area meter 98 % be principal plane the dull and stereotyped particle of 100} face, its average particulate diameter are 0.79 μ m, average particle thickness 0.11 μ m, average length-width ratio 7.2, average adjacent side is than 1.2. Synthesis example 3

(the modulation of emulsion B: { the dull and stereotyped grain emulsion of 100} the high-silver chloride, [AgCl that do not use the PVA compound to form with flat board₁₀₀])

In reaction vessel, add [H₂O 1200cc, gelatin (the sub-choline of disengaging that contains about 40 micromoles of methionine content/g is processed bone gelatin) 25g, NaCl 1g, HNO₃1N liquid 4.5cc, pH value 4.5], at 40 ℃ of constant temperature. The limit was stirred simultaneously and divide interpolation Ag-1 liquid (AgNO with 48cc/ within 12 second₃0.2g/cc) and X-1 liquid (NaCl (0.069g/cc). After 3 minutes, within 20 seconds, divide interpolation X-5 liquid (mixed liquor of KBr 0.012g/cc and NaCl 0.0014g/cc) with 62cc/. In addition, within 45 seconds, divide simultaneously mixing to add Ag-1 liquid (AgNO with 48cc/ after 3 minutes₃0.2g/cc) and X-1 liquid (NaCl 0.069g/cc). And as maturing process, add aqueous gelatin solution [H after 1 minute₂O 120cc, gelatin 10g, NaOH 1N liquid 7cc, NaCl1.7g]. After 4 minutes, be warmed up to 75 ℃ in 12 minutes, and after the slaking, assigned to 8.8cc/ at 32 minutes inner edges from 7cc/ and divide the linear flow velocity that increases in 25 minutes, it is 2.36 that the limit keeps PC1, adds simultaneously Ag-4 liquid and X-2 liquid. Then per 1 mole of silver 9.2 * 10^-4After the sensitizing coloring matter of mole interpolation table 6 record is over, in 6 minutes with flow velocity 11cc/ divide add Ag-2 liquid and X-3 liquid after, adjust PC1 to 1.21 with sodium chloride, then 75 ℃ of slakings 20 minutes.

, at 40 ℃ precipitate washing, implement desalination thereafter. Add gelatin 100g, emulsion is disperseed again, making the pH value is that 6.0, pAg is 7.3. Then get a part of emulsion, observe the electron micrograph (TEM photo) of the replica of particle. Thus, all 97% of the projected area meter of AgX particles be principal plane the tabular particle of 100} face, its average particulate diameter 0.72 μ m, average particle thickness 0.12 μ m, average length-width ratio 6.0, on average the adjacent side is than 1.15. Synthesis example 4

(the modulation of emulsion D: { the dull and stereotyped grain emulsion of 100} the high-silver chloride, [AgCl that do not use the PVA compound to form with flat board_99.6I _0.4])

In above-mentioned synthesis example 3, take as total silver amount 0.4 % by mole of the addition of iodine, in 1 liter, add sodium chloride-containing 33g, the aqueous solution of KI 1.95g (X-4) replaces (X-3) in addition, modulates equally emulsion D with above-mentioned emulsion C. Get the part of emulsion, observe the electron micrograph (TEM photo) of particle replication sample. Thus, all AgX particle projection area meter 98 % be principal plane the dull and stereotyped particle of 100} face, its average particulate diameter are 0.77 μ m, average particle thickness 0.12 μ m, average length-width ratio 6.4, average adjacent side is than 1.15. Synthesis example 5

(modulation of emulsion E: relatively use the dull and stereotyped grain emulsion of 111} high-silver chloride)

In 1.2 premium on currency, add sodium chloride 2.0g and inertia gelatin 2.4g, in 1 minute, while stirring add silver nitrate aqueous solution 60cc (silver nitrate 9g) and sodium chloride aqueous solution 60cc (sodium chloride 3.2g) to the container of 33 ℃ of maintenances according to two spray methods. Add and finish to add after 1 minute 1.44 mMs of crystalline controlling agent 1. And interpolation sodium chloride 3.0g after 1 minute. Then in 25 minutes, the temperature of reaction vessel is warmed up to 60 ℃. 60 ℃ carry out slaking in 16 minutes after, add 10% phthaloyl (Off Le) and change aqueous gelatin solution 290g and 1.0 mMs of crystalline controlling agent 1. With 28 minute with the flow that accelerate add silver nitrate aqueous solution 754cc (silver nitrate 113g) and sodium chloride aqueous solution 768cc (sodium chloride 41.3g) thereafter. Contain KI 0.48g, 11 milligrams of potassium ferrocyanidees and 6 iridium chlorides 1.5 * 10 with adding in 21 minutes to 28 minutes therebetween,^-8The sodium chloride aqueous solution 30cc of the 0.25M of mole.

Crystalline controlling agent 1

After the interpolation, add 1% potassium rhodanide 27cc and per 1 mole of silver 6.0 * 10^-4The sensitizing coloring matter of mole table 6 record. After this, being warmed up to 75 ℃ continues to stir 10 minutes.

After this, precipitate washing at 40 ℃, implement desalination, add gelatin 100g, emulsion is disperseed again, making the pH value is 6.0, and making pAg is 7.3. Then get a part of emulsion, observe the electron micrograph (TEM photo) of the replica of particle. Thus, all AgX particle projection areametric 97% is principal plane { the tabular particle of 111} face, its average particulate diameter 0.66 μ m, average particle thickness 0.13 μ m, average length-width ratio 5.0. Chemical sensitization

Emulsion 101-A～the 107-E of table 6, add 60 ℃ of thiosulfonic acid sodium and golden sensitizers (gold chloride) among 110-A～119-E and carry out best chemical sensitization, add 1-(5-MU phenyl)-5-mercapto-tetrazole, obtain chemical sensitization emulsion 101-A～107-E, 110-A～116-E. Synthesis example 6

(modulation of emulsion F: relatively use 100} high-silver chloride cubic granules emulsion)

Sodium chloride 17.6g is joined in the 1600cc 3% lime treatment aqueous gelatin solution, this aqueous solution is heated to 52 ℃, the limit keeps temperature limit high degree of agitation, and adds the aqueous solution 127cc of 0.19 mole of the aqueous solution 127cc that contains 0.15 mole of silver nitrate and sodium chloride-containing. Aqueous solution 412cc with 1.15 moles of the aqueous solution 412cc that continue to add to contain 0.85 mole of silver nitrate in 30 minutes and sodium chloride-containing. Contain KI 0.66g, 6 iridium chlorides 1.7 * 10 with interpolation in 20-30 minute therebetween,^-8Molar solution 100cc. , at 40 ℃ precipitate washing, implement desalination thereafter. Add gelatin 100g, emulsion is disperseed again, making the pH value is 6.2, and making pAg is 7.1. Then get a part of emulsion, observe the electron micrograph (TEM photo) of particle replication sample. Hence one can see that is cubic granules, average grain size 0.41 μ m (length of side).

Per 1 mole of silver adds 3.0 * 10 in this emulsion^-4The mole sensitizing coloring matter, same thiosulfonic acid sodium and the golden sensitizer (gold chloride) of adding, carry out best chemical sensitization at 60 ℃, add 1-(5-MU phenyl)-5-mercapto-tetrazole, obtain chemical sensitization emulsion 108-F, 109-F, 117-F, 118-F.

Embodiment 1

The modulation of photosensitive material

Do not cover a support surface execution corona electricity processing of polyvinyl resin on the two sides of paper after, setting contains the gelatin priming coat of neopelex, and be coated with in turn ground floor～layer 7 and consist of photographic negative, make the coating sample T1-T16 of the silver halide colour photographic sensitive material of layer formation shown below. The coating fluid of each photographic negative constituting layer is modulated in the following manner. The modulation of ground floor coating fluid.

Yellow colour former (ExY) 62g, colour stabilizing agent (Cpd-1) 8g, colour stabilizing agent (Cpd-2) 4g and colour stabilizing agent (Cpd-3) 8g are dissolved among solvent (Solv-1) 20g and the ethyl acetate 80ml, with this liquid 4g with high-speed stirred mulser (デ イ ゾ Le バ one) emulsion dispersion in the aqueous gelatin solution 220g that contains neopelex 23.5 % by weight, add entry modulation 900g emulsion dispersion thing A. On the other hand, with above-mentioned emulsion dispersion thing A and high silver chloride emulsion mixed dissolution, modulate the ground floor coating fluid of following composition.

With the same method modulation second layer～layer 7 coating fluid of ground floor coating fluid. Use 1-hydroxyl-3,5-two chloro-s-triazine sodium salts as each layer gelatin hardener.

In addition, distinguish full dose with 15.0mg/m at each layer²、60.0mg/m ²And 5.0mg/m²Add Ab-1, Ab-2 and Ab-3. (Ab-1) anticorrisive agent (Ab-2) anticorrisive agent (Ab-3) anticorrisive agent    

    

The high silver chloride emulsion that uses in each photosensitive emulsion layer is as follows.

Use the emulsion shown in the table 7 in cyan photosensitive emulsion layer and the green photosensitive emulsion layer. Red photosensitive emulsion layer

Chlorine silver bromide (1: 4 the mixture (silver-colored mol ratio) of the large scale emulsion A of cube, average grain size 0.50 μ m and the small size emulsion B of 0.41 μ m. The coefficient of alteration of particle size is 0.09 and 0.11. Each size emulsion is that 0.8 % by mole of silver bromide is contained in a part of part of the particle surface of matrix at silver chlorate all). Per 1 mole of silver halide adds respectively 6.0 * 10 to large scale emulsion^-5Mole sensitizing coloring matter 5 and 6 adds respectively 9.0 * 10 to small size emulsion^-5Mole sensitizing coloring matter 5 and 6. Sensitizing coloring matter 5

Sensitizing coloring matter 6And per 1 mole of silver halide adds following Compound I 2.6 * 10^-3Mole.

(Compound I)

In addition, for cyan perception, green perception and red perceptual emulsion layer, per 1 % by mole of silver halide can add respectively 1-(3-methylurea base phenyl)-5-mercapto-tetrazole 3.3 * 10^-3Mole, 1.0 * 10^-3Mole and 5.9 * 10^-4Mole.

And, at the second layer, the 4th layer, layer 6 and layer 7 respectively with 0.2mg/m²、 0.2mg/m ²、0.6mg/m ²And 0.1mg/m²Add.

In addition, at the perceptual emulsion layer of redness with 0.05mg/m²Add the copolymer (weight ratio 1: 1, mean molecule quantity 200000～400000) of methacrylic acid and butyl acrylate.

In addition, at the second layer, the 4th layer, layer 6 respectively with 6mg/m²、6mg/m ²And 18mg/m²Add catechol-3,5-disulfonic acid disodium.

In addition, for preventing radiation, add following dyestuff (expression coating weight in the bracket) at emulsion layer

(1mg/m ²)

(5mg/m ²) (6mg/m ²) (16mg/m ²) layer formation

The formation that below represents each layer. Numeral coating weight (g/m²). Silver emulsion represents silver-colored conversion coating weight. Support

The polyvinyl resin laminated paper

[in the polyvinyl resin of ground floor one side, contain Chinese white (TiO₂: content 16 % by weight, ZnO: content 4 % by weight) and fluorescent whitening agent (4,4 '-two (5-Jia base Ben Bing Evil azoles) stilbene 13mg/m²), cyan dyestuff (ultramarine) 96mg/m²] ground floor (blue or green perceptual emulsion layer)

Emulsion 0.26

Gelatin 1.20

Yellow colour former (ExY) 0.62

Colour stabilizing agent (Cpd-1) 0.08

Colour stabilizing agent (Cpd-2) 0.04

Colour stabilizing agent (Cpd-3) 0.08

Solvent (Solv-1) 0.20 second layer (anti-colour mixture layer)

Gelatin 0.58

Anti-blending agent (Cpd-4) 0.10

Colour stabilizing agent (Cpd-5) 0.018

Colour stabilizing agent (Cpd-6) 0.02

Colour stabilizing agent (Cpd-7) 0.01

Solvent (Solv-1) 0.01

0.09 the 3rd layer of solvent (Solv-2) (green perceptual emulsion layer)

Emulsion 0.26

Gelatin 0.85

Red colour coupler (ExM) 0.30

Ultra-violet absorber (UV-1) 0.01

Ultra-violet absorber (UV-2) 0.01

Ultra-violet absorber (UV-3) 0.01

Ultra-violet absorber (UV-4) 0.01

Colour stabilizing agent (Cpd-2) 0.02

Colour stabilizing agent (Cpd-4) 0.002

Colour stabilizing agent (Cpd-6) 0.01

Colour stabilizing agent (Cpd-7) 0.01

Colour stabilizing agent (Cpd-8) 0.04

Colour stabilizing agent (Cpd-9) 0.03

Colour stabilizing agent (Cpd-10) 0.01

Colour stabilizing agent (Cpd-11) 0.0001

Solvent (Solv-3) 0.07

Solvent (Solv-4) 0.07

0.22 the 4th layer of solvent (Solv-5) (anti-colour mixture layer)

Gelatin 0.58

Anti-blending agent (Cpd-4) 0.10

Colour stabilizing agent (Cpd-5) 0.018

Colour stabilizing agent (Cpd-6) 0.02

Colour stabilizing agent (Cpd-7) 0.01

Solvent (Solv-1) 0.01

Solvent (Solv-2) 0.09 layer 5 (red perceptual emulsion layer)

Emulsion 0.12

Gelatin 0.72

Cyan coupler (ExC-1) 0.13

Cyan coupler (ExC-2) 0.03

Colour stabilizing agent (Cpd-6) 0.01

Colour stabilizing agent (Cpd-7) 0.02

Colour stabilizing agent (Cpd-9) 0.04

Colour stabilizing agent (Cpd-10) 0.01

Colour stabilizing agent (Cpd-14) 0.10

Colour stabilizing agent (Cpd-15) 0.02

Colour stabilizing agent (Cpd-16) 0.02

Colour stabilizing agent (Cpd-17) 0.02

Colour stabilizing agent (Cpd-18) 0.02

Solvent (Solv-5) 0.17

Solvent (Solv-6) 0.02

Solvent (Solv-8) 0.01

Solvent (Solv-9) 0.01 layer 6 (ultraviolet absorbed layer)

Gelatin 0.55

Ultra-violet absorber (UV-1) 0.19

Ultra-violet absorber (UV-2) 0.06

Ultra-violet absorber (UV-3) 0.06

Ultra-violet absorber (UV-4) 0.05

Ultra-violet absorber (UV-5) 0.09

Solvent (Solv-7) 0.20 layer 7 (protective layer)

Gelatin 0.50

The propylene modified copolymer of polyvinyl alcohol

(modification degree 17%) 0.02

Liquid Paraffin 0.02

Surfactant (Cpd-13) 0.01

(ExY) yellow one-tenth agent

(ExY) red colour coupler of 60: 40 mixtures (mol ratio)

(ExC-1) cyan coupler of 60: 40 mixtures (mol ratio)(ExC-2) cyan coupler

(Cpd-1) colour stabilizing agent of 50: 25: 25 mixtures (mol ratio)

Number-average molecular weight 60,000 (Cpd-2) colour stabilizing agent(Cpd-3) colour stabilizing agentN=7～8 (mean value) are anti-blending agent (Cpd-4)

(Cpd-5) anti-colour mixture auxiliary agent of 1: 1: 1 mixture (mol ratio)(Cpd-6) stabilizing agent

Number-average molecular weight 600 m/n=10/90 (Cpd-7) prevent blending agent (Cpd-8) colour stabilizing agent

    

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

      

(Cpd-11) (Cpd-13) surfactant

7: 3 mixtures (mol ratio) (Cpd-14) (Cpd-15)

                

1: 1 mixture (mol ratio) (Cpd-16) (Cpd-17)

                (Cpd-18)

(UV-1) ultra-violet absorber (UV-2) ultra-violet absorber    

(UV-3) ultra-violet absorber (UV-4) ultra-violet absorber    

(UV-5 ultra-violet absorber (Solv-1)                            (Solv-2)      (Solv-3)                            (Solv-4)

      

(Solv-5)                            (Solv-6)

      

(Solv-7)                            (Solv-8)         

Use the high silver chloride emulsion shown in the table 7 in maintenance each layer with the photosensitive material of upper strata formation, obtain being coated with sample T1-T16. And, as shown in table 8, in the coating sample of T3 and T6, as the perceptual emulsion layer of green grass or young crops consists of the superiors, only replace the 5th (red perception layer) and ground floor (blue or green perception layer), obtain being coated with test portion T17, T18.

Table 7

Coating sample No	Emulsion		Remarks
				Blue or green perception layer	Green perception layer
	T1	101-A				118-F	Relatively
T2			102-B	118-F	Relatively
	T3	103-B				118-F	The present invention
T4			104-C	118-F	Relatively
	T5	105-D				118-F	Relatively
T6			106-D	118-F	The present invention
	T7	107-E				118-F	Relatively
T8			108-F	118-F	Relatively
	T9	109-F				110-A	Relatively
T10			109-F	111-B	Relatively
	T11	109-F				112-B	The present invention
T12			109-F	113-C	Relatively
	T13	109-F				114-D	Relatively
T14			109-F	115-D	The present invention
	T15	109-F				116-E	Relatively
T16			109-F	117-F	Relatively

Table 8

Coating sample No	Emulsion		Remarks
				Blue or green perception layer	Green perception layer
	T17	103-B				118-F	The blue or green perceptual layer the superiors
T18			106-D	118-F	The blue or green perceptual layer the superiors

Exposure

Use following exposure device, give and exposure by the degree of three looks decomposition with B, G, R three look laser. At this moment, for each sample, improve the revisal Laser output according to the best that obtains. Exposure device

Light source uses the (oscillation wavelength: 808.5nm) be the YAG Solid State Laser of exciting light source (oscillation wavelength: 946nm) by the LiNbO with conversion range structure with semiconductor laser GaAIAs₃The 473nm that goes out of SHG crystallization wavelength conversion and with semiconductor laser GaAIAs (oscillation wavelength: 808.5nm) be the YVO of exciting light source₄Solid State Laser (oscillation wavelength: 1064nm) by the LiNbO with conversion range structure₃SHG crystallization the wavelength conversion 532nm and the AlGaInP (oscillation wavelength: 680nm, Panasonic's electricity produce model ( イ プ) No.LN9R20) that go out. Each 3 look laser can move with vertical direction the scanning direction with the polygon mirror that AOM intensity modifies tone, sequential scanning exposure on colour-printing paper. Light quantity change by the temperature of semiconductor laser utilizes Peltier (ペ Le チ エ) key element to keep temperature necessarily to suppress. This scanning exposure is 600dpi, use the beam diameter of beam diameter determinator [1180GP/ PVC one system ス キ ヤ Application society's system (U.S.)] to measure, B, G, R are 65 μ m (differences of main scanning direction diameter/sub scanning direction diameter be 1% with interior circle bundle).

Sample in above-mentioned execution exposure carries out the Off イ of Fuji Le system society CP45-X processing processed (dry to dry 180 seconds) in 180 seconds. Implement 70 seconds following treatment process and process with the colour development for the treatment of fluid. The treatment process temperature-time replenishes liquid^*1 liter of rinsing of 40 ℃ of 15 seconds 38ml of 2 liters of blixs of 45 ℃ of 15 seconds 35ml of tankage colour development is 2. 3.-1 liter of 80 ℃ of 1 liter of drying of 40 ℃ of 10 seconds 90ml 10 seconds of 40 ℃ of 1O second-1 liter rinsings of 40 ℃ of-1 liter of rinsings in 10 seconds 1.

(3. → 1. rinsing is the trough counter-current mode)

^*Every 1m²The magnitude of recruitment of photosensitive material

Rinsing water 3. sees through water and supplies with rinsing 3. by sending against soaking into mould in above-mentioned processing, does not return rinsing by the contrary concentrated water that soaks into film and does not 2. use. In order to shorten conversion time between each rinsing, blade is set between groove, photosensitive material is passed through betwixt. In addition, use the winding-up device of 8-314088 number record of Unexamined Patent in each operation, setting the winding-up amount is per 1 groove 4-6 liter/min of winding-up circulation treatment fluid.

Each treatment fluid composed as follows

The colour developing solution tank liquor replenishes liquid

Water 700ml 700ml

Triisopropyl naphthalene (β) sodium sulfonate 0.1g 0.1g

Ethylenediamine tetra-acetic acid 3.0g 3.0g

1,2-hydroxy benzenes disulfonic acid disodium salt 0.5g 0.5g

Triethanolamine 12.0g 12.0g

Potassium chloride 15.8g-

KBr 0.04g-

Potash 27.0g 27.0g

Sodium sulfite 0.1g 0.1g

Disodium-N, two (sulfonic acid ethyl) the azanol 18.0g 18.0g of N-

N-ethyl-N (β-first sulfo group amide groups ethyl)

-3-methyl-4-amino aniline sulfate 8.0g 23.0g

Sodium-two-(2,4-disulfonic acid ethyl-1,3,5

-triazine radical-6)-diamino-stilbene-2,2 '-two sulphurs

Hydrochlorate 5.0g 6.0g

Add water 1000ml 1000ml

PH value (25 ℃) 10.35 12.80

Blix liquid is by the additional liquid of 2 compositions of following hybrid modulation.

Blix liquid bath liquid magnitude of recruitment is (by the every 1m of following amount²Add up to 38ml)

The 1st replenishes liquid 260ml 18ml

The 2nd replenishes liquid 290ml 20ml

Add water 1000ml

PH value (25 ℃) 5.0

The the 1st and the 2nd replenishes the composed as follows of liquid: the 1st replenishes liquid

Water 150ml

Ethylene biguanides nitrate 30g

Ammonium sulfite 1 water salt 226g

Ethylenediamine tetra-acetic acid 7.5g

Fluorescent whitening agent (SR-1) 1.0g

Ammonium bromide 30g

ATS (Ammonium thiosulphate) (700g/ liter) 340ml

Add water 1000ml

PH value (25 ℃) 5.82 SR-1The 2nd replenishes liquid

Water 140ml

Ethylenediamine tetra-acetic acid 11.0g

Ethylenediamine tetra-acetic acid iron (III) ammonium 384g

Acetic acid (50%) 230ml

Add water 1000ml

PH value (25 ℃) 3.35 rinsing liquid

Ion exchange water (each 3ppm of Ca, Mg is following)

Use the Off イ of Fuji Le system society TCD type processed concentration determination device to measure the colour developing sample reflection density of processing. Represent speed to give with the light exposure more essential than the colour developing concentration of photographic fog concentration high 1.0. The speed that represents the sample T1 that processed in 180 seconds in the perceptual occasion of green grass or young crops with 100 relative value represents the speed of the sample T9 that processed in 180 seconds with 100 relative value in green perceptual occasion. And, the light exposure logE that obtains take speed is corresponding to the concentration that increases by 0.5 light exposure and the contrast of difference as asking of the some concentration that speed is obtained, during coating sample T1-T18 coating, obtain by containing emulsion 101-A～108-F, placed 15 hours after the modulation of the coating fluid of 110-A～117-F, beyond the coating with poor (Δ S=(contrast of Sn)/(contrast of Tn) of the contrast in coating fluid period of the sample S1-S18 sample of the same modulation of sample T1-T18. And obtain poor (Δ T=(contrast of Tn processing in 70 seconds)/(Tn180 second process contrast)) of the speed processed in 70 seconds, photographic fog and the contrast of processing in 180 seconds. The results are shown in table 9,10.

Table 9

Blue or green perception layer
								Coating sample No	Processed in 180 seconds			Processed in 70 seconds			Remarks
Speed	Photographic fog concentration	The contrast changes delta S in coating fluid period	Speed	Photographic fog concentration	The contrast change Delta T
						T1	100		0.06	0.54	112	0.12	0.71	Relatively
T2	170	0.06	0.68	173	0.1			0.78							Relatively
						T3	175		0.03	0.89	178	0.03	0.96	The present invention
T4	95	0.06	0.57	97	0.1			0.72							Relatively
						T5	146		0.09	0.7	149	0.12	0.73	Relatively
T6	150	0.04	0.88	155	0.04			0.95							The present invention
						T7	139		0.08	0.65	140	0.1	0.78	Relatively
T8	135	0.06	0.68	138	0.12			0.52							Relatively
						T17	172		0.03	0.93	180	0.03	0.99	The present invention
T18	178	0.03	0.92	182	0.03			0.98							The present invention

Table 10

Green perception layer
								Coating sample NO	Processed in 180 seconds			Processed in 70 seconds			Remarks
Speed	Photographic fog concentration	The contrast changes delta S in coating fluid period	Speed	Photographic fog concentration	The contrast change Delta T
						T9	100		0.09	0.66	105	0.1	0.65	Relatively
T10	120	0.11	0.71	125	0.13			0.73							Relatively
						T11	130		0.05	0.96	133	0.05	0.99	The present invention
T12	85	0.09	0.72	88	0.11			0.71							Relatively
						T13	103		0.12	0.74	105	0.13	0.68	Relatively
T14	127	0.05	0.95	131	0.05			0.98							The present invention
						T15	115		0.08	0.72	128	0.13	0.68	Relatively
T16	110	0.08	0.61	118	0.15			0.54							Relatively

Comparison sheet 9,10 result as can be known, the coating sample T3 of the inventive example, T6, T11, T14 light splitting sensitizing characteristic are superior, the contrast change to the photosensitive material in coating period when modulating from full milk is few.

In addition, coating sample T3, the T11 that uses as can be known the PVA compound when forming dull and stereotyped particle is few with the contrast change in ISO coating fluid period, and has in the superiors and to contain that { coating sample T17, the T18 of the silver halide emulsion layer of the dull and stereotyped particle of 100} with the contrast change in ISO, low photographic fog concentration coating fluid period still less.

In addition, the present invention is coated with sample T3, T6, T11, T14 and does not observe the increase that produces photographic fog concentration in the occasion of processing rapidly as can be known, give and low photographic fog concentration, following the change of contrast of rapid processing few, is to have rapid processing and the photosensitive silve halide material of usually processing interchangeability.

Contrast, the emulsion layer emulsion particle be that { coating sample T7, T8, T15, the T16 speed of the dull and stereotyped particle of 111} and/or cubic granules are low, and the contrast change in coating fluid period greatly as can be known.

In addition, as can be known in that { the coating sample T1, T4, T9, the T12 speed that do not contain silver iodide in the emulsion layer of the dull and stereotyped particle of 100} are significantly low. Moreover, do not use coating sample T2, T5, T10, the T13 photographic fog of the sensitizing coloring matter of general expression (I) expression high, the contrast change in coating fluid period is large.

Embodiment 2

In modulation emulsion 103-B, replace the PVA compound-29 that adds polyvinyl alcohol water solution and use respectively beyond the equivalent PVA compound-5,12,18,43,46,49, modulate identically and make emulsion G, H, I, J, K, L. In coating sample T3, T17, replace emulsion 103-B and use in addition identical each sample that is modulated into of emulsion 103-G～103-L (the emulsion B that replaces 103-B uses emulsion G～L to modulate in addition) identically, the same with coating sample T3, T17, light splitting sensitizing characteristic is superior, contrast change to the period of coating when modulating from full milk is few, do not observe the increase in the photographic fog concentration of processing rapidly the occasion generation, give and low photographic fog concentration, and, can confirm to follow the change of contrast of rapid processing few, be the photosensitive silve halide material with rapid processing and interchangeability of usually processing.

Also have, for above-mentioned coating sample T1～T18, use laser scanning exposure actinometer (SMP-201A processed of Denso society under Fuji's description Off イ Le system (strain) FWH type processed and the mountain), special-purpose colour filter (Fuji's description Off イ Le system (strain) system) is corresponding to 10 seconds low-light (level)s and 10^-6The level of using with each actinometer exposure is given in the high illumination exposure of second. The light exposure of this moment is 300CMS.

Can affirmation in this result the same with the expose result of laser scanning exposure together of low-light (level), high illumination, each sample result be good for the inventive example.

Its form of implementation has all illustrated the present invention, unless specify, we do not limit the present invention in any details, and invention spirit and the scope shown in not opposing in the scope of appended claim preferably considered wider explanation.

Claims (8)

1. silver halide colour photographic sensitive material, it is characterized in that having at the reflection support and contain the silver halide emulsion layer that forms the cyanine colour coupler, contain the silver halide emulsion layer that forms the haematochrome colour coupler and contain in the silver halide colour photographic sensitive material of the silver halide emulsion layer that forms the uranidin colour coupler, at least one deck of this silver halide emulsion layer contains the silver emulsion particle by at least a light splitting sensitizing of the pigment of following general expression (I) expression, this silver emulsion particle is to have full projected area more than 50%, average { the tabular particle of 100} interarea of length-width ratio more than 2, contain the silver chlorate more than 80 % by mole, and contain silver iodide more than 0.1 % by mole for Quan Yinliang

General expression (I)

(in the formula, Z₁And Z₂Expression sulphur atom, selenium atom or oxygen atom; V₁And V₂The sub stituent of expression monovalence, but V₁And V₂Not the aromatic series base, in addition, the formation condensed ring that do not interosculate more than two of adjacency; R₁、R ₂Independently represent separately alkyl, M₁Expression equalizing charge ion pair, m₁The number more than 0 of expression neutralization minute charge of the electron necessity; L₁、L ₂And L₃The expression methine, n₁Expression 0,1 or 2, n₂And n₃The integer of expression 0～4).

2. the silver halide colour photographic sensitive material of claim 1 record, { the flat tabular particle of 100} master is { the tabular particle of 100} principal plane that has that forms in the presence of the polyvinyl alcohol compound of gelatin and following general expression (II) or following general expression (III) expression to it is characterized in that having this

General expression (II)

(in the formula, R³The alkyl of expression hydrogen atom or carbon number 1-6, R⁴The alkyl of expression hydrogen atom or carbon number 1-20, but D represents the ethylene unsaturated monomer of copolymerization, and a, b and c represent the content (% by mole), a is not 0) of each repetitive (comonomer),

General expression (III)

(in the formula, X₁The polymer of expression in the expression general expression (II);-S-represents thioether group; X₂Expression has the homopolymers of the acrylic monomer of ionic base, or has the acrylic monomer of ionic base and the copolymer of non-ionic monomer unit; M, n represent the content (X of each block₁Or X₂Weight/full weight amount).

3. the silver halide colour photographic sensitive material of claim 1 record, it is characterized in that containing the silver emulsion particle by at least a light splitting sensitizing of the pigment of above-mentioned general expression (I) expression, this silver halide particle is to have full projected area more than 50%, average { the tabular particle of 100} interarea of length-width ratio more than 2, contain the silver chlorate more than 80 % by mole, and be positioned at apart from reflection support emulsion layer farthest for the silver halide emulsion layer that Quan Yinliang contains the silver iodide more than 0.1 % by mole.

4. the silver halide colour photographic sensitive material of claim 1 record, it is characterized in that containing the silver emulsion particle by at least a light splitting sensitizing of the pigment of above-mentioned general expression (I) expression, this silver halide particle is to have full projected area more than 50%, average { the tabular particle of 100} interarea of length-width ratio more than 2, contain the silver chlorate more than 80 % by mole, and the silver halide emulsion layer that contains the silver iodide more than 0.1 % by mole for Quan Yinliang is positioned at apart from reflection support emulsion layer farthest, and is to contain the silver halide emulsion layer that forms the uranidin colour coupler.

5. the silver halide colour photographic sensitive material of claim 1 record is characterized in that silver emulsion implemented golden sensitizing.

6. the silver halide colour photographic sensitive material of claim 1 record, its feature is made of the laminate layers lamination that a plurality of polyethylene layers or polyester layer consist of at above-mentioned reflection support, is the reflection support that contains Chinese white and/or coloured pigment at least one deck of above-mentioned laminate layers.

7. color image forming method is characterized in that the silver halide colour photographic sensitive material of each record of claim 1-6 was processed below 75 seconds with the full processing time.

8. image forming method, it is characterized in that silver halide colour photographic sensitive material scanning exposure, in the image forming method that thereafter colour development is processed, this silver halide colour photographic sensitive material is the silver halide colour photographic sensitive material of each record of claim 1-6.