DE1622279A1 - Halogen silver photographic photosensitive element - Google Patents

Description

PATENTANWXLTB

.DR. E. WIEGAND DIPL-ING. W. NIEAAANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55 547Ä "

TELEGRAMMEiKARPATENT - - NUSSBAUMSTRASSE 10

January 31, 1968 W. 13 535/68 13 / never '. , ':'.

Shashin I ¹ IIm Kabushiki Kaislia Kanagawa (Japan).

■ Ph.otograph.isch.es licJatempf Indllch.es Hai ο gen silver el em ent

The invention tiezlehi; see, on a pliotographisch.es empXIndliCiaes Halogensilh'erelement '- "with a scliich.t that a Opposite fragments, discoloration and decrease in the density of reflection contains and in particular on a photographic.es lichtempflndliclies Ka.logensil "bereleinent with a Sch.ioh.tV the one fine dispersion of a solution of a protective agent one coloration in lead gray (antl-plumming-agent) -in one contains hydrophobic solvents. "

Silver silvery emulsions, especially those used on ginone rapier carriers, are often of that form in treatment, and especially in high-gloss dryness; an image discoloration, and a ¹ decrease in its reflectance density are not affected. If there is a 'through. Development of a formed, black, black silver image of a drying process.

ORIGINAL BATHROOM.

Satin finishers · - -. ·

(glazer) is subjected at high temperature, the silver image is discolored purple or lead gray and at the same time the reflection density of the silver image is reduced. This phenomenon is commonly referred to as "plumming ¹¹ (lead gray discoloration).

In order to prevent the formation of the above-described discoloration and Dichteäbnahme various compounds have been proposed as SehutJasätze for this ^a Plumming "phenomenon to photographic liehtempfinälichen silver halide emulsions. Examples of such preservatives with respect to the lead gray discoloration or * Plumming ¹¹ publication are l-phenyl-E5-'Ei © rcaptotetrazol, potassium salt of endothiophenyls thiadiazolinethiol and derivatives of 2, ^ a, 5,6a-tetrazaperhydropentalen ~ ij.4 ~ dithiQn and others.

In general, the protective agent against the ¹¹ Plumming is * "appearance of a coating composition from a photosensitive Halogensilberemulsionssehicht or other layers using the following procedure by mutual .. leibt. The protective agent against the above-described ⁿ Plumming ⁿ -Erscheinung is dissolved in an organic Lösungsmittelj, for example methanol and the resulting solution is a check lichtempflnälichen Ealogensilber-eiRUlsiort or an aqueous Qelatineiösung added or the protective · ».

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-3 -. ■ '. , -. "■■ '■■■■ ^;

medium with respect to the ^H Plvjjnraing "phenomenon can directly or in the form of an aqueous solution of a lichteapfindlichen Hafcgensilberemulsion or an aqueous gelatin solution is added.

However, the addition of some preservatives! opposite to the "PluDBuing" phenomenon is a serious decline the sensitivity of the photographic halogen silver emulsion due to a strong adsorption of the protective materials against "plushing" phenomena on light-sensitive Halogen silver grains connected "

The object of the invention is therefore to create a photographic light sensitive element which does not cause any lead-gray discolouration or plumaing, - that is, when it is t «®l @ h © aste - © lsi © ψeft coloring caused a decrease in density on drying at high temperature "Further, the invention aims to provide a photographic lichtempfindlichenHalogensil- i berelements with a layer which contains a means of protection against over-the discoloration or" Plumming "phenomenon, with substantially no decrease in sensitivity of the element occurs »

According to the invention, a photographic photosensitive silver halide element having a protective

009844 / 0.517

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medium compared to the ^{layer containing the "plumming 11} appearance, the protective agent compared to the" piuraming "appearance of the layer as a fine dispersion of a solution of the same in a non-volatile organic solvent which is dissolved in water under the manufacturing conditions of the photographic photosensitive element Λ / ν ,, 1 α £ λ * tss Lολλ \ * 1,2ίCa >/>! λο is incorporated, ■ is hardly soluble (less than 0.5), / if the pH value is below ¹ J , however, off the layer under the development conditions is dissolved out if the pH value is greater than 8.

The silver halide photographic photosensitive element according to the invention is prepared by one protective means against the "plumming" phenomenon in the organic solvent with those given above Properties (hereinafter, such an organic solvent as "alkaliphiles hydrophobic Solvent "is referred to) directly or with the aid of a hafsolvent, dissolves the solution prepared in this way in a halogen silver emulsion or an aqueous one Gelatin solution dispersed for the formation of the coating mass and applies them to a carrier and subsequently dries. Before developing the photographic photosensitive Element according to the experience is the protective

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agent against discoloration and decrease in diene ("plumming" appearance) in my emulsion layer in the form of particles of its solution in an alkaliphilic hydrophobic solvent, and therefore this protective agent is present in the emulsion layer in a protected state. The agent is therefore prevented from diffusing into other layers, and furthermore, since the protective agent with respect to the ¹¹ Plumming phenomenon graph of the photo- Λ photosensitive silver halide grains is isolated in the photographic light-sensitive element is an interaction between the protective agent with respect to the "Plumming" - Appearance and the Silberhäbgenid grains prevented. As a result, when the untreated photographic photosensitive element is stored, there is no deterioration in its photographic properties, such as a decrease in its sensitivity. In the course of the development (at a pH value above 8) the alkaliiphilic hydrophobic solvent is dissolved out of the layer *. In this way, the protective agent against the "plurming" phenomenon, which is now free from the protection by the solvent, shows an interaction with the halogenated silver grains, ie it exhibits its protective effect against the "plumming ¹¹ phenomenon. In other words, shows the photographs marriage

009844/0517

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light-sensitive element containing a protective agent against the "plumming ¹¹ appearance, according to the invention no deterioration in photographic properties when stored or kept in the untreated state and no" tlumming "appearance when dried by satinizing at high temperature after development. Γ

The alkaliphile used according to the invention HydHphobic solvents essentially need not be miscible with water and also easily soluble in one alkaline aqueous solution with a pH higher than 8 and also not be volatile, the necessary resolving power in relation to the material to be dissolved therein and must not have any adverse effects on the photographic Result in emulsion.

An example of the alkaliphilic used according to the invention hydrophobic organic solvent is represented by the following general formula (I)

'■> N - CH ₀ - CH - COOH (I)

R ¹ CO ^ I

wherein X represents a hydrogen atom or a methyl group and R and R * each represent an optionally substituted alkyl group, the total carbon number of R and R ^{1 being} in the range from 7 to 11.

4/0511

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When the total number of carbon atoms is lower than is, the water solubility becomes too high, and if it is higher than 11 ^ will be the compound in the alkaline aqueous solution not completely dissolved.

Examples of the compound represented by the above .general formula (Ϊ) are?

(1) 2 ° Methyi-3 ~ (N-n ^ hexyläcetamiäo) -propionic acid

N-GHg-CrH-COQH.

.N-CH ₂ -CH ₂ -COOH, C0 ^

2-methyl-5- (N-li-oc & ylacetainidoi} propionic acid

■ Ν - CH ₂ - CH - COOH CH CO - ^

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3- (N-n-butyloctanamido) propionic acid

N - CH ₂ - CH ₂ - COOH and

n-C "-I

(5) 3- / N-D-hexyloxypropyl) acetamido! -propionic acid

N - CH ₂ - CH ₂ -

COOH

CH CO

These compounds are novel compounds that can be prepared using the procedure described below. However, according to the invention also other alkaliphilic hydrophobic solvents that contain the meet the above conditions, apply.

As stated above, according to the invention, the above-mentioned protective agent against the "plumming ¹¹ phenomenon is dissolved directly in the alkaliphilic hydrophobic organic solvent or dissolved therein using an auxiliary solvent. The expression" auxiliary solvent ¹¹ used here is to be understood as a solvent which to facilitate the dissolution of the protective agent against the "plumming" phenomenon in the alkaline

09844/0517

p'hilen hydrophobic solvent, is used to reduce the viscosity of the solution and to facilitate the formation of the dispersion. The co-solvent may be water soluble or volatile and can from the system wähend the production of the photographic light-sensitive elements are removed or may not be water-insoluble volatile and therefore lement in demlichtempfindlichen ^E remain together with the älkaliphilen hydrophobic solvent during the manufacture of the photosensitive elements, provided that it is made soluble by the solvent and is leached out with the latter during development. If necessary, both types of auxiliary solvents can be used at the same time.

Examples of the former type of cosolvent are methanol, acetone, dimethylformamide, ethyl acetate, Methyl ethyl ketone or the like .. Examples of the latter type of solvents; which can be used (

are phosphoric acid esters or phthalic acid esters, however a methyl ester or an ethyl ester of the alkaliphilic hydrophobic solvent of the general ones given above Formula (I)> i.e. a compound of those shown below general formula

\ n-ch - ch - coor "(ii)

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wherein the radicals X, R and R ^{1 have} the same meaning as above in formula (i) and R ^{11 represents} a methyl group or an ethyl group, is particularly suitable due to the ease of solubilization and the desired dissolving power and viscosity.

Practical examples of co-solvents of the above given general formula (II) are listed below as intermediates in the preparation from compounds of formula (I) can:

(6) Ethyl 2-methyl-; 5- (N-n ~ hexy! Acetamide) propionate

y N - CHp - CH - COO - C ₉ H, - CH _x CO '■■■}. " ⁵

y OH,

(7) Ethyl 5- L ^N "(2-ethylhexyl) acetamido I propionate

CH - o

Χ ^N - ^CH 2 - ^CH 2 - ^C0 ° - ^C 2 ^H 5 CH, CO '. ■ '■

(8) Methyl-a-methylyl - ^ - (N-n-o ctylace tamido) propionate

ⁿ " ^C 8 ^H 17X

M- CH ₀ - CH - COO- CH CH ^ CO - ^ * t
3 CH

Methyl-3- (N-n ~ butyloetaminamido) -propionate and

^ H-CH ₂ -OH ₂ -COO-CH ₅ (10) methyl 3- ^ NO-hexyloxypropyl) -acetamido j -propionate

N - CH ₂ - CH ₂ - COO - CH ₃ CH ₅ CO / A

As a protective agent against the "Plumming" phenomenon can go to the application that it has ¹¹ -Erscheinung and the necessary solubility in the solvent the desired protection effect against the "Pluöming any connection with the proviso Typical examples of protecting itself against the ^w Pluraming ^w. - Appearances useful in accordance with the invention are listed below.

(ID (12)

KN \ ^ C "S

S 'it

it ^C

CIiJ CIi ₃ - C = '"^ C ./ ι. · HN ~ 'N. NH ι · I. ₌ Q. - K \ \

(13)

(IV)

-a;

HN HCS

S -C

Wed

y ^ -
[ X = -N. J- - · /
X \ I.
C .—

Λ. ι A,

(15)

(forgive οapanisehe -ii-uslegeschrlft 8582/1965 for compounds (ΤΙ) - (14) and US Patent 2,743,184 " for connection (15). ·

The manufacturing method for the alkaliphilic hydrophobic organic solvents mentioned above as compounds 1 to 5 will be explained below.

Establishing connection 1: _

A mixture of Ιοί gn ^ hexylamine, ioo g methyl- · methacrylate and 1 g Mtriumme thy lat was for 2 days heated to about 70 ° C on a water bath, whereupon the resulting solution of a distillation under reduced Has been subjected to pressure. There were 14og of methyl 2-hexylaminoisobutyrate obtained as a fraction with a boiling point of 80 ° C / 2 mm Hg. '-

To the total amount of the product, 84 g of freshly distilled acetic anhydride was slowly added. However, the amount of addition was set so that the temperature of the system was kept below 10 ° G ^: in order to avoid excessive heat build-up. After the addition of acetic anhydride, the product was heated for a further 30 minutes on a water bath and distilled under reduced pressure, 14> / g of a fraction having a boiling point of 130 ° G / 1 mm Hg.

BADORiGiMAi. "

The product thus obtained was with 450 ml of a aqueous 2N sodium hydroxide solution containing 45 ml of methanol contained, mixed and the mixture was at room temperature shaken, generating heat and clearing the solution. After further shaking the system, the resulting solution cooled and concentrated with Hydrochloric acid acidified to separate an oily material. This was extracted with ether, washed with water, dried over sodium sulfate, whereupon the solvent was distilled off under vacuum. 120 g of compound 1 were obtained.

Nitrogen analysis:

Found s 6.02 %, calculated s 6.11 %

Establishing connection 2:

Under cooling with water, 86 g of methyl acrylate was added dropwise with stirring to 129 S 2-ethyl ^ hpxylamin at 30 ^o C, km. At the end of the addition, the product obtained was 1 St &. heated for a long time on a water bath and then subjected to distillation under reduced pressure, whereby 170 g of a fraction having a boiling point of 91 ⁰ C / 1 mmHg were obtained. The fraction was treated with 92 g of freshly distilled acetic acid anhydride in the same way

1022279

treated as described above, and then the product was distilled under a reduced pressure. 180 g of a fraction with a boiling point of 140 to 14-5 ° C. / 1 mm Hg were obtained. The fraction was mixed with 500 ml of an aqueous 2N sodium hydroxide solution and then shaken to induce hydrolysis and to obtain a clear solution. The product obtained was similar acidified with hydrochloric acid, the product formed was üige with. Ether extracted, washed with water and dried, whereupon the solvent was distilled off under reduced pressure. Thereby 155 g of the compound was obtained.

Nitrogen analysis:

GefVi5.65 %, calc .: 5.76 %,

Preparation of compound 3;

A mixture of 100 g n-octylamine, 65 g Methylmeth- i acrylate, and 1 g of sodium methylate was lasting days heated to about 7O ⁰ C on a water bath and the product obtained was distilled under reduced pressure to obtain 95 g of an addition product as Praktion with a Boiling point of 107 ° C / l mm Hg were obtained. .

The total amount of the addition product was made with 58 g of freshly distilled acetic anhydride as in the

009844/0517

Preparation of compound 1 treated, followed by distillation under reduced pressure. 94 g of a fraction with a boiling point of 142 to 145 ° C./1 mm Hg were obtained. The fraction was dissolved in 250 ml of an aqueous ⁱ 2n sodium hydroxide solution containing 50 ml methanol, hydrolysed and then treated in the same manner as in the preparation of compound 1, with 78 g of the compound were obtained. 3

Nitrogen _{analysis: Λ}

Found i 5.29 %, calc.,: 5 ^ 5 %

Preparation of compound 4;

Similar to the preparation of compound 2, 88 g of n-butylamine were reacted with 86 g of methyl acrylate brought and the product was subjected to distillation under reduced pressure, whereby 12 ^ g of a fraction with a boiling point of 64 ° G / 5 mm Hg were obtained.

The total amount of the fraction was dissolved in 2 liters of ether and 100 g of triethylamine and added to this solution

118 g of octanoyl chloride were added dropwise with cooling and stirring admitted. Thereafter, the formed triethylamine hydrochloride was filtered off and the ether was removed by distillation. The product obtained was in 400 ml of a aqueous 2N sodium hydroxide solution containing 40 ml of methanol, as in the preparation of compound 1, hydrolyzed and after extraction of the product became the ether

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162227B -if -

removed by distillation and the product was taken under distilled under reduced pressure, with 50 g of the. link as a fraction with a boiling point of 195 to 203 ° C / 3mm Hg

were obtained. . ·

Nitrogen analysis:

Gef «: 5.23 #, Ber.i 5.16 #. .

Establishing the connection; 5:

^: '"■■■" ■ ■ .- ■■■■■ -. ■■ '■■ ι

As in the preparation of Compound 2, 53 g of ^ 3-hexyloxypropylamine (which can be prepared by the method described in Japanese Patent Publication Zl 563/1964) was treated with 28 g of methyl acrylate, and the obtained product was distilled under reduced pressure, whereby 71 g of an addition product were obtained as a fraction with a boiling point of 96 ° C / 1 mm Hg * The total amount of -

Addition product was mixed with 35 g of freshly distilled acetic anhydride, followed by 30 minutes was heated. At 70 ⁰ C, The product was subjected to distillation under (reduced pressure to obtain 73 g of aeyiierten. Product having a boiling point of 149 ° 0 / l mm Hg. The acetylated product was hydrolyzed in 150 ml of an aqueous 2N sodium hydroxide solution containing 15 ml of methanol. The product was extracted with ether, washed with water and dried, whereupon the solvent was distilled off under vacuum This gave $ 1- g of compound 5. ■

009844/0817

Nitrogen analyzes ^- Gef .: 4.99 %, Ber.s 5.13 %.

The invention is explained in more detail below with the aid of examples.

example 1

After adding suitable amounts of an anti-whistling agent, a stabilizer and a hardening agent, a photographic silver halide emulsion, the 4.0 g of a silver halide (chlorobromide silver, consisting of from 50 mol # silver chloride and 50 mol # silver bromide) and IX, 0 g gelatin per 100 g of the emulsion contained on one photographic baryta paper applied and dried. (Emulsion I).

In addition, the photographic emulsion of 10 ml 100 g each of the emulsion of a 0.3 # methanol solution the compound 11, 3 * 6-diphenyl-2,3a, 5,6a-tetrazaperhydropentalen-1,4-dithione, and appropriate amounts of the additives mixed and applied to a photographic baryta piper and dried (Emulsion II).

There was also added 0.03 g of the above compound 11 was dissolved in 1 ml of methanol and the resulting solution became uniform with 2.5 g of the alkaliphilic

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hydrophobic solvent, namely the compound 2,3- £ N- (2-ethylhexyl) -aeetamidoj-propionic acid / mixed. The solution was added to 100 g of the above photographic emulsion (see Emulsion I) and after adding appropriate amounts of additives the resulting emulsion was applied to a photographic Baryta paper (Emulsion III) applied.

Each of the three types of "

photographic lichtempfindSchen papers was exposed while SQ sec developed. at 20 ⁰ C in a conventional developer for photographic Lapier, a calender treatment (glazing) was subjected at 100 ° C, after which the sensitivity and the maximum reflection density of the material thus obtained were measured. Speed was based on the reciprocal of the exposure (C-.M.-S.) Multiplied by 100 required to obtain a density of 1.0. The results are compiled in Table I t below.

Table I. Max. Density emulsion Seriousness 1.61 I -. . 1.79 II 350
*. " 1.76 III 54.5

009844 / OS17

These results show that the emulsion II a high protective effect against the "Plumming" phenomenon had compared with the emulsion I that the sensitivity but the same _t usi about 40% of that of the emulsion was lowered * I. On the other hand, in the case of the emulsion III according to the invention, di © ^l! Pliiramlng ^w appearance was sufficiently reduced, although the decrease in sensitivity was only about 10 % of that of emulsion I.

-. V example. 2

After adding appropriate amounts of an anti-fogging agent, a stabilizer and a Hardener was a photographic emulsion, the Contained 4.5 g of a silver halide per 100 g of the emulsion, applied to a photographic bary1 and dried. '(Emulsion I?) "

In addition, 50 ml of the potassium salae of 5-mercapto " 3-phenyl-2-thiol-1,3 * 4-thia2olon, as under compound 15 indicated, dissolved in 2 ml of methanol and the resulting solution 100 g of the emulsion IF was added. After adding suitable Quantities of additives were then applied to the photographic light-sensitive emulsion thus prepared Baryta paper applied and dried (Emulsion "V).

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Furthermore, the risk of protection against the

^ - ^ psGheintsBg ^ namely connection 15 _a iii dissolved 2 ml of methanol and the so-formed solution% o? de uniformly with 2> 5 g of the alkaliiphilic hydropllobe solvent, namely de? Compound S ₄ , 3- | ^ «{3 ^ ie ^ loxypropyl) -acetamidoj-propiOKSäure _Ä with Yerwenäung of Öj5 g of the compound 6, ethyl« 2 * methyl-3- (Hn-he ^ l ^ raised as an auxiliary solvent, E The resulting mass was added to 100 g of the above-prepared piliotographic El slon IV and, after the addition of suitable amounts of additives, the photographic light-sensitive emulsion was applied to photographic paper and dried (emulsion VI) *

The three types of photö = * graphical photosensitive papers as in Example 1 is treated and the results are listed in Table II below - ..

■■■■;.; ■: - ^: '.'- "' ■ ■ ■; Table II ';'^:]; ¹ :;:;. Emulsion sensitivity

IV-. :. λ -. ■■ - ■; ■: ■■ ;; ■ --- ■■ Ff ⁰ - ^: ' - ■■ -' ■ ■ '. '-'------ i ") v ■■".; ... ^{; .;:} - ■ ^ ■ ■■ ^^ _vV: ^ _{Q:. l ·} ■ ^ ■ ^; ■; _: - ■■ : /r.;^ VI --- .. '' : = ■ ■ - .. "'■■■

BATH ORIGINAL ^ -

From the above data, it can be seen that in Emulsion 7, the "puffing * effect was prevented as compared with the case where Emulsion IV * was used. However, the sensitivity was lowered by about 40 Ji from that of Emulsion IY On the other hand, in Emulsion VI according to the invention, the "plumming" effect was sufficiently prevented and its sensitivity was only reduced by about 15% from that of Emulsion XV.

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Claims (1)

1 »PnotogpPapMsöhes liohtempftndliebes halogen silver element; with a layer- bearing TrUgQr, characterized in that at least one layer has at least one : "■". """.-.".".':"-'" ^: - ■■"'. ■. ■■ ".-" ■ ". ■■ ': ■■"'"." ■ - f *** p * 4r 4Ae * ■ ...- " SöhutssBiitt & i ^^ j gegeniber ^ AV ^ biaig inAleigrau xxnd einp- " ■ % dii * tt! U £ ~ ■■ ;. .ν: ■ --- ■ ";. ■■ - - ■. * ■, ■■; ■■ -" ■■. Äbnaisme ^ dli ^ Jichte {"Plmnming ^ -E ^ Tekfci contains, being. the middle of this layer is in the form of a fine dispersion its solution in a hiclit volatile "brganisehen Solvent included in the manufacture of pfeötogs'aphischen light-sensitive sleisients practical J ^ iMa is soluble in water> but from the layer under the J5Ät ^ «teiussg ^ is removed, voitiaMtn is * /. .- · ■ - ■ -.- 2 »/ Halogensiitorelement-naöh ^ ftPSppsietL Ig characterized by the fact that a non-addictive organic solvent is used, which under the production conditions of photographic light-sensitive elements, the pH value is lower ISTJ than 7, substantially water is not soluble _e and which is under the development conditions hei ^ a pH value of above 8 released from the Sehieht " 009844 / 0§17 BAD ORIGINAL ν j5. Halogen silver element according to claim 1 or 2, characterized in that the non-volatile organic solvent consists of a compound of the general Formula (I) * __. - CH - COOH where X is a hydrogen atom or a methyl group and R and R * each represent an optionally substituted alkyl group, the total number of carbon atoms of the radicals R and R * in the range from f to 11. 4. Halogen free element according to one of claims 1 to 3, characterized in that the connection of the general Formula (I) from the group of 2-methyl -> - (N-nhexy! Acetamidoj-propionic acid, 3- / N- (2-ethylhexyl) -acetamido-propionic acid, 2 »methyl-3- (N-n-ocfcylacetamido) propionic acid, 3-iN-n-butyloctanamido) propinic acid and 3- / fi- (^ -hexyloxypropyl) -acetamidoj-propionic acid was chosen 5. Halogensüberelement according to any one of claims 1 to 4> characterized in that the solution of the protective agent versus the "plumming" effect in an organic solvent is obtained by adding the protective agent directly to the non-volatile organic solvent. , 009044/0517 BATH ORIQiNAl: 6. Halogen over element according to one of the claims 3. to 4, characterized in that the solution of the protective agent versus the "plumming" effect in an organic Solvent by addition; of the protective agent to the slightly soluble organic solvent in the form a solution in. An auxiliary solvent is obtained. 7 »Hatogen silver element according to one of claims I to 6, 'characterized * that the auxiliary solvent from Methanol, acetone, dimethylformamide, ethyl acetate, methyl « ethy! ketone or a compound of the following general ones Formula (II) - COOR " where X is a hydrogen atom or a methyl group, R and Tt ¹ each represent an alkyl group or substituted alkyl group, the total number of carbon atoms of the radicals R and R 'being in the range from J to 2.1 and R "represents a methyl or ethyl grugs. 8. Halogen silver element according to claim Y _3, characterized in that the compound of the general formula (II) from the group of Äfchyl-2-methyl 1-3" (Nn » propionate, ethyl-3 ^ra fe ~ (p '.Ir Methy l ~ 2 «m © thyl» 3 = (N = n-oc ty lace tasaido) «« propionafc ^ tlothyl 5 «(nn-butylo c taminasiido)« propionate and M © th2rl = 3 ° £ N- (3 = · hexyloxypropyl) «ac © tsäaidol propionate is selected isfe _o · BADORiGlNAL 9. A method for Herat ellung ¥ on ® ± mm pho fco «graphic photosensitive halogen silver element according to ®in © ra der-claims 1 to 8, characterized in that, at least one layer is at least © in Schutsmittel against discoloration and reduction..dep Reflection thickness ("plumming" effect) combined in the form of a fine dispersion in a solution of the same in a non-volatile alkali-philic, hydrophobic, organic solvent in water under the conditions of the photographic photosensitive element at a pH value is soluble from below 7 toma * However, under the developing conditions at a pH <* value of above 8, it is dissolved out of the layer. ^ - XO. The method according - in Anspruoh 9 _S by one -that the Schutzmittel'unmittelbar: in the alkaliphilic hydrophobic organic solvent lcSsfc. Xl _a method according to claim 9 * characterized in that the protective agent is dissolved in the alkaliphilic hydrophobic organic solvent using an auxiliary solvent »' BATH ORIGINAL