DD213528A1 - METHOD FOR STABILIZING AND SMOKING UPHOLSTERY IN COLOR PHOTOGRAPHIC HALOGENIC SILVER MATERIALS - Google Patents

Abstract

The invention relates to the production of high quality color photographic materials based on halogen silver gelatin emulsions. The aim of the invention is to reduce the fog in the processing of such materials, in particular at elevated processing temperatures. The task to be solved is to achieve the desired fog reduction by suitable additions, without at the same time the sensitivity is reduced. The essence of the invention is described in that mono- to Tetraalkylhydrochinone and aromatically condensed thiazolium salts are added to the emulsions and / or auxiliary layers.

Description

VEB Filmfabrik Wolfen - ./ - Wolfen, 23.11.1982

PN 988 Pr / Mi

Dr, or or, OC, dl CI. , Fischor , Bach Manic , Tamm , 3öhm Wilschek

³ : G 03 C, 1/34

Stabilization and anti-fogging process for color photographic silver halide materials

Field of application of the invention

The invention relates to a process for stabilizing and preventing fogging in photographic materials based on silver halide emulsions which, during their preparation, contain stabilizing and antifogging additives.

Characteristic of the known technical solutions

In the development of exposed halogen silver materials known to occur next to the desired silver or. Dye image an additional so-called "veil", which is due to influences in the production of the emulsion * storage and processing * I

To prevent or reduce this fog, emulsion stabilizers or antifoggants are used, and it is often impossible to avoid loss of sensitivity. A good stabilizer is 5-methyl-7-hydroxy-1,3,4-triazaindolizine (hereinafter called "triazaindolizine"), which is a »a. the sensitivity is not reduced.

In contrast to black-black materials, a color photographic silver halide material consists of a large number of very thin layers; those high emulsions containing high concentrations of couplers and silver halide readily form fogs during processing, especially if the development at elevated temperature _a deh * is carried out above 30 ⁰ C ₅ 'Under these conditions, triazaindolizine and the most known anti-fogging agent is not effective enough is known ,, dp of dye stain can be reduced by addition of certain Hydrochimonderivate (e.g. "B" Dt "-0S 2,149,789 ) ,. which react with diffusing developer-oxidation product, but also their effect is not sufficient. They have been of ~ half with anti-fogging agent from the known group of heterocyclic mercapto compounds (Z ₀ B.Dt OS-2'034 064, GB-PS 1,522,673) are combined, however, occurs in good haze reduction of typical for these substances desensitizing effect ,

As another group of antifoggants, quaternary salts, for example, benzthiazol, have been described (e.g., Dt-OS 1 472 774); in the present case, however, they are unable to keep the veil sufficiently low »

goal of

The object of the invention is to reduce the fog in both fresh and stored color photographic silver halide material, especially when using elevated processing temperatures, without lowering the sensitivity _e

Explanation of the essence of the invention

The invention has the 'object' as an addition to Color "emulsions to find suitable compounds ^ when applied elevated processing temperatures _s stabilization and antifogging without desensitization allow _s particular"

This object is achieved in accordance with the invention dissolved ds & used for stabilization and fog prevention in photographic halogen silver materials combinations »consisting of

Compounds of the general formula

in the

n: 1 to 4,

R is identical or different, straight-chain or branched alkyl groups having a Gesamtkohlerofof number for all R from 5 to 40, and from compounds of the formula II,

II

in the

jt '

Atomic grouping to complete an optionally substituted aromatic system, alkyl having 1 to 5 carbon atoms, H alkyl having 1 to 8 carbon atoms, and also substituted by halogen, OH and carboxy or Sülfogruppen, wherein the compound in the latter two cases also as Betaine, any inorganic or organic acid anion (not applicable to betaines)

mean·

A particular advantage of the invention is _e Daib> the claimed \ combination in addition to the considerable reduction veil "· in. Contrary to many other stabilizers and clarifiers «· 'causes no desensitization«. The compounds may be added to any emulsion or adjuvant. The addition of karin may be made at any time between the end of post-maturity and the pouring of the emulsion ^. , ,

A further advantage of the invention consists in the fact that the subunits can be used together with other stabilizers i% .RTM. Triazaindolizine. Emulsions (for ₀ B _e Ag Br I, Ag Cl Br - emulsion ^ introduced 'be' 'the next · color couplers chemical and spectral sensitizers _s hardeners ^ wetting agents and other fotocheifli "see addenda," The color couplers can-preferably hydrophobic fat residual coupler or hydrophobic oil-couplers (cf. "H ₀ ¹ Böttcher u _e G. West, Hitt _e -Bl _e Chera," Ges _s DDR 26 _S 151 (1979); K _e Venkataräman "The Chemistry of Synthetic Dyes _s New York / London 1971, Bd, 4 ₈ p. 356 ff.) · '.

The introduction of the quaternary salts II in the emulsion is carried out by adding the aqueous odor alcoholic solution ₉ during '.: the hydroquinones I either alone or, together with the color coupler dispersed in gelatin: and added in this form of the emulsion in auxiliary layers "the amount of the emulsion; * I used hydroquinones is between 2 and 200 "are preferably 5 and IQO mol m _s of the .Quartärsalze II is between 0.05. and 5 * preferably Q ₅ I and. 2 m mol per mol of silver halide *. , j The most advantageous effect of the combination is " surprising and unpredictable " because the individual constituents I and II do not sufficiently reduce the haze and indicates different mechanisms of action of both substance classes. The compounds claimed according to the invention can be prepared by known methods.

The alkylhydroquinones I (see * Houben ~ Weyl, Methoden der orga-.nise.hen Chemie »4 _e Auf.lv, Bde ^ / Ic (1976)) are formed a) by alkylation of hydroquinone with olefins or

::.; , , - 5 - · '. , , - "-? ':.;.

Alcohols under acid catalysis,

b) by acylating hydroquinone and reducing the acyl to alkyl groups,

c) by reduction of the corresponding alkylquinones «

The thiazolium salts II are prepared by reacting the corresponding thiazoles with alkylating agents such as alkyl halides and sulfates or alkanesulfonates and sultones (cf R. C. Elderfield, Heterocyclic Chemistry, Bd * 5 (1957), U.S. Patent No. 2,503,776),

According to the mentioned methods, e.g. the following substances are shown:

Compound III: η-dodecylhydroquinone (F _e 104 ° C)

2,5-di-tert-butylhydroquinone (F.215 ⁰ C)

2 »5-bis (ll-dimethylpropyl) hydroquinone (F, 179 ⁰ C) of 2,5-bis (l _# l-dxmethylbutyl) hydroquinone (F _# 111 ° C) 2.5-bis (l-ethyl -l-methylpropyl) -hydroquinone (F _e 147 ^o C) 2,5-bis- (1,1,3,3-tetramethylbutyl) -hydro-

quinone (F.125 ⁰ C)

3-methylbenzothiazolium iodide (F.207 ⁰ C)

3- (Carboxymethyl) benzothiazolium bromide (F "258 ° C) 2,3-Dimethylbenzothiazolium perchlorate (F * 124 ° G) 3- (4-.succinobutyl) benzthiazolium betaine (F.267 ^O C)

As comparison substances, the following compounds are mentioned in the examples:

Verb, XIII: 1-phenyl-5-mercaptotetrazole Comp. XIV: ^ -Mercaptobenzimidazole-S-sulfonic acid

embodiments

The invention is explained in more detail below by way of examples, wherein the additives III-XII claimed according to the invention and the comparison substances XIII and XIV have the abovementioned meaning. ·· '' · ..... ·. '..' .. '·; _..-: .-. '. · '. '. '''·. -. '. ". '-

example 1

An ammoniacal gelatin silver bromide iodide emulsion for color positive that chemically sensitizes with gold compounds

verb , IV: verb • V: verb , VI: verb .VII: verb .viii: verb IX: verb X: verb , XI: verb • XII:

 - 6

was, is divided into 5 parts and receives as additives per mole of silver halide successively 27 mmol Triazaindolizin * the amounts indicated in Table 1 of compound IX ₄ 135 g of the yellow coupler p-stearoylaminobenzoyl-acetate-G '' chloroanilide as about 7''Oige dispersion _s in which the amounts of the compound IV given in table l to "were dispersed in gelatin solution, and the other usual additives"

After casting onto a substrate, the resulting photographic material is cut into strips which are exposed behind Orange ™ and gray filters and wedge and developed in the following high-temperature developer for 3 min. At 36.8 ⁰ C:

Ethylenediamine tetraacetic acid ~ di ~ Na * "salt Ig

Na ₂ SO ₃ 4.35 g

2 ~ Amino ~ 5-diethylaminotoluene hydrochloride 2.95 g

Na ₂ CO ₃ 17 _ä l g.

K Br 2 g with H ₂ O filled to 1 1,

After further processing (stop bath, bleach bath, fixer, watering), the stages are measured. The results (logarithm of the relative sensitivity at density 1.0 above the fog), where larger numbers of lower sensitivity and differences of 0.3 correspond to one aperture / minimum density ( _min ) are given in Table 1.

It can be seen that each of the two substances IV and IX alone, with appropriate dosage significantly reduces the fog, but that with the combination of both substances an extremely low haze is achieved · The sensitivity and the gradation are not adversely affected *

Example 2

An emulsion as in Example 1 is divided into 16 parts and receives as additives per mole of silver halide successively 27 mmol triazaindolizine, the amounts indicated in Table 2 of compound IX and III to VIII (the latter as a ~ 2 iger dispergate in 5% Gelatin solution or as an additive to the coupler dispersion),

"- = ': .. - .. ... .." .. .. ... - ^; - 7

- "7 ~.

107 g of yellow coupler XV

Cl

O, NH-SO ₉ -C _{1 fiH} (n)

OCH ₂ C ₅ H ₅

as about 7% dispersion in gelatin solution and the other usual additives.

After casting onto a substrate, the material is cut into strips, which are exposed behind orange and gray filters and wedge and developed in the developer of Example 1 2.3 or »4 min. At 35 ⁰ C. The results obtained after further processing and measurement are given in Table 2 analogously to Example 1.

It can be seen from the table that each of compounds III to VIII significantly lowers the fog, the effect increasing with increasing dosage to a level of 36 m mol per mol of silver halide (sample 5-8). The combination with Compound IX, which itself is a good antifoggant (Sample 2) _; further lowers the fog to values of 0.07 - 0.10 (2 min.). The sensitivity is slightly affected.

Example 3

The procedure is as in Example 2, with the difference that the emulsion is divided into 10 parts and as veiling reducing substances mentioned in Table 3 amounts of the compounds VIII

. ' , . ''·''' - '.' - '.' - ^: - * 8 -

: -. , , - 8th - .. . , /. '^; _; \ / ^; Ύ-

and IX to XIV are added. The results are shown in Table 3.

It can be deduced from this that, in combination with the dialkyl hydroquinone VIII, each of the quaternary salts IX to ΧΪ1 lowers the fog sufficiently; the sensitivity is not lowered when the quaternary salts are used in concentrations up to about 0.45 moles per mole of silver halide. The already known combinations of VIII with the mercapto compounds XIII and XIV (samples 9 and 10) have a desensitizing effect, in which case XIV also does not have a sufficient haze-reducing effect. , '· ... '. ',. ".'. ':''.-.'':

.- -. \ '''.' -

, , - - ' ... '. '''''. . i ". '· .. ".

Example 4

The procedure is as in Example 2, with the difference that the emulsion is divided into 9 parts and the amount of compounds IX and VIII given in Table 4 as veiling-reducing substances are added »the latter either as about 2 % x ges dispergate in 5 % Gelatin solution (Dispergat A) or as an additive to the Kupplerdispergat (Dispergat B) are introduced.

The sensitometric data presented in Table 4 show that these are independent of the mode of introduction of the alkylhydroquinone VIII,

Example 5; ';''. ^: \ '.' . "^':' · ^'.'. '.-' ./

A gelatin silver chloride bromide emulsion for color-positive which has been chemically sensitized with gilded joints is divided into 2 samples. Sample 1 receives as addenda per mole of silver halide successively 900 mg triazaindolizine, 60 mg of RG sensitizer Rr 1953 (cf. K.Venkataraman, The Chemistry Of Synthetic Dyes, New York 1952, vol. 2, p. 1180), 230 g of the "" cyan coupler XVI

OH

NH-CO-CH-O- / AC ₁ -H ₁ , (tert.)

C ₂ H, V = - ⁷ XVI

^0H

9 -

• .. 'ν.' , ; ; /. - 9 - ·., -:. ,

as ca * 7 * 5% dispersion in gelatin solution and the other conventional additives

In addition to the above-mentioned additives, sample 2 also receives 0.72 m mol of substance IX after the spectral sensitizer and (as about 3 % ± gel dispersion in gelatin) 27 m m.sub.i of substance VIII per mol of silver halide.

After casting strips are either fresh or after Heizschranklagerung (7 days at 50 ⁰ C) behind orange and gray filter and wedge exposed and processed as in Example 2 and evaluated (Table 6l).

In comparison to sample 1 (without antifoggant, the sample has low haze values, favorable haze kinetics with extension of the development time and good heating chamber stability. "It is also remarkable to increase the gradation g by the added antifoggant.

Example 6

A gelatin-silver bromide emulsion for color-positive, which was chemically sensitized with gold compounds, is divided into 2 samples. Both are given as additives per mol of silver halide in succession 900 mg triazaindolizine, 180 mg of the green sensitizer 9-ethyl-3 »3 ' · - bis- (4-sulfobutyl) -5,5'-diphenyl-oxatrimethine cyanine mono-Na salt (cf. German Patent 929,080), 140 g of the magenta coupler XVII as a ~ 5% dispersion in gelatin solution and the "

NH-CO-CH-O-

^C 15 ^H 31

XVII

egg. ; :. . .;.; : /. · ,: ..

other usual additions «

Apart from the aforementioned additives are - in each case after the spectral sensitizer - to sample 1 even 0.3 ηjiol the known AntischleiermitteXs XIXI to Sample 2 nor O _e 5 m mole of compound IX as well (3 $ Jige dispersion in gelatin) 12 m mol of the substance VIII per mol of silver halide *, processing and evaluation (Table 6) are carried out as in Example 5.,: .--; ·. , , -. '. · ..,. _: , .... '. . '; . ''. ..

Again, one recognizes the considerable fog reduction by the antifoggant contained in Sample 2, while the already known substance used in Sample 1 is not sufficiently effective. _t

Example 7 ·. '· -' '·' '. * ', · · ,,,

A color photographic heightening material for color-positive with interchangeable layer sequence contains the following layers:

a) as Uriterguß an emulsion as in Example 2, as an antifoggant 0.45 m mol of the substance IX and (as ca ~ 3 iger dispersion in gelatin solution) 18 m mol of the substance VIII per mole of silver halide and the rest in Example 2 added additives are added,

b) a gelatine interlayer,

'' '»' · ..

c) as an intermediate casting an emulsion as in Example 5, to which all additives of sample 2 in Example 5 are added,

d) a gelatin intermediate layer,

e) as a topping an emulsion as in Example 6, to which all additives of sample 2 in Example 6 are added,

f) a gelatin coating

The procedure is continued as in Example, with the difference that the strips after processing are measured separately behind filters of the respective complementary color for the .Spktralbereiche, and receives the sensitometric data given in Table 7, where b, g and r are the data the blue, green or red sensitive layer denotes «

In all 3 layers of the described material, the used antifoggant combination causes extraordinary

low haze values, a very favorable veiling kinetics with a longer development time and a good heating cabinet behavior can be achieved.

Example 8

An ammoniacal gelatin silver bromide iodide emulsion for color negative which has been chemically sensitized with gold compounds is divided into 2 parts. The sample 1 used as a type receives, as additives per mole of silver halide, successively 340 mg of triazaindolizine, 250 mg of the red sensitizer 5,5'-dimethyl-9-ethyl-3- (2-hydroxyethyl) -3 '- (3-sulfopropyl) thiacarbocyanine betaine (see DD-PS 11 108, Example 6), 36 g of Bl'augrünkupplers XVIII as ca »7% dispersion

OH

CO-NH- (CH ₂ ) ₄ -O-

ΤτΎ ^ Λ "- ': T:. V- XVIII

in gelatin solution and the other usual additives. In addition to the additives just mentioned, sample 2 still has 0.35 m mol of substance IX and 40 m mol of substance VIII (last as about 3% dispersion in gelatin solution) after the spectral sensitizer per mol of silver halide are cut into strips, exposed behind the yellow filter and wedge (factor 2) and developed in the figure below high temperature developer 3.25 min * at 37.8 ⁰ C "

Ethylenediamine tetraacetic acid di-Na salt 2g

Hydroxylamine sulfate 2g

2-Amino-5- (ethyl-β-hydroxyethylamino) -toluene 4 _t 8 g

K ₂ CO ₃ 30 g

Na ₂ SO ₃ 3.8 g

K Br. '. ..; '; ^: . , -. ''. 1,8-g. ' , · '. /,

KH CO ₃ 3.5 g

filled with H ₂ O to 1 1.

After further processing (stop bath * bleach * fixer, wash) the strips are measured »The results (relative sensitivity at density 0" l above the haze in apertures, where larger numbers correspond to lower sensitivity j minimum density D _in and gradation g) given in Table 8 «

The Antischlexermittelzusatz causes a considerable Schleiersenkung without the sensitivity is impaired »

Table 1

sample additive (m mol / mol .B ' Ag WB Hai) IgE 1.0 D. mm Verb β IV Verb. IX i - ' »45 Not measurable 0.83 '.' .. 2 ' 18 / 45 /light meß & ar. 0.48 , V 3 Ζ. .V 36 1 • i- ' 0.30 - ' ⁴ ''' - O ..: ± 2 0.14 ' 5. ' 36 ⁰ 1 2 0.07

: 'C O (Q IN N) (D ro in (O H (O ω VO · ο VO H IN H U K) H V7 " • rl ε ' H X) νθ IN xl CM J3 H JQ O in H VO CM (O O νθ Q CM CQ O O c Q O c Q H ca O O O O O ca O O Φ Φ φ φ φ O 6 e e 6 AJ φ ro K  in 4J 4J φ • Μ JJ JZXi 4-> (O in IO 4J in UJ JC χ: ro JZ UCQ JC Xi H ro CM CM O ft ro O UCQ ο O O • rt φ O CQ ft.  " •H H ft • O) • rl U • rl Φ • Η H •H • rl ce • π Φ co H H H C H H H   .C (O ce C C C co fO C ε P C • g CM JQ CQ νθ ro ιη ro ro H S co O ro O H ro ro CO H CM O CM CM, m ' Q H 6 O P O O O P P O O O O P O > in + J in  in in in in in ; W - JC O in m in in " in in co in in in in ft O) H C ro P O : H-. :   C H CM CM co nt ro H CM ο N O co ro H rv ^: .'- • Η α H H O CM H O H O H O p H O Q O ο O ρ O O O O P O O p -. · .- CM O in 1.7 H in in vo in in in 1.7 in ω O) H fs - · m 1.7 νθ rs VO% 1.6 vo N H νθ rs 1.6 Nft 1.7 Η ^; * X (O H in T in • in in ft in in • "t in O) JQ I O  "* nf U ι ι " I I I I I O I Q) *> ο Q O P O Ό ε H H H H O ^ ε ω ε- I H IN vo H co CM VO   > VO vo vO vO ro IN N IM + j * "· CM CM H  > ro H ro ro to ro H CM CM (D Yes ι I H H I-I ^ H H M O) Ι M H H M H W M H 3 Ο) H M H Η N > (Jl Q) IN "^ £) H CM ro in VO ω O H CM to H in νθ O H H H H H Q.

ri <u Xl

C CM ro CM O • O) IO cn O to cn ω O! • Η σ " ESSB MD O CM vi CM CM CM 7 * e O O ο O O ο : *; O X ro νΊ  Μ * ·> Ro H in vi ul IT'S ! X " UJ χ: χ: Xi ro to ro in in CD • Η H O in H vi CM .ri vi vi C ro C ε CM CM N ESSB ^ ^: O <ß O O O cn m '' &:: '   C.-Ι O ε ro HI Ή CM vi CM , ε Q O 9 O O O O/ H -ι *. ¹ :, O Λ0 I tn • Μ H in vi in tn Vi LU SZ .. .. _. in in in in m ω O) • Η Ή r-i vi vi H  Η C CM CM C vi vi • Η UV O co ω O O O O Q ri ro O O vi CM ο ο O O O O / Ο · Ö ^r ; CM Ö ...: : η in LU CO " ^ffl 1.7 fs. XIV IN Η; ' m in ι n: N in rs rs O CM : *. ::. ^: ·. in   ., * in in O in tn in in χ χ " O N '^ T L. ι O O O  · Ο · O O 0) X Hi >. X O H X X H M H 5> ..... ε M H X H M H N X H X r-i M X O H ε H xt e CVJ N + j >. ι i <0 CM «SI CM  a '. a Si 3 · N α> χ " ο VO ί- CM Ο. in rs co cn O

C--. ιη in O , VO tn cn vo CM O tn Q CM cn cn ro cn N vo VO in "Μ O O Ö O O O O O C ro CM H rn ω VO Ή ε Q • r * O ro to CM CM CM CM CM   : c -rt in O O O O O O O • Η ε α Γ> ro O ro to O cn O cn O § CvI. '.' ' ο O O O O O O O O Ή in Ui O) 1.5 tn in in I · vo 1.6 m 1.6 1.5 1.5 in 1.6 Γ * τ * ' ¹ «ο X μ -. ·· ': .JtV I in in tn in · C I I I I * - '· ^: · • .- ο O O O O ε , ir - ' ό tr * '- " ε H H> N ό α . < (O C (0 < ca ω < < CQ £ 3 (O © H ω , , ^. * ~ * '-'. 3.   > Q rri ω vo ω VO CO VO N t-l ro ro to ω ο CM ι- rl sf in VO N CO cn ο.

Tabelie 5

[. · 2 · ¹ ^ LO D. mn 9 ; 5 x. : ·, ^D min 9 . '. 4 · ".- .- .- ^D roin 9 3 * fresh rain 9 3 'Heizschr. rain 3,2 3,5 sample 1.7 1.7 0 * 17 0.06 · 3.3 4.0 ^L9E io 0.30 0.07 3.7 4.1 0.54 0.12 3.6 4.4 ¹ ^ i..0 0.34 0.08 3.5 3.9 ^L 9 ^E 1.0 0.56 0.17 1 2 1.65 1.6 1.45 1.7 1.55 1.6 1.45

Table 6     'V 2 * - -. ;. :; ". ^a min 9 ^:; 3 ·. = min A's : igE _{1 # 0} Dmin 9 3 * fresh ^D min G 3 · heating D: 'mxn 9 Table 7. ; : "- ^; " ^:: . :, -: r;> ^s -, .-; '- ;,' - ^: - ^: c ^;:; _:; , t · -; - r :. ^: '-' ; min 9 a:. 3 ·. ·; ; ' min 9 ^L9E io χ »: mxn 9 3 · fresh min 9 3 · heating min 9 sample ^l9E 1.0 0.14 0.06 2.5 0.28 0.08 2.8 1.6 1.65 0.41 0.10 2.8 2.9 IgE ₁ ^ o 0.27 0.07 2 * 5 2 * 8 0.30 0.10 2,2 2,4 Schich '*> - : 9 , ΐ. 1st year 0.09] 0, Ö6 20 * 06 2.3 3.2 4.2 ^a fi.o 0.09 0.07 0 ^ 06 r 3.4 3.7> 4.5 1.45 1.6 0.11 O, 12 fO.07 4, C 4.G> 4.5 0.09 0.06 0.05 3.4 3.5 4.3 ^l9e i> o 0.10 0.07 0.06 2.9 3.3 4.2 1 1.7 1 * 7 1 * 65 1 * 65 1.65 1:45 1.75 1.85 : i * 55 1 * 6 1.5 1.55 1.7 1 * 55 1.8 - (

 - 17 -

* 17 -

Table 8

sample ^E o ,1 D min 0 9 "i 5 .6 0 48 0 60 2 5 • ⁵ 0 , 18 70

- 18 -

Claims (5)

E rf i η d η g s a η s ρ r u c h 1, Method for stabilization and prevention of fogging in color photographic silver halide materials d a d u c h e e η η e. E. c h η e t γ that a combination of compounds of the general formula / I, OH   : ' .. '. Oh. , , · · .. in the n: 1 to 4, R: identical or different, straight-chain or branched alkyl groups having a total carbon number for all R from 5 to 40 mean »and from compounds of general formula II» 2. Method according to item 1, which has previously been stated, that the compounds of the formula I are used in amounts between 2 and 200 μmol, preferably 5 and 100 μmol, and the compounds of the general formula II in amounts between 0, 05 and 5, preferably 0.1 and 2 m mol per mol of silver halide are used * '2'"'''.''' · ''''' R: alkyl having 1 to 8 carbon atoms, also substituted by • «· '. '. , , Halogen, OH and carboxy or sulfonyl groups, where] the compound in the latter two cases may also be present as betaine X: any inorganic or organic acid · » anion used in betaines means »to be used · '..-;-;.; - . .. '; · - 19 - -. , ^ V ' 2: atomic grouping to complete an optionally substituted aromatic system, R ¹ ; AlkyVoiit 1 to 5 C atoms, H 3 "Method according to item 1, characterized in that the compounds of the formula I and II are introduced into emulsion and / or auxiliary layers» 4. The method of item 1, geke η η i η ETDA 'ζ e - d h ure, that the compounds of formula I introduced as a dispersed material in gelatin solution or dispersed together with the coupler,'' 5, method according to point 1, d a d u r c h e η η ζ eic hn e t that the emulsion 5-Γ dolizin is added ·