DE1950779A1 - Direct positive photographic recording material - Google Patents

Description

Direct positive photographic recording material

The invention relates to a direct-positive photographic recording material, consisting of a layer support and at least one direct positive photographic silver halide emulsion layer containing a cyanine dye.

It is known that the natural sensitivity of most silver halide emulsions is over a very limited range visible spectrum, generally in the blue region of the visible spectrum. It is also known that Certain dyes are able to sensitize silver halide emulsions, d. H. their sensitivity to light lasts longer Able to extend wavelengths.

It is further known to sensitize silver halide emulsions to transmitter which are intended for the production of direct-positive images. Emulsions of this type may contain a so-called electron acceptor as well as silver halide grains which have been fogged. The silver halide grains can thereby

for example with a combination of a reducing compound and a compound of a metal that is more electropositive than silver, have been veiled. One advantage of such direct-positive emulsions is that the high-light regions of the images obtained are practically free of fog. A disadvantage of the known direct-positive silver halide emulsions, however, is that they are not the high ones. Have sensitivity, which is required for many photographic applications. It has also proven to be disadvantageous that the known direct-positive silver halide emulsions do not have the desired selective sensitivity, in particular to radiation in the green to red region of the spectrum. Finally, it has been found that in some cases, e.g. B. when using the known indole cyanine dyes, the sensitivity de.r by adding color couplers. Emulsions is reduced in proportion to the duration of the preparation time of the _r emulsions. In view of this, such emulsions cannot be stored indefinitely before they are applied to a layer, but rather have to be used immediately after their production, ie used for the production of photographic recording materials.

The object of the invention was to find cyanine dyes for direct positive photographic silver halide emulsions, which does not address the disadvantages of the heretofore known cyanine dyes used for direct positive photographic emulsions have, which not only sensitize the silver halide of the emulsions excellently, but also the storage allow the emulsions to be used for a longer period of time.

It has been surprisingly found that cyanine dyes derived arylindoles 2-l-alkoxy-by, erhalogenid- sil-outstandingly effective electron and spectrally sensitizing dyes _v for direct-positive photographic

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are emulsions. As a result, the dyes enable the production of direct-positive photographic recording materials, so-called reversal materials or reversal systems, especially with fogged silver halide emulsions. The recording materials are characterized in that they both exhibit excellent general sensitivity as well as the desired sensitivity to radiation in the green to red range of the spectrum, with the maximum Sensitivities usually range from around 530 to 670 nra lie. Images formed with such recording materials are clear and sharp and have excellent contrast.

The invention thus provides a direct-positive photographic recording material consisting of a layer support and at least one direct-positive photographic material Silver halide emulsion layer containing a cyanine dye, which is characterized in that the silver halide emulsion layer contains a cyanine dye of the following structural form:

N = C-C = 1-L-L-C = -C-N-R

X ^e

'* ^Q 2 *

⁹ * ■ 'e

II N = sC-C = ^ - L5 == C-eCH = f CHJ ^ TT-N-R, X ^e

OR J

where mean:

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R is an optionally substituted alkyl radical;

Rj is an optionally substituted alkyl,

Alkenyl, aryl or alkoxy radical;

D and R ₂ each represent a hydrogen atom or an optionally substituted alkyl or aryl radical;

Q ₂ the atoms required to complete an indolyl radical;

Qj and Qj the complete heterocyclic ^ desensitizing acting rings with 5 or 6 ring atoms required atoms;

E and J each represent an optionally substituted aryl radical;

L is an optionally substituted methine radical;

X is an acid anion customary for cyanine dyes;

g »1 or 2;

m * 1, 2 or 3 and

η «1, 2, 3 or 4.

The new cyanine dyes used according to the invention have thus two S- to 6-membered, nitrogen-containing, heterocyclic ones Rings which are connected to one another by a methine radical, the first of the rings being an 1-alkoxy-2-arylindole ring is the one with its 3-carbon atom attached to the methine group is bound. The second heterocyclic ring consists of a so-called desensitizing ring, the with one carbon atom of its ring to the other side

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of the methine group to complete a cyanine dye. It preferably has the methine group 2 to 3 carbon atoms, i.e. H. the methine group consists of a dirnetine group or a trimethine group which may optionally be substituted.

The one represented by R in the general formulas I and II, optionally substituted alkyl radical is preferably an alkyl radical having 1 to 12, in particular 1 to 4, carbon atoms. R can thus be, for example, a methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl or dodecyl radical.

If Rj has the meaning of an optionally substituted alkyl radical, this preferably also has 2 to 12, in particular 1 to 4 carbon atoms and, in the case of an unsubstituted alkyl radical, consists, for example, of a methyl, ethyl, propyl, isopropyl, butyl , Hexyl, cyclohexyl, decyl or dodecyl radical. If R _{3 has} the meaning of a substituted alkyl radical, this can for example consist of a hydroxyalkyl radical, e.g. B * a β-hydroxyethyl or ω-hydroxybutyl radical, or an alkoxy «alkyl radical, e.g. β «a β-methoxyethyl or ω-butoxybutyl radical, or a carboxyalkyl radical, for example a β-carboxyethyl or ω-carboxybutyl radical, or an alkoxy radical, e.g. B. a methoxy or ethoxy radical, or a sulfoalkyl radical, e.g. B. a B-SuI foil thy 1- or ω-sulfobutyl radical, or a sulfatoalkyl radical, e.g. B. a * "> sulfato-ethyl or ω-sulfatobutylrtst, or a sulfatealkyirest, e.g. a ß-sulfatoethyl or ω-sulfatobutyl, or an acyloxyalkylrtst, 1, B. tieem e-Aettexylthyl- ,, γ- Acet'oxypropyl- or $ «9utyryloxybutylrest, or an AlkoxyctrbonyiaXkylrest, e.g. an O-Metboxycarbonyläthyl- or ω-Äthoxycarbonylbutylrest, or an aralkyl rust _for example a Benzyl- or Phenäthylrest"

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If Rj has the meaning of an optionally substituted one Alkenyl radical, this can for example consist of an allyl, 1-propenyl or 2-butenyl radical.

If R. has the meaning of an optionally substituted aryl radical, this preferably consists of an optionally substitute aryl radical of the phenyl or naphthyl series, do h. R. consists, for example, of a phenyl, naphthyl, Methoxyphenyl or chlorophenyl radical.

If Ώ and R ₂ are optionally substituted alkyl res th j, they also preferably have 1 to 12 _v, in particular 1 to 4 carbon atoms and consist, for example, of methyl, ethyl, propyl, isopropyl, butyl , Decyi- or Bodeeylresteii. Possess D and R _2, there are the meaning of optionally substituted aryl they are preferably aryl radicals the phenyl or Naphthylreihe, ie, D and R ₂ may be, for example phenyl ₉ tolyl, naphthyl, methoxyphenyl, chlorophenyl or nitrophenyl.

The illustrated heteroeyeliaehen by Q ₃ and Q ^, desensitizing acting rings may be other than the jeweiligenStickstoffatoa still have at least one further heteroatom, such as an oxygen, sulfur, selenium, or nitrogen atom, that is, Q ^ Q ~ W ia complete heterocyclic, 5- or 6 - membered rings, as they are typical for cyanine dyes.

In individual cases, Q, and Q ₇ can represent, for example, the atoms which are permanent »:

Nitrobenzsthiaxolylag, e.g. B. a 4-Hitrob®nzothiazole, S-nitrobenzothiazole, arNitrobenzothiszole or S-chloro-6-

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a naphthothiazole ring substituted by a nitro radical;

a nitrobenzoxazole ring, e.g. B. a 5-nitrobenzoxazole, 6-nitrobenzoxazole or S-chloro-6-nitrobenzoxazole ring;

a nitro substituted naphthoxazole ring;

a nitro substituted benzoselenazole ring, e.g. B. a 5-nitrobenzoselenazole, 6-nitrobenzoselenazole or 5-chloro-6-nitrobenzoselenazole ring;

a nitro-substituted naphthose lenazole ring ₉ ζ <, Β «, a 6-nitronaphthoselenazole ring;

a nitro substituted pyridine ring, e.g. B ", a 4-nitropyridine ring;

a 3,3-dialkyl-3H-pyrralo / 2,3-b-7-pyridine ring;

a nitro substituted quinoline ring, e.g. B. a 6-nitro-2-quinoline, 6-nitro-4-quinoline or 6-nitro-1-isoquinoline ring;

a 3,3-dialkylindolenin ring, e.g. B. a 3,3-dimethyl-5-nitroindolenine * or 3,3-dimethyl-6-nitroindolenine ring;

a nitro substituted imidazole ring, e.g. B. a 1-alkyl-5-nitrobenzimidazole, 1-aryl-5-nitrobenzimidazole or 1-alkyl-5-nitro-α-naphthimidazole ring;

a imidazo ^ _"4,5-b>, 7chinoxalinring, such as a 1-Alkylimidazo ^" 4.5-b_ _t 7chinoxalinring such. B. l-Ethylimidazo / '* 4 _l 5-b_7 ~ quinoxaline- or 6-chloro-l-ethylijnidazo ^ "4,5-b _o> 7quinoxaline-

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ring, or a l-alkenylimidazo ^ ~ 4,5-b_7quinoxaline ring, ζ. B. a 1-allylimidazo ^ 4,5-b-7-quinoxaline or 6-chlorol-allylimidazo ^ 4,5-b-7-quinoxaline ring, or a 1-arylimidazo 4,5-b-7-quinoxaline ring, e.g. B ^ a 1-phenylimidazo- ^ "4, S-b_7-quinoxaline or 6-chloro-1-phenylimidazo / ~ 4,5-b_7-quinoxaline ring;

a 3,3-dialkyl-3H-pyrrolo / 2,3-b-7-pyridine ring, e.g. B. a 3,3-dimethyl-3H-pyrrolo / 2,3-b-7-pyridine or 3,3-diethyl-3H-pyrrolo-2,3-b-7-pyridine ring;

a thiazolo ^ 4,5-b-7quinoline ring;

an optionally substituted indolyl ring, ζ. B. a 2-phenyl-3-indole or 1-methyl-Z-phenyl-S-indole ring.

E and J are preferably aryl radicals from the phenyl or naphthyl series; H. E and J can be, for example, phenyl, naphthyl, tolyl or chlorophenyl radicals.

The nethine residue represented by L can be represented by the following structural formula: -O

where T is a hydrogen atom or an alkyl radical, preferably a short-chain alkyl radical with 1 to 4 carbon atoms, or an aryl radical, preferably de.r phenyl or naphthyl series can. Xa individually, L can thus be, for example, a methine residue of the following structural formulas:

- CH-, -C (CH ₃ ) -, -C (C ₆ H ₅ ) -

X can be, for example, a chloride, bromide, jido, perchloride, tetrafluoroborate, sulfamate, thiocyanate, p-toluenesulfonate or methyl sulfate anion.

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Typical ones useful for making a direct positive photographic material according to the invention Examples of cyanine dyes are:

1. 1,1'-dimethoxy-2,2'-diphenyl-3,3 * -indolocarbocyanine perchlorate;

2. l-methoxy-l ^I -aethyl-2.2 ^l , lO-triphenyl-3,3 ¹ -indolocarbocyanine perchlorate,

3. l, l ^l -diethoxy-2,2'-diphenyl-3,3'-indolocarbocyanine perchlorate;

4. 1-Ethoxy-1'-Biethyl-2,2 ', 10-triphenyl-3,3'-indolocarbocyanine perchlorate;

5. 3 ^l -ethyl-1-methoxy-6 ^l -nitro-2-phenyl-3-indolothiacarbocyanine-p-toluenesulfonate;

6. l-ethoxy-3 ^l -ethyl-6 ^l -nitro-2-phenyl-3-indolothiacarbocyanine-p-toluenesulfonate;

7. 1,3-diallyl-l '- "ethoxy-2" -phenylimidazo ^ "4, S-b_7quinoxalino-3 ¹ -indolocarbocyanine perchlorate;

8. 1,3-diallyl-l ¹ -ethoxy-2 ^f -phenylimidazo / "4,5-b-7-quinoxalino · 3 · indolocarbocyanine perchlorate;

9. l'-methoxy-1,3, S-triraethyl-Snitro ^ -phenylindo-S '-indolocarbocyanine perchlorate;

10. 1-methoxy _r 1 ", 3 ', 3 ^f -tri" ethyl-2-phenyl-3-indolo-2- ^t pyrrolo- / ~ 2 _f Sb ^ / pyridocarbocyanine pyrchlorate;

11 l ^l -ethoxy-l, ^{3,3-trimethyl-5-nitro-2-t} -phenylindo 3 ^l indolocarbocyanin-p-toluenesulfonate;

12. 1 ^ Xthoxy-1 *, 3 *, 3 ^f -tri-ethyl-2-phenyl-3-indolopyrrolo - / "2,3-b-7-pyridocarbocyanine perchlorate.

The cyanine dyes which can be used according to the invention are extremely effective electron acceptors for direct positives are silver halide photographic emulsions.

Under a "desensitizing" ring are rings meant that after being converted into a symmetrical Garbo-

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! NSPECTED

cyanine dye and addition of the dye to a silver chlorobromide emulsion with 40 MoI- * chloride and 60 itel-l ^ i s Bromide in a concentration of 0.01 to 0.2 g of dye ^ at least one per mole of silver by electron capture about 80% loss of the emulsion's sensitivity to blue if it is exposed sensitometrically and for 3 minutes is developed in a developer of the following composition at room temperature:

N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite (anhydrous) 90.0 g

Hydroquinone ^ 8 ^ .0 g Sodium carbonate (monohydrate) 52.5 g

Potassium bromide 5.0 g

Made up to 1.0 liter with water

The desensitizing rings preferably have a structure such that, after being converted into a symmetrical one Carbocyaninfarbitoff and testing in the manner described for a practically complete desensitization of the Conduct test emulsion to blue radiation, d. H. to a more than about 90 to 95 days loss of sensitivity to blue radiation.

According to a particularly advantageous embodiment of the direct positive Recording material according to the invention has at least one silver halide emulsion layer one or more of the new cyanine dyes, the sa silver halide grains are veiled. The fogging of the silver halide grains can be carried out by customary known methods, for example by exposure to light or chemical fogging agents, e.g. B. stannous chloride, Formaldehyde and thiophosphorus dioxytL in an advantageous manner the emulsion can also be achieved by adding a reducing agent

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Connection, ζ. B. thiourea dioxide, and a compound a metal that is more electropositive than silver, e.g. B. a gold salt, such as potassium chloroaurate (see. British Patent 723 019), have been veiled.

According to an advantageous embodiment of a recording material according to the invention, the direct-positive silver halide emulsion layer can consist of a so-called solarizing silver halide emulsion layer. The emulsions used to produce such recording materials are silver halide emulsions which are produced either chemically or by the action of light have been obscured to a point which roughly corresponds to the maximum sensitivity of the Itakehr curve (see Mees "The Theory of the Photographic Process, MacMillan Co., New York, New York, 1942, pp. 261-297).

Processes for the preparation of solarizing emulsions are, for example, also from British patent specification 443 245 known. For example, it is known from this British patent to irradiate emulsions with X-rays, until the emulsion, when developed without additional exposure, blackened to the apex of the gradation curve will. British Patent 462 730 also discloses the use of light or chemicals, e.g. B. silver nitrate, organic sulfur compounds or dyes to convert common silver halide emulsions into solarizing, known direct-positive emulsions. US Pat. No. 2,005,837 also discloses the use of silver nitrate and other compounds in connection with the action of heat known to effect the solarization of silver halide. Finally, US Pat. No. 2,184,013 uses it of larger concentrations of non-acidic, spectral sensitizing dyes and reducing compounds

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known to effect solarization.

US Pat. No. 2,541,472 also discloses solarizing Emulsions known which are particularly suitable for exposure to light of longer wavelengths and the show the healing effect described in the book by Mees. These Emulsions contain an electron acceptor substituted by a nitro radical and other compounds in either chemically or with white light obscured emulsion. When using recording materials with such Emulsion layers will be a reverse exposure using minus-blue light from about 500 to 700 millimicrons, P preferably 520 to 540 millimicrons, with the latent image recorded by the emulsion layer in the exposed districts is practically destroyed.

The conventionally known silver halide developing solutions can be used for developing the photographic material according to the invention be used.

The concentration of the dyes in the silver halide emulsion layer can be very different. Expedient are concentrations of about 50 to about 2000 mg, preferably of about 400 to 800 mg, used per mole of silver halide.

^ According to an advantageous embodiment of a recording material according to the invention, there is the direct positive syllable Halide emulsion layer consisting of a layer made up of a silver halide emulsion with silver halide grains which is a center consisting of a water-insoluble silver salt or a center consisting of a water-insoluble Silver salt have existing core and an outer shell from a veiled, water-insoluble silver salt » which can develop silver without being exposed «Im

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Fall of such silver halide emulsion layers are the cyanine dyes are preferentially absorbed on the outer shell of the silver halide grains. The production of such Silver halide emulsions can, for example, according to the in U.S. Patent 3,367,778.

The silver halide emulsion layer of a recording material

according to the invention can also advantageously made from a highly sensitive, direct-positive silver halide emulsion layer with veiled regular monodisperse SiI halide grains and an electron accepting or female compound of the Belgian patent

695 366 known type exist. Ä

For the production of the recording material according to the invention, the conventionally known, photographically useful ones can be used Silver halides can be used, such as silver bromide, silver iodide, silver chloride, silver chlorobromide, SiI-berbromoiodide and silver chloroiodobromide.

Particularly advantageous results are obtained when the silver halide grains have an average grain size of less than about 1 micron, preferably less than about 0.5 micron *

The silver halide grains can be one of the usual forms, such as i silver halide grains used for the production of photographic materials can have, have. This means that the silver halide grains can have, for example, a regular or cubic or octahedral shape (cf., for example, Belgian patent specification 695 366). Preferably the grains have a uniform diameter distribution.

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According to a particularly advantageous embodiment of a photographic Recording material according to the invention has at least 95% by weight of the silver halide grains of the silver halide emulsion layer a diameter no more than about 40 liters, preferably no more than 30 $, from the mean Grain diameter deviates.

The mean grain diameter, i.e. H. the average grain size, can, for example, by the method described by Trivelli and Smith in the journal "The Photographic Journal ", Volume LXXIX, 1949, pages 330-338.

In the production of a recording material according to the invention the new dyes are preferably incorporated into the washed, finished silver halide emulsion and therein Thoroughly distributed according to known methods. It has proven expedient to use suitable dyes in the form of solutions Incorporate solvents into the emulsion. Suitable solvents are, for example, methanol, isopropanol, pyridine and water and mixtures of these solvents.

For the preparation of the silver halide emulsions, the usual known hydrophilic binders can be used, for example naturally occurring binders, such as. B. gelatin, Albumin, agar-agar, gum arabic * alginic acid and the like, as well as hydrophilic synthetic plastics, e.g. B. polyvinyl alcohol, Polyvinylpyrrolidone, cellulose ether and partially hydrolyzed cellulose acetate and the like.

Although the usual known silver halides, z. Bc silver chloride, silver bromide, silver chlorobremide, silver bromoiodide, silver chloro bromoiodide and the like. _t can be used, it has proven particularly advantageous for making the dock

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positive fogged silver halide emulsions to use a silver bromohalide as the silver salt, which is more than 50 MoI-I consists of bromide.

The silver halide emulsion layer of the recording material according to the invention and optionally further layers of the Recording material can with conventional known hardening agents be hardened or have been hardened, e.g. B. with the usual known aldehyde hardeners, z. B. formaldehyde and mucochloric acid, AzxTidine hardeners, hardeners made from derivatives consist of dioxane, oxypolysaccharides, e.g. B. Oxy strength and oxidized vegetable gums and the like.

The emulsion layers can also contain customary known additives, for example lubricants, stabilizers, Sensitivity-increasing compounds, light-filtering dyes, plasticizers, and the like. The emulsion layers can furthermore, if necessary, further spectral sensitizing dyes contain.

The recording material can advantageously also contain color couplers or else, the recording material may contain color couplers or other compounds which produce dyes Solutions are developed. The customary known monomeric and polymeric color couplers are used as color couplers in question, e.g. B. the known 5-pyrazolone color couplers, the known phenolic or naphtholic color couplers and the so-called open-chain color couplers with a reactive methylene group The color couplers can be incorporated into the direct-positive silver halide emulsion by customary known methods as described, for example, in U.S. Patents 2,322,027; 2,801,171; 1 055 155 and 1 102 028 and 2 186 849 are known.

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■ - 16 -

The recording materials of the invention can also be incorporated using the recording materials Developer compounds are developed, for example developer compounds based on polyhydroxybenzenes, aminophenols and / or 3-pyrazolidones.

Binders suitable for preparing the silver halide emulsions are described, for example, in US Pat. No. 3,039,873 described. Polymerized vinyl compounds can also optionally be used to produce the emulsions as described, for example, in U.S. Patents 3,142,568; 3,193,386; 3,062,674 and 3,220,844 are known. These include, for example, water-insoluble polymers of alkyl acrylates and alkyl methacrylates, acrylic acid and sulfoalkyl acrylates and sulfoalkyl methacrylates.

The support of the recording material according to the invention can consist of any of the conventionally known supports normally used in the manufacture of photographic recording materials. For example, the substrate can be made of glass, a plastic film, e.g. B. off Cellulose acetate, cellulose acetate butyrate, a polyester, e.g. polyethylene terephthalate, or a polystyrene or but also made of paper or a baryta paper or a paper coated with a Polyolefii ^, z. B. one with one Polyethylene layer or a polypropylene layer provided paper, which optionally to increase the adhesion of the emulsion to the support before applying the emulsion with electrons may have been irradiated.

The preparation of the dyes used according to the invention can be carried out by customary known preparative methods.

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The following is the preparation of some of the invention cyanine dyes used.

1.) Preparation of dye no. 1

1, I ¹ -Dimethoxy-2,2'-diphenyl-3,3'-indolocarbocyanine perchlorate '

H ₃ CON

CH-CH-CH

© STILL.

ClO,

2.23 g of 1-methoxy-2-phenylindole were dissolved in 10 ml of hot acetic acid, whereupon 2.0 g of trimethoxypropene and 1.0 ml of 48% hydrobromic acid were added with stirring. The mixture was allowed to cool and then diluted with excess ether. The ethereal layer which formed was decanted off, whereupon the viscous residue was dissolved in 60 ml of methyl alcohol. Thereupon 1.5 ml of OO perchloric acid were added, whereupon the mixture was chilled. The deposited precipitate was filtered off and washed with methanol, water and ether. After recrystallization from methanol and acidification with perchloric acid, 1.48 g of pure dye, corresponding to 52 % of theory, were obtained. The melting point of the dye was 228 to 23O ⁰ C.

2.) Preparation of dye no. 2

l-methoxy-l ^l - »ethyl-2,2 ^f , 10-triphenyl-S.S'-indolocarbo cyanine perchlorate

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H ₃ CON

© NCH-

cio,

1.26 g of S-formyl-1-methoxy ^ -phenylindole and 1.55 g of 1-methyl-2-methylenebenzyl-2-phenylindole were dissolved in 10 ml of hot acetic acid. Then 1.0 ml of 60% perchloric acid in 3 ml of acetic acid were added, whereupon the mixture was allowed to cool. After standing for 2 hours at room temperature, the solid precipitate which had separated out was filtered off and washed with methanol and ether. After recrystallization from methanol acidified with perchloric acid, 1.92 g of pure dye, corresponding to 59 % of theory, were obtained. The melting point of the dye
ranged from 258 to 259 ⁰ C.

3. Preparation of dye no. 5

3 '-Ethyl-1-methoxy-6 · -nitro ^ -phenyl-S-indolothiacarbo cyanine-p-toluenesulfonate

H »CON

p-TS *

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1.26 g of S-formyl-1-methoxy ^ -phenylindole, 1.98 g of 3-ethyl-2-methyl-6-nitrobenzothiazolium p-toluenesulfonate and 10 ml of acetic anhydride were refluxed for 1 minute. After cooling, an excess of ether was slowly added. The deposited solid precipitate was filtered off and washed with ether. After recrystallization from methanol acidified with p-toluenesulfonic acid, 2.64 g of pure dye, corresponding to 84 % of theory, were obtained.

4.) Preparation of dye no. 7

1,3-diallyl-l'-methoxy ^ * -phenylimidazo ^ ~ 4,5-b_7 · quinoxalino ~ 3'-indolocarbocyanine perchlorate

CH-CH = CH, I ² *

H ₃ CON

GlO,

CH ₂ CH = CH ₂

This dye was prepared according to the method described in the example, with the exception, however, that 2.18 g of 3-diallyl-2-methylimidazo ^ ~ 4,5-b_7-quinoxalinium-p-toluenesulfonate instead of 3-ethyl-2-ethyl- 6-nitrobenzothiazolium p-toluenesulfonate were used. After recrystallization from a mixture of 65 μl of acetonitrile and 1 ml of 60 % perchloric acid, 1.78 g of pure dye, corresponding to 60% of theory, were obtained. The melting point of the dye was 229 to 231 ° C.

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5. Preparation of dye no. 9

1 · -Methoxy-1,3,3-trimethyl-5-nitro-2'-phenyiindo-3 ' indolocarbocyanine perchlorate. -

H ₃ CON

CH = CH

ClO,

1.26 g of S-formyl-1-methoxy ^ -phenylindole, 1.30 g of 1,2,3,3-tetramethyl-5-nitro-3H-indolium-p-toluenesulfonate and 10 ml of acetic anhydride were refluxed for 1 minute heated. After cooling, excess ether was added. The ethereal layer was decanted and the viscous residue was dissolved in 25 ml of methanol. Then 1.0 ml of 60% perchloric acid in 5 ml of methanol was added. The mixture was then quenched, whereupon the deposited precipitate was filtered off and washed with methanol. After recrystallization from a mixture of methanol and acetonitrile, 1.20 g of pure dye, corresponding to 43 % of theory, were obtained. The melting point of the dye was 266 ° C.

6.) Preparation of dye no. 10

l-methoxy-l ', 3 ^f , 3 ^l -trimethyl-2-phenyl-3-indolo-2 ^l pyrrolo ^ 2,3-b_ / pyridocarbocyanine perchlorate

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^H 3 ^C0 \ / -CH-CH- ^, Η J ClO ₄ ⁶

1.26 g of 3-Forrayl-1-methoxy-2-phenylindole, 0.87 g of 1,3,3-trimethyl-2-methylene-2,3-dihydropyrrolo / 2,3-b-7-pyridine and 0.95 g of p -Toluenesulfonic acid monohydrate and 10 ml of acetic anhydride were heated to reflux temperature for 1 minute. The mixture ä was then cooled and diluted with ether was decanted after which the ethereal layer. The residue was dissolved in 25 ml of methanol, whereupon 1.0 ml of 60% perchloric acid in 5 ml of methanol was added. After cooling, the solid precipitate which had separated out was filtered off and washed with methanol. After a single recrystallization from acetonitrile, 1.78 g of pure dye, corresponding to 6 % of theory, were obtained. The melting point of the dye was 235 to 239 ^° C.

The following examples are intended to illustrate the invention in more detail.

Example 1 I.

First, dye No. 1, i.e. H. 1,1'-dimethoxy-2,2'-diphenyl-S ^ '- indolocarbocyanine perchlorate on its usefulness as an electron acceptor and spectral sensitizing dye for a fogged »direct positive photographic silver halide emulsion, tested.

It was a monodisperse Gelafcine silver bromoiodide emulsion with regular silver halide grains of an average grain

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size of about 0.2 micron by adding an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate simultaneously with vigorous stirring zu.einer aqueous gelatin solution of 70 ⁰ C within a period of about 35 minutes. 2.5 mole percent of the halide was iodide. The emulsion was quenched, noodled and washed in cold water in the usual manner. Thereafter, the emulsion was fogged with a reducing agent and a gold compound by first added 0.2 mg Thiohamstoffdioxyd per mole of silver, the emulsion is heated for 60 minutes at 65 ⁰ C and then 4.0 mg of potassium chloroaurate per mol of silver and the emulsion further 60 Was heated to 65 ^{0 C for minutes.} The dye to be tested was then added, in a concentration such that 50 mg of dye accounted for one mole of silver.

The resulting emulsion was then coated on a conventional cellulose acetate film support so that 100 mg of silver and 400 µg of gelatin were supported ^{on a support area of 0.929 m 2 (1 sq.ft.).}

A test strip of the resulting recording material was then placed in a conventional Eastman IB sensitometer Using light from a tungsten lamp and then exposed for 6 minutes at room temperature in a developer of the following Composition developed:

N-methyl-p-aminophenol sulfate 2.0g

Sodium sulfite (anhydrous) 90.0 g

Hydroquinone ^v 8.0 g

Sodium Carbonate (McNohydrate) 52.5 g

Potassium bromide 5.0 g

Made up to 1 * 0 liters with water

The recording material was then fixed, washed and dried in the usual way.

009820/1556

The evaluation showed the following:

The maximum density of the non-exposed areas was 1.38 and the minimum density in the exposed areas at 0.02. The maximum sensitivity was 650 nm and the relative sensitivity of the recording material was 3630. The recording material used for comparison purposes was identical Prepared and tested manner except that it did not contain any dye. It showed no reverse effect and had one MM ^^ XgJ ^ fyaJtiianil ^^ X ^ ä ^ X ^ aüXiC ^ iCXaÜ ^ XiX not measurable sensitive speed.

From the results obtained, it can be seen that the dye is excellent as a spectral sensitizing dye suitable for a direct positive silver halide photographic emulsion. By using the dye, excellent direct-positive photographic recording materials can be produced with excellent efficiency.

Excellent results were also obtained when a recording material of the type described was used, but whose silver halide ^{emulsion layer was additionally used as a color coupler 1- (2,4,6-trichlorophenyl) A} 3.3 ^l - (2 ^tf , 4 "-di-t. -amylphenoxyacetamido) contained benzamido-5-pyrazolone. In this case, the recording material is a tungsten light source was exposed, the light FIL by Wratten filter no. 61 and no. 16 was trated like. In addition, the recording material was prepared by the from the United States Patent 3,046 129 in Example (a), column 27, lines 27 ff., With the exception that the black and white development with Metol hydroquinone was omitted and that the color development was reduced to 1 minute and the development process in total darkness / to fix, and a purple image of excellent quality was obtained.

G09820 / 1 556

Example 2

Following the procedures described in Example 1, Dye # 2 was tested. When using this dye was the Density of the non-exposed areas at 1.70 and the exposed areas at 0.03. The maximum sensitivity was 660 nm, and the recording material had a relative sensitivity of 3800.

From these results it can be seen that the dye is excellent as an electron acceptor and a spectral sensitizing dye for a fogged direct positive photographic emulsion.

Example 3

Following the procedure described in Example 1, Dye No. 5 was tested. In this case, the density of the unexposed areas was 1.46 and the exposed areas was 0.06. The maximum sensitivity was 575 nm and the relative sensitivity of the emulsion layer was 3020. These ER results in turn show that the dye is an excellent electron acceptor and a spectral sensitizer Dye suitable for veiled, "direct-positive emulsions.

In the manner described, the dyes No. 7, 9 and 10 tested.

The results obtained in Examples 1 to 3 are summarized in Table I below:

0098 20/1556

Color fabric TABLE I. Judge minv expo
ned
Districts ■ - '■■ ■ "Sen ^ ÜQÜü" - concentrated
tion in g /
MoI
silver max. not- _;
exposed
Districts 0.02 .si ^ ir4n ^ # -
raaximum
ttH 0.70 ReI. Emp
sensitive
speed 1.38 0.03 650 Color
StOif f
No. 0.90 3630 1.70 0.106 U6O 1 0.70 3800 1.46 0.02 575 2 0.70 3020 1.26 0.04 565 5 0.60 3310 1.50 0.01 575 7th 0.70 3310 1.59 540 9 Comparison 0.00 2630 1.90 no turnaround time 10 <1

Example 4

To 1 mole of a gelatin-silver chloride emulsion made from 100 g of silver nitrate, 0.029 g of Dye No. 1 was added. The emulsion was then applied to a non-glossy paper support applied and flashed with white light so that a density of 1.2 was obtained when the recording material was developed in a developer which was prepared from 1 part by weight of the following concentrate:

N-methyl-p-aminophenol sulfate

Sodium sulfite (dehydrated) Hydroquinone Sodium carbonate (dehydrated) Potassium bromide Topped up with water

»With 2 parts by weight ·» water.

3.1 g 45 g 12 g 67.5 g MV- "1.0 liter

The YdA Liebt · Aufieichnungsmate HmI veiled by the action was then exposed in an imagewise manner, with the exposure

# 09120/1556

ORiGJNM. INSPECTED

226

a üKIiehen iUxMß ^ a ^ Eitpm was used, has by a

rfte * IfS ggeäiiasteKrt tfisräe ,. Ffis was excellent ^ uailüit ^ t fiefhEailiten ,. _s

cäann i «ErlKail * en _Jf if

^! üie? ra «bRS * iel £ ie. 'Nr, ^ ^ ₁ , ^,; &,» 7 _{; f} ^

P 1 Mot! my B »tatine-Si: lbje ^ rcitliQri ^ imt ^^ was to 40 ° C

wtmt, where each pH was _{adjusted to 7 r} 6. Can we * the 14 ml of a 40 * formaldehyde solution added, whereupon the. Was erwänt Enulsion again for 10 minutes at 40 ⁰ C. The pH was then adjusted to 6.0 and 0.21 g of Dye No. 5 was added. The emulsion was then applied to a layer support, whereupon the recording material obtained, as described in Example 4, was exposed and developed.

Direct positive images of excellent quality were obtained.

™ Correspondingly favorable results were obtained when

instead of dye no. 5, dyes no. I ₉ 4, 6, 8, 11 and 12 were used. ,

0 (19820/1556 _{ORIQ1NAL INSPECTED}

Claims (11)

PATENT CLAIMS (χ) Direct-positive photographic recording material, consisting of a layer support and at least one direct-positive photographic silver halide emulsion layer containing a cyanine dye, characterized in that the silver halide emulsion layer contains a cyanine dye of the following structural formulas: f} - T * L - C «C - N - R - X ^e OR E D or (I * g-1 5 OR J where mean: R is an optionally substituted alkyl radical; R _{3 is} an optionally substituted alkyl, alkenyl, aryl or alkoxy radical; D and R, each a hydrogen atom or an optionally substituted alkyl or aryl radical; & O9820 / 1556 Q ₂ the atoms required to complete an indolyl radical; Q ₃ and Q- the atoms required to complete heterocyclic desensitizing rings with 5 or 6 ring atoms; E and J each represent an optionally substituted aryl radical; L is an optionally substituted methine radical; X is an acid anion customary for cyanine dyes; g "1 or 2; m «1, 2 or 3 and η «1,2,3 or 4. 2. Direct-positive photographic recording material according to claim 1, characterized in that the silver halide emulsion layer contains a cyanine dye of the formula I, in which Q- is used to complete a desensitizing acting 2-aryl indole ring represents the required atoms. 3. Direct-positive photographic recording material according to claim 1, characterized in that the silver halide emulsion layer contains a cyanine dye of the formulas given, in which Q- and Q "are used to complete
represented by at least one nitro radical substituted, desensitizing rings required atoms. 4 »Direct-positive photographic recording material according to Claim 1, characterized in that the silver halide emulsion layer a cyanine dye one of the specified 009 8 20/15 56 Contains formulas, in which Q, and Q- represent the atoms which for Completion of one of the following, desensitizing, optionally substituted rings are required, namely one: Nitrobenzothiazole, Nitrobenzoxazole, Nitrobenzoselenazole, Imidazo / ~ 4,5-b_7quinoxaline-, 3,3-dialkyl-3H-pyrrolo / ~ 2,3-b_7pyridin-, S ^ -dialkyl-SH-nitroindole- or Thiazolo ^ 4,5-b_7quinoline ring. 5. Direct-positive photographic recording material after Claims 3 and 4, characterized in that the silver halide emulsion layer contains a cyanine dye of one of the formulas given, wherein Q, or. Q- represent the atoms required to complete a 5-nitro-2-phenylindole ring or a 6-nitrobenzothiazole ring. 6. Direct-positive photographic recording material according to claims 1 to 5, characterized in that the silver halide emulsion layer contains as cyanine dye: 1,1'-diiaethoxy ^^ wiphenyl-SjS'-indolocarbocyiiiinperchlorat; 1-methoxy-1 ^f -methyl-2,2 ·, 10-triphenyl-S ^ '- indolocarbocyanine perchlorate; 3 ¹ -ethyl-1-methoxy-6 ¹ -nitro-Z-phenyl-S-indolothiacarbocyanine-p-toluenesulfonate; 1,3-diallyl-l'-raethoxy-2 ^l -phenylimidazo ^ "4,5-b _ji> 7-quinoxalino-3 ^l -'indolocarbocyanine perchlorate; l ^l -methoxy-l _> 3,3-trieethyl-5-nitro-2 ^! -phenylindo-3 ^f -indolocarbocynine perchlorate or 1-methoxy-l ¹ , 3 ', 3 ^f -tri- «ethyl-2-phenyl-3-indolo-2 ^l -pyrrolo ^" 2,3-b _{i <p} 7pyridocarbocyanine perchlorate . 009820/1556 7. Direct-positive photographic recording material after Claims 1 to 6, characterized in that the silver halide grains of the silver halide emulsion layer are fogged. 8. Direct-positive photographic recording material according to claim 7, characterized in that the silver halide grains of the silver halide emulsion layer are obscured by a reducing agent and a gold compound. 9. Direct-positive photographic recording material according to Claims 1 to 8, characterized in that the silver halide emulsion layer contains a color coupler. 10. Direct-positive photographic recording material according to Claims 1 to 9, characterized in that the silver halide emulsion layer Contains monodispersed regular silver shark ogenid grains. 11. Direct-positive photographic recording material according to claims i to 10, characterized in that at least 95 weight I de? Silver halide grains of the silver halide emulsion layer have a grain diameter that does not deviate by more than 40 l from the mean cone diameter. 009820/1558