CN1129989A - Non-hydroquinone photographic developer composition and processing method - Google Patents
Non-hydroquinone photographic developer composition and processing method Download PDFInfo
- Publication number
- CN1129989A CN1129989A CN94193074A CN94193074A CN1129989A CN 1129989 A CN1129989 A CN 1129989A CN 94193074 A CN94193074 A CN 94193074A CN 94193074 A CN94193074 A CN 94193074A CN 1129989 A CN1129989 A CN 1129989A
- Authority
- CN
- China
- Prior art keywords
- ascorbic acid
- developer
- alkali metal
- developer composition
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/48—Polyoxyethylene
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A non-hydroquinone photographic developer composition consisting essentially of: (a) a developer selected from the group consisting of ascorbic acid and sugar-type derivatives thereof, or alkali metal salts and mixtures thereof, in an amount of 0.1 to 0.4 mol/liter (mol/l); (b) an effective amount of an auxiliary developing agent comprising a 3-pyrazolidone compound, an aminophenol or a mixture thereof; (c) an alkali metal sulfite in an amount less than or equal to 0.32 mol/l; (d) an alkali metal carbonate in an amount of 0.1 to 0.4 mol/l; (e) an alkali metal hydroxide in an amount of from 10 to 25 g/l where an ascorbic acid or sugar-type derivative thereof is present in the form of a free acid or from 3 to 15 g/l where an ascorbic acid or sugar-type derivative thereof is present in the form of an alkali metal salt; and (f) with the developer composition having a pH of from 10.3 to 12.5 at 25 DEG C; where the developer composition is useful for processing standard rapid access films while showing an especially advantageous effect in the processing of silver halide emulsions containing a hydrazine compound to achieve lith quality, and high dot quality in a stable development solution. In a preferred embodiment, the developer composition does not contain an alkanolamine.
Description
The present invention relates to a kind of non-hydroquinone photographic developer composition and the using method in photograph component develops thereof.More precisely, the present invention relates to a kind of non-quinhydrones developer composition, it is particularly useful in the development of various types of black-and-white photograph components developing and need not poisonous quinhydrones and exist to reach the hard contrast quality really.Even more precisely, it is favourable that photographic process composition of the present invention develops to the interior promotion silver halide magenta-sensitive emulsion of the hydrazine compound that is used to have contained the nucleator effect.
The hard contrast of black and white lithographic film is developed and is to use the special-purpose developer that belongs in " this sheet of lining " developer scope to develop for many years always.As U.S.P 4,988,604 is described, during with routine " this sheet of lining " developer, use " this sheet effect of lining " can reach the purpose of hard contrast, press the description of J.A.Z Yule in " Journal of the Franklin Institute; Volume 239; 221-230, (145) ", also be considered to the development of pollution.Traditional " this film developing agent of lining " be characterised in that and have as the quinhydrones of unique developer and the sulfite ion of low concentration is arranged, so that can not stop the development of pollution mechanism is arranged.But conventional " this sheet of lining " developer has many major defects of having generally acknowledged, and they have hindered its usability.For example, the quinhydrones that contains as unique developer owing to this developer manifests low capacity, and in addition, aldehyde tends to hydroquinone photographic developer reaction and causes undesirable variation aspect active developing.In addition, low sulfite ion concentration is not suitable for providing and effectively prevents atmospheric oxidn.As a result, make routine " this sheet of lining " developer solution deficient in stability.
A kind of use of known replacement routine " this sheet of lining " developer has been disclosed in U.S.P4, in 269,929.This patent has been described in the hard contrast that has hydrazine compound and alkaline developing solution to implement in the presence of together to take pictures element and has been developed, and the pH value of described developing solution is about 10 and be lower than 12 and contain the amino-compound as kicker of dihydroxy benzenes developer, 3-pyrazolidone developer, sulphite preservative agent and promotion contrast amount.
Although this developer composition that contains amino " kicker " can and produce improvement in capacity, stability aspect contrast, but wherein become amino-compound generally acknowledged immediately in the prior art as the inherent defect that " kicker " mixes in the developer composition, as toxicity, excessive volatility, lack dissolubility, cost height or the like, as at U.S.P 4, illustrated in 988,604.
Therefore, in relating to the scope of amino (kicker) compound being mixed photographic silver halide element itself, produced other suggestion, caused amino-compound to be used as what is called " kicker that mixes ", as at U.S.P 4,914, described in 003.In this " kicker that mixes " system, amino-compound that plays " kicker " effect and the hydrazine compound that plays " nucleator " effect are mixed in the silver halide magenta-sensitive emulsion, or in other the hydrophilic colloid layer, in photographic silver halide material, with photosensitive emulsion that so-called " wife's promotion " is provided or the photosensitive emulsion that contains hydrazine compound.In this respect, representational document for example has U.S.P 4,988, and 604,4,975,354 and 4,994,365 and international monopoly WO 92/15043 and WO 93/02389.
Also have, the title of D.L.Kerr publication recently is " AN ENVIRONMENTALLYIM-PROVED NUCLEATION PROCESS FOR GRAPHIC ARTS IMAGING " (IS ﹠amp; T ' s 46th Ann.Conf (1993), 268-270 page or leaf) described and discussed and the technology of the photosensitive emulsion that the summary wife promotes.
Yet these prior art systems at least still preferably depend on the developer that uses the quinhydrones base and preferably use the about 9-of pH scope about 10.8, and as U.S.P 4,988,604 is described.
Moreover from ecological and toxicology viewpoint, these important disadvantages are relevant with the described quinhydrones base developing system of use.For example, quinhydrones has irritated effect.Therefore, see the problem of using quinhydrones to have some operation and handle with regard to the viewpoint that adapts to health, safety and environmental criteria and regulation.
WO 93/11456 has described a kind of speed developer that contains the hydrazine film that is applicable to, it contains the alkanolamine of at least a 5-50g/l; At least a ascorbic acid developer; And the pH scope is at 10.7-about 12.0.This developer also can contain KOH and sal tartari.Yet as what hereinafter discuss, many alkanolamines all have undesirable toxicity.Excessive volatility and offending smell.In addition, alkanolamine has adverse influence to this sheet hard contrast image performance of lining.
The U.S.P.5 that is equivalent to European patent 0498968 that on August 19th, 1992 announced, 196,298 propose a kind of developing solution that is used for dip-type developing, its pH is at least 12.0, tool contains the above sugar derivatives of 0.4 mol, or its alkali metal salt, as 1-ascorbic acid and different-ascorbic acid, preferably do not contain other developer and sulfite ion.U.S.P 5,196, when being described as being of 298 developer solution can allow to handle discarded developer solution in easier mode on the environment, can develop to process photography material hard contrast quality ground.But U.S.P 5,196, and 298 also state this patent obtained whole benefits in the pH scope is 12.3-13.5, but this pH scope is higher, can not be that all users accept.
U.S.P 5,098, and 819 also disclose the developer composition that does not contain quinhydrones and alkali metal hydroxide.The non-hydroquinone photographic developer solution of this patent contains the developer that is selected from ascorbic acid and sugared type derivant thereof, and with sulphite, alkali carbonate and 3-pyrazolidone developer compound, wherein the pH scope of developer solution is 9.75-10.6.U.S.P5,098,819 developer composition of describing can be degraded when pH surpasses 10.6 left and right sides.Similarly, the Japanese Laid-Open Patent Application 59-191035 that on October 30th, 1984 announced discloses a kind of developer composition, it is particularly suitable for handling the silver halide magenta-sensitive emulsion that contains black dyes, wherein developer is described as being and contains ascorbic acid, alkali carbonate, alkali metal sulfite and alkali metal hydroxide, and the pH scope is 10-14.Yet two kinds of publications mentioning later all do not have this film developing agent in special the description, and more explanation can not show the detection data that the hard contrast quality is developed.
In any case, in these patent specifications, do not have open or propose to use these developers can be used to contain developer, to obtain the hard contrast image as the photographic silver halide material of the hydrazine compound of nucleator.
In fact, this tablet quality in non-hydroquinone photographic developer solution above-mentioned can not reach.
Therefore, this technology waits for that urgently discovery does not need the developer composition of hydroquinone photographic developer and can reach simultaneously the quality of hard contrast.
The purpose of this invention is to provide a kind of developer composition, said composition does not need to have hydroquinone type developer composition or alkanolamine, and the result has reduced the threat of healthy and environment and is easier to operation and processing.
Another purpose of the present invention provides a kind of stable developer composition, and it is suitable for the intermediate film of the standard of washing.
Another purpose of the present invention provides a kind of method of new acquisition hard contrast image, does not a kind ofly contain the quinhydrones developer and contains the photographic silver halide material that hydrazine compound is made nucleator by using.
The present invention these and in addition purpose can be by being reached described consisting of basically by the following non-hydroquinone photographic developer composition of forming:
(a) be selected from a kind of developer of ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof, its amount is 0.1-0.4 mol (mol/l).
(b) contain 3-pyrazolidone compound, the auxiliary developer of the effective dose of aminophenol compound or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.1-0.4mol/l;
(e) a kind of alkali metal hydroxide, when ascorbic acid or its sugared type derivant are when existing with free acid form, then the amount of alkali metal hydroxide be 10-25g/l or when ascorbic acid or its sugared type derivant be form with alkali metal salt when existing, then the amount of alkali metal hydroxide is 3-15g/l; With
(f) the pH value of developer composition is 10.3-12.5 in the time of 25 ℃, is more preferably 10.5 or 10.8-11.5 or 12.2.
In the preferred embodiment of the invention, developer composition also contains one or more following adding ingredients in addition:
(g) a kind of inhibitor that postpones unexposed silver halide development, its amount is 0.008-0.042 mol/l.
(h) organic antifoggant, its amount is 0.02-2g/l; With
(i) sequestrant, its amount is 0.5-3g/l.
Simultaneously, according to better embodiment of the present invention, inhibitor is selected alkali metal bromide; Organic antifoggant selects the composition of 0.01-0.1g/l benzotriazole and 0.01-0.1g/l phenyl mercapto-tetrazole (PMI) and sequestrant to select Na
2EDTA.
In the another one preferred embodiment, developer composition of the present invention does not contain alkanolamine or contains the alkanolamine that is lower than 5g/l.Best is that developer composition does not contain alkanolamine.Many alkanolamines all have the unwelcome character of toxicity, excessive volatility and unhappy smell.Many alkanolamines and water can both form azeotropic mixture, and this makes accurately provides developer solution complicated, and this compounds is also very expensive.In addition, alkanolamine can be accelerated the process of chemical development by consuming physical development.The image that this phenomenon makes generation than the image that does not have alkanolamine to obtain more in pelletized form, with obtain hard contrast in the purpose of this sheet be contradictory.
Find to use developer composition of the present invention can unexpectedly guarantee to provide the hard contrast quality and therefore high site quality and need not quinhydrones or alkanolamine exists.
Another one embodiment of the present invention comprises that the exposure that will contain as the hydrazine compound of nucleator with a kind of developer becomes the video photographic silver halide material to develop, this developer comprises the developer that is selected from ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof, basically do not have dihydroxy benzenes, term " does not have dihydroxyphenyl " and means the amount of dihydroxy benzenes to be lower than 5 * 10 basically
-4Mol/l and be preferably zero.Above-mentioned other developer composition composition also can be used for being combined into the embodiment of this method of the present invention.
Brief description of drawings
Fig. 1 shows the D-LogE curve of the photosensitive emulsion film that promotes in the EK that is washed 2000 CGP by the developer composition of developer composition of the present invention and some representational known technology.
Fig. 2 represents to wash by developer composition of the present invention and some representational prior art developer compositions the D-LogE curve of the photosensitive emulsion film that promotes in the EK2000 CLW.
Fig. 3 A represents by the D-LPgE curve of the conventional speed of the Fuji RO-100 that developer developed of developer composition of the present invention and EP 0498968 (U.S.P 5,196,298) with the photosensitive emulsion film.
Fig. 3 B represents by the D-LogE curve of the conventional speed of the Fuji RO-100 that developer developed of developer composition of the present invention and U.S.P 5,098,819 with the photosensitive emulsion film.
Fig. 3 C represents by the D-LogE curve of the conventional speed of the Fuji RO-100 that developer developed of developer composition of the present invention and Japanese patent application (OPI) 59-191035 with the sensitive emulsion sheet.
Fig. 4 A represents the D-LogE curve on the photosensitive emulsion film that the different prescription of developer composition of the present invention promotes in EK 2000 CGP.
Fig. 4 B represents that the developer composition of the present invention of different formulations promotes the D-LogE curve on the photosensitive emulsion film in EK2000 CLW.
Fig. 4 C represents that the developer composition of the present invention of different formulations is fast with the D-LogE curve on the photosensitive emulsion film at Fuji RO-100.
Fig. 5 A is illustrated in sodium hydrate content when using the ascorbyl developer formuia, and promptly the pH value is to promoting the influence of the D-LogE of photosensitive emulsion film in the EK200 CGP.
Fig. 5 B is illustrated in sodium hydrate content when using the ascorbyl developer formuia, and promptly the pH value is to promoting the influence of the D-LogE curve of photosensitive emulsion film in the EK200 CLW.
Fig. 5 C is illustrated in sodium hydrate content when using the ascorbyl developer formuia, and promptly the pH value is to the influence of Fuji RO-100 speed with the D-LogE curve of photosensitive emulsion film.
The explanation of preferred embodiment
In developer solution of the present invention, ascorbic acid and sugared type derivant thereof are used as main body isomeride and diastereo-isomerism and the sugared type derivant thereof that developer also comprises ascorbic acid, their salt and composition thereof.The appropriate developer that falls into above-mentioned scope also comprises, but be not limited to the l-ascorbic acid, d-red (erythro-) ascorbic acid (is erythorbic or arabo-ascorbic acid, d-Portugal (gluco)-anti-hematic acid, d-deoxidation-l-ascorbic acid, l-sandlwood (rhamno)-ascorbic acid, l-rock algae (fuco) ascorbic acid, d-Portugal heptan (gl-ucohepto)-ascorbic acid, sorb (sorbo) resists two hematic acid, imino group-l-ascorbic acid, ω-breast (lacto) ascorbic acid, Fructus Hordei Germinatus (malto) ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal (gluco) ascorbic acid, d-gala (galaco) ascorbic acid, the ancient Lip river (gulo) of l-ascorbic acid, with l-A Luo (allo) ascorbic acid.
Ascorbic acid of the present invention and ascorbic acid sugar type derivant comprise its alkali metal salt, and in the work developer solution, its common consumption is 0.1-0.4mol/l, or more than, preferential consumption 0.14-0.28mol/l.Although the usable range of developer is 0.1-0.4mol/l, the use amount of developer can surpass 0.4mol/l under certain conditions, generally reduces the amount of auxiliary developer in this case, as essential phenidone.Being used for preferred ascorbic acid compound of the present invention as developer is alkaline metal ascorbate and l-ascorbic acid.
The sugar derivatives of ascorbic acid of the present invention and ascorbic acid is dissolved in the developing solution with the form of free acid, perhaps can be used as alkali metal salt and introduces, preferably its sodium salt or sylvite, or the potpourri of free acid form and salt thereof.Under the situation of the developer that uses salt form, required alkali metal hydroxide amount is less so that form the pH value of 10.3-12.5, for example, uses the alkali metal hydroxide about 3-15g/l usually.The opposing party exists, if only use the free acid of sugar, then generally uses the alkali metal hydroxide of 10-25g/l, so that regulate pH to 10.3-12.5.Be used for developing solution of the present invention as developer, the example of ascorbic acid that other is available and sugared type derivant has been described in U.S.P 5,098, and in 819 and 5,196,298, the content of described patent disclosure is incorporated herein as a reference.
Comprise 3-pyrazolidone (or derivatives thereof) (phenidone), amino-acid compound, perhaps the auxiliary developer of its potpourri also can be included in the developing solution of the present invention, so that improve the developing powder of developer composition.For example at U.S.P 5,098, available 3-pyrazolidone is disclosed in 819, the content of this patent disclosure comprises that preferred 1-phenyl-3-pyridine alkane ketone is herein incorporated by reference this paper.The suitable amino phenol that can use comprises right-methylamino-phenol (metol) and U.S.P 4,914,003 those disclosed, and the disclosure of this patent is introduced as reference.The auxiliary developer that uses effective dose is to reach high density and hard contrast.Usually the use amount of these materials is 0.001-0.12mol/l, for the use amount of 3-pyrazolidone 0.001-0.006mol/l preferably, or is 0.001-0.02mol/l for the use amount of right-amino phenol.
Developer composition of the present invention can successfully use and hydroquinone type developer or alkanolamine that need not be any.Yet other important condiment comprises alkali metal sulfite concerning developer composition of the present invention, preferred sodium sulphite, and its use amount is up to 0.32mol/l, and preferably 5-30g/l is (when using Na
2SO
3The time), it is as preservative agent and the stabilizing agent that prevents air oxidation.Other available sulphite is disclosed in U.S.P 5,098,819, and it is incorporated herein as a reference.
Whole advantage of the present invention can obtain in pH scope 10.3-12.5, and better scope is from 10.5 or 10.8-11.5 or 12.2.In addition, it is existence by alkali carbonate that the basicity of developer composition remains in the desired scope, as 0.1-0.4mol/1 or following sodium carbonate or potassium, preferably 0.14-0.28mol/l.Preferred alkali carbonate is that the alkali metal oxide with 3-25g/l uses, to regulate the pH scope to desired scope.Whether the amount of the alkali metal hydroxide that adds depends in part on developer and uses with free acid form, as using with free acid form, then the use amount of alkali metal hydroxide is generally 10-25g/l, if developer uses with salt form, then the use amount of alkali metal hydroxide is 3-15g/l usually.
In general, alkali carbonate is more less than the causticity component that alkali metal hydroxide produces.Yet on the other hand, alkali carbonate and alkali metal hydroxide more generally are to need more amount to regulate the pH value.Weigh its advantages against its disadvantages, the basicity of preferably establishing developer solution in the present invention is each consumption by any selection alkali carbonate and alkali metal hydroxide, and adds alkali metal hydroxide to carry out the accurate adjusting of best pH by replenishing.
Developer composition of the present invention also contains various other conventional adjuvant and condiment, and they play other various desired effects.For example, the condiment of these interpolations includes, but not limited to additional developer, antifoggant, damping fluid, sequestrant, swelling controlling agent, development accelerator except that quinhydrones etc.
Yet in the preferred embodiment of the present invention, developer solution contains some other condiment, comprises each in inhibitor, organic antifoggant and the sequestrant.
For example, be that sodium bromide or its content of potassium are about 0.008-0.04mol/l as preferred inhibitor.Typical organic antifoggant preferably includes the composition of benzotriazole and phenyl mercapto-tetrazole, and its each amount is respectively 0.01-0.1g/l.For example, at U.S.P 4,975, disclose effective benzotriazole in 354, the disclosure of this patent is incorporated herein as a reference.Typical mercapto-tetrazole is 1-phenyl-5-mercapto-tetrazole.
In addition, the present invention also comprises the antifoggant that uses other, as U.S.P 5,098,819 and 5,196,298 disclosed those, the content of these patent disclosures is incorporated herein as a reference.
Usually preparation can use in the developer formuia a spot of sequestrant with chelating component or water in existing trace metal ion.Be used for typical sequestrant of the present invention and be disclosed in U.S.P5,098,819, be herein incorporated by reference this paper.And use amount is 0.5-3g/l, preferably 0.5-2.0g/l usually.Be used for the preferably Na of above-mentioned amount of sequestrant of the present invention
2EDTA.
Developing solution of the present invention can be used for the development of various types of photographic materials, especially the monochrome photography material comprises conventional intermediate film, Fuji RO-100 film as Fuji Photo Film company limited, and contain photographic silver halide material, EK2000 CGP and the EK 2000 CLW films produced as Eastman Kodak company as the hydrazine compound of nucleator.Yet, use developer solution of the present invention to be not limited to this and be understood to and expand other black and white material such as radiography recorded material and duplicating material, process photography recorded material and duplicating material and microfilm to.
Yet when reaching the hard contrast quality and therefore reaching high net-point quality so that Plate making printing photographic material and the photographic silver halide material that contains the nucleator hydrazine compound develop when using developer solution of the present invention, it is especially clear that advantage of the present invention becomes.
Can take conventional branch layered scheme by the photographic material that developer solution of the present invention develops, as U.S.P 5,198,298 is disclosed, and this patent is incorporated herein as a reference.
Can be used for another kind of film example of the present invention is to contain the photographic silver halide material of hydrazine compound as nucleator.This photographic material is shown in as U.S.4 with regard to the composition aspects of its layer structure, light-sensitive silver halide latex, interior kicker and other photographic material, in 975,3554,4,988,604 and 4,994,365.The content of these patent disclosures is incorporated herein as a reference.
The limiting examples of hydrazine compound has following compounds:
Other hydrazine compound that can be used for photographic material is included in RESEACH DISCLOSURE, described in the list of references of Item 23516 (November nineteen eighty-three, 346 pages) and this article, and at U.S.P 4,080,207,4,269,929,4,276,364,4,278,748,4,385,108,4,459,347,4,560,638,4,478,928,4,737,452,4,284,764,4,686,167,5,100,761,5,006,445,4,960,672,4,971,890,4,971,888,4,950,578,5,061,594,5,017,456,5,028,510, European patent 217,310, describe in European patent 286,840 and the BrP 2,011,391.Hydrazine compound can be incorporated into the hydrophilic colloid layer of any photographic material, as silver halide emulsion layer, middle layer, retentivity coating etc.
The content of the hydrazine compound in the photographic material, according to every mole of silver halide meter in the phase photosensitive material, preferably 1 * 10
-6Mol-5 * 10
-2Mol particularly preferably is 1 * 10
-5Mol-2 * 10
-2Mol.
The photographic material that develops by developing solution of the present invention can form image by the exposure of special-purpose by any irradiation source.
In order to wash, preferably use automatic operating equipment, this equipment is equipped with the system of replenishing rinse solution automatically.The back of development step is to end showing step, for example only show that in about 90 following uses solution continued for 15 seconds as 3% acetic acid solution, it then is the photographic fixing liquid bath, for example use commercially available from the market fixer, as the F-O-G that has bought from Fuji Hunt Photographic Ch-emicals company, using 30 seconds down at about 90 °F, then is washing or stabilizing step.At last, photographic material carries out drying by standard schedule.
The following examples are that explanation is of the present invention but do not constitute restriction to it, and all consumptions all calculate with every liter of gram, unless indication is arranged in addition.
To represent the photography property of developer formuia of the present invention (solution 7) and JP 59-191035 (solution 1), European patent 0498968 (solution 2 and 3), U.S.P 5, the embodiment of 098,819 ( solution 4,5 and 6) and Kodak RA 2000 hydroquinone photographic developers (reference solution) that can buy from the market compares.The prescription of various developers is summarized in following table 1-1.
Table 1
Composition 123456 71-ascorbic acid 30-----30D-sodium ascorbate-184 110 31.5 79.3 25.5-sodium sulfite 30--5.0 12.5 2.5 30 sodium metabisulfites-----1.9-sodium carbonate 30-----, 30 potash---24.0 26.4 24.0-Na2EDTA------1.0Na
4EDTA---0.6 2.3 0.6-phenidone 0.3--2.0--0.34-(methylol)-4-methyl isophthalic acid-phenyl-3-----1.04 2.0-pyrazolidone BTA---0.09-0.09 0.021-phenyl-mercapto-0.08 0.08 0.008-0.008 0.01 basic tetrazolium sodium bromide---, 2.7 10.0 2.7-KBr-25 25---2.0 NaOH 15.4-----14.5 potassium hydroxide-55.6 45.5----pH 12.5 12.35 13.0 10.38 10.16 10.04 12.05
Three kinds of dissimilar photographic films develop by the various developer solutions that will test.It is interior promotion (1B) types of having bought from the market that two kinds of films are arranged, be CGP of Kodak (Kodak) (being used for screen (halftonework)) and the CLW of Kodak (Kodak) (being used for line version (linework)), and the third film is the intermediate film of having bought from the market, i.e. Fuji RO-100 film.
Used development conditions was 30 seconds 90 of temperature for CGP and CLW development time, and was 25 seconds for the RO-100 film.Afterwards, used only apparent bath of liquid (3% acetic acid solution) down 15 seconds in 90 °F.Used down photographic fixing bath of liquids (the F-O-G fixer of having bought from Fuji Hunt Photo-graphic Chemicals company) 30 seconds at 90 °F then with rigidizer.
The result is illustrated among Fig. 1,2,3A, 3B and the 3C with graphic interpretation, wherein+and the result of expression Kod-ak RA 2000; △ represents solution, the result of developer; Zero and+respectively represent the result of solution 2 and 3; ▲, zero and represent the result of solution 4,5 and 6 respectively; Represent to represent the result of solution 7 of the present invention with ◇.
More particularly, Fig. 1 represents the interior D-logE curve that promotes the photosensitive emulsion film of EK2000 CGP of the application of the invention developer composition and some representational known technology developer composition flushings.
Fig. 2 represents the developer combination agent of the application of the invention and the interior D-logE curve that promotes the photosensitive emulsion film of EK 2000 CLW of some representational known developer composition flushings.
Fig. 3 A represents to use by the Fuji Ro-100 speed of the developer development of developer composition of the present invention and European patent 0498968 (U.S.P5,196,298) the D-logE curve of photosensitive emulsion film.
Fig. 3 B represents to use by the Fuji RO-100 speed of the developer development of developer composition of the present invention and U.S P 5,089,819 the D-LogE curve of photosensitive emulsion film.
Fig. 3 C represents to use by the Fuji RO-100 speed of the developer development of developer composition of the present invention and open (OPI) 59-191035 of Jap.P. the D-LogE curve of photosensitive emulsion film.
As for result itself, the very steep gradient of D-LogE curve of solution 7 of the present invention shows the hard contrast quality of Kodak CGP and CLWIB photosensitive emulsion among Fig. 1 and 2.This effect is unexpected really, because the hard contrast quality (can provide hard contrast but D for other known technology EP 0498968 that studied on EK CGP film
MaxLow out of a clear sky) and U.S.P.5,098,819 non-hydroquinone photographic developer chemicals is unobserved, and is indicated as the solution 1-6 curve among Fig. 1 and 2.Kodak RA 2000 developers are observed the hard contrast quality, and this developer is conventional hydroquinone type developer, but the curve of solution 7 is steeper than KodakRA 2000, and this shows with developer composition of the present invention better than the performance of Kodak photosensitive emulsion.
Among Fig. 3 RO-100 standard speed is shown that with the contrast slope of the D-logE curve of photosensitive emulsion (not containing hydrazine) solution 7 can obtain comparable and useful results than other ascorbyl chemicals.Also have, according to Fig. 1,2 and 3C shown in, Japanese Laid-Open Patent Application 59-191035 prescription (improving density under low step number) is observed high photographic fog amount.Press shown in Fig. 1 and 2, the solution of European patent 0498968 is in several acquisitions down of height step (step) low-density unsatisfactory.
In this example, adjust sulphite, bromide, alkali metal hydroxide, ascorbic acid and pH value (all amounts are g/l, unless indication is arranged in addition) by table shown in the 2-1 so that the result of the film of three kinds of used same types among evaluation and the comparative example 1.Use identical development conditions as embodiment 1.
Table 2-1
Embodiment B C D ENa
2CO
330 30 30 30Na
2SO
35 15 30 30 phenidone, 0.3 0.3 0.3 0.3Na
2EDTA 1.0 1.0 1.0 1.0 benzotriazoles 0.02 0.02 0.02 0.02PMT 0.01 0.01 0.01 0.01KBr 1.0 2.0 1.0 4.0NaOH, (97%) 15.62 19.26 12.23 15.141-ascorbic acid 50 50 30 30 deionizations, (DI) water is made 11 11 11 11 final pH 10.99 11.49 11.50 12.18
The result is summarised among Fig. 4 A, 4B and the 4C, wherein+expression Embodiment B the result; △ represents the result of Embodiment C; The result of zero expression embodiment D; With+expression embodiment E the result.
In general, Fig. 4 A shows that the different formulations of developer composition of the present invention is to promoting the D-logE curve on the photosensitive emulsion film in the EK2000 CGP.
Fig. 4 B shows that the different formulations of developer composition of the present invention is to promoting the D-logE curve on the photosensitive emulsion film in EK 2000 CLW.
Fig. 4 C shows that the different formulations of developer composition of the present invention is fast with the D-LogE curve on the photosensitive emulsion film to Fuji RO-100.Embodiment 3
Detect the sodium hydrate content of three kinds of used among the embodiment 1 same type films and the therefore effect of pH value with used prescription among the table 3-1 (all amounts all are g/l, except that other has indication).Use the development conditions identical with embodiment 1.
Table 3-1
Embodiment B G HNa
2CO
330 30 30Na
2SO
330 30 30 phenidone, 0.03 0.03 0.03Na
2EDTA 1.0 1.0 1.0 benzotriazoles 0.02 0.02 0.02PMT 0.01 0.01 0.01KBr 1.0 1.0 1.0D-sodium ascorbates 36.8 36.8 36.8NaOH (97%)-5.14 7.88ID water are made 11 11 11 final pH 10.25 11.29 12.01
The result summarizes in Fig. 5 A, 5B and 5C, wherein+expression embodiment F the result; △ represents the result of Embodiment C; Result with zero expression embodiment H.
Fig. 5 A shows sodium hydrate content under the condition of the prescription that develops with ascorbyl, and promptly the pH value is to promoting the influence of photosensitive emulsion film D-LogE curve in the EK2000 CGP.
Fig. 5 B shows sodium hydrate content under with ascorbyl developer formuia condition, i.e. pH value is to the influence of the D-LogE curve of promotion photosensitive emulsion film in the EK2000 CLW.
Fig. 5 C shows sodium hydrate content under use ascorbyl developer formuia condition, and promptly the pH value is used the influence of the D-LogE curve of photosensitive emulsion film to Fuji RO-100 speed.
The result who is shown in Fig. 5 A-5C has proved the unexpected importance of the pH value of selecting, and especially internally promotes (IB) film.Embodiment 4
Except the D-LogE extra curvature, also use identical developer formuia, and on identical three kinds of films of embodiment 1, carried out net-point quality research with the EK RA 2000 of solution 1-7 and embodiment 1 (table 1-1).In general, net-point quality is the standard method of estimating hard contrast developer quality.The hard contrast quality is good more, and net-point quality is good more.The site is steep more, and (numerical rating) is low more for designed numerical value.
Use the topped amount in 10,50 and 90% site of the total area.Low step number density in base fog result and the curve map is compared.Also detect and measure D
MaxAnd the result that (Grad) is worth of gradient (Gradie-nt), the result of these analyses is summarized as follows.
Table 4A
The RA of EK as a result that contains hydrazine photosensitive emulsion (EK CGP film) light sensitivity 2000 solution 1 solution 2 solution 3 solution 4 solution 5 solution 6 solution 7D with different developer flushings
Max5.20 5.20 4.60 4.11 5.21 5.22 5.21 5.25Grad 12.6 7.2
*13.8 12.6 7.9 8.3 7.8 15.7B.F., 0.02 0.87 0.04 0.03 0.03 0.03 0.03 0.03 note: gradient is measured between density 1.0-3.0.The gradient that has * number be 1.5～
3.0 between density measurement.
The net-point quality that contains hydrazine photosensitive emulsion (EK CGP film) that table 4B washes with different developers
EK RA 2000 solution 1 solution 2 solution 3
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 5 2-3 3-4 NA NA NA 3-4 2 3-4 3 1-2 3
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 667667667 2-3 1 2-3 notes: 1) net-point quality grade
Excellent=1, fine=2, good=3, good=4, poor=5, very poor=6, special poor
＝7
2) detect 10%, 50%, 90% area
Table 5A
The RA of EK as a result that contains hydrazine photosensitive emulsion (EK CLW film) the light sensitivity 2000 solution 1 solution 2 solution 3 solution 4 solution 5 solution 6 solution 7D that in different developers, wash
Max4.44 4.60 3.50 3.27 4.80 4.77 4.65 4.65Grad 19.9 5.4
*7.0 6.4 4.8 5.1 4.6 26.1B.F., 0.02 0.87 0.03 0.03 0.03 0.03 0.03 0.03 note: gradient (Grad) is to measure between density 1.0 and 2.0.
The gradient of band * is the density measure between 2.0 and 3.0.
The net-point quality that contains hydrazine photosensitive emulsion (EK CLW film) that table 5B washes in different developers
EK RA 2000 solution 1 solution 2 solution 3
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 533 NA NA NA 5 2-3 3-4 423
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 667667667211 notes: 1) net-point quality grade
Excellent=1, fine=2, good=3, good=4, poor=5, very poor=6, special poor
=72) detect 10%, 50%, 90% area
Table 6A
The conventional speed photosensitive emulsion of flushing in different developers
The light sensitivity of (Fuji RO-100 film) is EK RA 2000 solution 1 solution 2 solution 3 solution 4 solution 5 solution 6 solution 7D as a result
Max5.31 5.22 5.26 5.11 5.29 5.30 5.20 5.25Grad 8.0 6.0
*11.2 14.8 7.0 6.3 5.5 5.6B.F., 0.04 0.79 0.18 0.08 0.05 0.04 0.04 0.05 note: gradient (Grad) is to measure between density 1.0-3.0.
The gradient of being with * number is to measure between 1.5～3.0.
Table 6B
The conventional speed sensitization breast that in different developers, washes
The net-point quality of agent (Fuji RO-100 film)
EK RA 2000 solution 1 solution 2 solution 3
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 667 NA NA NA 5 2-3 7 4-5 3-4 6
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 66766766765 4-5 notes: 1) net-point quality grade
Excellent=1, fine=2, good=3, good=4, poor=5, very poor=6, extreme difference
＝7
2) detect 10%, 50%, 90% area.
Table 7A
In different developers, wash contain the hydrazine photosensitive emulsion and
The light sensitivity result of existing RA photosensitive emulsion
EK CGP film EK CLW film
Example B example C example D example E example B example C example D example ED
Max5.19 5.20 5.20 5.23 5.35 4.46 4.40 4.45Grad 12.9 18.9 24.4 19.3 21.5
*15.1
*24.8
*25.3
*B.F. 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02FUJI RO-100 film
Example B example C example D example ED
Max5.25 5.25 5.25 5.25Grad, 7.4 7.5 7.1 6.2B.F., 0.04 0.04 0.04 0.04 note: gradient is measured between density 1.0-3.0.Being with * number gradient is in density 1.0
And the mensuration between 2.0.
Table 7B
That washes in different developers contains hydrazine photosensitive emulsion (CGP﹠amp; CLW) and the net-point quality of conventional RA photosensitive emulsion
EK CGP film
Example B example C example D example E
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 52 1-2 3-4 1 1-2 3-4 1 2-3 2-3 1 2-3
EK CLW film
Example B example C example D example E
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 4-5 2-3 131131111 1-2
FUJI RO-100 film
Example B example C example D example E
10%50%90% 10%50%90% 10%50%90% 10%50%90% class 6s 67657657655
Table 8A
The light sensitivity result who contains hydrazine photosensitive emulsion and conventional photosensitive emulsion who in different developers, washes
EK CGP film EK CLW film
Example F
1Example G
2Example H
3Example F example G example HD
Max5.11 5.19 5.23 4.13 4.27 4.33Grad 5.2 11.9 19.9 4.7 19.9
*17.2
*B.F. 0.02 0.02 0.02 0.02 0.02 0.02
FUJI RO-100 film
Example F example G example HD
Max5.53 5.21 5.21Grad, 5.5 6.8 7.0B.F., 0.03 0.04 0.05 note: gradient (Grad) is measured between density 1.0-3.0.Be with * number gradient to be
Between density 1.0 and 2.0, measure.
1NaOH of no use, pH 10.27;
2Use NaOH, pH 11.30;
3Use NaOH, pH
12.00
Table 8B
That washes in different developers contains hydrazine photosensitive emulsion (CGP﹠amp; CLW) and the net-point quality of conventional RA photosensitive emulsion
EK CGP film
Example F example G example H
10%50%90% 10%50%90% 10%50%90% class 665 4-5 2-3 4424
EK CLW film
Example F example G example H
10%50%90% 10%50%90% 10%50%90% class 6665344 2-3 3-4
FUJI RO-100 film
Example F example G example H
10%50%90% 10%50%90% 10%50%90% class 6s 67667665
When having described the present invention in detail and having consulted specific embodiments of the present invention, the those skilled in the art of affiliated technical field can understand that the variations and modifications of being done all do not depart from the spirit and scope of the present invention.
Claims (37)
1, a kind of non-hydroquinone photographic developer composition consists essentially of:
(a) a kind of developer that is selected from ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof, its amount is 0.1-0.4 mol (mol/l);
(b) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.1-0.4mol/l;
(e) a kind of alkali metal hydroxide, when ascorbic acid or its sugared type derivant exist with free acid form, then the amount of alkali metal hydroxide is 10-25g/l, perhaps when ascorbic acid or its sugared type derivant be when existing with alkali metal salt, then the amount of alkali metal hydroxide is 3-15g/l; With
(f) the pH value of developer composition is 10.3-12.5 in the time of 25 ℃.
2, the non-hydroquinone photographic developer composition of claim 1, wherein said developer are selected from l-ascorbic acid, the red ascorbic acid of d-, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
3, the non-hydroquinone photographic developer composition of claim 1, wherein said developer comprises the alkali metal salt of ascorbic acid.
4, the non-hydroquinone photographic developer composition of claim 1, wherein said developer composition do not contain alkanolamine or contain the alkanolamine that is lower than the 5g/l amount.
5, the non-hydroquinone photographic developer composition of claim 1, wherein said developer composition does not contain alkanolamine.
6, a kind of non-hydroquinone photographic developer composition consists essentially of:
(a) be selected from a kind of developer of ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof, its amount is 0.1-0.4 mol (mol/l);
(b) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.1-0.4mol/l;
(e) a kind of alkali metal hydroxide, when ascorbic acid or its sugared type derivant exist with free acid form, then the amount of alkali metal hydroxide is 10-25g/l, and when ascorbic acid or its sugared type derivant existed with the form of alkali metal salt, then the amount of alkali metal hydroxide was 3-15g/l; With
(f) the pH value of described developer composition is down 10.3-12.5 and another or multiple at 25 ℃
(g) postpone the inhibitor that unexposed silver halide develops, its amount is 0.008-0.042mol/l;
(h) organic antifoggant of 0.02-2g/l; With
(i) 0.5-3g/l integrated agent.
7, the non-hydroquinone photographic developer composition of claim 6, wherein said developer are selected from l-ascorbic acid, the red ascorbic acid of d-, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
8, the non-hydroquinone photographic developer composition of claim 6, wherein said developer comprises the alkali metal salt of ascorbic acid.
9, the described non-hydroquinone photographic developer composition of claim 6, wherein said inhibitor comprises sodium bromide; Described organic antifoggant comprises the potpourri of benzotriazole and 1-phenyl-5-mercapto-tetrazole; Comprise Na with described sequestrant
2EDTA.
10, the non-hydroquinone photographic developer composition of claim 6, wherein said developer composition does not contain alkanolamine.
11, a kind of method that makes the development of the monochrome photography material that exposes into image comprises with a kind of developer composition described photographic material is developed, and described developer composition consists essentially of:
(a) be selected from a kind of developer of ascorbic acid and sugared type derivant or alkali metal salt and composition thereof, its amount is 0.1-0.4 mol (mol/l);
(b) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.1-0.4mol/l amount;
(e) a kind of alkali metal hydroxide, when ascorbic acid or its sugared type derivant exist with free acid form, then the amount of alkali metal hydroxide is 10-25g/l, or when ascorbic acid or its sugared type derivant existed with the form of alkali metal salt, then the amount of alkali metal hydroxide was 3-15g/l; With
(f) the pH value of described developer composition is 10.3-12.5 down at 25 ℃.
12, the method for claim 11, wherein said developer are selected from l-ascorbic acid, d-red-ascorbic acid, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
13, the method for claim 11, wherein said developer comprises the alkali metal salt of ascorbic acid.
14, the method for claim 11, wherein said developer comprise the inhibitor that the unexposed silver halide of at least a delay develops in addition, and its amount is 0.008-0.4mol/l; 0.02-2g/l organic antifoggant; Sequestrant with the 0.5-3g/l amount.
15, the method for claim 11, wherein said developer composition does not contain alkanolamine.
16, a kind of monochrome photography material of the one-tenth image that makes exposure method of developing comprises that this developer composition consists essentially of with a kind of developer composition described material that develops:
(a) be selected from a kind of developer of the alkali metal salt and composition thereof of ascorbic acid, ascorbic acid sugar type derivant, ascorbic acid, its amount is 0.14-0.28mol/l;
(b) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.14-0.28mol/l;
(e) alkali metal hydroxide of 3-25g/l;
(f) inhibitor of 0.08-0.04mol/g;
(g) organic antifoggant of 0.02-0.2g/l; With
(h) chelate of 0.5-2g/l; With the pH value of described developer composition be 10.3-12.5 25 ℃ the time.
17, the described method of claim 16, wherein said developer are selected from l-ascorbic acid, d-red-ascorbic acid, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
18, the method for claim 16, wherein said developer comprises the alkali metal salt of ascorbic acid.
19, the method for claim 16, wherein said inhibitor comprises sodium bromide; Described organic antifoggant comprises the potpourri of benzotriazole and 1-phenyl-5-mercapto-tetrazole; Comprise Na with described sequestrant
2EDTA.
20, the method for claim 16, wherein said developer composition does not contain alkanolamine.
21, a kind of method that obtains the hard contrast image, this method comprise with a kind of developer composition develops the photographic silver halide material that contains hydrazine compound of the one-tenth image of exposure, and this developer composition consists essentially of:
(a) be selected from a kind of developer of ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof, its amount greater than 0.1 mol (mol/l) and
(b) essentially no dihydroxy benzenes.
22, the method for claim 21, wherein said developer are selected from l-ascorbic acid, d-red-ascorbic acid, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
23, the method for claim 21, wherein said developer contains the alkali metal salt of ascorbic acid.
24, the method for claim 21, wherein said developer composition does not contain alkanolamine.
25, a kind of method that obtains the hard contrast image, this method comprise makes the photographic silver halide material that contains hydrazine compound that exposes into image develop with a kind of developer composition, and this developer composition consists essentially of:
(a) a kind of developer that is selected from ascorbic acid and sugared type derivant or its alkali metal salt and composition thereof composition thereof, its amount is 0.1-0.4 mol (mol/l);
(b) there is not dihydroxy benzenes basically;
(c) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(d) be less than or equal to the alkali metal sulfite that 0.32mol/l measures;
(e) alkali carbonate of 0.1-0.4mol/l amount;
(f) a kind of alkali metal hydroxide, when ascorbic acid or its sugared type derivant are when existing with free acid form, then the amount of alkali metal hydroxide is 10-25g/l, or ascorbic acid or its sugared type derivant be when existing with the form of alkali metal salt, and then the amount of alkali metal hydroxide is 3-15g/l; With
(g) the pH value of described developer composition under 25 ℃ is 10.3-12.5.
26, the method for claim 25, wherein said developer are selected from l-ascorbic acid, d-red-ascorbic acid, d-Portugal-ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
27, the method for claim 25, wherein said developer comprises the alkali metal salt of ascorbic acid.
28, the method for claim 25, wherein said developer composition also comprise the inhibitor that the unexposed silver halide of at least a delay develops, and its amount is 0.008-0.04mol/g; 0.02-2g/l organic antifoggant; Sequestrant with 0.5-3g/l.
29, the method for claim 28, wherein said inhibitor comprises sodium bromide; Described organic antifoggant comprises the potpourri of 1-phenyl-5-mercapto-tetrazole of the benzotriazole of 0.01-1.0g/l and 0.01-1.0g/l; Comprise Na with described sequestrant
2EDTA.
30, the method for claim 25, wherein said photographic silver halide material comprises at least a sensitive emulsion layer or hydrophilic colloid layer, described layer contains the amino-compound of effective dose to play the effect of introducing kicker, with at least a sensitive emulsion layer or the hydrophilic colloid layer that contains the nucleator compound, described nucleator compound comprises that the hydrazine compound or derivatives thereof of effective dose is to play nucleator.
31, the method for claim 25, wherein said developer composition does not contain alkanolamine.
32, a kind of developing method of photographic silver halide material that hydrazine compound is made the silver halide magenta-sensitive emulsion of nucleator that contains that exposes into image that makes, this method comprises with a kind of developer composition develops described photographic silver halide material, and described developer composition consists essentially of:
(a) be selected from a kind of developer of the sugared type derivant of ascorbic acid, ascorbic acid, alkali metal salt of ascorbic acid and composition thereof, its amount is 0.14-0.28mol/l;
(b) auxiliary developer of effective dose comprises 3-pyrazolidone compound, amino phenol or its potpourri;
(c) be less than or equal to the alkali metal sulfite of 0.32mol/l;
(d) alkali carbonate of 0.14-0.28mol/l;
(e) alkali metal hydroxide of 3-25g/l;
(f) inhibitor of 0.0084-0.0420mol/g;
(g) organic antifoggant of 0.02-0.2g/l;
(h) sequestrant of 0.5-2g/l; With
(i) the pH value of described developer composition under 25 ℃ is 10.3-12.5.
33, the method for claim 32, wherein said developer are selected from l-ascorbic acid, d-red-ascorbic acid, d-Portugal ascorbic acid, b-deoxidation-l-ascorbic acid, l-sandlwood-ascorbic acid, l-rock algae ascorbic acid, d-Portugal heptan-ascorbic acid, sorb ascorbic acid, imino group-l-ascorbic acid, W-breast ascorbic acid, Fructus Hordei Germinatus ascorbic acid, the Arabic ascorbic acid of l-, l-Portugal ascorbic acid, d-gala ascorbic acid, the ancient Lip river ascorbic acid of l-and l-A Luo ascorbic acid.
34, the method for claim 32, wherein said developer comprises the alkali metal salt of ascorbic acid.
35, the described method of claim 32, wherein said inhibitor comprises sodium bromide; Described organic antifoggant comprises the potpourri of benzotriazole and 1-phenyl-5-mercapto-tetrazole; Select Na with sequestrant
2EDTA.
36, the described method of claim 32, wherein said photographic silver halide material comprises at least a sensitive emulsion layer or hydrophilic colloid layer and at least a sensitive emulsion layer or the hydrophilic colloid layer that comprises the hydrazine compound or derivatives thereof that has been effective in the nucleator action that has been effective in the amino-compound of introducing the kicker action that comprise.
37, the method for claim 32, wherein said developer composition does not contain alkanolamine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7802493A | 1993-06-18 | 1993-06-18 | |
| US08/078,024 | 1993-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1129989A true CN1129989A (en) | 1996-08-28 |
| CN1053970C CN1053970C (en) | 2000-06-28 |
Family
ID=22141455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94193074A Expired - Fee Related CN1053970C (en) | 1993-06-18 | 1994-06-10 | Non-hydroquinone photographic developer composition and processing method |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | USH2048H1 (en) |
| EP (1) | EP0738400B1 (en) |
| JP (1) | JPH09500221A (en) |
| CN (1) | CN1053970C (en) |
| AT (1) | ATE199461T1 (en) |
| AU (1) | AU689168C (en) |
| DE (1) | DE69426780T2 (en) |
| MY (1) | MY111751A (en) |
| SG (1) | SG34338A1 (en) |
| WO (1) | WO1995000881A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104765244A (en) * | 2015-04-30 | 2015-07-08 | 石家庄太行科工有限公司 | Environment-friendly type developing solution and preparation method and application thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0732619A1 (en) * | 1995-02-21 | 1996-09-18 | Agfa-Gevaert N.V. | Developing method and method for developing an exposed photographic silver halide material |
| US6379877B1 (en) | 1995-02-21 | 2002-04-30 | Agfa-Gevaert | Method for developing an exposed photographic silver halide material |
| US5942379A (en) * | 1995-08-10 | 1999-08-24 | Eastman Kodak Company | 3-pyrazolidone compounds and photographic developer solutions containing same |
| US5589323A (en) * | 1996-01-23 | 1996-12-31 | Sun Chemical Corporation | Chemically stable ascorbate-based photographic developer and imaging process |
| US5702875A (en) * | 1996-06-28 | 1997-12-30 | Eastman Kodak Company | Weakly alkaline ascorbic acid developing composition, processing kit and method using same |
| US5866309A (en) * | 1997-10-22 | 1999-02-02 | Fitterman; Alan S. | Method for processing roomlight handleable photographic elements |
| US5932398A (en) * | 1997-11-14 | 1999-08-03 | Eastman Kodak Company | Kit for roomlight processing of black-and-white photographic elements |
| US5871890A (en) * | 1997-11-14 | 1999-02-16 | Eastman Kodak Company | Method for processing roomlight handleable radiographic films using two-stage development |
| ES2224757B1 (en) * | 1998-10-13 | 2005-12-16 | Luis Casademunt Garre | PHOTO REVIEWER FOR THE PROGRESS OF EFFECTIVE SENSITIVITY IN FILMS WITH WHITE AND BLACK EMULSION. |
| US6277290B1 (en) | 1999-12-17 | 2001-08-21 | Metafix Inc. | Process for recovering silver from photographic solutions |
| CN102591133A (en) * | 2012-03-03 | 2012-07-18 | 合肥通用无损检测技术有限责任公司 | Developing solution and preparation method thereof |
| CN103343068A (en) * | 2013-06-18 | 2013-10-09 | 厦门市豪尔新材料有限公司 | Glue stripping agent |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE530885A (en) | 1953-08-03 | |||
| US4269929A (en) | 1980-01-14 | 1981-05-26 | Eastman Kodak Company | High contrast development of photographic elements |
| US4740453A (en) * | 1984-12-27 | 1988-04-26 | Fuji Photo Film Co., Ltd. | Silver halide photosensitive material containing a compound capable of releasing a photographically useful group |
| JPS61233734A (en) | 1985-04-09 | 1986-10-18 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and formation of image by using it |
| JPS61267759A (en) | 1985-05-22 | 1986-11-27 | Fuji Photo Film Co Ltd | Formation of negative image |
| US4975354A (en) | 1988-10-11 | 1990-12-04 | Eastman Kodak Company | Photographic element comprising an ethyleneoxy-substituted amino compound and process adapted to provide high constrast development |
| US4988604A (en) * | 1990-05-24 | 1991-01-29 | Eastman Kodak Company | High contrast photographic element including an aryl sulfonamidophenyl hydrazide containing both thio and ethyleneoxy groups |
| DE69119742T2 (en) | 1991-02-14 | 1997-01-23 | Agfa Gevaert Nv | Photographic development process using an ascorbic acid derivative |
| EP0501546A1 (en) | 1991-02-26 | 1992-09-02 | Agfa-Gevaert N.V. | High contrast developer containing an aprotic solvent |
| EP0531582B1 (en) | 1991-09-12 | 1997-01-15 | Agfa-Gevaert N.V. | Stabilized ascorbic acid developer |
| EP0569580A1 (en) * | 1991-12-02 | 1993-11-18 | E.I. Du Pont De Nemours And Company | Improved developer systems for hydrazine containing films |
| US5236816A (en) | 1992-04-10 | 1993-08-17 | Eastman Kodak Company | Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements |
| GB9226488D0 (en) | 1992-12-19 | 1993-02-17 | Ilford Ltd | Photographic developing solution |
| US5503966A (en) | 1994-07-22 | 1996-04-02 | International Paper Company | Photographic developing compositions and use thereof in the processing of photographic elements |
-
1994
- 1994-06-10 CN CN94193074A patent/CN1053970C/en not_active Expired - Fee Related
- 1994-06-10 AT AT94919380T patent/ATE199461T1/en not_active IP Right Cessation
- 1994-06-10 WO PCT/US1994/006353 patent/WO1995000881A1/en active IP Right Grant
- 1994-06-10 EP EP94919380A patent/EP0738400B1/en not_active Expired - Lifetime
- 1994-06-10 DE DE69426780T patent/DE69426780T2/en not_active Expired - Lifetime
- 1994-06-10 AU AU10922/95A patent/AU689168C/en not_active Ceased
- 1994-06-10 JP JP7502861A patent/JPH09500221A/en active Pending
- 1994-06-10 SG SG1995002196A patent/SG34338A1/en unknown
- 1994-06-16 MY MYPI94001548A patent/MY111751A/en unknown
-
1995
- 1995-02-14 US US08/388,600 patent/USH2048H1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104765244A (en) * | 2015-04-30 | 2015-07-08 | 石家庄太行科工有限公司 | Environment-friendly type developing solution and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU689168C (en) | 2001-11-22 |
| EP0738400A4 (en) | 1996-06-18 |
| MY111751A (en) | 2000-12-30 |
| DE69426780T2 (en) | 2001-10-04 |
| SG34338A1 (en) | 2000-12-19 |
| EP0738400B1 (en) | 2001-02-28 |
| AU1092295A (en) | 1995-01-17 |
| CN1053970C (en) | 2000-06-28 |
| ATE199461T1 (en) | 2001-03-15 |
| AU689168B2 (en) | 1998-03-26 |
| JPH09500221A (en) | 1997-01-07 |
| DE69426780D1 (en) | 2001-04-05 |
| WO1995000881A1 (en) | 1995-01-05 |
| USH2048H1 (en) | 2002-09-03 |
| EP0738400A1 (en) | 1996-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1053970C (en) | Non-hydroquinone photographic developer composition and processing method | |
| CN1487358A (en) | Concentrated colourful develeper composition for silver halide photographic sensitive material use and processing method thereof | |
| US4636456A (en) | Process for forming a photographic image | |
| CN1071464C (en) | A method of processing using a low volume thin tank processing system | |
| CN1230700A (en) | Color paper with improved wet abrasion sensitivity | |
| CN1332391A (en) | Heat flushing iamging element containing ion exchange reducer | |
| JP2876078B2 (en) | Development processing method of silver halide photosensitive material | |
| CN1329275A (en) | Photographic element containing ion-exchange reducing agent | |
| CN1436316A (en) | Silver-halide-contg. photothermographic element for improved scanning | |
| CN1532630A (en) | Blue sensitive film with desived image tone for radiation photograph | |
| CN1620631A (en) | Single part color photographic developer concentrate | |
| CN1301989A (en) | Imaging element containing protected photographic compound | |
| EP0696759B1 (en) | Method for processing a silver halide photographic light-sensitive material | |
| CN1079957C (en) | Developer for photographic siliver halide photosensitive material and developing method using the same | |
| JP3804704B2 (en) | Color developing solution for silver halide color photographic light-sensitive material and processing method using the same | |
| JPH04219753A (en) | Developing solution for alkaline black and white photograph | |
| CN1353336A (en) | Developing agent composition and developing method of photographic coloured negative film | |
| CN1329283A (en) | Photographic roll film developing method and material | |
| JP3356616B2 (en) | Method for developing silver halide photosensitive material | |
| JPH10213887A (en) | Treatment of black and white silver halide photographic sensitive material | |
| JP2652503B2 (en) | Color developing solution and processing method of silver halide color photographic light-sensitive material using the same | |
| JPH08272055A (en) | Method for processing silver halide photographic sensitive material | |
| JPH10221821A (en) | Method for processing black-and-white silver halide photographic sensitive material | |
| JP2002229161A (en) | Black-and-white developing composition and its use method | |
| JPH08304978A (en) | Color development processing method for silver halide color photosensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: FUJITSU - HUNT PHOTOGRAPHIC CHEMICAL CO., LTD. TO: FUJITSU - HUNT PHOTOGRAPHIC CHEMICALS PRIVATE CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: Singapore Tusa Applicant after: Fuji Hunter photographic chemicals Pte Ltd Address before: new jersey Applicant before: Fuji Hunter photographic Co |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |