DE2110521B2 - COLOR PHOTOGRAPHIC MULTI-LAYER RECORDING MATERIAL - Google Patents

Description

55

The invention relates to a multilayer color photographic recording material which contains hydrophilic co-oid layers of variously sensitized silver halide emulsions in which, during color development, an oxidized primary emulsion is reacted. aromatic amine as FarbentwieSdei-vefbihdung with color couplers, color images are generated, wherein at least one of the hydrophilic KoUoidschichten ^nt a dispersion of a nioht-diffusing 4 ^'vef fäf * buhgsmittels contains based on a sec-Alkylhydrochinonderivats.

It is generally known that color fog can easily occur in the erosion layer B during color development of color photographic recording materials, the formation of which is attributable to it. be that the Farbcntwicklerverbindung-en upon exposure VOA Uift oxygen oxidizes aod the oxidized Farbentwicklerverbjndangen with Farblpipplern in such districts domes, has been generated in Denes no silver image, the occurrence of color fogging is festzusteflpn particularly in piss Aufaeichnungsmaterialien which contain in the light-sensitive Schiebten color couplers.

In order to prevent the occurrence of color fog in color photographic recording materials, it is known in the records as an anti-discoloration agent Incorporate hydroquinone derivatives. From US-PS 24 03 721, for example, the use of 2,6-di-n-dodecylhydroquinone, from U.S. Patent 27 28 659 the use of 2-n-alkylhydrocbinones, z. B. 2-n-dodecyl hydroquinone, of U.S. Patent 2,732,300 the use of unsymmetrical dialkyihydroquinones. z. B. 2-sec-octadecyl-5-methylhydroquinone and from US Pat. No. 2,701,197, the use of sulfonated hydroquinones, e.g. B. sulfonated sec-undecylhydroquinone known.

However, it has been shown that the alkyl and dialkyl hydroquinones used hitherto have certain Clinging to power. Many of them are difficult to manufacture in two to four-step processes, others have molecular weights that are too low to be used in multilayer color photographic recording materials migrate between the individual layers, resulting in undesirable side effects, while others crystallize during or after the coating process and deliver poor quality layers while in turn other rtlkylhydroquinones are subject to oxidation during the coating or during the Develop colored by-products.

The object of the invention is to provide a multilayer color photographic recording material with a Indicate anti-discoloration agents in which the air oxidation of color developing agents is certain is prevented and no crystallization of the anti-discoloration agent he follows

The invention was based on the knowledge that this object can be achieved that one as Anti-discoloration agent uses a mixture of isomers of at least two secondary dedocylhydroquinones.

The invention accordingly provides a multilayer color photographic recording material, which contains hydrophilic colloid layers of variously sensitized superhalide emulsions in which in color development by reacting an oxidized primary aromatic amine as Color developer compound with color couplers color images are generated, at least one of the hydrophilic KoUoidschichten a dispersion of a non-diffusing anti-discoloration agent on the Contains base of a sec-alkylhydroquinone derivative which is characterized in that it consists of eleven isomeric mixtures as a non-diffusing anti-discoloration agent contains at least two sec-dodecylhydroquinones

In the simplest of mixtures that are two different containing sec-dodecylhydroquinones is one thing Compound usually in a concentration of 1 to 99 wt .-% and the other compound in one

_ λ from 99 to 1 % by weight «a ·. Preferably • compound in a concentration of 5 Tfe and the other compound in a j from 95 to 5 wt .-% wr. BrSndung ^ e the most varied mixtures of .j - * - inoneo can be used. So

ΐ be used: from 2-sec.-Dodee ^ hydr <x: biaonea, in the compounds in the number r arrangement (positional isomers) of the Kohne differentiate in the alkyl groups,

_ "Ι from ^ -Di-sec-dodecvüiydroquinones,

which the compounds differ in the number ld / or the arrangement of the carbon atoms in the alkyl group on one of the two substituents " ^r -, Ah

he the one described under 1. and 2.

10

; Mixtures used are mixtures of isomers of a 2-sec-dodecylhydroquinone, mixtures of isomers of a 2.5-di-sec-dodecylhydroquinone or mixtures of a 2-sec-dodecylhydroquinone (a single compound or mixtures of two or more isomers) and a 23-di -sec-dodecylhydroquinone (a single compound or mixtures of 2 or more isomers). The isomer mixtures used according to the invention are expediently prepared by reacting hydroquinone with the corresponding primary olefin in the presence of a Lewis acid at elevated temperatures over a longer period of time, so that isomeric forms of the primary olefin are formed which are substituted with the hydroquinone to form at least one minosubstituted sec-dodecyl hydroquinone and at least one disubstituted sec-dodecyl hydroquinone react in one reaction stage. An inert solvent, preferably a water-immiscible solvent, for example benzene, nitrobenzene, is expediently used for the reaction mixture. Toluene or xylene is used. Lewis acids are protons and proton donors, for example acids, as well as metal atoms that are able to form coordination systems with water or ammonia, the sulfur of sulfur dioxide, sulfuric acid, sodium bisulfite as well as atoms and free radicals with incomplete electron shells. Particularly suitable Lewis acids are sulfuric acid, phosphoric acid, hydrochloric acid, sodium bisulfate, monosodium phosphate, zinc chloride, aluminum chloride, boron trifluoride, benzenesulfonic acid, silicon dioxide-aluminum oxide mixtures and acidic ion exchange resins. It has proven advantageous to heat a solution of the hydroquinone in a solvent together with the Lewis acid in order to remove any moisture from the mixture in the form of an azeotropic mixture and then the primary olefin while increasing the temperature of the reaction mixture to a temperature of about 130 to admit to about 24O ⁰ C for a prolonged period of time. The rate at which the olefin is added to the reaction mixture, the rate of heating and the reaction time can be controlled so that the desired mixture of isomers is present in the final product. The most favorable reaction conditions depend on the particular mixture of isomers desired and can easily be determined. After the reaction has ended, the reaction mixture is cooled and poured into a suitable organic solvent, for example ligroin. The Lewis acid mrd ducch. fftaäer-eja or some other suitable measure removed The unreacted olefin is separated by ßes $ latipn at reduced pressure, then by distilling the isomeric mixture at reduced pressure or by some other suitable measure from the remaining reaction slurry. The hot isomer mixture can thereby be split before an air oxidation that it is kept under a sackcloth atmosphere.

Examples of particularly advantageous according to the invention Usable isomer mixtures are:

Mix 1

2- {l -methyumdecylJhydrGquinone,
2- (1-Ethyidecyljhydroquinone,
2- (l -ButyloctyJJhydroquinone,
2- (1 · Aipylheptyi) hydroquinone,
2,5-di (1-methylundecyOhydroquinone,

-äthyldecyOhydroquinone,

-butyloctyOhydroquinone,

-propylnonyljhydroquinone,
2,5-di (1-amylnepty ^ hydroquinone,
2- (l -methylundecyl) -5- (l -propylnonyljhydroquinone,
2- (l -methylundecyl) -5- (l -ethyldecyljhydroquinone,
2- (l -methylundecyl) -5- (l -butyloctytyhydroquinone,
2- (l -methylundecyl) -5- (l -amylheptyl) hydroquinone,
2- (l-ethyldecyl) -5- (l-butyloctyl) hydroquinone,
2- (1-butyloctyl) -5- (1-amylheptyl) hydroquinone and
2- (1-propylnonyl) -5- (1-amylheptyljhydroquinone.

Mixture 2

Like mixture 2, but with the following additional compounds:

2- (l -propylnonyl) hydroquinone,
2- (1-Ethyldecyl) -5- (I-propylnonyl) hydrochiaon,
2- (l-Ethyldecyl) -5-5 (l-amylhepty!) HydrO4: hinonund
2- (1-propyl nonyl) -5H 1 -butyloctyl hydroquinone.

Mixture 3

Like mixture 2 but contains 2 - (! - propylnonyl) hydroquinone instead of 2- {l-amylheptyi) hydroquinone and 2- (l-ethyldecyl) -5- (l-propylnonylhydroquinone, 2- (1-Ethyldecyl) -5- (1 -amylheptyl) -hydroquinone and 2- (l-propylnonyl) -5- (l-butyloctyl) hydroquinone in place of of 2- (1-propylnonyI) -5- (1 -amylheptyl) hydroquinone and 2- (1 ■ butyloctyl) -5- {1 -amylheptyl) hydroquinone.

Mix 4

2- (1-methylundecyl hydroquinone and
2,5-di- (1-methylundecyl hydroquinone.

Mix 5

2- (l -methylundecyl hydroquinone,

2,5-di (1-methylundecyOhydroquinone,

2,5-Di (I -ethyldecyl) hydroquinone and

2- (1 -methylundecyl) -5- (1 -ethyldecyOhydroquinone.

The mixtures used according to the invention are eutectic mixtures or nearly eutectic mixtures. The isomer mixtures can be in the known photographic hydrophilic colloids, e.g. B. gelatin, albumin, collodion, gum arabic, Agar-agar, cellulose derivatives, for example alkyl esters of carboxylated cellulose, hydroxyethyl cellulose, polymers such as those from US Pat. No. 2,949,442 known amphoteric copolymers, polyhydric alcohol, polyvinylpyrrolidone and copolymers

21 10621

of an alkyl acrylate, aflcycarbonylacetoxya! - Jigfteicrylat and a Suuoalkylacrylat or the Acryisiure, as known from US Pat. No. 3,488,708, for example, are dispersed. The one at Rauroteraperassir Let the liquid isomer mixtures disperse without using a solvent. CSe at Isomer mixtures which are not liquid at room temperature are expediently in F wm a solution in

1. a high-boiling organic "crystaloid" Solvent, i.e. one handy in water insoluble organic solvent iuit niedua Molecular weight with a boiling point greater than about 175 ° C, for example alkyl esters of phthalic acid, e.g. B. methyl phthalate ethyl phthahu, Propyl phthalate n-butyl phthalate di-n-butyl phthalate, n-amyl phthalate isoamyl phthalate and dioctyl phthalate esters of phosphoric acid, e.g. Triphenyl phosphate tricresyl phosphate, diphenyl mono-p-tert-butyl phenyl phosphate or

2. low-boiling organic solvents, such as z. B. short-chain aikylaeetaien, ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, j8-ethoxyethyl acetate Methylcellosol acetate and acetylacetone

dispersed.

The dispersions which can be prepared from the isomer mixtures in hydrophilic colloids are notable characterized in that they are prior to storage at temperatures below room temperature. during and after the coating of the substrate does not crystallize. The one using the isomer mixtures The dispersions produced are also distinguished by the fact that they do not lead to discoloration. the Dispersions can be incorporated into any layer of a multilayer photographic recording material, in which anti-stain agents are used. For example, you can incorporated into one or more photosensitive layers of a multilayer recording material will. They can be used in photographic recording materials, which contain color couplers in the light-sensitive emulsion layers, or in recording materials, which do not contain any color couplers can be used. In the case of multilayer recording materials it can either be camera-sensitive recording materials or such as are used for the production of color prints. The recording materials can Usual support from, for example, paper, cellulose acetate or synthetic polymers, such as those commonly used have.

The isomer mixtures are dispersed in the hydrophilic colloids in concentrations of from 0.01 to 90, preferably from 1 to 85% by weight, based on the dry hydrophilic colloid. The optimum concentration depends on the particular photographic recording material in which the anti-discoloration agent is to be used. S ^; e can be easily determined by known methods.

The isomer mixtures used according to the invention bring about a reduction in the oxidized form any color developing agent to the aromatic primary amine Developer compound or to a form that does not couple with a color coupler. To prevent the Migration by development in a photosensitive layer deposited oxidized color developing agent in another layer with discoloration The other layer has hydrophilic layers arranged between two light-sensitive slides Colloid layers containing a mixture of isomers Proven to be very effective.

The following examples are intended to explain the invention in more detail.

example 1

A. That from US-PS 27 28 659 as an anti-staining agent known ^ -Di-n-dodeolhydroquinone, hereinafter designated as anti-discoloration agent X, was in a four-step process according to US Pat. No. 2,728,659. Column 8, lines 48-68, prepared, F. 108-110-C

B. A mixture of isomers of sec-dodecylhydroquinones was made as follows:

To a 500 ml four-necked flask in an oil bath equipped with a stirrer, a distillation head, a dropping funnel and a thermometer, 55 g of hydroquinone, 8 g of a silica-alumina catalyst and 100 ml of toluene were charged. The reaction mixture was heated with stirring, an azeotropic toluene / water mixture being distilled off. After about 75 ml of the mixture had been distilled off, the temperature of the flask was about 130 ^° C. 150 ml of 1-dodecene were then added to the hot reaction mixture temperature of the oil bath at 230 ° C heated the reaction temperature rose over a period of two hours at 220 ⁰ C. After an hour had long been adhered to a temperature of 220 to 225 ° C, a further 100 ml of 1-dodecene was added dropwise so rapidly added, that the temperature of the reaction mixture did not drop. After stirring for a further three hours at this temperature, the flask was removed from the oil bath. The reaction product was kept under a nitrogen atmosphere to avoid oxidation. After the reaction mixture had cooled to 120 ° C., it became Carefully poured into 500 ml of ligroin and the silica-alumina catalyst was filtered off rt and washed with ligroin. The ligroin was then distilled off from the reaction product at atmospheric pressure. The unreacted dodecene was drawn off by distillation under reduced pressure, a ^{fraction boiling at 78 HO 0} CZ10 mm Hg being collected. The reaction product was distilled in the vacuum created by means of an oil pump, a fraction boiling at 210-250 ° C./0.15 mm Hg being collected. The yield of reaction product was 185 g, corresponding to 83% of the theoretical amount of 226 g, based on the amount of hydroquinone used. The mixture of isomers obtained, hereinafter referred to as anti-discoloration agent A, was liquid at room temperature. A gas chromatogram showed that the mixture consisted of 12 out of fifteen possible disubstituted isomers (95% by weight) and four out of five possible monosubstituted isomers (5% by weight).

C. Dispersions of the following composition were prepared from the anti-discolouring agents A and X:

50 g anti-discoloration agent,

25 g trieresylphosphate,

60 g gelatin dissolved in 600 ml water.
Immediately after their preparation, the dispersions were applied to customary layer supports in such a way that a layer support area of T m * 6470 mg of gelatin accounted for.

< The result was the following ".

. Compound X immediately crystallized, which is evident from a photomicrograph of the cross section of generated 'layer was recognizable. In the case of the layer produced from "Anti-discoloration Agent A", no crystallization found.

In another experiment, the anti-staining agent A and X containing dispersions were held for two hours at a temperature of 4O ⁰ C and then examined for crystal formation. Crystal formation occurred only in the dispersion containing the anti-discoloration agent X. During storage, the dispersion containing the anti-discoloration agent X turned blue due to the oxidation of the hydroquinone to a colored quinhydrone. The results obtained show that an isomer mixture which can be used in accordance with the invention is superior to the anti-discoloration agent X in terms of its resistance to oxidation.

Example 2

It became another well-known anti-stain agent. namely 2.5-di-tert-octylhydroquinone (cf. US-PS 20 08 032 and 20 08 337) - hereinafter referred to as anti-discoloration agent Y - with the in Example IB described anti-stain agent A compared. For this purpose, two dispersions were made manufactured as follows:

1. A solution of 40 g of the anti-discoloration agent Y in 20 g of tricresyl phosphate was prepared The solution was dispersed in one liter of 8% aqueous gelatin.

2. It became a solution of 40 g of anti-stain agent A made in 20 g of tricresyl phosphate. The solution was also 8% in one liter dispersed aqueous gelatin.

The two dispersions were left to stand for two weeks at a temperature of -3.9 ° C (25 ° F) and 45% Stored relative humidity Crystallized from the dispersion containing the anti-discoloration agent Y the anti-stain agent off. To the inferior quality of the anti-discoloration agent Y containing To show dispersion, the dispersion was melted and filtered. This left a considerable amount Part of the crystallized anti-discoloration agent Y on back to the filter. In contrast, in the dispersion of the anti-discoloration agent A, no crystal formation occurred on. The dispersion passed the filter with no residue.

Example 3

Three multi-layer color photographic record paper layers of the following: Aoßjaus are made by one Dfchtstafen lighted, color developed, washed and dried

Recording material No. 2

-Color cup-

^! , 1080 mg DäHrtyph- As material no. 1, but with 280 mg anti-discoloration agent X / m ² in layer 2, dispersed as described in Example 2. ~ - '

Recording material no. 3,

Like material no. 1 ", but with 200 fng · anti-discoloration agent A / m ⁴ in layer 2, dispersed as described in example 2.

The effectiveness of the anti-stain agents A and X was determined by determining the amount of in layer 3 The blue-green dye formed is determined by the reaction of oxidized color developing agent of Layer 1 with the Layer 3 coupler. The results obtained are in the listed in the following table:

Material no.

Anti-discoloration agent

Density of
blue-green
Dye

25 1 without 0.95 2 X 0.64 3 A. 0.42

The results show that the anti-discoloration agent A which can be used according to the invention was clearly superior to the known anti-discoloration agent X in terms of its effectiveness.
The cyan color coupler used in layer 3 was a coupler of the type known from US Pat. No. 2,801,171. The yellow color coupler used in layer 1 is an α-pivalylacetanihd coupler of the type known from US Pat. No. 3,265,506. The silver halide emulsion used was a silver bromide iodide emulsion. The color developing, bleaching and fixing solutions used had the following compositions:

Color developing solution

Benzyl alcohol

Sodium hexametaphosphate

anhydrous sodium sulfite

Sodium carbonate monohydrate

Sodium bicarbonate

Potassium bromide

Sodium chloride

Hydroxy amine sulfate

Farfeemwctder «·)

pH value at 23yS ° C

Mh water aaigefi9It adf 1 Utter

►) 4-Amino-N-adi $ H * - φ

12.6 ml
2.0 g

2.1g
26.8 g
25g
0.48 g
0.7 g
2.1g
42g

Sodium nitrate

45.0 g

age

Boric acid

borax

With water aiagefaltasf 1 Later

mg

ίο

Fixing solution

Sodium thiosulfate

Sodium bisulfite

Av anhydrous sodium acetate

Sodium citrate

Boric acid

Potassium aluminum sulphate (granules)

Made up to 1 liter with water

223.0 g

12.0 g

14.0 g

1.7g

5.0 g

24.0 g

Example 4

A mixture of 50 g of anti-discoloration agent A and 60 g of gelatin in 600 ml of water was passed through three times given a colloid mill. The dispersion obtained was in comparison with the dispersions of Example 1 about 19% lighter. The liquid anti-discoloration agent did not require any additional solvent to make a durable dispersion. In the photographic Tests showed that this dispersion with a corresponding dispersion in a solvent was practically identical.

Example 5

Further dispersions were prepared according to the method described in Example IC, this time but instead of gelatin equivalent amounts of CoHodium, agar-agar, hydroxyethyl cellulose, polyvinyl alcohol, Polyvinylpyrrolidone or a copolymer of methyl acrylate, S-Acrylcyloxy-1-methylpropane-1-sulfonate, The sodium salt and 2-acetoacetoxyethyl acrylate were used Results obtained as described in Example IC.

Example 6

There were two multilayer color photographic recording materials A and X of FIG US-PS 22 52 718 known type made. They consisted of a layer support, a red-sensitized one Gelatin silver bromide iodide emulsion layer, a gelatin layer, a green sensitized gelatin silver bromide iodide emulsion layer a gelatin layer containing a bleachable yellow dye; and a blue-sensitive gelatin-silver bromide iodide emulsion layer in the order given. In the gelatin layers between the photosensitive ones Layers, however, were anti-discoloration-nikel

Sections of the recording materials Α _: were exposed to the correct image and then according to the US-RS 22 52 718 known, VeriaHreÄ "While a blue-green discoloration of purple occurred in the developed image, the recording material was &". && of any discoloration. 1

Example 7

There were two multilayer Farbaufeeighirtl materials 1 and 2 according to Example Column 7, IeIc _JO to column 8, line 28 of US Pat. No. 2,956,879, in which the following layers were applied to a substrate:

1. One, a yellow color coupler and an anti-discoloration agent containing blue-sensitive gelatin silver chlorobromide emulsion layer, 2. a gelatin layer,

3. a green-sensitive one containing an anti-discoloration agent Gelatin silver chlorobromide emulsion layer,

4. An ultraviolet light absorbing compound and an anti-discoloring agent containing

Gelatmeschicht and

5. an anti-discoloration agent containing, red-sensitive hs Gelatin silver bromide iodide emulsion layer.

The recording materials were identical to the ^{recording material described in Example 2 of the} above-mentioned US Pat. identical with the exception that the recording material I is a dispersion of the anti-discoloration agent X, as in Example 1A and IC

described as an anti-stain agent in each of the one Anti-discoloration-containing layers were used. The crystallization of the anti-discoloration agent X from the dispersion before, during and after

.o ° "<J ^chtun g ^sv ° '-irang led to serious

Coating defects.

^ f ^Recording material 2 corresponded to the

An? V ⁿ Ä ^materiai ' ^{mh, with the} exception that from An impeding the dispersion of the

«£ r" L? f ^r i ^{Ung 'by means of X in} each of a Antiverftr-ΪΚ ^enthaIt layers a dispersion of fc h "t T ^gSmiUels · ^K * ^m was ^Examples IB uad tratenT Ä et ^verwend. In this case

Ah _S ohn "t" of the AufzeichnungsmateriaUen ^ 1 2 1, and exposed and after the developing process known from

end

J X were divided among specially prepared dispersions, that before, during

so that was.

A containing A is neither crystal clear nor A the end.

exit. of special

* Θ? Μ

1 M. \ J XJ Cu I

iGelaunei-Sübirhal ^ lenidemulsion layer with «32.1 mg GeMine, 2.4 mg silver halide, 10.7 mg a coupler providing a ggibeh dye +), dissolved in 10.7 mg di ^ butyl phthalate as coupler solvent;

Layer 3:

Gelatin layer with 10.7 mg gelatin,

Layer 4:

Gelatin layer without silver halide with t'0.7 mg Gelatin and 535mg of a biaogreen Dye-supplying coupler + +), dissolved in 5.35 mg Di- ^ butyl phthalate as a coupler solvent.

Recording material E (according to rfinduftg):

This recording material differed from recording material D only in that layer 3 additionally contained 2.86 mg of the isomer mixture.

The amounts of secOodecylhydroquinone used were the amounts of 2,5-Di-SeC-OG-tylhydroquinone used equivalent to.

Sections of the recording materials were exposed in a sensitometer to white light through a test object with graduated density levels (21 levels with a density range from O ₁ O to 3.0). The exposed sections were then developed as follows at 70 " C:

Recording material B

This recording material differed from recording material A only in that layer 3 additionally contains 1.07 mg 2,5-di-sea-octylhydroquinone of the following formula:

secr

Color development +) 10 min. Interrupter fixer + +) 5 min. To wash 5 min. Bleach + + +) 5 min. To wash 5 min. Freeze + ⁺ + ⁺ ) 5 min. To wash 10 min. dry

-lake.

OH

Recording material C

This recording material differed from recording material A only in that layer 3 additionally contained 2.14 mg of 2,5-di-sea-octylhydroquinone

Recording material D (according to the invention):

This recording material differed from recording material A only in that layer 3 additionally i, 43 mg of an isomer mixture of sec-dodecyihydroquinones, prepared as described in Example IB

+) The color coupler consisted of:

a-Kvalyl-2-chk) ro-5-3K2. '* -
acetanffid of the formula:

to also the stripes B and C
Anti-discoloration agent
Layer 3 ineffective
Migration oxidized

⁺ ) A color developer solution as described in lines 15-25 of column 8 of US Pat. No. 3,700,453 was used

^{+ +} ) A break fixer as described in lines 38-44 of column 8 of US Pat. No. 3,700,453 was used.

% o ^{+ + +} ) A bleach bath as described in lines 30-35 of column 8 of US Pat. No. 3,700,453 was used

+ + + +) The breaker fixer bath described was used.

If no oxidized color developing agent (generated as a result of the Development of the exposed silver halide of layer 3) migrates through layer 3 into layer 4, so no blue-green dye is produced in layer 4. In this case, the test strip must be yellow Appearance of only a yellow dye in layer 2 due to coupling between oxidized color developing agent and the iron yellow dye-forming color coupler of layer 2 is produced.

In practice, however, some oxidized color developer molecules migrate which do not stick to the Color couplers of the layer 2 have implemented in the layer 4, in which they are with the one present here Color coupler producing a blue-green color

so dome fabric. The result is a green-looking test strip in which the yellow dye of layer 2 absorbs blue light and the added blue-green dye of layer 4 absorbs red light (white minus blue minus red results in green).
The five test strips show the following:
The punishments of the Ai & SaclliuUUgSiaaEMigls Λ tst ^ m ^ as a result of the Abwesemliiäh. of an outdoor exercise center or blanket for the

21 VQ 621

That used to carry out the experiments (production of recording materials B and C) octylhydrochi (iön \ yüfde produced by the following method: ''

OH

2CHi = CH (CH ₂ ) JCH ₃

toluene

Cleavage HC— ^ s
catalyst ^

A 1 liter three-necked round bottom flask equipped with a mechanical stirrer and a distillation column was heated by means of an electrically heatable jacket. Then 220 g (2 moles) Hydroquinone, 448 g (4 moles) of 1-octene, approximately 5 g of cleavage catalyst and 150 ml of toluene were added. That

OH

Water was distilled off in the form of an azeotropic mixture, whereupon the residue took 6 hours Pressure was heated to 107 ° C. The reaction mixture was then extracted with ethyl acetate and filtered, and the filtrate was concentrated under reduced pressure and was then distilled.

Claims (1)

t color photograpteches multi-layer the hydrophobic colloid g p tea aits different seasibflized powdered hookah emulsions contains, is those at the Farbeatwicktaag by converting an oxidized primary aromatic amine as a color picker oil πώ fOTbkupplera color images are generated, where At the very least, ele of the hydrophilic koiioidscichten a dispersion of a non-diffusing anti-stain agent on the basis of a sec-ABcylhjti.u contains quinone derivative, characterized in that that it is a mebt-diffusing and-is discoloration medium isomeric aas at least contains two sec-dodecylhydroquinones Z multilayer color photographic recording material according to claim 1, characterized characterized that it is aicht-diffandierendes Anti-discoloration agent from a mixture of isomers a) at least one mono-seaidodecylhydroquinone with 1-methylundecyl-, 1-ethyldecyl-, 1-propylnonyl-, 1-butyloctyl or 1-amylheptyl radicals as sec-dodecyl substituents and b) at least one 2.5-sec-dodecylhydroquinone with 1-methylundecyl, 1-ethyldecyl, 1-propylnonyl, Contains 1-butyloctyl or 1-amyiheptyl residues as see-dodecyl substituents 3. Multilayer color recording material according to claim 1, characterized in that it consists of an isomeric mixture as the non-diffusing anti-discoloration agent a) at least two mono-sec-dodecylhvdroquinone isomers with 1-methylundecyl, 1-ethyldecyl, 1-propylnonyl, 1-butyloctyl or 1-amylheptyl radicals as sea-Dodecylsubstuenten and b) at least two di-sec-dodecylhydroquinor isomers with 1-methylundecyl, 1-ethyldecyl,! -propylnonyl, 1-butyloctyl or 1-amylheptyl radicals contains as sec-dodecyl substituents 4. Multilayer color photographic recording material according to claim 1, characterized characterized uß as a non-diffusing anti-discoloration agent from a mixture of isomers a) four mono-sec-dodecylhydroquinone isomers with 1-methylundecyl, 1-ethyldecyl, 1-propylnonyl, 1-butyloctyl or 1-amylheptyl radicals as substituents ?, and b) twelve 2,5-di-sec-dodecylhydroquinone isomers with 1-methylundecyl-, 1-ethyldecyl-, 1-propylnonyl-, Contains 1-butyloctyl or 1-amylheptyl radicals as substituents.