DE2135153A1 - SPECTRAL SENSITIVENESS DIRECT POSITIVE EMULSION - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN ,, ,"·"

Spectrally sensitized direct positive emulsion

The invention relates to photographic halide emulsions produced by means of polymethine sensitizers containing an Iaoindolinone ring, are spectrally sensitized.

Purely the sensitization of common negative silver halide emulsions are numerous sensitizing dyes, e.g. mono- or trimethine cyanines, merocyanines or rhodacyanines known.

However, the known sensitizing dyes do not work mostly not for sensitizing direct positive emulsions, i.e. such emulsions that are produced after normal exposure and development to be processed into positive images, since they generally flatten the gradation cause. On the other hand, compounds have already been described that are only used as sensitizing dyes for direct positive emulsions e are useful. In the case of negative emulsions, these compounds cause obscuration, and theirs Sensitization effect is unsatisfactory. As a sensitizing dye For example, indooyanines have been used for direct positive emulsions, which provide a very favorable sensitization for the red spectral range, but their effectiveness is not yet entirely satisfactory. The same applies to the one in the German patent specification 1 153 246 described direct positive sensitizing dyes for the green spectral range as well as for those in 0 S

AG 844 - 1 -

209884/1135

1 522 415 mentioned bisthiazolyl bsw. Selenazolyl compounds.

The invention is based on the object of developing sensitizing dyes for direct positive emulsions which are sufficiently intense with regard to their sensitizing effect and which do not adversely affect the gradation.

We have now found a photographic material having at least one direct positive silver halide exnulsion layer which passes through. Polymethine sensitizers which contain an isoindolenone ring are spectrally sensitized.

Sensitizers of the following formula can preferably be used:

.Q-

0 == < _N > CH-CH = CH-Ö C = OH-

in which mean

R ^{1 is} a saturated or unsaturated aliphatic group with preferably up to 6 carbon atoms which substitutes

A-G 844 - 2 -

209884/1135

may be, for example with phenyl, hydroxy or halogen such as chlorine or bromine or aryl, preferably phenyl, the may also be substituted, e.g. with alkyl or alkoxy with preferably up to 3 carbon atoms or halogen like fluorine, chlorine or bromine

2
R. Hydrogen or halogen such as chlorine, bromine or iodine

R ^ 1) a saturated or unsaturated aliphatic ^ group with preferably up to 6 carbon atoms, which can be substituted, for example with phenyl, hydroxy or halogen such as Fluorine, chlorine or bromine, carboxyl, esterified carboxyl, carbamoyl, sulfo or esterified sulfo

2) Cycloalkyl such as cyclohexyl or

3) Aryl, in particular phenyl, which can optionally be substituted

η 0 or 1

X ^ any anion, e.g. halide, such as chloride, Bromide or iodide, perchlorate, sulfate, methyl sulfate, p-toluenesulfonate and the like;

Q the completion of a 5- or 6-limb heterocyclic ring required ring members; the heterocyclic group may be a fused one Contain benzene or naphthalene ring and other substituents; those in cyanine chemistry come into question common heterocycles such as those of the thiazole series (e.g. thiazole, 4-methylthiazole, 5 = methylthiazole, 4,5-bimethylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4,5-diphenylthiazole etc.), those of the benzothiazole series (e.g. Benz-

A-G 844 - 3 -

209884/1135

thiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzthiazole, 7-chlorobenzthiazole, 6-bromobenzthiazole, 5-iodobenzthiazole, 6-iodobenzothiazole, 4-methylbenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole, 5-methylbenzthiazole, phenylbenzthiazole, 5-phenylbenzthiazole, 6-phenylbenzthiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-Äthoxybenzthiazol, 6-Äthoxybenzthiazol, 5,6-Dimethoxybenzthiazol, 5,6-Methylendioxybenzthiazol, 5-diethylaminobenzothiazole, 6-diethylaminobenzothiazole, 6-nitro-benzothiazole, 5-0arboxybenzthiazole, 5-sulfobenzothiazole, 6-cyano-benzothiazole, 5-trifluoromethyl, 5-benzoylbenzthiazole / tetrahydrobenzothiazole / etc. -2-d7thiazole, naphtho / 2, Td / thiazole, 7-methoxynaphto / 2,1-d / thiazole, 8-methoxynaphto / T, 2-6J thiazole etc.) »those of the selenazole series (e.g. 4-methylselenazole or 4- Phenylselenazole) those of the benzoselenazole series (e.g. Ben zoselenazole, 5-chlorobenzoselenazole, Siö-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-methoxybenzoselenazole, tetrahydrobenzoselenazole etc.), those of the naphtoselenazole series (e.g. B. naphto ./Ϊ,2-d/ selenazole or naphtoen / 2,1- ), those of the oxazole series (e.g. oxazole, 4-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, etc.), those of the benzoxazole series (e.g. benzoxazole, 5-chlorobenzoxazole, 6-chlorobenzoxazole, 5,6-dimethylbenzoxazole, 5 -Phenylbenzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-dialkylaminobenzoxazole, 5-carboxybenzoxazole, such Naphthoxazole series (e.g. Naphto ^, 2-d / oxazole, Naphto / 2,1-d / oxazole

A-G 844 - 4 -

209884/1135

or Haphtho / 2,3-d7 oxazole), those of the 3,3-dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3 »3,5-trimethylindolenine, 3,3-dimethyl-5-methoxyindolenine, etc.) those of the 2- Pyridine series (e.g. pyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-methylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,6-dimethylpyridine, 4,5-dimethylpyridine, 4,6-dimethylpyridine , 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 3-hydroxypyridine, 4-hydroxypyridine, 5-hydroxypyridine, 3-phenylpyridine, 4-phenylpyridine, 6-phenylpyridine, etc.), those of the 4-pyridine series (e.g. 2-methylpyridine , 3-methylpyridine, 2,3-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 2-hydroxypyridine, 3-hydroxypyridine, etc.), those of the 2-quinoline series (e.g. quinoline , 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, S-oxo-S.öjTfS-tetrahydro -quinoline, etc.), such of the 4-quinoline series (e.g. ohinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), those of the isoquinoline series (e.g. isoquinoline or 3,4-dihydroisoquinoline), those of the thiazoline series (e.g. thiazoline, 4-methylthiazoline, etc.) Oxazakn also those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine, pyrimidone or thiqpyrimidone series. The aryl groups and heterocyclic groups can be further substituted in any way, for example by further alkyl groups with, preferably up to 3 O atoms, such as methyl or ethyl, halogen such as chlorine or bromine, hydroxyl, alkoxy with preferably up to 3 carbon atoms such as Methoxy or ethoxy, hydroxyalkyl,

AG 844 - 5 -

209884/1135

Alkylthio, aryl such as phenyl or aralkyl such as benzyl, amino, substituted amino, nitro and the like.

The following compounds, for example, are suitable. Unless otherwise stated, the absorption maxima are in methanolic solution measured. In the following table ACOH mean glacial acetic acid and DMSO dimethyl sulfoxide.

link

Abs.max. Sens.max, (mn) (nra)

C ₂ H ₅

458

555

490

585

481

575

A-g 844

- 6 209884/1135

link

Abs.max. Sens.max. (nm) (mn)

_r ) = CH-CH-CH ^ (~ ^ C ₂ H ₅

NO

C ₂ H ₅ SO ₄ 472
(ACOH)

565

^ S w ^ CH, 0 < _N > = CH-GH = CH - <^ I

CH,

431

510

449 545

CH

ClO,

450 545

-G 844

209884/1135

A-G 84-4

Connection Abs.max.
(nm).

Sens.max. (nm)

8 O = (JJ) = CH-CH = GH- / "'

GH 466

603

-GH, 0

GH, GlO, 470
(ACOH)

550

CH 545 (acetone)

ClO,

CH-CH = CH

CH

GlO, 58Q (acetone)

209884/1135

link

Abs.max.
(nm)

Sens.max. (nm)

.CH,

CE

NOr

ClO,

483
(Acetone)

570

OCH

4-90

580

CH, CH

3 OCH,

CH,

OCH,

474

570

468 550

A-Q 844

2Ü9884 / 1135

link

AO

2135153 From 3rd max. Sens.max. (nm) (nm)

⁶ O = W> = OH-CH = CH

Y \ - / J

460 550

17 0 <"> = CH-CH = CH

454 550

C ₂ H ₅

Cl

01 Cl
-VJ- C

= CH-CH = CH - ^ _ | I.

C ₂ H ₅ J β

-S 844

- 10 -

462 560

463
(DMSO)

540

209884/1135

Connection Paragraph max. Sens.max. (nm) (nm)

CH-GH = CH

CH.

OCH

ClO,

CH-CH = CH

J r

ClO,

480
(Acetone)

481 (ACOH)

550

570

Cl Cl '

464 (DMSO)

545

470

560

-G

- 11 -

209884/1135

Link

24

CH-CH = CH- (

J)

Cl

Abs.max.
(nm)

Sens.max. (nm)

(Acetone)

565

25th

^H 2

ClO,

425

495

³ ^ -CI

CH,

NO, 419

490

CH, 437

520

J Q

A-G

- 12 209884/1135

link

Abs.max. Sens.max. (nm) (mn)

CH-CH = CH-Qj

434

520

29 0 < _w > CH-CH = CH- <'

G ₂ H ₅

457

555

H ₃ C CH ₃

CH-CH = CH

OCH,

CH,

483

580

³¹ 0 < _N > = CH-CH = CH

A-G 844

448
(Acetone)

ClO ₄

- 13

209884/1135

540

link

Abs.max. (rim)

Sens.max. (nm)

459 550 (acetone)

OCH,

486

580

The preparation of the dyes by condensation of N-substituted 3-formylmethyleneisoindolinones with 2-methyl quaternary salts of heterocyclic nitrogen bases is described by H.-R. Müller and M. Seefelder in Liebigs Ann. Chem. 728: 88-98 (1969).

In the case of normal negative emulsions, those according to the invention show Dyes to be used wisely usually do not sensitize, but actually reduce the overall

A-G 844

- 14 -

209884/1135

sensitivity and intensify the unwanted gray haze. In contrast, these dyes work in direct reversal emulsions a spectral sensitization of particularly high sensitivity and of excellent steepness of the Gradation.

Even in the presence of water-soluble or emulsified color components this good awareness remains. The usual wetting agents, Hardeners, stabilizers, whiteners and other additives may be present.

The dyes of this constitution have the further advantage of producing less colored layers, so that they can also be used advantageously with paper emulsions.

The production of direct positive emulsions that can be sensitized with the dyes according to the invention, is, inter alia, in German patents 606 392 and 642 222 or in British patents 581 773 or 655 009. The emulsions can also advantageously be added by adding a reducing agent Compound, for example stannous chloride, and a metal that is more electropositive than silver, for example a gold salt such as potassium chloroaurate as described in British Patent 723 019.

The emulsions can also contain mercury or thallium salts as described in German patent specification (P 16 22 256.3) are described. The sensitizers are added to the direct positive emulsions in the same way as with negative emulsions, preferably just before the

AG 844 - 15 -

209884/1135

Pouring from alcoholic or aqueous solution. In general, amounts are between 5 and 200, preferably 20 and 70 mg per kg emulsion is suitable.

example

45 mg of the sensitizer 3 are used as a 1: 1000 solution in methanol to 1 kg of a direct positive emulsion created by chemical obscuration by means of ammonia and excess silver nitrate and the per kilogram of casting solution 0.4 mol Silver halide with an iodine content of 2.5 mol percent, based on silver, was added with stirring and 10 minutes further digested. Then 10 ml of a 4% aqueous solution of saponin as a wetting agent and 25 ml of a 5% Solution of mucochloric acid added. Then it is cast in the usual way on a layer support made of cellulose acetate.

The dried layer is exposed in a sensitometer with white light and developed for 5 minutes at 20 ⁰ C MIDER following composition:

Light exposed and 5 minutes at 20 ⁰ C with a developer

p-methylaminophenol 3.5 g

Sodium sulfate anhydrous 60 g

Hydroquinone 9 r

Sodium carbonate anhydrous 40 g

Make up to 1 liter of potassium bromide 3.5 g with water

finally it is fixed in the usual way. A positive image of the step wedge is obtained with excellent whites and excellent gradation. The spectral sensitization curve is shown in FIG. Figure 1 shows the

A-G 844 - 16 -

9884/1135

likelihood curve without sensitizer for comparison again.

If the sensitizer 3 is replaced by the same amount of the compound 8, those in FIG. 3 and correspondingly are obtained with compound 9 the sensitization curve shown in FIG. The sensitization curve of FIG. 5 is obtained at same processing with connection 17.

AG 844 - 17 -

2Ü9884 / 1135

Claims (4)

Claims . Direct positive photographic light sensitive material with at least one spectrally sensitized silver halide emulsion layer, characterized in that in the layer a polymethine sensitizer with an isoindolinone ring is included. 2. Photographic material according to claim 1, characterized in that that the sensitizer corresponds to the following formula: R ² Q = / ^ = CH-CH = CH-C C = CH-CH) _n = NI w as R ¹ in which mean R is a saturated or unsaturated aliphatic group or aryl, preferably phenyl or substituted phenyl, R hydrogen or halogen R ^ 1) a saturated or unsaturated aliphatic group, 2) cycloalkyl or 3) aralkyl or 4) aryl η 0 or 1 X is any anion Q the completion of a 5- or 6-limb heterocyclic ring required ring members. AG 844 - "18 - 2U9884 / 1135