DE1547694A1 - Photographic material - Google Patents

Description

15476? *

PATENTANWÄLTE 17/25/65 »« «Ϊμ» « _Τ ϊ April 28, OO

DR.-ING. WOLFF, H.BARTELS, XJÖi ^ & lJiXK

υκ. DKAINUC5, υκ.-ιΐΝο. IiCLU Χ) τΜ.ί4λ (Μ »1ίΑΧΧΧΧΧΧΧΧΧ

β monks ₂₂ , Thi ^ *,!,. e / m

TELEPHONE 293297 Reg.No. 120 31o

Lastnian Kodak Company, 34 3 State Street, Rochester, New York State, United States of America

Photographic material

Silver Halide Crystals in Photographic Emulsions are known to have both surface and internal photosensitivity. That Ratio of these two types of sensitivity can be great to be different. The silver halide crystals of most photographic emulsions are high in ratio from surface to inner sensitivity.

Silver halide crystals, their ratio of internal sensitivity surface sensitivity is very high, e.g. on page 261 of the book by Mees "The Theory of the Photographic Process ", 1954 and in" J. of the Optical Society of America ", 31, p. 382, (1941) as well as in U.S. Patent 2,592,250.

From the USA patents 2,996,382 and 3,178,282 it is BAD OBlGlNM-

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furthermore known that combinations of emulsions with predominantly surface sensitivity and emulsions with overwhelming inner sensitivity and veiled Silver halopenide crystals sensitivity and contrast properties possess which the corresponding institutions of the individual emulsions alone considerably overlap are. However, such emulsion combinations have the Disadvantage that they, especially when they are with Onium salts and / or alkylene oxide polymers to very high levels of sensitivity have been sensitized, easily developing veils produce. In order to suppress this chemical haze, such emulsions have already been used. Antifoggants, which can often have a mercapto function in their molecules, added. Ls got jer but it shows thatP. with the veil at the same time the sensitivity is decreased.

It has now surprisingly been found that. certain heterocyclic nitrogen compounds having a mercapto function in contrast to these structurally very similar compounds without a mercapto function as well as in contrast to mercapto compounds not containing a heterocyclic ring, excellent antifoggants for especially unveiled silver halopenide crystals with predominantly Surface sensitivity and veiled., Predominantly Containing intrinsically sensitive silver halopenide crystals Mixtures of photographic emulsions or combinations of the corresponding silver halide

BATH ORIGINAL

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Crystals each for contained l.muIsions, which are are in the immediate vicinity. Ls was found "daft if the heterocyclic lercapto nitrogen compounds only Silver halide crystals borrowed (veiled) from the innards adsorbed, which veil aildunp of development is prevented as far as possible, without the detection and the contrast of the emulsions is impaired.

The discovery therefore relates to a rhotorraphic material, consisting of one; Carrier with at least one silver halide emulsion layer, achieved from a remix of an irulsion with Si 11 obtain enide crystals with predominantly surface-sensitive cit and an emulsion with silver halide crystals ; it predominantly veiled, inner-fictional Crystals or with at least 2 layers of silver halide emulsion, generated from an emulsion with siller halide crystals with predominantly superficial clien sensitivity as well as an emulsion with predominantly veiled, inner-sensitive Crystals, the silver halide layer or the layers include an antifoggant having a "lercapto" function contain, characterized in that the veiled silver halide crystals act as antifoggants a heterocyclic nitrogen compound having a mercapto function adsorbed, which pebundcn on a carbon atom is, which is in a-Stellunp to a nitrogen atom of a heterocyclic ring. '

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It has been found that there is a considerable loss of sensitivity occurs when the emulsion contains predominantly surface-sensitive silver halide crystals or grains contains, nit the a fiercapto function in α-position to the Heterocyclic containing nitrogen atom bonded to carbon Nitrogen compound is treated, Am important The feature of the invention is thus that the antifoggant consists of the predominantly intrinsically sensitive silver halide crystals or grains is adsorbed.

Those present in the emulsion combinations of the invention are latent (essentially) on the surface of their crystals Imaging emulsions are those that have a relatively high degree of surface sensitivity, while their inner sensitivity is low. The ones in the Emulsion combinations of the invention present, (essentially) emulsions that provide latent images inside their crystals have a high degree of intrinsic sensitivity, but only a relatively low surface sensitivity. In contrast to the inner-sensitive emulsions containing fogged silver halide crystals remain the crystals of the surface-sensitive emulsions practically unveiled,

For the production of the predominantly surface-sensitive crystals containing emulsions, the known photosensitive silver halides, such as silver chloride, silver bromide, Silver chlorobromide, silver chloroiodide, silver bromoiodide

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and silver chlorobromoiodide, but preferably silver broiaoiodide be used.

Suitable emulsions which form latent images on the surface of the silver halide crystals are described, for example, by Trivelli and Smith in "The Photographic Journal", Vol. LXXX, pages 285/288 (1940). Characteristic of this type of photographic emulsions is that they are measured by a photographic test method in which a sample of the emulsion is petrarpetrare on a transparent support and the photographic material obtained is exposed to a light intensity scale for 0.01 to 1.0 seconds and then in a developer Λ (whose composition is given below) b minutes is developed at 20 ⁰ C long, have a sensitivity which, measured at a density of 0.1 above fog UCN is prefer than the density of using the same L -mulsion, which after it has been exposed to the same V.'cise, bleached for 5 minutes in an aqueous solution containing 0.3% potassium fericyanide at about 15 ° C. and then in a developer B (the composition of which is given below is specified) has been developed for 5 minutes at about 18 ° C,

The developer A is a kind of "surface image developer", while developer B is a so-called internal one, which has a high degree of dissolution for silver halide Developer is.

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The cracl of the inner sensibility of (übericreml) ol.erf lächenevi ^ f inulicl.en emulsions undergoes i; eit "cheiulrii Vc riincieruncen, d. H. the emulsion in question is poorly relative wenir. inncrci:; be sensible; but it can also have one have a fair amount of inner windward finiteness, without the latter killer as the subject matter is. These latent images advance on the surface of the Irulsions which form silver halide crystals can have a have a high or a low contrast, since with Vcrwenciunr both types of emulsions achieved beneficial effects can be.

The surface-sensitive emulsions are also characterized characterized that they have a uaxinal density of proper.als Acquire about 0.50, home on a carrier in an etv.'a

2
540 mp of silver per 0.09 m of carrier surface are applied accordingly and the material obtained is exposed under a step wedge and developed for 12 minutes in a developer L (the composition of which is discussed below). Particularly perfect results will be iir. others with surface silver iodide halide, such as B. silver bromoiodide emulsions which form predominantly latent images on the surface of the silver halide crystals obtained. Such enulsions can contain from about 0.5 to about 99 mole percent "iodide".

The emulsion combinations of the invention underlying

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The I. emulsions with silver halide crystals of predominantly internal sensitivity contain veiled silver halopenide crystals that form latent images inside the crystals. Any of the silver halides used in the production of this type of photographic emulsions, such as e.g. B. veiled silver chloride, bromide, chlorobromide or chlorobromoiodide can be used. Suitable photographic emulsions which form latent images in the interior of the silver halide crystals are e.g. ii. in U.S. Patents 2,592,250, 2,99b,382, and 3,17P,282. It is characteristic of such photographic emulsions that they are examined by a photographic test method in which a sample of the emulsion in an unveiled state is tread on a transparent carrier and the material obtained is 0.1 to 1.0 seconds long on a light intensity scale exposed, then bleached for 5 minutes in a solution containing 0.31 potassium ferricyanide at about 18 ° C. and finally developed in a developer B composed as described below, show a sensitivity measured at a density of 0.1 above the Haze, is noticeably greater (e.g. at least 1.4 lop E greater) than the sensitivity of an identical sample of the emulsion which, after being applied to a transparent carrier and exposed in the same way, for 6 minutes a temperature of 20 ⁰ C (b8 F) was developed in the developer.

Those underlying the emulsion combinations of the invention Emulsion fractions that provide internal images are provided

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partially or completely obscured their use. The stranding is sufficient to provide a density of at least 0.5 if 1 mole (ApX) of the veiled emulsion together with 3 moles (ArX) of the surface-sensitive emulsion, corresponding to a Ce including height of about 540 mm, Silver (as silver halide) is applied to about 0.0 'of a carrier and the photographic material obtained is developed in developer U for 5 minutes. The surface -D _x '' ^{ert of unweared} , internally sensitive silver halide-containing emulsions is normally perineper than about 0.30 when these emulsions are

IiI f I Λ

lightens and lanp 8 minutes in the developer described below to be developed.

The concealment of the emulsions with predominantly internal Sensitivity can be carried out in different ways become, such as Ii. by exposure of the emulsion or with chemical agents, etc. These photographic emulsions, d, h. Silver halopenide emulsions which have high internal fog but low surface sensitivity can be used also, starting from an emulsion, can be obtained which have both an intrinsic sensitivity and has a surface sensitivity. In this case it will this emulsion obscures, whereupon the surface image with a potassium fericyanide solution is bleached. After a further process of making veiled interior emulsions containing latent images are not

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layered inner sensitive emulsions of an energetic one Radiation, such as B. X-rays exposed.

The ratio of the surface sensitive emulsion to the veiled, inner sensitive emulsion can, depending on the emulsion types used, the contrast of the emulsions and the other known variables are largely changed will. Very advantageous results are obtained when the molar ratio of surface-sensitive emulsion to veiled inner sensitive emulsion at least 1: 1 or greater. For example, even at 42: 1 molar ratios, beneficial results will be obtained obtain. If the moip percent of fogged, inner-sensitive emulsion is that of the surface-sensitive emulsion exceed such. B. at a molar ratio of 1: 3 of surface-sensitive to veiled inner-sensitive emulsion, there may be a slight loss of sensitivity occur, but the contrast of the combination of these emulsions is considerably greater than that of the used surface sensitive emulsion alone. Accordingly beneficial results can e.g. B. can always be obtained when the molar ratio of surface sensitive Emulsion to inner sensitive, fogged emulsion is about 42: 1 to 1: 3.

The developers A, B and C used for testing the various emulsions had the following compositions:

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⁽ "rar;H'i

Λ. N-'lethyl-p-aninophenol sulfate 0.31

. ', atrium sulfite, dehydrated 3L /, 6

iiyclrocliinon ο

Sodium carbonate, dehydrated 1 °, 7

Kaliuiibromid u ,. ^c ü

Citric acid Ο, υΚ

Fill up Kaliuni.ietabisulf it 1.5 liters with a lasser.

N-.iuthyl-p-amino phenol sulfate 2, <

Sodium sulfite, drained D (V hydroquinone ', J.

₄ \ at riuir; carbon ate, .Vonohydrate 5 2.5 Potassium Bronide 5

;. at r i uut Ii iosulphate 1``> with lasser; Liters filled up.

C. .'.-. ' ethyl p-ariinophenol sulfate 2.5

! »Atrium sulfite, dehydrated 3" iivdrochincn 2.5

λ at riuFinet aborat 1ü Potassium bromide 0.5

filled up with water to liters.

The Lrfindunp can Miscliunpen of surface-sensitive Emulsions and veiled internal sensitive emulsions form a layer of photographic material. However, it is also useful to use both types of emulsions

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separate, but immediately adjacent layers of the pitotc raphisciicn 'atcrials to arrange. I. earth those who suffer different J :::. ulsicnen in the form of separate layers If an Irishman is rare, the infiltration may suffer without forming a layer of the photographic material, there also the veiled, inner sensitive emulsion trans * parent «emit * is to let the light through sufficiently, so dar · those in this; Fall the more crazy closer to the surface area 1 atm. In the rest can be done by the triiper emulsion layer also be carried out by the carrier, provided that the Tear itself is transparent. The surface-sensitive emulsion is, however, preferable to the more advantageous work-up via the veiled inner sensitive emulsion applied. On the other hand, it is also erroneous, both emulsions blended together as a layer over a veiled, to apply inner-sensitive emulsion layer, whereby the latter either with the veiled one present in the mixture, internal sensory emulsion of the same or of it can be different

The antifoggants used erfindunrsreiää ¹ are heterocyclic, F.indestens a mercapto-containing Stickstoffverbindunpen, the mercapto function is attached to a stationary in-cc Stellunc to a nitrogen atom of the heterocyclic nucleus carbon atom. Such a

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bindunpen underlying heterocyclic nucleus can be one or more heterocyclic rings, their heteroatoms except may consist of nitrogen, oxygen, sulfur, selenium or tellurium, the heteroatoms at least must belong to a ring. With the corresponding monoheterocyclic Nitrogen compounds are the heteroatoms members of a single heterocyclic ring, which optionally with one or more not containing heteroatoms Rings can be condensed. In contrast, corresponding diheterocyclic nitrogen compounds contain condensed nitrogen compounds heterocyclic rings in which the heteroatoms belong to two heterocyclic rings.

Particularly suitable heterocyclic nitrogen compounds are those which are derived from azoles, oxazoles, selenazoles, triazoles, e.g. B, 1,2,4-triazoles, especially those with an amino group in addition to the mercapto function, diazoles, such as, for example, imidazoles, benzimidazoles, and imidazolines, Pyrimidines, 1,2,4-triazines, s-triazines, monoazoles, such as benzoxazoles and benzothiazoles, azaindenes, such as. B. Tetrazaindenes and the like.

Particularly advantageous heterocyclic nitrogen compounds containing mercapto functions have been found to be those of general formula

f \

N * C - SX

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proven, in which mean:

Z the non-metallic atoms required to complete a 5 to 6, preferably 5-membered heterocyclic ring of a heterocyclic compound, and X is a hydrogen atom, an alkali metal atom, such as. B. a sodium or potassium atom, a KIi ₄ -RcSt or a residue of an organic amine, e.g. B. a triethylamine, triethanolamine or morpholine radical. Accordingly, the mercapto function can be an -SÜ group or a salt group, e.g. B. a -SNa group. · Many of these heterocyclic compounds can also be in tautomeric form, e.g. B. be present as a "thione", in which case the mobile hydrogen atom of the mercapto function is bound to the nitrogen, d. h, the = C-SX group becomes the ^ C = S group.

Particularly favorable L results are obtained with mercaptoazoles, especially S-f-ercqtotetrazolen.

The latter have the following formula:

N = N

N N-R

V /

SX

where R is a hydrocarbon or non-hydrocarbon rest, d. H. an alkyl or aryl radical or a radical with still other atoms or groups besides carbon and

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V.asserstcff represents and X the already nnee ^ ebenc iicdeutunjT owns, ato: r.c and groups that perebenenfal Is feir.einsam ir. with carbon and ί '-' form hydrogen atoms R, are ζ. υ. i.aloeenatoif.e oc = er alkoxy-, phenoxy-, cyano-,, '. itro-, Anino-, substituted aryn-, SuI Eo-, i, ulfa: nyl-, substituted Sulfauyl-, 5ulfonylrhenyΪ-, Sulfonylnlkyl-, F lucsvil fonyl SuIf onanidopkenyl-, SuIf on iir.i do alkyl-, Carbonxyl-, Carhoxvlat-Carbair.yl-, Carbar.ylplienyl-, carbainylalkyl-, carbonyla 1! vl- or carbonylphynyl groups.

Particularly advantageous 5-mercaptotetrazoles are the 1-pienyl-5-nercaptotetrazoles the formula:

SX

where R ^{1 is} a hydrocarbon radical with up to 22 carbon atoms and X has the meaning already given. Fl ¹ can e.g. ß. consist of an alkyl, aryl, alkaryl, aralkyl or alkaralkyl radical, preferably an alkyl radical with 1 to 8 carbon atoms.

The -NhCOR-kest on the phenyl ring can be in the o-, m- or n-position to the one with a heterocyclic nitrogen atom

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- 15 connected carbon gate of the Phenylrinrs.

licrartire 5-mercaptotetrazole can be obtained by reacting wn 1 -Air.inophenyl-S-mercaptotetrazole hydrochloride with an S; iurcchloride of the formula R ¹ C (KU. The T- (aminophenyl) -S-rcercaptotetrazole itself can be obtained from aminoacetanilide ( ο-, m- or p-) obtained with thiophosgene, whereby the corresponding acetanidodophenylisothiocyanate is formed, which is reacted with an azide, whereupon the "isothiocyanate" containing the mercaptotetrazolrinp with concentrated hydrochloric acid to form 1- (aminophenyl) -5- The formation of mercaptotetrazole hydrochloride is described by Stolle and Strittiraier in J. for practical Clicm. 133, pages 00/04 and by Stolle and Fr. Lienke-Stark, ibid 124, pages 201-300, a further process for Production of 1-phenyl-5-mercaptotetrazole, which is described in Chem. Ber. Z £ _ _t 77, is based on the reaction of an acetamidophenyl-substituted thiosemicarbazide with nitrous acid,

For the reaction with the mercaptotetrazole ^{hydrochloride suitable acid chlorides R 1} COCl are, for. B. the chlorides of acetic acid, acetoacetic acid, difluoroacetic acid, propionic acid, valeric acid, isovaleric acid, caproic acid ^ caprylic acid, undecanoic acid, stearic acid, benzoic acid, o-acetoxybenzoic acid, antranilic acid, 3-amino-ö-nitrobenzoic acid, p-2,4-tolylacetic acid , Methylsulfonic acid,

009S08 / 1377 bad original

o-toluenesulfonic acid, benzenesulfonic acid , p-bromobenzenesulfonic acid and o-formylbenzenesulfonic acid.

Linige special, particularly advantageous heterocyclic Nitrogen compounds are e.g. D, 2-mercapto-1-phcnyltetrazo1, 2-mercapto-5-phenyl-1,3,4-oxadiazole, 1- (3-caprimido) -phenyl-S-mercaptotetrazole, 1 - (5-Pelargonamido) -phenyl -5 mercaptotetrazole, 2, ϋ-dimethyl-1,3,3a, 7-tetrazainden-4-thiol, 2-mercaptobenzoxazole, 1-phenyl-S-mercaptotetrazole, 5-ethyl - () - methy 1-1,2, 3a, 7-tetrazainden-4-thiol, 2-mercaptoimidazole, 4-methyl-1,2,3a, 7-tetrazainden-6-thiol, 4-thiono-4a-azanaphthalene, 2-: icrcaptof.-naphthoxazol-2-thionothiazolidone, 4-mercapto-1 -thia-3,5,7-triazainden, 4 - () xy-6-methyl-1, 2, 3a, 7-th tra ζ a in den-3-thiol, 3-Mereapt0-1,2,4-triazole, 2-mercapto-5- (p-oxyphenyl) -1,3,4-oxadiazole and 2-mcrcaptobenzothiazole.

Lines of these heterocyclic mercapto compounds become in U.S. Patent 3,017,270.

The adsorption of the antifoggants to the veiled, intrinsically sensitive silver halopenide crystals can be achieved by adding the antifoggant to the emulsion prior to application to a support. The antifoggant may be used in w ater or other innocuous for the emulsion solvent such, for example, acetone or lower alcohols and derpl. dissolved and added in the form of its solution.

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Uie containing the anti-fogging agent adsorbed, veiled silver halide crystals can then with the Oberf lächer.pf indli even silver halide crystals having emulsions are mixed, whereupon the mixture of emulsions on the Ί rarer aufpetrarcn will. On the other hand, the treated with the antifoggant inner sensitive, veiled silicon oxide crystals containing emulsion and the surface sensitive Emulsion containing silver halide crystals, such as this preferably happens, in separate, iet'cch immediately adjacent layers are applied to the tracer, The antifoggant or agents are therefore not working a mixture of the emulsion with inner sensitive crystals and the emulsion with surface sensitive crystals added, since this would cause a desensitization of the latent surface image-providing emulsion.

The antifoggants are expediently used in such amounts that the intrinsically sensitive, emulsion containing fogged crystals about 50 mg to about 5 g, preferably about 100 mg to about 2?, the antifoggant or agents are omitted.

The surface sensitive emulsion containing crystals the emulsion combination can be chemically sensitized by known methods. This emulsion can be used with

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naturally active gelatine can be matured or sulfur, selenium or tellurium compounds can be added, such as IJ. those in U.S. Patents 1 574 9 <M, 1 623 499 and 2 4K) 089.

The latent, surface-forming emulsions of the emulsion combination can also be used with salts of ldelnctallen, such as Ruthenium, rhodium, palladium, iridium or platinum salts be treated, liierfür peeipnete characteristic Compounds consist e.g. of ammonium chloropalladate, Potassium dichloroplatinate and katriochloropalladite. Derartire Connections are used for sensitization purposes Concentrations applied below those concentrations which are an essential veil prevention cause how it z. B, in U.S. Patent 2,448,060 or as an antifoggant in higher concentrations, as described in U.S. Patents 2,500 and 2 5öö 203. is described.

Containing surface-sensitive silver halide crystals Emulsion can also be chemically sensitized with gold salts as described in US Pat. No. 2,399,08 or stabilized with gold salts, as described in U.S. Patents 2,597,856 and 2,597,915. Suitable gold salts are e.g. B. Potash chloroaurite, Potassium aurithiocyanate, potassium chloroaurate, gold trichloride and 2-aurosulfobenzothiazole methiochloride.

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These Lmulsioiien can also chemically with reducing agents, Vi ic z. ß. i-inn- (II j-salts, as described in a US Pat. No. 2,457,850, or with polyamines, such as, for example, III, ethylene triamine, as described in US Pat. No. 2,557,850. !, or with polyamines such as spermine, as described in UhA patent specification 2,521,925, or with bis (i? -ar.iine; ithyl) sulfide or its water-soluble salts, as described in US patent specification 2,521 92ü is described, be sensitized.

Those used in the emulsion combinations of the Urfindunp l.mulsions with surface-sensitive silver halopenide crystals can be very highly sensitized and still produce only a very small amount of veil when developing one latent image. These emulsions can therefore also be used by others Sensitizer additives than the chemical sensitizers already described, such as. H, especially alkylene oxide polymers contain, Derartipe polymers are derived from 2 to 4 carbon atoms containing alkylene oxides, such as /'.thylene oxide, propylene oxide and butylene oxide.

The production of such alkylene oxide polymers, which also are referred to as polyalkylene glycols, is, for example, in the Book by Lllis "The Chemistry of Synthetic Resins" (1935), Pages 990/994. Their use as sensitizers in photographic emulsions is described in the United States patents 2,423,549 and 2,441,389. Other polymeric alkylene oxides that can be used as sensitizers

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cirnen in Si lbcrhaloeenicicr.ulsioncn, ability ζ. b. by condensation an organic containing an active r.assorstoffaton Connection with an alkylene oxide polymer or by Condensation of the compound containing the active hydrogen atom π it the alkylene oxide during the polymerization of the the latter can be obtained.

For the sensitization of the surface sensitive silver halopenide crystals Emulsions containing Ie can also contain various other alkylene oxide polymers, in particular condensation products of alkylene oxides with organic compounds containing an active 1 hydrogen atom are used, containing examples of such active hydrogen atoms organic compounds, c-. H. Compounds in which at least a hydrogen atom ,, z. B, by reacting with metallic ! .atrium, Mcthylna ^ nesiuiri odid, etc. can be substituted, are Alkolicle, anine, '! Creaptane, carboxylic acids, amides, hydrocarbons, v.ie z. B. acetylene, so.ie compounds with an active methylene group, such as. b. iir. Dibenzoylmethane is present. Suitable are z. B. Condensation products of alkylene oxides with glycols, such as the P to 1P carbon atoms, compounds described in U.S. Patent 2,240,472 and British Patent 443,559, as well as condensation products of alkylene oxides with aliphatic acids, such as. B. lauric acid or aminoessipic acid, Condensation products ^ of alkylene oxides with aliphatic Amines or amides, such as. B. Laurylamide, or condensation

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BATH ORIGINAL

products of alkylene oxides with phenols, such as. b. phenol

the
The production of these condensation products is described in US Pat. No. 1,970,578. Condensation products of alkylene oxides with "hexitol dehydration products", as described in US Pat. No. 2,400,532, can also be used. Examples of other suitable alkylene oxide polymers are e.g. B, U.S. Patents 2,074,019, 2,917,4SO, 2,8437, and 2,944,900, and British Patents 845,340, 947,790, 945,857, 949,643, and 949,044. The molecular weight of the polymeric sensitizing agent should be at least 300. Advantageous condensation products of ethylene oxide with long-chain alcohols, acids, amines or amides have a molecular weight of about 700. Particularly good results are obtained with condensation products made from ethylene oxide and long-chain compounds that have 12 or more carbon atoms in their chain, or with polyethylene glycols with molecular weights of 1500 to 400 degrees or higher. Such sensitizers consisting of alkylene oxide polymers are expediently used in concentrations of about 0.05 to about 5 g, preferably 0.1 to about 2 g, per mole of silver halide of the emulsion in question.

The photographic emulsions of the emulsion combinations containing the surface-sensitive silver halide crystals of the invention may also contain sensitizers

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5 A 7 6 9 4

which have at least one onium salt group in their Molcki'l. Such compounds preferably contain one or more «" "sodium salt groups consisting of quaternary ammonium, quaternary phosphonium and / or ternary sulfonium salt groups, while the polyonium salts are one of a quaternary ammonium, quaternary phosphonium or ternary sulfonium group Ordering onium salt soup contain, the ritteis of the Oniui.i *> atoms and at least one two organic ones Remainder with the onium atom of another uniuusalzrrunpe is connected, ciie also from a quaternary Aiinioniui.-i-, quaternary phosphonium or ternary sulfonium:,. salzrrur> re bes can stand.

Appropriate Oniu: .salts are ζ. ύ. fiulfoniur.il auryltrifithylar.T / .on iunper ch 1 crat, λ ony 1 d ire t hy 1 su 1 f ο η iui :; -γ -toluenesulphonate, n-lccyltriethylphosphonium ::: - p -toluenesulphonate,. ^<: Thy len-bis (oxymethy ^LTRI: thylphosrlioniur.ch lorict) Xthy let.-b is (oxynethy1-o-picoliniunrerchIorat) Ί etranethylen-uis (oxy ¹ ethyltriinetnylphcsphcniuK.bror.id) uiu "the ^ l .

Other advantageous ouaternary Ai.mcniun, r.uptcmfire thosrhoniun and ternary sulfonium salts v; earth e.g. L. in U.S. Patents 2,271,223, 2,271,623, 2,275,727, 2,2S3 22b, 2,944,900, 2,940 F51, 2,940 S55 and 2,944 P.9R and in British Patent D77 ^C 04. These onium salt sensitizers are found in the surface

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sensitive emulsions of the emulsion combinations of the Lrfindunp ,, preferably in concentrations of about 0.1 to 5 ρ per?! Ol silver halide, used.

The surface-sensitive emulsions can also pen also not z. B. cyanine or merocyanine dyes spectrally be sensitized and anti be. lubricants or stabilizers, \ sic polvoxbenzenes, azole or azaind compounds, Saccharides, metal salts, such as. B. Cadmium, lead, Contain mercury, gold or other precious metal salts.

For the production of the emulsion combinations of the Brindunp underlying emulsions can be used for the Uispertiierunp des Silver halide gelatin or another colloidal material, such as. B. albumin, a cellulose derivative or a polyvinyl compound can be used, although gelatin is available will.

the emulsion layers produced from the emulsions described as well as additional or different layers if necessary of a material made from cien emulsions can with eincüi hartunqsraittel, such as ß. an aldehyde, an aziridine compound, a compound derived from dioxane with mirterffektunp, or with Oxypolysaccaric'en, v; ie "Oxystürke" or other "oxy plants" uniriis "are hardened.

iJiesc photographic emulsions can use sensitizing dye e, antifoggants and others in Lmulsior.cn that-

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contain components used of this type as described in the U.S. Patents 2 99ü 3R2 and 5 17 ^ 2Γ2 are described. They can also be used to create a wide variety of riioto ^ raphisciien color and black- '.. ciPr.ir.tcriii licn as they in the cited patents can be used.

I. · ie the anti-skid agents of the! .Rfindunp-containing emulsion combinations can apply to the most varied of flexible debris, v.ic them allrei.icin for the production of rhotorraphic "materials are used, such as gellulose nitrate filins, Cellulose acetate, polyvinyl acetate, polystyrene iline, PolyrJtliyltererb.thalat for Ire and derrl. aufretra.i / en will. You can also use flasher, paper and in particular with polyethylene or an ethylene-butene polymer coated papers can be used as a carrier.

!. earth in the for the development of I.iiiUlsionkombinations the photographic material containing irindunn used Developer solution determined additives, such as B. a Silver halide solvents, can be used If necessary, a silver halide solvent will be used to achieve further advantages when used, the sensitivity is markedly increased especially in those cases in which those of the iodide content of the surface-sensitive emulsion in the emulsion combination of the invention is low. Except I. Sodium thiosulfate and sulfite can also be used for this purpose

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T547694

water-soluble thiocyanates or water-soluble quaternary ammonium compounds, such as, for example, those in the USA patent 2 over 48 over 4 described, as a silver halopenide solvent be used. How pezeirt has turned out to be also possible by adding iodide ions, e.g. B. in the form of potassium iodide, developers of the present type, in particular in the development of surface-sensitive emulsions photographic materials containing low iodide content Achieve such smooth lines.

The following examples are intended to explain the principles further.

example 1

Line veiled, inner sensitive gelatin silver chloride bromide emulsion prepared as in Example 4 of U.S. Pat 2,996,382, was prepared with a highly sensitive, sensitized with sulfur and gold compounds Gelatin silver bromide iodide emulsion, the one high surface sensitivity and a low interior Sensitivity possessed, mixed. The one used, with sulfur and gold compounds sensitized silver bromoiodide emulsion corresponded to an emulsion as described in Example 1 of the patent mentioned.

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The surface and internal sensitivities of these emulsions were practically the same as those described in Example 1 of US Pat. No. 2,9 ⁽ Jb 382).

The surface sensible emulsion of the Kurd on a common riltral on its own and combined with the veiled, inner sensitive emulsion on the face. A sensitizing agent made from an onium salt and an icrcaptoazole were added to the emulsion. The üniuinsalz used consisted of Tetradecaniethyl en-b is- (pyridiniui.iperchlorat j \ ^;.;; hrenü us used xrcaptoazol of 1 - (3 - (aprar, ido) phenyl-5-n ercaptctct razo one existed..! The last-mentioned compound was dissolved in ethanol, whereupon the solution of the veiled, inner-lipid emulsion was added.

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Ί Λ is I. L L L I

film ι, r.

Surface sensitive silver bromide iodide

cmulsion, aufretraren in an? 5 in ρ Ae rro about 0.09 at the water area corresponding '! cnne;

over a surface infinite silver bromide iodide emulsion, aufectr.apcn in a üf5 me Ar pro ctv; a 0.09 c-π inert rf la clic corresponding ilen ^ e about a veiled, inner-sensitive silver chloride bromide emulsion, which contained 175 nc Ae per approximately 0.09 square meter carrier area;

Surface sensitive silver bronze emulsion, which contained 1 ρ onium salt per mole of ArX, in an OSS, no silver per approximately 0.09 of carrier surface corresponding 'Menpe;

Like coating Xr, 3, iedccli η it 4-r onium salt per mole of AcX in the silver bromide iodide ion;

Surface-sensitive silver bromide-dide emulsion, which contained 4 ρ onium salt per Mo1 AfX, applied in a 085 rar Ap, per etv; a 0.09 qrn Träjrerflache corresponding lenpe over a veiled, sensitive to silver chlorobromide emulsion, which contained 175 rrc * silver per approximately 0.09 qra ΐ rape rf pool.

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TAbLLLH I (continued)

Film Kr.

Surface sensitivityc silver bromide iodide

emulsion with 4 g of onium salt added per 1 mole

2 ApX applied at a rate of 85 mg Ap per 0.09 m

Träperfläche corresponding menu over a veiled inner sensitive silver chlorobromide emulsion layer, the 175 mg ApX per approx of the mercaptoazole.

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The films obtained were exposed in an intensity scale sensitometer and developed at 20 ^° C. in a developer with the following composition:

i-PhenyI-3-pyrazolidone 1 ς

Hydroquinone 20 g

Sodium sulfite “dehydrates 50 ρ

Sodium metaborate (8, IUO) 20 g

Sodium anthraquinone sulfonate. 0 _t 1 ρ

Potassium bromide 15.0 ρ made up to 1 liter with water 9.6)

The ones with films no. 1 to 6 at different development times The sensitorometric results obtained are summarized in Table II below;

OO9IO8 / t377

II

Film Lr. Lntivicklun? TSzeit Veil Relative

in "inuter. Lr.nfind- ',, ert

Ity

12 20

9 15

8 14

5 6

0.12 IZk) 1.2 0.1 b 51U 1.2 0.30 3Su 2.9 0, bO 225 3.8 0.1 (j 230 1.1 0.32 210 1.1 0.14 112 1.0 0.32 320 0.5 0.11 570 2.1 0.19 ■ 2.7

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- 51 -

From the experimental results communicated, it was found that " the heterocyclic ones containing a. ". crcarto function Nitrogen compounds made from particularly effective antifoggants for rhotofrrapiiischc .'iatcrialien represent the one Surface sensitive pulse layer directly above a inner, veiled 1st emulsion layer (on your Trills) when the. '! Ercapto function has Connection of the sensitive, veiled I. emulsion is added.

Obvious results were obtained if, instead of 1 - (S-Capranidojphcnyl-S-raercaptotetrazole, other nitrogen-containing, heterocyclic ereapto-compounds, such as 1 - (3-Pelarfonaiido) -S-rhcnyl-Sr .icrcantotetrazol, 2, b-diraethyl-1, 5,5a, 7-tctrazainden-4-tnicl, 2-. ^%> ercartobenzoxazole, i-phenyl-S-mercaptotetrazole, Z - '^ ercaptooinidazole, 5-mercarto-1, 2,4-triazole and 2-mercaptobenzothiazole were used. Otherwise, the same results were obtained when using other oenium salts, such as, for example, λ, λ ¹ -athvlenedi (oxymethylpyridinium perchlorate), 1,10-decamethylene-bis-triethylaiumunonium perchlorate , Bis (laurylmethylsulfonate-p-toluenesulfonate), K-decyltriethylphosphonium-p-toluenesulfonate, lauryltriethylanmvonium perchlorate, nonyldinrethylsulfonium-p-toluenesulfonate or decylpyridinium perchlorate ethylene were used instead of tetradecamidinium perchlorate-bischlorate-bischlorate.

The heterocyclic mercapto nitrogen compound will not the inner sensitive, veiled emulsion, but rather added to the surface-sensitive emulsion, so occurs

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a very considerable loss of sensitivity under certain circumstances. When the experiments described were repeated with 4 to 1 μmc of the mercaptoazole per mole of ApX in the surface-sensitive emulsion, a sensitivity loss of up to 20 % was found. If the experiment was repeated with a concentration of 0.5% of the rlercaptoazole per oil silver halopenide in the surface-sensitive luulsion, the loss of sensitivity was 99%.

Example 2

i-.ic described in Example 1, various films were the following structure:

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Filni No.

- 33 -

TABl-LLL III

Surface sensitive gelatin silver bromide

iodide emulsion with 0P5 mg Ar (.as ApX) per etva 0.09 qia ΐ rape rf pool over a veiled, inner sensitive 75 mn Aj '(as A ^ X) per approximately L-emulsion splint containing 0.09 m² of support surface;

Same as Film # 1 except that the obscured, intrinsically sensitive emulsion was per mole Silver halide 0.5 ρ 1- (3-capramido) -phenyl-5-mercaptotetrazole contained;

Same as film Kr .. 1, except that the surface-sensitive Emulsion 1.0 ρ tetradecamethylene bis (pyridinium perchlorate) contained per mole of AqX;

Same as film Kr. 1, except that the surface-sensitive Emulsion 1.0 g tetradecamethylene bis (pyridinium percivlorate) per mole of AgX and the obscured inner sensitive emulsion per mole of AgX 0.5 g of 1 - (5-capramido) -phenyl-5-ir.ercaptotetrazole contained.

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The films were exposed as described in Öcisriel 1 and developed, with the fclcendcn l.rr> cbnisse received \ .urder,:

T Λ B LLL L IV

oeschiclitunr iintwick lunrs- veil! '. el ρ ti ve' \ '> r; i.ui

^ r. time i.r.rfiiu'-

in minutes

ο ■ v, 12 153 1, r2

.i _f 53 2 ·· 1 5.3

υ. 0.0- 11 "- '" 1, H)

0.21 400 2.5

t 5.10

ü 0.21 4 70 1.91

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154769 *

Example 5

(As described, the information can be written on the inside using alkylene oxyupolyi.ercn Sensitized uerden, full ei sic defiant only one r-c rings .Sd: Icier at cor I.r.tv.ick create luiif,

Pas in .eisyiel 1 beschricl enc '.'niunsnlz vur-.' E turcii a Polyethylene · glycololeyl. "Itf.er replaces, ccr mis a ::; Kendensptio-nsrroukt from 0 Icy Ih Jl.oliol rit uivc ^ ahr 25! oils .trylenoxyi icstiinJ. -urcen, as described in i-eisriel 1, which the net c roc ve 1 i sch ei; '! orcantosti el »st of!" connections lonbiniert r.it this. Mky lciipxydrnlyjierer, entiia It ends I'.escl · iclitun ^ eri 1 clicht um ', devi ekelt, so v: urdcn (based on a l.estir.rtc ; ".rf i ι;,! Ii dil.i · i l) lower: .cl. Ic i ernivenus erluiltcr. than at i-cn des. '■ -. lkylcnexydr olyrrrc rl linen containing :: escbi chtunr-en

Lilts; icci.ciuk vorteill-.aftc I r ^ cbnisse vairden erl.alten, the characteristic iicterecy-clisd.cn '.ercnrtosticl-stoFfvcrb j ndunoen in Silberbialot-cni de.üulsicnskoinbinationen used v.urden that sewolil tia-s ₁ .CR IUi .sf »Iz as well as an alkyl oxydrolyr.

The natural salt and / or the alkylene oxy-alcohol can, instead of in the corresponding emulsion layer, also be unturpebraclit in the lntv; i disgusting, without dndurcli bccintriiclitint v, the advantageous oil effect. the Alkylenoxydrolymere passed z \> from..:

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Polyäthylcnoxydoleinester, Polyethylene oxydnonylphenol ether, K-methylmyristylaminopolyethylene oxide, Polyäthyleiioxydo ley lather, N-methyl-n-dodecylaninopolyethylene oxide, Polyethylene oxide, polyethylene oxide, polypropylene oxide ethylene oxide), Polyethoxyethyl-bis-sulfuric acid

Polyethoxyethyl-bis-carboglutamic acid (Ka-SaI)

1000 1145 1045 1500 1145 1540 4000 3000 (mg «1500)

(mg = 1600)

The numbers behind the compounds represent the average molecular weights of the polyethylene oxide chains.

Alkylene oxide polymers of the type described are e.g. Am U.S. Patents 3,017,271, 2,674,619 and 3,022,335.

Example 4

Mercapto compounds that do not have at least one heterocyclic Ring contain either cause a loss of sensitivity, which can amount to about 25 to more than 100 l. Possibly they even enlarge the veil instead of lessening it. This resulted from experiments in which films, as described in Example 2, but the following mercapto compounds

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(1) Thbacetanilide

(2) thiobenzamide

(3) 2 <mercaptoadipic acid

(4) p-mercapto benzoic acid

(5) 2- (2-mercaptoethylamino) ethanol

were used.

Example 5

Various films were made as described in Example 2, but using the following heterocyclic ones, none Compounds containing mercaptofuction:

O) benzotriazole

(2) 5-phenyl tetrazole

(3) 2-methylbenzothiazole

(4) 4-Oxy-6-methyl-1,3,3a, 7-tetrazaindene

(6) 2,5-dimethyl-7-oxy-1,4,7a-triazaindene

produced * which then, as described in Example 1, exposed and developed. It was found that the obtained Fog values at a certain sensitivity level were 50 to over 2001 greater than the corresponding values Values of corresponding coatings which, according to the invention used heterocyclic mercapto nitrogen compound,

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The emulsion combinations of the oil tuners can be used in the same way as those in the United States patents
2 99b 3S2 and 3 178 282 and provide images with significantly reduced development haze. Therefore, such emulsion combinations can e.g. B. also for the detection and measurement of very small doses
of gamma rays, such as those found in artificial radioisotopes, can be used.

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Claims (1)

1 B Λ 7 R Ρ 4 - 39 P a t c η t a η s ρ r ü c- h e r ~
1. "Photopraphisches material consisting of a ^carrier. Ip, it comprises at least a Silberhalop.enideiaulsionsschicht Rait, erzeurt from a mixture of a Linulsion r.it Silberhalofrenidhristallen with predominantly Obcrflächenenpfindlichkeit and a Lmulsion with Silberhalonenidkristallen with überwiepend fogged, inner-sensitive crystals oder.nit rcindestens 2 silver halide solution layers, produced from an emulsion with silver halide crystals with predominantly surface sensitivity and a layer with overly veiled, inner-sensitive crystals, the silicon halide layer or the layers containing an anti-fogging agent, which is characterized by an anti-fogging agent veiled CiIberhalopenid crystal contain as an antifoggant a heterocyclic nitrogen compound with a Ncrcaptofunktion adsorbed, which is bonded to a carbon atom, which is in a position to a nitrogen atom of a hete rocyclic ring is located. 2. Photographic material according to claim 1, characterized in that it is a compound of the formula as an anti-fogging agent N = C - SX, where mean: 009808/13 77 Z the completion of a 5- or b-membered heterocyclic Ring of a heterocyclic compound non-metallic atoms and SX a mercapto function. 3. Photographic material according to Claims 1 and 2, characterized in that it is a mercaptoazole as the antifoggant contains. 4. Photographic material according to claims 1 to 3, characterized characterized that it is a 5-mercaptotetrazole as an anti-fogging agent contains. 5. I'hotorraphisches .Material according to claims 1 to 4, characterized labeled as an antifoggant 1- (3-capramido) -pheny1-5-mereapto-tetrazole contains. ü. Photographic material according to claims 1 to 5, having a silver halide emulsion layer formed from a mixture of one I. emulsion with silver halopenide crystals with predominantly upper f lächencnpfindlichkeit and a Lmulsion with Silberhalorcnidkristallen with predominantly veiled intra-sensitive Kristi'llefi, characterized in that the CaP Hmulsionsschicht is sclnvcf elsensibi lisiert. 7. Photorrnphisches material according to Ansprucii ü, characterized in that there is one emulsion layer as a sensitizer ; .. redden it? a. (. 'niursiilzr.runpe O'. 'cr an alkylene oxide poly- 0098 08/13 77 BATH ORIGINAL 154769 * Contains here. 8. Photographic material according to claims 1 to 5, with 2 different silver halide emulsion layers »characterized in that the layer with the silver halide crystals is sulfur-sensitized with predominant surface sensitivity and optionally additionally contains a sensitizer with at least one üniumsälz & group or an alkylene oxide polymer . BATH