CN1166620A - Silver halide photographic material - Google Patents

Silver halide photographic material Download PDF

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Publication number
CN1166620A
CN1166620A CN 96112623 CN96112623A CN1166620A CN 1166620 A CN1166620 A CN 1166620A CN 96112623 CN96112623 CN 96112623 CN 96112623 A CN96112623 A CN 96112623A CN 1166620 A CN1166620 A CN 1166620A
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expression
silver halide
particle
emulsion
layer
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CN 96112623
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CN1100284C (en
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山下清司
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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Abstract

Disclosed is a silver halides photographic photosensitive material, comprising a photosensitive silver halides emulsion layer arranged on a support body, a top surface protective layer and a hydrophilic colloid layer which is different from the other two layers. The silver halides particles which are contained in at least one type emulsion of the silver halides emulsion layer are flat particles which account for at least 50 percent of the whole projection area, with the content of silver chloride more than 20 mol percent. The shape ratio of the flat particles is more than 2. In the hydrophilic colloid layer outside the emulsion layer and the surface protective layer, the meanings of R<10>-R<18> are illustrated in the instruction and are contained in formula (I) which demonstrates the non-leachability solid particle decentralized dye formula. Sulphydryl compound with water soluble groups is contained in at least one layer of the hydrophilic colloid of the support body.

Description

Silver halide photographic sensitive material
The invention relates to silver halide photographic sensitive material, particularly when handling black and white with automatic processing machine and use silver halide photographic sensitive material, in low liquid waste processing, the pollution for the treatment of fluid and follow the fault when handling few, the performance that adapts to darkroom light is extremely excellent, and gives the technology of the infrared sensor high detection efficient that various transfer mechanisms are used.
The present invention is also about silver halide photographic sensitive material with to the method for its processing, particularly about being suitable for handling silver halide photographic sensitive material that medical X-ray takes a picture and to the method for its processing in extremely low liquid waste treatment system.
In recent years, also more and more higher along with the requirement of fast processing to reducing the additional requirement for the treatment of fluid.For this reason, Tu Yinliang is reduced and become main tendency.At this moment,, and can not detect the position of photosensitive material, become and carry bad reason owing to the red place sensor light-proofness that is arranged in the induction system that contains automatic processing machine reduces.
Though special opening discloses a kind of method by using certain infrared ray absorbing pigment improvement to detect in clear 62-299959 number, but this method must make the silver halide particle adsorpting pigment, this had both increased the burden in the treatment process (particularly photographic fixing), make the coating operation become complicated, on the black and white material that has the visibility region absorption of pigment own, observation silver image, problem occurred simultaneously.Though the special a kind of bad method that detects of improving that discloses for clear 63-131135 number of opening, be to resemble the light diffusing particles of utilizing above-mentioned as the silver halide particle, but because by only utilizing refractive index, reduced screening effect to detecting, under the situation of silver halide particle, owing to increased the burden of stop bath, reducing the very sternness that becomes under the situation of replenishing liquid and fast processing.
In order to adapt to fast processing, developed the good solid disperse dye of decolourising property in processing in recent years.
The sensor dyestuff must meet the following conditions:
(1) must have corresponding infrared sensor and suitably divide light absorption.
(2) should have the not active of photograph chemistry.Promptly the performance to the halogenation photographic emulsion can not produce harmful effects such as sensitivity, vision degradation or image fog.
(3) should be residual on the sensitive photographic material after the processing harmful be painted.
(4) in solution or in the sensitive photographic material, aging stability will be got well.
Though particularly for satisfying the condition of (3), and can use the decolourising property dyestuff, but when using the decolourising property dyestuff, but can not satisfy so-called rapid processing and reduce the requirement that replenishes treating fluid, and because the decolourising property dyestuff is diffused in other layer repeatedly, so can not satisfy the condition of (2), the present situation of Here it is decolourising property dyestuff.
Be diffused into the dyestuff of other layer and give the dyestuff that in sealer, adds earlier, further can cause pollution during duplicating to the platen of the transfer mechanism that contact with photographic material with on screen intensifier paper.
About the high tabular particle of silver chloride content, prior art has a lot.As the tabular particle example that has (111) face on principal plane, can enumerate following patent document: special public clear 64-8326 number, special public clear 64-8325 number, special public clear 64-8324 number, spy are opened flat 1-250943 number, special fair 3-14328 number, special fair 4-81782 number, special fair 5-40298 number, special fair 5-39459 number, special fair 5-12696 number and spy and are opened clear 63-213836 number, spy and open clear 63-218938 number, spy and open clear 63-281149 number, spy and open clear 62-218959 number.
Can enumerate as the tabular particle prior art that on principal plane, has (100) face and to open flat 5-204073 number, spy the spy and open clear 51-88017 number, spy and patent document such as open clear 63-24238 number.Open in flat 6-059360 number relevant for the { record of 100} flat board that contains silver chloride the spy.
In these records, only not for the record that shows extremely excellent photographic property in making up with Infrared dyes.
This situation is arranged in recent years, and in medical field, from the viewpoint in environmental protection, saving space, strong request reduces the liquid waste processing amount.For this reason,, attempt to increase the development main ingredient in the developer solution and the amount of auxiliary development main ingredient, improve the pH value of developer solution as essential its activity that improves for the treatment of fluid.
Yet we think owing to the activity that improves developer solution is easy to take place oxidation deterioration, make the Treatment Stability variation, and in the improvement to developer solution only, there are critical value in extremely low additionalization and the low waste liquidization of developer solution.
As the development main ingredient of black-and-white development, known to have and used new development main ingredient ascorbic acid to replace the technology of the p-dihydroxy-benzene of usefulness in the past.The spy open flat 4-270343 number, the spy opens in flat 6-019069 number that concrete disclosing arranged.
Wish to occur extremely low additionalization of developer solution and be suitable for the high such photosensitive material of new developer solution Treatment Stability.
So in the automatic processing machine disposal system, the hope more urgent than the past is miniaturization, the low power consumptionization that makes the fast processing automatic processing machine.In the photosensitive material that drying washing was handled, though generally be to utilize hot blast to make the method for water evaporates, improve the film hardness of photosensitive material, water cut is suppressed to low-levelly when washing, and is favourable to the rapid draing photosensitive material.
, when improving the film hardness of photosensitive material, in above-mentioned disposal route, because the photographic property of photosensitive material significantly worsens, muting sensitivityization and area with high mercury video picture are insufficient, and cause that contrast dies down.
Therefore, first purpose of the present invention provides a kind of silver halide photographic sensitive material, use the few silver halide photographic sensitive material of silver coating amount, in replenishing the liquid measure method that seldom automatic processing machine of (so waste liquid amount seldom) is handled, has the detection efficiency of the photosensitive material sensor of corresponding various transfer mechanisms.
Second purpose of the present invention is to be additional on first purpose, is provided at low replenishing to carry out automatic processing machine when handling, and treatment trough and treating fluid not have the silver halide photographic sensitive material of pollution.
The 3rd purpose of the present invention is to be additional on the 1st or the 2nd purpose, is provided at when handling photosensitive material, and the photographic fog that darkroom light produces seldom and improved dyestuff and duplicated the silver halide photographic sensitive material that pollutes.
The 4th purpose of the present invention provides and a kind ofly can obtain good photographic property in handling fast and/or seldom replenishing developer solution, and good sensitive photographic material of drying property and its disposal route.
Problem of the present invention is finished by following means.
(1) on supporter, has the sealer of one deck photonasty silver halide emulsion layer and the superiors at least; and in the silver halide photographic sensitive material of the gelatinous layer different with this two-layer water wettability; it is characterized in that: at the emulsion that is coated in the photonasty silver halide emulsion layer on this supporter; at least a is that the full projected area of contained silver halide particle is at least 50% in this emulsion; length breadth ratio is at the dull and stereotyped particle more than 2; the silver chloride content of this emulsion is that 20 (mol) are more than the %; contain the non-property separated out of following formula (I) expression in the water wettability colloid layer except that photonasty silver halide emulsion layer and sealer; dispergated solia particle dyestuff; and the water wettability colloid layer on supporter one deck at least contains the sulfhydryl compound that following formula (II) is represented.
(changing 5)
General expression (I)
In the formula, R 10And R 11Represent alkyl, aralkyl or alkylene, R respectively 12And R 14Expression hydrogen atom or mutual former subgroup essential when forming 5 or 6 yuan of rings, the R of linking 13The expression aryl ,-N (R 19) (R 20) ,-SR 21Or-OR 22, R 19Expression hydrogen atom, alkyl or aryl, R 20Expression aryl, sulfonyl or acyl group.In addition, R 19And R 20Can link mutually and form ring.R 21And R 22Represent aryl respectively.R 15, R 16, R 17And R 18Represent alkyl, R respectively 15And R 16, R 17And R 18Can link and form ring.
(changing 6)
General expression (II)
In the general expression (II), Z represents directly or indirectly to have-SO 3M ,-COOR 1,-OH reaches-NHR 2In at least one heterocycle, M represent hydrogen atom, alkali metal atom, or level Four ammonium or level Four phosphorus base, R 1Alkyl, the R of expression hydrogen atom, alkali metal atom or carbon number 1～6 2The alkyl of expression hydrogen atom, carbon number 1～6 ,-COR 3,-COCR 3Or-SO 2R 3, R 3Expression hydrogen atom, fatty group or aromatic series base.
In photosensitive material, use common not photo etching; not photo etching as the spy open clear 51-6017 number, spy open clear 61-20028 number, spy open put down in writing in clear 53-7231 number; be to have to prevent from when the sealer of sensitive photographic material contacts with other object, to cause; then, produce static mark, scratch and use particle for purposes such as the surface that makes sensitive photographic material are easy to slip over critical function.For photosensitive material, photo etching must not paid indispensable function, on the other hand, in automatic processing machine is handled, exist because of photo etching not gets off from the photosensitive material surfacial spalling, and particularly in low liquid waste treatment system, and the problem of pollution treatment trough.
In the present invention; (2) attempt to solve at such problem, also attempting by making the particle diameter that contains in the sealer by following formula (III) expression is that the photosensitive material of above-mentioned (1) of the insoluble synthetic polymer particle of 0.2～10 μ m alkali addresses the above problem.
(changing 7)
Figure A9611262300101
In the formula, R 1Expression methyl or halogen atom, R 2Expression methyl or ethyl.R 3Expression hydrogen atom, methyl, L represent the concatenating group of divalent.A represents ethylene unsaturated monomer, and the two-fold that does not have in a monomer more than 2 is strong.P represents 0～2, and q represents 0 or 1.W represents that 3-60 (mol) %, X represent 30～96.5 (mol) %, and Y represents that 0.5～25 (mol) %, Z represent 0～30 (mol) %.W+X+Y+Z=100 (mol) % wherein.
(3) according to (1) or (2) described silver halide photographic sensitive material, it is characterized in that: at least one side of supporter, Tu Yinliang is at 0.5～1.5g/m 2, the photonasty silver halide particle of this emulsion layer utilizes selenium compound to carry out sensitizing, the opposite side of photosensitive material emulsion layer, and the swelling rate of full water wettability colloid layer is 130～200%.
(4) according to (1), (2) or (3) described silver halide photographic sensitive material, it is characterized in that: in the contained silver halide particle, projected area is at 50-100% in this emulsion layer, and length breadth ratio is at the tabular silver halide particle of 3-30.
(5) according to (1), (2), (3) or (4) described silver halide photographic sensitive material, it is characterized in that: have the layer that contains the non-isolated conductive materials.
(6) a kind of silver halide photographic sensitive material disposal route is characterized in that: handling with automatic processing machine in the method for silver halide photographic sensitive material, the development main ingredient that contains following formula (IV) expression in the developer solution, handle the sensitive photographic material of putting down in writing in (1)～(5) with the developer solution that does not contain p-dihydroxy-benzene, development time is 5～30 seconds.
General expression (IV)
(changing 8)
Figure A9611262300111
In the formula, R 1, R 2Represent hydroxyl, amino, sulfydryl or alkylthio group respectively.P, Q represent hydroxyl, carboxyl, alkoxy, sulfo group, amino, alkyl or aryl respectively, perhaps, and expression P and the Q R that mutually combines 1, R 2Replace two ethene carbon atoms and Y and replaced carbon atom, formed the former subgroup of 5-8 unit ring simultaneously.Y represents=O or=N-R 3R 3Expression hydrogen atom, hydroxyl, alkyl or acyl group.
(7) according to the disposal route of (6) described silver halide photographic sensitive material, it is characterized in that: the magnitude of recruitment of this developer solution is every 1m 2Photosensitive material 25～200ml.
Below describe the present invention in detail.
Explanation about general expression (I).
Use R 10, R 11, R 15, R 16, R 17, R 18And R 19The alkyl of expression is a carbon number from 1 to 10, preferably the alkyl (for example, methyl, ethyl, propyl group, butyl, isobutyl, amyl group, hexyl etc.) of from 1 to 6 nothing displacement.R 15And R 16, R 17And R 18Also can interlink and form ring (for example: cycloalkanes, cyclohexane etc.).
Use R 10And R 11The aralkyl of expression has been got 7-12 carbon number, and aralkyl is (for example benzyl, phenethyl etc.) preferably, also can have sub stituent (for example, methyl, carboxyl, alkoxy, chlorine atom etc.).
Use R 10And R 11The alkylene of expression has 2-10 carbon dust, alkylene preferably, for example can enumerate 2-pentenyl, vinyl, propenyl, 2-butenyl group, 1-propenyl.
Use R 13, R 19, R 20, R 21And R 22The aryl of expression is carbon number 6-12, the best phenyl or naphthyl enumerated.Aryl also can be replaced, and can be the base of dissolving dye not in any development treatment as sub stituent.For example can enumerate methyl, ethyl, chlorine atom, methoxyl, methoxycarbonyl etc.
Use R 20The expression sulfonyl, preferably have 1-10 carbon number alkyl or aryl, sulfonyl, for example can enumerate mesyl, p-toluenesulfonyl, benzenesulfonyl, ethane sulfonyl etc.
Use R 20The acyl group of expression preferably has alkyl or aryl, the acyl group of 2-10 carbon number, for example can enumerate acetyl group, propiono, benzoyl group etc.
R 10And R 11Alkyl preferably.
Preferably make R 12And R 14Link and form 5 yuan of rings or 6 yuan of rings.
R 13Preferably-N (R 19) (R 20) ,-SR 21Or-OR 22, more preferably-N (R 19) (R 20).
R 19Alkyl or aryl preferably.
Preferably make R 13In-N (R 19) (R 20) R 19, R 20In any one is an aryl, more preferably make R 19And R 20In any one is an aryl.With regard to R 19, R 20Phenyl most preferably.
With regard to combination, R 10And R 11Preferably alkyl, R 13Be-N (R 19) (R 20) ,-SR 21Or-CR 22Wherein, more preferably make R 12And R 14Link and form 5 or 6 yuan of rings, R 13For-N (R 19) (R 20).Wherein especially with R 19, R 20In any one when being preferably aryl, make R 19And R 20In any one is an aryl for most preferably.
Below show the instantiation of dyestuff of the present invention, but the present invention is not limited only to these.
[changing 9]
[changing 10]
Figure A9611262300141
[changing 11]
Figure A9611262300152
[changing 12]
Compound R 38
????20???????CH 3????21???????C 2H 5????22???????n-C 3H 7????23???????n-C 4H 9????24???????n-C 5H 11????25???????n-C 6H 13
[changing 13]
Figure A9611262300172
[changing 14]
Figure A9611262300181
Compounds X
????31??????O ????32??????S ????33??????N-CH 3
[changing 15] compound 34
Figure A9611262300182
Compound 35
Figure A9611262300183
R 11=-CH 2-CH=CH 2Compound 36
Figure A9611262300184
[changing 16] Compound 37 R 42=-SO 2CH 3Compound 38
[changing 17]
With the dyestuff of the present invention (to call dyestuff of the present invention in the following text) of general expression (I) expression, can be with reference to US3,671, No. 648, US2,095, No. 854, spy are opened flat 6-43583 number etc. and are synthesized with reference to following synthetic example.
(synthesizing of compound 1)
With 9.8g1,2,3,3-tetramethyl-5-carboxyl India rhenium P-toluene sulfonate, 6g1-[2,5-two (anilino-methene) cyclopentylidene]-ニ benzene ァ ニ リ ニ ュ ゥ system tetrafluoro ボ レ-ト, 100ml ethanol, 5ml acetic anhydride, 10ml diethylamine, stirred 1 hour down for 100 ℃ in ambient temperature, the crystallization of separating out is filtered.Carry out crystallization again with 100ml methyl alcohol, obtaining the 7.3g compound.
Fusing point: more than 270 ℃, λ max:809.1nm, ε: 1.57 * 10 5(dimethyl increase put sulfone).
Other compound is also in kind synthetic.
Dyestuff of the present invention is the non-property separated out preferably, that is, before and after development treatment, spectrum not have the dyestuff of variation basically.So-called non-stripping property of the present invention is meant when this dyestuff flooded for 30 seconds in 25 ℃ of water, still has more than 97% to be retained in the photosensitive material.
The λ max of dyestuff of the present invention in photosensitive material is about 700-1100nm, and preferably 800-1000nm is more preferably 850-950nm.The absorption of visible light part or very little is even or have pair photographic property also harmless.
Dyestuff of the present invention uses with the solia particle dispersed.
When solia particle is disperseed, though can use the spy to drive clear 52-92716 number, international dispersion machines such as the bowl mill put down in writing in 88/074794, vibromill, planetary ball mill, sand mill, colloid mill, injector-type mill, tumbling mill, preferably the medium dispersion machine of longitudinal type or lateral type of disclose.
Any situation no matter, can with solvent (as water, alcohol etc.) coexistence, preferably use the surfactant that disperses usefulness.As the surfactant that disperses usefulness, main use spy opens clear 52-92716 number, the international anionic surfactant who discloses record in No. 88/04794.In addition, can use anionic property polymkeric substance, nonionic or cationic surfactant as required.Preferably use the anionic surfactant.
After dyestuff of the present invention dissolved in appropriate solvent, a small amount of solvent of adding dyestuff of the present invention also can obtain powdery particles.At this moment, can use the surfactant of above-mentioned dispersion usefulness.Perhaps, at first dissolve, subsequently, change PH again and make its micro-crystallizationization by the way of control pH value.
Disperse particles of the dyestuff of the present invention in the dispersion, mean grain size are 0.005-10 μ m, 0.01-1 μ m preferably, and preferred 0.01-0.5 μ m, according to circumstances, most preferred is 0.01-0.1 μ m.
Can be used for 0.001g/m according to dye solids microparticle dispersion of the present invention 2-1g/m 2Scope apply, preferably with 0.005g/m 2-0.5g/m 2, most preferably with 0.005g/m 2-0.1g/m 2
Added the water wettability colloid layer of dyestuff disperse particles of the present invention, can not be as sealer (the superiors) and emulsion layer.When adding dyestuff in sealer (the superiors), its harm is at the roller of the roller of transfer mechanism and automatic processing machine or is close to the transfer printing that sensitive photographic material causes dyestuff each other.
Have, in the time of in adding silver halide emulsion layer to, the dyestuff of part dissolving is adsorbed on the silver halide, owing to produce look sensitizing, the dark room lamp optical property is degenerated, and produces desensitization in the exposure wavelength zone again.
Add layer as dyestuff of the present invention, can consider in the middle layer between sealer and emulsion layer or be arranged on middle layer between several emulsion layers, be arranged on the water wettability colloid layer of coating under close bottom between the coating under emulsion layer and the supporter or the supporter etc. itself.
As the gel coating amount that contains dye coating at 0.02-1g/m 2, 0.1-0.6g/m 2Best.
Optical sensor, by making luminous light emitting diode or the semiconductor laser of wavelength more than 700nm, light source and keep being subjected to the luminous sensitivity peak value near 900nm, have the range of sensitivity and be used in combination at the light activated element of 700-1200nm.GL-514 (シ ャ-プ Co., Ltd. system), TLN108 (Toshiba Corporation's system) etc. can be enumerated as light emitting diode, PT501 (シ ャ-プ Co., Ltd. system), TPS601A (Toshiba Corporation's system) etc. can be enumerated as light activated element.
About using the automaton of this optical sensor system, available from above-mentioned each society.
Below describe with regard to the compound of general expression (II) expression.
In the general expression (II), Z directly or indirectly is combined with from-SO 3M ,-COOR 1,-OH and-NHR 2In select a kind of several heterocycle residue at least, for example oxazole ring, thiazole ring, imidazole ring, selenazoles ring, triazole ring, tetrazole ring, thiadiazoles ring, oxadiazoles ring, dibazol ring, pyrimidine ring, thiazine ring, triazine ring, sulphur diazine ring, or other carbocyclic ring and the ring that combines with heterocycle, for example benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxazole ring, benzo selenazoles ring, Nai Bing oxazole ring, three azaindole piperazine rings, two azaindole piperazine rings, four azaindole piperazine rings.
As best heterocycle residue, can enumerate: imidazole ring, tetrazolium, benzimidazole ring, benzothiazole, benzoxazole ring, triazole ring etc.
M in the general expression (II) represents hydrogen atom, alkali metal atom, level Four ammonium or level Four phosphorus base.R 1The alkyl of expression hydrogen atom, alkali metal atom or carbon number 1-6, R 2The alkyl of expression hydrogen atom, carbon number 1-6 ,-COR 3,-COOR 3Or-SO 2R 3, R 3Expression hydrogen atom, fatty group (for example, carboxyethyl, sulfoethyl) or these bases of aromatic series base (for example, phenyl, 4-sulfophenyl) also can have sub stituent.
Below illustrate among the present invention used, the best examples of compounds of general expression (II) expression.
[changing 18]
[changing 19]
Figure A9611262300241
[changing 20]
[changing 21]
Figure A9611262300261
[changing 22]
Figure A9611262300271
[changing 23]
Figure A9611262300281
Compound shown in the general expression (II) is known, also can utilize the method for following document record synthetic.
No. 2585388, United States Patent (USP), No. 2541924, the U.S., special public clear 42-21842 number, the spy opens clear 53-50169 number, No. 1275701, BrP, D, A, バ-ジ ュ ス Chi, " ジ ャ Na Le ォ Block ヘ テ ロ サ ィ Network リ ッ Network ケ ミ ス ト リ " (D, A, Ber ges et al. " Journal of Heterocyclic chemistry ") the 15th volume No. 981 (No. 1978), " ザ メ ケ ミ ス ト リ ォ Block ヘ ラ ロ サ ィ Network リ ッ Network ケ ミ ス ト リ ", ィ ミ ダ ゾ-Le ァ Application De, デ リ バ テ ィ Block ス, パ-ト ェ (" The chemistryof Heterocylic chemistry " Imidazole and Deri-vatives partI), 336～9 pages, Network ミ カ Le ァ Block ス ト ラ Network ト (Chemical Abstract), 58, No. 7921 (1963), 394 pages, E ホ ガ-ス, " ジ ャ-f Le ォ Block Network ミ カ Le ソ サ ィ ェ テ ィ (E.Hoggarth " Journal of Chemical Society ") 1160～7 pages (1949); and S.R. サ De ラ-W. カ ロ; " ォ Le ガ ニ Star Network Off ァ Application Network シ ョ ャ Le グ Le-プ レ Ha-シ ョ Application "; the ァ ォ デ ミ ッ カ プ レ ス (S.R.Sandier; W.Karo; " Organic Fanctloral GroupPreparation " Academic Press 312-5 of society page or leaf of society, (1968) M. シ ャ system De system and (M.Chamdon, et.al,), Block Le Application De ラ ソ シ ェ ラ シ ミ-Network De Off ラ Application ス (Bulletinde la Societe chimique de France), 723 (1954), D.A. シ ャ-1)-, D.W. ァ レ ィ, ジ ャ-f Le ォ Block ゼ ァ ソ リ カ Application カ ミ カ Le ソ サ ェ ィ (D.A.Shirley, D.W Alley, J, Amer.Chem.Soc), 79,4922 (1954) A. ボ-Le, W. マ-チ バ Le ト, ベ リ Star ヒ テ (A.Wohl, W.Marchwald, Ber.) (De リ Star chemistry will), 22 volumes, 568 pages of (1889) ジ ャ-f Le ォ Block ァ Na リ カ Application カ ミ カ Le ソ サ ェ テ ィ (J.Amer.chem.Soc), 44,150～10 pages, No. 3 017270, United States Patent (USP), No. 940,169, BrP, special public clear 49-8334 number, the spy opens clear 55-59463 number, ァ De バ Application ス De ィ Application ヘ テ ロ サ ィ カ ッ Network Network ミ ス ト リ-(Advanced in Heterocyclic chemistry), the west is unique is permitted No. 2716707, ザ Network ミ ス ト リ-ォ Block ヘ テ ロ サ ィ Network リ Star Network ュ Application ベ ヮ Application ズ ィ ミ ダ ゾ-Le ァ Application De デ リ バ テ ィ プ ズ (The chemistry ofHeterocyclic CompoundsImidazole and Derivalives) Vol 1,385 pages of ォ Le ガ ニ Star Network シ Application セ シ ス (Org.Synth) IV.569 (1963), ベ リ ッ ヒ テ (Ber.) 9,465 (1976), ジ ャ-f Le ォ Block ァ Na リ カ Application Network ミ カ リ ソ サ ィ ェ テ ィ (J.Amer.chem.Soc) 45,2390 (1923), the spy opens clear 50-89034 number, the spy opens clear 53-28426 number, the spy opens clear 55-21007 number, special open 40-28496 number;
The compound of general expression (II) expression preferably is contained in any one deck on the supporter.For example; can enumerate silver halide emulsion layer, other water wettability colloid layer (middle layer, sealer, Yellow filter layer, anti-halation layer etc.); though above-claimed cpd is contained in silver halide emulsion layer, dyestuff disperse particles of the present invention interpolation layer or other the adjoining course, and preferably the desensitization of taking a picture beyond the emulsion layer is little.
Its addition is preferably 1 * 10 -5～1 * 10 -1G/m 2, more preferably 5 * 10 -5～5 * 10 -2G/m 2, 1 * 10 -3～1 * 10 -2G/m 2
The adding method of these compounds in emulsion can be according to the method for common interpolation photographic emulsion additive.For example, be dissolved in the mixed solvent of methylol, ethyl alcohol, methyl cellosolve, acetone, water or these solvents, also can be used as solution and add.
The compound of general expression (II) expression can be used for adding to takes a picture with any procedure in the manufacture process of emulsion.Also can after making, add in any stage before coating by emulsion.
The interpolation of general expression of the present invention (II) compound can prevent to reduce because of Infrared dyes makes the dark room lamp optical property.
The represented best example of polymkeric substance of general expression (III) (form and all represent with mol ratio) below is shown, but the present invention is not limited to these.
Below, st represents that styrene, MMA represent that methyl isobutyrate, EMA represent that ethyl isobutyrate, MA represent that methacrylic acid, AA represent acrylic acid.
(P-1)st(20)MMA(70)MA(10)
(P-2)st(15)MMA(75)MA(10)
(P-3)st(55)MMA(25)MA(20)
(P-4)st(30)MMA(65)MA(5)
(P-5)st(7)MMA(90)MA(3)
(P-6)st(25)MMA(70)AA(15)
(P-7)st(40)MMA(55)AA(15)
(P-8)st(20)EMA(70)AA(10)
(P-9)st(10)EMA(75)AA(15)
(P-10)st(15)EMA(70)MA(15)
(P-11) st (10) MMA (80) acryloyl group
Hydroxyethyl phthalic acid (10)
(P-12) st (15) MMA (75) acryloyl group hydroxyethyl succinate
(サクシネ-ト)(10)
(P-13) st (18) MMA (75) acryloyl group hydroxyethyl succinate
(7)
(P-14) the adjacent benzene of cl-st (15) EMA (70) acryloyl group hydroxyethyl
Dioctyl phthalate (15)
(P-15) P-CH 3-st (40) EMA (55) methacryl
Hydroxyethyl succinate (5)
(P-16)P-CH 3-st(10)MMA(80)MA(10)
(P-17)P-CH 3-st(15)MMA(80)MA(5)
(P-18)Cl-st(15)MMA(70)、MA(15)
(P-19)Cl-st(3)EMA(92)、MA(5)
(P-20)Cl-st(10)MMA(80)、AA(10)
(P-21)st(20)MMA(60)MA(10)EMA(10)
(P-22) st (20) MMA (70) MA (5) butyl acrylate (5)
(P-23)Cl-st(10)EMA(65)MA(15)st
(10)
Coating amount as the insoluble synthetic polymer particle of contained alkali in sealer (to call not only agent in the following text) is 0.001～0.3g/m 2, 0.01～0.15g/m preferably 2As the average particle size of photo etching not is 0.2～10 μ m, preferably 2-8 μ m.At this moment, not photo etching of the present invention accounts for 50 (weight) of total coating amount can bring into play effect of the present invention more than the %, is preferably in more than 70%.The not photo etching that share this moment is not particularly limited.For example also can be the organic compound of polyisobutylene acid methyl esters, polystyrene one class, also can be the mineral compound of silicon dioxide one class.In addition not photo etching of the present invention is mixed more than two kinds mutually and use, it is more abundant that its effect is brought into play.
Among the present invention, 70 (weight) of used not photo etching total amount are present in more than the % in the sealer in photosensitive material, and preferably 80 (weight) are more than the %, and most preferred is that 90 (weight) are more than the %.
As above-mentioned, the average particle size of not photo etching of the present invention is preferably more than the 2 μ m, but distributes as particle diameter, preferably makes more than the 3 μ m to have very big distribution with the following particle diameter of 3 μ m.This is that the following not photo etching of 3 μ m mainly is the sliding capability and the gloss of sense of control luminescent material owing to the stripping performance of the above not photo etching energy sense of control luminescent material of 3 μ m.Usually cause that the sedimentation and the peeling off when handling of coating in the liquid is the above particles of 3 μ m.Composition more than the 3 μ m like this is effective especially in the present invention.
Effective especially aspect the outermost gel content reduction of not photo etching of the present invention in the photosensitive material design that is accompanied by the high temperature fast processingization, outermost gel content is preferably at 0.7g/m 2Below, 0.2g/m 2More than, more preferably at 0.5g/m 2Below, 0.3g/m 2More than, even this situation also can demonstrate the not photo etching sedimentation that prevents from effectively to apply in the liquid and peeling off of photo etching not when handling.
Below tell about and pay the not matte shot degree of the sensitive photographic material of photo etching of the present invention.
In this manual, said matte shot degree is the degree of expression " surfaceness ".The surfaceness of herein saying is the smooth finish that causes surface irregularity in very closely-spaced, normally thinks the perceptual result of " smooth " or " rough ".The assay method of this matte shot degree has a variety of, can be by any surface finish meter, optical microscope, scanning electron microscope are observed configuration of surface, can enumerate Bake (バ ッ Network) smoothness, the Bake smoothness of putting down in writing among the JISP8119 as the average smooth finish in surface, be defined as follows: be useful area 10cm 2Surface plate, with 1kg/cm 2Pressure when being pressed in determined, under the pressure reduction of about 370mmHg, measure the required second number of air that flows through 10ml, with second numerical table show smoothness.That is, second number is big more, and expression matte shot degree is more little, and second number is more little, and expression matte shot degree is big more.For high-acruracy survey Bake smoothness, preferably use air micrometer type test apparatus, particularly use the Wang Yan formula smoothness of putting down in writing among the J.TAPPI paper pulp test method(s) No.5 to measure.Can obtain the good Bake smoothness of repeatability (Yamamoto ゥ, paper パ skill association difficulty, 20 (2), 17～24 (1966)) very easily.
Even the not luminosity at emulsion side or its back side produces zero amount problem, also be fine, the Bake smoothness is preferably below 1000 seconds, preferred especially below 300 seconds.
Below emulsion is elaborated.
In the silver emulsion that contains spreading agent and silver halide particle at least, the total projection area of this silver halide particle is more than 50% (preferably 60～100%, be more preferably 70～100%) is than at the tabular particle more than 2 as the shape of principal plane (100) or (111) face.Said herein tabular particle be shape than (diameter/thickness) than 1 big particle.Principal plane is meant the maximum exterior surface of tabular particle.The thickness of this tabular particle is below 0.35 μ m, and preferably 0.05～0.3 μ m is more preferably 0.05～0.25 μ m.Preferred shape is more preferably 3-30 than more than 2, and most preferred is that 5-20 is good especially.The diameter of herein saying is meant that the projected area with this tabular particle has the equal areas diameter of a circle, and thickness is meant two distances between principal plane, and this silver halide particle contains Cl -More than the %, preferably 30～100 (mol) % is more preferably 40～100 (mol) % at 20 (mol), most preferred 50～100 (mol) %.
About the formation method that (111) face in the emulsion of the present invention is examined as the emulsion of principal plane, detailed argumentation is arranged in following document, and special public clear 64-8326 number, special public clear 64-8325 number, special public clear 64-8324 number, special fair 1-250943 number, special fair 3-14328 number, special fair 4-81782 number, special fair 5-40298 number, special fair 5-39459 number, special fair 5-12696 number and special public clear 63-213836 number, spy open clear 63-218938 number, spy and open clear 63-281149 number, spy and open clear 62-218959 number.As (100) face as the prior art of the tabular particle of principal plane, the spy open flat 5-204073 number, spy open clear 51-88017 number, spy open clear 63-24238 number, specially be willing to discuss to some extent in flat 5-264059 number.
Among the present invention, can use the karyomorphism of putting down in writing in these prior arts to become method arbitrarily.
Below tell about by the physics slaking under the silver halide grains existence of the present invention and make particle dissolution, form the method that the substrate particle crystallization is grown up.
Use the fine grain emulsion additive process, adding diameter is below the 0.15 μ m, preferably below the 0.1 μ m, is more preferably the AgX fine grain emulsion of 0.06～0.006 μ m, utilizes Ostwald's glass method that this tabular particle is grown up.This fine grain emulsion also can add continuously, also can continue to add.This fine grain emulsion is by being located at the mixer supply that reaction vessel closely is close to, AgNO 3Solution and X -The salt solusion supply is modulated continuously, also can directly add to continuously in the reaction vessel, also can the continuous or continuation interpolation in the back of batch modulation in advance in other container.This fine grain emulsion can also can add with the powder of drying with aqueous interpolation.This dried powder is mixed with water before interpolation, with aqueous interpolation.The mode that the particulate of interpolation was disappeared in 20 minutes is added, and more preferably the mode that disappeared at 10 seconds～10 minutes of the particulate of Tian Jiaing is added.When die-out time is long, between particulate, produce slaking, because particle size becomes big, not ideal.Therefore, preferably total amount has not once been added.This particulate preferably is substantially devoid of the twin crystal particle of volume.The multiple twin crystal particle of herein saying is meant that each particle has the particle of 2 above twin planes.Said being substantially free of is meant multiple twin crystal population ratio below 5%, preferably below 1%, more preferably below 0.1%.Most preferably do not contain 1 heavy twin crystal particle.Preferably also be substantially free of spiral dislocation.Being substantially free of herein also by aforementioned regulation.
It is AgCl, AgBr, AgBr I (I that the halogenide of this particulate is formed -Content is preferably at 10 (mol) below the %, more preferably at 5 (mol) below the %) and the mixed crystal more than 2 kinds in them.Other details can be with reference to the description in the special 4-214109 of Yuanping City number.
Total addition level necessity of particulate accounts for more than 20% of silver halide total amount, preferably more than 40%, and more preferably 50～98%.
The Cl of particulate -Content is preferably more than 10%, and more preferably 50～100%.
When becoming, during slaking and the spreading agent when growing up, can use over known AgX emulsion spreading agent, but preferably use methionine to contain the gel of rate, more preferably contain the gel of 0-30 μ mol/g as 0-50 (μ mol/g) as karyomorphism.This gel is preferably in slaking, uses when growing up, and can form the more complete tabular particle of Boping of diameter distribution.Preferably use the synthetic high polymer of putting down in writing in the following document to make spreading agent, special public clear 52-16365 number, Japan take a picture association's will, 29 volume (1), 17,22 (1966), with periodical 30 volume (1), 10,19 (1967), with periodical 30 volumes (2), 17) (1967), with periodical 33 volume (3), 24 (1967).The pH value that particulate adds when growing up must be preferably 3-10, more preferably 4-9 more than 2.0.
PCl must be more than 1.0, preferably more than 1.6, and 2.0-3.0 more preferably.
These growth conditions are for preferred especially as the tabular particle of principal plane (100) face.
PCl herein is to the activity amount [Cl of Cl ion in the solution -] be defined PCl=-log[Cl -].T.H.James work THE THEORY OF THE RHOTOGRAPHIC PROCSS, has done detailed argumentation by the 4th edition in the 1st chapter.
PH value is lower than at 2.0 o'clock, for example (100) face is made the tabular particle of principal plane, and the growth of its transverse direction is suppressed, and shape is than reducing, and often the lining ability of emulsion also reduces, and is low and helps to change.PH value is 2.0 when above, and laterally growth rate uprises, and shape is high than also, obtain the also high emulsion of lining ability, but photographic fog is very high, is easy to hang down help to change.
PCl is lower than at 1.0 o'clock, has promoted longitudinally to grow up, and shape is than reducing, and the lining ability of emulsion is also low, and is low and helps to change.When PCl was higher than 1.6, the shape ratio uprised, though the lining ability has increased, photographic fog uprises easily, was low and helped to change.At this moment, when silver halide grains causes that the substrate particle is grown up, PH 6 or more and/or PCl more than 1.6, though photographic fog is low, but compare with helping to change under the sensitivity situation at height, shape is higher than more, the lining ability is also high more.
About emulsion monodispersity of the present invention, for single dispersion degree, when considering with special when opening the coefficient of alteration of the method definition of putting down in writing among the clear 59-745481, below 30% for well, be preferably in more than 5%, below 25%.During especially for the photosensitive material of hard, be preferably in more than 5%, below 25%.
As selenium sensitizer used among the present invention, can use over disclosed selenium compound in the patent.That is, add the selenide of labile selenium compound and/or stable type usually, at high temperature best more than 40 ℃, re-use after emulsion stirred certain hour.As labile selenium compound, preferably use special public clear 44-15748 number, special public clear 43-13489 number, spy open flat 2-130976 number, spy open flat 4-109240 number etc. in the compound of record.As concrete unstable selenium sensitizer; can enumerate different selenium cyanic acid salt (as the different selenium cyanic acid of the aliphatics salt of the different selenium cyanate of allyl), selenium urea class, selenium ketone, selenium amide-type, selenium carboxylic acids, (as the acid of 2-selenium diethyl ketone, 2-selenium butyric acid), selenium ester class, diacyl selenide class (as two (3-chloro-2,6-dimethoxy benzoyl) selenide), selenium phosphoric acid salt, hydrogen phosphide selenide class, two (oxygen phosphinylidyne) selenide class, colloidal metallic selenium etc.
Though below show the instantiation of the used best selenium compound of the present invention, the present invention is not only for these.
[changing 24]
Figure A9611262300361
[changing 25]
Figure A9611262300362
[changing 26]
Figure A9611262300371
[changing 27]
[changing 28]
Figure A9611262300381
[changing 29]
Figure A9611262300382
[changing 30]
Be dissolved in these selenium sensitizers in water or the organic solvents such as methyl alcohol, ethanol separately or in their mixed solvent, or open form that flat 4-140738 number, spy open record in flat 4-140739 number when the chemical sensitization, add with the spy.Be preferably in chemical sensitization and begin preceding interpolation.Employed selenium sensitizer is not limited to a kind, the above-mentioned selenium sensitizer that two or more kinds may be used.Also can and use unsettled selenium compound and stable selenium compound.
The addition of used sensitizer among the present invention, according to the activity of used selenium sensitizer, the kind of silver halide and size, the temperature and time of slaking, and different, preferably every 1mol silver halide adds 1 * 10 -8More than the mol.1 * 10 -7More than the mol, 1 * 10 -5Below the mol, better.Chemical curing temperature when using the selenium sensitizer is preferably more than 45 ℃.More preferably more than 50 ℃ below 80 ℃.PAg and PH are any.For example can both obtain effect of the present invention in the very wide scope of pH value from 4 to 9.
Have ag halide solvent in the presence of carry out selenium sensitizing, better effects if.
As operable ag halide solvent in the present invention, can enumerate: have by at United States Patent (USP) 3,271, (a) organic sulfur ethers of record in clear 54-1019 number and 54-158917 number is opened in No. 157, No. 3531289, No. 3574628, spy, and ag halide solvent, the spy that the spy opens the thiocarbonyl group that (b), the sulphur urine inductor of record in clear 53-82408 number, 55-77737 number, 55-2982 number, (c) oxygen that the spy opens record in clear 53-144319 number or sulphur atom and nitrogen-atoms separate opens the imidazoles (d), sulphite (e), thiocyanate of record in clear 54-100717 number etc.
As good especially solvent thiocyanate and tetramethyl sulphur urine are arranged.The amount of solvent for use is different with kind, and for example, when using thiocyanate, preferably consumption is that every 1mol halogenation is with 1 * 10 -4～1 * 10 -2Mol.
Silver emulsion of the present invention, in chemical sensitization by and with sulphur sensitizing and/or golden sensitizing, can obtain high sensitivity, hang down photographic fog.
Sulphur sensitizing is normally added the sulphur sensitizer, at high temperature, preferably more than 40 ℃ emulsion is stirred the regular hour.
And golden sensitizing is normally added golden sensitizer, more than 40 ℃ emulsion is stirred the regular hour in that high temperature 1 is best.
In above-mentioned sulphur sensitizing, can use known sulphur sensitizer.For example, thiosulfate, thiourea, allyl isothiocyanate salt, cystine, P-toluene sulphur hydrochlorate, rhodanine etc. can have been enumerated.Also can use other sulphur sensitizer of putting down in writing in the following document, United States Patent (USP) 1,574, No. 944,2,410, No. 689,2,278, No. 947,2,728, No. 668,3,501, No. 313,3,656, No. 955 each instructionss, Deutsche Bundespatent 1,422, clear 55-45016 communique is opened in No. 869, special public clear 56-24937 number, spy.In order to increase the sensitivity of emulsion effectively, the addition of sulphur sensitizer must be sufficient.Under all conditions such as size of PH, temperature, silver halide particle, this amount can be changed change in sizable scope, but the silver halide of every 1mol should be 1 * 10 -7More than the mol, 5 * 10 -4Below the mol.
As the golden sensitizer of above-mentioned golden sensitizing, the oxidation number of gold can be+1 valency, and valency also+3 can use the gold compound of common usefulness as golden sensitizer.As representative example, can enumerate: gold oxide hydrochlorate, potassium chloroaurate, gold trichloride, potassium gold thiocyanate, potassium auriiodide, four cyanogen gold acid amides, ammonium gold thiocyanate, pyridine gold trichloride etc.
The addition of gold sensitizer as standard, to every 1mol silver halide, is preferably in 1 * 10 according to various conditions and different -7More than the mol, 5 * 10 -4Below the mol.
When chemical slaking, about ag halide solvent and selenium sensitizer or and the interpolation time and the order of the sulphur sensitizer of selenium sensitizer and usefulness and/or golden sensitizer etc., there is no need to do particular restriction.For example, can in chemical slaking initial stage (best) or chemical slaking are carried out, add above-claimed cpd simultaneously, perhaps add by the different interpolation time.During interpolation, above-claimed cpd can be dissolved in the water and add, and also can be dissolved in water to mix in the organic solvent obtain, in single liquid such as methyl alcohol, ethanol, acetone or mixed liquor, adds.
The addition of selenium sensitizer and sulphur sensitizer and time spent is 1: 9～9: 1 with the equivalent mol ratio of selenium and sulphur, and 5: 5～7: 3 better.
Among the present invention, as record in No. 3,622,318, No. 635841, the BrP, United States Patent (USP), the particle of so-called halogen changing type (conversion hysteria) is effective especially.The halogen converted quantity for silver amount 0.2～2mol% preferably, is more preferably 0.2～0.6mol%.
In iodine silver bromide emulsion, to have a particle of high iodine degree layer structure good especially portion and/or surface within it.
Among the present invention,, can obtain the higher silver emulsion of sensitivity by preferred tabular silver halide particle surface transformation is become high iodine degree type.
Silver halide as particle surface before the halogen conversion is formed, and content of iodine is preferably below 1mol%, more preferably below 0.4mol%.
When carrying out the halogen conversion, exist the method for ag halide solvent effective especially,, sulfide compound, thiocyanate, four displacement sulphur urine are arranged as best solvent with said method.Wherein, sulfide compound and thiocyanate are effective especially, for every 1mol silver halide, preferably use 0.5g～5g thiocyanate, 0.2～3g thioether.
Among the present invention, open clear 61-230135 and the clear 63-25653 of Te Kai number record, when developing, can and use the compound that discharges inhibitor as the spy.
When silver halide was made, in silver halide particle formation or the physics maturing process, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or their complex salt, rhodium salt or its complex salt, molysite or iron complex salt etc. also can coexist.
When particle formed, as thiocyanate, sulfide compound, thiazolidine Ethodan, four displacement sulphur were urinated so-called ag halide solvent and also can be existed.Wherein, thiocyanate, four displacement sulphur urine and thioether are preferred solvents among the present invention.
In protective seam of the present invention and/or emulsion layer,, can more be of value to and improve effect of the present invention if contain at least a in polyethylene oxide and the water-soluble polymers.
As best oxidation of ethylene compounds used among the present invention, can enumerate with the special general expression of putting down in writing in the clear 60-76742 communique (I-1), the compound of (I-2) and (I-3) expression, the compound of using general expression (II) equally and (III) representing opened.
Can enumerate examples of compounds I-1～I68, II-1～II-18 and the III-1～III-21 that puts down in writing in the same communique as concrete examples of compounds.
As best water-soluble polymers used among the present invention, can enumerate the spy and open～the 10 page of hurdle, lower-left of row, the 7th page of hurdle, lower-left of flat 1-234843 communique 17 9 row records, the compound and the Compound P-1～P-18 of general expression (P) expression in the particularly same communique, and special compound and the examples of compounds P-1～P-14 that opens general expression (II) expression of putting down in writing in the flat 1-241537 communique.Preferably use the special water-soluble polymers of putting down in writing in flat 3-77940 communique and the 3-246535 communique of opening.
Preferably use glucose polymer and its inductor as water-soluble polymers, in glucose polymer and its inductor, preferably starch, glucosyl group because of, cellulose, lichenin, glucosan, nigeran etc., particularly preferably be glucosan and its inductor.
The molecular weight of these water-soluble polymerss preferably 1000～100,000 is more preferably 2000～50,000.
Used synthetic or water-soluble polymers among the present invention accounts for total gel coating amount preferably more than 10% in sensitive photographic material, be preferably in 10～30%.
When increasing total coating amount of hydrophilic gel, moisture contained in the development treatment operation also increases, the viewpoint of the load fast processing from reduce drying process, and this is not so good.Yet, unilateral as total coating amount of hydrophilic gel in the present invention to each, 3.0～1.0g/m preferably 2, be more preferably 1.5～2.5g/m 2
In the present invention, the sheet of each supporter survey silver coating amount is 0.5～1.5g/m 2, 1.0～1.45g/m preferably 2, be more preferably 1.2～1.4g/m 2
Silver halide photographic sensitive material of the present invention (to call the sense material in the following text) by adding hard coat agent in coating in the liquid, carries out crosslinkedly with gel in the hydrophilic gel layer, gives forming dura mater earlier.
The swelling rate of sense material of the present invention is 130～200%, is preferably 140～190%, is more preferably 150～180%.
Swelling rate among so-called the present invention, its definition is opened put down in writing in clear 58-111933 number identical with the spy.
Below, the compound of development main ingredient general expression (IV) best among the present invention is elaborated.
In the general expression (IV), R1, R2 are respectively that hydroxyl, amino, mercapto amount or alkylthio group (as methyl mercapto, ethylmercapto group), amino can have sub stituent, amino as displacement, can enumerate alkyl displacement amino (as methylamino, ethylamino, n-fourth amino, hydroxyethylamino), acylamino-(as acetylamino, benzoyl amino), alkane sulfonamido (as methanesulfonamido), aryl-sulphonamidic base (as benzenesulfonamido-, P-tosyl amino), the alcoxyl carboxylic amino (as methoxy carboxylic amino) of 1～10 carbon.Hydroxyl, amino, alkane sulfonamido, aryl-sulphonamidic base can have been enumerated as the preferred embodiment of R1, R2.
P, Q represent hydroxyl, carboxyl, alkoxy, alkyl, sulfo group, amino, aryl respectively, or the mutually combine carbon atom of two ethene carbon atoms of R1, R2 displacement and Y displacement of P and Q forms the former subgroup of 5-8 unit ring simultaneously.Alkoxy, alkyl, amino, aryl also can be replaced.As the instantiation of ring structure, can with-O-,-C (R 9) (R 10)-,-C (R 11) two ,-C (two O)-,-N (R 12)-,-N is second-class to constitute.Wherein, R 9, R 10, R 11And R 12Represent respectively hydrogen atom, alkyl (preferably 1-10 carbon, replaceable.As sub stituent can be hydroxyl, carboxyl, sulfo group etc.), hydroxyl or carboxyl.This 5-8 unit ring can form saturated or undersaturated condensed ring.
Can enumerate dihydroxy furanone ring, dihydroxy-pyrrolidine quinoline ring, pyrone ring, cyclopentenone ring, cyclonene ring, pyrrolones ring, pyrazolone ring, pyridone ring, nitrogen heterocyclic hexanone ring, uracil ring etc., can enumerate dihydroxy furanone ring, cyclopentenone ring, cyclonene ring, pyrazolone ring, nitrogen heterocyclic hexanone ring, uracil ring as 5-8 unit ring as best 5-8 unit ring.
Y represents=O or=N-R 3, R 3Expression hydrogen atom, hydroxyl, alkyl (as methyl, ethyl) or acyl group (as acetyl group).Alkyl, acyl group can be replaced.Hydroxyalkyl (as methylol, hydroxyethyl), sulfoalkyl (as sulphur methyl, sulfoethyl), carboxyalkyl (as ethyloic, carboxyethyl) can have been enumerated as the displacement alkyl.
General expression of the present invention (IV) instantiation below is shown, but the present invention is not limited in these.
[changing 32]
Figure A9611262300451
[changing 33]
[changing 34]
Figure A9611262300461
[changing 35]
Figure A9611262300462
[changing 36]
Figure A9611262300471
[changing 37]
This wherein, alkali metal salt such as the ascorbic acid represented of I-1 or arabo-ascorbic acid (enantiomter of ascorbic acid) and their lithium salts, sodium salt, sylvite preferably.
The common consumption of development main ingredient is 0.01-0.8mol/l, is preferably 0.05-0.4mol/l.The development main ingredient of above-mentioned general expression (IV) expression is preferably also used with the auxiliary development main ingredient that shows super additivity.
As the auxiliary development main ingredient that shows super additivity auxiliary development main ingredient of 1-benzene-3-pyrazolidine ketone or the auxiliary development main ingredient of P-aminophenols are arranged.
As the auxiliary development main ingredient of 1-benzene-3-pyrazolidine ketone 1-benzene-3-pyrazolidone, 1-benzene-4 are arranged, 4-dimethyl-3-pyrazolidone, 1-benzene-4-methyl-4-methylol-3-pyrazolidone, 1-benzene-4,4-dihydroxymethyl-3-pyrazolidone, 1-benzene-5-methyl-3-pyrazolidone, 1-P-aminobenzene-4,4-dimethyl-3-pyrazolidone, 1-P-tolyl-4,4-dimethyl-3-pyrazolidone, 1-P-tolyl-4-methyl-4-methylol-3-pyrazolidone etc.Wherein 1-benzene-4-methyl-4-pyrrole methylol-3-pyrazolidone is preferred.
As the auxiliary development main ingredient of P-hydrogen base phenols N-methyl-P-amino phenol, N-(3-hydroxyethyl)-P-amino phenol, N-(4-hydroxy benzenes) aminoacetic acid, 2-methyl-P-amino phenol, P-benzyl amino phenol etc. are arranged, wherein N methyl-P amino phenol is preferred.
Among the present invention, in the time of will together being used in combination with the preferably development main ingredient of general expression (IV) expression and 1-benzene-3-pyrazolidine ketone or P-amino phenol with auxiliary development main ingredient, the former consumption is 0.01～0.5mol/l preferably, latter's consumption is 0.001～0.1mol/l preferably, and latter's consumption is more preferably 0.005～0.05mol/l.
Used developer solution when handling sense material of the present invention for promoting to develop, can contain amino-compound.Also can use the spy to open clear 56-106244 number, spy opens clear 61-267759 number, spy and opens the amino-compound of record in flat 2-208652 number.
The pH value of used developer solution is 8.0～13.0, is preferably 8.3～12 that 8.5～10.5 is better when handling sense material of the present invention.
Can contain in the used best developer solution among the present invention promising setting pH value PH buffering agent carbonate (as, sodium carbonate, sal tartari etc.).The addition of carbonate is preferably more than 0.3mol/l more preferably at 0.4～2mol/l, most preferably is 0.4-1mol/l.
Used developer solution when handling sense material of the present invention, for setting in the used alkaline agent of pH value, except that above-mentioned carbonate, usually can and with water-soluble inorganic alkaline metal salt (as NaOH, potassium hydroxide etc.).Specifically available other, as PH buffering agents such as sodium hydrogen phosphate, dipotassium hydrogen phosphate, dibastic sodium phosphate, potassium hydrogen phosphates, in addition, also available spy opens in clear 60-93438 number the PH buffering agent of record.
When handling sense material of the present invention in the used developer solution, for preventing that silver from polluting the agent of available silver contamination preventing, open the compound of record in flat 1-200249 number, 4-362942 number, 5-303179 number, 5-53257 number as the public clear 62-4702 of spy number, special public clear 62-4703 number, spy.
Handle in the used developer solution of sense material of the present invention, except use as above-mentioned amino-compound and adjuvants such as alkaline agent or silver-colored contamination preventing agent, also can add as potassium bromide, potassium iodide one class development shadow inhibitor, as organic solvents such as dimethyl formamide, methyl fiber ソ Le Block, ethylene glycol, ethanol, methyl alcohol, prevent agent as photographic fogs such as 5-methylbenzotrazole, 5-chlorobenzotriazole, 5-bromobenzene and triazole, 5-butylbenzene and triazole, benzotriazoles.
The antioxidant of used sulphite has sodium sulphite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite etc. in the developer solution when handling sense material of the present invention.The consumption of sulphite is more than 0.01mol/l, and is preferred especially at 0.02-2.5mol/l.
Other also can use L.F.A. メ ィ ス Application work T Off ォ ト グ ラ Off ィ ッ Network. プ ロ セ ッ シ Application グ. and ケ ミ ス ト リ-" Off ォ-カ Le. 226-229 item, the United States Patent (USP) 2 of プ レ ス periodical (1966); 193; No. 015,2; antioxidant of record during 592, No. 364, spy are opened clear 48-64933 number etc.
And then also can contain toner as required, surfactant, water softening agent, hard coat agent etc.
As the sequestrant in the developer solution ethene diamino two o-hydroxy acetic acid are arranged, diaminopropanes four acetic acid, nitrogen three acetic acid, hydroxyethyl ethene diamino three acetic acid, the dihydroxy ethyl aminoacetic acid, ethene diamino two acetic acid, ethene diamino dipropionic acid, diglycinee, divinyl triammonium five acetic acid, the hydroxyethyl diglycinee, 1,3 one two aminopropanols, four acetic acid, triethylene tetramine six acetic acid, anti-cyclohexane diamine four acetic acid, ethene diamino four acetic acid, ethanol ether diamino four acetic acid, four times of methylphosphonic acids of ethene diamino, divinyl triammonium pentamethyl phosphonic acids, nitrogen three methane phosphonic acids, 1-hydroxy ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid, 1,1-two inferior phosphono group ethane-2-carboxylic vinegar, the inferior phosphono group butane-1 of 2-, the 2-4-tricarboxylic acids, 1-hydroxyl-1-phosphonous acid base propane-1,3, the 3-tricarboxylic acids, catechol-3, the 4-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate etc.Wherein good especially have divinyl triammonium five acetic acid, triethylene four ammonia six acetic acid, 1,3-two aminopropanols four acetic acid, ethanol ether diamino four acetic acid, hydroxyethyl ethene diamino three acetic acid, two-Ya phosphono group butane-1,2,4-tricarboxylic acids, 1,1-two inferior phosphono group ethane-2-carboxylic acids, nitrogen three methane phosphonic acids, four times of methane phosphonic acids of ethene diamino, divinyl triammonium five alkane phosphonic acids, 1-hydroxy propylidene-1,1-di 2 ethylhexyl phosphonic acid, the amino ethylidene-1 of 1-, 1-di 2 ethylhexyl phosphonic acid, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid and their salt.
In disposal route of the present invention, the magnitude of recruitment of developer solution is every 1m 2Photosensitive material is 25-200ml, and preferably 30-180ml is more preferably 60-150ml.
In processing sense material method of the present invention, development time is preferably 5-30 second, and 5-25 is good especially second.
The used best non-property separated out conductive material is done a record among the present invention.
When the non-stripping property among so-called the present invention is meant with automatic processing machine processing photosensitive material, do not separate out basically, specifically, the amount of separating out only accounts for 0-1 (weight) % of addition.
As used best conductive material among the present invention, can use crystalline metal oxide particle for containing oxygen defect and used metal oxide, contain the xenogenesis atom that minute quantity forms the alms giver, generally say high preferred especially of electric conductivity, the latter, owing to do not make silver emulsion cause photographic fog, so preferred especially.ZnO is arranged, mix the TiO of impurity as the metal oxide example 2, SnO 2, Al 2O 3, In 2O 3, SiO 2, MgO, BaO, MoO 3, V 2O 5Deng, or their composite oxides, ZnO, mix the TiO of impurity 2And SnO 2, best.As the example that contains the xenogenesis atom, for example,, can add Al, In etc., for SnO to ZnO 2, can add Sb, Nb, P, halogen etc., and for TiO 2, can add Nb, Ta etc., all be effective.The addition of these xenogenesis atoms is 0.01-30mol% preferably, is more preferably 0.1-10mol%.And then, for improving the microparticulate and the transparency, when making particulate, can add silicon compound.Best conductive material metal oxide microparticle has electric conductivity among the present invention, and its volume resistivity is 10 7Below Ω/cm, 10 5Good especially below Ω/cm.
About these oxides, all on the books in the spy opens clear 56-143431 number, 56-120519 number, 58-62647 number etc.
And then, in the public clear 59-6235 of spy number, put down in writing, can use above-mentioned metal oxide attached to the conductive material on other crystallinity metal oxide particle or the fibrous material (as titanium dioxide).
Available particle size is preferably in below the 1 μ m, and when when 0.5 μ m is following, stable fine after the dispersion is easy to use most.In order to reduce light scattering as far as possible, when the electroconductive particle below the use 0.3 μ m, particularly preferably be and form the transparent feel luminescent material.Though the lower limit to particle size does not have particular provisions, because more than the 0.01 μ m, electric conductivity is good, so be preferred.
Metal oxide microparticle is a needle-like or when fibrous, its length is preferably in below the 30 μ m, and diameter is preferably in below the 1 μ m, length below 10 μ m, diameter below 0.3 μ m, length good especially more than 3.
The metal oxide with electric conductivity that these are best among the present invention can be made coating liquid with bonding agent and apply, at this moment, and preferably more thereon with the bonding agent coating.
Best metal oxide and bonding agent used among the present invention apply meeting better simultaneously.There is not particular restriction as bonding agent, but, for example, can use water-soluble binder as gel and glucose, polyacrylamide, starch, polyvinyl alcohol (PVA) one class, also can use the synthesized polymer bonding agent of poly-(first) acrylate, polyvinyl acetate, poly-urethane, Polyvinylchloride, Polyvinylchloride fork styrene/butadiene copolymers, polystyrene, polyester, tygon, polyoxyethylene, polypropylene, polycarbonate etc. under organic solvent, the form that these polymeric binders can aqueous dispersion is used.
These metal oxides can will use after its ball shape and the fibrous mixing.
The content of used best metal oxide is 0.0005-1.0g/m among the present invention 2, 0.0010-0.5g/m 2Best, 0.0050-0.3g/m 2Good especially.
In the scope of not damaging effect of the present invention, not photochemical and membranous in the cambium layer of best metal oxide in by the present invention in order to improve, also can add heat-resistant agent, weatherability agent, inorganic particulate, water soluble resin, latex etc.
For example, in by the present invention, add inorganic fine particles in the best metal oxide cambium layer.As the inorganic particles sub-instance that adds, silicon dioxide, colloidal silica, aluminium oxide, alumina sol, porcelain earth, talcum, mica, lime carbonate etc. can have been enumerated.The mean grain size of particulate is preferably 0.01-10 μ m, and 0.01-5 μ m is better, is 0.05-10% to the weight ratio that applies solid constituent in the liquid, and 0.1-5% is good especially.
Also can add the rigidizer of various organic or inorganics in the coating agent of the present invention.These rigidizers both can be low molecular compounds, can be again macromolecular compounds, and these rigidizers both can use separately, use capable of being combined again.
As low molecule rigidizer, can use " the ザ セ ォ リ-ォ Block ザ Off ォ ト グ ラ Off ィ ッ Network プ ロ セ ス (The Theory of the Photographic Process) " the 4th edition that writes as テ ィ-ェ ィ チ ジ ェ-system ス (T.H.James), the low molecule rigidizer of putting down in writing in the 77-88 page or leaf, wherein, have the best of vinyl sulfonic acid, '-aziridino, epoxy radicals, triazine ring, open clear 53-41221 number the spy, the low molecular compound of record is better in 60-225143 number.So-called macromolecule rigidizer is meant to have more than at least 2 and opposite base, the molecular weight of hydrophilic colloid such as gel is the compound more than 2000 in a part; as with the base of hydrophilic gel precursor reactants such as gel, aldehyde radical, epoxy radicals, active halogenide (dichloro three azine groups, chlorotoluene vinyl, chloroethene sulfonyl etc.), active ethylene group, active ester groups etc. are for example arranged.
As macromolecule rigidizer used among the present invention, dialdehyde starch is preferably for example arranged, polyacrolein, United States Patent (USP) 3,396, the polymkeric substance with aldehyde radical as acrolein copolymer of record in No. 029, has United States Patent (USP) 3,623, the polymkeric substance of the epoxy radicals of record in No. 878, the polymkeric substance with dichlorotriazine base of record in リ サ-チ デ ィ ス Network ロ-ジ ャ-will 17333 (1978) etc., the spy opens the polymkeric substance with active ester groups of record in clear 56-66841 number, the spy opens clear 56-142524 number, United States Patent (USP) 4,161, No. 407, the spy opens clear 54-65033 number, record has an active ethylene group in リ サ-チ デ ィ ス Network ロ-ジ ャ-will 16725 (1978) etc., or has the polymkeric substance of the base that forms its precursor.Open in clear 56-142524 number record the spy, according to long interval, the active ethylene group of combination or the polymkeric substance that forms its precursor base also are preferred on main polymer chain.
Tell about used best electric conductive polymer or latex among the present invention below.Used electric conductive polymer do not have particular determination, feminine gender, the positive, beet alkalescence and nonionic any can, it is negative and positive that wherein best is.Be more preferably negative sulfonic acid system, carboxylic acid system, phosphoric acid based polymer or latex, tertiary amine system, level Four ammonium system, phosphorus system.These electric conductive polymers, for example can enumerate special public clear 52-25251 number, spy and open the negative based polymer or the latex of record in clear 51-29923 number, special public clear 60-48024 number, the positive based polymer or the latex of record in No. 4118231, special public clear 57-18176 number, 57-56059 number, 58-56856 number, United States Patent (USP) etc.
The instantiation of these electric conductive polymers or latex is below described, but not only for these.
[changing 38] P-1
Figure A9611262300531
(mean molecular weight 150,000) P-2 P-3
Figure A9611262300533
X: y=70: 30 (mean molecular weight 4.5 ten thousand)
Figure A9611262300534
X: y=50: 50 (mean molecular weight 1.2 ten thousand)
[changing 39] X: y=30: 70 (latex) P-6
Figure A9611262300542
(mean molecular weight 10,000)
Figure A9611262300543
(mean molecular weight 30,000)
Just treating fluid is had the good non-property separated out this point among the present invention,, preferably use metal oxide as conductive material.
The interpolation layer of used preferred conductive metal oxide, polymkeric substance and latex not merely is limited to the side that has emulsion on the supporter among the present invention, for example can enumerate in protective seam, middle layer, emulsion layer, UV layer, anti-halation layer, following coating.In these,, particularly preferably be down coating, middle layer, anti-halation layer as protective seam preferably, middle layer, anti-halation layer, coating down.
The present invention be applicable to printing photosensitive material, mocromembrane with photosensitive material, medical X-ray photosensitive material, industrial X ray photosensitive material, general negative film photosensitive material, general TV rehearse record photosensitive material etc. black and white silver halide sensitive photographic material and general colour negative photosensitive material, generally color TV is rehearsed the record photosensitive material.Preferably be used for medical X ray photosensitive material.
Used various adjuvants in sensitive photographic material of the present invention do not have specific limited, below for example can using
The corresponding position of project
1) the silver emulsion spy opens the 8th page of hurdle, bottom right 6 of flat 2-68539 communique
With its method for making row～10th page upper right hurdle 12 row, 3-24537
Number the 2nd page of hurdle, bottom right 10 of communique walks to the 6th page of upper right hurdle 1
Row, the 10th page of upper left hurdle 16 walk to the 11st page of hurdle, lower-left
19 row, spy open flat 4-107442 number.
2) chemical sensitization method spy opens the 10th page of upper right hurdle of flat 2-68539 communique
13 row are opened flat 5-3132 to upper left hurdle 16 row, spy
No. 82.
3) antifoggant, spy open the 10th page of hurdle, lower-left of flat 2-68539 communique
Stabilizing agent 17 row are to 7 row and the 3rd page of hurdles, lower-left, the 11st page of upper left hurdle
2 row are to the 4th page of hurdle, lower-left.
4) hue improvements agent spy opens the 2nd page of hurdle, lower-left of clear 62-276539 communique
20 row, spy open flat 3-94 to 7 row to the 10th page of hurdle, lower-left
The 6th page of hurdle, lower-left of No. 249 communiques 15 row are to the 11st page of right side
Last hurdle 19 row.
5) beam split sensitizing coloring matter spy opens the 4th page of hurdle, bottom right of flat 2-68539 communique 4 row
To the 8th page of hurdle, bottom right.
6) surfactant, spy open the 11st page of upper left hurdle of flat 2-68539 communique
Anti-live agent 14 and walk to the 12nd page of upper left hurdle 9 row.
7) photo etching, smooth spy do not open the 12nd page of upper left hurdle of flat 2-68539 communique
Agent, plasticizer 10 walk to upper right hurdle 10 row, the 14th page of hurdle, lower-left 10 row
1 row to the hurdle, bottom right.
8) the hydrophilic colloid spy opens the 12nd page of upper right hurdle of flat 2-68539 communique
11 walk to hurdle, lower-left 16 row.
9) the hard coat agent spy opens the 12nd page of hurdle, lower-left of flat 2-68539 communique
17 walk to the 13rd page of upper right hurdle 6 row.
10) the supporter spy opens the 13rd page of upper right hurdle 7 of flat 2-68539 communique
Walk to 20 row.
11) the transverse cut method spy opens the 4th page of upper right hurdle of flat 2-264944 communique
20 walk to the 14th page of upper right hurdle.
12) dyestuff, mordant spy open the 13rd page of hurdle, lower-left 1 of flat 2-68539 communique
Row is 9 row to the 14th page of hurdle, lower-left.The 3-24537 public affairs
Report hurdle, 16 pages of bottom rights, the 14th page of hurdle to the, lower-left.
13) poly-Hydroxybenzenes spy opens the 11st page of upper left hurdle of flat 3-39948 communique and arrives
The 12nd page of hurdle, lower-left, EP patent 452772A number
Communique.
14) floor structure spy opens flat 3-198041 communique.
15) the developing method spy opens the 16th page of upper right hurdle of flat 2-103037 communique
7 the row to the 19th page of hurdle, lower-left 15 the row and the spy open flat 2-
The 3rd page of hurdle, bottom right of No. 115837 communiques 5 row are to the 6th page
Upper right hurdle 10 row.
Below just the present invention specify, the present invention is not limited to this.
Embodiment 1
(100) preparation of the dull and stereotyped emulsion A of face
The 1582ml gel solution of packing in reaction vessel [gel-1 (methionine contains rate and is about 40 μ mol/g, breaks away from the gel that sub-choline is handled) 19.5g, contains the 1 equivalent HNO of 7.8ml 3Solution, PH4.3], 13ml NaCl-1 liquid (in 100ml, containing 10gNaCl), temperature keeps 40 ℃, simultaneously with the 62.4ml/ branch, adds 15.6ml Ag-1 liquid at every turn and (contains 20g AgNO among the 100ml 3) and X-1 liquid (containing 17.05g NaCl among the 100ml), mix.Stir after 3 minutes,, add 28.2ml Ag-2 liquid at every turn and (contain 2g AgNO among the 100ml simultaneously with the 80.6ml/ branch 3) and X-2 liquid (containing 1.4g KBr among the 100ml), mix, stir after 3 minutes, simultaneously with the 62.4ml/ branch, each 46.8ml Ag-1 liquid and X-1 liquid of adding, mix, stir after 2 minutes, add 203ml gel solution (pH value that contains gel-1 13g, NaCl 1.3g and be furnishing table 1 adds 1 equivalent NaOH liquid) again.After PCl is set at 1.8, be warmed up to 75 ℃, PCl is set at 1.8 post curings 42 minutes.Again with per minute 2.68 * 10 -2The interpolation speed of mol is added 20 minutes AgCl fine grain emulsions (mean grain size 0.1 μ m).After the interpolation, slaking added sinking agent after 10 minutes, cooled the temperature to 35 ℃, carried out the sedimentation washing.Adding gel solution, is 6.0 at 60 ℃ of downward modulation PH.Observe the photo (following note is made TEM) of the transmission electron microscope of this particle replicate sample.The emulsion that obtains is that benchmark calculates the dull and stereotyped particle of high-silver chloride (100) face that contains 0.44mol%AgBr with silver.The style characteristic value of this particle is described below.
(than shape than 2 big full projected areas of tabular particle/total sub-projected area of AgX particle and) * 100=a 1=90%
[average shape of tabular particle is than (mean diameter/average thickness)]=a 2=9.3
(mean diameter of tabular particle)=a 3=1.67 μ m
(average thickness)=a 4=0.18 μ m
(111) preparation of the dull and stereotyped emulsion B of face
Prepare the dull and stereotyped particle of silver chloride as follows.
The insoluble gel 30g of solution (1)
Brilliant wall controlling agent A 0.5g
Brilliant wall controlling agent B 0.5g
[changing 40]
Brilliant wall controlling agent A
Brilliant wall controlling agent B
Figure A9611262300582
NaCl??????????????4g
H 2O??????????????1750ml
Solution (2) AgNO 37.6g
Add water 30ml
Solution (3) NaCl 2.8g
Add water 30ml
Solution (4) AgNO 324.5g
Add water 96ml
Solution (5) NaCl 0.3g
Add water 65ml
Solution (6) AgNO 3101.9g
Add water 400ml
Solution (7) NaCl 37.6g
Add water 400ml
Solution (2) and solution (3) are stirred in the solution (1) that joined 35 ℃ of maintenances down in 1 minute simultaneously, in 15 minutes, solution temperature is raised to 50 ℃.Form the particle that is equivalent to total silver amount about 5.7% this moment.Then, in 24 minutes, simultaneously solution (4) and solution (5) are added, in 40 minutes, solution (6) and solution (7) are added simultaneously again, obtain the dull and stereotyped emulsion of silver chloride.
After utilizing sedimentation that emulsion is washed desalination, add 30g gel and water, add 2.0g Phenoxyethanol and the 0.8g kayexalate as tackifier again, transferring PH with NaoH again is 6.0, disperses again.
The emulsion that obtains like this is a 1=90%, a 3=1.55um, a 4=0.18um, a 2=8.6, the coefficient of alteration that is equivalent to circular projection's area diameter is that (111) face of 19% is as the dull and stereotyped emulsion of the silver chloride of principal plane.
The preparation of tabular particle C.
In 1 premium on currency, add 6.0g potassium bromide, 7.0g mean molecular weight 10,000 5 thousand low-molecular-weight gels, remain on 55 ℃, utilize the double shed method, in 37 seconds, add the aqueous solution that 37ml silver nitrate aqueous solution (silver nitrate 4.00g) and 38ml contain the 5.9g silver bromide while stirring.After then adding the 18.6g gel, be warmed up to 70 ℃.In 22 minutes, add 89ml silver nitrate aqueous solution (silver nitrate 9.80g) again, add the ammonia spirit of 7ml 25% this moment.After keeping carry out physics slaking in 10 minutes under the temperature this moment, add 6.5ml 100% acetum again.The limit keeps the PAg8.5 limit with control double shed method, adds 153g silver nitrate aqueous solution and kbr aqueous solution in 35 minutes.Then, add the potassium rhodanide solution of 15ml 2N.Under the temperature, the physics slaking cooled the temperature to 35 ℃ after 5 minutes at this moment.Obtain a 1=95%, averaging projection's area diameter a 3=1.50 μ m, thickness a 4=0.185 μ m, average shape compare a 2=8.1, the variation in diameter coefficient is single { the pure silver bromide tabular of 111} particle that disperses of 18.5%.
After this, remove the solubility salt with sedimentation.Be warmed up to 40 ℃ again, add 30g gel and 2.35g Phenoxyethanol and the 0.8g kayexalate as tackifier, transferring PH with NaOH and liquor argenti nitratis ophthalmicus is 5.90, and PAg is 8.00.
{ the preparation of the dull and stereotyped emulsion D of 100}AgBrCl
Add the 1582ml gel solution to reaction vessel and (gel-1 (methionine contains the gel that the sub-choline of disengaging that rate is about 40 μ mol/g is handled) 19.5g, contain 7.8ml 1NHNO 3Liquid, PH4.3), 13ml NaCl-1 liquid (in 100ml, containing 10gNaCl), keep 40 ℃ of temperature, simultaneously with the 62.4ml/ branch, add 15.6ml Ag-1 liquid at every turn and (contain 20gAgNO among the 100ml 3) and X-1 (containing 7.05gNaCl among the 100ml).Mix and stir after 3 minutes,, add 28.2ml Ag-2 liquid at every turn and (contain 2gAgNO among the 100ml simultaneously with the 80.6ml/ branch 3) and X-2 liquid (containing 1.4g KBr among the 100ml).Mix and stir after 3 minutes, again with the 62.4ml/ branch, each 46.8ml adds Ag-1 liquid and X-1 liquid simultaneously, mix and stir after 2 minutes, after adding 203ml gel solution (contain 13g gel-1,1.3g NaCl, for transferring the 1N NaOH liquid of PH to 5.5), PCl being adjusted to 1.8, be warmed up to 75 ℃, PCl is adjusted to 1.8 after-ripening and divided 10 minutes.After this, plant with control double shed method, with 2.68 * 10 -2Mol/ divides interpolation speed to add Ag-3 liquid (100%AgNO among the 100ml 350ml), X-3 liquid (58.8g NaCl among the 100ml), be 1.8 times at PCl, grew up 20 minutes.
After the interpolation, slaking added sinking agent, is cooled to 35 ℃ after 10 minutes, carried out the sedimentation washing, added gel solution, was 6.0 at 60 ℃ of downward modulation PH.Observe the photo (following note is made TEM) of transmission electron microscope of the replicate sample of this particle.The emulsion that obtains is high-silver chloride { the dull and stereotyped particle of 100} that benchmark calculates the AgBr that contains 50mol% approximately with silver.The shape performance number of this particle is as follows.
(shape frequently 2 big tabular particle total projection area/total AgX particle projected areas and) * 100=a 1=90%
(average shape of tabular particle is than (mean diameter/average thickness))=a 2=9.3
(mean diameter of tabular particle)=a 3=1.67 μ m
(average thickness)=a 4=0.18 μ m
In adjusting tabular particle B, by adding (6) liquid and (7) when liquid is grown up, (7) liquid is made the mixed liquor of potassium bromide and potassium chloride, make that shape is roughly contained rate with the identical silver chloride of tabular particle B than shapes of particle such as, particle sizes is (100) face of 17% chlorine silver bromide flat board emulsion E as principal plane.Other condition is identical with the condition of making tabular particle B.
The preparation of monodispersion cubic silver emulsion
Dissolving 32g gel in 1 premium on currency, in being warmed to 53 ℃ container, add 0.3g potassium bromide, 5g sodium chloride and 46mg compound [I] after
[changing 41]
Figure A9611262300601
Utilize the double shed method, add the aqueous solution that 444ml contains the 80g silver nitrate in 20 minutes, 452ml contains the aqueous solution of 45g potassium bromide and 5.5g sodium chloride, afterwards, use the double shed method again, add in 25 minutes that 400ml contains the 80g silver nitrate aqueous solution and 415ml contains 46.4g potassium bromide, 5.7g sodium chloride and the sour potassium (10 of hexachloro iridium (III) -7Mol/mol silver), the cube list that is made into average particle size (area diameter projected) 0.34 μ m divides chlorine silver bromide particle F (coefficient of alteration 10% of area diameter projected).
After utilizing coacervation that this emulsion is carried out desalting processing, adding 62g gel, 1.75g Phenoxyethanol, making PH is 6.5, and PAg is 8.5.
Chemical sensitization
With the particle A～F that as above modulates, stir on the limit, and the limit is keeping implementing chemical sensitization under 60 ℃ of states.At first, every 1mol silver halide is added 10 -4Mol thiosulfonic acid compound-I, then, adding the 1.0mol% diameter at total silver amount is 0.10 μ mAgBr particulate, adds 1 * 10 at every mol Ag again -6Mol sulphuric dioxide urine, under this state, implemented reduction sensitization 22 minutes.Then add (at every molAg) 3 * 10 respectively -4Mol 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four azine ketone and sensitizing coloring matter-1,2.Add lime chloride again.Continue to add sodium thiosulfate (6 * 10 -6Mol/mol Ag) and selenium compound-1 (4 * 10 -6Mol/molAg).Add gold chloride 1 * 10 again -5Mol/molAg and potassium rhodanide 3.0 * 10 -3Mol/mol Ag, be cooled to 35 ℃ after 40 minutes.
The preparation of emulsion like this (chemical slaking) just finishes.
[changing 42]
Thiosulfonic acid compound-I
C 2H 5?SO 2?SNa
Sensitizing coloring matter-1
Figure A9611262300611
Sensitizing coloring matter-2
Selenium compound-I
The preparation of emulsion layer coating liquid
Each composition that adds in emulsion, the sheet side of each supporter is pressed the coating liquid that the note coating weight is modulated emulsion layer.
2.6-two (hydroxylamino)-4-lignocaines-1,3,5
-three azine 1.7mg/m 2
Glucose (mean molecular weight 30,000 9 thousand) 0.45g/m 2
Sodium apolate 33mg/m 2
(mean molecular weight 600,000) (containing the emulsion adding ingredient)
Gel 1.1g/m 2
(containing the emulsion adding ingredient)
Hard coat agent
1,2-two (ethene sulphonyl acetamide) ethane 55mg/m 2
P-dihydroxy-benzene sodium monosulfate 0.11g/m 2
Dyestuff emulsion b (as the dye solids composition) 4.0mg/m 2
Dyestuff emulsion m (as the dye solids composition) 4.0mg/m 2
Infrared dyes is disperseed the addition of thing (as the dye solids composition) table 1 record and is added layer
Compound example 1 of the present invention
[changing 43]
Dyestuff-b
Dyestuff-m
Figure A9611262300632
Each composition of the preparation sealer of sealer coating liquid is pressed note coating amount modulation sealer coating liquid.Gel 0.60g/m 2Benzene isothiazoline 1.4mg/m 2Sodium polyacrylate (mean molecular weight 4.1 ten thousand) 17mg/m 2Adjuvant-1 35mg/m 2Adjuvant-2 5.4mg/m 2Adjuvant-3 22.5mg/m 2Adjuvant-4 0.5mg/m 2Photo etching-1 (averaged particles footpath 3.7 μ m) 72.5mg/m not 2Or not any (note) in the photo etching-2 in table 1
[changing 44]
Adjuvant-1 C 18H 33O (CH 2CH 2O) 10H
Adjuvant-2 C 8F 17SO 3K
Adjuvant-3
Adjuvant-4
No photo etching-1
Figure A9611262300643
〔x/y/z＝76.3/17.5/6.2)
The preparation gel 0.50g/m of no photo etching-2 poly-methyl methacrylate middle layer coating liquid 2The benzene isothiazoline
1.4mg/m 2Sodium polyacrylate (mean molecular weight 4.1 ten thousand)
17mg/m 2The addition Infrared dyes of addition compound example (17) table 1 record of sulfhydryl compound compound example of the present invention (12) table 1 record is disperseed the addition of thing (as the dye solids composition) table 1 record
Compound example 1 of the present invention
(preparation of supporter)
(1) coating is disperseed the preparation of thing B under with dyestuff
Open the method for record in clear 63-197943 number with the spy, following compd B-1 is carried out the ball milling hybrid processing.
[changing 45]
Compd B-1
Figure A9611262300651
In 2 liters of bowl mill, pack into 434ml water and 791ml 6.7%Triton * 200 (registered trademark) surfactant [TX-200 (registered trademark)] aqueous solution are added 400ml zirconium dioxide (ZrO again 2) pearl, content was pulverized 4 days.Afterwards, add 160g 12.5% gel.Deaeration removes by filter ZrO after handling 2Pearl.When observable dyestuff disperseed thing, it was between 0.05～1.15 μ m that the dye particle of pulverizing has very wide scope, and mean grain size is 0.37 μ m.
Carry out again centrifuging remove 0.9 μ m above than the big dye particle.
Obtain such dyestuff and disperse thing d.
(2) preparation of supporter
Carry out corona discharge on the tygon terephthalate thin slice of twin shaft extension thickness 175 μ m, the first time masking liquid that utilizes cable converter to descend note to form applies, and coating amount is 4.9ml/m 2, drying is 1 minute under 185 ℃.
Then the 1st time same coating is set at its reverse side.The compd A-9 that in employed tygon terephthalate, contains 0.04wt%.Butadiene-styrene copolymer latex solution (solid constituent 40% Butadiene weight ratio=31/69) 158ml2 contains the emulsifying dispersant B-2 of 0.4wt% at the solid constituent of latex in 4-two chloro-6-hydroxyl-S-three azine sodium salts 4% solution 41ml distilled water 801ml ※ latex solution.
(changing 46)
Emulsifying dispersant B-2
Figure A9611262300661
(3) coating of coating down
On the 1st coating on above-mentioned two sides, by the coating amount of putting down in writing below, on each sheet side, on the two sides, apply the 2nd time coating of following composition according to lines (ヮ ィ ャ-バ-ュ-ダ-) mode, dry down at 155 ℃.
Gel 80mg/m 2
Dyestuff disperses thing B (as the dye solids composition) 8
Compd B-3 1.8
Compd B-4 0.27
The poly-methyl methacrylate 2.5 of photo etching mean grain size 2.5 μ m not
(changing 47)
Compd B-3
C 12H 20O(CH 2CH 2O) 10H
Compd B-4
Figure A9611262300671
The preparation of photographic material
Utilize extrusion, will giving earlier simultaneously, the coating liquid in emulsion, sealer and the middle layer of modulation is coated under identical conditions on the two sides of paying the PET support of 175 μ m of coating down simultaneously.Each amount of medicament of the gel content of emulsion layer and emulsion layer is for each certain emulsion of coating amount, and amount of medicament all will change after each coating.
The silver coating amount of each photographic material is according to the amount (g/m shown in the table 1 2) set.The middle layer is configured in the centre of sealer and emulsion layer.
Table 1
Record as any one unilateral coating amount
Constitute photographic material The silver amount that the is coated with g/m of emulsion layer 2 Infrared dyes is disperseed thing I The sulfhydryl compound in middle layer Sealer ス ッ ト agent kind
Sealer mg/m 2 Middle layer mg/m 2 Emulsion layer mg/m 2 Compound (12) mg/m 2 Compound (17) mg/m 2
1 the present invention, 2 ＂, 3 comparative examples, 4 the present invention, 5 comparative examples, 6 ＂, 7 ＂, 8 ＂, 9 ＂, 10 ＂, 11 the present invention, 12 comparative examples, 13 the present invention, 14 ＂ ?A?1.4 ?B?＂ ?C?＂ ?D?＂ ?E?＂ ?F?＂ ?A?＂ ?A?＂ ?A?＂ ?A?＂ ?A?＂ ?A?1.7 ?A?1.2 ?B?1.4 No ＂ ＂ ＂ ＂ ＂ ＂ 20 no ＂ ＂ ＂ ＂ ＂ 20 ＂ ＂ ＂ ＂ ＂ do not have ＂ ＂ 20 20 ＂ ＂ ＂ No ＂ ＂ ＂ ＂ ＂ ＂ ＂ 20 no ＂ ＂ ＂ ＂ 3 ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ do not have 3 ＂ ＂ ＂ 3 ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ do not have 3 ＂ ＂ ＂ ???1 ???＂ ???＂ ???＂ ???＂ ????? ???＂ ??????? ???＂ ???＂?? ?????? ???＂ ????? ???＂ ???2 ???1 ???1 ???2
Utilizing the special method of opening record in clear 58-111933 number to measure the swelling rate of gained photographic material, is 180%.
Concentrate the preparation of developer solution
Adjust remembering the concentrated developer solution A of the different anti-hematic acid sodium of prescription down as the development main ingredient
Divinyl triammonium five acetic acid 8.0g
Sodium sulphite 20.0g
Sodium carbonate 1 water salt 52.0g
Sal tartari 55.0g
Sodium isoascorbate 60.0g
4-methylol-4-methyl isophthalic acid-benzene-3-pyrazolidone 13.2g
3,3-hexichol-3,3-two sulphur propionic acid 1.44g
Diethylene glycol 50.0g
Add entry and be taken as 1 liter
Transferring pH value with NaOH is 10.1.
The preparation of developer replenisher solution
With 2 times of above-mentioned concentrated developer solution dilutions, make developer replenisher solution and use.
The preparation of development mother liquor
Go up 2 and to state concentrated developer solution, be diluted with water to 4 liters, the developer solution of per 1 liter of dilution adds the primer fluid of the following composition of 55ml, with the developer solution of PH9.5 as the development mother liquor.
Primer fluid
Potassium bromide 11.1g
Acetic acid 10.8g
Add entry and be taken as 55ml.
The preparation of concentrated fixing solution
By following formulation concentrated fixing solution.
Water 0.51
Ethylene dinitrilotetra-acetic acid 2 water salt 0.05g
Sodium thiosulfate 5 water salt 200g
Sodium bisulfite 98.0g
NaOH????????????????????????2.9g
Transfer PH5.2 with NaOH, add water and make 1 liter.
Photographic fixing replenishes the preparation of liquid
With 2 times of above-mentioned concentrated fixing solution dilutions, do photographic fixing and replenish the liquid use.
The preparation of photographic fixing mother liquor
Go up 2 and to state the concentrated fixing solution dilute with water and make 4 liters, pH value is 5.4.
The processing of photographic material
Use has improved the automatic processing machine CEPROS30 of Fuji's photographic roll film (strain) society system of drive system and aperture opening ratio 0.02, on one side use above-mentioned development mother and photographic fixing mother liquor to handle photographic material, Yi Bian with every 1m 2Developer replenisher solution and the additional liquid of photographic fixing that photosensitive material replenishes 50ml replenish.
The process temperature processing time
Develop 35 ℃ about 8 seconds
35 ℃ of photographic fixing are about 8 seconds
Wash 25 ℃ about 6 seconds
55 ℃ of dryings are about 5 seconds
The evaluation of fixing performance
Use above-mentioned treating fluid and show machine certainly,, be cut into four sizes, in the darkroom, handle photographic material 1-14.No matter whether photographic fixing, the film after handling of detecting by an unaided eye is estimated, and the results are shown in table 2.
The evaluation of darkroom light stability
Use commercially available darkroom film machine-No.8U according to Fuji's photographic film (strain), by exposing with the rising degree of relative blackness to darkroom light.Comparison other disperses the photographic material 3 of thing 1 for adding Infrared dyes, makes the rise evaluation of estimate that likens the darkroom light stability to of the melanism rising value under 0.2 condition of photographic material 3 melanism concentration when carrying out above-mentioned processing after the exposure.
Therefore, the stability of this big more darkroom of value light is poor more.
Use the evaluation of detecting property of infrared eye
Use the X-ray television of Shimadzu Seisakusho Ltd.'s (strain) system: ZS-15, carry out the transportation performance test of photographic material.According to having or not the judgement of carrying bad phenomenon to detect performance " can " with " can not ".The results are shown in table 2.
The evaluation of Infrared dyes duplicating property
With kapok white glove wiping photographic material 1～14.If several Infrared dyes of making carbon copies on white glove are arranged in the affirmation photographic material, then show in the practicality to have problems.
Table 2
Photographic material Fixation performance The darkroom light stability Detecting property with infrared eye The duplicating of red outer dyestuff
????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 But ＂ not cocoa must cocoa cocoa cocoa can not cocoa But but but ＂ not cocoa can not cocoa must cocoa ＂ ＂ But but ＂ ＂ ＂ ＂ ＂ can not cocoa cocoa ＂ ＂ But ＂ ＂ ＂ ＂ ＂ ＂ can not cocoa cocoa ＂ ＂
Embodiment 2
The evaluation for the treatment of fluid pollution situation
Above-mentioned treating fluid, after showing the photographic material 1～14 that will be cut into 4 kinds of sizes in the machine certainly, handling 1000, the melanism rate of developed silver reaches 40%.With the naked eye estimate the turbidity of developer solution, stop bath afterwards.Its result uses not the present invention of photo etching-1, no matter is the transparency for the treatment of fluid, and the still sediment at the bottom of showing trough is all good than the present invention who uses photo etching-2 not.
, have only the photographic material that satisfies the present invention's formation to solve all problems, the object of the invention has also just reached.By above argumentation, effect of the present invention also is conspicuous.
Embodiment 3
Just the same with the method for making of making photographic material 1,4 among the embodiment 1, still, change hard coat agent and silver coating amount, make the test portion of table 3.
In addition, the swelling rate is measured according to the definition of record herein.
Table 3
Photographic material Emulsion The silver amount g/m that each is unilateral 2 Swelling rate (%)
????15 ????16 ????17 ????18 ????19 ????20 ????21 ????22 ????23 ????A ?????? ????＂ ????＂ ????＂ ????＂ ????＂ ????C ?????? ????＂ ????＂ ????1.7 ????1.7 ????1.4 ????1.4 ????1.4 ????1.2 ????1.4 ????1.4 ????1.2 ????250 ????180 ????250 ????190 ????160 ????160 ????190 ????160 ????160
(evaluation of photographic property)
Use above-mentioned treating fluid and automatic processing machine, according to above-mentioned compensation process, (melanism rate 40% is treated to running status 1000 of the photographic materials that is cut into 4 kinds of sizes.
The X レ ィ ォ Le ソ ス Network リ-Application HG-M that uses Fuji's photographic film (strain) society system was from each photographic material exposure of two side direction 0.1 second, from developing to 30 seconds (developing 8 seconds) of dried, change processing speed, handle 45 seconds (developing 13 seconds), feel the sensitivity evaluation.
Photographic material 15 was handled 30 seconds, and the sensitivity that obtains is decided to be 100, the photographic sensitivity of each photographic material, when developed concentration reach handled in 45 seconds obtain maximum concentration 50% the time, given exposure is represented with the photographic material 1 and the inverse of its ratio.Big that of value with expression sensitivity serves as preferred.In addition, the difference that developed concentration uses supporter and unexposed portion to be applied concentration represents that maximum concentration uses the difference of supporter concentration to represent.1Dmax is paying under the maximum exposure amount in the table 4, and the developed concentration of handling 30 seconds is abundant state of saturation, when identical with the Cmax of handling 45 seconds, with zero expression, when unsaturated with * expression.The test portion of * expression, showing develops in its development time does not finish.
(evaluation of drying property)
In the automatic processing machine of this experiment, when the various test portions of 35cm * 35cm (big angle size) are handled 120 seconds, estimate by the test portion that touches out in dry section exit.
Zero: dry good
*: wetly problem
The results are shown in table 4, photographic material of the present invention in 120 seconds handle, can obtain handling the sensitivity that is equal to mutually with 180 seconds, and Dmax is illustrated in the processing in 120 seconds and has finished sufficient development.The stability of sensitivity and gray shade scale is very high, and good that of drying property is exactly photographic material of the present invention.
Table 4
Photographic material Handled in 30 seconds Handled in 45 seconds Drying property (handling in 30 seconds)
Sensitivity Dmax Sensitivity ??DmaX
????15 ????16 ????17 ????18 ????19 ????20 ????21 ????22 ????23 ??100 ??100 ??110 ??120 ??120 ??120 ??80 ??60 ??60 × × ○ ○ ○ ○ × × × ??110 ??110 ??120 ??120 ??120 ??120 ??100 ??75 ??70 ??3.9 ??3.9 ??3.5 ??3.5 ??3.5 ??3.0 ??3.2 ??3.1 ??2.6 × ○ × ○ ○ ○ ○ ○ ○
Embodiment 4
(being coated with the preparation of the supporter of conductive layer)
As the 2nd time coating of supporter of embodiment 1, according to the amount of following record, coating electrically conductive layer on, the two sides unilateral at each according to the lines mode carries out drying, makes supporter.
Gel 19mg/m 2
SnO 2/ Sb (weight ratio 9/1, average material footpath 0.24 μ m)
160mg/m 2
(preparation of photographic material)
On above-mentioned ready supporter, with the method identical with embodiment 1, emulsion layer, middle layer, the sealer of coating test portion 11 same recipe of coating and embodiment 1 on the two sides.If this coating test portion is α-1.
Removing adjuvant 1 from the prescription of the sealer of coating test portion α-1 establishes this coating test portion and is coating test portion α-2.
(mensuration of surface impedance value)
With each test portion of test portion 11, α-1, α-2, under 25 ℃ of 10%RH environment,, measure surface impedance value (logSR) through 6 hours.
(the low disposal route of replenishing, and estimate)
Use the automatic processing machine and the treating fluid that use among the embodiment 1, from new liquid, supplementary condition is that 5ml/ is cut into 4 sizes, each test portion for test portion 14, α-1, α-2, reach 40% according to visualization ratio and expose, handle 1000 (being cut into 4 kinds of sizes), 30 seconds processing times.
Estimate, how much are the film development degree of uniformity that comparison process is crossed and the foam of developer solution, about developing evenly, 900～1000 film is handled in observation, note work when the inhomogeneous generation of developing is a lot *, developing has inhomogeneous generation slightly, and note is made △ when in fact having no problem, and note does not do zero when almost finding non-uniform phenomenon.
The foam of record developer solution, observe handled 1000 after under running status developing trough, when paying on roller if any bubble, record " having " in table 5, record " nothing " when almost not finding not have bubble paying.
Coating test portion α-2 with conductive layer shown in the table 5 has extremely excellent static characteristic in extremely low additional processing of this experiment, almost do not produce foam and the uneven phenomenon of developing.
Table 5
Photographic material Conductive layer ?log(SR) The bubble of developer solution Develop evenly not
????11 ???α-1 ???α-1 Not having has 13.5 measuring can not 11.0 Have or not × △ ○
Coating test portion α-1, α-2, its swelling rate all is 175%, drying property is the same good with test portion 11.No matter be to handle 30 seconds or 45 seconds, photographic properties such as sensitivity, Dmax are all the same with test portion 11, have same performance.

Claims (7)

1; a kind of silver halide photographic sensitive material; it is characterized in that: in silver halide photographic sensitive material, contain on supporter the photonasty silver halide emulsion layer of one deck at least; sealer with the superiors; and the hydrophilic colloid layer different with these; the emulsion of the photonasty silver halide emulsion layer that applies on this supporter is at least a to be that the total projection area of contained silver halide particle in this emulsion is at least 50%; the shape ratio is at the dull and stereotyped particle more than 2; the silver chloride containing ratio of this emulsion is more than 20mol%; contain the dispergated dyestuff of the non-property separated out solia particle in the hydrophilic colloid layer beyond photonasty silver halide emulsion layer and sealer with following general expression (I) expression; and the hydrophilic colloid layer on the supporter contains the sulfhydryl compound that following general expression (II) is represented in one deck at least.
[changing 1]
General expression (I)
In the formula, R 10And R 11Represent alkyl, aralkyl or alkylene respectively, R 12And R 14Represent hydrogen atom respectively or be connected to each other to form 5 or 6 yuan of necessary former subgroups of ring, R 13The expression aryl ,-N (R 19) (R 20) ,-SR 21Or-OR 22, R 19Expression hydrogen atom, alkyl or aryl, R 20Expression aryl, sulfo group or acyl group, R 19And R 20Can interlink and form ring, R 21And R 22Represent aryl respectively, R 15, R 16, R 17And R 18Expression alkyl, R 15And R 16, R 17And R 18Can link and form ring.
[changing 2]
General expression (II)
In the formula, Z represents directly or indirectly to have-SO 3M ,-COOR 1,-OH and-NHR 2In at least one complex loop, M represents hydrogen atom, alkali metal atom or level Four amino or level Four phosphorus base, R 1The expression hydrogen atom, alkali metal atom, or the alkyl of 1-6 carbon, R 2The alkyl of 1-6 carbon of expression hydrogen atom ,-COR 3,-COOR 3Or-SO 2R 3, R 3Expression hydrogen atom, fatty group or aromatic series base.
2, according to the silver halide photographic sensitive material of claim 1 record, it is characterized in that: it is the insoluble synthetic polymer particle of particle diameter 0.2～10 μ m alkali with following general expression (III) expression that sealer contains.
[changing 3]
In the formula, R 1Expression methyl or halogen atom, R 2Expression methyl or ethyl, R 3Expression hydrogen atom, methyl, L represents that the concatenating group of divalent, A represent ethylene unsaturated monomer, do not have two-fold more than 2 in monomer in conjunction with (key), P represents 0～2, q represents 0 or 1, W represents 3～60mol%, X represents 30～96.5mol%, Y represents 0.5～25mol%, and Z represents 0～30mol%, herein W+X+Y+Z=100mol R 10%.
3, according to the silver halide photographic sensitive material of claim 1 or 2, it is characterized in that: at least one side of supporter, Tu Yinliang is 0.5～1.5g/m 2, and the photonasty silver halide particle of this emulsion layer carries out sensitizing by selenium compound, and the swelling rate of total hydrophilic colloid layer of the opposite side of sensitive photographic material emulsion layer is 130～200%.
4, according to the silver halide photographic sensitive materials of claim 1,2 or 3 records, it is characterized in that: in this emulsion layer in the contained silver halide particle be projected area 50～100%, shape is than at 3～30 tabular silver halide particle.
5, according to the silver halide photographic sensitive material of claim 1,2,3 or 4 records, it is characterized in that: the layer that contains the non-property separated out conductive material is arranged.
6, a kind of disposal route of silver halide photographic sensitive material, it is characterized in that: handling with automatic processing machine in the method for silver halide photographic sensitive material, contain in the developer solution and remember the development main ingredient that general expression is represented down, in the developer solution that does not contain p-dihydroxy-benzene, the sensitive photographic material of record in the development treatment claim 1,2,3,4 or 5, development time was at 5～30 seconds.
General expression (IV)
[changing 4]
General expression (IV)
Figure A9611262300041
In the formula, R 1, R 2Represent hydroxyl, amino, sulfydryl or alkylthio group respectively, P, Q represent that respectively hydroxyl, carboxyl, alkoxy, sulfo group, amino, alkyl or aryl, P and Q interosculate R 1, R 2The carbon atom of ethene carbon atom that expression displacement is two and Y displacement forms the former subgroup of 5～8 yuan of rings simultaneously, and Y represents=O, or=N-R 3, R 3Expression hydrogen atom, hydroxyl, alkyl or acyl group.
7, according to the disposal route of the silver halide photographic sensitive material of record in the claim 6, it is characterized in that: the magnitude of recruitment of this developer solution, by every 1m 2Photosensitive material is 25～200ml.
CN 96112623 1995-07-20 1996-07-20 Silver halide photographic material Expired - Fee Related CN1100284C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP205123/1995 1995-07-20
JP20512395A JPH0934055A (en) 1995-07-20 1995-07-20 Silver halide photographic sensitive material
JP205123/95 1995-07-20

Publications (2)

Publication Number Publication Date
CN1166620A true CN1166620A (en) 1997-12-03
CN1100284C CN1100284C (en) 2003-01-29

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Application Number Title Priority Date Filing Date
CN 96112623 Expired - Fee Related CN1100284C (en) 1995-07-20 1996-07-20 Silver halide photographic material

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CN (1) CN1100284C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106661338A (en) * 2014-08-22 2017-05-10 富士胶片株式会社 Color developing composition, lithographic printing original plate, method for making lithographic printing plate, and color developer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106661338A (en) * 2014-08-22 2017-05-10 富士胶片株式会社 Color developing composition, lithographic printing original plate, method for making lithographic printing plate, and color developer
CN106661338B (en) * 2014-08-22 2019-09-27 富士胶片株式会社 Color composition, original edition of lithographic printing plate, lithographic printing plate method for platemaking and color developing agent

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