CN1301990A

CN1301990A - Imaging element containing block photographic compound

Info

Publication number: CN1301990A
Application number: CN00135984A
Authority: CN
Inventors: W·K·斯卢萨雷克; 杨希强; M·E·欧文; D·H·利维; J·B·莫贝里; J·J·赛菲尔特; J·H·雷诺; L·M·欧文
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1999-12-30
Filing date: 2000-12-15
Publication date: 2001-07-04
Also published as: TW588213B; JP2001242605A; KR20010082583A; EP1113316A2; EP1113326A2; CA2328695A1; BR0010438A; EP1113326A3; EP1113316A3

Abstract

This invention relates to an imaging element comprising an imaging layer having associated therewith a compound of Structure I: wherein: the substituents are as defined in the application.

Description

The imageable element that comprises block photographic compound

The present invention relates to a kind of imageable element, it comprises obstruction (blocked) photographic compound, for example developer.

Camera work is making great efforts to provide the convenience simple method of picked-up photo to write down their daily life for the consumer for a long time always.The tradition color photography is attempted by providing the Photoactive silver-halide film that contains that is applicable to handheld camera to satisfy this requirement.After the exposure, just be loaded with latent image on the film, it only just displays later in suitable washing processing.This class component always adopts the developer solution of at least a kind of developer that includes the imaging effect to handle camera-exposed plate, realizes washing processing.

The chromophoric dyestuffs of knowing generates film need form image such as the reductive agent p-aminophenol or the p-phenylenediamine (PPD) developer.This type of reductive agent is present in the developer solution usually, makes the photographic film element of developer solution and exposure be in reactivity then during washing processing and gets in touch.The isolation of developer and film element is necessary always, because if developer directly is attached to desensitization and undesirable photographic fog that usually can cause silver emulsion in the sensitizing photographic element.Therefore; a large amount of effort have been carried out; attempt to produce a kind of developer that effectively, blocks; it can be incorporated in the silver emulsion element but can not bring disadvantageous desensitization or photographic fog effect; and under development conditions, slough obstruction (going protection), thereby make developer freely participate in imaging (generation of dyestuff or silver metal) reaction.

United States Patent (USP) 3,342,599 is authorized Reeves, discloses the application of Schiff alkali developer precursor.Shleigh and Faul, (all researchs of quoting here are open publishes (DudleyAnnex by Kenneth Mason publishing company to have described the quaternary ammonium obstruction of color developer and the acetylamino obstruction of p-phenylenediamine (PPD) in " research is open " (129 (1975) pp.27～30), 12a North Street, Emsworth, Hampshire P010 7 DQ, Britain)).Subsequently, United States Patent (USP) 4,157,915 is authorized people such as Hamaoka, and United States Patent (USP) 4,060,418, authorizes Waxman and Mourning, has described the preparation and the application in look diffusion transfer usefulness image reception sheet material of the p-phenylenediamine (PPD) that blocks.

All these explore all failures in actual product is used, and reason is one or more following points: the desensitization of sensitizing silver halide; Deoppilation dynamics slowly unacceptable; Protected developer instability causes storing back photographic fog increase and/or Dmax (maximal density) and reduces, and lacks the straightforward procedure that the obstruction developer is discharged.

The latest developments of blocking and changing chemical aspect have caused premium properties to block the appearance of p-phenylenediamine (PPD).In particular, at United States Patent (USP) 5,019, the compound with " 'beta '-ketoester " type protection (or obstruction) group (β-ketoacyl base blocking group strictly speaking) has been described in 492.Appearance along with 'beta '-ketoester blocks chemistry now may only just change the p-phenylenediamine (PPD) developer into active form with certain and be attached in the film system when needing them to develop.

The developer that this β-ketoacyl base blocks can wherein comprise two nucleophilic reagents (dinucleophile) by a kind of alkaline-based developer, and for example azanol discharges from the film layers that comprises them.

This kind blocks developer and is attached in the photographic element, normally adopts the colloid gelatin dispersion realization of this obstructions developer.This kind dispersion can adopt the technical method of knowing to prepare, wherein developer precursor is dissolved in high-vapor-pressure organic solvent (for example ethyl acetate), also together with in a kind of low-steam pressure organic solvent (for example dibutyl phthalate), carry out emulsification with the aqueous solution of surfactant-gelatin then under some situation.Emulsification generally adopts colloid mill to carry out, and after finishing, adopts technical evaporation of knowing or washing to shift out the high-vapor-pressure organic solvent.

Therefore, exist so far the such imageable element and the needs of method, they can simply absorb the photo method for the consumer provides convenience always.Particularly, exist such imageable element always, particularly take a picture and the needs of the quick imageable element of photo-thermal, it comprises a kind of developer of following form, that is, kept stable before developing always, yet, thereby, do not need the existence of two nucleophilic reagents in case, imageable element is developed by heating this element and/or will being applied to beginning washing processing process on this element such as washing processing liquid such as alkali or acid solution or pure water.The existence of this kind developer chemistry will provide washing processing very fast film, can finish flushing in low-cost photographic booth simply, efficiently.

Similarly, other photographic compounds need be attached in the photograph component, make them before developing, keep stable, discharge rapidly then.This kind photographic compound comprises colour coupler, dye well dye matrix, electron transfer agent etc., will discuss more fully below.

The present invention relates to a kind of obstruction compound, later on by 1,2-removes mechanism and decomposes in thermal activation for it, and discharging takes a picture goes up useful group.In preferred embodiments, the useful group of photograph is a kind of developer.

In one embodiment, thermal activation preferably occurs between about 100～160 ℃ temperature.In another embodiment, thermal activation preferably occurs in and adds under acid, alkali or the water existence and between about 20～100 ℃ temperature.

The invention still further relates to a kind of sensitization photograph component, comprise support and have the compound that blocks compound, this blocks compound and passes through 1 later in thermal activation, and 2-removes mechanism and decomposes, and discharging takes a picture goes up useful group.

The present invention also relates to a kind of image formation method in addition, comprises the following steps: that the photograph component of image mode exposure carries out thermal development, and wherein this element has the obstruction compound, it passes through 1 later in thermal activation, 2-removes mechanism and decomposes, and discharging takes a picture goes up useful group, thereby forms developed image; Scan described developed image, reproduce thereby form the 1st electron image by described developed image; Described the 1st electronical record is digitized into is a kind of digital image; Revise described digital image, reproduce thereby form the 2nd electron image; And store, transmit, print or show that described the 2nd electron image reproduces.

The invention still further relates to a kind of disposable camera, it has photosensitive photograph component, and element comprises support and has the compound that blocks compound, and this blocks compound and passes through 1 later in thermal activation, and 2-removes mechanism and decomposes, and discharging takes a picture goes up useful group.

The invention still further relates to a kind of image formation method, comprise the following steps: in having the disposable camera of well heater, to make photosensitive photograph component to expose by image mode, this element comprises support and passes through 1 later in thermal activation, and 2-removes the mechanism decomposition and discharging the upward obstruction compound of useful group of taking a picture; The element that exposes is somebody's turn to do in heat flush in camera then.

In embodiment more preferably, this photograph component comprises the imaging layer, and this layer has a kind of structure I compound that interrelates with it:

Wherein:

PUG takes a picture to go up useful group;

LINK1 is to be connected base with LINK2;

TIME is regularly (timing) group;

L is 0 or 1;

M is 0,1 or 2;

N is 0 or 1;

Y is C, N, O or S;

X replaces or unsubstituted aromatic yl group or electron withdraw group;

W is hydrogen, halogen or replacement or unsubstituted alkyl (preferably containing 1～6 carbon atom), naphthenic base (preferably containing 4～6 carbon atoms), aryl (for example phenyl or naphthyl) or heterocyclic group, perhaps W can with T or R ₁₂Combine and constitute a ring, w is 0～3 when Y is C, w is 0～2 when Y is N, w is 0～1 when Y is O or S, these 2 W can constitute a ring altogether when w is 2, and 2 W groups can constitute a ring or 3 W groups can constitute an aromatic yl group or dicyclo substituting group altogether altogether when w is 3.

R ₁₂Be hydrogen or replacement or unsubstituted alkyl, naphthenic base, aryl or heterocyclic group, perhaps R ₁₂Can constitute a ring altogether with T;

T replaces or unsubstituted alkyl naphthenic base, aryl or hexa-member heterocycle group, and t is 0,1 or 2, and condition is, if X is a cyano group, and m and n each naturally 0, then t is 1 or 2; If X be sulfuryl (sulfono) group and a and l each naturally 1 and m and n each naturally 0, then t is 1 or 2; If t is 2 then 2 T groups can constitute a ring altogether;

A is 1 when X is monovalence, and a is 1 or 2 when X is divalence; And

B is 0 when X is monovalence, and b is 1 when X is divalence.

Each alkyl group preferably comprises 1～6 carbon atom; Each group of naphthene base preferably comprises 4～6 carbon atoms; Each aromatic yl group is phenyl or naphthyl preferably.

In the preferred embodiment of the invention, LINK1 and LINK2 have the structure II: Wherein

X represents carbon or sulphur;

Y represents oxygen, sulphur or N-R ₁, R wherein ₁Be replacement or unsubstituted alkyl or replacement or unsubstituted aryl;

P is 1 or 2;

Z represents carbon, oxygen or sulphur;

R is 0 or 1;

Condition is, p and r are 1 when X is carbon, and Y is an oxygen when X is sulphur, and p is 2, and r is 0;

(being LINK1) of # representative and PUG or with the key (being LINK2) of TIME;

The key (being LINK2) of (being LINK1) of $ representative and TIME or the carbon that replaces with T (t).

Fig. 1 represents washing processing equipment of the present invention and the process that forms visual image by scanning element of the present invention with the block scheme form.

Fig. 2 represents a kind of block scheme, the electronic signal process process of carrying picture intelligence that expression is derived by the colour cell of scanning the present invention development.

In the structure I, PUG for example can be photographic dye or photograph reagent. The photograph reagent here is a kind of part, it can be again after release with the photograph element in component react. This type of upper useful group of taking a picture, for example comprise that colour coupler (for example, visual colour coupler, development inhibitor releasing coupler, competition colour coupler, polymer colour coupler and other form colour couplers), development restrainer, bleaching accelerator, bleaching inhibitor, inhibitor discharge developer, dye well dye matrix, developer (for example resisting developer, dyestuff generation developer, developer precursor and silver halide developing agent), silver ion fixer, electron transfer agent, ag halide solvent, silver halide complexing agent, reductones, visual toner, visual preliminary treatment and post processing stabilizing agent, curing agent, hardener, fogging agent, ultra-violet absorber, nucleator, chemistry and spectral sensitizer or desensitiser, surfactant and precursor thereof and even other and become known for the additives of photographic material.

PUG can pre-formed chemical seed in blocking compound or is existed with the form of precursor. For example, pre-formed development restrainer is bonding to blocking group, and perhaps can be connected to can be on the d/d timing group of the privileged site of particular moment and photographic material for development restrainer. PUG for example can be the compound that preformed dyestuff or deprotection group generate later on dyestuff.

In the preferred embodiment of the invention, PUG is developer. This developer can be color developer, black-and-white development agent or crosslinked-oxidized developing agent. They comprise amino phenols, phenylenediamine, quinhydrones, pyrazolidone (pyrazolidinones) and hydrazine. The example of developer is described in United States Patent (USP) 2,193, in 015,2,108,243,2,592,364,3,656,950,3,658,525,2,751,297,2,289,367,2,772,282,2,743,279,2,753,256 and 2,304,953.

The example that can be used as the PUG group of developer is:

Wherein

R ₂₀Hydrogen, halogen, alkyl or alkoxyl;

R ₂₁It is hydrogen or alkyl;

R ₂₂Hydrogen, alkyl, alkoxyl or alkene dioxy base (alkenedioxy); And

R ₂₃、R ₂₄、R ₂₅、R ₂₆And R₂₇Hydrogen, alkyl, hydroxyalkyl or sulfo group alkyl.

The above mentions, and in the preferred embodiment of the invention, LINK1 or LINK2 have the structure II:Wherein

X represents carbon or sulphur;

Y represents oxygen, sulphur or N-R₁, R wherein₁To replace or unsubstituted alkyl or replacement or unsubstituted aryl;

P is 1 or 2;

Z represents carbon, oxygen or sulphur;

R is 0 or 1;

Condition is, p and r are 1 when X is carbon, and Y is oxygen when X is sulphur, and p is that 2, r is 0;

(being LINK1) or and the T of $ representative and TIME_(t)The key (being LINK2) of the carbon that replaces.

Connect basic example and for example comprise,

TIME is timing group. This kind group is known technically, and for example (1) utilizes the group of nucleophilic aromatic substitution reaction, is disclosed in United States Patent (USP) 5,262, in 291; (2) utilize group (United States Patent (USP) 4,146,396, Japanese application number 60-249148 of hemiacetal cracking reaction; 60-249149); (3) utilize along group (United States Patent (USP) 4,409,323 of the electron transfer reaction of conjugated system; 4,421,845; Japan application number 57-188035; 58-98728; 58-209736; 58-209738); And (4) utilize the group (United States Patent (USP) 4,248,962) of intramolecular nucleophilic substitution reaction.

The example of timing group can be illustrated by structural formula T-1～T-4.

Wherein

Nu is nucleophilic group;

E is a kind of electrophilic group, comprises one or more carbon-or hetero-aromatic ring, comprises the electron deficient carbon atom in the ring;

LINK 3 is a kind of connection bases, provides 1～5 atom along directapath between the nucleophilic position of Nu and the electron deficient carbon atom among the E; And

C is 0 or 1.

This kind timing group for example comprises:This class timing group is described in greater detail in United States Patent (USP) 5,262, in 291.

Wherein

V represention oxygen atom, sulphur atom or group

R ₁₃And R₁₄Represent separately hydrogen atom or substituting group;

R ₁₅Represent substituting group; D represents 1 or 2.

R ₁₃And R₁₄, when the two represents substituting group, and R₁₅, this three's exemplary comprises:

R wherein₁₆Represent aliphatic series or aromatic hydrocarbons residue or heterocyclic group; R₁₇Represent hydrogen atom, aliphatic series or aromatic hydrocarbons residue or heterocyclic group, R₁₃、R ₁₄And R₁₅Represent separately divalent group, any 2 ring structures of formation that are bonded to each other in the middle of them. The object lesson of the group that general formula (T-2) represents is listed below.

Wherein Nu1 represents nucleophilic group, and oxygen or sulphur atom then can be used as the example of parent nuclide; The E1 representative is subjected to the electrophilic group of Nu1 nucleophillic attack; The LINK4 representative connects base, so that Nu1 and E have the space arrangement that intramolecular nucleophilic substitution reaction can occur. The group object lesson of general formula (T-3) representative is listed below.

Wherein V, R₁₃、R ₁₄And corresponding regulation is identical in the implication of d and the general formula (T-2). In addition, R₁₃And R₁₄Can couple together and consist of a phenyl ring or heterocyclic ring, perhaps V can with R₁₃Or R₁₄Couple together and consist of a phenyl ring or heterocyclic ring. Z₁And Z₂Represent independently of one another carbon atom or nitrogen-atoms, x and y represent 0 or 1 separately.

The object lesson of timing group (T-4) is listed below.

Useful compound is the structure III developer that blocks in the especially preferred photograph:

Wherein:

Z is OH or NR ₂R ₃, R wherein ₂And R ₃Be hydrogen or replacement or unsubstituted alkyl group, perhaps R independently ₂And R ₃Couple together and constitute a ring;

R ₅, R ₆, R ₇And R ₈Be hydrogen, halogen, hydroxyl, amino, alkoxy, carbon acylamino, sulfonamido, amino-alkyl sulfinyl or alkyl, perhaps R independently ₅Can with R ₃Or R ₆Connect and/or R ₈Can be connected to R ₂Or R ₇On, constitute a ring;

T is replacement or unsubstituted alkyl, naphthenic base, aryl or hexa-member heterocycle group, and t is 0,1 or 2, and condition is, if X is a cyano group, and m and n each naturally 0, then t is 1 or 2; If X sulfuryl group and a and l each naturally 1 and m and n each naturally 0, then t is 1 or 2; If t is 2 then 2 T groups can constitute a ring altogether;

R ₁₂Be hydrogen or replacement or unsubstituted alkyl, naphthenic base, aryl or heterocyclic group, perhaps R ₁₂Can constitute a ring altogether with T or W;

X replaces or unsubstituted aromatic yl group or electron withdraw group;

Y is C, N, O or S;

A is 1 when X is monovalence, and a is 1 or 2 when X is divalence; And

B is 0 when X is monovalence, and b is 1 when X is divalence.

W is hydrogen, halogen or replacement or unsubstituted alkyl, naphthenic base, aryl or heterocyclic group, perhaps W can constitute a ring altogether with T, W is 0～3 when Y is C, w is 0～2 when Y is N, w is 0～1 when Y is O or S, these 2 W can constitute a ring altogether when w is 2, and 2 W groups can constitute a ring altogether when w is 3, and perhaps 3 W groups can constitute an aromatic yl group or dicyclo substituting group altogether.

Can be used for heterocyclic group 5-or the 6-unit heterocyclic ring preferably in structure I and the III compound, comprise one or more heteroatomss, for example N, O, S or Se.This type of group for example comprises, replaces or groups such as unsubstituted benzimidazolyl, benzothiazolyl, benzoxazolyl, benzothienyl, benzofuranyl, furyl, imidazole radicals, indazolyl, indyl, isoquinolyl, isothiazolyl, isoxazolyl, oxazolyl, picolinyl, purine radicals, pyranose, pyrazinyl, pyrazolyl, pyridine radicals, pyrimidine radicals, pyrrole radicals, quinaldine based, quinazolyl, quinolyl, quinoxalinyl, thiazolyl, thiadiazolyl group, thiatriazole base, tetrazole radical, thienyl and triazolyl.

When mentioning a certain specific part or group among the application, this means that this part can be unsubstituted or replace upward one or more substituting groups (until the number of maximum possible).For example, " alkyl " or " alkyl group " is meant and replaces or unsubstituted alkyl, and " aromatic yl group " then refers to replace or unsubstituted benzene (until 5 substituting groups) or more senior aromatic systems.Usually, unless concrete regulation be used in the substituting group that replaces on the molecule here and comprise any group, no matter replace or unsubstituted, as long as it does not destroy the desired performance of photographic uses.Substituting group example on any above-mentioned group can comprise known substituting group, for example: and halogen, as chlorine, fluorine, bromine, iodine; Alkoxy, particularly those what is called " low alkyl group " (in other words, 1～6 carbon atom), for example methoxyl, ethoxy; Replace or unsubstituted alkyl, particularly low alkyl group (for example, methyl, trifluoromethyl); Alkylthio (for example, methyl mercapto or ethylmercapto group), particularly those of 1～6 carbon atom; Replace and unsubstituted aryl, particularly those of 6～20 carbon atoms (for example phenyl); And replacement or unsubstituted heteroaryl, particularly have 5-～6-unit ring, comprise 1～3 heteroatoms in the ring, be selected from N, O or S person (for example, pyridine radicals, thienyl, furyl, pyrrole radicals); Acid or hydrochlorate group, below for example described in the middle of those any one; And technical other known groups.

Alkyl substituent can comprise " low alkyl group " (in other words, 1～6 carbon atom) clearly, for example methyl, ethyl and so on.Have, about any alkyl group or alkylidene group, know, they can be branching or that do not have branching or ring-type.

It is the representative example that can be used for useful compound in the photograph of the present invention below: structure

This blocks the developer preferred combination in one or more imaging layers of imageable element.The consumption that blocks developer, in every layer of adding at its preferably between 0.01～5g/m ², more preferably 0.1～2g/m ², 0.3～2g/m most preferably ²They can be layers quality or that be non-quality of element.Blocking developer can be included in the individual component that contacts with this imageable element during washing processing.

Imageable element is through after the image mode exposure, blocking developer can be activated under the condition that has acid or alkali between the imageable element flush period in washing fluid, can be by heating imageable element between the imageable element flush period and/or by between flush period, making imageable element and individual component, for example laminate film contacts and activates.Laminate film randomly comprises additional processing chemicals, for example is disclosed in " research open " 1996, issue 389, the joint X IX of item number 38957 and XX (below be called (" the open I of research ").Here the joint of indication all refers to the joint of " the open I of research ", unless point out separately.This type of chemicals comprises, for example sulphite, azanol, hydroxamic acid etc., antifoggant, for example alkali halide, nitrogen-containing heterocycle compound and so on, sequestering agent, for example organic acid, and even other adjuvants, for example buffering agent, sulfonated polystyrene, color spot reduce agent, biocide, desilverization agent, stabilizing agent and so on.

This blocks compound and can any type of photograph system use.A kind ofly can be used for implementing representative color egative film of the present invention structure, can below element SCN-1 be that example is illustrated: element SCN-1

????SOC	The surface cuticula
????SOC	The surface cuticula	????BU	Recorded in blue layer unit
????IL1	The 1st middle layer	????BU	Recorded in blue layer unit
????IL1	The 1st middle layer	????GU	Green glow recording layer unit
????IL2	The 2nd middle layer	????GU	Green glow recording layer unit
????IL2	The 2nd middle layer	????RU	Ruddiness recording layer unit
????AHU	The antihalation layer unit	????RU	Ruddiness recording layer unit
????AHU	The antihalation layer unit	????S	Support
????SOC	The surface cuticula	????S	Support

Support S can be reflection or preferred transparent usually.When for reflection, support is white, any traditional support form that can take present colour positive element to be adopted.When support when being transparent, it can be colourless or light color, the traditional support that can take present color negative film element to adopt, for example colourless or light color transparent film support.The existing technically deep understanding of the details of support structure.The example of useful support is poly-(vinyl acetal) film, plasticon, poly-(ethylene glycol terephthalate) film, poly-(naphthalene dicarboxylic acids glycol ester) film, polycarbonate film and relevant film and resin material, and even paper, fabric, glass, metal and can bear other supports of estimating treatment conditions.This element can comprise extra play, for example filter layer, middle layer, cuticular layer, bottom, antihalation layer and so on.Transparent and the reflection support structure that comprises the bottom of strengthening adhesion usefulness is disclosed in " the open I of research ", saves in the X V.

Photograph component of the present invention also is suitable for comprising a kind of magnetic recording material very much, as be disclosed in " research open ", item number 34390,1992-11 perhaps comprises transparent magnetic recording layer, the layer that for example comprises magnetic-particle in transparent support bottom surface one side, for example be disclosed in United States Patent (USP) 4,279,945 and United States Patent (USP) 4, in 302,523.

In the middle of blue, green and ruddiness recording layer unit B U, GU and the RU each by 1 or more a plurality of hydrophilic colloid layer constitute, comprise at least a kind of radiation-sensitive silver emulsion and colour coupler, wherein comprise at least a kind of colour coupler.Preferably, green and ruddiness record cell is subdivided at least 2 recording layer subunits, with record tolerance that raising is provided and reduce visual granularity.In the simple structure of conception, each a layer unit or a layer subunit are made up of the single hydrophilic colloid layer that contains emulsion and colour coupler.When being present in certain one deck unit or the colour coupler of layer in the subunit and being coated in the non-hydrophilic colloid layer that contains emulsion layer, the hydrophilic colloid layer that contains colour coupler is placed in the position that can receive from the oxidation state color developer of emulsion during developing.Usually, the layer that contains colour coupler is and contains the hydrophilic colloid layer that emulsion layer adjoins.

For guaranteeing excellent image definition and help making and use in camera that the layer of all sensitizing preferably is placed on common support surface.When being in the film form, exposure light shone all sensitizing layers earlier when the roll film mode of this element should guarantee to walk to roll up in camera, just shone the support surface that is loaded with these layers then.Have, for guaranteeing the image that exposure forms on element excellent sharpness is arranged, the gross thickness of all layer of unit, support top should be controlled.Usually, the sensitizing layer on the support front, middle layer and protective seam gross thickness are less than 35 μ m.

Any convenient combination of selecting from traditional radiation-sensitive silver emulsion all can be attached in this layer unit and be used to provide spectral absorption characteristics of the present invention.The most frequently used perbromide emulsion that contains a small amount of iodide of preferred use.For reaching higher washing processing speed, can use perchloride emulsion.The silver chloride of radiation-sensitive, silver bromide, iodine silver bromide, silver iodochloride, chlorine silver bromide, bromine silver chloride, iodine chlorine silver bromide and iodine bromine silver chloride particle are all at the row of consideration.Particle can be rule or irregular (for example, sheet).In platy shaped particle emulsion, platy shaped particle accounts for those of at least 50 (preferably at least 70, randomly at least 90) % of total particle projected area, is particularly advantageous for the speed that improves under certain particle size.Reach the standard of sheet, requiring the ratio of diameter of equivalent circle (ECD) and its thickness of 2 main parallel surfaces of particle is 2 at least.Clear and definite preferred platy shaped particle emulsion is that the platy shaped particle mean diameter-thickness is 5 than at least, more preferably greater than 8 those.Preferred average platy shaped particle thickness is less than 0.3 μ m (most preferably less than 0.2 μ m).The super-thin sheet-shaped grain emulsion, promptly average platy shaped particle thickness is especially satisfying less than those of 0.07 μ m.These particles preferably can form surface latent image, so that they can produce the negativity image when carrying out washing processing with the surface development agent form of color negative film form of the present invention.

The example of tradition radiation-sensitive silver emulsion can be referring to " the open I of research " of above-referenced, " I emulsion grain and preparation thereof ".The chemical sensitization of emulsion comprises any form, can be referring to joint IV, " chemical sensitization ".The compound that can be used as chemical sensitizer for example comprises, active gelatin, sulphur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorus or their combination.Chemical sensitization usually in the pAg level between 5～10, the pH level is between 4～8, temperature is carried out under 30～80 ℃ condition.Spectral sensitization and sensitizing dyestuff comprise any traditional form, can be referring to joint V, " spectral sensitization and desensitization ".Dyestuff can be applied to any moment of photograph component before getting on (for example during the chemical sensitization or after) or side by side joins in silver halide grain emulsion and the hydrophilic colloid at emulsion.For example, the solution that dyestuff can be in water or in the alcohol or add as the solid particulate dispersion form.The typical emulsions layer also comprises a kind or multiple antifoggant or stabilizing agent, and they can take any traditional form, and example can be seen in joint VII, " antifoggant and stabilizing agent ".

Being used for silver halide particle of the present invention can be according to technical known method preparation, for example " the open I of research " of above-referenced, and James, " photographic process theory ".These methods comprise, known method on for example preparation of ammonia process emulsion, neutrality and acid emulsion preparation and the other technologies.These methods generally all relate to water soluble silver salt and mix in the presence of protecting colloid with water-soluble halide salt, and during generating silver halide by precipitation temperature, pAg, pH value etc. are controlled at suitable numerical value.

During solids precipitation, can introduce a kind or multiple adulterant (the particle absorption outside desilver and the halogenide) to improve particle properties.For example, in emulsion of the present invention, can there be " the open I of research " joint I " emulsion grain and preparation thereof ", trifle G, " granule modified condition and adjusting ", any in the disclosed various conventional dopant in section (3), (4) and (5).In addition, special imagination to be comprising the transition metal six coordinate complex of a kind or multiple organic ligand, as is disclosed in people's such as 0 cm the United States Patent (USP) 5,360,712, as adulterant particle mixed.

Expect in the face-centered cubic lattice of particle adding a kind of energy especially by forming the adulterant that shallow electron trap (below be called SET) improves imaging speed, can be referring to " research be open ", project 36736,1994-11 publication.

The SET adulterant can work at any position in particle.Generally speaking, effect is benchmark with silver being attached to particle when the SET adulterant preferably, (leaning on) outer 50% o'clock.The best particle zone of SET combination is the zone that is made of 50～85% silver in the total silver that constitutes particle.SET can once all introduce, and perhaps joins in the reaction vessel successively in the process that particle continues to precipitate.Usually, the suggestion that forms the SET of adulterant adds concentration and is, at least 1X10 ^-7The every moles of silver of mole is until being up to its solubility limit, generally the highest about 5X10 ^-4The every moles of silver of mole.

The SET adulterant is known can to reduce reciprocity failure effectively.Particularly advantageous is to use iridium six coordinate complex or Ir ^{+ 4}Complex compound is as the SET adulterant.

To providing the invalid iridium adulterant of shallow electron trap (non--the SET adulterant) also can join in the silver emulsion particle, to reduce reciprocity failure.

Improve with regard to the reciprocity law with regard to effective, iridium can be present in any position in the grain pattern.Improve effect for making the iridium adulterant produce reciprocity law, the preferred site of iridium adulterant in grain pattern be in the total silver that constitutes particle before 60% to last 1% (before most preferably last 3%) formed in the zone of particle.Adulterant can once all be introduced, and perhaps joins in the reaction vessel successively in the process that particle continues to precipitate.Usually, improve the non--SET iridium adulterant suggestion of reciprocity law with its minimal effective concentration adding.

The contrast of photograph component can by with the six coordinate complex (NZ adulterant) that contains nitrosyl or sulfo-nitrosyl ligand be adulterant to particle doped, and be further enhanced, for example can be referring to people such as McDugle, United States Patent (USP) 4,933,272.

The adulterant of intensifying can be attached to any position easily in the grain pattern.Yet if the NZ adulterant is present in particle surface, it will reduce the light sensitivity of particle.It is therefore preferable that the NZ adulterant should be positioned at such position: promptly, make and be separated by at least 1% between they and the particle surface (most preferably at least 3%) to constitute total precipitated silver of silver iodochloride particle.For the preferred NZ concentration of dopant of intensifying between 1X10 ^-11～4X10 ^-8The every moles of silver of mole, especially preferred concentration is between 10 ^-10～10 ^-8The every moles of silver of mole.

Though provided the general preferred concentration range for of various SET, non--SET iridium and NZ adulterant above, know, in these general ranges, can find out the concrete optimum concentration range that is fit to concrete purposes by conventional test.Expect using SET, non--SET iridium and NZ adulterant especially, can use either alone or in combination.For example, especially expect comprising the particle of SET adulterant and non--SET iridium adulterant combination.Similarly, the also combinable use of SET and NZ adulterant.The NZ and the iridium adulterant of the non-SET dopant type of use equally, also capable of being combined.At last, the combination of non--SET iridium adulterant and SET adulterant and NZ adulterant.The situation of these a kind of three aspect adulterant array modes in back, from the general most convenient of consideration of precipitation operation be, at first be incorporated into the NZ adulterant, follow by the SET adulterant, at last in conjunction with non--SET iridium adulterant.

Photograph component of the present invention can provide emulsion form silver halide in typical case.Photographic emulsion generally comprises to emulsion being coated with into the vehicle (or carrier) of a photograph component layer.Useful vehicle comprises naturally occurring material; for example albumen, protein derivatives, cellulose derivative are (for example; cellulose esters), gelatin (for example; alkali treated gelatin; as ox bone or animal glue; perhaps acid-treated gelatin, for example pig skin gelatin), deionized gelatin, gelatine derivative (for example, acetylation gelatin, phthalate gelatin etc.) and as " the open I of research " described other vehicles.What also can be used as vehicle or vehicle spreading agent is hydrophilic, permeable colloid.These comprise synthetic polymer peptizator, carrier and/or cementing agent, for example polymkeric substance, hydrolyzed poly vinyl acetate, polyamide, polyvinylpyridine, the methacrylamide copolymer of polyvinyl alcohol (PVA), poly-(vinyl lactam), acrylamide polymer, polyvinyl acetal and acrylic acid and alkyl methacrylate and sulfo group Arrcostab.Vehicle can any photographic emulsion in emulsion in useful content exist.Emulsion also can comprise any known condiment that is useful in the photographic emulsion.

Though can use the photosensitive silver of any useful quantity silver halide form in the element that the present invention uses, preferably, total silver amount is less than 10g/m ²Preferred silver amount is less than 7g/m ², more preferably the silver amount is less than 5g/m ²The silver of lesser amt can improve the optical property of element, thereby can adopt this element to produce more clear photograph.Silver-colored other important benefit with lesser amt is that they can make the element rapid development and the desilverization.For realizing the exposure latitude of 2.7logE at least, simultaneously the photo of preparing to amplify is kept suitably low graininess grade conversely speaking,, the overlay capacity of silver halide coating in element need be every square metre of support surface areas of 1.5 gram silver coating at least.

BU comprises at least a kind of weld and forms visual colour coupler; GU comprises at least a kind of rosaniline dyes and forms visual colour coupler; RU comprises at least a kind of cyan dye and forms visual colour coupler.Any dyestuff easily forms the combination of visual colour coupler and all can use.The example that conventional dyes forms visual colour coupler can be seen in " the open I of research " above-mentioned, X. " dyestuff forms visual colour coupler and correctives ", B. " visual colour coupler ".This photograph component also can comprise other image improvement compounds, for example " development restrainer-release " compound (DIR).The further useful DIR that can be used for element of the present invention is technical known, and example is described in: United States Patent (USP)

3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 and patent disclosure GB 1,560,240; GB 2,007, and 662; GB 2,032, and 914; GB 2,099, and 167; DE2,842,063, DE 2,937, and 127; DE 3,636, and 824; DE 3,644,416 and following European patent open: 272,573; 335,319; 336,41 1; 346,899; 362,870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.

The DIR compound also is disclosed in " developer-inhibitor-release (DIR) colour coupler that autochromy is used ", C.R.Barr, J.R.Thirtle and P.W.Vittum, " photographic science and engineering " volume 13, p.174 (1969).

Common way is in homogencous dyes imaging layer unit, to be coated with 1,2 or 3 independent emulsion layer.When coating 2 or more a plurality of emulsion layer in the simple layer unit, select them to have different light sensitivity usually.In the time of above the higher emulsion of light sensitivity is applied to the lower emulsion of light sensitivity, high speed in the time of can arriving than 2 kinds of emulsion blending.When the low emulsion of light sensitivity is coated on above the higher emulsion of light sensitivity, high contrast in the time of can arriving than 2 kinds of emulsion blending.Preferably, the emulsion that light sensitivity is the highest is positioned at the most approaching exposure irradiation bomb; The slowest emulsion is positioned at the position near support.

Preferably one or more layers of the present invention unit subdivision is at least 2, more preferably 3 or more a plurality of subunit layer.Preferably, all photosensitive silver halide emulsions in this colour record cell all have photoreception of spectrum in same visible spectrum zone.In such embodiments, though all silver emulsions that are attached in this unit all have spectral absorption according to the invention, expect in spectral absorption, to exist between them fine difference.In embodiment preferred more, the sensitizing of slow silver emulsion especially will be regulated particularly, compensating this layer unit meta light-shading effect of the very fast silver emulsion of face thereon, so that provide along with exposure (amount) keeps responding with the image mode uniform spectra from low to high always for photographic recording material.Therefore, preferably in the slow emulsion of the layer unit that is segmented, adopt higher proportion peak light absorption spectrum sensitizing dye, with the peak value shielding and the broadening (on-peakshielding and broadening) of compensation bottom photoreception of spectrum.

Middle layer IL1 and IL2 are hydrophilic colloid layers, and main effect is to mix in order to reduce color--promptly, prevent from that the oxidation state developer is not able to do in time to react with colour coupler as yet just to move in the adjacent recording layer unit.The middle layer prolong aspect the diffusion path length that the oxidation state developer must cross over be part effectively.Intercept and capture the effectiveness of oxidation state developer for increasing the middle layer, traditional method is to be incorporated into the oxidation state developer.Anti-stain agent (scavenger of oxidation state developer) can be from " research discloses 1 ", X. " dyestuff imaging agent and correctives ", and D. " tone correctives/stabilization " selects in the section (2).1 kind or multiple silver emulsion are perbromide emulsion in GU and RU, when therefore having the intrinsic photonasty to blue light, preferably are incorporated into the Yellow filter dyestuff in IL1, for example Carey Lea silver or the yellow washing fluid dyestuff that can fade.Suitable Yellow filter dyestuff can be selected from " the open I of research ", and the joint VIII " absorbs and scattering material ", those that enumerate among the B. " absorbing material ".In element of the present invention, there is not pinkish red painted filter among IL2 and the RU.

Antihalation layer unit AHU comprises washing fluid usually can remove the light absorbing material that maybe can decolour, for example a kind of pigment or dyestuff or its combination.Suitable material can be selected from " the open I of research ", those that enumerate in the joint VIII " absorbing material ".The common alternative site of AHU is at support S and is coated between the recording layer unit near support.

Surface cuticula SOC is a hydrophilic colloid layer, be used to be provided at transmit and washing processing during to the physical protection of color negative film element.Each SOC also for those or will bring into play the position that the accrete adding of maximum effectiveness is provided convenience near the color negative film element surface.In some cases, surperficial cuticula is subdivided into superficial layer and middle layer again, and the latter plays the effect at interval between condiment and the adjacent recording layer unit in superficial layer.In the common variation of another kind, condiment is distributed between superficial layer and the middle layer, and wherein the latter comprises and adjacent recording layer unit condiment compatible with each other.Most typically be, SOC comprises such as following condiment, and for example coating additive, plastifier and lubricant, antistatic agent and matting agent are referring to " the open I of research ", joint IX.Those that " the coating physical property is improved and used condiment " is cited.The SOC that overlaps above the emulsion layer also preferably comprises ultraviolet absorber in addition, for example referring to " the open I of research ", joint VI." ultra-violet dye/fluorescer/luminescent dye ", those that section (1) is cited.

This layer sequence of unit of substituted component SCN-1 can adopt alternative sequence of unit, and this alternate orders is selected particularly suitable for some emulsion.When adopting perchloride emulsion and/or thin (less than 0.2 μ m average particle thickness) platy shaped particle emulsion, all possible location swap all can be taked between BU, GU and the RU, and blue light can not appear to subtracting the danger that blue record pollutes, because these emulsions show insignificant intrinsic photonasty in visible spectrum.Based on same reason, need in the middle layer, not add blue-light absorbers.

Not not simultaneously, traditional way is that the addition of dyestuff imaging colour coupler in speed is top is limited in less than the stoichiometric by silver to emulsion layer in dyestuff imaging layer unit on speed.The function of top speed emulsion layer is that part of family curve that produces just above least density--that is, being lower than between the exposure region of all the other one or more emulsion layer threshold value light sensitivity in this layer unit--.Do like this, under the prerequisite of not sacrificing imaging speed, the quantity that adds granularity the highest bigger film speed emulsion layer in the dye image record is reduced to bottom line.

In the superincumbent discussion, blue, green and ruddiness recording layer unit has been mentioned and has been comprised Huang, magenta and cyan image colour coupler respectively, as the way that the color negative film unit field that is used to print positive is accustomed to taking.The present invention also is applicable to traditional as mentioned above color negative film structure.The colour reversal chip architecture then will be taked similar form, and different is that painted illiteracy cover colour coupler will not exist; In canonical form, development inhibitor releasing coupler will not exist yet.In preferred embodiments, this color negative film element is intended to be used for uniquely scanning, to produce 3 independent electronic color records.Therefore, the actual tone of visual dyestuff of generation is unimportant.Important only is that the dye image that generates in each layer unit can come with the difference that each remainder layer unit is produced.For this separating capacity is provided, a kind or multiple dyestuff imaging colour coupler that expectation selects each layer unit to comprise are positioned at different spectrum ranges with generation and have a video dyestuff that absorbs half-peak breadth.In blue, green or red spectrum is interval, whether form Huang, magenta or the cyan dye of the half-peak bandwidth that has as for blue, green or ruddiness recording layer unit, as the traditional color negative film unit that is used to print positive, or other make things convenient for the half-peak breadth absorption region of spectrum range arbitrarily, (300～400nm) to visible light and until near infrared (700～1200nm) near ultraviolet, all unimportant, as long as absorbing the half-peak bandwidth, the visual dyestuff in each layer unit is continuous in the wavelength coverage of non-common extension basically.Term " non-basically common extension wavelength scope " is meant that every kind of visual dyestuff demonstrates the absorption half-peak bandwidth of being continuous at least 25 (preferred 50) nm spectrum range, and this interval is not occupied by the absorption half-peak bandwidth of the visual dyestuff of another kind.It is desirable to, visual dyestuff has the separate characteristics of the half-peak bandwidth of absorption.

When a layer unit comprises 2 or during the different emulsion layer of more a plurality of speed, preparation can be reduced like this from the visual granularity of the image that electronical record is watched or read: dye image has one at different spectrum ranges and absorbs the half-peak bandwidth, is different from other emulsion layer dye images in this layer unit.The layer unit that this technology is particularly suitable for being comprised further is subdivided into the element of the different subunit of speed.This makes might generate multiple electronical record at every layer of unit, corresponding to having the different dyes image that the photosensitive emulsion layer of same spectra forms.By the formed digital recording of dye image that the top speed emulsion layer forms, be used to produce the dye image that is positioned at just above that part of vision of least density by scanning.The 2nd and the 3rd optional electronical record on higher exposure levels then can generate by other dye image that has each other on spectrum that scanning is formed by all the other one or more emulsion layers.These digital recordings comprise than low noise (low granularity), can be used for the image that the regeneration preparation is watched between the exposure region that is higher than slow emulsion layer threshold exposure level.The technology that this kind reduces granularity is disclosed in the United States Patent (USP) 5,314,794 of Sutton in more detail.

Each layer unit of color negative film of the present invention unit produces a characteristic curve γ value less than 1.5 dye image, and this helps obtaining the exposure latitude of 2.7logE at least.The acceptable minimum tolerance of polychrome photograph component is to be the most extreme white (for example bride's wedding gauze kerchief) and the most extreme required tolerance of accurate recording of deceiving (for example, bride bridegroom's evening dress) situation that occurs in photographic uses probably.Exposure latitude equals 2.6logE, can just hold typical bride and the bridegroom scene of marrying.Preferred exposure latitude is 3.0logE at least, because this will provide a kind of photographer of allowing the safety allowance of error to occur on exposure is selected.Bigger exposure latitude is then especially preferred, because can still obtain the ability of accurate image reconstruction like this under than the mistake situation.Yet in the color negative film element of preparing printingout, the unusual scene visual attractive force of being printed off when low of γ value will have certain loss, and when the color negative film unit when overscanning produces digital dye image record, then contrast can be improved by the adjusting to electronic signal information.When element of the present invention adopted reflecting bundle scanning, beam passed each layer unit with twice.In fact this will make γ value (Δ D/ Δ log E) also double by doubling of variable density (Δ D).Therefore, suggestion adopt be low to moderate 1.0 or even 0.6 γ value, and exposure latitude all is feasible up to about 5.0logE or higher.Preferred γ equals about 0.55.Especially preferred γ is between about 0.4～0.5.

Replace to use colour coupler, also the dye image that alternately tradition of using in any multicolor imaging is added generates compound and is included in indigo plant, the green and ruddiness recording layer unit.The generation of dye image is to realize by destruction, generation or the removal of selection as the dyestuff of exposure function.For example, the method for bleaching of silver-colored dyestuff be know and commercial be used for by the visual dye selection destruction that added form dye image.The example of silver dye bleach process can be referring to " the open I of research ", joint X, " dye image colour coupler and modifier ", A. " silver dye bleach ".

As everyone knows, can join in indigo plant, the green and ruddiness recording layer unit generating visual dyestuff in advance, selected dyestuff should be fixing at the beginning, but along with correspondingly the dyestuff chromophore being discharged in the moveable part with oxidation state developer generation redox reaction.This kind compound is referred to as redox dye releasing agent (RDR) usually.Wash the removable dyestuff that discharges off, just form the image of excess dye, can scan this image.Also can be with the removable dye transfer that discharges to receiving on the body, they are fixed in the mordanting layer at this.Then, can the reception body that be loaded with image be scanned.At the beginning, receiving body is the color negative film element part of the whole.Scanning when being the reception body of element part of the whole, the typical case receive body comprise transparent support, near the mordanting layer that is loaded with dye image below the support and near the white reflecting layer below the mordanting layer.Peeled off from color negative film element at the reception body, so that under the scan condition of dye image, the support of this reception body can reflect, when the dye image image is found a view, this situation is often selected, or transparent, and this kind situation allows dye image is scanned.RDR and the dye image transfer system that is comprised thereof are described in " research is open ", volume 151,1976-11, item number 15162.

Should also be appreciated that dye image can comprise at the beginning and to be compound movably, but then changes into fixing during image mode is developed.Utilizing the image transfer system of this type imaging dyestuff to be applied to previously disclosed dye image transfer system has already suffered.These and other image transfer system compatible with way of the present invention is disclosed in " research is open ", volume 176,1978-12, item number 17643, XX III " image transfer system ".

For the needs that adapt to scanning once proposed many modification technology at color negative film element, for example can be referring to " the open I of research ", joint X IV " feature of convenient scanning ".As long as this type systematic compatible with color negative film element structure described above, all considers to be used for enforcement of the present invention.

Also imagine, imageable element of the present invention can be used with non-traditional sensitizing program.For example, do not adopt the imaging layer of preparing between red, green and blue area that sensitizing is spectrum, but, make photosensitive material have of the brightness of 1 white-sensitive layer, and 2 color sensitive layers are with record scene look news with the record scene.After the development, the image of formation can carry out scanner uni digitizing reprocessing, to reproduce whole colors of original scene, for example is disclosed in US 5,962, in 205.This imageable element also can comprise the emulsion of panchromatic sensitizing, and follows color separation exposure.In this embodiment, developer of the present invention will produce a kind of painted or neutral image, and this image cooperates color separation exposure, can intactly collect the various colours of original scene.In this kind element, image can be by the combination of the silver-colored density of developing, a kind or multiple traditional colour coupler, and perhaps by " deceiving " colour coupler, for example the resorcinol colour coupler generates.Color separation exposure can by suitable optical filtering sequentially perhaps side by side (be referred to as " colour filter array ") by filter element discrete on the space and carry out usually.

Imageable element of the present invention can also be the black and white image forming material, for example comprises panchromatic sensitizing silver emulsion and developer of the present invention.In this embodiment, the generation of image can be by the silver-colored density of developing after the washing processing, perhaps realizes by a kind of colour coupler that can produce the dyestuff that can be used for carrying neutral visual colour gamut.

When forming tradition Huang, magenta and cyan image dyestuff, so that through read after tradition exposure color photographic material is carried out chemical development when writing down the scene exposure value, the response of red, the green and recorded in blue unit of this element can be distinguished exactly by the density of studying separately.Density measurement is the light of measuring by the transmission of sample institute, wherein adopts the optical filtering of selecting color that each relatively independent passage is resolved in the image mode response of the visual dyestuff generation unit of RGB (red, green, blue photaesthesia).Usually adopt Status M optical filtering to measure to be intended for use the response of the color negative film element that carries out optical printing; The colour reversal film that adopts the direct transmission of Status A optical filtering preparation of determine to watch.In integral density is measured, do not wish a side or the afterbody absorption of imperfect visual dyestuff can cause a little passage to mix, at this moment, the part of for example pinkish red passage overall response may be from the absorption of the offset peak of the visual dyestuff record of yellow or cyan in the neutral characteristics curve or the two.This kind human factor can be ignored when measuring the film spectral sensitivity.By the suitable mathematics manipulation to the integral density response, the contribution of the offset peak density that this kind is disagreeable can be proofreaied and correct fully, as long as when analytic density, supposes that the response of given color record is independent of the spectral contribution of other visual dyestuffs--this point establishment.Analytic density is measured and is summarized in " photographic science and engineering SPSE handbook, W.Thomas chief editor, John Wiley and Sons, New York, 1973, joint 15.3 " color density mensuration ", pp.840～848.

Can reduce pattern noise by the following method: the color negative film element of scanning through exposing and washing changes adjusted electronical record into certain again subsequently and can watch form to obtain the electronical record handled of image frame.Image definition and color can pass through each layer γ ratio design code in narrow range, avoid simultaneously or reduce other performance deficiencies as far as possible, reach raising, in this process, the glory record is become electronic form, and then change the color image that to watch into.Though the remainder of pattern noise and picture information can not be separated by printingout or by handling the electron image record, but can write down by the adjustment electron image and improve curve overall shape and precipitous feature, wherein the electron image record is owing to provided by low γ ratio color negative film element, so have low noise, a kind of like this mode is to adopt known motion picture film printing technique not accomplish.Therefore, image can become from the electron image record regenerating that is transformed by following color negative film element: promptly, this backsheet member is better than those elements that is transformed in a similar manner by the traditional color negative film element that is designed for optical printing.The excellent imaging characteristic of described element in red, green and recorded in blue unit each γ ratio all can realize less than 1.2 o'clock.In a more preferred embodiment, each γ value of red, green and recorded in blue unit is all less than 1.15.In a further preferred embodiment, red and color production unit sensitive to blue light respectively shows the γ ratio less than 1.10.In the most preferred embodiment, red, the green and quick color production unit of blue light respectively shows the γ ratio less than 1.10.In all cases, preferably, each color cell shows the γ ratio less than 1.15, and more preferably, they show the γ ratio less than 1.10, and further preferably, they show the γ ratio less than 1.05.The γ ratio of each layer unit does not need to equate.The low γ ratio of this kind is that the interlayer between each layer unit interacts, and also is called the interlayer effect and is in low-level sign, it is believed that it is the reason that image quality improves after scanning and the electronics colour-separation drafting.Obviously harmful image feature because of chemical interaction between the layer unit produces need not force down it with electronic method during visual colour-separation drafting.This kind interaction usually is difficult to, even if be not impossible, adopts known electron image handling procedure to be suppressed.

In the invention process, the unit of best usability photosensitiveness excellence.The light sensitivity of this kind unit should be at least about ISO 50, preferably is at least about ISO 100, more preferably is at least about ISO200.Light sensitivity is especially preferred up to ISO 3200 or higher unit.The speed of color negative film photograph component or photonasty and be inversely proportional to through the regulation density required exposure amount more than photographic fog after the washing processing for obtaining.γ is that the film speed of about 0.65 color negative film element is defined as ansi standard PH2.27-1981 (ISO (ASA speed)) clearly by American National Standards Institute (ANSI) (ANSI) and relates to particularly in each color layers, for produce the required average exposure level of density more than 0.15 least density in the green light sensitive of color film and minimum light sensitivity color record cell the two each.This definition is consistent with the evaluation of International Standards Organization (ISO) film speed.With regard to the application's purpose, if the γ of colour cell is not equal to 0.65, then ASA or ISO speed should be calculated like this:, determine before the speed according to the miscellaneous stipulations mode, linear amplification or separate and amplify this γ-log E (exposure) curve is until the numerical value that equals 0.65.

The present invention also imagines, and photograph component of the present invention is in the application that is referred to as usually aspect the disposable camera (or " band camera lens film " device).This kind camera is sold together with the film of packing in advance, and whole then camera turns back to developing machine together with the exposed plate of staying camera inside.The disposable camera that uses among the present invention can be technical known any this type of camera.Such camera can provide technical known concrete feature, the means of for example fast door equipment, roll film means, film trasport means, waterproof case, list or many camera lenses, camera lens selection approach, various aperture, focus or focal length lens, control light condition, indicates the means of regulating aperture time or lens properties and confession camera to be used for service condition directly is recorded in means on the film according to light condition or user.These features include but not limited to: provide manually or automatic film-transporter and reset simplifying the internal structure of an organization that shutter uses, as be described in Skarman, United States Patent (USP) 4,226,517; The device of automatic exposure control is provided, as is described in people such as Matterson, United States Patent (USP) 4,345,835; Protection against the tide, as be described in people such as Fujimura, United States Patent (USP) 4,766,451; Provide inner and outside film overcoat, as be described in people such as Ohmura, United States Patent (USP) 4,751,536; Be provided on the film means of record service condition, as be described in people such as Taniguchi, United States Patent (USP) 4,780,735; The camera that camera lens is housed is provided, as is described in Arai, United States Patent (USP) 4,804,987; Film rack with the excellent anti-performance of curling is provided, as is described in people such as Sasaki, United States Patent (USP) 4,827,298; View finder is provided, as is described in people such as Ohmura, United States Patent (USP) 4,812,863; The camera lens of regulation focal length and velocity of shot is provided, as is described in people such as Ushiro, United States Patent (USP) 4,812,866; Many films container is provided, as is described in people such as Nakayama, United States Patent (USP) 4,831,398 and people such as Ohmura, United States Patent (USP) 4,833,495; The film that provides antifriction characteristic to improve, as be described in Shiba, United States Patent (USP) 4,866,469; Winding mechanism is provided, rotating shaft or resilience sleeve, as be described in Mochida, United States Patent (USP) 4,884,087; 135 film cassettes or the magazine that can take out vertically are provided, as are described in people such as Takei, United States Patent (USP) 4,890,130 and 5,063,400; The electronic flash means are provided, as are described in people such as Ohmura, United States Patent (USP) 4,896,178; But the outside executive component of realizing exposure usefulness is provided, as is described in people such as Mochida, United States Patent (USP) 4,954,857; Provide to have the film bearing of improveing perforation and the means of described film film trasport, as be described in Murakami, United States Patent (USP) 5,049,908; Internal mirror is provided, as is described in Hara, United States Patent (USP) 5,084,719; And provide silver emulsion on the bobbin that is applicable to tight coiling, as be described in people such as Yagi, european patent application 0,466,417A.

Though the installation of this film on disposable camera can be adopted technical known any way, after especially preferred film is installed in disposable camera, when exposure finishes, batch by the thrust magazine immediately.The thrust magazine is disclosed in people's such as Kataoka United States Patent (USP) 5,226,613; The United States Patent (USP) 5,200,777 of Zander; People's such as Dowling United States Patent (USP) 5,031,852; And people's such as Robertson United States Patent (USP) 4,834,306.Be fit to use the narrow fuselage disposable camera of thrust magazine to be described in people's such as Tobioka United States Patent (USP) 5,692,221 by this kind mode.Comparatively put it briefly, the camera that is suitable as the limiting demensions of disposable camera use most is generally rectangle, can satisfy easy operating and carry, and for example is placed in the pocket, and at this moment, camera as described herein occupies limited volume.The cumulative volume of this kind camera should preferably less than 380 cc, be more preferably less than 300 cc, most preferably less than 220 cc less than about 450 cubic centimetres (cc).The ratio of the degree of depth of this kind camera-highly-length generally will be about 1: 2: 4 ratio, and wherein the amplitude of each size is about 25%, so as to provide operation and carry comfortable.Generally speaking, in spendable minimum-depth depends on the dress lens focus and in the load axle and the size of magazine.The preferred finishing of most of corner angle of this camera is the radius-of-curvature of about 0.2～3 cm.The use of thrust magazine is especially favourable to the present invention, because make scanner search out the special scenes that absorbs on the film easily like this, some often cause the puzzlement of the factor of image quality deterioration like this to protect film to exempt from dust, cut and wearing and tearing simultaneously.

Though any known phtographic lens all can be used in the camera of the present invention, be installed in the preferably simple aspheric surface plastic lens of phtographic lens in the disposable camera of the present invention.The focal length of this camera lens is between about 10～100mm, and the lens opening is between f/2～f/32.Focal length is preferably between about 1 5～60mm, most preferably between about 20～40mm.Be used for image, preferred focal length equals cornerwise 25% scope in rectangle exposure zone.The expectation lens opening is between f/2.8～f/22, and preferred lens opening is between about f/4～f/16.The MTF of camera lens (modulation transfer function) spatial frequency in film plane equals can be low to moderate 0.6 or lower under every millimeter on 20 lines (1pm) condition, but the invention is intended to be, preferably up to 0.7, or most preferably 0.8 or higher numerical value.Camera lens MTF is higher, and the photo that produces is comparatively clear usually.Especially imagination adopts many camera lenses to arrange, and comprises 2,3 or more composition lens member, and they are preferably consistent with function described above.

Dress washing processing ability, for example heating element in camera can comprise.The design of this kind camera comprises its application in picture-taking and display system, is disclosed in U.S. Patent Application Serial Number 09/388,573, and 1999-09-01 submits to.The use of disclosed disposable camera especially is preferred for implementing the present invention in the described application.

Photograph component of the present invention preferably adopts known technology to carry out the image mode exposure, comprises " the open I of research ", the technology in the joint X VI of being described in.Typical this kind process relates to the light between the visible region that is exposed to spectrum, typical this kind exposure is the exposure of on-the-spot image by camera lens, although exposure also can be the image that the image (as the image of Computer Storage) that is exposed to storage forms by luminescent device (for example, light emitting diode, CRT and so on).The quick imageable element of this photo-thermal also can utilize various form of energy to realize exposure, comprise between the ultraviolet ray and infrared of electromagnetic wave spectrum, and electron beam and β ray, gamma-rays, x-ray, alpha ray, neutron ray and other form particulate ripple class radiation energy, can be incoherent (random phase) or relevant (phase bit) form that laser instrument produces.Exposure is monochromatic, countenance or panchromatic, the spectral sensitization situation of concrete visual sense photohalogenation silver and deciding.

Element discussed above can be used as material and is used for some or all of following process: scanning of image is to produce the electronic reproduction of this picked-up image, then numeral processing is carried out in this reproduction, so that handle, store, transmit, export or show this image in the electronics mode.

The present invention blocks compound and can be used in such photograph component, and it comprises any or all of above-mentioned feature, but but prepares to adopt different development treatment forms.To itemize the type of these systems below.

The type I: heat flush system of processing (the quick imaging of thermal imaging and photo-thermal), this washing processing are uniquely by heating causes to imageable element.

The type II: low volume system, this moment film development by contacting beginning with Treatment Solution, but the cumulative volume of the volume of this Treatment Solution and processed imaging layer is equally matched.The system of this type can comprise the adding of non-solution-treated equipment, for example heating or apply laminated layer when handling.

The type III: the traditional photography system, wherein the washing processing of film element is by contacting realization with traditional photography washing processing solution, and the volume of this kind solution is compared very big with imaging layer volume.

Type I: the quick imaging system of temperature-sensitive and photo-thermal

According to one aspect of the invention, should block developer and be attached in the quick imageable element of photo-thermal.The quick imageable element of photo-thermal, as the sort of type described in " research open " 17029, for referencial use in these receipts.The quick imageable element of photo-thermal can be disclosed A type or a Type B in " the open I of research ".A type element comprises photothermographic silver halide, reductive agent or developer, activator and coating vehicle or cementing agent in the reaction association.In this kind system, developing process is reduced to argent along with silver ion in the photothermographic silver halide and realizes.The Type B system can comprise all the components of A type system, also includes the salt or the complex compound of organic compounds and silver ion in addition.In this kind system, this organic complex is reduced during developing, thereby generates argent.This organic silver salts will be referred to as silver and give body.The list of references of describing this type of imageable element for example comprises United States Patent (USP) 3,457,075,4,459,350,4,264,725 and 4,741,992.

The photographic composition that the quick imageable element of photo-thermal comprises mainly is made up of Photoactive silver-halide.In the quick image forming material of Type B photo-thermal, it is believed that the latent image that is formed by silver halide plays the catalyst action as imaging anabolic process after the washing processing described above.In these systems, preferred Photoactive silver-halide concentration silver in every mole of photosensitive material of 0.01～100 mole of Photoactive silver-halide is given body.

The Type B photograph component comprises a kind of redox imaging combination, and it comprises organic silver salt oxidizing agent.This organic silver salts is to the more stable silver salt of light ratio, but when be heated to 80 ℃ or higher, have the formation that can impel the silver image down at the photocatalyst (that is photothermographic silver halide) and the reductive agent of exposure.

Suitable organic silver salts comprises the organic compound silver salt with carboxylic group.Its preferred example comprises aliphatic carboxylic acid silver salt and aromatic carboxylic acid's silver salt.The preferred example of aliphatic carboxylic acid silver salt comprises docosanoic acid silver, silver stearate, oleic acid silver, lauric acid silver, capric acid silver, myristic acid silver, palmitic acid silver, maleic acid silver, fumaric acid silver, silver tartrate, furancarboxylic acid silver, linoleic acid silver, butyric acid silver and camphoric acid silver, their potpourri etc.Can also can be used effectively by the silver salt of halogen atom or oh group replacement.The preferred example of aromatic carboxylic acid's silver salt and other carboxylated compounds comprises silver benzoate, replace silver benzoate, for example 3,5-dihydroxy-benzoic acid silver, o-toluic acid silver, m-methyl benzoic acid silver, p-methylbenzoic acid silver, 2,4-dichlorobenzoic acid silver, acetaminobenzoic acid silver, to Phenylbenzoic acid silver etc., gallic acid silver, tannic acid silver, phthalic acid silver, terephthalic acid (TPA) silver, silver salicylate, phenylacetic acid silver, l, 2,4,5-benzenetetracarboxylic acid silver, for example be described in United States Patent (USP) 3, the silver salt of the 3-ethyloic in 785,830-4-methyl-4-thiazoline-2-thioketones and so on, and for example be disclosed in United States Patent (USP) 3, the aliphatic carboxylic acid silver salt of the thioether-containing group in 330,663.

What expect especially is the silver salt of following compounds: the compound that sulfydryl and thioketones replace, have the 5-of containing an or 6-annular atoms, and wherein at least 1 is nitrogen, and other annular atomses comprise carbon and maximum 2 heteroatomic heteronucleus that are selected from oxygen, sulphur and nitrogen.Typical preferred heteronucleus comprise triazole, return Zuo, oxazole, thiazole, thiazoline, imidazoline, imidazoles, diazole, pyridine and l triazine.The preferred example of these heterogeneous ring compounds comprises 3-sulfydryl-4-phenyl-1,2, the silver salt of 4-triazole, the silver salt of 2-mercaptobenzimidazole, 1-phenyl-5-sulfenyl returns the silver salt of azoles, the silver salt of the amino thiadiazoles of 2-sulfydryl-5-, the silver salt of 2-(2-ethyl-ethylene glycol acylamino-) benzothiazole, the silver salt of 5-carboxyl-1-methyl-2-phenyl-4-sulfo-pyridine, the silver salt of mercapto-triazine, the silver salt of 2-mercaptobenzoxazole, United States Patent (USP) 4,123, silver salt described in 274, for example 1,2, the silver salt of 4-thyroidan derivant such as 3-amino-5-dibenzylsulfide-1,2, the silver salt of 4-thiazole; Thione compounds, 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thioketones for example, as be disclosed in United States Patent (USP) 3,201 is in 678.Other do not contain the sulfydryl of heteronucleus or the examples of compounds of thioketones replacement can be listed below: the silver salt of mercaptoacetic acid, silver salt (wherein alkyl group has 12～22 carbon atoms) as the S-alkyl mercapto acetic acid, as be described in the Japanese patent application 28221/73, the silver salt of carbodithioic acid, for example silver salt of the silver salt of methyl-carbithionic acid and sulphamide.

In addition, also can use the silver salt of the compound that comprises imino group.The preferred example of this compounds comprises the silver salt of benzotriazole and derivant thereof, as is described in Jap.P. and discloses in 30270/69 and 18146/70, for example silver salt of benzotriazole or methylbenzotrazole etc., the silver salt of the benzotriazole that halogen replaces, the silver salt of 5-chlorobenzotriazole etc. for example, 1,2, the silver salt of 4-triazole, 3-amino-5-sulfydryl benzyl-1,2, the silver salt 4-triazole, the 1H-tetrazolium, as be described in United States Patent (USP) 4, in 220,709, the silver salt of imidazoles and imdazole derivatives etc.

Also find to be easily, use half soap of silver, in the middle of this preferred example be docosanoic acid silver with docosanoic acid wait a mole blend, can prepare and the analysis content of silver equals 14.5% by precipitation from the sodium salt of commercially available docosanoic acid.The clear sheet for preparing on the transparent film backing layer requires clear coat, for this reason, can use the complete soap of docosanoic acid silver, comprise to be no more than about 4 or 5% free docosanoic acid, and the analysis silver content is about 25.2%.The method of making silver-colored soap dispersion is technically to know, and is disclosed in " research is open " 1983-10 (23419) and United States Patent (USP) 3,985,565.

The silver salt complex compound also can pass through the silver ion class, and for example the aqueous solution of silver nitrate is mixed with the organic coordination liquid solution of silver-colored coordination with preparation and prepared.Mixed method can take any form easily, comprises using in the silver halide precipitation method.Can adopt stabilizing agent to avoid the flocculation of silver complex particle.Stabilizing agent can be any in the middle of known those useful materials on the photography, such as but not limited to, surfactant gelatin, polyvinyl alcohol (PVA) or polymerization or monomer.

They were in close on the catalysis meaning during the coating method of photothermographic silver halide particle and organic silver salts should guarantee to develop.They can be coated with the layer that becomes to adjoin, but preferably mix before coating.The conventional hybrid technology can be referring to above-mentioned " research open ", in item number 17029 and United States Patent (USP) 3,700,458 and the Japanese patent application No. 32928/75,1 3224/74,17216/75 and 42729/76 delivered.

Also can comprise the reductive agent except that blocking developer.The reductive agent that is used for organic silver salts can be any material, can be the organic substance of argent with silver ion reduction preferably.The traditional photography developer, for example 3-pyrazolidone, quinhydrones, p-aminophenol, p-phenylenediamine (PPD) and catechol are useful, however hindered phenol reductive agent preferably.The concentration that reductive agent preferably exists accounts for 5～25% of the quick imaging layer of photo-thermal.

Disclosing varied reductive agent aspect the dried silver-colored system, comprise amidoxim, for example phenyl amidoxim, 2-thienyl amidoxim reach phenoxy group-phenyl amidoxim, azine (for example, 4-hydroxyl-3,5-dimethoxy benzaldehyde azine); The combination of aliphatic carboxylic acid aryl hydrazide and ascorbic acid, for example combination of 2,2 '-two (methylol) propionyl beta-phenyl hydrazides and ascorbic acid; The combination of the combination of polyhydroxy benzenes and azanol, reductone and/or hydrazine, for example combination, piperidino hexose reductone or formyl-4-procarbazine, the hydroxamic acid of quinhydrones and two (ethoxyethyl group) azanols, for example benzohydroxamic acid, to hydroxyphenyl hydroxamic acid and adjacent alanine hydroxamic acid; The combination of azine and sulfonamido phenol, phenothiazine and 2 for example, 6-two chloro-4-phenylsulfinyl amino-phenols; Alpha-cyano-phenylacetic acid derivatives, for example alpha-cyano-2-methylphenyl acetic acid ethyl ester, alpha-cyano-ethyl phenylacetate; Two-betanaphthol, for example 2,2 '-dihydroxy-1-dinaphthalene, 6,6 '-two bromo-2,2 '-dihydroxy-1,1 '-dinaphthalene and two (2-hydroxyl-1-naphthyl) methane; Two-betanaphthol and 1, the combination of 3-dihydroxy benzene derivatives (for example, 2,4 dihydroxy benzophenone or 2,4-dihydroxy acetophenone); 5-pyrazolone, for example 3-methyl isophthalic acid-phenyl-5-pyrazolone; Reductone, for example dimethylamino hexose reductone, dehydration dihydro aminohexose reductone and dehydration dihydro-piperidones-hexose reductone; Sulfoamino-group phenol reductive agent, for example 2,6-two chloro-4-benzene-sulfonamido phenol and to the phenylsulfinyl amino-phenol; 2-phenyl dihydroindene 1,3-diketone etc.; Benzodihydropyran, for example 2, the 2-dimethyl-7-tert-butyl group-6-hydroxychroman; 1,4-dihydropyridine, for example 2,6-dimethoxy-3,5-two carbonyl ethoxys (dicarbethoxy)-1,4-dihydro pyridene; Bis-phenol, for example two (the 2-hydroxyl-3-tert-butyl group-5-aminomethyl phenyl)-methane; 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-; 4,4-ethylidene-two (the 2-tert-butyl group-6-methylphenol); And 2, two (3, the 5-dimethyl-4-hydroxyphenyl) propane of 2-; Ascorbic acid derivates, for example palmitic acid 1-acid ascorbyl ester, ascorbyl stearate and unsaturated aldehyde and ketone, for example benzyl and diacetyl; Pyrazolidine-3-ketone; And some dihydroindene-1, the 3-diketone.

The optium concentration of organic reducing agent in the quick imageable element of photo-thermal changes with following factors: the image of the quick imageable element of for example concrete photo-thermal, requirement, washing processing condition, concrete organic silver salts and concrete oxygenant.

The quick imageable element of photo-thermal can comprise toner, also is called activator-toner or toner-accelerator.The combination of toner degree also can be used in the quick imageable element of photo-thermal.The example of useful toner and toner combination is described in, and for example " studies openly " 1978-06, item number 17029, and in the United States Patent (USP) 4,123,282.The example of useful toner for example comprises phthalimide, the adjacent dicarboximide of N-hydroxyl, N-potassium-phthalimide, succinimide, N-hydroxyl-1; 8-naphthalimide, 2; 3-benzodiazine, 1-(2H)-2; 3-diazepinone, 2-acetyl group 2,3-diazepinone, salicylamide, benzamide and dimethyl urea.

Flushing back image stability agent and latent image keep stabilizing agent also to can be used in the quick imageable element of photo-thermal.The stabilizing agent that the quick imaging technique of any photo-thermal is known also can be used in the quick imageable element of photo-thermal described herein.The example of the useful stabilizing agent that illustrates comprises the stabilizing agent and the stabiliser precursor of photolytic activity, for example is described in United States Patent (USP) 4,459, in 350.The example of other useful stabilizing agents comprises the azolinethione stabiliser precursor of pyrroles's thioether and obstruction, and the carbamyl stabiliser precursor, for example is described in United States Patent (USP) 3,877, in 940.

The quick imageable element of photo-thermal preferably comprises various colloid and polymkeric substance, and they can separately or combine as vehicle and cementing agent, and can be in various layers.Useful material is hydrophilic or hydrophobic.They are transparent or semitransparent, comprise naturally occurring material, for example gelatin, gelatine derivative, cellulose derivative, glycan such as glucosan, gum arabic and so on; And synthetic polymer material, for example water-soluble polyethylene based compound such as polyvinyl pyrrolidone and acrylamide polymer.Other available synthetic polymers comprise the vinyl compound of dispersion, for example are the latex form, particularly can improve those of photograph component dimensional stability.Effectively polymkeric substance comprises water-fast acrylate polymer, for example alkyl acrylate and alkyl methacrylate, acrylic acid, sulfo group acrylate, and have those of cross-linking part.Preferred high molecular weight material and resin comprise poly-(vinyl butyral), cellulose acetate butyrate, poly-(methyl methacrylate), poly-(vinyl pyrrolidone), ethyl cellulose, polystyrene, poly-(vinyl chloride), chlorinated rubber, polyisobutylene, butadiene-styrene-multipolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-acetate ethylene copolymer, poly-(vinyl alcohol) and polycarbonate.When adopting organic solvent to prepare coating, the organic soluble resin directly can be mixed in the coating formulation and be coated with.When being coated with by aqueous solution, any useful organic soluble material all can the latex form or other fine grained dispersion forms in conjunction with entering.

The quick imageable element of photo-thermal disclosed herein can comprise the known condiment that helps useful image to generate.The quick imageable element of photo-thermal can comprise development correctives, sensitizing dye, hardener, antistatic agent, plastifier and lubricant, coating additive, fluorescer, absorption and the filter dye of the effect that improves film speed, for example be described in " research is open ", 1978-12, item number 17643 and " research is open ", 1978-06 is in the item number 17029.

Each layer of the quick imageable element of photo-thermal can be applied on the support by coating program known on the camera technique, comprises dip-coating, air knife blade coating, the coating of curtain formula or adopts the extrusion coated of hopper.Require, can be coated with 2 or more multi-layered simultaneously.

The quick imageable element of described photo-thermal preferably comprises thermal stabilizer, so that help to make the quick imageable element of photo-thermal to keep stable before exposure and washing processing.This kind thermal stabilizer can improve the stability of the quick imageable element of photo-thermal at lay up period.Preferred thermal stabilizer is 2-bromo-2-arylsulfonyl acetamide, for example 2-bromo-2-p-methylphenyl sulphonyl acetamide; 2-(trisbromomethyl sulphonyl) benzothiazole; And 6-replace-2, two (the trisbromomethyl)-s-triazines of 4-, for example 6～methyl or 6-phenyl-2, two (the trisbromomethyl)-s-triazines of 4-.

Preferably continue to be enough in the quick imageable element of photo-thermal, produce the time of the latent image that can develop and to keep enough exposure intensities with the image mode exposure.

After the quick imageable element image mode exposure of photo-thermal, the latent image of formation can develop by various modes.The simplest is that the quick imageable element integral body of photo-thermal is heated to the heat flush processing temperature.The whole heating of this kind only relates to the quick imageable element of photo-thermal is heated to about 90 ℃～180 ℃ temperature until forming the image that develops, and for example finishes in about 0.5～about 60 s.Increase or reduction heat flush processing temperature, can adopt the short or long washing processing time.Preferred heat flush processing temperature is between about 100 ℃～about 160 ℃.The heater means that the quick imaging technique of photo-thermal is known can be used to provide for the quick imageable element of photo-thermal of exposure the washing processing temperature of requirement.Heater means for example is, simple hot plate, flatiron, roller, heating drum, microwave applicator, adds hot-air, steam etc.

According to conception, the washing processing machine style of the quick imageable element of this photo-thermal and element are stored and the circulating film magazine or the cartridge of use interrelate.Have again, be stored in the data of film or the washing processing or the condition of scanning that magazine also can be used to modified elements.The method of finishing these steps in the imaging system is disclosed in same assignee, common unsettled U.S. Patent Application Serial Number 09/206586 and the United States Patent (USP) 6,062,746 and 6,048,110.Also expect, can adopt certain device, so that utilize the washing processing machine to write information on element, these information can be used to regulate washing processing, the scanner uni image shows.Such system is disclosed in EP application number 1,008,901, and 2000-06-14 is open, and U. S. application sequence number 09/333,092, and 1999-06-15 submits to.

Heat flush processing is preferably carried out under environmental pressure and damp condition.Condition beyond normal atmosphere pressure pressure and the humidity also can be used.

The component of the quick imageable element of photo-thermal can be placed on the interior any position of element of the image that requirement can be provided.Require, a kind or various ingredients can be present in one or more layers of element.For example, in some cases, be preferably, comprise into reductive agent, toner, stabilizing agent and/or other condiment of certain percentage in the cuticular layer on the quick imaging recording layer of the photo-thermal of element.This can reduce the migration of some condiment in each layer of element in some cases.

According to one aspect of the invention, block developer and join in the thermal imaging element.In the temperature-sensitive imageable element, image is by forming with imaging mode heating element.This kind element for example is described in " research is open " 1978-06, in item number 17029 and the United States Patent (USP) 3,080,254,3,457,075 and 3,933,508.Heat energy and imaging means can be hot exposure source of the known image mode of any thermograph technology and means.The thermal imaging means for example can be the Infrared Heating means, laser, microwave heating means and so on.

Type II: low volume washing processing:

According to the present invention on the other hand, this obstruction developer is attached to and prepares to adopt in the photograph component of low volume washing processing.Low volume washing processing is defined as such washing processing, and the developer solution volume that is wherein applied is between about 0.1～about 10 times, preferred about 0.5～about 10 times of needed liquor capacities of photograph component swelling.This kind washing processing process can apply by solution, the compound action laminated and heating of exterior layer is realized.Relevant type I above low volume washing processing system can comprise: the described any element of the quick imaging system of photo-thermal.In addition, expect especially that also joint described any component in front one is so long as to the formation of latent image in the initial film element and stablize unwanted, all can completely remove, and any moment after exposure adopts following method to contact for implementing photographic processing.

Type II photograph component can be accepted some or all in the following processing:

(I) directly applies solution on film, can adopt following any means, comprises spraying, ink-jet, coating, gravure method etc.

(II) is immersed in film in the body lotion that comprises washing processing solution.This kind method also can take element is flooded or passes through the mode of a little magazine.

(III) is incorporated into a kind of auxiliary washing processing element layer on this imageable element.This laminated washing processing element that gets on can have provides the washing processing chemicals, remove the chemicals use or the effects such as picture information on the transfer latent image recording film element.The image that is transferred can be transferred on this auxiliary washing processing element according to image mode by dyestuff, dye matrix or Ag-containing compound and generate.

(IV) element heats in any convenient manner, comprises simple hot plate, flatiron, roller, heating drum, microwave heating means, adds hot-air, steam and so on.Heating in front before any one of treatment step I～III, during, afterwards or from start to finish (overall process) carry out.Heating can make the washing processing temperature between room temperature～100 ℃.

Type III: legacy system:

According to another aspect of the present invention, this obstruction developer joins in the traditional photography element.

Can adopt in numerous photograph job operations of knowing any according to traditional photography element of the present invention, use any flushing in numerous traditional photography process solutions of knowing, for example be described in " the open I of research " or T.H.James chief editor, " photograph procedural theory ", the 4th edition, Macmillan, New York, 1977.The sustainable any time length of developing process is also carried out under any washing processing temperature, as long as be fit to change into the needs of acceptable image.In this class operating mode, can utilize the present invention to block existing for of developer is used for the developer that a kind of element or multiple colored record develop with washing processing solution additional development effect is provided, thereby improve the coating weight of the signal or the minimizing image forming material of shorter development time acquisition, perhaps between all colours optical recording, produce balanced development.Under the washing processing situation of negativity element, element is accepted the processing (promptly this developer will generate painted visual dyestuff with colour coupler) of color developer, accepts oxygenant and solvent processing then, to remove silver and silver halide.Under the washing processing situation of reversal film colour cell, element at first with the black-and-white development agent (in other words, this developer does not generate illuminating colour with the colour coupler compound) handle, accept the processing (being often referred to chemical ashing or light ashing) of ashing silver halide subsequently, handle with color developer then.Preferred color developer is a p-phenylenediamine (PPD).Especially preferredly be:

4-amino-N, N-diethylaniline hydrogen chloride,

4-amino-3-methyl-N, N-diethylaniline hydrogen chloride,

4-amino-3-methyl-N-ethyl-N-(2-(methane sulfonamido) ethylaniline sesquisulfate hydrate (sesquisulfate hydrate),

4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl) aniline sulfate,

4-amino-3-α-(methane sulfonamido) ethyl-N, N-diethylaniline hydrogen chloride, and

4-amino-N-ethyl-N-(2-methoxy ethyl)-meta-aminotoluene two p-toluenesulfonic acid.

The method that the formation of dye image or amplification are adopted relates to, and generates a kind of inertia transition metal ion complex oxygenant that reductive agent is used with dye image, and its example is disclosed in Bissonette, United States Patent (USP) 3,748,1 38,3,826,652,3,862,842 and 3,989,526 and Travis, United States Patent (USP) 3,765,891, and/or peroxide oxidant, for example be disclosed in Matejec, United States Patent (USP) 3,674,490, " research is open " volume 116,1973-12, item number 11660, and Bissonette, " research is open " volume 148,1976-08, item number 14836,14846 and 4847.This photograph component especially can be applicable in for example following method to form dye image:

People's United States Patent (USP)s 3,822,129 such as Dunn, Bissonette United States Patent (USP) 3,834,907 and 3,902,905, people's United States Patent (USP)s 3,847,619 such as Bissonette, Mowrey United States Patent (USP) 3,904,413, people's United States Patent (USP)s 4 such as Hirai, 880,725, Iwano United States Patent (USP) 4,954,425, people's United States Patent (USP)s 4 such as Marsden, 983,504, people's United States Patent (USP)s 5 such as Evans, 246,822, Twist U.S.Patent No.5,324,624, Fyson EPO 0487616, people WO90/13059 such as Tannahill, people WO 90/13061 such as Marsden, people WO 91/16666 such as Grimsey, Fyson WO91/17479, people WO 92/01972.Tannahill WO 92/05471 such as Marsden, Henson WO92/07299, people such as TwistWO93/01524 and WO93/114602 and Wingender Germany OLS 4,211,460.

After the development, can bleach-photographic fixing is removing silver or silver halide, and washing and dry.

After in case Huang, magenta and cyan dye picture record form in the photograph component of washing processing processing of the present invention, can adopt conventional art to give the picture information of each color of light record for change and this record is carried out the people is conversion, so that produce the visual image of color balancing subsequently.For example, can be at blue, the green and interval scanography sequentially of red spectrum element, perhaps can interval to be attached to single scanning intrafascicular with blue, green and red spectrum, and separately and see through blue, green and red filter, thereby form the independent beam split scanning beam that writes down at each color of light with light beam.A kind of simple technique is this photograph component of parallel sweep path point by point scanning of putting between horizontal along a series of.The light intensity that sees through element at a certain analyzing spot is by sensor senses, and the latter is converted to electric signal with the irradiation of accepting.The most general way is with the further conversion of electronic signal, to be formed with the visual electronical record of usefulness.For example, electric signal can pass through analogue-to-digital converters, then together with sending into digital computer corresponding to the locating information of pixel (point) position in the image.In another embodiment, this electronic signal is encoded with colourity or hue information, a kind of to be fit to be used for image reconstruction be visible electronical record thereby form, for example computer monitor displayed image, television image, printed image and the like.

Consider that many imageable elements of the present invention will be accepted scanning before removing silver halide from it.Residual silver halide will produce a kind of muddy coating, and this is found that the scanning image quality of this kind system can adopt the scanner according to the diffuse illumination optical principle to be improved.Anyly technically knownly be used for producing the luminous technology of diffusion and all can use.Preferred systems comprises: reflecting system, utilize a kind of diffusion depression, and its inwall specialized designs becomes can produce the height diffuse reflection; And transmissive system, wherein the diffusion of unidirectional light beam is to utilize a kind of being placed on to be used for the optical element of scattered beam on the beam path and to finish.This kind element can be glass or plastics, wherein combine the scattering that a kind of composition can produce requirement, can promote the scattering that requires thereby perhaps passed through surface treatment.

One of challenge that runs into the process of the information generation image of extracting out from scanning is that the information number of pixels that can Gong watch only is the part of the number of pixels that comparable classical photographic printing provided.Therefore, what is more important in scanned imagery improves the quality of available picture information as far as possible.Strengthening tonal value and reducing lopsided pixel signal influence as far as possible is the conventional art that improves image quality, a kind of conventional art that as far as possible reduces lopsided pixel signal influence, be that the reading that each PEL (picture element) density reading is adjusted to according to adjacent image point be multiply by a certain weighted mean value that (weighting) coefficient obtains, wherein big more from the pixel weighting coefficient that gets closely.

The Density Calibration slip that element of the present invention adopts is to derive according to one or more slip zones that once were subjected to reference on the unexposed photographic recording material part of exposure, specifically can be referring to people's United States Patent (USP)s 5 such as Wheeler, 649,260, people's United States Patent (USP)s 5,563 such as Koeng, 717, and people's United States Patent (USP) 5,644,647 such as byCosgrove.

The exemplary systems of sweep signal conversion comprises the technology of the quality that improves picture record as far as possible, is disclosed in: Bayer United States Patent (USP) 4,553,156; People's United States Patent (USP)s such as Urabe 4,591,923; People's United States Patent (USP)s such as Sasaki 4,631,578; Alkofer United States Patent (USP) 4,654,722; People's United States Patent (USP)s such as Yamada 4,670,793; Klees United States Patent (USP) 4,694,342 and 4,962,542; Powell United States Patent (USP) 4,805,031; People's United States Patent (USP)s such as Mayne 4,829,370; Abdulwahab United States Patent (USP) 4,839,721; People's United States Patent (USP)s such as Matsunawa 4,841,361 and 4,937,662; People's United States Patent (USP)s such as Mizukoshi 4,891,713; Petilli United States Patent (USP) 4,912,569; People's United States Patent (USP)s such as Sullivan 4,920,501 and 5,070,413; Kimoto et al United States Patent (USP) 4,929,979; People's United States Patent (USP)s such as Hirosawa 4,972,256; Kaplan United States Patent (USP) 4,977,521; Sakai United States Patent (USP) 4,979,027; Ng United States Patent (USP) 5,003,494; People's United States Patent (USP)s such as Katayama 5,008,950; People's United States Patent (USP)s such as Kimura 5,065,255; People's United States Patent (USP)s such as Osamu 5,051,842; People's United States Patent (USP)s such as Lee 5,012,333; People's United States Patent (USP)s such as Bowers 5,107,346; Telle United States Patent (USP) 5,105,266; People's United States Patent (USP)s such as MacDonald 5,105,469; And people's United States Patent (USP) 5,081,692. such as Kwon

Scan period, the technology of color balancing was disclosed in people such as Moore, United States Patent (USP) 5,049, and 984 and Davis, United States Patent (USP) 5,541 is in 645.

The color digital record is in case after gathering, the reproduction that is used to export when in most cases printing by various conversion or in video display or as conventional printed matter, seem happy color balancing image, and keep the color authenticity (fidelity) of carrying picture information.Scanning back is disclosed in people such as Giorgianny to the optimization technique that the signal that is loaded with image carries out conversion, and United States Patent (USP) 5,267 is in 030.People such as Giorgianny are at United States Patent (USP) 5,267, and the signal transformation technology of describing in 030 in conjunction with Fig. 8 together, is represented as the especially optimization technique of color balancing image when obtaining to watch.

The further example that those skilled in the art control colorful digital picture information ability is disclosed in Giorgianni and Madden, " digital color management ", Addison-Wesley, 1998.

The mode that the block scheme of Fig. 1 is provided by the picture information that is provided by color negative film element of the present invention is supposed to use.Adopt 2 pairs of color negative film elements of the present invention 1 of image scanner to carry out transmission scan through image mode exposure and photography washing processing.The scanning beam of most convenient is a beam of white light, it is after seeing through layer unit and through beam split behind the optical filtering, and picture record-ruddiness recording layer cell image writes down (R), green glow recording layer cell image record (G) and recorded in blue layer cell image record (B) thereby form independently.Substitute the light beam beam split, also can make indigo plant, green and red filter is sequentially crossing with light beam at each pixel position.In another kind of sweeping scheme, the indigo plant of separating, green and red beam are produced respectively by light emitting diode, can point to each pixel position.When adopting detector array, for example array charging coupling device (CCD) pursues picture element scan to element 1, perhaps adopt linear array (or row array) detector, when for example linear array CCD lines by line scan, produce the order of a kind of R, G and B image elements signal, can utilize the spatial positional information of scanner to proofread and correct this order.Signal intensity and positional information are transfused to workstation 4, and are electronic form R ', G ' and B ' with information translation, so they can be stored in any convenience in the storer 5.

In mobile imaging (motion image) industry, common way is to utilize the telecine conversion device to be converted to vision signal color negative film information.Have 2 types of telecine equipments the most general: (1) utilizes flying-spot scanner or (2) CCD of photomultiplier tube detectors, as sensor.The scanning beam that this kind device will pass color negative film at each pixel position is converted to voltage.Subsequently, provide signal Processing, thereby electric signal is reversed the positive image of acquisition.Signal is input to and forms image on the CRT monitor through amplifying and modulation then, perhaps records on the tape and stores.Though the simulation and the processing of digital image are all at the row of consideration, but preferred elder generation becomes digital form with signal and carries out conversion again, because present most computer all is digital, can be convenient to utilize common computer peripheral like this, for example tape, magnetic disc and CD.

Video monitor 6 is used to receive on request the digital image information of revising, R ", G " and B ", the picture information that can watch reception from workstation.If do not rely on the cathode-ray tube (CRT) of video monitor, available LCD panel and any other electron image viewing apparatus easily replace.Video monitor generally relies on picture opertaing device 3 to work, and 3 can comprise keyboard and cursor, so that make the workstation operating personnel be imported that transformation directive is revised shown video image and by any image of digital image information regeneration.

Any amended image all can be seen when they are incorporated into video display 6 and be stored in the memory storage 5.Amended picture information R " ', G " ' and B " ' can deliver to output unit 7 to generate the visual image that reproduces.Output unit can be any Write of traditional element easily, for example printing machine of thermal dye transfer, ink-jet, static, electric photograph, static, thermal dye sublimation or other types.Be printed onto on the platinum paper with CRT (cathode-ray tube (CRT)) and LED (light emitting diode), also at the row of consideration.This output unit can be used to control the exposure of traditional silver halide chromatics paper.Output unit is created a kind of output medium of watching with reproducing image 8 that is loaded with.Image in this output medium is only the final terminal user of confession and watches and pass judgment on the foundation that its noise (granularity), sharpness, contrast and colour balance are used just.Image on the video display also can finally be watched and estimates its noise, sharpness, colour gamut, colour balance, contrast and color reproduction (fidelity) for the terminal user, and can be used as image and transmit between the different departments of the global webpage of Internet.

Adopt the arrangement of Fig. 1 type, the image that comprises in the color negative film element of the present invention is converted to digital form earlier, handles, and causes the considerable form of seeing again, and whole process is according to people such as Giorgianni, United States Patent (USP) 5,267, and the program described in 030 is carried out.Color negative film recording materials of the present invention can with United States Patent (USP) 5,267, any proper method described in 030 is used.In a kind of preferred embodiment, people such as Giorgianni provide a kind of will " carry picture intelligence " and be converted to the method and the means of image transform and/or storage metering yardstick from R, the G of transmission scanner and B, and this kind measurement standard is corresponding to the reference picture generator tricolor signal of film or printing paper Write, thermal printer, video demonstration etc. for example.These metering numerical value will be corresponding to being the appropriate desired numerical value of color image that reproduces on above-mentioned device.For example, selection is the specific video display with reference to picture generator and selects the metering of intermediate image data as this R ' with reference to video display, G ' and B ' intensity adjustments signal (encoded radio), then for a certain input film, from scanner carry picture intelligence R, G and B will be converted into corresponding to being appropriate coding numerical value R ', G ' and the B ' that reproduces the desired data of this input imagery on the reference video display.Carry picture intelligence from R, G and B and to the derivation of the mathematic(al) manipulation of above-mentioned coding numerical value, produce one group of data.For reaching abundant sampling and cover the selected exposure figure of exposure scope demarcated, the exposure by pattern generator produces, and is input in the exposure device.This exposure device produces the three primary colors exposure on film, thereby generates a kind of resolution chart of being made up of about 150 colored pieces.Resolution chart can adopt the method for various suitable applicable cases to produce.These methods comprise: adopt exposure sources, for example sensitometer, adopt the output unit of color imaging equipment, record (descending) shines the image of the test object of known reflection coefficient with known luminaire, perhaps adopts the known method of photography to calculate three primary colors exposure numerical value.If adopt the input film of friction speed, red, the green and blue exposure of each film must be regulated rightly, so that the relative speed difference between the film is compensated.So every kind of film all accepts to be fit to the exposure of the suitable numerical value of its red, green and blue speed.Film after the exposure washes with chemical method.Read the film color piece with transmission scanner, and R, the G and the B that produce corresponding to each colored piece by the transmission density meter carry picture intelligence.Signal-numerical value the figure of coding numerical value generator produces RGB intensity-modulation signal, is fed into then with reference in the video display.Regulate R ', G ' and B ' the coding numerical value of every kind of test color,, can point out in fact that video display test color is consistent with the negative film color after positive test color or the washing processing until color-match equipment corresponding to instrument or observer.The conversion equipment generation is a kind of carries the conversion of picture intelligence numerical value to R ', G ' and B ' the coding numerical value of corresponding test color from R, the G relevant with film test color and B.

Be converted to the desired mathematical operation of intermediate data and form for R, G and B being carried picture intelligence by the order of matrix operation and enquiry form (LUT).

Referring to Fig. 2, in the preferred embodiment of the invention, it is the appropriate desired intermediate data numerical value of color image that reproduces on the reference output device that year picture intelligence R, the G of input and B change into according to following process, corresponds respectively to R ', G ' and B ' output and carries picture intelligence:

(1) R, G and B carry picture intelligence, corresponding to film transmissivity measured value, being used for receiving and store computer from the film scanner signal by one dimension enquiry form LUT1, are converted to corresponding density.

(2) carry out conversion by the matrix 1 that produces by conversion equipment subsequently from the density of step (1), carry picture intelligence in the middle of generating.

(3) density of step (2) randomly utilizes one dimension enquiry form LUT2 to make amendment, and the derivation principle of this form is that the neutral colour gamut density of input film is converted to reference to visual neutral colour gamut density.

(4) density of step (3) is changed by one dimension enquiry form LUT3, generates corresponding R ', G ' and the B ' output be sent to reference to output device and carries picture intelligence.

Know that each enquiry form is normally prepared for each input color.In one embodiment, can adopt 3 one dimension enquiry forms, each is respectively applied for the red, green and blue optical recording.In another embodiment, can adopt the multi-dimensional query form, for example be described in D ' Errico, United States Patent (USP) 4,941 is in 039.It is to be noted, above the output with reference to output device of step 4 carry picture intelligence and can take the code numerical value different with device, perhaps a picture intelligence is carried in this output still needs further adjusting, thereby becomes the code numerical value that is fit to concrete device.This kind adjusting can be finished by the combination of further matrixing or the conversion of one dimension enquiry form or this type of conversion, so that be ready to be sent to transmission, storage, printing rightly or adopt the output of their any step of regulation device demonstration to carry picture intelligence.

In the 2nd kind of preferred embodiment of the present invention, carry picture intelligence from R, the G of transmission scanner and B and be converted into a kind of image transform and/or storage metering yardstick, this metering yardstick is corresponding to single measurement and description with reference to picture record device and/or medium, and the metering numerical value of wherein all input medias is all corresponding to supposing that this is to absorb the three primary colors numerical value that the former scene of picked-up will produce under the identical condition of this scene with input media with reference to device and medium.For example, if be chosen to be specific color negative film with reference to image-recording medium, and intermediate image data measurement standard is chosen to be the RGB density measurement value with reference to film, then with regard to input color egative film of the present invention, from R, the G of scanner and B carry R ', G ' that picture intelligence is converted into and B ' density values will corresponding to, suppose this with reference to color negative film with the same terms of color negative film recording materials exposure of the present invention under the exposure visual numerical value that will produce.

Demarcated the selected exposure resolution chart of exposure scope for reaching abundant sampling and covering, the exposure by pattern generator produces, and is input in the exposure device.This exposure device produces the three primary colors exposure on film, thereby generates a kind of resolution chart of being made up of about 150 colored pieces.Resolution chart can adopt the method for various suitable applicable cases to produce.These methods comprise: adopt exposure sources, for example the output unit of sensitometer, employing color imaging equipment writes down and shines the image of the test object of known reflection coefficient with known luminaire, perhaps adopts the known method of photography to calculate three primary colors exposure numerical value.If adopt the input film of friction speed, red, the green and blue exposure of each film must be regulated rightly, so that the relative speed difference between the film is compensated.So every kind of film all accepts to be fit to the exposure of the suitable numerical value of its red, green and blue speed.Film after the exposure washes with chemical method.With transmission scanner read the film color piece in the R, the G that obtain each colored piece and B carry picture intelligence and by R ', G ' and the B ' density values of transmission density generation corresponding to each colored piece.The conversion equipment generation is a kind of carries picture intelligence numerical value to R ', the G ' of the corresponding test color of reference color negative film and the conversion of B ' density from R, the G relevant with film test color and B.In another kind of preferred embodiment, if be chosen to be specific color negative film with reference to image-recording medium, and the metering of intermediate image data is chosen to be this regulation R ' with reference to the step 2 of film, G ' and B ' intermediate density, then with regard to input color egative film of the present invention, from R, the G of scanner and B carry R ', G ' that picture intelligence is converted into and G ' intermediate density will corresponding to, suppose this with reference to color negative film with the same terms of color negative film recording materials exposure of the present invention under the exposure visual numerical value that will produce.

Therefore, each input film of demarcating according to the inventive method will be created in the numerical value that equals such on the possible extent: promptly, it reproduces the desired R ' of color image, G ' and G ' code numerical value rightly corresponding to the reference color negative film on the reference output device.Do not carry out conversion in the conversion that the film of Biao Dinging also can be used for deriving according to similar model film, transformation results will be similar to described above.

Be converted to the desired mathematical operation of intermediate data and form for R, the G of this preferred embodiment and B being carried picture intelligence by the order of matrix operation and one dimension enquiry form (LUT).Usually need provide 3 forms for 3 kinds of input colors.Know, also can finish with reference to conversion according to other embodiments, promptly adopt single mathematical computing and mathematical operation combination, implement by some calculation procedures by host computer, these steps include but not limited to, matrix algebra, the algebraic expression that relies on one or more years of picture intelligence and n-dimension LUT.In one embodiment, the matrix 1 of step 2 is 3 * 3 matrixes.In a more preferred embodiment, the matrix 1 of step 2 is 3 * 10 matrixes.In preferred embodiments, the one dimension LUT3 in the step 4 carries picture intelligence enforcement conversion according to the family curve of color photographic paper color photo paper to the centre, thereby reproduces normal colour positive image colour gamut.In another kind of preferred embodiment, the LUT3 of step 4 is according to that revise, more pleasant, and the visual colour gamut that for example has low visual contrast is carried picture intelligence to the centre and carried out conversion,

Because the complicacy of this type of conversion it should be noted that by R, G and B and finishes to the most handy usually three-dimensional LUT of the conversion of R ', G ' and G '.The three-dimensional LUT of reference can be according to J.D ' Errico at United States Patent (USP) 4,941, and 039 disclosure is made.

Know that when image was in electronic form, image processing was not limited to concrete variation described above.When image is in this kind form, also can adopt additional image transform, include but not limited to, standard scene balanced algorithm (determining correction), colour gamut conversion to density and colour balance according to one or more regional density in the egative film with the γ that amplifies the film under-exposure, the non-habitual that utilizes the number of turns and unintelligible shading or applicability contrast regulate, blood-shot eye illness alleviates and non-applicability or applicability granularity suppress.Have again, also can carry out technical conversion, varifocal, cut picture and make up with other images or carry out technical other known conversion image.In case image overcorrect has also been finished further to after image processing and the conversion, image just can be sent to a distant place or writes on the spot on various output unit by the electronics mode, include but not limited to the electronic signal memory device of silver halide film or paper Write, thermal printer, electric photographic printer, ink-jet printer, display monitor, CD CD, optics and magnetic and storage of technical known other types and display device.

In another embodiment of the present invention, can use people such as Arakawa at United States Patent (USP) 5,962,205 extract goods and method in described brightness and colourity sensitizing and image.

The preparation example

The following examples are used to illustrate that the typical case that the present invention uses blocks the synthetic of compound.

The D1-16 preparation

Epoxypropane (1,7.2mL, 105mmol), methane sulfinic acid sodium (9.19g, 90mmol) and monobasic sodium phosphate monohydrate (16.56g) in 100mL90 ℃ water, heat 18h.The solution cooling is then with 4 * 100mL ethyl acetate extraction.Extract is dry and simmer down to solid on sodium sulphate.2 yield is 6.42g (46mmol, 52%).

2 (3.32g, 24mmol), compound 3 (4.08g, 20mmmol) and dibutyltin diacetate (0.05ml) at 60ml 1, the solution in the 2-ethylene dichloride at room temperature stirred 7 days, crude product mixture is purified on silica gel by column chromatography, the yield of D-16 is 6.15g (18mmol, 90%), 80～82 ℃ of m.p. (fusing point), ESMS:ES+m/z343 (M+1,100%).The preparation of D-17

Sodium borohydride (3.95g, 104mmol) room temperature, 45min in the time mark part join compound 4 (9.11g be 50mmol) in the suspended matter in methyl alcohol (150mL).Add entry (50mL), distill out methyl alcohol.Residue is with extracted with diethyl ether; Extract is dry and simmer down to grease on sodium sulphate.5 yield is 8.85g (48 mmol, 96%).

5 (4.05g 22mmol), 3 (4.08g, 20 mmol) and the solution of 0.05 mL dibutyltin diacetate in methylene chloride (20mL), at room temperature stirs 20h.Reaction mixture dilutes with ether (100mL), and with the water aftertreatment, thereby obtain crude product, purify on silica gel by column chromatography then.The yield of D-17 is 5.49g (14mmol, 71%), m.p.149～151 ℃, ESMS:ES+m/z 389 (M+1,100%), ES-m/z 387 (M-1,35%).

Photograph embodiment

Described in washing processing condition such as the example.Unless indicate separately, after the development, remove silver halide by being immersed in the Kodak Flexicolor Fix solution without exception.Generally speaking, omit this step, with the increase on the density measurement value of acquisition about 0.2.The component of using in the example is as follows.The complete list that also comprises all chemical constitutions.

Silver salt dispersion SS-1:

The gelatin and the 6569g distilled water that in the reaction vessel that stirs, add the 431g lime treatment.Obtain solution comprises 214g benzotriazole, 2150g distilled water and 790g2.5mol NaOH (solution B).Potpourri in the reaction vessel is adjusted to 7.25 with pAg, pH to 8.00 by adding solution B, nitric acid and NaOH on demand.

0.54 the 4L solution of mol nitrate joins in the reaction vessel by 250 cc/min, by adding solution B simultaneously, makes pAg maintain 7.25.This process lasts till that liquor argenti nitratis ophthalmicus exhausts, and potpourri is by super centrifugal concentrating this moment.The silver salt dispersion that obtains comprises the fine grained of benzotriazole silver.

Silver salt dispersion SS-2:

The gelatin and the 6569g distilled water that in the reaction vessel that stirs, add the 431g lime treatment.Obtain solution comprises 320g1-phenyl-5-mercapto-tetrazole, 2044g distilled water and 790 g2.5 mol NaOH (solution B).The potpourri of reaction vessel is adjusted to 7.25 with pAg, pH to 8.00 by adding solution B, nitric acid and NaOH on demand.

0.54 4 L solution of mol nitrate join in the reaction vessel by 250 cc/min, by adding solution B simultaneously, make pAg maintain 7.25.This process lasts till that liquor argenti nitratis ophthalmicus exhausts, and potpourri is by super centrifugal concentrating this moment.The silver salt dispersion that obtains comprises the fine grained of 1-phenyl-5-mercapto-tetrazole.

Silver emulsion

The emulsion that uses in these examples all is the iodine silver bromide platy shaped particle that precipitates by technical known classic method.Following table 1 is listed various emulsion, with and content of iodine (all the other supposition are bromides), its size and the sensitizing dye that is used for giving photoreception of spectrum.All these emulsions are all handled by technical known chemical sensitization, thereby have best photonasty.

Table 1

Emulsion	Photoreception of spectrum	Content of iodine (%)	Diameter (μ m)	Thickness (μ m)	Dyestuff
Emulsion	Photoreception of spectrum	Content of iodine (%)	Diameter (μ m)	Thickness (μ m)	Dyestuff	????EY-1	Yellow	????1.3	????0.54	??0.084	????SY-1
????EY-2	Yellow	????4.1	????1.25	??0.137	????SY-1	????EY-1	Yellow	????1.3	????0.54	??0.084	????SY-1
????EY-2	Yellow	????4.1	????1.25	??0.137	????SY-1	????EY-3	Yellow	????2	????1.23	??0.125	????SY-1
????EY-4	Yellow	????2	????0.45	??0.061	????SY-1	????EY-3	Yellow	????2	????1.23	??0.125	????SY-1
????EY-4	Yellow	????2	????0.45	??0.061	????SY-1	????EY-5	Yellow	????2	???0.653	??0.093	????SY-1
????EM-1	Pinkish red	????1.3	????0.55	??0.084	SM-1+SM-2	????EY-5	Yellow	????2	???0.653	??0.093	????SY-1
????EM-1	Pinkish red	????1.3	????0.55	??0.084	SM-1+SM-2	????EM-2	Pinkish red	????4.1	????1.22	??0.111	?SM-1+SM-3
????EM-3	Pinkish red	????2	????1.23	??0.125	?SM-1+SM-3	????EM-2	Pinkish red	????4.1	????1.22	??0.111	?SM-1+SM-3
????EM-3	Pinkish red	????2	????1.23	??0.125	?SM-1+SM-3	????EM-4	Pinkish red	????2	????0.45	??0.061	?SM-1+SM-3
????EM-5	Pinkish red	????2	???0.653	??0.093	?SM-1+SM-3	????EM-4	Pinkish red	????2	????0.45	??0.061	?SM-1+SM-3
????EM-5	Pinkish red	????2	???0.653	??0.093	?SM-1+SM-3	????EC-1	Blue or green	????1.3	????0.55	??0.084	????SC-1
????EC-2	Blue or green	????4.1	????1.2	???0.11	????SC-1	????EC-1	Blue or green	????1.3	????0.55	??0.084	????SC-1
????EC-2	Blue or green	????4.1	????1.2	???0.11	????SC-1	????EC-3	Blue or green	????2	????1.23	??0.125	??SC-1+SC-2
????EC-4	Blue or green	????2	????0.45	??0.061	??SC-1+SC-2	????EC-3	Blue or green	????2	????1.23	??0.125	??SC-1+SC-2
????EC-4	Blue or green	????2	????0.45	??0.061	??SC-1+SC-2	????EC-5	Blue or green	????2	???0.653	??0.093	??SC-1+SC-2

Colour coupler dispersion CDM-1:

Prepare a kind of oil base (oil is as dispersion medium) colour coupler dispersion by traditional approach, comprise colour coupler M-1 and tricresyl phosphate, weight ratio 1: 0.5.

Colour coupler dispersion CDM-2:

Prepare a kind of colour coupler dispersion by traditional approach, comprise colour coupler M-2, do not contain additional permanent solvent.

Colour coupler dispersion CDC-1:

Prepare a kind of oil base colour coupler dispersion by traditional approach, comprise colour coupler C-1 and dibutyl phthalate, weight ratio 1: 2.

Colour coupler dispersion CDC-2:

Prepare a kind of oil base colour coupler dispersion by traditional approach, comprise colour coupler C-2 and dibutyl phthalate, weight ratio 1: 1.

Colour coupler dispersion CDY-1:

Prepare a kind of oil base colour coupler dispersion by traditional approach, comprise colour coupler Y-1 and dibutyl phthalate, weight ratio 1: 0.5.Structure

Example 1:

All coatings of example 1 all comprise single photographic layer, and according to the listed formulation of table 1-1, different is to change the developer that adds.All coatings all prepare on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Developer adopted the zirconia bead with in the aqueous slurry form of filling a prescription following 3 days.Every adding 1g developer adds 0.2g triisopropyl sodium naphthalene sulfonate, 10g water and 25 mL beads.After the grinding, filter and take out the zirconia bead.Slurry refrigeration is until use.

Table 1-1: basic recipe

Composition	Coating weight
Composition	Coating weight	Silver (from emulsion E-1)	????0.54g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Silver (from emulsion E-1)	????0.54g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Alkali releasing agent (trichloroacetic acid guanidine)	????0.81g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Alkali releasing agent (trichloroacetic acid guanidine)	????0.81g/m ²	Salicylamide	????0.86g/m ²
1-phenyl-5-mercapto-tetrazole	????0.32g/m ²	Salicylamide	????0.86g/m ²
1-phenyl-5-mercapto-tetrazole	????0.32g/m ²	The gelatin of lime treatment	????4.31g/m ²
Developer	????2.2?mmol/m ²	The gelatin of lime treatment	????4.31g/m ²

The coating that is formed into is subjected to 3.04 log Lux light sources by discontinuous wedge, the exposure after 3000K sentences Daylight 5A and the optical filtering of Wratten 2B optical filtering.Time shutter is 1s.After the exposure, coating is carried out heat flush processing by contact 20s with heating plate.Under various different plate temperature conditions, a large amount of film strip have been handled, in the hope of obtaining best silver processing conditions.Obtain 2 parameters in these these data:

A. initial temperature, T ₀:

Equal 0.5 the needed temperature of maximal density (Dmax) corresponding to generation.This temperature is low more, illustrates that the developer activity is high more, and is good more.

B. peak value resolution, D _p:

Under the best plate temperature, peak value is differentiated corresponding to being worth down:

D_{p} = \frac{D_{\max} - D_{\min}}{D_{\min}}

D _pNumerical value is high more, and the signal to noise ratio (S/N ratio) that developer produces is high more, good more.

Table 1-2 provides the result of the coating (or coating) of example 1 use.Listed project is developer, initial temperature T ₀And relative resolution, D _pThe Comparative Examples developer is technical known material.

Table 1-2

Coating	Developer	????T ₀(℃)	????D _p
Coating	Developer	????T ₀(℃)	????D _p	C-1-1 (Comparative Examples)	????DC-1	????191	????0.23
C-1-2 (Comparative Examples)	????DC-2	????141	????3.98	C-1-1 (Comparative Examples)	????DC-1	????191	????0.23
C-1-2 (Comparative Examples)	????DC-2	????141	????3.98	I-1-1 (the present invention)	????D-17	????144	????5.55

This shows to show, developer of the present invention equates with the Comparative Examples developer or initial temperature while preferably producing, and can produce the peak value resolution of obvious improvement.

Example 2

Following example is implemented according to the example that is similar to the front, and different is that alkali releasing agent (trichloroacetic acid guanidine) has been cancelled from coating formula.The formulated that all coating examples are all listed according to following table 2-1 changes being to change the developer that adds.Developer adding method is identical with example 1.All coatings all prepare on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Table 2-1

Composition	Coating weight
Composition	Coating weight	Silver (from emulsion E-1)	????0.54g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Silver (from emulsion E-1)	????0.54g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Salicylamide	????0.86g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Salicylamide	????0.86g/m ²	1-phenyl-5-mercapto-tetrazole	????0.32g/m ²
The gelatin of lime treatment	????4.31g/m ²	1-phenyl-5-mercapto-tetrazole	????0.32g/m ²
The gelatin of lime treatment	????4.31g/m ²	Developer	????2.2?mmol/m ²

The coating that is formed into is subjected to 3.04log Lux light source by discontinuous wedge, the exposure after 3000K sentences Daylight 5A and the optical filtering of Wratten 2B optical filtering.Time shutter is 1s.After the exposure, coating is carried out heat flush processing by contact 20s with heating plate.Under various different plate temperature conditions, a large amount of film strip have been handled to find out best silver processing conditions.Method according to example 1 is measured 2 sensitization parameters.The parameter that obtains is presented among the table 2-2.

Table 2-2

Coating	Developer	????T ₀(℃)	????D _p
Coating	Developer	????T ₀(℃)	????D _p	C-2-1 (Comparative Examples)	????DC-1	????164	????3.61
C-2-2 (Comparative Examples)	????DC-2	????170	????3.20	C-2-1 (Comparative Examples)	????DC-1	????164	????3.61
C-2-2 (Comparative Examples)	????DC-2	????170	????3.20	I-2-1 (the present invention)	????D-28	????140	????6.49
I-2-2 (the present invention)	????D-29	????164	????5.40	I-2-1 (the present invention)	????D-28	????140	????6.49

This shows to show that developer of the present invention can provide low initial temperature that the peak value resolution of remarkable improvement can be provided simultaneously.

Example 3

Following example is implemented according to the example that is similar to the front, and different is that the developer and the coating formula of adding change.The crystallization developer that adds prepares according to following ball milling program.The developer, 0.15g polyvinyl pyrrolidone, 8.85g distilled water and the 10 mL zirconia beads that in 10g sample altogether, add the 1g combination.Slurry ball milling 24h.After the grinding, the zirconia bead takes out by filtering.Slurry refrigeration is until use.

The coating example wherein changes the developer group that is added by change and constitutes by the formulation that table 3-1 lists.The pH regulator of coating is to 6.0 unified numerical value.All coatings all prepare on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Table 3-1

Composition	Coating weight
Composition	Coating weight	Silver (from emulsion E-1)	????0.86g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Silver (from emulsion E-1)	????0.86g/m ²
Silver (from silver salt SS-1)	????0.54g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Salicylamide	????1.08g/m ²	Colour coupler M-1 (from colour coupler dispersion CDM-1)	????0.54g/m ²
Salicylamide	????1.08g/m ²	1-phenyl-5-mercapto-tetrazole	????0.32g/m ²
The gelatin of lime treatment	????6.09g/m ²	1-phenyl-5-mercapto-tetrazole	????0.32g/m ²
The gelatin of lime treatment	????6.09g/m ²	Developer	????1.08g/m ²
Melt pH	????6.0	Developer	????1.08g/m ²

The exposure of the coating that is formed into after being subjected to 5500K, 2.40 log Lux light sources and Wratten 2B optical filtering and filtering by discontinuous wedge.Time shutter is 10s.After the exposure, coating is carried out heat flush processing by contacting with heating plate.Fresh picture resolution and high humility raw material shelf characteric at coating (coating) are assessed.It is minimum density than coating behind the minimum density of comparatively fresh coating and the placement 24h in the heated oven of 50 ℃ and 80% relative humidity that high humility is preserved test.This experimental result is stated among the table 3-2.

Table 3-2

Coating	Developer	T _{Washing processing}℃	Fresh D _p	?RSK ΔD _min
Coating	Developer	T _{Washing processing}℃	Fresh D _p	?RSK ΔD _min	C-3-1 (Comparative Examples)	????DC-5	????180	There is not image	-
C-3-2 (Comparative Examples)	????DC-2	????170	??0.90	??0.20	C-3-1 (Comparative Examples)	????DC-5	????180	There is not image	-
C-3-2 (Comparative Examples)	????DC-2	????170	??0.90	??0.20	C-3-3 (Comparative Examples)	????DC-6	????160	??2.33	??0.67
C-3-4 (Comparative Examples)	????DC-7	????180	??0.56	??-	C-3-3 (Comparative Examples)	????DC-6	????160	??2.33	??0.67
C-3-4 (Comparative Examples)	????DC-7	????180	??0.56	??-	C-3-5 (Comparative Examples)	????DC-3	????170	??0.63	??0.15
C-3-6 (Comparative Examples)	????DC-4	????170	??2.11	??0.45	C-3-5 (Comparative Examples)	????DC-3	????170	??0.63	??0.15
C-3-6 (Comparative Examples)	????DC-4	????170	??2.11	??0.45	C-3-7 (Comparative Examples)	????DC-8	????180	??0.25	??-
I-3-1 (the present invention)	????D-16	????170	??1.38	??0.02	C-3-7 (Comparative Examples)	????DC-8	????180	??0.25	??-
I-3-1 (the present invention)	????D-16	????170	??1.38	??0.02	I-3-2 (the present invention)	????D-28	????150	??2.90	??0.25

This table clearly illustrates that the present invention blocks developer to have than the fresh picture resolution of Comparative Examples excellence and the balance between the high humility raw material bin stability.The low-down coating of resolution can not produce is enough to write down the density that high humility is preserved signal.

Example 4

Following example comprises the coating according to the method preparation that is similar to example 3.The change that formulation for coating material relates to is following pointed.

The formulation that coating example according to the form below 4-1 provides.4 kinds of developers of the present invention have been assessed.Formulation is coated on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Table 4-1

Composition	Coating weight
Composition	Coating weight	Silver (from emulsion E-1)	????0.86g/m ²
Colour coupler C-2 (from colour coupler dispersion CDC-2)	????1.08g/m ²	Silver (from emulsion E-1)	????0.86g/m ²
Colour coupler C-2 (from colour coupler dispersion CDC-2)	????1.08g/m ²	Developer	????0.86g/m ²
Antifoggant AF-1	????15g/m ²	Developer	????0.86g/m ²
Antifoggant AF-1	????15g/m ²	Hardener B-1	????58g/m ²
The gelatin of lime treatment	????3.23g/m ²	Hardener B-1	????58g/m ²
The gelatin of lime treatment	????3.23g/m ²	Developer	????0.86g/m ²

The coating that is formed into be subjected to 5500K, the 2.40 log Lux light sources exposure after Wratten 2B optical filtering filters by discontinuous wedge.Time shutter is 1/50s.After the exposure, coating is immersed among activator A or the B and reaches 15s, and is laminated to and comprises 1.08g/m ²On the reception coating of gelatin.Then, this film combination bag is realized washing processing by contact 10s with 50 or 70 ℃ of heating plates, then the assessment image.From (corresponding to) block the cyan dye image that color developer D-28, D-38 and D-39 (sample) observe negativity. from blocking on the black-and-white development agent D-30, observe silver color territory image.The result sums up in table 4-2. and the density of measuring from every kind of coating is Status M red density.The concentration of activator A:(in distilled water)

2.65% sodium carbonate

0.63% sodium bicarbonate

0.1% sodium bromide

0.2% sodium sulphite activator B:74.5 g/L KOH

The 8g/L potassium sulfite

The 2g/L potassium bromide

Table 4-2

	Developer	Activator/time/temperature	D _max
I-4-1	D-28	A/10"/70C	0.53
		A/10"/90C	1.40
		B/10"/50C	0.40
		B/10"/70C	2.25
		B/10"/90C	4.92
		I-4-2	D-38	A/10"/50C	0.09
A/10"/70C	0.89
A/10"/90C	1.20
I-4-3	D-39			A/10"/70C	0.56
		A/10"/90C	0.92
		B/10"/70C	0.43
		B/10"/90C	1.26
		I-4-4	D-30	A/10"/50C	0.21
A/10"/70C	0.24
A/10"/90C	0.26
B/10"/50C	0.12
B/10"/70C	0.19
B/10"/90C	0.29

Example 5

Following example class is similar to previous examples, and different is to block developer and take out from contain emulsion layer, and be placed in the independent laminated layer.Coating is similarly to contain the activation of alkaline bath liquid.

The formulation that emulsion coating example is listed according to following table 5-1.Coating is made up of emulsion layer and lip-deep gelatin cuticular layer thereof.Formulation is coated on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Table 5-1

Composition	Coating weight
Composition	Coating weight	Silver (from emulsion E-1)	????0.86g/m ²
Colour coupler C-2 (from colour coupler dispersion CDC-2)	????1.08g/m ²	Silver (from emulsion E-1)	????0.86g/m ²
Colour coupler C-2 (from colour coupler dispersion CDC-2)	????1.08g/m ²	Antifoggant AF-1	????15mg/m ²
The gelatin of lime treatment	????3.23g/m ²	Antifoggant AF-1	????15mg/m ²
The gelatin of lime treatment	????3.23g/m ²	The cuticular layer gelatin	????0.43g/m ²
Hardener B-1	????66mg/m ²	The cuticular layer gelatin	????0.43g/m ²

Laminated layer is made up of developer and gelatin, and is coated with according to the prescription that following table 5-2 lists.Developer quality coating weight is proofreaied and correct at the equivalents of molecular weight and the agent of per molecule released development.Formulation is coated on poly-(ethylene glycol terephthalate) support of 7 mil thick.

Table 5-2

Composition	Coating weight
Composition	Coating weight	Developer	????0.67me./m ²
The gelatin of lime treatment	????1.61g/m ²	Developer	????0.67me./m ²
The gelatin of lime treatment	????1.61g/m ²	Hardener B-1	????29mg/m ²

The coating that is formed into be subjected to 5500K, the 2.40 log Lux light sources exposure after Wratten 2B optical filtering filters by discontinuous wedge.Time shutter is 1/50s.After the exposure, coating is immersed among activator A or the B and reaches 15s, and is laminated on the coating that comprises developer.Then, this film combination bag is realized washing processing by contact 15s with 50 or 70 ℃ of heating plates, then the assessment image.From the situation of all developers, observe the cyan dye image of negativity.The result sums up in table 5-3.The density that every kind of coating is measured is Status M red density.

The concentration of activator C:(in distilled water)

5.0% sodium carbonate

0.14 the concentration of Triton x-200E surfactant activator D:(in distilled water)

5.0% potassium hydroxide

0.20 Triton X-100 surfactant

Table 5-3

Coating	Developer	Activator/time/temperature	??D _min	???D _max	??D _p
Coating	Developer	Activator/time/temperature	??D _min	???D _max	??D _p	??C-5-1	DC-6 (coating weight=1.17g/m ²)	??C/15”/70C	??0.06	??0.27	??3.5
	??D/15”/50C	??0.10	??0.17	??0.7		??C-5-1		??C/15”/70C	??0.06	??0.27	??3.5
	??D/15”/50C	??0.10	??0.17	??0.7	??I-5-1	D-28 (coating weight=0.86g/m ²)		??C/15”/70C	??0.07	??0.43	??5.1
	??D/15”/50C	??0.03	??0.23	??7.0	??I-5-1			??C/15”/70C	??0.07	??0.43	??5.1
	??D/15”/50C	??0.03	??0.23	??7.0	??1-5-2		D-38 (coating weight=1.09g/m ²)	??C/?15”/70C	??0.13	??0.84	??5.5
					??1-5-2			??C/?15”/70C	??0.13	??0.84	??5.5

Activator is used in employing always and under washing processing condition of equal value, 2 kinds of developers of the present invention are compared aspect density formation more excellent with the Comparative Examples developer.Picture resolution, developer of the present invention in all cases is all better.

Example 6

Made multilayer imageable element shown in Fig. 6-1, be enough to satisfy the image be used to be intended to take the quick imageable element of panchromatic photo-thermal of real scene and form ability in order to show that developer of the present invention can provide.

Fig. 6-1

The surface cuticula	????0.16g/m ²Gelatin 0.25g/m ²Hardener-1
The surface cuticula	????0.16g/m ²Gelatin 0.25g/m ²Hardener-1	Yellow photographic layer	????0.39g/m ²The iodine silver bromide is from emulsion EY-1 0.6g/m ²The iodine silver bromide is from emulsion EY-2 0.32g/m ²Benzotriazole silver is from SS-1 0.32g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.54g/m ²Colour coupler Y-1 is from dispersion CDY-1 0.86g/m ²Developer D-28 0.86g/m ²Salicylamide 4.3g/m ²Gelatin

Green photographic layer	????0.39g/m ²The iodine silver bromide is from emulsion EM-1 0.6g/m ²The iodine silver bromide is from emulsion EM-2 0.32g/m ²Benzotriazole silver is from SS-1 0.32g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.54g/m ²Colour coupler M-1 is from dispersion CDM-1 0.86g/m ²Developer D-28 0.86g/m ²Salicylamide 4.3g/m ²Gelatin
Green photographic layer		Red photographic layer	????0.39g/m ²The iodine silver bromide is from emulsion EC-1 0.6g/m ²The iodine silver bromide is from emulsion EC-2 0.32g/m ²Benzotriazole silver is from SS-1 0.32g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.54g/m ²Colour coupler Y-1 is from dispersion CDC-1 0.86g/m ²Developer D-28 0.86g/m ²Salicylamide 4.3g/m ²Gelatin
Support	Polyethylene terephthalate (7 mil thick)	Red photographic layer

Formed coating is subjected to 5500K, the exposure of 2.40 log Lux light sources after Wratten 2B optical filtering filters by discontinuous wedge.Time shutter is 0.1s.After the exposure, the coating coating is finished heat flush processing by contact 20s with 145 ℃ heating plate.Subsequently, coating reaches photographic fixing by soak 2 min at 15 ℃ in the Flexicolor stop bath.Utilize status M colour curve to read green grass or young crops, magenta and yellow density, the density of acquisition is provided in the table below among the 6-1.All form quite plentiful visual distribution density this point as can be seen from all 3 kinds of Color Channels, these coatings can be used as useful photograph component and absorb polychrome information.

Table 6-1

Record	??Dmin	??Dmax
Record	??Dmin	??Dmax	Blue or green	????0.58	????1.43
Pinkish red	????0.8	????2.12	Blue or green	????0.58	????1.43
Pinkish red	????0.8	????2.12	Yellow	????0.64	????1.68

The film element of this example further is encased in again in the single lens reflex camera that is equipped with 50 mm/f1.7 camera lenses.The exposure control of camera is set in ASA100, and takes live scene with this photograph component.Element is by developing at 145 ℃ of heating 20s, and this element forms clear and legible negativity color image after soaking in the Flexicolor stop bath.

Formed image scans with Kodak PhotoCD scanner.So the digital image file that obtains is loaded into Adobe Photoshop (in the 5.0.2 version (software)), utilizes this software that colour gamut and colourity are carried out digital modifications, thereby changes acceptable image into.This image utilizes computer monitor to show for watching with the soft copy form.Then, this image file is sent on Kodak 8650 dye sublimation printers (printer), thereby is converted to the hard copy output that to accept quality.This has showed the application of element in complete imaging chain that comprises The compounds of this invention.

Example 7:

Made multilayer imageable element shown in Fig. 7-1, be enough to satisfy the image be used to be intended to take the quick imageable element of panchromatic photo-thermal of real scene and form ability in order to show that developer of the present invention can provide.The sandwich type element of this example does not need wet washing processing step just can produce image.

Fig. 7-1

The surface cuticula	????0.11g/m ²Gelatin 0.32g/m ²Hardener-2
The surface cuticula	????0.11g/m ²Gelatin 0.32g/m ²Hardener-2	Yellow fast	????0.54g/m ²The iodine silver bromide is from emulsion EY-3 0.17g/m ²Benzotriazole silver is from SS-1 0.17g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.29g/m ²Colour coupler Y-1 is from dispersion CDY-1 0.46g/m ²Developer D-28 0.46g/m ²Salicylamide 2.3g/m ²Gelatin
Yellow at a slow speed	????0.27g/m ²The iodine silver bromide is from emulsion EY-4 0.16g/m ²The iodine silver bromide is from emulsion EY-5 0.15g/m ²Benzotriazole silver is from SS-1 0.15g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.25g/m ²Colour coupler Y-1 is from dispersion CDY-1	Yellow fast

	????0.40g/m ²Developer D-28 0.40g/m ²Salicylamide 2.0g/m ²Gelatin
		Yellow filter layer	????0.08g/m ²SY-2 ????1.07g/m ²Gelatin
Pinkish red fast	????0.54g/m ²The iodine silver bromide is from emulsion EM-3 0.17g/m ²Benzotriazole silver is from SS-1 0.17g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.29g/m ²Colour coupler M-2 is from dispersion CDM-2 0.46g/m ²Developer D-28 0.46g/m ²Salicylamide 2.3g/m ²Gelatin	Yellow filter layer	????0.08g/m ²SY-2 ????1.07g/m ²Gelatin
Pinkish red fast		Yellow at a slow speed	????0.27g/m ²The iodine silver bromide is from emulsion EM-4 0.16g/m ²The iodine silver bromide is from emulsion EM-5 0.15 g/m ²Benzotriazole silver is from SS-1 0.15g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.25g/m ²Colour coupler M-2 is from dispersion CDM-2 0.40g/m ²Developer D-28 0.40g/m ²Salicylamide 2.0g/m ²Gelatin
The middle layer	????1.07g/m ²Gelatin	Yellow at a slow speed
The middle layer	????1.07g/m ²Gelatin	Blue or green fast	????0.54g/m ²The iodine silver bromide is from emulsion EC-3 0.17g/m ²Benzotriazole silver is from SS-1 0.17g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.29g/m ²Colour coupler C-1 is from dispersion CDC-1 0.4g/m ²Developer D-28 0.46g/m ²Salicylamide 2.3g/m ²Gelatin
Blue or green at a slow speed	????0.27g/m ²The iodine silver bromide is from emulsion EC-4 0.16g/m ²The iodine silver bromide is from emulsion EC-5 0.15g/m ²Benzotriazole silver is from SS-1	Blue or green fast

	????0.15g/m ²Silver-1-phenyl-5-mercapto-tetrazole is from SS-2 0.25g/m ²Colour coupler C-1 is from dispersion CDC-1 0.40g/m ²Developer D-28 0.40g/m ²Salicylamide 2.0g/m ²Gelatin
		Antihalation layer	????0.05g/m ²Carbon 1.6g/m ²Gelatin
Support	Polyethylene terephthalate (7 mil thick)	Antihalation layer	????0.05g/m ²Carbon 1.6g/m ²Gelatin

The coating that is formed into be subjected to 5500K, the 1.8 log Lux light sources exposure after Wratten 2B optical filtering filters by discontinuous wedge.Time shutter is 0.1s.After the exposure, the coating coating is finished heat flush processing by contact 20s with 145 ℃ heating plate.Cyan, magenta and sodium yellow density utilize Status M colour curve to read, thereby obtain as the contained density of following table 7-2.Be clear that from these density values this coating can be used as useful photograph component and takes polychrome information.

Table 7-2

Record	??Dmin	??Dmax
Record	??Dmin	??Dmax	Blue or green	????0.38	????1.47
Pinkish red	????0.72	????2.65	Blue or green	????0.38	????1.47
Pinkish red	????0.72	????2.65	Yellow	????0.68	????1.80

The film element of example 5 further is encased in again in the single lens reflex camera that is equipped with the 50mm/f1.7 camera lens.The exposure of camera control is set in ASA100, and on said elements without taking photos by using flashlights indoor live scene.After this element is no longer done any processing to element and is handled by developing at 145 ℃ of heating 20s.

Formed image scans with Nikon LS2000 film scanner.So the digital image file that obtains is loaded into Adobe Photoshop (in the 5.0.2 version), utilizes this software that colour gamut and colourity are carried out digital modifications, thereby changes acceptable image into.This image utilizes computer monitor to show with the soft copy form.Then, this image file is sent on the Kodak8650 dye sublimation printer (printer), thereby is converted to the hard copy output that to accept quality.This has showed the application of element in complete imaging chain that comprises The compounds of this invention.

Example 8:

In simulation system, measure to investigate the deoppilation dynamics of developer of the present invention.Obtain relevant dynamic (dynamical) information with 2 kinds of independent technology.

1.0.1 mM blocks developer D-n at methyl sulfoxide (DMSO, the anhydrous 99.8+9% of Aldrich), at 130 ℃ or other design temperatures, heat in nitrogen atmosphere.Follow the tracks of the disappearance of blocking developer as follows: at the sample of branch quantity such as different time takes out at interval, cooling rapidly uses high-pressure liquid chromatography (HPLC) to analyze then in cooling bath.So, obtain relevant deoppilation reaction rate constants (k) and half life period (t _1/2).

2. also can monitor pyrolytic reaction by surveying the color developer that discharges as follows: the reaction solution among the DMSO of taking-up aliquot, the color developer that order discharges is under the pH10 condition, and C-3 is converted into dyestuff by colour coupler.Dye quantity in the 1cm sample cell, sentence the spectrophotometer quantitative test at～568nm, so just can obtain reaction rate constants.

Typical consequence is provided in the table below among the 8-1.As can be seen, no matter blocking developer, the present invention adopt which kind of method all can obtain the t lower than Comparative Examples _1/2Numerical value.t _1/2Numerical value is low, shows that developer is more active, thereby satisfying.

Table 8-1

Block developer	????t _1/2, mm method 1	????t _1/2, min method 2
Block developer	????t _1/2, mm method 1	????t _1/2, min method 2	DC-3 (Comparative Examples)	????6.83	????7.60
DC-4 (Comparative Examples)	????20.16	????18.2	DC-3 (Comparative Examples)	????6.83	????7.60
DC-4 (Comparative Examples)	????20.16	????18.2	D-6 (the present invention)	????0.944	????0.893
D-16 (the present invention)	????0.587	????0.722	D-6 (the present invention)	????0.944	????0.893
D-16 (the present invention)	????0.587	????0.722	D-28 (the present invention)	??-	????0.45

Claims

1. an imageable element comprises the imaging layer, and this layer has the structure I compound that interrelates with it: Wherein:

PUG takes a picture to go up useful group;

LINK1 is to be connected base with LINK2;

TIME is a timing group;

L is 0 or 1;

M is 0,1 or 2;

N is 0 or 1;

Y is C, N, O or S;

X replaces or unsubstituted aromatic yl group or electron withdraw group;

W is hydrogen, halogen or replacement or unsubstituted alkyl, naphthenic base, aryl or heterocyclic group, perhaps W can with T or R ₁₂Combine and constitute a ring, w is 0～3 when Y is C, w is 0～2 when Y is N, w is 0～1 when Y is O or S, these 2 W can constitute a ring altogether when w is 2,2 W groups can constitute a ring altogether when w is 3, and perhaps 3 W groups can constitute an aromatic yl group or dicyclo substituting group altogether.

A be 1 or when X is divalence a be 1 or 2; And

B is 1 when X is divalence, and b is 0 when X is monovalence.

2. the imageable element of claim 1, wherein PUG be colour coupler, development restrainer, bleaching accelerator, bleaching inhibitor, the agent of inhibitor released development, dye matrix, developer, silver ion fixer, electron transfer agent, ag halide solvent, silver halide complexing agent, reductone, image toners, visual pre-service and aftertreatment stabilizing agent, rigidizer, hardener, fogging agent, ultra-violet absorber, nucleator and chemistry or spectral sensitizer, desensitiser, surfactant and precursor thereof,

3. the imageable element of claim 1 or claim 2, wherein LINK has the structure II: Wherein

X represents carbon or sulphur;

P is 1 or 2;

Z represents carbon, oxygen or sulphur;

R is 0 or 1;

4. the imageable element of any one in the above claim, wherein TIME is a timing group, is selected from the group that (1) utilizes nucleophilic aromatic substitution reaction; (2) utilize the group of hemiacetal cracking reaction; (3) utilize along the group of the electron transfer reaction of conjugated system; And (4) utilize the group of intramolecular nucleophilic substitution reaction.

5. the imageable element of any one in the above claim, wherein the compound of structure I has the structure III:

Wherein:

X replaces or unsubstituted aromatic yl group or electron withdraw group;

Y is C, N, O or S;

A is 1 when X is monovalence, and a is 1 or 2 when X is divalence; And

B is 0 when X is monovalence, and b is 1 when X is divalence.

W is hydrogen or halogen or replacement or unsubstituted alkyl, naphthenic base, aryl or heterocyclic group, perhaps W can constitute a ring altogether with T, w is 0～3 when Y is C, w is 0～2 when Y is N, w is 0～1 when Y is O or S, these 2 W can constitute a ring altogether when w is 2, and 2 W groups can constitute a ring altogether when w is 3, and perhaps 3 W groups can constitute an aromatic yl group or dicyclo substituting group altogether.

6. the imageable element of claim 1, it is the quick imageable element of photo-thermal, photo-sensitive cell or thermal imaging element.

7. image formation method comprises that the imageable element of any one carries out step of developing in the above claim of image mode exposure.

8. the method for claim 7, wherein said development comprise the time of Temperature Treatment about 0.5～about 60 ss of element between about 90 ℃～about 180 ℃ of described image mode exposure.

9. image formation method comprises the imageable element of any one in the image mode exposure and the above claim of developing is scanned, the step of reproducing with the 1st electron image that forms described image mode exposure.

10. image formation method, comprise through the image mode exposure, develop and the claim 1～6 of scanning in any one formed the 1st electron image of imageable element reproduce and carry out digitizing to form the step of digital image.

11. an image formation method comprises the following steps:

The imageable element of any one carries out thermal development to form the image that develops in the claim 1～6 of image mode exposure;

Described developed image scans, and reproduces so that form the 1st electron image by described developed image;

Described the 1st electronical record is carried out digitizing to form digital image;

Revising described digital image reproduces to form the 2nd electron image; And

Store, transmit, print or show that described the 2nd electron image reproduces.