US2432864A - Photographic elements bearing silver halide emulsion layer and adjacent light-insensitive colloid layer containing silver derivatives of azoles - Google Patents

Photographic elements bearing silver halide emulsion layer and adjacent light-insensitive colloid layer containing silver derivatives of azoles Download PDF

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US2432864A
US2432864A US573460A US57346045A US2432864A US 2432864 A US2432864 A US 2432864A US 573460 A US573460 A US 573460A US 57346045 A US57346045 A US 57346045A US 2432864 A US2432864 A US 2432864A
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mercapto
silver
layer
silver halide
halide emulsion
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Dimsdale Wilfrid Hampden
Robinson Richard Robert
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Ilford Imaging UK Ltd
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    • 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
    • G03C1/35—Antiplumming agents, i.e. antibronzing agents; Toners
    • G03C1/355—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/13—Antibronze agent or process

Definitions

  • This invention relates-to photographic lightsensitive elements, toco-mpounds which serve as improvers for photographic sil-ver halide emulsions, and particularly to compounds which improve the quality of the developed photographic images obtained in such emulsions.
  • These compounds may be introduced into ⁇ the emulsion itself, or into a subcoat, supercoat or backing A.layer,'or 'they may be'included in the Wrapping materials used.
  • the compounds may be applied 'in ⁇ solution fto 'the emulsion before or during development, e. g. by including them 'in the developing solution used.
  • These compounds iso used, .not l'only improve the maximum image density obtainableand serve as anti-bronzing agents, but also reduce the level ⁇ of foginthe Adevelopedimage.
  • the .present invention is concerned With. a methodof including ⁇ the compounds in the pho- Ato-sensitive .element itself .in a form such that anytendency .for lthe compoundto reduce the speed ofthe photo-sensitive emulsion .is reduced or -eliminated.
  • aphotographic emulsion ⁇ or toa colloid medium other Ythan'the emulsion which forms a vWaterperr-nealcle layer vin a photographic .element including a silver halide .emulsion layer, a silver derivative of a ⁇ compound which, when added in itsfree state, or in the4 state of its alkalimetal derivative, improves the quality 'of photoygraphic. images developed in such emulsion layers.
  • L The term added is intended to mean ⁇ that the siiver derivative ,itself is added orthat reagents are added which reactamong themselves to form the ⁇ silver derivative.
  • silver derivative is intendedto mean a derivative resulting from replacement of hydrogen ⁇ in the said compound by silver.
  • the silver derivatives are added to colloid media which are to be used for coating layers in Contact Withthe silver halide emulsion layer or layers.
  • the silver derivative may be included in Aa supercoat layer, e. g., a colloid layer-coated on top of the photographic emulsion layer and forming, for example, anouter layer of the element, or may be .includedin a subcoatlayer, e. g., a colloid layer v lying between a photographic'emulsion layer and a support layer, or may be included in an inter-layer between two emulsion layers. It may, however, be present in other layers, for example a backing layer.
  • Fig. 1 is a cross section of a film bearing a silver halide emulsion layer ⁇ and a superposed layer containing an anti-bronzing agent of the type described below;
  • Fig. 2 is a cross section of a similar lm wherein the silver halide layer is outermost;
  • Fig. 3 is a cross section of a similar film wherein a colloid layer containing an anti-bronzing agent is disposed between two emulsion layers;
  • Fig. 4 is a cross section of a modified lm wherein the two layers are on opposite surfaces.
  • a iilm support l is provided with a silver halide emulsion layer 2 on which there is disposed a water-permeable colloid layer 3 containing an anti-bronzing agent of the type disclosed below.
  • a lm support I is provided with a water-permeable colloid layer 4 containing an anti-bronzing agent as herein disclosed on which there is disposed a silver halide emulsion layer 5.
  • the element of Fig. 3 consists of a nlm support I bearing silver halide emulsion layers 6 and 8. between which there is disposed a water-permeable colloid layer 'l containing an anti-bronzing agent as herein disclosed.'
  • the element of Fig. 4 consists of a lm support l bearing a silver halide emulsion layer 9 on one surface and having disposed on the other surface a water-permeable eolloid layer l containing a herein disclosed anti-bronzing agent.
  • the silver derivative is included in a supercoat or in the emulsion layer itself, that it should be in a very fine state of subdivision in the layer in which it is incorporated.
  • a convenient method of use is to form the silver derivative in situ in the colloid medium in which it is to be dispersed, for example by the double decomposition of a soluble silver salt and an alkali-metal derivative of the compound in a gelatin medium.
  • the invention may be applied to all varieties of compound which are capable of improving the quality of the developed image and which will form silver derivatives.
  • EXAMPLE I 1 gram of 1-phenyl-2-methyl-5-mercapto- 1.3.4-triazole was dissolved in 3.6 ccs. of a 40% aqueous solution of sodium carbonate (Cryst). This solution was added to 250 ccs. of a 4.4% solution of gelatin (containing a small quantity of dispersing agent) and made up to 500 ccs. with water. 77.7 ccs. of a 1% aqueous solution of silver nitrate was added to 250 ccs.
  • EXAMPLE II The procedure given in Example I was followed with the variations that the compound used was l-phenyl--mercapto-tetrazole, it was dissolved in 5.0 ccs. of the sodium carbonate solution and the quantity of silver nitrate solution taken was 95.5 ccs. All other conditions remained the same EXAMPLE IV
  • the silver derivative of lr-phenyl--mercapto tetrazole was prepared and added in finely divided condition to silver chloride and silver bromide emulsions, one part of the silver derivative being added per 1000 parts of emulsion. Tests were made as before and gave the results set out in Table IV.
  • a photographic element comprising a silver halide emulsion layer and, in Contact therewith,
  • a Water-permeable light-insensitive colloid layerl which contains a silver derivative of a compound selected from the class consisting of -mercaptotetrazoles, -mercapto-1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and monomercapto monazoles.
  • a photographic element comprising a silver halide emulsion layer and an outer water-permeable light-insensitive colloid layer in contact with saidemulsion layer, said outer layer containing a preformed silver derivative of a compound selected from the class consisting of 5- mercapto-tetrazoles, 5 mercapto-1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in aL-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
  • a compound selected from the class consisting of 5- mercapto-tetrazoles, 5 mercapto-1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in aL-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mer
  • a photographic element comprising a silverhalide emulsion layer of which the predominant silver halide is silvei ⁇ chloride and, in contact therewith, a water-permeable light-insensitive colloid layer which contains a silver derivative of a compound selected from the class consisting of -mercapto tetrazoles, 5 mercapto 1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positionsvto the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
  • a photographic element comprising a silver halide emulsion layer of Which the predominant silver halide is silver chloride and an outer waterpermeable light-insensitive cclloid layer in contact with said emulsion layer, said outer layer containing a silver derivative of a compound selected frum the class consisting of 5-mercaptotetrazoles, 5-mercapto-1.3.4triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in na-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
  • a photographic element comprising a paper support carrying a silver halide emulsion layer and an outer Water-permeable light-insensitive colloid layer in Contact with said emulsion layer, said outer layer containing a silver derivative of a compound selected from the class consisting of 5-mercapto-tetrazoles, 5-rnercapto-1.3.4triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
  • WILFRID HAMPDEN DIMSDALE RICHARD ROBERT ROBINSON.

Description

DCC- 16, 1947. 1 w. H. DIMSDALE ET Al. 2,432,864
PHOTOGRAPHIC ELEMENTS BEARING SILVER HALIDE EMULSION LAYER AND ADJACENT LIGHT-INSENSITIVE COLLOID LAYER CONTAINING SILVER DERIVATIVES OF AZOLES F11-ed Jan. 1a, 1945 v 'F/azj SILVER DERIVATIVES OFSULFUR-AZ SILVER HALIDE EMULSION LAYER FILM SUPPORT SILVER HALIDE EMULSION LAYER WATER-PERMEABLE COLLOID LAYER CONTAINING SILVER DERIVATIVES OF SULFUR'AZOLES FILM SUPPORT SILVER HALIDE EMULSION LAYER WATER-PERMEABLE GOLLOID LAYER CONTAINING SILVER DERIVATIVES OF SULFUR'AZOLES SILVER HALIDE EMULSION LAYER FILM SUPPORT y r I I SILVER HALIDE EMULSION LAYER FILM SUPPORT WATER-PERMEABLE GOLLOID LAYER CONTAINING SILVER DERIVATIVES 0F SULEURAZOLES INVENTORS W/LFR/D HAM/DEN D/MSDALE ggd R/OHA no Roa En r Roem/50N' A TTOPJI/E Y Patented Dec. 16, 1947 'PHOTOGRAPHIC ELEMENTS BEARING SIL- `VER HALIDE EMULSION LAYER AND AD- JACENT LIGHT-INSENSITIVE HCOLLQID LAYER CONTAINING TIYES OF AZOLES SILVER DERIVA- `Wilfrid Hampden Dimsdale and Richard VRobert Robinson, Ilford, England, assignors to Ilford Limited, Ilford, England, aritish company Application January 18, 1945,:Se1'ial No. 573,460 In Great Britain February 3, 1944 5 Claims.
This invention relates-to photographic lightsensitive elements, toco-mpounds which serve as improvers for photographic sil-ver halide emulsions, and particularly to compounds which improve the quality of the developed photographic images obtained in such emulsions.
In the production ofphotographic .images in silver halide emulsions, and particularly in the case of emulsions consisting primarily of silver chloride, the maximum image density obtainable is not always so great as may be desired. Moreover,'the .common practice of hot-glazing photographic prints tends to affect adversely the image colour, giving a poor quality black which has a bronzed appearance, and also reduces the effective maximum density obtainable Yin the image.
In British Patent No. 561,875 methods are` described for improving the quality of -the developed photographic images which comprise treating the emulsions With 5-'mercapto tetraz`oles.`
These compounds may be introduced into `the emulsion itself, or into a subcoat, supercoat or backing A.layer,'or 'they may be'included in the Wrapping materials used. Alternatively, the compounds may be applied 'in `solution fto 'the emulsion before or during development, e. g. by including them 'in the developing solution used. These compounds, iso used, .not l'only improve the maximum image density obtainableand serve as anti-bronzing agents, but also reduce the level `of foginthe Adevelopedimage. As stated in the said patent,`- compounds used to reduce the fog level'frequently cause a serious reduction in the speed of the -emulsion, and it is an advantage of the Ycompounds .described inthe said patent that `the reduction ,'inspeed whichthey cause .is not serious. Nevertheless, .in'the case of many Lof :the compounds,v 'some 'reduction in nspeed is caused by their use, as indicated by the figures set out in Table I of the said patent.
There are other classes of compounds which serve to increase the maximum image density obtainable and serve as anti-bronzing agentsamong which are -mercapto-1.2.4-triazoles described .in U. SxapplioationNo. 553,270. These compounds, Wheni'incorporatedin `the emulsion `or, `developer also serve to 'decrease the fog level in the. developed image, and also 'sometimes effect a decrease inthe 'speed l`of the emulsions.
Whilst the method 'ofusing such compounds jdescribed in the `said 111; S. application Serial No.
558,270, filed October 11, 1944, ydoes not lead to a loss in speed of the emulsion, since thecompounds are not. applied, until' the emulsion has alreadybeen developed, thefmethod entails that the user needs to employ special fixing, `,glaz/:ing orothersolutions containing the compounds, It would ,clearly be an advantage for the manufacturer-.to be able to include Jthe `compoundin the photosensitive element as` marketed, providing thatits presence in such element didnotunduly reduce the speed of thephoto-sensitive emulsion.
.The .present invention is concerned With. a methodof including `the compounds in the pho- Ato-sensitive .element itself .in a form such that anytendency .for lthe compoundto reduce the speed ofthe photo-sensitive emulsion .is reduced or -eliminated.
According to thisinvention there is` added to aphotographic emulsion `or toa colloid medium other Ythan'the emulsion which forms a vWaterperr-nealcle layer vin a photographic .element including a silver halide .emulsion layer, a silver derivative of a `compound which, when added in itsfree state, or in the4 state of its alkalimetal derivative, improves the quality 'of photoygraphic. images developed in such emulsion layers. L The term added is intended to mean `that the siiver derivative ,itself is added orthat reagents are added which reactamong themselves to form the `silver derivative. The mere addition ofthe free compound or of fits alkali-metal derivative to a silver. halide .emulsion with the consequent Vpossible formation of somesilverde- .rivaux/e by react-ion with part of the einerv ,of
the emulsion itself =is lnot included Withnthe meaning of the term and does not give the same results as are'obtained bythe process of this invention.
The term silver derivative is intendedto mean a derivative resulting from replacement of hydrogen `in the said compound by silver.
In a preferred form Yof the invention the silver derivatives are added to colloid media which are to be used for coating layers in Contact Withthe silver halide emulsion layer or layers. For example, the silver derivative may be included in Aa supercoat layer, e. g., a colloid layer-coated on top of the photographic emulsion layer and forming, for example, anouter layer of the element, or may be .includedin a subcoatlayer, e. g., a colloid layer v lying between a photographic'emulsion layer and a support layer, or may be included in an inter-layer between two emulsion layers. It may, however, be present in other layers, for example a backing layer.
The pho-tographic elements described in the preceding paragraphs are illustrated in the accompanying drawing wherein:
Fig. 1 is a cross section of a film bearing a silver halide emulsion layer` and a superposed layer containing an anti-bronzing agent of the type described below;
Fig. 2 is a cross section of a similar lm wherein the silver halide layer is outermost;
Fig. 3 is a cross section of a similar film wherein a colloid layer containing an anti-bronzing agent is disposed between two emulsion layers; and
Fig. 4 is a cross section of a modified lm wherein the two layers are on opposite surfaces.
Referring more particularly to the drawing, in Fig. 1 a iilm support l is provided with a silver halide emulsion layer 2 on which there is disposed a water-permeable colloid layer 3 containing an anti-bronzing agent of the type disclosed below.
In Fig. 2 a lm support I is provided with a water-permeable colloid layer 4 containing an anti-bronzing agent as herein disclosed on which there is disposed a silver halide emulsion layer 5.
The element of Fig. 3 consists of a nlm support I bearing silver halide emulsion layers 6 and 8. between which there is disposed a water-permeable colloid layer 'l containing an anti-bronzing agent as herein disclosed.'
The element of Fig. 4 consists of a lm support l bearing a silver halide emulsion layer 9 on one surface and having disposed on the other surface a water-permeable eolloid layer l containing a herein disclosed anti-bronzing agent.
It is desirable, especially where the silver derivative is included in a supercoat or in the emulsion layer itself, that it should be in a very fine state of subdivision in the layer in which it is incorporated. Thus, a convenient method of use is to form the silver derivative in situ in the colloid medium in which it is to be dispersed, for example by the double decomposition of a soluble silver salt and an alkali-metal derivative of the compound in a gelatin medium.
The invention may be applied to all varieties of compound which are capable of improving the quality of the developed image and which will form silver derivatives.
The following are typical classes of compounds which may be used, as their silver derivatives, in accordance with this invention.
(a) Compounds of the type described in British Patent No. 561,875. These are -mercapto tetrazoles and specific examples are:
1-phenyl-5-mercapto-tetrazole 1-a-naphthyl--mercapto-tetrazole 1--naphthyl-5-mercapto-tetrazole 1-p-diethylamino phenyl-5-mercapto-tetrazole l-o-methoxy phenyl--mercapto tetrazole l-p-chlor phenyl-5-mercapto-tetrazole 1benzyl5-mercapto-tetrazole 1-cyclohexyl-5-rnercapto-tetrazole 1-methy1-5-mercapto-tetrazole 1-ethyl-5-mercapto-tetrazole (b) The -mercapto-1.2.4-triazoles described in U. S. application Serial No. 558,270, referred to above. Specific examples of these are:
1.2-dimethyl-5-mercapto-1.3.4-triazole 1-ethyl-2-methyl-5-mercapto-1.3.4;-t1fazole 1-phenyl-2-methy1-5-mercapto-1.3.4triazole l-phenyl-5-mercapto-1.3.4-triazole l-benzyl-S-mercapto-1.3.4-triazo1e 1 -methyl-2-ethyl-5-mercapto- 1.3.4-triazole 1-methyl-2-n-hexyl--mercapto-1.3.4-triazole l-p-hydroxy phenyl-2-methyl-5-mercapto-1.3.4-
triazole l-p-arnino phenyl-2-methyl-S-mercapto-1.3.4-
triazole 1a-naphthyl-2-phenyl-5-mercapto-1.3.4-triazole 2-a-naphthyl-5-mercapto-1.3.4-triazole 1.2-diphenyl-5-mercapto-1.3.4-triazo1e (c) Heterocyclic nitrogen compounds containing two nitrogen atoms in the ring and one, two or three sulphur atoms attached to carbon atoms which are in fic-position to the nitrogen atoms (compounds containing a single sulphur atom linked to a carbon atom which is a to both nitrogen atoms are included but are generally less eflicient). Examples of this class of compound are:
2.5-dimercapto-1.3.4-thiodiazole 2-mercapto-5-amino-1.3.4-thiodiazole 1-mercapto-4-hydroxy-phthalazine 1.4-dim-ercapto-phthalazine 2.5-dimercapto-3-methyl-1.3.4-thiodiazole 2-hydroxy-4-mercapto pyrimidine 2 :4-dimercapto-pyrimidine 2 :4-dimercapto-quinazoline Trithio barbituric acid (d) Mercapto hydroxy diazoles, an example of which is:
2-mercapto-4-phenyl-5-hydroXy1.3.4 thiodiazole.
(e) Dimercapto monazoles, an example of which is:
2.4-dimercapto quinoline.
(f) Mono mercapto monazoles, examples oi which are:
2-mercapto-benzthiazole 2-mercapto-benzoxazole 2-mercapto-quinoline 2-mercapto-6-7-benzbenzthiazole (i. e., naphthathiazole) 4-mercapto-quinoline.
EXAMPLE I 1 gram of 1-phenyl-2-methyl-5-mercapto- 1.3.4-triazole was dissolved in 3.6 ccs. of a 40% aqueous solution of sodium carbonate (Cryst). This solution was added to 250 ccs. of a 4.4% solution of gelatin (containing a small quantity of dispersing agent) and made up to 500 ccs. with water. 77.7 ccs. of a 1% aqueous solution of silver nitrate was added to 250 ccs. of a 4.4% solution of gelatin (containing a small quantity of disture wascooledto'dorm afsrnall amountrofronn- -Jal'd'ehyde a'd'ded and ttlfien, 1 after' stari'ding; was coated at 80 F. asA afsupercoatr (fai afstandard silverfbromideemulsion-'asmsedi 'or aryfbro- Timide prlinting paper.Y 4"and T:Cb -a ta 'da-rdrsi-lver chloride Iemulsiorifasyusediirikordiriary ffooritact" Aor gas1ight printing paper; ftheV ul'sion ilayers `being carried f onfpaper 1-s',upp'cr-ts. Testfsaniples `of the fdriedfcoatings were 4exposedrbehindaidensity rstep wedge,` developed and xfed. :'JSome Isamples Wereidried normally ramd othersilwere dried on -alcommerc'ial hotiglazin'g machine.
'Control samples, 'in fwhi'ch the triazole voorn- :p'oundfwas Lomitted Vfrom @the gelation "superooat, -were similarly processedaand'tne speed andimanimum image density (Dmax) Were determinedior Fthe I.various1samples. The fre's'ultslobtained were .fassetrout1in-.the` following" Tabler:
vTable .Y
.randltheereslts.nbtainedfwere .fasssettoufzfixtzthe ses SilverBroinidCoatings4 `Si1verChlorldlGoatings following Table II:
AZThese speed values 'are calculatedas before. Again "there is no measurable' loss in Jspee'din vfthe jcaseof the silver chloride emulsiorrcoatingsj'b'ut there is `some loss in-thecase'of the silver bromide emulsion coatings. MHowever,l a comparable test on the silver bromide material =using Ja superco'a't containing the free compound(i."'e.,riot"'asithe Asilverderivati-ve) sh'ovved "a speed value only-T5 lof* that of 'the 'test "sample o'f the above Table"'[I. 'The testsamples `in all cases vshowed* 4a markedly llessdegree of bronzing Aafter hot-glazing, `than "the "control *rt-should 1'te pointedout-therme speed' vfigures given V:in this "example `are not 'comparable with 1130 I "PatenNo': 561;'8'75. `thoughthe ysame"compound is `in use; "for the reason that 4Vin I'the' present 'case very much larger quantities of the compound have Ebeent'aken in ythe' examples-and 'the-fernulsionsl used are different.
11i-EXAMPLE rIII 'free generar procedure- Forex-amples'"nano 1111 Vwas"followed using concentrations-oi 1-`partfdf Vthe @silver-derivative! "in- 50'00 Cparte f'i fthe fge tin Ksincerco'at solution, |other compounds' than Table `III .'Slver Broniide Coatings VSilver Chloride .Coatings i.
AD normallyJ ""Dvm hot- "l 'Dm normally r"D hot- Compound mariee gled "d1-ieu lzed Control Test Control Test Control Test Control Test 2.4-di-me1capto pyrimidine 1. 91 1.94 1. 70 2.05 1. 74 1.86 1. 46 2.00 1-mercapto-4-hyd10xypl1thalazne l. 83 1. 94 1. 58 1. 99 1. 75 l. 90 l. 45 l. 98 Z-mercapto-benzthiazole 1.83 1.89 1. 58 1. 94 1. 75 1. 86 1. 45 1. 97 2.4.dimercapt0 quinoline 1.82 1.85 1.71 1.90 1.80 1.83 1.53 1.86
parable test on the silver bromide material using a supercoat containing the free compound (i. e., not as the silver derivative) showed a speed value only 1% of the speed of the test sample of the above Table I. `The test samples in all cases showed a markedly less degree of bronzng after hot-glazing than the control.
EXAMPLE II The procedure given in Example I Was followed with the variations that the compound used Was l-phenyl--mercapto-tetrazole, it was dissolved in 5.0 ccs. of the sodium carbonate solution and the quantity of silver nitrate solution taken was 95.5 ccs. All other conditions remained the same EXAMPLE IV The silver derivative of lr-phenyl--mercapto tetrazole was prepared and added in finely divided condition to silver chloride and silver bromide emulsions, one part of the silver derivative being added per 1000 parts of emulsion. Tests were made as before and gave the results set out in Table IV.
The bronzed effect of the control samples, shown particularly on the hot-glazed samples, was substantially eliminated in the test samples and, though some loss in speed Was caused by the addition of the silver derivativeto the bromide emulsion, this loss was less than is caused by the addition of the free compound. An increase inv Dmax was effected in all cases.
What we claim is:
1. A photographic element comprising a silver halide emulsion layer and, in Contact therewith,
a Water-permeable light-insensitive colloid layerl which contains a silver derivative of a compound selected from the class consisting of -mercaptotetrazoles, -mercapto-1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and monomercapto monazoles.
2. A photographic element comprising a silver halide emulsion layer and an outer water-permeable light-insensitive colloid layer in contact with saidemulsion layer, said outer layer containing a preformed silver derivative of a compound selected from the class consisting of 5- mercapto-tetrazoles, 5 mercapto-1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in aL-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
3. A photographic element comprising a silverhalide emulsion layer of which the predominant silver halide is silvei` chloride and, in contact therewith, a water-permeable light-insensitive colloid layer which contains a silver derivative of a compound selected from the class consisting of -mercapto tetrazoles, 5 mercapto 1.3.4-triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positionsvto the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
4. A photographic element comprising a silver halide emulsion layer of Which the predominant silver halide is silver chloride and an outer waterpermeable light-insensitive cclloid layer in contact with said emulsion layer, said outer layer containing a silver derivative of a compound selected frum the class consisting of 5-mercaptotetrazoles, 5-mercapto-1.3.4triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in na-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
5. A photographic element comprising a paper support carrying a silver halide emulsion layer and an outer Water-permeable light-insensitive colloid layer in Contact with said emulsion layer, said outer layer containing a silver derivative of a compound selected from the class consisting of 5-mercapto-tetrazoles, 5-rnercapto-1.3.4triazoles, diazoles containing up to three sulphur atoms attached to carbon atoms which are in a-positions to the cyclic nitrogen atoms, mercapto hydroxy diazoles, dimercapto monazoles and mono mercapto monazoles.
WILFRID HAMPDEN DIMSDALE. RICHARD ROBERT ROBINSON.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,057,764 Brunken Oct. 20, 1936 2,066,099 Dieterle Dec. 29, 1936 2,221,805 Leermakers Nov. 19, 1940 2,377,375 Russell June 5, 1945 FOREIGN PATENTS Number Country Date 390,037 Great Britain Mar. 30, 1933
US573460A 1944-02-03 1945-01-18 Photographic elements bearing silver halide emulsion layer and adjacent light-insensitive colloid layer containing silver derivatives of azoles Expired - Lifetime US2432864A (en)

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US2699393A (en) * 1950-04-15 1955-01-11 Agfa Ag Fur Photofabrikation Photographic process for the direct production of positive images
US2843491A (en) * 1956-05-23 1958-07-15 Eastman Kodak Co 2-mercapto-1, 3, 4-oxadiazoles as antifoggants
US2939789A (en) * 1958-06-06 1960-06-07 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3206311A (en) * 1961-05-05 1965-09-14 Polaroid Corp Stacked photosensitive elements
US4202695A (en) * 1971-12-09 1980-05-13 Agfa-Gevaert N.V. Photographic Lippmann emulsions
US5543281A (en) * 1995-02-17 1996-08-06 Eastman Kodak Company Mercaptotetrazole transition metal salts for control of cyan stain
US6730467B1 (en) 1998-01-26 2004-05-04 Eastman Kodak Company Sensitization of cubic AgCl emulsions with improved wet abrasion resistance
US6790600B2 (en) 2003-02-07 2004-09-14 Eastman Kodak Company Method of color photographic processing for color photographic papers

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US2628167A (en) * 1948-04-29 1953-02-10 Du Pont Method of making colloid silver halide emulsions containing thallium
US2950972A (en) * 1954-11-24 1960-08-30 Gen Aniline & Film Corp Photographic emulsions having increased sensitivity to x-ray and gamma ray radiation
BE545888A (en) * 1955-03-08
US2839405A (en) * 1955-03-08 1958-06-17 Eastman Kodak Co Inorganic salt antifoggants for photographic emulsions
BE545887A (en) * 1955-03-08
BE545779A (en) * 1955-03-08
BE548727A (en) * 1955-06-21
BE579710A (en) * 1958-06-16
DE1772903A1 (en) * 1968-07-19 1971-06-16 Agfa Gevaert Ag Photographic material
JPS53134430A (en) * 1977-04-27 1978-11-24 Mitsubishi Paper Mills Ltd Silver halide photosensitive materials for multiilayer color photograph

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GB390037A (en) * 1928-01-31 1933-03-30 Ig Farbenindustrie Ag An improvement in photographic emulsions
US2057764A (en) * 1933-07-22 1936-10-20 Agfa Ansco Corp Manufacture of stabilized silver halide emulsions
US2221805A (en) * 1939-02-02 1940-11-19 Eastman Kodak Co Photographic emulsion
US2377375A (en) * 1943-12-14 1945-06-05 Eastman Kodak Co Thiosalicylic acid antifoggant

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GB390037A (en) * 1928-01-31 1933-03-30 Ig Farbenindustrie Ag An improvement in photographic emulsions
US2066099A (en) * 1928-01-31 1936-12-29 Agfa Ansco Corp Photographic emulsion
US2057764A (en) * 1933-07-22 1936-10-20 Agfa Ansco Corp Manufacture of stabilized silver halide emulsions
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US2377375A (en) * 1943-12-14 1945-06-05 Eastman Kodak Co Thiosalicylic acid antifoggant

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699393A (en) * 1950-04-15 1955-01-11 Agfa Ag Fur Photofabrikation Photographic process for the direct production of positive images
US2843491A (en) * 1956-05-23 1958-07-15 Eastman Kodak Co 2-mercapto-1, 3, 4-oxadiazoles as antifoggants
US2939789A (en) * 1958-06-06 1960-06-07 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3206311A (en) * 1961-05-05 1965-09-14 Polaroid Corp Stacked photosensitive elements
US4202695A (en) * 1971-12-09 1980-05-13 Agfa-Gevaert N.V. Photographic Lippmann emulsions
US5543281A (en) * 1995-02-17 1996-08-06 Eastman Kodak Company Mercaptotetrazole transition metal salts for control of cyan stain
US6730467B1 (en) 1998-01-26 2004-05-04 Eastman Kodak Company Sensitization of cubic AgCl emulsions with improved wet abrasion resistance
US6790600B2 (en) 2003-02-07 2004-09-14 Eastman Kodak Company Method of color photographic processing for color photographic papers
US20040180303A1 (en) * 2003-02-07 2004-09-16 Schwartz Paul A. Method of color photographic processing for color photographic papers
US20040197714A1 (en) * 2003-02-07 2004-10-07 Eastman Kodak Company Method of silvery recovery from color photographic processing
US6838233B2 (en) 2003-02-07 2005-01-04 Eastman Kodak Company Method of color photographic processing for color photographic papers

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