DE1911330A1 - Spectral sensitizing agenet - Google Patents

Abstract

Red-sensitising of colour photographic emulsion is carried out with cpd. of formula (where R = H, halogen, alkyl, alkoxy, aryl, methylene dioxide or condensed benzene ring, R' = H or methyl, R" = alkyl, Y = S or Se, X - is anion, n is integer 1-5).

Description

Optically sensitized photographic material Pstentalrmessage . . . (r 16 76 029.1) The main application relates to new benzazole compounds, e.g. Benzthiazole, benzselenazole, benzoxazole or quinoline compounds, which by a hydroxyl-containing aliphatic ether groups are substituted and the use of such compounds as spectral sensitizers for photographic silver halide emulsions.

The compounds of the main application are represented by the following formulas A and B, the compounds of the formula B in particular being good optical sensitizers: in which: X = S, Se, O, -CH = CH-; n = 1-100, preferably 1-10, especially 1-5; R = an organic radical, for example alkyl, preferably with up to 3 O atoms, in particular methyl, alkylthio, likewise preferably with up to 3 C atoms, in particular methylthio; RI = an ethyleneoxy or a 1,2-propyleneoxy unit which can be substituted, for example a 3-phenoxy-1,2-propyleneoxy unit; R11 = saturated or unsaturated aliphatic groups with preferably up to 5 carbon atoms, it being possible for the alkyl groups to be substituted, for example, with sulfo, sulfonamide, carboxyl, carbamyl, halogen, such as chlorine or hydroxy; III RIII = an organic radical, preferably a) a monomethine group which carries a heterocyclic group consisting of a 5- or 6-membered heterocyclic ring with nitrogen as a ring member and optionally fused benzene rings, e.g. an oxazole, benzoxazole, naphthoxazole , Thiazoline, thiazole, benzthiazole, naphthiazole, selenazole, benzselenazole, naphthoselenazole, thiadiazole, imidazole, benzimidazole or 2- or 4-quinoline ring; these rings can optionally be further substituted; b) a trimethine chain which is substituted in the meso position by an alkyl radical having 1-3 carbon atoms and which has a terminal heterocyclic group of the definition given under a); c) a renta or heptamethine chain which can be substituted by an alkyl radical with up to 3 carbon atoms and which has a terminal heterocyclic group of the definition given under a); d) a methine chain with 2 or 4 carbon atoms, which terminally bears a cyclic ketomethylene radical customary in cyanine chemistry, preferably a rhodanine, thiohydantoin, thiobarbituric acid or pyrazolone radical, and which is replaced by alkyl or alkoxy radicals with up to 5 carbon atoms Atoms can be substituted; or e) a cyclic ketomethylene radical, such as, for example, a rhodanine, thiohydantoin, thiobarbituric acid or pyrazolone radical.

In the further processing of the subject matter of the main application it has now been found that dyes from the series of isophorone dyes which contain a group according to (Ia) or (Ib), are particularly suitable for sensitizing light-sensitive photographic silver halide emulsions in the long-wave spectral range of light. The isophorone dyes according to the invention correspond to the following general formula (II): where: R = hydrogen, halogen such as chlorine or bromine, alkyl or alkoxy with up to 3 carbon atoms, aryl, a methylenedioxy group, or a fused-on benzene ring, which in turn may be substituted; RI = hydrogen or methyl; RII = alkyl with up to 4 carbon atoms; Y = sulfur or selenium; X0 = any anion such as chloride, bromide, iodide, perchlorate or p-toluenesulfonate; n = an integer from 1 to 5, preferably 1 to 3.

The synthesis of the sensitizing dyes (II) according to the invention takes place according to the following reaction scheme: The intermediate stages (III) are produced according to the process specified in the main patent. The synthesis of compound (V) should be cited here as an example.

For example, 35 g of 2-methylthio-6-hydroxgbenzthiazole, dissolved in 160 cc of dry dioxane, with 45 g of propylene oxide and 1.5 g KOH im Autoclave at 100-110 ° C for 6 hours for reaction.

The reaction product is poured into water and the separated oil is extracted with chloroform. The solvent is evaporated and the residue (approx. 47 g) is distilled in vacuo. Two fractions can be isolated: 1) 0.4 mm 204-228 ° C = (V, n = 2) 2) 0.6 mm 230-240 ° C = (V, n = 3) According to the elemental analysis, these are the compounds (V, n = 2) and (V, n = 3). The compound (V, n = 1) (melting point 720) is formed when only 15 g are used instead of 45 g of propylene oxide.

The bases (V) can easily be quaternized, e.g. with dimethyl sulfate, Diethyl sulfate, methyl iodide, ethyl iodide, methyl p-toluenesulfonate, propane sultone or other quaternizing agents.

The quaternary salts obtained in this way can now be used in a manner known per se with the condensation product (IV) of 2-methyl-3-alkyl-benzazolium salts and isophorone condensed to form the sensitizing dyes (II) according to the invention.

The sensitizing dyes of the present invention can be used in any Silver halide emulsions are used.

The silver halide used is silver chloride, silver bromide or mixtures thereof, possibly with a low content of silver iodide of up to 10 mol% suitable. The silver halides can be dispersed in the usual hydrophilic compounds be, for example in carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, Alginic acid and its salts, esters or amides or preferably in gelatin.

The sensitizing dyes to be used in accordance with the present invention are preferably used in the photographic emulsion after chemical ripening and added before potting. The methods used for this are those of ordinary skill in the art well known. The sensitizing dyes are generally in the form incorporated by solutions of the emulsion. Of course, you need to use the solvent Gelatine must be compatible and must not have any adverse effects on the photographic Exercise properties of the emulsion. The amount of sensitizing dye added can vary within wide limits, e.g.

between 2-200 mg, preferably between 10-60 mg per kg of the silver halide emulsion. The concentration of the paraffin can depending on the particular requirements adapted to the type of emulsion, the desired sensitizing effect, etc. will. The most suitable concentration for any given emulsion can be determined by the tests customary in photographic practice were found without difficulty will.

The emulsions can also contain chemical sensitizers, e.g. Reducing agents, such as tin (II) salts, polyamines, such as diethylenetriamine, or sulfur compounds, as described in US Patent 1,574,344. For chemical sensitization the specified emulsions can also contain salts of noble metals such as ruthenium, Contain rhodium, palladium, iridium, platinum or gold, as in the article by R. Koslowsky, Z.Wiss. Phot., 46, 65-72 (1951).

As chemical sensitizers, the emulsions can also be polyalkylene oxides, in particular contain polyethylene oxide and derivatives thereof.

The emulsions according to the invention can contain the usual stabilizers contain, such as homopolar or salt-like compounds of mercury with aromatic or heterocyclic Rings, like mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Azaindenes, preferably tetra- or pentazaindenes, are also suitable as stabilizers, especially those substituted with hydroxyl or amino groups. Such Compounds are described in the article by Birr, Z.Wiss.Photo., 47, 2-59 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, such as.

Phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and similar.

Die'Emulsionen can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.

Furthermore, those sensitized with the dyes according to the invention can Emulsions contain color couplers, especially those to produce a b; caustic green Partial image.

The synthesis and the spectral properties of the new dyes (II) are to be explained using the following examples: Dye 1 40 g of 2,5-dimethyl-3-ethyl-6-methoxybenzselenazoliuDtosylat and 26 g of isophorone are heated to 150 ° C. for 17 hours. The reaction product is triturated with a lot of water, after the water has been removed, the remaining smear is dissolved in warm methanol, filtered and the filtrate is treated with KI solution. The compound (vi) precipitates out as a brown lower base (25 g, melting point 2130).

In addition, 2.6 g (V, n = 1) are quaternized with 1.5 g of dimethyl sulfate. The resulting salt is mixed with 5 g of (VI) in 50 cc of pyridine and 6 cc of triethylamine Cooked for 15 minutes. After cooling, it is poured into ether, decanted and rubbed viscous residue several times with ether, decanted again and treated the residue with hot methanol. The dye becomes crystalline and can be hot Methanol are recrystallized.

Mp. 242-245 absorption maximum in methanol 670 nm sensitization maximum 720 nm The course of the sensitization is shown by curve 1 in the illustration of dye 2 100 g of 2-methyl-3-ethyl-4,5-benzobenzothiazolium tosylate and 70 g of isophorone are heated to 1600 (bath temperature) for 18 hours.

The work-up is carried out as in Example 1. The yield of intermediate (VII) 0 after recrystallization from alcohol is approx. 20 g mp 193. 2.4 g of this intermediate product and 2.45 g of the quaternary salt from (V, n = 1) are dissolved in 25 cc of pyridine and 2.5 cc of triethylamine and boiled for approx 3 minutes on the reflux condenser. The dye is worked up as in Example 1. 0.3 g of pure dye is obtained.

Fp. 1740, absorption maximum 675 nm, sensitization maximum 725 nm The course of sensitization is shown by curve 2 in the illustration of dye 3 3.1 g of the compound (V, n = 2) are quaternized with 1.3 g of dimethyl sulfate (at 700). The salt thus obtained is heated to 1200 for 15 minutes with 4.7 g of the intermediate product (via) described in Example 2, 40 cc of pyridine and 5 cc of triethylamine.

Allow to cool, pour into ether, decant and grind the semi-solid Residue several times alternating with ether and water. In the end, the residue warmed with ethanol on the steam bath. The paraffin now crystallizes and can be sucked off. It is washed with plenty of ethanol and a mixture of methanol / chloroform recrystallized.

Fp. 1740, absorption maximum 670 nm, sensitization maximum 725 nm The course of sensitization is shown by curve 3 in the illustration of dye 4 9 g of base (V, n = 3) are quaternized with 3.1 g of dimethyl sulfate at 1100. 7.5 g of salt are formed. It is mixed with 7.2 g of compound (VII), 100 cc of pyridine and 7.5 com of triethylamine and refluxed for 15 minutes. The work-up is carried out as in Example 3. The crude dye (2.1 g) is recrystallized twice from methanol / chloroform (2: 1).

Mp. 1640 absorption maximum 670 nin sensitization maximum 730 nm The course of sensitization is shown by curve 4 in the illustration of dye 5 The synthesis of this dye is carried out in a manner similar to the previous dyes from the intermediate and the quaternary salt from (V, n = 1), m.p. 2130 absorption maximum 665 nm sensitization maximum 700 nm.

The sensitization curves 1 to 4 shown in the drawing were obtained as follows: The photographic emulsion used is a highly sensitive silver chlorobromide emulsion with 0.2 mol of halosilver per kg of emulsion, 42 mol% of which is silver bromide, which also contains the usual additives such as 0.35 g of saponin Wetting agent, 3 ml of an aqueous-methanolic solution of N, N ', N "-Trisacryloyl-hexahydro-1,3,5-triazine as hardening agent and 0.3 g 1,3,3a, 7-tetraaza-4- hydroxy-6-methylindene, and 10 g of a blue-green coupler of the following structure The dyes according to the invention are dissolved in methanol or acetone and added in an amount of 10 mg per kg of emulsion.

Claims (2)

Patent claims: 1. Photographic material with at least one silver halide emulsion which contains a spectral sensitizing azole compound with a hydroxyl group-containing mono- or polyether substituent, according to patent application P 16 70 029.1, characterized in that it contains a compound of the following formula as a red sensitizer: in which: R = hydrogen, halogen, alkyl or alkoxy, aryl, a methylenedioxy group or a fused-on benzene ring; RI = hydrogen or methyl; RII - alkyl; Y = sulfur or selenium; = = any anion; n = an integer from 1 to 5. 2. Photographic material according to claim 1, characterized in that that additionally contain a color coupler for generating a cyan partial image is.