DE2041200C3 - Light-sensitive, red-sensitized silver halide emulsion - Google Patents

Description

general formula

-, - Cl = CH-C L =

R ₁ - N (- CH = CH) "

wherein Ri is an alkyl group, substituted alkyl group. Allyl group, aralkyl group, substituted aralkyl group or aryl group, R2 and R3 hydrogen atoms, alkyl groups, substituted alkyl groups, allyl groups. Aralkyl groups, substituted aralkyl groups and aryl groups, Ra a hydrogen atom, an alkyl group or aryl group, Z a non-metallic atom grouping necessary to complete a 5- or 6-membered heterocyclic ring, d the numbers 0.1 or 2 and η the numbers 1 or 2 and at least one further supersensitizing compound of the following general formula _{0 (} j _er

CH = CH-,

SO ₁ M

NHCO

SO ₃ M

Y N

Ro

whereY = CH- or -N-. the radicals Rs, Rt, Rj and Re Hydrogen atoms, hydroxyl groups. Alkoxyl groups. Aryloxyl groups, substituted aryloxyl groups, halogen atoms, heterocyclic nuclei, Alkyhhiognippen. heterocyclic thio groups, arylthio groups. Amino groups, Alkylamino groups, substituted alkylamino groups, arylamino groups, substituted arylamino groups, heterocyclic amino groups or aryl groups and A denotes the radicals Ai indicated below or A2, where at least one of the radicals Rs. Re, R7 and Rg contain a -SCbM group when A corresponds to one of the radicals mentioned under A2 and Ai

^ A

or "R

CH = CH

SO, M

SO ₃ M

means

In addition, the silver halide emulsion of the present invention can at least one compound of the following general formula

SO ₃ M

55

60

contain, in which IR9 is an acylaminoggroup of the sulfo group, R ^ a emeÄcy1aimhogfuppe ^ ina <Ri1 ¹ ^ Hi hydrogen atom ^

Hydrogen oäem ljpp tmean.

where the connection is at least> i «rie3Sdlfogrtippe

ΖΌ 41 200

In the above general formula I the radicals Ri, R2 and R3 consist of the sensitizing dye preferably

15th

Methyl, ethyl, propyl, /? - hydroxyaryl, 0-acetoxyethyl, sulfatoethyl, carboxymethyl, / f-carboxyethyl, y-carboxypropyl, 0-sulfoethyl, y-sulfopropyl, 6-sulfobutyl , Vinylmethyl, benzyl, phenethyl, p-carboxybenzyl, p-sulfophenathyl or phenyl groups, and the heterocyclic ring containing the radical Z composed of thiazoles such as thiazole itself, and thiazoles with methyl or phenyl groups in the ring, benzothiazoles such as benzothiazole themselves, and benzothiazoles with ring substituents, such as halogen atoms, alkyl, alkoxy or phenyl groups in the benzene ring, naphthothiazoles, such as «naphthothiazole, / 3-naphthothiazole, tetrahydronaphthothiazole, and naphthothiazoles with ring substituents, such as, for example, alkoxy groups in any benzene ring , such as alkyl and phenyl groups in the ring, benzoxazoles such as benzoxazole itself and benzoxazoles with ring substituents such as halogen atoms, methyl, ethyl, ethoxy, hydroxyl and phenyl groups in the benzene ring, naphthoxazoles such as «-naphtho xazole and ^ -naphthoxazole, selenazoles such as 4-methylseienazole and 4-phenylselenazole, benzoselenazoles such as 5-chlorobenzoselenazole. 5-methylbenzoselenazole,
5-methoxybenzoselenazole, and

5-HydroxybenzoseienazoI.Naphthoselenazoles such as Λ-naphthoselenazole and 0-naphthoselenazole, thiazolines such as thiazoline itself, and 4-methylthiazoiis 2-quinolines such as 2-quinoline itself, and 2-quinolines with ring substituents except in the 2-position, such as halogen atoms. Methyl, methoxy and hydroxyl groups in the benzene rings, 4-quinolines, such as 4-quinoline itself, and 4-quinolines with ring substituents except in the 4-position, such as methyl or methoxy groups in the benzene rings, benzimidazoles, such as 13-diethylbenzimidazoI,
1 ^ -Diäthyl-S-chlorobenzimidazole and ^ -Diäthyl-S.ö-dichlorobenzimidazole, 33'-DialkylindoIenines like
3,3'-dimethylindolenine, 3,3 ', 5-triethylindolenine and 3,3', 7-trimethylindolenine, 2-pyridines. such as 2-pyridine itself, and 2-pyridines with ring substituents, except in the 2-position, such as methyl groups, and 4-pyridines such as 4-pyridine itself

The sensitizing dye represented by the general formula (I) is a dye having four hetero groups with two ketomethylene groups directly bonded, by which silver halide emulsions can be sensitized with the coexistence of a dye used in the silver dye bleaching process. Since these dyes per g-mol of silver have a far greater sensitivity even in the case of adding a small amount of the dye compared to the usual basic iganinfarbstoffen that these dyes sithaltenden pnotographischen layers are free from a _"s iestfäibungnäch'der! Treatment. -

3ESe sopersehsajilizing connection of the presenting given general formula Π contains

35

40

45 as a substituted aryloxy group a phenoxyl, o-toloxyl or p-sulfophenoxyl group as " Halogen atom, a chlorine or bromine atom as a heterocyclic nucleus, a morpholinyl or Piperidyl group as an alkylthio group, a methylthio or ethylthio group as heterocyclic thio group, a benzothiazylthio group, as substituted Alkylamino, a methylamino, ethylamino, propylamino, dimethylamine, Diethylamino, dodecylamino, cyclohexylamine, / J-Hydroxyäthylamino-, Di / Miydroxyathylamino- or JJ-sulfoithylamino group, as substituted Arylamino group an o-sulfoanilino, m-sulfoanilino, p-sulfoanilino, o-anisylamino, m-anisylamino, p-anisylamino, o-toluidino, m-toluidino, p-toluidino, o-carboxyanilino, m-carboxyanilino-.p-carboxyanilino-, hydroxyanilino-, naphthylamine- or Sulfonaphthylamino group, as heterocyclic amino group a 2-benzothiazolamino or 2-pyridylamino group.

In the general formula HI given above, the acylamino group preferably consists of one

Acetamide, sulfobenzamide,
♦ -Methoxy-S-sulfobenzamide - ^ - ethoxybenzamide, 2,4-diethoxybenzamide. p-Toluylamino, 4-methyl-2 methoxybenzamide, 2-phenylamino, -naphthylamino, 2-naphthylamino, 2,4-dimethoxybenzamide, 2-phenylbenzamide or 2-thienylbenzamide group.

The sensitizing dyes represented by the general formula I are preferably used together used with a novolak-type formalin condensate of a polyhydroxybenzene and formaldehyde, being a substituted benzene with 1 to 3 hydroxyl groups on the benzene ring under a polyhydroxybenzene understand is

The polyhydroxybenzene can be represented by the following general formulas IVa, IVb, IVc and IVd:

55

(IVa)

(IVb)

(OH) _n

# 625 *

on

(IVd)

wherein Ri2 and Ru are each an OH-, OM-, ORm-, NHi-. NHRm, N (Rm) ₂ , NHNHz or NHNHRm group. Rm is an alkyl group with 1 to 18 carbon atoms, an aryl group or aralkyl group, M is an alkali metal or alkaline earth metal, Xi is an OH group or a halogen atom, Xz is a halogen atom, n ', ji ² . n * and n * each mean the numbers 1, 2 or 3, but n * and / i ⁴ do not have the value 3 at the same time.

Sensitizing dyes according to the invention accordingly of general formula (I) are in British patents 4,87,051 and 489335 as well as the U.S. Patent 25 04 615 listed

Part of the connections according to the general Formula (H) is mentioned, for example, in U.S. Patent Nos. 2,171,427, 2660,578 and 25,95,030. A Process for producing a formalin condensate is briefly explained below

The condensate of polyhydroxybenzene can be produced by the usual production process for phenol-formaldehyde resins of the novolak type (WR Sorenson, TW Campbell. Preparative methods of polymer chemistry, lohn Wiley and Sons, Inc. [1961]). The poly-hydroxybenzene is dispersed in water by adding concentrated hydrochloric acid and 37% formalin is heated at 100 ⁰ C during 30 minutes to! Hour maintained under stirring. Then, if necessary, hydrochloric acid is further added and heating is continued with stirring. After the reaction has ended, the 3s reaction product is poured into cold water and the resulting precipitate can be purified. In an example, to 415 parts of p-hydroxybenzoic acid dispersed in 1,000 parts of water with vigorous stirring, 25 parts of hydrochloric acid having a concentration of 35% or more and 245 parts of 37% formalin were added ⁰ C with stirring and kept at this temperature for 30 minutes and then further added to this 20 parts of concentrated hydrochloric acid and continued the reaction for 30 minutes. At this point, 20 parts of concentrated hydrochloric acid were further added and stirring was continued until the reaction solution became cloudy. After about 1 hour and 30 minutes, stirring was stopped and the mixture poured into 3000 parts of cold water with stirring. The obtained precipitate was filtered off, redissolved in 1,000 parts of methanol as it was and without drying, and then precipitated with water. The product was filtered off and dried to obtain the desired product. Other condensates can be obtained in the same way simply by using other polyhydroxybenzenes in place of the p-hydroxybenzoic acid used in the above process. The condensation unit (degree of polymerization) of the condensate obtained in the preparatory process is 2 to 10, as in the case of conventional novolak resins.

For the purposes of the invention, condensates with condensation units from 2 to 10 are preferably with Condensation units of 2 to 5 and a molecular weight of 300 to 800 are available.

Examples of sensitizing dyes within the scope of the invention are given below:

C ₂ H ₅

= CH-C =

C = CH-C = C C - = C C = S

H ₃ C ₂ O

C ₂ H ₅

C ₂ H ₅ OC ₂ H ₅

I Il Γ

H ₃ CO

Ii I Il Γ

C-N C-N

I. i 1. -. J.

C = CH-C = C C = C C

s s

C ₂ H ₅

13th

H ₃ C

H, C

/ X, OC ₂ H ₅ O

14th

C ₂ H ₅

CNCN - C ₂ H ₅

C = CH-C = C C = O C = S

X / X / s s

-S _x

Χν / ^ ν / ⁰

C ₂ H ₅

H ₅ QN

OC ₂ H ₅ O CH ₂ COOH

Il I Il I

C - N C - N

I I I I

= CH = CH = C C = C C = S

X / X /

S S

O QH ₅ O CH ₂ COCH

Il Γ Il I ς - ν C - ν

CH-CH = C C = C C = S S S

/ V ^s \

L ί C

XvXn /

C ₂ H ₅

O QH ₅ OC ₂ H ₅

Il Γ Il I

C - ν C - ν

I I I I

C C = C C = S

X / X /

S S

/ VSn

^ Ο (CH ₂ J ₃ SO ₃ H

N C-N

(CH ₂ J ₃ SO ₃ H

C-N C-N

_Ν /
QH ₅

= CH-CH = CH-CH = C ϊ - ^c _x ? ->

S _x

(1-10)

OC ₂ H ₅ O

C-NC-N-C ₂ H ₅

= CH-CH = CH-CH = C = C

C = S

(Ml)

C ₂ H ₅

The sensitizing dyes represented by the general formula (I) become that in the silver dye bleaching process applied photographic layer together with one for the silver dye bleaching process appropriate dye added. In particular, the sensitizing dye becomes that with Added to water washed emulsion before drawing, before an azo dye is added

In combination with the sensitizing dyes Dyes used in accordance with the general formula (1) consist of dyes such as are customary are used in the silver dye bleaching process and preferably contain phenolic Hydroxyl groups or sulfonate groups. Suitable

■ 5 dyes are in Japanese patent publications 10 280/61, 9 587/64 and 25 768/64 and in U.S. Patents 32 64 109, 34 54 402, 3178 291. 33 85 706, 3455 695, 3259498, 3244 525, 3304 181, 33 22 543, 32 10 190, 34 54 40t, 32 11 554 and 32 23 527 listed, for example

-CO-NH OH OCH ₃ OH

HO ₃ S

SO ₃ H

NH

SO ₃ H

OCH ₃

SO ₃ H NH ₂

SO ₃ H

CH,

- C

CH,

SO ₃ H

SO ₃ H

CH ₃

C \ - <f V-CO-NHOH

OH

Cl f Y VN = N ^> -N = N

HO ₃ S SO ₃ H OCH ₃

SO ₃ H

SO ₃ H

<5O9 652/136

20 41

17th

H ₃ C-CO-HN- / V-CO-NH OH

HO ₁ S

OCH,

SO ₃ H OCH ₃

18th

OH

SO ₃ H

NH,

HO ₁ S

R - NH OH

HO ₃ S

SO ₁ HI HO ₃ S

OCH ₁

-N = N

SO ₃ H

OH NH-R

H ₂ C CH,

CH ₂

where R is a p-toluenesulfone group or 4-acetylaminobenzoyl group CH ₁ - CO - NH OH OCH ₃ OH NH - R

HO ₃ S SO ₁ H j HO ₃ S SO ₃ H

OCH ₃

wherein R is a benzoyl, 4-acelylaminobenzoyl or 4-benzoylaminobenzyl group.

". 60 drawing aid and hardener mixed and used on one

Example of baryta paper mounted.

A sensitizing dye or a sensitizing dye. The results are summarized in Table III.

fabric and a supersensitizer became one

Silver iodobromide emulsion (iodine 7.0 mol percent) tensile!. Development 5 minutes:

sets and sufficiently stirred for 20 minutes 6 $ p-methylaminophenol 1 g

Then, 19.0 g of a dye of the following hydroquinone became 3 g Structural formula per g-mol of silver halide added, sodium sulfite (anhydrous) 13 g

sufficiently stirred, with an ordinary upper potassium bromide ¹ ■ ·

19th

Sodium carbonate (anhydrous) water to 1000 ml 2.:Wash 5 minutes

3. Fixation 5 minutes: crystalline sodium thiosulphate Potassium metabisulphite water to 1000 ml

4. Water wash 5 minutes

5.Curing 5 minutes:

30% aqueous formaldehyde solution

Sodium bicarbonate water to 1000 ml

6. Water washing 5 minutes 7. Dye bleaching 15 minutes:

Structural formula of the dye used

20th

g thiourea

Potassium bromide
2-amino-3-hydroxyphenazine
Concentrated hydrochloric acid
5 g of water to 1000 ml
g 8. Water wash 5 minutes

9. Bleach-fix 10 minutes:
Tetrasodium ethylenediamine tetraacetate
Sodium carbonate anhydrous
ml ίο ferric chloride
g sodium sulfite (anhydrous)

Sodium thiosulfite (crystalline)
800 ml of water
10. Water wash 20 minutes

HO ₃ S SO ₃ H HO ₃ S

Structural formulas of the supersensitizer SO ₃ H used

NH

table

Sensitizing Supersensitizer Relative Sensitive Dye and quantity (red sensitivity)

(mg / g-mol silver sensitivity)

halide)

1-1 + H-I (950) 1.78 I-1 2.16 1-2 + 11-2 (950) 1.70 1-2 2.12 1-3 + Π-3 (950) 1.50 1-3 1.78

28 g 18g 3 mg ml

G

(IN THE)

(II-2)

(Π-3)

Claims (9)

: "Claims: ¹ * 1. Light-sensitive, red-sensitized silver halide emulsion with a bleachable dye for silver dye bleaching processes , characterized by at least one sensitizing dye of the general formula below 0 R ₂ PR, i-CH = CHU ₁ - Cl- CU -C), = C C - N C - N C = S wherein Ri is an alkyl group, substituted alkyl group, allyl group, aralkyl group, substituted aralkyl group or aryl group, Rz and Ra are hydrogen atoms, alkyl groups, substituted alkyl groups. AUyl groups a aralkyl groups, substituted aralkyl groups and aryl groups, R «a hydrogen atom, an alkyl group or aryl group, Z a non-metallic atom grouping necessary to complete a 5- or 6-membered heterocyclic ring, (/ the numbers 0.1 or 2 and π the numbers 1 or 2 and at least one other supersensitizing compound of the general formula below Y N NH-A-NH N Y (U) R ₁ , 35 Rr wherein Y-CH- or -N-, the radicals Rs. R *. R? and Rs hydrogen atoms, hydroxyl groups. Alkoxyl groups, aryloxyl groups, substituted aryl oxyl groups, halogen atoms, heterocyclic nuclei. Alkylthio groups, heterocyclic thio groups. Arylthio groups, amino groups, alkylamino groups, substituted alkylamino groups, arylamino groups, substituted arylamino groups, heterocyclic amino groups or aryl groups and A the Ai or A2 radicals indicated below, where at least one of the radicals Rs, Rt, R? and Rs contains a -SCbM group if A is one of the corresponds to residues mentioned under A2 and A1 - ^ 3- CH = CH - ^ ~ y ~ SO ₁ M SO ₁ M SO ₁ M 50 55 60 SO ₁ M SO ₁ M CONH SUN _-1 M SO ₁ M or - ^ VcH ₂ -CH ₂ - <O ^ ~ SOjM S0., M as well as / ~ A- / ~ V- -sS or means. 2. Photosensitive, red-sensitized silver halide emulsion according to Claim 1, characterized in that that they additionally contain at least one compound of the following general formula SO ₁ M (III) contains in which R9 is an acylamino group or sulfo group, Rio is an acylamino group and Ru Mean hydrogen atom or a sulfo group. and the compound has at least one sulfo group 3. Light-sensitive, red-sensitized silver halide emulsion according to Claims 1 and 2. characterized in that the residues Ri, Ri and Rj of the sensitizing dye from methyl, ethyl, Propyl - ^ - Hydroxyäthyl - ^ - Acetoxyithyl- ^ ulfatoäthyl-, Carboxymethyl-, 0-carboxyathyL y-carboxypropyl-, 0-sulfoethyl-, y-sulfopropyl-. 4-sulfobutyl-. Vinylmethyl, benzyl, phenylthyl. p-carboxybenzyl, nipp p-sulfophenethyl or phenyl, and the. the radical Z containing heterocyclic ring from thiazoles benzothiazoles naphthothiazoles oxazoles, Benzoxazoles Naphthoxazoles Selenazoles Benzoselenazoles Naphthoseknazoles, Thiazolinen, 2-quinolines, 4-quinolines. Benzimidazoles 3,3'-dialkylindolenines, 2-pyridines and 4-pyiidines exist. 4. light-sensitive, red-sensitized silver halide emulsion according to claims 1 to 3, thereby characterized in that the supersensitizing compound is a substituted aryloxy group o-Toloxyl or p-Sulfophenoxykjruppe, as heterocyclic Nucleus a morpholinyl or piperidyl group, as heterocyclic thiogne lip a benzothiazylthio group, as substituted alkylamino group a 0-hydroxyäthylamino-, EK - ^ - hydroxyäthylamino- or jJ-SuIfoäthylaminogruppe, as substituted Arylamino group an o-sulfoanilino, m-sulfoanilino, p-sulfoanilino, o-anisyuunino, m-anisylamino, p-anisylamino, o-tohiidino, m-Toluidino-, p-Toluidino-, o-CarboxyanUino-, m-carboxyanilino, p-carboxyanifino, hydroxyanilino, Naphthylamino or sulfonaphthylamino group and as a heterocyclic amino lip a 2-benzothiazolamino or 2-pyridylamino group contains 5. Light-sensitive, red-stabilized silver halide emulsion according to Claim 2, characterized that the acylamino group in the compound of general formula III from an acetamide, sulfobenzamide, 4-methoxy-3-sulfobenzamide, 2-ethoxybenzamide, 2,4-D thoxybenzamide. p-toluylamine-, 4-methyl-2-methoxybenzainide-. 2-phenylamino, 2-naphthylamino, 2,4-dimethoxybenzamide, 2-phenylbenzamide or 2-thienylbenzamide group 6. Light-sensitive, red-sensitized silver halide emulsion according to claims 1 to 5. thereby characterized in that it further contains a formalin condensate 7. Light-sensitive, red-sensitized silver halide emulsion according to Claim 6, characterized that the formalin condensate consists of a condensate of formaldehyde and a polyhydroxybenzene of the general formulas below (OH) ₁₁ , COR ₁₂
(OH) "2 SO ₂ R ₁ ,
(OH) "3 OH X ₂ CH, consists, in which R12 and Ru are each an OH-. OM-, ORu-, NHz-, NHRm-, N (Rm) ₂ -. NHNH2 or NHNHRu group, Rm an alkyl group with 1 to 18 carbon atoms, an aryl group or aralkyl group, M. an alkali or alkaline earth metal. Xi is an OH group or a halogen atom, Xz is a halogen atom, n \ rf, rfi and n · each represent the numbers 1.2 or 3, with n being ³ and if not simultaneously having the value 3. 8. Light-sensitive, red-sensitized silver halide emulsion according to claim 7, characterized in that the condensate has 2 to 5 condensation units and a molecular weight of 300 to 800 owns 9. A light-sensitive, red-sensitized silver halide emulsion according to any one of claims I to 8. characterized in that, as a bleachable dye, it is a compound of the following Formula contains: HO ₃ S SO ₃ H HO ₃ S SO ₃ H The invention relates to photosensitive. red-sensitized silver halide emulsions with a bleachable dye for the silver color softening process. It is known that monochrome or multicolor photographic images can be produced by the super color bleaching method can be obtained. In this process, the image is first made as a silver image on a uniform using a dye-colored light-sensitive layer by the usual exposure and development process recorded and then the dye present in this layer according to the amount of in the layer of existing silver is decomposed with the help of the silver dye bleaching bath Silver removed, leaving a layer of color with a reverse gradation to that of the original silver image is obtained. The silver dye bleaching process involves the use of a multi-layer material three or more color component images with spectral ranges of different sensitivity advantageous to get 11m multicolored recordings. Such a material has, for example, a red-sensitive material containing a cyan dye on a support Layer a green-sensitive layer containing a magenta dye, a film layer to lower the Eigenempdct of the layers below the filter layer and one Blue-sensitive layer containing yellow dye as top layer One of the disadvantages of the overcolor mekh process is that the photosensitivity of a colored photographic layer decreases considerably because the maximum wavelength of the sensitivity practically corresponds to the maximum absorption wavelength of a dye. The sensitivity of a photosensitive layer in the silver dye bleaching process is lower than that of others color photographic process. Therefore, there is one of the major difficulties in the silver dye bleaching process in the production of a layer with sufficient sensitivity In the preparation of silver halide emulsions, the silver halide becomes a sensitizing dye added in order to thereby enlarge the spectral range of the sensitivity of the silver halide emulsion and thus to sensitize it optically. One in one The sensitizing dye used in the light-sensitive material for the silver dye bleaching process must be meet the following conditions. The sensitizing dye must not have an adverse effect on the sensitivity and stability of the emulsion, in particular during storage. Furthermore, the sensitizing dye must not cause any residual coloration after the Treatment or development of the photographic material remains. The sensitizing dye must also be used must be firmly adsorbed on the silver halide grains so that it is not caused by the silver dye bleaching process appropriate dye is replaced. Otherwise, the presence decreases the sensitizing effect of the dye suitable for the silver dye bleaching process. Many of those previously used for silver halide materials The sensitizing dyes used are not suitable for the silver dye bleaching process For example, basic cyanine dyes show a tendency to desorption from the superhalide bodies nern by a dye with sulfonate groups like them can be used for the silver dye bleaching process. Betaine cyanines can be used as sensitizing dyes used for photographic layers in the silver dye bleaching process, but they retain often a slight residual color For example, suitable sensitizing dyes are described in US Pat. No. 2,50,4,615. Furthermore, in the DT-AS 12 13 240 described silver halide emulsions which can be bleached in the silver dye bleaching process Contain dye and are sensitized with merocyanines. With these known materials however, there is a problem that the sensitizer does not come from the silver halide grain through the dye is displaced. The object of the invention is therefore to determine a sensitization of photosensitive Silver halide emulsions with a bleachable dye for the silver dye bleaching process, the compounds to be used for sensitization not by the bleachable dye from the silver halide grain be displaced. The problem is solved with a light-sensitive, red-sensitized Süberhalogenidemülsion with a bleachable dye for the silver dye bleaching process, which is characterized by at least one sensitizing dye