DE1522421A1 - Optically sensitized photosensitive material - Google Patents

Description

PATENT DEPARTMENT LEVERKUSEN

Dec 12, 1968

Optically sensitized photosensitive material

The invention relates to light-sensitive layers, in particular silver halide emulsion layers, which are spectrally sensitized by means of a novel sensitizing dye β.

Increasing the sensitivity of light-sensitive layers, in particular silver halide emulsion layers Addition of sound substances that expand the spectral sensitivity range of light-sensitive substances has been around since known for a long time. Numerous substances have been described for the sensitization of silver halide emulsion layers which essentially belong to the class of cyanine dyes. However, these known substances often have disadvantages, the z. B. consist in the fact that their sensitization effect is unsatisfactory that they give the layer an annoying coloration lend or that they the photographic process in itself adversely affect. This is especially true for special

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zielle photograph! real process or special photographic materials. DIT adsorption aa silver ■ oll to strong, "tin, daf dlt Sensibllisierungswirkung" ög * liehet vtnig by andtrt necessary accessories wit Vetzmittel and emulsifiers, stabilizers, color couplers, aushleichbart farbstofft _v Wtißtöntr is so disturbed. Bit sensitization must also be guaranteed under extreme conditions, with increased temperature and fatigue. The sensitization dyes can also cause susceptibility to strengthen the door handle, so that basic cyanine dyes are the case. Sound dtn Stnsibillsitrungsfarbstofftn be further btstimmtt Stnsibllisierungstigtnschafttn _t desired wherein in addition to a Auer-calibrating Sensibilisisrungsinttnsität especially sin Beglichst sttiltr waste dts Sensibilisitrungsbtrtichts be mentioned. For the reasons mentioned, there is considerable interest in discovering new sensitizing dyes that do not affect the stated disadvantages.

The invention is based on the object of finding sensitizing dyes for the sensitization of light-sensitive layers, in particular silver halide emulsion layers, which do not have the disadvantages cited above.

It has now been found that light-sensitive materials, especially silver halide, are excellent in the density

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§AD ORIGINAL

with cyanine dyes !! can be spectrally sensitized, which are characterized by a four-membered ring within the methine chain derived from squaric acid.

Sensitizing dyes have proven to be particularly suitable proved by the following formula:

R «Ο" R «

ψ R jL R

ψ R

C-C =

left
C JBr- 6-C

what mean?

Z si the non-metallic ring members to complete a 5- or 6-membered heterocyclic ring which can contain a fused benzene or naphthalene ring; Z includes the heterocycles customary in cyanine chemistry, such as those of the benzothiazole series

(e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, " 6-chlorobenzothiazole ,. 7-chlorobenzothiazole, »4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 6-bromobenzothiazole ,. 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzene Mazolj 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-xthoxybenzothiazole, Tetrahydrobenzothiazole, 5,6-dimethoxybenaothiazOl, 5-, 6-methyl-endioxybenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiaacl, etc.) »those of the naphthothiazole series (e.g. ok-

90β "β3Γ / 1138

. V522421

Naphthothiazole ß-Haphthothiazole, 5-methoxy-ß-naphthothiazole 5-Xthoxy-ß-naphthothiazole, 7-ethoxy-ßif.naphthothiazole, 8-methoxy- <& - naphthothiazole, etc.) »those of the selenazole series (e.g. 4-methylselenazole, 4-phenylselenazole, etc.), such the benzoselenazole series (e.g. benzoselenazole, 5-chlorobenzene ■ elenazole, 5-methoxybenzoeelenazole, 5-hydroxybenzoselenazole, Tetrahydrobenzoielenazole, etc.), those of the naphthoeelenazole series (e.g. ß-iaphthoselenazole, β-haphthoselenazole, etc.), those of the thiazoline series (e.g. thiazoline, 4-methylthiazoline, etc.), those of the 2-quinoline series (e.g. quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-xthoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), those of the 4-quinoline series (e.g. quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), those of the 3 »3-rialkylindolenine series, (e.g. 3,3-dimethylindolenine, etc.), those of the 2-pyridine series (e.g. Pyridine, 3-methylpyridine, 4-methylpyridine, 4-methylpyridine, 5-methylpyridine, 3 »4-dimethylpyridine, 3,5-dimethylpyridine, 3,6-dimethylpyridine, 4,5-dimethylpyridine, 4-chloropyridine, 5-chloropyridine. 6-chloropyridine, 3-hydroxypyridine, 4-hydroxypyridine, · 5-hydroxypyridine, 4-phenylpyridine, 6-phenylpyridine, etc.), those of the 4-pyridine series (e.g. 2-methylpyridine, 3-methylpyridine, 2-chloropyridine, 3-chloropyridine, 2,3-dimethylpyridine, 2-hydroxypyridine, 3-hydroxypyridine, etc.), those of the TMadiazole, imidazole or benzimidazole or those of the pyrimidine or pyrroline series;

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R = Waeeeretoff, alkyl with preferably up to 6 carbon atoms;

R '»an alkyl group or an olefinically unsaturated aliphatic group with preferably up to 5 carbon atoms, e.g. B. methyl _t ethyl, allyl, which can be substituted with halogen such as chlorine, hydroxyl, alkoxy, carbonamides, acidic groups such as sulfo, phosphoric acid or carboxyl, ζ. B. ■ μ »-Sulfopropyl, as -sulfobutyl, u9-eulfoäthjl, uö * -carboxypropyl, ms -carboxybutyl, ufl -carboxyätyl, 2-chloro-3-sulfopropyl, 2-hydroxy-3-sulfopropyl and the like, also Cycloalkyl such as cyclohexyl, aralkyl such as benryl or phenylethyl, or aryl such as phenyl. _RH

χ s -S-, -Se- or the groupings -N- or -C (R) _-

R "= hydrogen, alkyl or alkenyl with preferably up to eu 5 carbon atoms, cycloalkyl or aryl, in particular phenyl.

The sensitizing dyes t to be used in the manner according to the invention are chemically as pentamethine cyanine betaine to grasp. They are beneficial in several ways. In particular against the well-known pentamethine cyanine dyes show the dyes according to the invention - in particular di · der Benzthiazole and benzeelenazole series - due to the higher symmetry

and those reinforced by the oxygen-substituted four-membered ring Resonance stabilization spectrally very narrow sensitization ranges, which in contrast to normal Pentamethincyaninen by are characterized by a rapid decrease in sensitivity towards the short-wave side. This property makes the dye

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especially «valuable for color photographic materials where it depends on the separation of the color sensitivity of the layers as well as possible.

This is especially true for the long-wave red seneiblUtLerenÄea Benzselenazole series dyes. Another advantage of the dyes according to the invention over normal fentamethines is that excellent heat stability of the emulsions sensitized with it, i.e. the sensitivity of the emulsion is constant on exposure between room temperature and higher temperature (e.g. 50 °). the Materials sensitized with the new dyes are resistant to emulsion additives such as hardeners, stabilizers, Color coupler etc.

For example, dyes of the following form are suitable Dye I:

B ^ \ X

0 Mp 289-291 with decomposition, absorption maximum 647 mn

Dye II:

9098

Mp 307-309 ° with decomposition, absorption maximum 665 nm A-O 200 - 6 -

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152242

Dye III: Pp 328-332 ° with decomposition, absorption maximum 657 nm

dye

Mp> 360 ι absorption maximum 690 nm Dye V: Mp- ^ 360 ⁰ , absorption maximum 677 nm

OCH ₄

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Dye TIt Mp- ^ 360, absorption maximum 670 Dye till

- OCH,

Melting point 310-515 ° below the step, abaorptionesaxlBUB

dye TIIIt

M.p. 360, absorption maximum 672

CH,

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dye Ht

152242

Pp-7-321-323, Absorption Maacimuin 652

dye Is

Pp 307-310 ° with decomposition, absorption maxiiauiB

Dye XI:

Pp? -311-3H , absorption maximum 670

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Dye XXIi

OCH,

CR - v

Mp 249-254 with decomposition, absorption maximum 662 Dye XIIIi Fp> 360 t absorption maximum HVι dye

9oH _K PC-)

,H,

Mp * 560, absorption maximum

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Dye IVt

X — jCH,

Mp 518-320 ° with decomposition, absorption maximum 652 na FarbetoffXTlL

CH ₂ CH ₂ COOH ^^

CH ₂ CH ₂ COOH

V-CIL =:

Fp-? 360 °, absorption maximum 665 nm

dye

CH ₂ CH ₂ COOH

CH ₀ CH ₉ COOI

Mp 286-294 ° with decomposition, absorption maximum 670 na

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Dye XTIIIt

CHSCE ₉ COOE 2

CB ₀ CH ₀ COOB, 2 2

Fp7 560 γ absorption aximua 680 not Dye III »

CH ₂ CH ₂ COOH

CH ₂ CH ₂ COOH

Mp 282-290 tinttr shattering, absorption iiaxiBi at 675 nm Dye XXi

CH ₂ CH ₂ COOH

H ₂ CH ₂ COOH

-OC

Mp 289-295 anttr decomposition, absorption maximum 665 nm

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Dye ΣΧΙ;

CH ₂ CH ₂ COOH

CH ₂ CH ₂ COOH

Pp 292-299 with decomposition, absorption maximum 655 ma

Dye IXIIs

(CH ₂ )

LoH = XV ^ h =

Pp 244-246 ° with decomposition, absorption maximum 650 nm A-G 200

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Dye IXIII ι Mp 242-246 with decomposition, absorption maximum 665 nm Color XIIYt Mp 316-317 with decomposition, absorption maxima 620 nm Dye XXV: Mp 326-328 ° with decomposition, absorption maximum 700 mn

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Dye XIVI;

approx.

Pp 279-281 ° with decomposition, maximum absorption 650 nm

The new dyes are generally prepared by condensation of heterocyclic dyes customary in cyanine chemistry 2-methyl quaternary salts or 2-methylene bases with squaric acid or Squaric acid derivatives - such as. B. squaric acid mono- or dialkyl esters optionally in solvents such as. B. butanol, hexanol Cyclohexanol in the presence of an organic base such as pyridine. In cases of particularly poorly soluble quaternary salts can also nor a solvent of the same such as phenol or m-cresol be admitted. The manufacture of the square door is described in Angew. Chemie 78 (1966), 927.

Dye Is

5.3 g of 2,3-dimethylbenzthiazolium p-toluenesulfonate are added with 0.57 g Squaric acid in 100ml n-butanol with the addition of 3ml pyridine 3 hours cooked, during which the dye separates out Washed alcohol and recrystallized from pyridine. Yield 1g, mp 289-291 ° (decomposition)

Dye X;

3.3 g of 2-methyl-3-ethyl-5-mβthoxyben ^ βelenazolium-p-toluenesulfonate are heated to boiling with 0.44 g of squaric acid in 50 ml of butanol. After adding 3 ml of pyridine, the mixture is boiled for 30 minutes, the Dye crystallized out. Green needles with yellow ones are obtained

Metallic luster. Fp 307-3 ^^? Ärs ^/ eWulf) Yield 0.6 g

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3.5g of 2, S-Dimethyl ^ -äthylbeiusselenazolium-p-toluenesulfonate be Boiled for 1 hour with 0.49 g of squaric acid in 50 ml of n-butanol with the addition of 3 ml of pyridine. The pure dye that is deposited will Sucked off and washed with methanol. Yield 1g, melting point 311-314 °

Dye XXIIi

0.6 g of squaric acid are dissolved in 50 ml of boiling butane1, with a solution τοη 2.7 £ 2-methyl-3-sulfoprcpylbenzthiazoliumbetain crosslinked in 25 ml of m-cresol and after adding 10 ml of pyridine Boiled for 3 hours «The heat solution is then in a vacuum concentrated and then with 1 ToI. Acetone and 1 volume of ether were added. Of the deposited dye is filtered off, washed with acetone and recrystallized by dissolving in alcohol-H ₂ O and adding acetone.

Yield 1.2 g,? P 244-246 ° (decomposition) Dye XIIVt

T g of 1,3-3-trimethyl-2-methylene indoline are mixed with 2 g of squaric acid boiled in 50 ml of n-butanol for 2 hours. The auekrietalliaierte dye is filtered off with suction and washed with methanol and ether. Yield 4.7 g, mp 316-317 ° (Zereetzmig)

The preparation of photographic silver halide emulsions essentially comprises three steps:

1. Precipitation of the silver halide in the presence of a protective colloid and physical ripening,

2. Removal of the excess water-soluble salts resulting from the precipitation from the emulsion, in general by washing and

3 · di · chemical ripening or post-ripening, which serves to to give the emulsion the desired sensitivity.

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BATH ORIGINAL

The sensitizing dyes according to the invention can can be used in any silver halide emulsions. Ala silver halide are silver chloride, silver bromide or mixtures thereof, possibly with a low content of SiI beriodid up to 10 mol-36 suitable. The silver halides can be dispersed in the usual hydrophilic compounds eein, for example carboxymethyl cellulose, polyvinyl alcohol, Polyvinylpyrrolidone, alginic acid and its salts, esters or amides or * preferably gelatin.

The sensitizing dyes to be used in the present invention are preferably added to the photographic emulsion after chemical ripening and before casting added. The methods used for this are generally known to the average person skilled in the art. The sensitizing fibers are generally in the form of solutions e.g. B. incorporated in alcohol or alcohol / water mixtures of the emulsion. Of course, the solvents must be compatible with gelatin and must not have any adverse effects on the exert photographic properties of the emulsion. Water, Methanol or mixtures thereof are generally used as the solvent used. The amount of sensitizing dye added can vary within wide limits, e.g. B. between 2-200 mg preferably between 10-60 mg per kg of the silver halide emulsion. The concentration of the dye can vary

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Requirements, depending on the type of emulsion, the desired sensitizing effect, etc. can be adjusted. The most suitable concentration for any given emulsion can be determined by those used in photographic practice Tests to be determined without difficulty.

The emulsions can also contain chemical sensitizers, e.g. B. Reducing agents, such as Zlnn-II salts, polyamines, such as diethylenetriamine or sulfur compounds, as in America Niche patent 1,574,944 described. For chemical sensitization, the specified emulsions can also contain salts of noble metals such as ruthenium, rhodium, palladium, iridium, Contains platinum or gold, as described in the article by R. Koslowsky, Z. Wies. Phot. 46, 65-72, (1951). As chemical sensitizers, the emulsions can also be polyalkylene oxides, in particular polyethylene oxide and derivatives thereof contain.

The emulsions according to the invention can contain the usual stabilizers, such as. B. homopolar or e & luurtlg · compounds of mercury with aromatic or heterocyclic compounds Rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts, and other mercury compounds. Also suitable as stabilizers are azaindenes, preferably tetra- or pantaazaindenes, in particular those which are linked with hydroxyl or amino groups are substituted. Such compounds are described in the article by Birr, Z. Wies. Phot. 47, 2-58 (1952)

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described. Other suitable stabilizers include: heterocyclic mercapto compounds, e.g. B. Phenylmercaptotetrazole, quaternary benzothiazole derivatives, benztriaeol and similar.

The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted ones Aldehydes that contain a carboxyl group, such as mucobromic acid, Diketones, methanesulfonic acid esters, dialdehydes and like that.

The emulsions according to the invention can be used for a wide variety of photographic processes. For example, for recording materials, for copy materials, for reprctechnical films, for X-ray films, for materials that are used for

the silver salt diffusion process are suitable for color photographic Materials, for silver dye bleaching processes and others.

The sensitizers to be used in the manner according to the invention are also suitable for spectral sensitization electrophotographic layers, preferably those layers containing photoconductive zinc oxide in an insulating Contains binders distributed.

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Another distinct advantage of the sensitizing dyes according to the invention e lies in the combination with suitable over-sensitizers; the sensitizing effect of the sensitizing dye β can thereby be increased considerably. For this purpose The compounds described in French patent 1,426,623 are particularly suitable.

Example

A highly sensitive gelatin silver bromide emulsion containing ▼ on 3 M © 1 # silver iodide, the blue-green coupler that connects the following formula

W **

and also the usual additives such as saponin as a wetting agent, formaldehyde as a hardener and 2s-mercapto-5-chloro-benzoxazole-7 ~ containing sulfonic acid as a stabilizer is divided into two parts. For sample 1, 10 mg per kg of emulsion dee dye II and added 10 mg per kg of emulsion of the known pentamethine cyanine of the following formula to the sample 2?

I-CH = CH-CH = CH-I

^ S «Then the two emulsion samples are known to catfish

poured onto a paper pad and dried.

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The layers obtained bo are behind a step wedge with the

20 ° and 50 ° as well as exposed behind a red filter. Huh Ullicher development in a color developer and bleach fixation the following relative sensitivities (in steps of the wedge) are obtained.

1 (Dye II) Behind
Red filter at 20 ° at 50 sample 2 22nd H 14th sample 18th 10 12th

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Claims (7)

Claims : JLI l / U, spectrally sensitized light-sensitive material with a content of a cyanine dye as sensitizing dye, which contains two nitrogen-containing heterocycles linked by a methine chain, characterized in that the methine chain is interrupted by a 1-oxy-3-oxo-cyclobutene ring. 2. Spectrally sensitized photosensitive material after Claim 1, characterized in that a silver halide emulsion layer is contained as the photosensitive layer. 3. Spectrally sensitized photosensitive material after claims 1 and 2, characterized by a content of a sensitizer of the following formula: _ A— where mean: Z = the non-metallic ring links to complete a 5- or 6-membered heterocyclic ring, the may contain a fused benzene or napthalln ring; R = hydrogen or alkyl with preferably up to 6 carbon atoms; R ¹ * is an alkyl group or an olefinically unsaturated aliphatic group, cycloalkyl, aralkyl or aryl. AG 200 - 22 - -. 909831/1139 BATHROOM ORIGINAL I = -S-, -Se- or the groupings -N- or -C (R ")« -
R "= hydrogen, alkyl or alkenyl, cycloalkyl or aryl. 4. Spectrally sensitized photosensitive material after Claim 3, characterized in that Z is the completion a benzothiazole length or benzselenazole ring required Ring members mean. 5. Spectrally sensitized photosensitive material according to claims 3 and 4, characterized in that R is hydrogen and R ^{1 is} an alkyl group. 6. Spectrally sensitized photosensitive material after Claim 3, characterized by a content of a sensitizing dye the formula: 7. Spectrally sensitized photosensitive material according to Claim 3, characterized by a content of a sensitizing dye the formula CH ₂ -COOH CH ^ -COOH 909831/1139
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