CN1327175A - Concentrated liquid colour developing agent of silver halide colour photographic material and developing processing method - Google Patents
Concentrated liquid colour developing agent of silver halide colour photographic material and developing processing method Download PDFInfo
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- CN1327175A CN1327175A CN 01102347 CN01102347A CN1327175A CN 1327175 A CN1327175 A CN 1327175A CN 01102347 CN01102347 CN 01102347 CN 01102347 A CN01102347 A CN 01102347A CN 1327175 A CN1327175 A CN 1327175A
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Abstract
A concentrated liquid color developer composition for a silver halide color photographic material which comprises at least one compound represented by the following formula (I) or (II): R1- (OC2H4)n-OH (I) wherein R1 represents an alkyl group having from 1 to 3 carbon atoms, and n represents an integer of from 4 to 9; R2-SO3M (II) wherein R2 represents an alkyl group having from 4 to 10 carbon atoms, and M represents a cation.
Description
The present invention relates to be used to handle the concentrated liquid color developer composition of silver halide color photographic materials and the developing method of using it.More specifically, the present invention relates to a kind of developing method, it can effectively prevent from the colour development pool wall to form crystallization and owing to the pollution that tar causes color developing tank occurs, and can the fine precipitation that prevents crystallization on the developing tank.
The disposal route of silver halide photographic material (for example silver halide color photographic materials) generally includes colour development step (the promptly colored development step that forms), desilverization step and photographic fixing step (for example water-washing step) as basic step.In the colour development step, by the silver of color developer and silver salt reaction formation progressively video picture dyeing and development.In desilverization step, the silver of the development that forms in the colour development step is had the bleaching agent oxidation of oxidative function, becomes silver salt, it and not the silver halide of usefulness remove from photographic layer by the fixing agent that forms soluble-salt.Perhaps, the oxidation of silver salt and removing by blixing solution of it are carried out in one step.The photographic fixing step is the step that is used to regulate the image layer environment, is used for the stability of the image that long-time protection forms, and it comprises and washing with water, water and stop bath washing, and perhaps stabilizing solution is replaced and is used for washing.
Except water-washing step, all treatment step is used in the aqueous solution (becoming Treatment Solution) of the processing chemical substance that contains one or more and is carried out.Because each Treatment Solution all is low-down concentration, consider economic point of view, but storage area and workability are normally unaccommodated, manufacturer is preparing the Treatment Solution of serviceable condition, then they are transported to treatment of laboratory, store them in treatment of laboratory.
For addressing this problem, two kinds of methods of conventional use, be that a kind of method is the ratio according to treatment solution compositions, prepare the processing chemical substance that constitutes treating fluid with the form of chemical substance powder potpourri, the form of solid processing agent with packing offers the development laboratory, before in the development laboratory, using the solid processing agent water is dissolved, be diluted to debita spissitudo, make treating fluid, another kind method is that the processing chemical substance of combination is dissolved into high concentration, with the packaged of concentrated liquid treating agent in container, offer the development laboratory, with the dissolving of concentrated liquid treating agent water equal solvent, be diluted to the concentration of prescription before in the development laboratory, using, make treating fluid.
Consider transportation cost and storage area, solid processing agent is favourable, but its inconvenience is to dissolve in the development laboratory, the dust of chemical substance scatters, chemical substance must mix, shortcoming is that the aqueous chemical material must be contained in (container for the treatment of agent) in the different containers under ordinary temp, mixes with minute Powdered chemical substance of packing respectively.
On the other hand, the major advantage of concentrated liquid treating agent is to save the dissolving work in the development laboratory, but the transportation and the storage problem that exist solid processing agent not have.Therefore, solid processing agent and liquid treating agent all have merits and demerits respectively, do not find that a kind for the treatment of agent can be at economy and environment (as reducing the treating agent volume, reduce waste canister, save the storage area, reduce transportation cost), simplification work (as saving the work of Treatment Solution preparation work) and security and various aspects be all satisfactory.
In recent years, improving aspect the solid processing agent, although obtained certain progress, (for example Canadian Patent 831 as the preparation method of the treating agent that discloses tablet form, 928), but,, more need the concentrated liquid treating agent from working simple angle and in order to increase the purpose of development treatment amount as the development treatment agent of in the development laboratory, using.Therefore need further to improve the concentrating degree of liquid treating agent, obtain the liquid treating agent that tightness degree is similar to solid processing agent.Yet do not produce obstruction for storage-stable concentrated liquid treating agent with in application, the concentrated liquid treating agent should be to have saturation solubility or lower uniform solution, and therefore further thickening is very difficult.
About the concentrated liquid treating agent, very early before with regard to the known gelatinization of black-and-white development Treatment Solution, in order to concentrate and other multiple purpose is also carried out gelatinization to color developer.For example,, attempt color developer is carried out thickening, also disclose application technology for the concentrated liquid treating agent of color photographic materials by using alginic acid as thickening imparting agent (being thickening agent).Yet the gelatinization of color developer does not improve the concentrating degree of handling chemical substance by improving solubleness, just delays precipitation, even or precipitation occurs and delay insoluble matter caking or set time.Therefore, although gelatinization can effectively prolong the serviceable life of a bit handling chemical substance, it can not effectively solve reduces the volume problem of handling chemical substance, so gelatinization is not a kind of technology of developing the liquid treating agent advantage.
The liquid treating agent of color photographic materials is by color developer, and bleaching agent and fixing agent or blixing agent and stabilizing solution are formed.In these treating agents, color developer contains the p-phenylene diamine derivative as developer, and this concentration of developer is low relatively, and this has limited thickening greatly, and this makes this developer be easy to precipitation in preservation.In addition because the oxidation in air easily of this developer, this developer in preservation through the time variation gradually.Therefore, the developer of air oxidation becomes tarry matters, is attached on the chamber wall, and this has hindered the recovery and reuse of container.Therefore, the color developer of Nong Suoing has the air oxidation of color developer in developer precipitation (because restriction of solubleness), the preservation and the color stain various problems of final container.
The method of the precipitation that prevents color developer is disclosed in many patents, comprise JP-A-6-194797 (" JP-A " used herein is meant " unexamined open Japanese patent application "), for example, disclose and added N alone or in combination, N-disubstituted benzenes amine derivative, alkyl diphenyl base ether disulfonic acid, anionic surfactant, aromatic sulphonic acid, p-toluenesulfonic acid or alkanolamine.Any one of these methods all has and necessarily prevents the effect that precipitates, but these effects are also all not enough, so these methods and do not mean that and solved this problem in fact.
And,, promote exploitation than the conventional more effective preservative agent of hydroxylamine salt that uses in order to prevent the air oxidation of colour development solution.Dialkyl group azanol and hydroxy alkyl hydrazine with better protective effect are disclosed in JP-A-4-443.Improved some preservation effects by adding these protective agents, but still needed further to improve.
As mentioned above, prevent that in order to improve the use adaptability of concentrated liquid development treatment agent, to press for color developer from generating precipitation, promptly improves solubleness and storage stability.
As a kind of method that addresses this problem, in JP-A-11-174643, disclose the vinyl urea and had the effect that the good middle developer generation that prevents the agent of concentrated liquid development treatment precipitates.Therefore, prevent agent, need prevent identical with the vinyl urea or better that precipitation from generating effect as such precipitation generation.
Because with above-mentioned concentrated liquid development treatment dilution agent, preparation colour development solution or colour development developer, in color developing tank, silver halide color photographic materials is handled by colour development, the colour development solution composition continues precipitation as colour development, this causes the phenomenon that the precipitated crystal of the composition of colour development solution upwards spreads along the development pool wall, or produces pollution by tar on the development pool wall, and the processing of colour development solution subsequently is active to be reduced.This method also need address these problems.
Therefore, first purpose of the present invention is to provide a kind of concentrated liquid developer composition of color photographic materials, it does not produce the precipitation of insoluble matter in storage process, can color not occur, can not cause the photography property variation yet even contain the color developer of high concentration owing to air oxidation makes the container of Treatment Solution or Treatment Solution.
Second purpose of the present invention is to provide a kind of concentrated liquid developer composition that is installed in the container, and Bao Zhuan developer composition can stably be preserved a very long time like this.
The 3rd purpose of the present invention is to provide a kind of colour development disposal route, it at an easy rate pack processing be contained in concentrated liquid developer composition in the container, and can stably keep the amount of developer composition.
The 4th purpose of the present invention is to provide a kind of colour development disposal route, and it can prevent from crystallization to occur on the colour development pool wall at an easy rate, and can prevent the pollution of the color developing tank that tar causes.
Concentrated liquid agent composition by following colour development, form and developing method that the concentrated liquid treating agent is contained in the container have been finished these purposes of the present invention.
(1) the concentrated liquid color developer composition of silver halide color photographic materials comprises at least a formula (I) or compound (II):
R
1-(OC
2H
4)
n-OH (I) is R wherein
1Expression has the alkyl of 1-3 carbon atom, and n represents the integer of 4-9;
R
2-SO
3M (II) is R wherein
2Expression has the alkyl of 4-10 carbon atom, and m represents kation.
(2) the as above described concentrated liquid color developer of bar (1) composition, wherein said concentrated liquid color developer composition contain at least a formula (II) expression compound and at least a be selected from polyglycol (condition be the mean molecular weight of polyglycol be 2000 or still less), the compound of urea and polyvinylpyrrolidone.
(3) as above bar (1) or (2) described concentrated liquid color developer composition, wherein said concentrated liquid color developer composition is installed in the container.
(4) a kind of developing method of silver halide color photographic materials, it comprises uses the colour development solution that obtains by bar (1), (2) or (3) described concentrated liquid color developer composition in the dilution or the developer of colour development, carries out colour development in 2 minutes 30 seconds processing time.
(5) a kind of developing method of silver halide color photographic materials, it comprises uses the colour development solution that obtains by bar (1), (2) or (3) described concentrated liquid color developer composition in the dilution or the developer of colour development, carries out colour development under 40 ℃ or higher treatment temperature.
Finished the present invention based on following knowledge: when concentrated liquid color developer composition comprises at least a formula (I) or compound (II) and color developer, even developer may be very high concentration, insoluble matter can not precipitate yet in storage process, concentrated liquid color developer composition is not easy to air oxidation, therefore improved the stability of color developer composition, comprise store and up to the colour development treating agent be used during in, be difficult to occur because color appears in Treatment Solution and Treatment Solution container that air oxidation causes, and when in developing pool, handling photographic material, effectively prevented to pollute, and reduced the photography property variation by being deposited in the color developing tank that forms on the color developing tank and cause by tar.
" concentrated liquid color developer composition " used herein is meant and is suitable for being contained in concentrated liquid treating agent in the container with the concentrated liquid state, it is by being dissolved into high concentration with the chemical substance of handling, to offer the development laboratory, it is different from so-called solid processing agent.According to concentrated liquid color developer composition of the present invention usually in the development laboratory water equal solvent be diluted to the concentration of prescription, as Treatment Solution.This concentrated liquid color developer composition is put into treatment pond after can be diluted, perhaps puts into respectively in the treatment pond with dilution water, dilutes therein, makes Treatment Solution.
According to the present invention, by the adding formula (I) in developing solution or (II) compound of expression, can suppress the precipitation of colored developer, therefore can design agent composition with high concentration.Easily, formula (I) or (II) compound of expression have and prevent owing to occur the effect of color on Treatment Solution that the air oxidation of developing solution causes and the Treatment Solution chamber wall.The mechanism that prevents color is also not really clear, is owing to having prevented that the result of precipitation from appearring in developer, is not easy to oxidized color developer but can infer.Because precipitation does not appear in developer in colour development solution, not oxidation stably remains in the concentrated liquid color developer composition, photography property without the time variation, can improve the storage stability of this agent composition.And, in the color photographic materials processing procedure, effectively prevented from the development pool wall, to occur crystallization and because the pollution of the color developing tank that tar causes.
When concentration that increases developer in order to shorten the colour development processing time or raising colour development time, to compare with the development of following photographic layer, the development of last photographic layer is excessive, promptly so-called color balance variation.In contrast, found can improve the variation of above-mentioned color balance in rapid development when the diluted developer of concentrated liquid color developer of the present invention as colour development solution or colour development.
Particularly, 2 minutes 30 seconds or still less and/or 40 ℃ or higher fast and/or in the high-temperature color development treatment, this effect is shown effectively.
At first, when this concentrated liquid color developer composition contains a kind of color developer, the compound of at least a formula (II) expression, with at least a be selected from polyglycol (condition be the mean molecular weight of ethylene glycol be 2000 or still less), the compound of urea and polyvinylpyrrolidone, prevent container color appears, on the colour development pool wall precipitated crystal to vertical spread, color developing tank by the effect highly significant of the pollution of tar and the photography property variation that causes.Particularly, owing to promoted the effect (because above-mentioned composition of the present invention) that prevents to ascribe to lower floor and the uneven variation of the unbalanced color of upper strata development progress, can further shorten the processing time.
Description of drawings
Fig. 1 is the view of the container (bottle) of a kind of agent composition in specific embodiments of the present invention.
Fig. 2 opens the view of container (bottle) hermetic unit of an agent composition in specific embodiments of the present invention for perforation nozzle.
The representative meaning of numeral:
188: perforation nozzle
214: nozzle bore
300: bottle (container of photograph processing agent)
302: container body
304: external thread (threaded portion)
308: have the tygon of cutting line
310: lid (retaining element)
312: bottom (when packing into)
314: opening
Describe the present invention in detail by following details.
The specific embodiment of the compound of formula (I) expression comprises the compound shown in following.In these compounds, preferred (I-3), (I-4), (I-5), (I-9), (I-10) and (I-11).
The compound of formula (I) expression:
(I-1)????CH
3-(OC
2H
4)
4-OH
(I-2)????CH
3-(OC
2H
4)
5-OH
(I-3)????CH
3-(OC
2H
4)
6-OH
(I-4)????CH
3-(OC
2H
4)
7-OH
(I-5)????CH
3-(OC
2H
4)
8-OH
(I-6)????CH
3-(OC
2H
4)
9-OH
(I-7)????C
2H
5-(OC
2H
4)
4-OH
(I-8)????C
2H
5-(OC
2H
4)
5-OH
(I-9)????C
2H
5-(OC
2H
4)
6-OH
(I-10)???C
2H
5-(OC
2H
4)
7-OH
(I-11)???C
2H
5-(OC
2H
4)
8-OH
(I-12)???C
2H
5-(OC
2H
4)
9-OH
(I-13)???C
3H
7-(OC
2H
4)
4-OH
(I-14)???C
3H
7-(OC
2H
4)
5-OH
(I-15)???C
3H
7-(OC
2H
4)
6-OH
(I-16)???C
3H
7-(OC
2H
4)
7-OH
(I-17)???C
3H
7-(OC
2H
4)
8-OH
(I-18)???C
3H
7-(OC
2H
4)
9-OH
The specific embodiment of the compound of formula (II) expression comprises the compound shown in following.In these compounds, preferred (II-3), (II-4), (II-5), (II-9), (II-10) and (II-11).
The compound of formula (II) expression:
(II-1)????CH
3-(CH
2)
4-SO
3Na
(II-2)????CH
3-(CH
2)
5-SO
3Na
(II-3)????CH
3-(CH
2)
6-SO
3Na
(II-4)????CH
3-(CH
2)
7-SO
3Na
(II-5)????CH
3-(CH
2)
8-SO
3Na
(II-6)????CH
3-(CH
2)
9-SO
3Na
(II-7)????CH
3-(CH
2)
10-SO
3Na
(II-8)????CH
3-(CH
2)
4-SO
3H
(II-9)????CH
3-(CH
2)
6-SO
3H
(II-10)???CH
3-(CH
2)
8-SO
3H
(II-11)???CH
3-(CH
2)
6-SO
3K
(II-12)???CH
3-(CH
2)
8-SO
3K
As mentioned above, be that according to the assemblage characteristic of concentrated developer composition of the present invention said composition can be thickened to extra high concentration, its technical characterictic is to have overcome the restriction of thickening.According to the concentrating degree of concentrated developer composition of the present invention be duty solution (i.e. developer of Xian Yinging or mother liquor (storage pond solution)) 1.5-10 doubly, preferably doubly at 2-8, more preferably doubly at 3-5.In every liter of concentrated developer composition, formula (I) and/or (II) shown in compound concentrations (being total concentration when containing two or more compounds) be 0.01-200g, preferably at 1-100g, more preferably at 5-50g.
Have with the form that in a composition, comprises all the components that contains in the working solution according to concentrated developer composition of the present invention that (promptly to form (one-part constitution) be favourable to a part, but when not preferred these constituents are in contact with one another a very long time, these constituents can be divided into two or more liquid parts, (ISO5989 is commonly referred to a part according to international standard to make two parts (two-part) or three parts (three-part) composition, two parts or three parts are formed), effect of the present invention and feature can not be divided into several sections and lose because of concentrating developer composition.Being preferably used as a part especially according to developer composition of the present invention forms.
Container according to concentrated liquid developer of the present invention will be described below.In the present invention, this developer is installed in the polyethylene can so that use to be provided, and is favourable.
Usually, liquid developer composition is installed in transportation in the proper container, stores and uses.As first necessary condition of developer container modulator material is should be to the developer composition non-activity and enough stablize (necessary condition 1).With the necessary condition of necessary condition 1 no less important be to have enough oxygen barrier character, developer composition be prepared into be used during in do not cause air oxidation (necessary condition 2).An other necessary condition is that the container of discarding is can be recycled (necessary condition 3).Because the development activity of concentrated liquid development treatment agent descends with the reduction of pH in storage process, preferably do not contact with carbon dioxide in air.Therefore, the material of this container should be that chamber wall has imperviousness (necessary condition 4) to carbon dioxide and oxygen.Nearly all material that satisfies necessary condition 2 also satisfies necessary condition 4.
Considering from necessary condition 2 and 4, developer composition is packed into to storage and transport in the container of oxygen and carbon dioxide barrier, is favourable.Consider that from actual life of developer composition preferably the material of container being related to becoming the transmitance at the airborne time per unit per unit area of normal temperature and pressure with thickness is 2.5 * 10
-7Cm
3/ cm
2/ sec/atm or lower, preferred 2.5 * 10
-8Cm
3/ cm
2/ sec/atm or lower.On the other hand, consider that from necessary condition 4 viewpoints chamber wall is 7 * 10 to the carbon dioxide transmitance
-7Cm
3/ cm
2/ sec/atm or lower container of material are considered to necessary.Therefore, the material of container has been limited greatly.
Consider from imperviousness, begin under many situations the liquid development treating agent to be encased in the vial, seal standby air.Yet, because the vial Heavy Weight, and broken easily, use comprises the bottle that the sheeting of plastics is made usually now, it has the effect of high performance barrier gas, and plastics are stable to alkaline developer.Although the plastic material of known composition is barrier air effectively, to prevent air (oxygen) oxidation, increase the storage stability of liquid developer, on the other hand, owing to be combined material, be difficult to returnable, their are each uses all as can not returnable and be dropped, and this has increased environmental pressure.
Because the favourable part of the colour development solution of the compound that contains formula (I) or (II) represent is that they are not easy to oxidation by air (as mentioned above), can not obtain actual storage stability so do not use this combined material container yet.Therefore even can select to satisfy the single composition plastics of above-mentioned necessary condition 2 and 4 value that is suitable for the air transmission coefficient of plastic containers material of the present invention can be higher than 10 times of above-mentioned value.Can satisfy necessary condition 3 at an easy rate by the plastics of using single composition, this also is distinctive advantage of the present invention.
A king-sized advantage is that tygon (it is not used by routine is because it is not enough to the barrier properties of air, although it can be recycled at an easy rate) has as the feasible protective nature according to liquid development agent container of the present invention.
The preferred embodiment of color developer container material of the present invention comprises vibrin, acrylate resin, ABS resin, epoxy resin, with polyamide such as nylon, urethane resin, polystyrene resin, polycarbonate resin, PVA, Polyvinylchloride, polyvinylidene chloride, and polyvinyl resin.In these materials, constitute material preferred polyester resin such as the polyethylene terephthalate or the Polyethylene Naphthalate of container, or polyolefin such as tygon and polypropylene are as homogenous material.In all material, tygon most preferably, preferably polyethylene, high density polyethylene, so-called HDPE are preferably as the material of container.Particularly preferred density is at 0.951-0.9769g/cm
2HDPE (have density in this scope, melt index (MI) is at 0.3-7.0, more preferably at 0.3-5.0) has gas permeability and molding performance easily.In order to keep space accuracy and thickness homogeneity, slush molding can be advantageously used in container formation.
If desired, in the tygon that can in concentrated liquid developer composition container of the present invention, use, add the pigment that the alkaline developer composition is not had a negative impact, for example carbon black and titanium white, lime carbonate and the plastifier that has compatibility with tygon.But the preferably polyethylene ratio is 85% or higher tygon, and do not contain plastifier, and more preferably the tygon ratio is 95% or higher tygon, and do not contain plastifier.
The shape and the structure of loading the container of concentrated liquid developer composition of the present invention can design arbitrarily according to purpose.Except common bottle arrangement, can also use and disclosedly among JP-A-58-97046, JP-A-63-50839, JP-A-1-235950 and the JP-A-63-45555 can expand and the container of shrinkage type the container of JP-A-58-97046, JP-A-62-246061 and the disclosed flexible dividing plate of JP-A-62-134626.
When this container is loaded into developer composition, preferably developer composition is filled into the mouth of container, reduce upper space as much as possible, security with further raising air oxidation, pass through when perhaps filling developer composition with sheaf space on the nitrogen replacement, so that developer composition does not contact with airborne oxygen, still the invention is not restricted to these fill methods.
When being used in the automatic processor according to developer composition of the present invention, the container that developer composition is housed is installed on the processor, developer composition in the container is injected in the developer pond of development, or directly be injected in the developer pond, the internal tank water washing of formula ratio, the water that is used for washing is poured the developer pond then into, as the water of preparation developer.This method is to have utilized superiority of the present invention most effectively.For water washing internal tank with formula ratio, preferred especially spraying system washing, but the invention is not restricted to this method.Slurry is used effectively by this developer preparation method, therefore, can reduce from the discharge capacity of development laboratory discard solution.
Therefore, particularly preferred embodiment of the present invention is a kind of simple developing system, has guaranteed its environmental safety and job security by the combination of above-mentioned developer composition.For example, the automatic processor that the development treatment of silver halide color photographic materials is used according to the inventive method carries out, the container that developer composition for example will be housed is installed on the processor, composition in the container is injected in the developer pond of development, the inside of jet cleaning container, wash the processing composition that is attached on the chamber wall off, and slurry is used to prepare developer.In this situation, the opening automatic setting of container cover, when the container of developer composition is installed on the automatic processor, discharge liquid content reposefully.And, according to JP-A-6-82988 and JP-A-8-220722 disclosed method, can wash and needn't wash by hand by inside with washings jet cleaning container, be more prone to owing to can handle the recycle of discarded container neatly.In addition, owing to utilize the water of washings as part dissolving developer again, this just needn't abandon the water as waste liquid.By according to the invention process developer composition, can recognize the notion of this system for the first time, it be highly concentrate and have content closely, its flowability can keep a very long time.
As the description of embodiment, the structure of bottle 300 is described with reference to accompanying drawing 1 below to carrying out above.Bottle 300 is the container of photograph processing agent, and it is suitable for the developing method of agent composition coupling system, but is not limited to this bottle according to the container of the present composition.
As shown in Figure 1, bottle 300 has container body 302.Container body 302 forms hollow form by resin material (being high density polyethylene, i.e. HDPE) in embodiment of the present invention.The upper end of container body 302 is tapered, and diameter reduces gradually, forms cylindrical neck and divides 306, has external thread 304 at its outer peripheral portion.The upper part opening of neck portion 306, above-mentioned developer is put into or is taken out by opening.Tygon (LDPE) thin layer element 308 is equipped with in upper end in the upper part of neck portion 306.At thin layer element 308 the intersection otch is arranged, design makes the application perforation nozzle can open thin layer element 308 at an easy rate, makes content outflow in the bottle.Comprise the thin layer element 308 of LDPE and comprise that the container body 302 of HDPE makes the solution in the container have reliable sealing performance.
Cover fixedly film of 310 conducts on the bottle 300.Cover 310 openings to neck portion 306, for having the cylindrical of bottom, the internal thread 318 of external thread 304 on circumferential portion has corresponding to neck portion 306 in lid 310.Lid 310 can be twisted screw thread to neck portion 306, twists screw thread to neck portion 306 by covering 310, and the bottom 312 of lid 310 is pressed onto on the tygon thin layer element 308, and tygon thin layer element 308 can be fixed on the neck portion 306.Form circular opening 314 in lid 310 bottom 312, tygon thin layer element 308 can be perforated, and makes to cover 310 and open.
Bottle is placed in the visualization portion of processor, is inverted, perforation nozzle is opened tygon thin layer element 308, and the content from the bottom with bottle is injected into the developer pond.With perforation with open the hermetic unit of bottle, it is also as the (operating) water nozzle that discharges wash-bottle inwall behind the content as perforation nozzle for perforation nozzle.
Except the formula (I) or (II) compound of expression, be described below according to the constituent of developer composition of the present invention.
Developer composition is alkaline external phase liquid, contains the constituent that contains in the conventional color developer of dissolved state.Wherein contain color developer, preferred example is known primary aromatic amine color developer, particularly, is the p-phenylene diamine derivative.The representational example of p-phenylene diamine derivative is as follows, but the invention is not restricted to this.
Recently, in the black and white photosensitive material, add colour coupler sometimes, use the conventional colour development solution that uses then and form the black and white image to form black color.Therefore, colour development solution of the present invention also can be used this photosensitive material and handles.
1) N, N-diethyl-p-phenylenediamine (PPD)
2) 4-amino-3-methyl-N, the N-diethylaniline
3) 4-amino-N-(beta-hydroxy ethyl)-methylphenylamine
4) 4-amino-N-ethyl-N-(beta-hydroxy ethyl) aniline
5) 4-amino-3-methyl-N-ethyl-N-(beta-hydroxy ethyl) aniline
6) 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl) aniline
7) 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl) aniline
8) 4-amino-3-methyl-N-ethyl-N-(β-amsacrine ethyl) aniline
9) 4-amino-N, N-diethyl-3-(beta-hydroxy ethyl) aniline
10) 4-amino-3-methyl-N-ethyl-N-(beta-methoxy-ethyl) aniline
11) 4-amino-3-methyl-N-(β-ethoxyethyl)-N-ethylaniline
12) 4-amino-3-methyl-N-(3-carbamyl propyl group)-N-just-propyl group aniline
13) 4-amino-3-methyl-N-(4-carbamyl butyl)-N-just-propyl group aniline
14) N-(4-amino-3-aminomethyl phenyl)-3-hydroxyl pyrrolidine
15) N-(4-amino-3-aminomethyl phenyl)-3-(hydroxymethyl) pyrrolidine
16) N-(4-amino-3-aminomethyl phenyl)-3-pyrrolidine carboxylic acid amides
Preferred compound 5 in above-mentioned p-phenylene diamine derivative), 6), 7), 8) and 12), special preferred compound 5) and 8).When they were solid state, these p-phenylene diamine derivatives were generally the form of salt, as sulfate, hydrochloride, sulphite, napadisilate, toluene sulfonate.These agent compositions mix with water with predetermined ratio, as the developer working fluid (or further being diluted to developing solution) that develops.In working fluid, the concentration of every liter of developing solution primary aromatic amine color developer is preferably 2-200mmol, more preferably at 12-200mmol, is more preferably at 12-150mmol.
Further preferably contain polyglycol, ethylidene-urea and polyvinylpyrrolidone according to liquid development treating agent of the present invention.By the compound and/or (II) the compound combination of expression of using these compounds and formula (I) expression, particularly the compound with formula (II) expression makes up, can improve the anti-air oxidation performance of concentrated liquid development treatment agent and container and agent composition and color occur, can improve the color balance in the rapid development especially.
As polyglycol, example is diethylene glycol, a triethylene glycol and polyglycol (mean molecular weight: 200,300,400,600,1000,1540,2000,4000,6000,20000), preferred example is diethylene glycol, a triethylene glycol and polyglycol (mean molecular weight: from 1000 to 2000).
Following compounds can be used as the example of ethylidene-urea, in these compounds, and preferred compound (E-11).
Poly--N-2-vinylpyrrolidone and poly--N-2-vinylpyrrolidone/vinyl alcohol can be used as the example of polyvinylpyrrolidone.
From 1000 to 2000) and gather-composition of N-2-vinylpyrrolidone more preferably use formula (I) and/or (II) compound, diethylene glycol, triethylene glycol and the polyglycol of expression (mean molecular weight:.In the middle of these, preferably use the compound of formula (II) expression.
Ethylene glycol, the content of ethylidene-urea and polyvinylpyrrolidone do not limit especially, but they each content is at 0.1-100g, preferably at 1-50g, more preferably at 5-20g.
According to the purpose photographic material, in some cases, agent composition of the present invention can contain a spot of sulfite ion, does not contain in other cases.This is because sulfite ion produces adverse influence to photography character sometimes in handling according to the colour development of purpose photographic material, although it helps preserving significantly.
According to the kind of materials used, azanol also is can contain the component that also can not contain in the composition, and this is because azanol influences photography character sometimes, and this is owing to it has silver development activity, is used as the preservative agent of developing solution simultaneously again.
Preferably contain inorganic preservative agent according to concentration agent composition of the present invention, as above-mentioned azanol, sulfite ion and organic preservative agent.Organic preservative agent used herein is meant some organic compounds, and when it being joined in the Treatment Solution of photographic material, it can reduce primary aromatic amine color developer rate of deterioration.That is, organic preservative agent of this paper is meant and has the organic compound that prevents color developer air oxidation function, wherein hydroxylamine derivative; hydroxamic acid, hydrazides, phenol; alpha-alcohol ketone, alpha-amido ketone, carbohydrate; monoamine, diamine, polyamines; quaternary ammonium salt, nitroxyl, alcohol; oxime, hydrazine compound and condensed ring amine are effective especially organic preservative agents.These organic preservative agents are at JP-A-63-4235, JP-A-63-30845, JP-A-63-21647, JP-A-63-44655, JP-A-63-53551, JP-A-63-43140, JP-A-63-56654, JP-A-63-58246, JP-A-63-43138, JP-A-63-146041, JP-A-63-44657, JP-A-63-44656, United States Patent (USP) 3,615,503,2,494,903, open among JP-A-52-143020 and the JP-B-48-30496 (term used herein " JP-B " is meant " Jap.P. of having examined is open ").
In addition, if desired, in JP-A-57-44148 and JP-A-57-53749 disclosed multiple material, in JP-A-59-180588 disclosed salicylic acid, in JP-A-54-3532 disclosed alkanolamine, in JP-A-56-94349 disclosed polyethyleneimine and at United States Patent (USP) 3, disclosed aromatic polyhydroxy compounds can be used as preservative agent in 746,544.Except above-mentioned alkanolamine, preferably add other alkanolamine, for example triethanolamine and triisopropanolamine, replace and unsubstituted dialkyl group azanol as two thio-ethyl azanol and diethyl hydroxylamines, or aromatic polyhydroxy compounds.
In above-mentioned organic preservative agent, especially preferably use hydroxylamine derivative, their detailed content is referring to disclosed among JP-A-1-97953, JP-A-1-186939, JP-A-1-186940 and the JP-A-1-187557.From improving the colour development stability of solution and improve viewpoint stable the processing continuously and consider, preferred especially hydroxylamine derivative and amine applied in any combination.
Example as above-mentioned amine has disclosed cyclammonium among the JP-A-63-239447, the disclosed amine of disclosed amine and JP-A-1-186939 and JP-A-1-187557 among the JP-A-63-128340.
If necessary, chlorion can join according in the concentration agent composition of the present invention.Under many kinds of situations, colour development solution (the colour development solution of colored printing material particularly) contains the amount of chlorion usually 3.5 * 10
-2-1.5 * 10
-1The mol/ liter, but because chlorion is discharged in the developing solution as the development accessory substance usually, needn't join in the developer in many cases.Set the amount of chlorion in the developer (being original agent composition), make that chlorine ion concentration reaches above-mentioned concentration level in the developing pool when reaching when turning round the balanced combination thing.In the developing solution of many printing photography materials, when chlorine ion concentration surpasses 1.5 * 10
-1The mol/ liter, developing postpones, and this is disadvantageous for rapid development character, and weakens color density.If concentration is less than 3.5 * 10
-2The mol/ liter, under many situations that prevent photographic fog not by preferably.Because the silver halide photographic material of many photographies does not contain silver chloride usually, therefore needn't control chlorine ion concentration in the development treatment, the agent composition of use does not contain chlorion usually as constituent.
For agent composition, owing to be similar to chlorion, bromide ion also is dissolved out from photographic material to be handled in the solution, and accumulation, therefore needs the control bromide ion concentration, to keep equilibrium concentration.For photographic material, the concentration of bromide ion is preferably in 1-5 * 10 in the colour development solution
-3The mol/ liter is for printing material, preferably 1.0 * 10
-3Mol/ rises or still less.Bromide ion can be had more and to join in the agent composition, to reach above-mentioned bromide ion concentration scope.
Iodide ion is dissolved out in the developing solution from the color photographic materials that is used for photographing, but the photographic material that is used to print does not contain silver iodide usually.The concentration of iodide ion is 5 * 10 in the developing solution
-5Mol/ rises to 5 * 10
-4Mol/ if necessary, can add iodide ion in the agent composition, to keep this concentration about rising.
When adding the halogen ion in the composition, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride and lime chloride can be used as chlorion examples of substances are provided.In these, preferred sodium chloride and potassium chloride.
Provide examples of substances that sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganous bromide, nickelous bromide, comprise cerium bromide and thallium bromide are arranged as bromide ion.In these, preferred sodium bromide and potassium bromide.
Provide examples of substances that sodium iodide, potassium iodide, lithium iodide, calcium iodide, magnesium iodide and thallium iodide are arranged as iodide ion.In these, preferred sodium iodide and potassium iodide.
When photographic material to be processed was chromatics paper, because the photographic plane white background is that white is an important photographic quality, therefore using whitening agent, to reach the chromatics paper white appearance extremely important.The character of whitening agent according to them is joined in the photographic material, but can use the method for in development treatment, permeating photographic material from Treatment Solution.In this case, in order to obtain the purpose of very white effect, select suitable whitening agent to add Treatment Solution according to the character of whitening agent.Therefore, in many cases, when whitening agent is joined colour development solution, has high pH value usually.
In many cases, use the stilbene radicals whitening agent, particularly, preferably use two (triazine radical amido) stilbene radicals and 4,4 '-diamido-2,2 '-two sulfo-stilbene radicals whitening agent.
The preferred especially stilbene radicals whitening agent that uses is 4,4 '-two triazine radical amidos-2,2 '-two sulfo-stilbenes, but the invention is not restricted to this compound.
The present invention can use the stilbene radicals whitening agent of conventional known easy acquisition, or these stilbene radicals whitening agent can be synthetic at an easy rate according to known method.
This stilbene radicals whitening agent can join desilverization solution or photographic material and as colour development solution, when it being joined in the colour development solution, its concentration is preferably 1 * 10
-4Mol/ rises to 5 * 10
-2The mol/ liter is more preferably 2 * 10
-4Mol/ rises to 1 * 10
-2The mol/ liter.Determine its addition in agent composition of the present invention, make the whitening agent that contains this concentration in the work developing solution.
At 9.5-13.0, at 9.0-12.2,, can add other known developing solution component according to the pH of concentrated liquid agent composition of the present invention own more preferably at 9.9-11.2 from the colour development pH value of solution of its preparation.
In order to keep above-mentioned pH value, preferably add alkaline reagent and buffering agent.The example of operable alkaline reagent and buffering agent comprises carbonate, phosphate, borate, tetraborate, Para Hydroxy Benzoic Acid salt, glycyl salt, N, N-dimethylaminoethyl salt, leucine salt, nor-leucine salt, guanine salt, 3,4-Dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propane diol, valine salt, proline salt, trihydroxy aminomethane salt, and lysine salt.To join colour development molten when drawing together carbonate, phosphate, tetraborate and Para Hydroxy Benzoic Acid salt, have good especially shock-absorbing capacity in pH value 9.0 or higher high pH scope, and low price, therefore especially preferably use these buffering agents.In the developer of every mole of development, add the concentration of buffering agent in the composition at the 0.01-2 mole, preferably at the 0.1-0.5 mole.Add alkaline reagent and regulate the value of the pH of developing solution (wherein containing buffering agent) to prescription.
The object lesson of these alkaline reagents and buffering agent comprises sodium carbonate, sal tartari, sodium bicarbonate, saleratus, tertiary sodium phosphate, tripotassium phosphate, disodium hydrogen phosphate, dikalium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), dipotassium tetraborate, adjacent Para Hydroxy Benzoic Acid sodium (sodium salicylate), 5-sulfo-2-Para Hydroxy Benzoic Acid sodium (5-thiosalicylic acid sodium), 5-sulfo-2-Para Hydroxy Benzoic Acid potassium (5-thiosalicylic acid potassium), NaOH, potassium hydroxide, and lithium hydroxide.But, the invention is not restricted to these compounds.
Above-mentioned buffering agent is joined in the developer of colour development, its preparation is preferably at 0.1mol/ liter or more, particularly preferably in 0.1mol/ liter-0.4mol/ liter by amount of dilution.
In the present invention, the preferred potassium hydroxide that uses preferably uses potassium hydroxide as alkaline reagent except sal tartari, and part potassium hydroxide replaces with lithium hydroxide, and it further improves and prevents to precipitate nucleus formation in the developing pool.
Can use multiple sequestrant in the agent composition of the present invention, it is that the precipitation that prevents of other composition in the colour development solution (for example calcium and magnesium) generates agent or the solution-stabilized improver of colour development.The example of these sequestrants comprises nitrilotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine tetraacetic acid; N, N, N-trimethylene phosphonic; ethylenediamine N, N, N '; N '-tetramethylene sulfonic acid, trans cyclohexane ethylenediamine tetraacetic acid (EDTA), 1; the 2-diaminopropanetetraacetic acid, glycoletherdiaminotetraacetic acid, ethylenediamine-neighbour-hydroxyphenyl acetic acid; ethylenediamine succinic acid (SS type), N-(2-carboxylatoethyl)-L-aspartic acid, Beta-alanine oxalic acid; 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acids; 1-hydroxyl acetal-1,1-di 2 ethylhexyl phosphonic acid, N; N '-two (2-hydroxy benzenes methyl) ethylenediamine N, N '-oxalic acid and 1; 2-dihydroxy benzenes methyl 4, the 6-disulfonic acid.
If desired, these sequestrants can two or more applied in any combination.
The addition of these sequestrants should be enough to make the metal ion-chelant of colour development solution, and for example, this amount is about 0.1g-10g sequestrant in every liter of colour development solution.
If desired, can contain development accelerant according to agent composition of the present invention.
If desired, can add JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-123806, disclosed thioether group compound in JP-B-45-9015 and the United States Patent (USP) 3,813,247, among JP-A-52-49829 and the JP-A-50-15554 disclosed right-phenylene-diamino compound, JP-A-50-137726, JP-B-44-30074, disclosed quaternary ammonium salt among JP-A-56-156826 and the JP-A-52-43429, United States Patent (USP) 2,494,903,3,128,182,4,230,796,3,253,919, JP-B-41-11431, United States Patent (USP) 2,482,546,2,596,926, with 3,582, disclosed amine compound in 346, and JP-B-37-16088, JP-B-42-25201, United States Patent (USP) 3,128,183, JP-B-41-11431, JP-B-42-23883 and United States Patent (USP) 3,532, disclosed poly-alkane olefinic oxide and 1-phenyl 3-pyrazolidone and imidazoles in 501 are as development accelerant.
If desired, in according to agent composition of the present invention, can add any antifoggant.Alkali halide such as sodium chloride, potassium bromide and potassium iodide and organic antifoggant can be used as antifoggant.The representational example of organic antifoggant comprises nitrogen-containing heterocycle compound such as benzotriazole, the 6-nitrobenzimidazole, the different indazole of 5-nitro, the 5-methylbenzotrazole, 5-nitrobenzene and triazolam, 5-chlorinated benzotriazole, the 2-thibendole, 2-thiazolyl tolimidazole, indazole, hydroxyl azepine indolizine and adenine.When using organic antifoggant, set addition, make the scope of the concentration of antifoggant from the developing-solution of 1 liter of developing solution of agent composition preparation or development at 0.05-5mmol.
Except according to surfactant of the present invention, can use the kinds of surface activating agent if desired, for example can use alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid.
Be used for of the present invention from its preparation color developing composition and the developer of colour development or colour development solution as described above.
When photographic material to be processed is the colored printing material, be used for colour development treatment temperature of the present invention at 30-55 ℃, preferably at 35-55 ℃, more preferably at 40-55 ℃.The development treatment time is 5-90 second, preferably in 15-60 second.The video picture rate is preferably less, and every square metre of photographic material is at 20-600ml, preferably at 30-120ml, particularly preferably in 15-60ml usually.
On the other hand, when photographic material is colour negative or color reverse film, the development treatment temperature is at 30-55 ℃, and preferably at 35-55 ℃, more preferably at 40-55 ℃, the development treatment time is 20 seconds-6 minutes, preferably in 30-200 second, more preferably in 60-150 second.Particularly, under the colour negative situation, be preferably 1-4 minute.The video picture rate is preferably less, and every square metre of photographic material is at 20-1000ml, preferably at 50-600ml, particularly preferably in 100-400ml usually.When concentrated developer composition and water join respectively in the developing solution, the video picture rate is the total amount of developer composition and water.
The present invention is preferred for colour negative.
Can prepare according to several different methods according to developer composition of the present invention.Following three kinds can obtain good result.However, it should be understood that the following three kinds of methods that the invention is not restricted to.Method A:
In advance low amounts of water is joined in the mixing pit, under agitation add continuously and form compound.Method B:
To form the powder of compound in advance, in a period of time, potpourri be joined in the low amounts of water of mixing pit.Method C:
To form compound in advance and be divided into two or more sets, it comprises those that are pre-mixed, and every group is dissolved in water or the hydrophilic mixed solvent, makes concentrated solution, and these concentrated solutions are mixed.
The preparation method can use the part combination of these methods.
In the present invention, after desilverization step,, wherein use bleaching agent (bleaching agent) and blixing solution and handle for by prepare the development step of colour development solution from developer composition of the present invention.When photographic material is the colored printing material, this Treatment Solution can also contain above-mentioned suitable whitening agent, preferably uses the stilbene radicals whitening agent.
As being used to bleach or the bleaching agent of blixing solution, can use known bleaching agent, particularly, the preferred organic complex salt (for example aminopolycanboxylic acid's complex salt) that uses iron (III), or organic acid such as citric acid, tartrate and maleic acid, persulfate, and hydrogen peroxide.
In these compounds, from the viewpoint of fast processing and environmental protection, the organic complex salt of preferred especially iron (III).Be used to form the polycarboxylic acid of iron (III) organic complex salt and the example of salt thereof and comprise biodegradable EDDS (SS type), N-(2-carboxylatoethyl)-L-aspartic acid, Beta-alanine oxalic acid, methyliminodiacetic acid, in addition, ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, 1,3-diaminopropanetetraacetic acid, trimethylen-edinitrilo-tetraacetic acid, nitrilotriacetic acid(NTA), CDTA, imino group triacetic acid, and glycoletherdiaminotetraacetic acid.These compounds can be with any form of sodium salt, sylvite, ammonium salt and lithium salts.In these compounds, preferred EDDS (SS type), N-(2-carboxylatoethyl)-L-aspartic acid, the Beta-alanine oxalic acid, ethylenediamine tetraacetic acid, 1, the 3-diaminopropanetetraacetic acid, and methyliminodiacetic acid, this is because their iron (III) complex salt has photography property.(in above-claimed cpd, " SS type " is meant that compound has two unsymmetrical carbons, and each in two all has SS type absolute configuration.) these ferric ion complex salts can use with the form of complex salt, perhaps can form the ferric ion complex salt in the solution of using ferric ion, for example, iron sulfate, iron chloride, ferric nitrate, ammonium ferric sulfate, and ferric phosphate are with sequestrant such as aminopolycanboxylic acid.Can use sequestrant to surpass the amount that is used to form the ferric ion complex salt.In these iron complexs, preferred aminopolycanboxylic acid's iron complex, their addition is at the 0.01-1.0mol/ liter, preferably at the 0.05-0.50mol/ liter, more preferably at the 0.10-0.50mol/ liter, most preferably at the 0.15-0.40mol/ liter.
Bleaching time is usually at 30 seconds to 6 minutes and 30 seconds, and preferably at 1 minute to 4 minutes and 30 seconds, the bleaching time of colored printing material was at 30 seconds to 2 minutes.
Preferred liquid lime chloride, blixing solution or fixed solution contain multiple known organic acid (for example glycollic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfo-succinic acid), organic base (for example imidazoles, methylimidazole), or the compound of disclosed formula (A-a) expression among the JP-A-9-211819, with the compound of disclosed formula (B-b) expression among the JP-A-9-211819, as kojic acid.In every liter of Treatment Solution, the addition of these compounds is preferably at 0.005-3.0mol, more preferably at 0.05-1.5mol.
In blixing solution of the present invention or fixed solution, can use multiple known fixing agent.Their example comprises thiosulfate such as sodium thiosulfate and ATS (Ammonium thiosulphate), thiocyanate such as thiocyanic acid sodium and ammonium sulfocyanate, sulfo-ether compound such as ethylene thioglycolic acid and 3,6-two sulfo-s-1,8-ethohexadiol and water-soluble silver halide solvent (being solubilizer) are as thiourea.These compounds can use separately, also can two or more applied in any combination.And the present invention also can use special blixing solution, as the disclosed blixing solution that contains fixing agent and halogenide (as a large amount of potassium iodides) combination among the JP-A-55-155354.Especially preferably use thiosulfate, particularly ATS (Ammonium thiosulphate) in the present invention.In every liter of solution, the addition of fixing agent is preferably at the 0.3-2 mole, more preferably at 0.5-1.0.
Be used for blixing solution of the present invention or the preferred pH of fixed solution at 3-8, more preferably at 4-7.When pH is lower than this scope, solution is rotten, and cyan dye becomes leuco dye rapidly, although desilverization character is enhanced.When pH is higher than this scope, the desilverization is slack-off, is easy to occur stain.
Being used for liquid lime chloride pH of the present invention is 8 or lower, and preferred pH is at 2-7, particularly preferably in 2-6.When pH is lower than this scope, solution is rotten, and cyan dye becomes leuco dye rapidly, although desilverization character is enhanced.When pH is higher than this scope, the desilverization is slack-off, is easy to occur stain.
If desired, in order to regulate pH, hydrochloric acid can be added in solution, sulfuric acid, nitric acid, supercarbonate, ammoniacal liquor, potassium hydroxide, NaOH, sodium carbonate, and sal tartari.
And blixing solution of the present invention can contain other multiple whitening agent, defoamer, and surfactant, and organic solvent are as polyvinylpyrrolidone and methyl alcohol.
Preferred blixing solution of the present invention and fixed solution contain sulfurous acid ion and discharge compound such as sulphite (for example sodium sulphite, potassium sulfite, ammonium sulfite etc.), hydrosulfite (for example ammonium bisulfite, sodium bisulfite, potassium bisulfite etc.), and metabisulphite (for example partially potassium bisulfite, sodium metabisulfite, ammonium bisulfite etc. partially) and aryl sulfinic acid as to toluenesulfinic acid and-the carboxyl benzenesulfinic acid is as preservative agent.According to sulfurous acid ion or sulfinic acid ion, the content of these compounds is preferably at about 0.02-1.0mol/ liter.
Except above-claimed cpd, the bisulfite adduct of ascorbic acid, carbonyl and carbonyls also can be used as preservative agent.
And, if desired, can use damping fluid, whitening agent, sequestrant, defoamer and mildewproof agent.
According to the blixing of the present invention processing time in 5-240 second, preferably in 10-60 second, treatment temperature is at 25-60 ℃, preferably at 30-50 ℃.Every square metre of photographic material is at 20-250ml, preferably at 30-100ml, particularly preferably in 15-60ml.
Photographic material of the present invention washs and/or stabilizing step after desilverization step (as fixing or blixing) usually.
The amount of slurry can be selected very wide scope in the washing step, main characteristic (for example material of Shi Yonging such as colour coupler) and application according to photographic material, the temperature of washings, the quantity of kitchen sink (quantity of washing stage), and other multiple condition.In aforementioned condition, the relation of water consumption in the quantity of kitchen sink and the multistage contracurrent system, can be from Journal of the Societyof Motion Picture and Television Engineers, 64, the method that 248-253 (May nineteen fifty-five) describes obtains.The quantity in stage is usually preferably at 3-15, particularly preferably in 3-10 in the multistage contracurrent system.
According to the multistage contracurrent system, the slurry amount can significantly reduce, yet, owing to increased the residence time of water in the pond, the problem of bacterial multiplication can appear, consequent suspended matter is attached on the photographic material.The method of disclosed minimizing calcium ion and magnesium ion concentration can be as overcoming the very effective method of this problem in JP-A-62-288838.And, can use disclosed isothiazolone compounds of JP-A-57-8542 and thiabendazole, the isocyanuric acid sodium of disclosed chloro antiseptic such as chlorination among the JP-A-61-120145, disclosed benzotriazole and copper ion among the JP-A-61-267761, bohkin bohbai no kagaku (antibiotic and antimycotic chemistry) with Hiroshi Horiguchi, by Sankyo Shuppan Co., Ltd. publish (1986), the Biseibutsu no Mekkin that Eisei Gijutsukai writes, Sakkin, the Bohkin Bohbai Zai Jiten that bohbai Gijutsu (sterilization of microorganism and antimycotic technology) is write by Kogyo Gijutsuki publication (1982) and Nippon Bohkin Bohbai gakkai (antibiotic and antifungal agent dictionary).
According to the multistage contracurrent system, the slurry amount can significantly reduce to the level of the stabilizing solution that equals to have used so far, so it is called as water washing replacement stabilizing solution sometimes.For stabilized image, can also use the stabilizing solution that has used so far in some cases.Therefore, washing step can be by carrying out in conjunction with one or more systems, and these systems comprise conventional water washing system, and stabilizing solution system, photographic fixing solution system are replaced in water washing.
Can behind water-washing step, handle, also can not carry out washing step and directly carry out by stabilizing solution.Compound with photographic fixing function for example by the aldehyde compound of formalin representative, is used to regulate film pH and stablizes damping fluid and the ammonium compounds of pH to being suitable for dyestuff, also can join in the stabilizing solution.Particularly, (it is to residual basic fuchsin colour coupler non-activity can to add aldehyde such as formaldehyde, acetaldehyde and pyroracemic aldehyde in the Treatment Solution, can prevent that dyestuff from fading and the generation of stain), United States Patent (USP) 4,786, disclosed methylol compound and hexamethylene tetramine in 583, disclosed Hexahydrotriazine among the JP-A-2-153348, United States Patent (USP) 4,921, the bisulfite addition product of disclosed formaldehyde in 779, disclosed azo methyl amine (azolylmethylamine) in the European patent 504609 and 519190.Yet any above-mentioned washings and stabilizing solution have the washing function, and function is identical basically for they, except whether adding fixer, therefore they are described below together.
Can further add in stabilizing solution and washings as the surfactant of dewatering agent with EDTA is the sequestrant as water softener of representative.And, in stabilizing solution and washings, can further add whitening agent and rigidizer.In photographic material of the present invention is handled, when photographic material is directly handled with stabilizing solution, and do not carry out water-washing step, can use disclosed known method among JP-A-57-8543, JP-A-58-14834 and the JP-A-60-220345.
In addition, preferably use sequestrant such as 1-hydroxyl-acetal 1,1-di 2 ethylhexyl phosphonic acid and ethylenediamine tetramethylene phosphonic acid and magnesium compound and bismuth compound.
The pH of water-washing step and stabilizing step is preferably at 4-10, more preferably at 5-8.Can be according to the multiple use and the property settings temperature of photographic material, but usually at 20-50 ℃, preferably at 25-45 ℃.
After one or more washings and/or stabilizing step, carry out drying steps.From reducing the transfer viewpoint of water to image film, may need to use squeegee roller and fabric by absorb the material that from kitchen sink, takes out at once, carry out rapid draing.As improving one's methods of exsiccator aspect,, to strengthen dry air, can carry out rapid draing by the shape that increases temperature and adjust blow-out nozzle although be natural.And, as disclosed among the JP-A-3-157650, regulate the angle and the exhaust gas discharging method of blowing, also effectively be beneficial to and quicken drying.
Can be used for photographic material of the present invention is described below.
As the silver halide that is used for according to photographic material of the present invention, can use silver chloride, silver bromide, (iodine) chlorine silver bromide and iodine silver bromide, but purpose for fast processing, the preferred chlorinity that uses is at 98 moles of % or higher chlorine silver bromide emulsion (it is substantially devoid of silver iodide), or silver chloride emulsion." be substantially devoid of silver iodide " and be meant agi content, more preferably at 0.01 mole of % or lower preferably at 0.1 mole of % or lower.Especially preferably contain silver iodide not at all.
Have the flat particulate of iodine silver bromide inner structure or the photographic material that non-flat sandwich construction particulate is mainly used in photography, for example multi layer colour negative film and color reverse film.
In order to improve the sharpness of image, the hydrophilic colloid layer of photographic material of the present invention preferably contains the dyestuff (particularly oxygen cyanine dye) that can decolour by handling, open in EP-A-337490 27-76 page or leaf, so that photographic material in the optical reflection density at 680nm place 0.70 or higher, perhaps the water-fast resin bed of holder contains 12% or titanium dioxide of being handled to tetravalence alcohol (for example trimethyl olethane) by divalence of more (preferred 14% or more) surface.
Be preferred for photographic material of the present invention and contain disclosed germifuge among the JP-A-63-271247, to prevent the breeding on hydrophilic colloid layer mould and bacterium, this can make the image variation.
As the holder that is used for according to photographic material of the present invention, cellulosic triacetate, the photographic material that poly-(ethylene terephthalate) and poly-(vinylnaphthalene two acid esters (naphthalate)) is used to photograph, the paper (resinous coat paper) of laminating with tygon that mixes with white pigments, poly-(ethylene terephthalate) film that is used to show with mixing with white pigments is used for the colored printing material.
Photographic material of the present invention can expose with visible or infrared light.Exposure can be high strength exposure in low intensity exposure or short time, and in back one situation, preferably each pixel exposure time is lower than 10
-4The laser scanning exposure of second.
For silver emulsion and other material (for example adjuvant) of being used for according to photographic material of the present invention, layer (layer arrangement etc.) is formed in photography, with the disposal route and the treatment additive that are used to handle photographic material, disclosed in EP-A-0355660, JP-A-2-33144 and JP-A-62-215272, preferred use those be listed in the table below in 1.
| Additive types | ?RD?17643 | ????RD?18716 | ?RD?307105 | |
| ????1 | The chemistry emulsion | 23 pages | 648 pages, right hurdle | 866 pages |
| ????2 | Sensitizer | 648 pages, right hurdle | ||
| ????3 | Photoreception of spectrum agent and telegraphy photo etching | The 23-24 page or leaf | 648 pages, right hurdle to 649 page, right hurdle | The 866-868 page or leaf |
| ????4 | Whitening agent | 24 pages | 647 pages, right hurdle | 868 pages |
| ????5 | Light absorber filters dyestuff and ultraviolet absorber | The 25-26 page or leaf | 649 pages, right hurdle to 650 page, left hurdle | 873 pages |
| ????6 | Bonding agent | 26 pages | 651 pages, left hurdle | The 873-874 page or leaf |
| ????7 | Plastifier and lubricant | 27 pages | 650 pages, right hurdle | 876 pages |
| ????8 | Coating additive and surfactant | The 26-27 page or leaf | 650 pages, right hurdle | The 875-876 page or leaf |
| ????9 | Antistatic agent | 27 pages | 650 pages, right hurdle | The 876-877 page or leaf |
| ????10 | Matting agent | The 878-879 page or leaf |
Disclosed cyan coupler also can be used for the present invention in JP-A-2-33144, EP-A-0333185 and JP-A-64-32260.
By in the presence of the high boiling organic solvent shown in the last table 1 (or not having high boiling organic solvent) but the latex polymer of using load (at United States Patent (USP) 4,203, open in 716) dipping, or by using water insoluble but be dissolved in the polymer dissolution of organic solvent, preferably cyanogen look, magenta and yellow colour former emulsification are distributed in the gluey aqueous solution of water wettability.
United States Patent (USP) 4,857, disclosed homopolymer or multipolymer in 449 the 7th hurdles, hurdle-15 or the WO88/00723 12-30 page or leaf can be used as preferred water insoluble but be dissolved in the example of the polymkeric substance of organic solvent.Particularly, consider the stability of coloured image, preferred methacrylate base or acrylamide-based polymers.
Preferred use the compound of the colored photographic fixing of disclosed improvement among the EP-A-0277589 with according to pyrazolo pyrroles (pyrazoloazole) colour coupler in the photographic material of the present invention, pyrrolo-triazole colour coupler or acyl group acetamide yellow colour former applied in any combination.
As cyanogen look colour coupler, except listing in phenol colour coupler and the naphthols colour coupler of describing in the table known references, preferably use disclosed cyanogen look colour coupler among JP-A-2-33144, EP-A-0333185, JP-A-64-32260, EP-A-0456226, EP0484909, EP0488248 and the EP-A-0491197.
Except listing in the 5-pyrazolone magenta colour coupler of describing in the table known references, disclosed magenta colour coupler among also preferred in the present invention use WO92/18901, WO92/18902 and the WO92/18903.Except these 5-pyrazolone magenta colour couplers, can use known pyrazolo pyrroles colour coupler among the present invention.Consider color, fixation performance and colorability, at first preferably use disclosed pyrazolo pyrroles colour coupler (coupler) among JP-A-61-65245, JP-A-61-65246, JP-A-61-14254, EP-A-226849 and the EP-A-294785.
As yellow colour former, preferably use known acyl group monoacetylaniline colour coupler, preferred especially EP-A-0447969, JP-A-5-107701, JP-A-5-113642, EP-A-0482552 and the disclosed colour coupler of EP-A-0524540.
As having suitably diffusible coloured dye color coupler, disclosed colour coupler in preferred United States Patent (USP) 4,366,237, BrP 2,125,570, EP-B-96873 and the Deutsche Bundespatent 3,234,533.As the colour coupler that is used to correct the unnecessary absorption of coloured dyestuff, preferably disclosed formula (CI) in the 5th page, (CII), (CIII) or (CIV) the yellow cyanogen colour coupler (being specially 84 pages compound YV-86) of expression in EP-A-456257; Disclosed yellow magenta colour coupler ExM-7 (202 pages), Ex-1 (249 pages) and Ex-7 (251 pages) among the EP-A-456257; United States Patent (USP) 4,833, disclosed pinkish red cyanogen look colour coupler CC-9 (8 hurdle) and CC-13 (10 hurdle) in 069; United States Patent (USP) 4,837, the colour coupler (2) (8 hurdle) in 136; The colourless masking coupler agent of disclosed formula (A) expression in the claim 1 among the WO92/11575 instantiation compound of 36-45 page or leaf (particularly).
Comprise following compounds as the example that can discharge the compound (comprising colour coupler) of the useful compound residual groups of photography after reacting at oxidation product with developer.
Development restrainer discharges compound:
The 11st page of disclosed formula of EP-A-378236 (I), (H), (III) or (IV) compound of expression (T-101 (30 pages) particularly, T-104 (31 pages), T-113 (36 pages), T-131 (45 pages), T-144 (51 pages) and T-158 (page 58)); The compound (particularly D-49 (51 pages)) of the 7th page of disclosed formula of EP-A-436938 (I) expression; The disclosed formula of EP-A-568037 (1) compound (particularly compound (23) (11 pages)); With EP-A-440195 the 5th and 6 pages of disclosed formulas (I), (II) or compound (III) (particularly 29 pages I-(1));
The bleaching accelerator discharges compound:
The compound (particularly 61 pages compound (60) and compound (61)) of the 5th page of disclosed formula of EP-A-310125 (I) or (I ') expression; Compound (particularly 7 pages compound (7)) with disclosed formula (I) expression in the JP-A-6-59411 claim 1;
Part discharges compound:
United States Patent (USP) 4,555, the compound that disclosed LIG-X represents in 478 claims 1 (particularly the capable compound of 21-41,12 hurdles);
Leuco dye discharges compound:
United States Patent (USP) 4,749, the compound on 641 3-8 hurdles;
Fluorescent dye discharges compound:
United States Patent (USP) 4,774, the compound that disclosed COUP-DYE represents in 181 claims 1 (particularly I-11 compound, 7-10 hurdle);
Development accelerator discharges or the photographic fog agent discharges compound:
United States Patent (USP) 4,656,123 the 3rd hurdles (1), the compound (particularly compound (I-22), 25 hurdles) of (2) or (3) expression; The compound that the 75th page of capable ExZK-2 of 36-38 of EP-A-450637 represents; With
The released dye compound, it removes the back color restoration:
United States Patent (USP) 4,857, the compound of disclosed formula (I) expression in 447 claims 1 (particularly Y-1-Y-19,25-36 hurdle).
Preferred additives is following listed except colour coupler:
The dispersion medium of oil-soluble organic compound:
The Compound P of JP-A-62-215272-3, P-5, P-16, P-19, P-25, P-30, P-42, P-49, P-54, P-55, P-66, P-81, P-85, P-86 and P-93 (140-144 page or leaf);
The latex that is used for the impregnation oils soluble organic compound:
United States Patent (USP) 4,199,363 disclosed latex;
The cleanser of developer oxidation product:
United States Patent (USP) 4,978,606 54-62 are capable, the compound of second bar (I) expression (particularly I-(1), I-(2), I-(6) and I-(12), 4 and 5 hurdles); With United States Patent (USP) 4,923,787 5-10 are capable, the compound that second bar is represented (particularly compound 1, the 3 hurdle);
Stain inhibitor:
The 4th page of EP-A-298321,30-33 line (I), (II) or (III) compound of expression (particularly I-47, I-72, III-1 and III-27,24-48 page or leaf);
The decolouring inhibitor:
The compd A of EP-A-298321-6, A-7, A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42, A-48, A-63, A-90, A-92, A-94 and A-164 (69-118 page or leaf); United States Patent (USP) 5,122, the Compound I I-1-III-23 on 444 25-38 hurdles (particularly III-10); The I-1-III-4 (particularly II-2) of EP-A-471347 8-12 page or leaf; With United States Patent (USP) 5,139, the A-1-A-48 on 931 32-40 hurdles (particularly A-39 and A-42);
Be used to reduce the compound that color reinforcing agent and blend of colors prevent the agent consumption:
The compound (particularly I-46) of EP-A-411324 5-24 page or leaf I-1-II-15;
Formaldehyde purifying agent:
The compound (particularly SCV-8) of EP-A-477932 24-29 page or leaf SCV-1-SCV-28;
Rigidizer:
The compound H-1 that JP-A-1-214845 is the 17th page, H-4, H-6, H-8 and H-14; United States Patent (USP) 4,618, the compound (H-1-H-54) of 573 13-23 bar (VII) to (XII) expression; The compound (H-1-H-76) (particularly H-14) of the 8th page of bottom right bar of JP-A-2-214852 (6) expression; With United States Patent (USP) 3,325, disclosed compound in 287 claims 1;
The development restrainer precursor:
The Compound P-24 of JP-A62-168139 the 6th and 7 pages, P-37 and P-39; United States Patent (USP) 5,019, disclosed compound in 492 claims 1 (particularly compound 28 and 29, the 7 hurdles);
Fungicide and germifuge
United States Patent (USP) 4,923,790 3-15 hurdle Compound I-1-III-43 (particularly II-1, II-9, II-10,11-18 and 111-25);
Stabilizing agent and antifoggant:
United States Patent (USP) 4,923,793 6-16 hurdle Compound I-1 are to (14) (I-1 particularly, 60, (2) and (13)); United States Patent (USP) 4,952,483 25-32 hurdle compound 1-65 (particularly compound 36);
The chemistry emulsion:
The triphenyl phasphine selenide; Disclosed compound 50 among the JP-A-5-40324;
Dyestuff (being dyestuff):
JP-A-3-156450 15-18 page or leaf compound a-1 is to b-20 (particularly a-1, a-12, a-iS, a-27, a-35, a-36, and b-5), the V-1 to V-23 of 27-29 page or leaf (particularly V-1); The F-I-1 to F-II-43 of EP-A-445627 33-55 page or leaf (particularly F-I-11 and F-II-B); The III-1 and the III-3 of EP-A-457153 17-28 page or leaf); The crystallite dispersion liquid of the Dye-1 to Dye-124 of WO88/04794 8-26 page or leaf; The compound 1-22 (particularly compound 1) of EP-A-319999 6-11 page or leaf; The Compound D-1 of EP-A-519306 3-28 page (1)-(3) any one expression is to D-87; United States Patent (USP) 4,268, the compound 1-22 of 622 3-10 bars (I) expression; With United States Patent (USP) 4,923, the compound (1) of 788 2-9 bars (I) expression is to (31);
Ultraviolet absorber:
The compound (18b)-(18r) that JP-A-46-3335 6-9 page (I) 101-427 represents; Compound (3)-(66) of EP-A-520938 10-44 page (I) expression, the compound H BT-1-HBT-10 of the 14th page (III) expression; Compound (1)-(31) with EP-A-521823 2-9 bar (I) expression.
The present invention can be used for the colour negative of conventional application and process photography application.The present invention can also be preferably used for the disclosed film unit (term used herein " JP-B-U " is meant " Japanese Utility Model of having examined is open ") of being furnished with lens among JP-B-2-32615 and the JP-B-U-3-39784.For example, No. the 17643rd, RD, 28 pages, No. the 18716th, RD, the 647th page to No. the 307105th, 648 pages on left hurdle and RD from right hurdle, discloses in 879 pages and has been suitable for holder of the present invention.Preferred holder is the polyester holder.
Be preferred for colour negative of the present invention and have magnetic recording layer.Being used for this magnetic recording layer of the present invention will make an explanation below.Be used for this magnetic recording layer of the present invention on holder, being coated with coating, wherein in bonding agent, be dispersed with magnetic-particle based on the coating solution of water-based or organic solvent.The example that is used for magnetic-particle of the present invention comprises ferromagnetic iron oxide such as γ-Fe
2O
3, adhere to γ-Fe of Co
2O
3, the magnetic iron ore of adhering to Co contains the Co magnetic iron ore, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system barium ferrite, strontium ferrite, ferrous acid lead, and calcium ferrite.The iron oxide that preferably adheres to Co is as adhering to γ-Fe of Co
2O
3The shape of magnetic-particle can be needle-like, ellipticity, spherical, cubic and tabular arbitrarily.Its specific surface area (SBET) is preferably at 20m
2/ g or more and preferred especially 30m
2/ g or more.
Can be used for magnetic-particle bonding agent comprise thermoplastic resin, thermoset resin, the radiation-curable resin, reactive resin, acid, alkali or Biodegradable polymkeric substance, natural polymer (for example cellulose derivative, carbohydrate derivative), with their potpourri, as disclosed among the JP-A-4-219569.Above-mentioned resin Tg-40 ℃ to 300 ℃ and weight average molecular weight 2,000-1,000,000.The example of bonding agent comprises ethylenic copolymer, cellulose derivative such as cellulose diacetate, primary cellulose acetate, cellulose acetate propionate, acetylbutyrylcellulose and cellulose tripropionate, acryl resin, and polyvinyl acetal resin.Also preferably use gel.Special preferred cellulose two (three) acetates.By adding epoxy radicals, '-aziridino or isocyanates based cross-linker, can be cured processing to bonding agent.The example of isocyanates based cross-linker comprises isocyanates such as toluylene group diisocyanate, 4, the 4-methyl diphenylene diisocyanate, own methylene diisocyanate and Xylene Diisocyanate, and the reaction product of these isocyanates and polyvalent alcohol (for example reaction product of 3mol toluylene group diisocyanate and 1mol trihydroxymethyl propane), the polyisocyanate that these isocyanates obtain by condensation, they are open in JP-A-6-59357.
Magnetic recording layer can provide improve lubricated, adjust the function that curling, antistatic, antisticking and head wear and tear.Perhaps can provide another functional layer with these functions and at least a or multiple particle to be preferably to have Mohs hardness is 5 or the lapping compound of higher aspheric surface inorganic particle.The composition of aspheric surface inorganic particle is preferably oxide, as aluminium oxide, and chromium oxide, silicon dioxide, titania etc., carbonide such as silit and titanium carbide and fine particle such as adamas.The surface of lapping compound can be handled with silane colour coupler or titanium colour coupler.These particles can be joined magnetic recording layer, also can be coated to the outside surface (protective seam, lubricating layer) of magnetic recording layer, can use above-mentioned bonding agent simultaneously, the preferred use bonding agent identical with the magnetic recording layer bonding agent.Photographic material with magnetic recording layer is at United States Patent (USP) 5,336,589,5,250,404,5,229,259,5,215,874 and EP466130 in open.
Use description to polyester holder of the present invention below, but details comprises and is different from above-mentioned photographic material, processing, film and work embodiment at Kokai-Giho, open among the No.94-6023 of Kogi (Hatsumei-Kyokai, March 15,1994).Be used for polyester of the present invention and comprise that two pure and mild aromatic dicarboxylic acids are as necessary component, example as aromatic dicarboxylic acid has 2,6-, 1,5-, 1,4-and 2,7-naphthalene dicarboxylic acids, terephthalic acids, isophathalic acid and phthalic acid have diglycol, TRI ETHYLENE GLYCOL, cyclohexanedimethanol, bisphenol-A and bis-phenol as the example of glycol.The polymkeric substance of their polymerizations comprises homopolymer such as polyethylene terephthalate, Polyethylene Naphthalate, poly-cyclohexanedimethanol phthalic acid ester etc.Preferably include 2 of 50mol% to 100mol% especially, the polyester of 6-naphthalene dicarboxylic acids.At first preferably polyethylene 2,6-naphthoic acid ester.Their mean molecular weight is approximately 5,000 to 200,000.The Tg that is used for polyester of the present invention is 50 ℃ or higher, preferred 90 ℃ or higher.
In order to guarantee the adhesion of holder and photographic material composition layer, preferably to carrying out surface activation process, as chemical treatment, mechanical treatment, Corona discharge Treatment, flame treatment, ultraviolet is handled, and high frequency is handled, and glow discharge is handled, activate plasma is handled, laser treatment, and acid mixture is handled, and ozone Oxidation Treatment, preferred ultraviolet rays is handled flame treatment in the middle of them, Corona discharge Treatment and glow discharge are handled.Undercoat can be individual layer, also can comprise two-layer or more multi-layered.
The bonding agent that is used for undercoat comprises the monomer that is selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and the maleic anhydride multipolymer as initiation material, and polyethyleneimine, epoxy resin, grafting gel, NC Nitroncellulose and gel.Make the compound that holder expands comprise resorcinol and parachlorophenol.The gel rigidizer that is used for undercoat comprises chromic salts (chrome alum chromalum), aldehyde (formaldehyde, glutaraldehyde), isocyanates, active halide compound (2,4-two chloro-6-hydroxyl-S-three azines), epichlorohydrin resins and active vinyl sulfone(Remzaol compound.Also can contain SiO, TiO
2, inorganic fine particle or polymethyl methacrylate copolymer fine particle (0.01 to, 10 μ m) be as matting agent.
Photographic material of the present invention preferably contains matting agent.Matting agent can join emulsion layer, also can join backing layer, but especially preferably joins the outermost layer of emulsion layer.Matting agent can be dissolved in Treatment Solution, also can be insoluble to Treatment Solution, and preferred two types are used in combination.For example, preferably use polymethylmethacrylate, poly-(methyl methacrylate/methacrylic acid=9/1 or 5/5 (mol ratio)), and granules of polystyrene.Mean particle size is at 0.8-10 μ m, and size distribution is preferably narrower, and preferred particulates sum 90% or more particles are between 1.1 times of 0.9 to of particle mean grain size.In order to increase eliminate optical property, preferably add particle diameter 0.8 μ m or fine particle still less simultaneously.For example, enumerated polymethylmethacrylate (0.2 μ m), poly-(methyl methacrylate/methacrylic acid=9/1 (mol ratio), 0.3 μ m), granules of polystyrene (0.25 μ m), and silica gel (0.03 μ m).
Total film thickness of all hydrophilic colloid layers of photographic material of the present invention (emulsion layer is positioned at its side) preferably at 28 μ m or still less more preferably at 23 μ m or still less, is more preferably at 18 μ m or still less, most preferably at 16 μ m or still less.And, film expansivity T
1/2Preferably or still less, more preferably or still less at 20 seconds at 30 seconds.T
1/2Be meant that film thickness reaches the time of 1/2nd film thickness, when 90% of 30 ℃ of maximum swelling film thickness that reach when handling 3 minutes and 15 seconds down in colour development solution, as saturated film thickness.Film thickness is meant the film thickness that 25 ℃, relative humidity 55% (preserving 2 days) record, T
1/2Can use A.Green etc., Photogr.Sci.Eng., 19 volumes, 2, the dilatometry that the 124-129 page or leaf is described is to measure.By in as the gel of bonding agent, adding rigidizer or, can regulating T by changing the condition of storage after being coated with
1/2And preferred swelling coefficient is at 150%-400%.Swelling coefficient can be used following formula from the maximum swelling film THICKNESS CALCULATION that obtains under these conditions: (maximum swelling film thickness-film thickness)/film thickness.Preferably provide hydrophilic gel layer (being referred to as backing layer) on photographic material of the present invention, it is positioned at the another side of emulsion layer, and total dry film thickness is at 2-20 μ m.In backing layer, preferably include above-mentioned light absorber, filter dyestuff, ultraviolet absorber, antistatic agent, rigidizer, bonding agent, plastifier, lubricant, coating additive and surfactant.The swelling coefficient of backing layer is preferably at 150-500%.
Embodiment
Specifically describe the present invention below with reference to embodiment, but never should therefore limit the scope of the invention.
1 pair of precipitation of embodiment stabilization
Preparation has the color developer composition of following composition, is used to detect the stabilization to precipitation.Color developer composition diethylene-triamine pentaacetic acid 6.0g4,5-dihydroxy phenyl-1, compound shown in the 3-sodium disulfonate 1.0g sodium sulphite 15.0g sal tartari 100.0g table 1 is referring to table 1 disodium-N, and two (sulfonation the ethyl)-hydramine 24.0g4-amino of N--3-methyl-N-ethyl-N-(β hydroxyethyl) aniline sulfate 20.0g water adds to 1.0 liters of pH (regulating with potassium hydroxide) 11.0
The color developer composition of preparation is put in the vial, preserved for 4 weeks down at-5 ℃.The visualization liquid condition, divide 5 grade evaluation: ◎: do not produce precipitation, zero: produce slight muddiness, △: produce some precipitation, *: clearly observe to produce and precipitate, * *: obviously produce precipitation.The result is shown in Table A.
With contain precipitation and prevent that No. 1 control sample of agent from comparing, the 2-11 control sample of the conventional known compound of using shows and does not prevent to precipitate the generation effect, even have also be seldom a bit prevent to precipitate the generation effect, and 13-24 number any one sample of the present invention of adding The compounds of this invention, all not observing precipitation produces, even precipitation occurs and also be seldom a bit, observed precipitation prevents that effect is equal to or greater than that the disclosed precipitation that prevents produces agent (ethylidene-urea of No. 12 sample) among the JP-A-11-174643.
Embodiment 2
Aging storage stability
The concentrated developer composition of preparation among the embodiment 1 is poured in tygon (HDPE) bottle, and the bottleneck sealing stored for 8 weeks down at 40 ℃ and 50 ℃ respectively with bottle.Visualization adds the state of liquid in each bottle of thermmal storage, divide 5 grade evaluation: ◎: color does not appear in bottle and developer composition, zero: composition is observed light discolouration, △: bottle is observed light discolouration, *: clearly observe the bottle variable color, * *: the obvious variable color of bottle.The result is also shown in Table A.
Table A
| Sample number | Add compound | Addition (g/l) | Precipitation | Heating | Remarks | |
| 40℃ | ?50℃ | |||||
| 1 | No | ????- | ×× | ×× | ×× | Contrast |
| 2 | Toluenesulfonic acid sodium salt | ????10 ????30 | × △ | × × | ×× ×× | Contrast |
| 3 | Nonyl diphenyl ether sodium disulfonate | ????10 ????30 | × × | × × | ×× ×× | Contrast |
| 4 | Diglycol | ????10 ????30 | ×× × | × × | ×× ×× | Contrast |
| 5 | Triethylene ethylene glycol | ????10 ????30 | ×× △ | × ?× | ×× ×× | Contrast |
| 6 | Polyglycol (mean molecular weight: 400) | ????10 ????30 | × △ | × × | × × | Contrast |
| 7 | Polyglycol (mean molecular weight: 2000) | ????10 ????30 | × ○ | × × | × × | Contrast |
| 8 | Propane sulfonic acid sodium | ????10 ????30 | × × | × △ | × × | Contrast |
| 9 | The undecane sodium sulfonate | ????10 ????30 | ○ ○ | × △ | × △ | Contrast |
| 10 | Control compound 1 | ????10 ????30 | × ○ | × △ | × × | Contrast |
| 11 | Control compound 2 | ????10 ????30 | × ○ | × △ | × × | Contrast |
| 12 | Ethylidene-urea | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ○ | Contrast |
| 13 | Instantiation compound (I-3) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 14 | Instantiation compound (I-4) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 15 | Instantiation compound (I-9) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 16 | Instantiation compound (I-10) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 17 | Instantiation compound (I-11) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 18 | Instantiation compound (II-3) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 19 | Instantiation compound (II-4) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 20 | Instantiation compound (II-5) | ????10 ????30 | ○ ◎ | ○ ◎ | ○ ◎ | Invention |
| 21 | Instantiation compound (II-3)/diglycol (blending ratio 4/1) | ????10 ????30 | ◎ ◎ | ◎ ◎ | ◎ ◎ | Invention |
| 22 | Instantiation compound (I-10)/polyglycol (mean molecular weight: 2000) (blending ratio 4/1) | ????10 ????30 | ◎ ◎ | ◎ ◎ | ◎ ◎ | Invention |
| 23 | Instantiation compound (I-10)/instantiation compound (II-3) (blending ratio 4/1) | ????10 ????30 | ◎ ◎ | ◎ ◎ | ◎ ◎ | Invention |
| 24 | Instantiation compound (I-10)/poly--N-vinylpyrrolidone (blending ratio 4/1) | ????10 ????30 | ◎ ◎ | ◎ ◎ | ◎ ◎ | Invention |
Control compound 1:C
2H
5-(OC
2H
4)
3-OH
Control compound 2:CH
3-(OC
2H
4)
3-OH
Prevent to precipitate No. 1 salt that generates agent and compare with not containing, use the 2-11 control compound of conventional known compound color in bottle and agent composition, all to occur, therefore do not demonstrate the effect that prevents color, even have also just seldom a bit, and add the present invention 13-24 sample of any one The compounds of this invention, some sample preparation agent compositions are observed some variable colors, but bottle is not a bit observed variable color, prove according to compound of the present invention to have a significant effect with contrasting to compare for 2-11 number.And, prove that preventing color effects is equal to or greater than that the disclosed precipitation that prevents produces agent (ethylidene-urea of No. 12 sample) among the JP-A-11-174643.From found that when compound of the present invention and diglycol, polyglycol or the polyvinylpyrrolidone applied in any combination of table 1, perhaps when compound applied in any combination that the compound of formula (I) expression and formula (II) are represented, can obtain extraordinary result.
Embodiment 3
The test of photography property
1. colour negative test
Use commercial obtainable film as follows (they are all by Fuji Photo Film Co., and Ltd. produces), ratio is as follows:
Film A:FUJICOLOR SUPER100 (24 exposure films),
Production firm's sequence number: V09140
Film B:FUJICOLOR SUPER400 (24 exposure films),
Production firm's sequence number: N24112
Film C:FUJICOLOR SUPER GACE800 (24 exposure films),
Production firm's sequence number: M74128
Film D:FEJJICOLOR nexia H400 (40 exposure films),
Production firm's sequence number: CA56-303
These film processing ratios are film A/ film B/ film C/ film D=4/4/1/1
2. photography property exposure test
Above-mentioned sample film B passes through standard C light source and neutral colored continuous wedge (density gradient: 0.4AD/cm, density range: 0.02-4.8) expose, to measure light sensitivity according to international standard 1SO5800 (being used to measure the method for colour negative light sensitivity).This exposed sample is used for following development treatment, observes photography character (light sensitivity, gradient and photographic fog).
3. development treatment
By following development treatment device colour negative is handled, and prescription.
As processor, revise the processing time of automatic processor FP-363SC (by Fuji Photo Film Co., Ltd. produces), make it become the experiment processor.Open system and automatic preparation system by Braking mode, processor provides video picture mechanism.The processor profile is as described below.(label is 300 to above-mentioned plastics (HDPE) bottle among Fig. 2, by label each unit is described hereinafter) arrange one by one and install, Open Side Down, when the bottle opening, as shown in Figure 2, bottle is shifted to perforation nozzle 188 from above, perforation nozzle 188 is opened the plastic layer 380 as bottle cap, and the content in the bottle is injected in the developer pond.Then, be injected in the bottle, wash from the nozzle bore 214 of perforation nozzle 188 water with formula ratio.The water that is used for washing joins the developer pond, as the thinned water of preparation developer.
Shown in treatment step and each Treatment Solution composed as follows.Treatment step step process time treatment temperature video picture rate pool volume
(℃) (ml) 25 seconds 40 5 3.6 fixing (1) 25 second 40-3.6 fixing (2) 25 seconds 40 7.5 3.6 stable (1) 14 second 40-1.9 stable (2) 13 seconds 40-1.9 stable (3) 13 seconds 40 30 1.9 dry 20 seconds per 1.1 meters of wide photographic materials of 60 video picture rate: 35mm (corresponding to 24 exposed plates) of (liter) colour development 2 minutes 30 seconds 41.0 15 10.3 bleaching
Stablize to (1) at inverse system from (3) to (2).Also fix in inverse system, fixed spool connects by reverse pipeline from (2) to (1).Solution fixed spool (2) (15ml is corresponding to the video picture amount) with stabilization pond (2).And, from developing solution to the blanching step transfer amount, be respectively the wide photographic material 2.0ml of per 1.1 meters 35mm to the wash solution transfer amount from liquid lime chloride to fixing rapid transfer amount with from fixed solution.And be 6 seconds every kind of situation transfer time, and this time was included in the processing time of back.
The composed as follows of every kind of Treatment Solution described.Colour development solution
Pond solution developer diethylene-triamine pentaacetic acid 2.0g 4.0g4; 5-dihydroxy phenyl-1; 3-sodium disulfonate 0.4g 0.5g disodium-N, the compound that two (sulfonation the ethyl)-hydroxylamine 10.0g 15.0g sodium sulfite 4.0g 9.0g KBr 1.4g of N--4-amino-3-methyl-N-ethyl-N-(β hydroxyethyl) 5.5g 12.5g aniline sulfate potash 39g 59g table B describes adds to 1.0 liters of 1.0 liters of pH (regulating with sulfuric acid and potassium hydroxide), 10.10 11.20 liquid lime chlorides referring to table B referring to table B water
Pond solution developer 1,3-diaminopropanes pentaacetic acid ferric acid ammonium monohydrate 120g 180g ammonium bromide 50g 70g butanedioic acid 30g 50g maleic acid 40g 60g imidazoles 20g 30g water add to 1.0 liters of 1.0 liters of pH (regulating with ammoniacal liquor and nitric acid), 4.6 4.0 fixed solutions
Pond solution developer ATS (Ammonium thiosulphate) (750g/ liter) 280ml 750ml ammonium sulfite aqueous solution (72%) 20g 80g imidazoles 5g 45g1-sulfydryl-2-(N, the N-dimethyl aminoethyl) tetrazolium 1g 3g ethylenediamine tetraacetic acid 8g 12g water adds to 1.0 liters of 1.0 liters of pH (regulating with ammoniacal liquor and nitric acid), 7.0 7.0 stabilizing solutions (developer solution equals pond solution) SPTS 0.03g to Nonylphenoxy poly epihydric alcohol 0.4gl (diglycidyl average degree of polymerization: 10) disodium ethylene diamine tetraacetate 0.05g1,2,4-triazole 1.3g1,4-two (1,2,4-triazol-1-yl methyl) piperazine 0.75g1,2-benzisothiazole-3-ketone 0.10g water adds to 1.0 liters of pH 8.5
4. test and test result
Preparation is by 5 times of concentrated solutions of the developer prescription of the colour development of describing in the aforesaid clause 3 development treatment conditions.(" concentrate " in the liquid treating agent is meant the ratio value in the prescription of agent composition concentrate, is not meant the concentrate that causes owing to reasons such as evaporations.) the developer composition that will concentrate development pours in above-mentioned plastics (HDPE) bottle, 40 ℃ of down aging 10 weeks.The developer that bottle is installed in the processor of above-mentioned modification prepares part, is discharged into the developer pond from plastic bottle according to above-described method concentrating the developer composition that develops, and with the washings dilution, prepares developer like this in each developer pond.Each above-mentioned pond solution of preparation is respectively poured in the treating agent, handled 30% exposed plate (30% exposure is because silver halide particle is 30% in the sensitization rate under the average photography conditions of colour negative) of above-mentioned film, video picture from the developer pond.Reach 1.0 times of developing pool volume when the developer consumption that develops, by being used for sensitometric wedge exposure (wedge exposure), test pieces to above-mentioned film B is carried out development treatment, photography character with following shown in the photography character handled by standard compare.Treatment step and treatment solution compositions that standard is handled are as follows.Except colour development solution, it is identical with the composition that uses in the above-mentioned processing that Treatment Solution has.Treatment step step process time treatment temperature video picture rate pool volume
(℃) (ml) 50 seconds 38 5 3.6 fixing (1) 50 second 38-3.6 fixing (2) 50 seconds 38 7.5 3.6 stable (1) 30 second 38-1.9 stable (2) 20 seconds 38-1.9 stable (3) 20 seconds 38 30 1.9 dry 1 minute 30 seconds per 1.1 meters of wide photographic materials of 60 video picture rate: 35mm (corresponding to 24 exposed plates) of (liter) colour development 2 minutes 30 seconds 38.0 15 10.3 bleaching
Stablize to (1) at inverse system from (3) to (2).Also fix in inverse system, fixed spool connects by reverse pipeline from (2) to (1).Solution fixed spool (2) (15ml is corresponding to the video picture amount) with stabilization pond (2).And, from developing solution to the blanching step transfer amount, be respectively the wide photographic material 2.0ml of per 1.1 meters 35mm to the wash solution transfer amount from liquid lime chloride to fixing rapid transfer amount with from fixed solution.And be 6 seconds every kind of situation transfer time, and this time was included in the processing time of back.
The composed as follows of every kind of Treatment Solution described.Colour development solution
Pond solution developer diethylene-triamine pentaacetic acid 2.0g 4.0g4; 5-dihydroxy phenyl-1; 3-sodium disulfonate 0.4g 0.5g disodium-N, two (sulfonation the ethyl)-hydroxylamine 10.0g 15.0g sodium sulfite 4.0g 9.0g KBr 1.4g of N--diethylene glycol (DEG) 10.0g 17.0g ethylidene-urea 3.0g 5.5g4-amino-3-methyl-N-ethyl-N-(β hydroxyethyl) 4.7g 11.4g aniline sulfate potash 39g 59g hydroxylamine sulfuric ester 2.0g 4.0g water add to 1.0 liters of 1.0 liters of pH (regulating with sulfuric acid and potassium hydroxide) 10.07 10.51
Photography property is compared as follows.Be that each test pieces of processed back (cross and be used for sensitometric sample wedge exposure) is represented by following color balance difference.The color balance difference approaches 0 more, and expression equals the color balance handled by standard by the color balance that carries out test processes.The result who obtains is shown in table B.Color balance difference: △ (R-G)=[(the R density when test processes)-(G density when test processes)]-[(the R density when standard is handled)-(G density when standard is handled)]
Wherein to be respectively in logarithm exposure amount (logE) be that (the antilogarithm value of exposure is 1,000cms) for 3.0 o'clock density for R density and G density
Table B
| Sample number | Add compound | Addition (g/l) | Color balance difference: △ (R-G) | Remarks |
| 1 | No | ????- | ????-0.4 | Contrast |
| 2 | Paratoluenesulfonic acid sodium salt | ????20 ????40 | ????-0.25 ????-0.25 | Contrast |
| 3 | Nonyl diphenyl ether sodium disulfonate | ????20 ????40 | ????-0.23 ????-0.24 | Contrast |
| 4 | Diglycol | ????20 ????40 | ????-0.26 ????-0.25 | Contrast |
| 5 | Triethylene ethylene glycol | ????20 ????40 | ????-0.27 ????-0.26 | Contrast |
| 6 | Polyglycol (mean molecular weight: 400) | ????20 ????40 | ????-0.21 ????-0.21 | Contrast |
| 7 | Polyglycol (mean molecular weight: 2000) | ????20 ????40 | ????-0.26 ????-0.25 | Contrast |
| 8 | Propane sulfonic acid sodium | ????20 ????40 | ????-0.21 ????-0.22 | Contrast |
| 9 | The undecane sodium sulfonate | ????20 ????40 | ????-0.22 ????-0.22 | Contrast |
| 10 | Control compound 1 | ????20 ????40 | ????-0.21 ????-0.20 | Contrast |
| 11 | Control compound 2 | ????20 ????40 | ????-0.24 ????-0.23 | Contrast |
| 12 | Ethylidene-urea | ????20 ????40 | ????-0.25 ????-0.24 | Contrast |
| 13 | Instantiation compound (I-3) | ????20 ????40 | ????-0.19 ????-0.15 | Invention |
| 14 | Instantiation compound (I-4) | ????20 ????40 | ????-0.18 ????-0.16 | Invention |
| 15 | Instantiation compound (I-9) | ????20 ????40 | ????-0.11 ????-0.10 | Invention |
| 16 | Instantiation compound (I-10) | ????20 ????40 | ????-0.09 ????-0.08 | Invention |
| 17 | Instantiation compound (I-11) | ????20 ????40 | ????-0.10 ????-0.08 | Invention |
| 18 | Instantiation compound (II-3) | ????20 ????40 | ????-0.08 ????-0.06 | Invention |
| 19 | Instantiation compound (II-4) | ????20 ????40 | ????-0.10 ????-0.08 | Invention |
| 20 | Instantiation compound (II-5) | ????20 ????40 | ????-0.12 ????-0.10 | Invention |
| 21 | Instantiation compound (II-3)/diglycol (blending ratio 4/1) | ????20 ????40 | ????-0.06 ????-0.04 | Invention |
| 22 | Instantiation compound (I-10)/polyglycol (mean molecular weight: 2000) (blending ratio 4/1) | ????20 ????40 | ????-0.05 ????-0.05 | Invention |
| 23 | Instantiation compound (I-10)/instantiation compound (II-3) (blending ratio 4/1) | ????20 ????40 | ????-0.06 ????-0.04 | Invention |
| 24 | Instantiation compound (I-10)/poly--N-vinylpyrrolidone (blending ratio 4/1) | ????20 ????40 | ????-0.05 ????-0.05 | Invention |
Control compound 1:C
2H
5-(OC
2H
4)
3-OH
Control compound 2:CH
3-(OC
2H
4)
3-OH
From table found that of B: by the adding formula (I) or (II) compound of expression, even also can stably keep photography character between the storage life at developer composition.And, prevent that with JP-A-11-174643 (No. the 12nd, sample, ethylidene-urea) is disclosed precipitation from generating agent and comparing, observe the present invention and obviously have and prevent to precipitate nucleus formation.From table B found that when formula (I) or when the compound of (II) representing and diglycol, polyglycol or polyvinylpyrrolidone applied in any combination, perhaps when compound applied in any combination that the compound of formula (I) expression and formula (II) are represented, can obtain extraordinary result.
The colour negative sample that embodiment 41. is used to detect
Use the sample number 101 conduct test photographic materials among United States Patent (USP) 6,013,426 embodiment 1, carry out following test.2. the preparation of concentrated colour developer and composition stable property testing
The developer for preparing colour development respectively wherein contains the colour development replenishers that development treatment experiment complimentary close is described respectively, formula (I), (II) compound shown in Biao Shi compound or the table C.The above-mentioned developer composition that obtains is concentrated into 3 times respectively, puts into HDPE bottle (a part of composition).Obtain composition sample 31-47 thus.
The methods of describing according to embodiment 1 and 2 detected prescription sample number 31-47 in bottle sealing state through the time stability and the stability of air oxidation.For colour stability, select test condition at 40 ℃.
Obtain the result shown in table C.3. the test of photography property
Carry out the photography property test to carrying out pretreated No. 101 photographic material sample, the processor that applicating adn implementing example 3 is identical, treatment step, exposure and processing operation, except being used for sensitometry, No. 101 sample expose, pond solution reaches the running balance in processor, the processor transfer rate of using among the embodiment 3 increases by 10%, the temperature of each treatment step also changes thereupon, colour development solution as follows is used as color developing tank solution, put into above-mentioned bottle by the concentrated colour developer of following formulation, the mode identical with embodiment 3 is installed in the processor, automatically the developer of preparation is as the developer of colour development thus, and the stabilizing solution of the regular convention formula that describes below is as stabilization pond solution and its developer.According to the method identical photography property is estimated, promptly, photography property is estimated by the color balance difference of developing with standard typical value as photography character with embodiment 3.
The result who obtains is shown in table C.
Shown in treatment step and each Treatment Solution composed as follows.Treatment step step process time treatment temperature video picture rate pool volume
(second) (℃) (ml) (liter) colour development 135 42.0 15 10.3 bleaching 22.5 41 5 3.6 fixing (1) 22.5 41-3.6 fixing (2) 22.5 41 7.5 3.6 stable (1) 12.5 41-1.9 stable (2) 11.7 41-1.9 stable (3) 11.7 41 30 1.9 dry per 1.1 meters of wide photographic materials of 27 62 video picture rate: 35mm (corresponding to 24 exposed plates)
Stablize to (1) at inverse system from (3) to (2).Also fix in inverse system, fixed spool connects by reverse pipeline from (2) to (1).Solution fixed spool (2) (15ml is corresponding to the video picture amount) with stabilization pond (2).And, from developing solution to the blanching step transfer amount, be respectively the wide photographic material 2.0ml of per 1.1 meters 35mm to the wash solution transfer amount from liquid lime chloride to fixing rapid transfer amount with from fixed solution.And be 5.4 seconds every kind of situation transfer time, and this time was included in the processing time of back.
The composed as follows of every kind of Treatment Solution described.Colour development solution
Pond solution developer diethylene-triamine pentaacetic acid 2.8g 3.4g catechol-3, the compound that 5-disulfonic acid disodium 0.27g 0.35g sodium sulphite 3.9g 5.3g sal tartari 39.0g 39.0g table C describes (referring to table C) 4.7g 6.0g disodium-N, two (sulfonation the ethyl)-hydramine 1.5g 2.0g potassium bromide 1.3g 0.3g potassium iodide 1.3mg of N--4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-purine 0.05g-hydramine sulfuric ester 2.4g 3.3g2-methyl 4-[N-ethyl-N-(β hydroxyethyl) ammonia 4.5g 6.5g yl] aniline sulfate water adds to 1.01 1.01pH (regulating with sulfuric acid and potassium hydroxide) (the diglycidyl average degree of polymerization: 10) disodium ethylene diamine tetraacetate 0.05g1,2-benzisothiazole-3-ketone 0.10g water adds to 1.01PH 8.5 to 10.05 10.18 stabilizing solutions (developer solution equals pond solution) SPTS 0.03g to Nonylphenoxy poly epihydric alcohol 0.4gl
As mentioned above, bleaching is identical with embodiment 3 with the Treatment Solution prescription of fixing step (with developer).
Table C
Remarks: the polyglycol mean molecular weight that use (1) is 1000.
| Sample number | Add compound | Precipitation | Color (℃) | Color balance | Remarks |
| 31 | No | ????×× | ???×× | ????-0.30 | Contrast |
| 32 | Polyglycol (mean molecular weight: 1000) | ????△ | ????△ | ????-0.27 | Contrast |
| 33 | Ethylidene-urea | ????△ | ????△ | ????-0.25 | Contrast |
| 34 | Poly--the N-vinylpyrrolidone | ????△ | ????△ | ????-0.25 | Contrast |
| 35 | Instantiation compound (I-10) | ????○ | ????○ | ????-0.18 | Invention |
| 36 | Instantiation compound (II-2) | ????○ | ????○ | ????-0.15 | Invention |
| 37 | Instantiation compound (II-5) | ????○ | ????○ | ????-0.14 | Invention |
| 38 | Instantiation compound (I-10)/polyglycol (blending ratio 4/1) | ????○ | ????◎ | ????-0.10 | Invention |
| 39 | Instantiation compound (I-10)/ethylidene-urea (blending ratio 4/1) | ????◎ | ????○ | ????-0.13 | Invention |
| 40 | Instantiation compound (I-10)/poly--N-vinylpyrrolidone (blending ratio 4/1) | ????◎ | ????○ | ????-0.12 | Invention |
| 41 | Instantiation compound (II-2)/polyglycol (blending ratio 4/1) | ????◎ | ????◎ | ????-0.05 | Invention |
| 42 | Instantiation compound (II-2)/ethylidene-urea (blending ratio 4/1) | ????◎ | ????◎ | ????-0.05 | Invention |
| 43 | Instantiation compound (II-2)/poly--N-vinylpyrrolidone (blending ratio 4/1) | ????◎ | ????◎ | ????-0.04 | Invention |
| 44 | Instantiation compound (II-5)/polyglycol (blending ratio 4/1) | ????◎ | ????◎ | ????-0.06 | Invention |
| 45 | Instantiation compound (II-5)/ethylidene-urea (blending ratio 4/1) | ????◎ | ????◎ | ????-0.05 | Invention |
| 45 | Instantiation compound (II-5)/poly--N-vinylpyrrolidone (blending ratio 4/1) | ????◎ | ????◎ | ????-0.05 | Invention |
| 47 | Instantiation compound (I-10)/instantiation compound (II-3) (blending ratio 1/1) | ????◎ | ????◎ | ????-0.10 | Invention |
(2) addition of every kind of compound is the 30g/ liter, and when adding two kinds of compounds, total amount is the 30g/ liter.4. test result
From table found that of C: according to 35-46 sample that carries out high temperature, short time rapid development of the present invention and the color balance difference between No. 1 control sample of handling under the standard development conditions is 0.18 or still less, when according to compound of the present invention and polyglycol, urea or polyvinylpyrrolidone applied in any combination, the color balance difference is 0.13 or still less, this shows that sample of the present invention has the preferable image performance.
And, from result's the result of table C, when the 35-37 sample is compared with the 32-34 control sample, can find adding formula (I) or (II) expression compound according to sample of the present invention, preventing that crystalline deposit from generating, preventing the control sample that color and photography property all are better than using conventional known compound aspect all.When with according to sample of the present invention relatively, promptly No. 35 sample and 38-40 sample are relatively, No. 36 sample and 41-43 sample are relatively, No. 37 sample and 44-46 sample are relatively, if in the compound that further polyglycol, ethenylidene urea or polyvinylpyrrolidone is joined formula (I) or (II) represent, can further improve effect of the present invention.And, when 38-40 sample and 41-43 sample and 44-46 sample compare respectively, if polyglycol, ethenylidene urea or polyvinylpyrrolidone and when going into the compound applied in any combination of formula (II) expression, compare when making up with the compound combination of formula (I) expression with them, effect of the present invention, particularly, more remarkable about the stability of photography character.
The invention effect
By to the color developing composition adding formula (I) that is used for silver halide color photographic materials or (II) expression compound, can prevent that between the storage life composition generates precipitation and color appears in composition itself or color appears in its container, can keep stable image property.Therefore, can increase the concentration of color developer composition.
And, can use out of use polyethylene can in conventional color developing composition.
In addition, when will be, can improve the color balance that in rapid development, is easy to occur and degenerate according to the diluted developer as developing solution or development of concentrated liquid development treatment of the present invention agent.Particularly, in 2 minutes 30 seconds or still less fast colourful development treatment and/or 40 ℃ or higher high-temperature color development treatment, show especially effectively and improve the color balance performance.
When formula (I) or (II) compound of compound, particularly formula (II) expression of expression is with conventional known polyglycol, ethenylidene urea or polyvinylpyrrolidone applied in any combination, can further improve these effects.
Although the present invention is described in detail with reference to their specific embodiments, it is made amendment, and without departing from the spirit and scope of the present invention, be conspicuous for those skilled in the art.
Claims (5)
1. concentrated liquid color developer composition that is used for silver halide color photographic materials, it comprises at least a formula (I) or compound (II):
R
1-(OC
2H
4)
n-OH (I) is R wherein
1Expression has the alkyl of 1-3 carbon atom, and n represents the integer of 4-9;
R
2-SO
3M (II) is R wherein
2Expression has the alkyl of 4-10 carbon atom, and M represents kation.
2. according to the described concentrated liquid color developer of claim 1 composition, compound and at least a mean molecular weight that is selected from that wherein said concentrated liquid color developer composition contains at least a formula (II) expression are 2000 or the compound of polyglycol still less, urea and polyvinylpyrrolidone.
3. according to claim 1 or 2 described concentrated liquid color developer compositions, wherein said concentrated liquid color developer composition is installed in the container.
4. the developing method of a silver halide color photographic materials, it comprises that application is used for the colour development solution that the concentrated liquid color developer composition of silver halide color photographic materials obtains or the developer of colour development by dilution, carry out colour development in 2 minutes 30 seconds processing time, wherein said concentrated liquid color developer composition contains at least a formula (I) or compound (II):
R
1-(OC
2H
4)
n-OH (I) is R wherein
1Expression has the alkyl of 1-3 carbon atom, and n represents the integer of 4-9;
R
2-SO
3M (II) is R wherein
2Expression has the alkyl of 4-10 carbon atom, and M represents kation.
5. the developing method of a silver halide color photographic materials, it comprises that application is used for the colour development solution that the concentrated liquid color developer composition of silver halide color photographic materials obtains or the developer of colour development by dilution, 40 ℃ (or carry out colour development under the higher treatment temperature, wherein said concentrated liquid color developer composition contains at least a formula (I) or compound (II):
R
1-(OC
2H
4)
n-OH (I) is R wherein
1Expression has the alkyl of 1-3 carbon atom, and n represents the integer of 4-9;
R
2-SO
3M (II) is R wherein
2Expression has the alkyl of 4-10 carbon atom, and M represents kation.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP165892/2000 | 2000-06-02 | ||
| JP165891/2000 | 2000-06-02 | ||
| JP2000165891A JP2001166440A (en) | 1999-09-29 | 2000-06-02 | Color developing composition for silver halide color photographic sensitive material |
| JP2000165892A JP2001109115A (en) | 1999-08-04 | 2000-06-02 | Concentrated liquid color developer composition for silver halide color photographic sensitive material and developing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1327175A true CN1327175A (en) | 2001-12-19 |
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|---|---|---|---|
| CN 01102347 Pending CN1327175A (en) | 2000-06-02 | 2001-02-05 | Concentrated liquid colour developing agent of silver halide colour photographic material and developing processing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102759849A (en) * | 2012-06-30 | 2012-10-31 | 乐凯胶片股份有限公司 | Color photographic developing solution |
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2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102759849A (en) * | 2012-06-30 | 2012-10-31 | 乐凯胶片股份有限公司 | Color photographic developing solution |
| CN102759849B (en) * | 2012-06-30 | 2017-05-10 | 乐凯胶片股份有限公司 | Color photographic developing solution |
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