DE2160714A1 - Color photographic material - Google Patents

Description

21607H

PATENT LAWYERS

. H. LEINWEBER dipl.ing. H. ZIMMERMANN

8 Munich 2, Rosental 7, 2. Auig.

Part addr. Lelnpat Munich Telephone (0811) 2 <05 »··

Postal check account: Munich 22045

December 7, 1971

Our sign

POS 26 767

MITSUBISHI PiPEH MILLS, LTD., Tokyo / Japan Color photographic material

The invention relates to an improvement in the method of introducing anionic color couplers for color development or from rinsing agents with a chemical structure similar to that of the color couplers, into the protective colloid binders of the overlying ones Emulsion layers, intermediate layers or other layers of multilayer photosensitive material. For example, it is a method of introducing diffusion-resistant color couplers into the emulsion layers of a photographic material known as the "Agfa" or "Fischer process". The method according to the invention is an improvement on this Procedure.

The above method, which is the basis for the inventive Veranren is based on the method described in US Pat. No. 2,186,849 (1940), which is based on Agfa iitisco Corp., Binghamton, N.Y. According to this

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Process are long-chain hydrocarbons with 11 to 18 carbon atoms, as so-called "ballast groups", are introduced into the molecules of the color couplers and furthermore Carboxylic acid or sulfonic acid groups introduced to the compounds to make water soluble. Fundamental disadvantages of this process are based on the fact that the color coupler molecules are poorly soluble in aqueous medium and the considerable increase in the viscosity of an aqueous medium Solution of hydrophilic colloidal binders such as gelatin, polyvinyl alcohol and the like, which are mixed into the solution make it difficult to apply this solution as a coating. The color couplers tend to form micelles, which deteriorate the hue of the obtained color image. That developed Silver image tends to be included in the dye formed, making the bleaching process difficult. at In these processes, the most difficult problem is the excessive increase in the viscosity of the aqueous binder solutions due to the mutual influence between the color coupler molecules and the binder molecules. By the The method according to the invention solves this problem. Furthermore, substances such as color couplers are present which are used in the Coupling color development with the oxidation intermediates of color developers, but such unstable dyes result in that they decompose immediately or form leuco dyes which are so stable that they prevent formation not allow proper dyes, if necessary, substances may also be present, which redox reactions with the oxidation intermediate of the color developer and reduce the intermediate so that coupling does not occur. These substances are often used as detergents for the oxidation

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Intermediate products of color developing agents used which diffuse away from an emulsion layer; included the detergents are placed in an intermediate layer between the "two emulsion layers", causing a mixture of colors is prevented. These detergents have a similar chemical structure to the color couplers, see above that they can be achieved by introducing ballast groups and anionic Groups and incorporation into the interlayers of a multilayer color photographic material resistant to diffusion can be made. In this case too, the improved method is according to the invention, as in the above Fall, effective and there will be the extraordinary increase in viscosity of the coating solutions of intermediate layers effectively prevented due to the mutual effect between the detergents and the binding agent molecules.

The process of the present invention is intended to address various difficulties in introducing the Agfa couplers, or of detergents of similar structure, in the layers of a multilayer color photographic material avoided will. The main difficulty of the extraordinary increase in the viscosity of the binder solutions, as well as others Difficulty can to some extent durghh appropriate selection of couplers, detergents or binders be avoided. In the method according to the invention can however, all of the above difficulties are completely avoided.

The essence of the invention is based on achieving complete dispersion of anionic color couplers or anionic detergents of a similar structure and in the

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Prevention of viscosity increase due to the mutual action of the couplers or rinsing agents with the binders. Furthermore, in the process of the invention, the micelle formation of the couplers in the binder or the inclusion of the developed silver grains can be avoided in the dyes formed around these grains. This is done through a dispersion system from couplers or flushing agents due to complex formation with coacervate particles, which is achieved by Reaction of anionic polymers with phthalic acid esters with a cationic polymer in an aqueous medium are formed.

The formation of coacervate particles of suitable size is facilitated by the selection of cationic and anionic polymers favored; furthermore, excessive cation groups in the obtained coacervate particles become anionic couplers or detergent molecules are attracted to the surface of the coacervate particles and form a complex, each molecule is firmly adsorbed on the particle surface. Since this particle surface is sufficiently wide, the couplers become or detergent completely dispersed. Therefore, it also occurs in the event that the coupler or detergent is dispersed in Form added to the coating solutions of the emulsion layers or intermediate layers and with hydrophilic colloid binders, such as gelatin, polyacrylamide and the like forming these layers are mixed, no agglomeration the coacervate particles enter more. As a result, agglomeration or micelle formation occurs not only in the couplers prevented, but also the degree of mutual influence

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Solution between couplers or detergents remains quite small, so that the viscosity increase of the coating solutions is considerable is reduced.

The invention thus creates an improved method for the production of multilayer material, in which Kupp / ßr in the emulsion layers or adjacent Layers have been introduced and optionally detergent in the emulsion layers or interlayers between were introduced into the emulsion layers.

In the invention, the cationic polymer used in the above case is made of a polymeric one organic hydrophilic compound containing a cationic nitrogen-containing group such as various aliphatic ones Amines, aromatic imines or other organic bases such as pyridine, morpholine, piperazine and guanidine, which are fully or partially quarternized.

Typical examples of such connections are:

(I) poly-2-vinyl pyridine

(II) poly-4-vinyl pyridinium methyl p-toluenesulfonate

(III) poly-4-vinylbenzyltrimethylammonium chloride

(IV) poly-4-vinylbenzyltriethanolammonium chloride

(V) poly-4-vinylbenzylmethylmorpholinium chloride

(VI) Poly-4-vinylbenzyldimethylcyclohexylammonium chloride

(VII) Polymethacryl dimethylaminoethanol ester benzyl chloride

(VIII) Acetic acid salt of partially aminoguanidized polyvinyl ethyl ketone.

(Ia) .kminoguanidized dialdehyde starch.

- 6 - Ί 0 9 ίί 2 7 / C) 9 C) 3

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The structural formulas of these compounds are in the following is shown schematically:

(D

H _x C

N.

■ ycH,

(II)

CH-CH ₂

- ^ N-- CH,

(III)

. CH-CH,

C.

C ₂ H ₄ OH

CH ₂ -, NC ₂ H ₄ OH

C ₂ H ₄ OH

(IV)

2 Ο 9 Π 2 7/0 9 0

-ClI-ClL

H, C CH ₀ -CH, ^ \ / '

CH ₂ .1

• (ν)

-CH-OH ,, ·

CH ₂ -

CH, OH ₀ -CH ₀

, K * CH

CH

s I

CH ₂ -CH ₂

(VI)

CH, I *

rC-CH,

C = OI
0-M

Ou ₂ - Q

(VII)

i- CH ₀ -CII

C- I

C = N-NH-C KH _x

| · Il \ ⁵

CH, NH 00C-CH,

(VIII)

-CH ₀ -CH- ² I.
C = OI
CH,

CH ₉ OH

I ^ά

CH-0.

-O-CH

CH-

ClI CH

I I

OH OH

CH ₉ OH

CH-CH-O-CH-HC = O HC = O

CH ₉ OH I ^ά
O-CH-CH-O-CII-

HC

Il

N
NH ^

C-NH,

I "·. I '

NH ".. _ NH OH ⁰

CH

Il

N NH

6-NH,

(IX)

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All of the above compounds are cationic polymers.

On the other hand, there is the anionic polymer, which is another compound participating in coacervation represents, from such a phthalic acid derivative that the reactive NIL or OH-G groups of gelatin, polyvinyl alcohol or starch are partially or completely acetylated with phthalic acid to form an amide or ester, and this phthalic acid derivative has one free carboxyl group per substituent (i.e. from a monoester or monoamide consists), as can be seen from the formulas listed below. Example of such phthalic acid derivatives are:

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ROR ¹

Il H I

CH 'ΰ O Ν ·

Il H I Il

(0Η ₂ ) ₄

O = C

OH UII
/ \

In the case of gelatin

CH ₀ -CH-Ch ₀ -GH-CH ₀ -CH

HO

O HO

In the case of polyvinyl alcohol

CH ₂ OH

- O-CH CH-

CH CH

I I

OH O OH I \
O = C. . C = O

In case of strength

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- ίο -

Accordingly, each of the above three kinds of polymers has an anionic property due to the many carboxyl groups and forms a complex with the above-mentioned cationic polymer, making it with the polymer in one aqueous medium is brought into contact, the complex formation not only at acidic pH, but also within a largely fluctuating pH range takes place. Any other dibasic acid can be used except Use phthalic acid, a similar anionic polymer is formed in the same way. The anionic polymer can also form a complex when it comes into contact with the above-mentioned cationic polymer in an aqueous solvent is brought; however, coacervation does not always occur since the cationic ones used according to the invention Polymers have strong hydrophilic properties. Even if phase separation occurs, the solution will separate only in two phases and generally no coacervate forms in the form of oily drops of suitable size. In this With regard to this, the phthalic acid derivative is specific. This anionic Polymers are made sufficiently hydrophobic when ortho-substituted benzene nuclei are in large numbers in the molecular chain are arranged, as can be seen from the formulas listed below. It can therefore be assumed that the Ratio of hydrophilic and hydrophobic properties of the complex in a suitable manner on the hydrophobic side is shifted and the phthalic acid derivative in this way a phase separation in an aqueous medium to form a dispersion of a complex agglomerate in the form of oily droplets of suitable size.

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The coacervate lichen so formed are also specific and are extremely enriched in numbers in nitrogen-containing residues which are cationic to the cationic polymer Give properties. A large number of excess cationic groups therefore remained on the coacervate particles without sufficient neutralization with the anionic groups so that the molecules of the anionic coupler or the anionic detergents of a similar structure, with the cationic groups forming a complex in the coacervate particles are able to enter, as already described above.

Due to the complex formation, however, the effect of the hydrophilic groups in the two polymers is partially lost, so that the coacervate becomes very unstable. If the solution has a higher concentration, coacervation may occur cannot be carried out successfully, as in the case of the known coacervate which is composed of gelatin and gum arabic because the thus obtained coacervate tends to agglomerate when an anionic coupler solution is admitted. However, if the reaction takes place in a dilute aqueous solution of a non-domestic water-soluble Polymers such as gelatin, polyvinyl alcohol, polyacralamide, hydroxyethyl cellulose or hydroxypropyl starch a coacervate is formed in a very simple manner even with a higher concentration of the solution. beyond that the particle sizes of the coacervate are usually sufficiently fine and extremely stable, even if a solution an anionic coupler or scavenger is added to the dispersion of the coacervate particles to adhere the molecules adsorb to the surface of the coacervate particles

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the coacervates are usually sufficiently stable and do not agglomerate at all.

The coacervate particles thus obtained are extremely fine and cannot be detected without the aid of an optical microscope. Usually the diameter of the coacervate particles is about 1 to 10 µm. If the particles are cast in a thin layer on a film and dried, the film will be practically transparent. Even when these particles are complexed and converted into dyes with the anionic couplers used in the invention, the particles cannot be seen by the naked eye and therefore appear to be uniform in color.

Process for the preparation of the above-mentioned phthalic acid derivatives and the degree of substitution of phthalic acid are described below;

A process for making phthalic acid derivatives is known from U.S. Patent No. 2,525,753 (1950) or other references. This process makes 100 parts Gelatin reacted with 7 parts of phthalic anhydride. According to this procedure, all reactive ε-amino groups become the gelatin is almost completely substituted; even with a substitution to this extent, one can use a suitable phthalic acid derivative due to the hydrophobic or lipophilic properties of the gelatin as such. When using polyvinyl alcohol, which as having such strong hydrophilic properties leaves it a preferred phthalic acid derivative having a degree of substitution Manufacture from about $ 50 by making 100 parts

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Reacts polyvinyl alcohol with more than 300 parts of phthalic anhydride, corresponding to a substitution of an average of one OB group in two vinyl alcohol units by phthalic acid. The derivative can be easily prepared, as in the case of phthalic acid esters of cellulose, in the usual manner by reacting polyvinyl alcohol with phthalic anhydride in glacial acetic acid in the presence of anhydrous sodium acetate as a catalyst. When using starch, a similar procedure as above can also be used. However, the phthalic acid ά & ηνα £ ι obtained tends to be colored, so that a special method is preferred in the invention, which leads to a colorless product with a degree of substitution of about $ 33. Ils starting material in this process is a glucose polymer with a relatively low molecular weight and little branching, such as amylose, soluble starch or dextrin, and there are 100 parts of starting material with about 130 parts of phthalic anhydride at room temperature in a solvent such as formamide or dinethyl sulfoxide, in Reacted in the presence of anhydrous sodium acetate or potassium carbonate as a catalyst. The monoester obtained has an average of one phthalic acid residue per glucose unit per molecule, is free from discoloration and has a relatively low viscosity and a suitable ratio of hydrophobic and hydrophilic properties and is thus preferably suitable for the intended purpose. Furthermore, starch derivatives, such as hydroxypropyl starch and hydroxyethyl starch, which are easily soluble in cold water and also have a low degree of denaturation, are preferably used as the starting material. .

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It goes without saying that the mixed derivatives with other dibasic acids and / or monobasic acids are also useful for the desired purpose. For example, mixed derivatives with maleic acid or are suitable Acetic acid. In particular, the combination of / maleic acid, which as such has crosslinking and hardening properties due to the presence of double bonds, to the The advantage that no hardening agent is required and that the "obtained coacervate particles" have increased stability.

As couplers or rinsing agents in the process according to the invention, anionic couplers or rinsing agents with a structure similar to that of the known Agfa color-sensitive material can be used as such. Moreover, one can achieve a non-diffusing effect even if the number of K _o hlenstoffatome or ballast groups, which were introduced into the coupler molecules in order to obtain the non-diffusing effect is very low. For example, homologues of couplers which do not have sufficient non-diffusing properties if no hexadecyl group has been introduced can have sufficient non-diffusing properties even if only one decyl group is introduced. Further, depending on the molecular structures of the couplers, there are some cases where the introduction of two octyl groups having eight carbon atoms is preferred or the introduction of diphenyl groups or phenylphenol groups ((~ S-®- {~ S-) is more effective than the introduction of long-chain alkyl groups. The effects of form

^! and molecular weights of these ballast groups fluctuates greatly with the structure of the other parts of the molecule and the intrinsic - 15 -

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shafts of the coacervate particles, which form a complex. Because of this, the number of carbon atoms may be this Basic groups are not strictly limited, as in the case of the known diffusion-resistant Agfa couplers. However, the number of carbon atoms is in the range which is easy experience has shown that it can be derived from the known couplers. For this reason, the invention can be known Couplers which are produced in large quantities or couplers which are easily produced by the similar method to the known ones Have couplers made, use with advantage. It is also advantageous that the method according to the invention can largely be adapted for the various areas of application.

The detergents with a similar structure to the couplers are explained in more detail below. VI As already mentioned, substances which are originally couplers but give dyes which decompose instantly are common anionic, but hardly known, with the exception of the specific diphenyldihydrazone derivatives listed below:

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209827/0903 ORIGINAL BATHROOM

18 37 ii

KH NH

WaO

(Diphenylhydrazone detergent1)

Decompose- decomposition

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NH

Clutch _χ

■ Ν

¹ I.

C ₂ H ₅

(Oxidation intermediate product of the developing agent)

N 0

(Azomethine magenta dye)

(Monohydrazone, without color)

As examples of the so-called "white coupler" detergents, which have similar structure to the couplers, and how the couplers couple, but first of all colorless leuco bases that are too stable to form actual To carry dyes through further oxidation, the following two compounds may be mentioned: -17-

209827 / OS0 3. = ■ -.

Ο ΓΗ

£ I ³

C = OH ₉ C "' ^X CH-C-NH'O" NC ₁₇ H,

I in \ τ

H ₉ C CH ₉ ^

SO ₃ Na

In addition, hydroquinone, p-aminophenol, resorcinol and many phenol derivatives are known as substances which are oxidation intermediates of color developing agents by redox reactions inactivate, most of these substances being non-ionic. In the invention, anionic compounds that by introducing sulfonic acid or carboxylic acid esters into the above-mentioned Phaiol derivatives were used. Examples of such compounds are 2-dodecylhydroquinone-5-sulfonic acid (Sodium salt), 2,5-dioctylhydroquinone-3-sulfonic acid, 2,4-dioctylphenol-6-carboxylic acid and 4-decyl-1,3-resorcinol-6-sulfonic acid.

As hydrophilic colloidal binders for forming the main bodies of the photographic layers are within the scope of the present invention General description gelatine, casein, starch, gum urabicum, hydroxyethyl cellulose, carboxymethyl starch, polyvinyl alcohol, Polyacrylic acid, polyacrylamide, polyvinylpyrolidon, Viriy line thy Läther-MaLe insäureanhydrid-Mischpolpolymer, Styroli'lfj Io i rinn.urefjrihydr.id mixed polymers, Vi ny Lace ta t-Viny LakohoL-

2 0SU77 / 000 3 rad OFHGlNAL -I «-

To understand mixed polymers, as well as derivatives thereof or similar substances. In addition to the colloidal binders, which as such are water-soluble, emulsions or latices of hydrophobic homopolymers or copolymers of acrylonitrile, acrylic acid ester, methacrylic acid ester, vinyl acetate and styrene in the hydrophilic colloidal binders also be present. Furthermore, substances which, in combination with hardeners, can restore their original water lose solubility and thereby become water-repellent, also present as hydrophilic colloidal binders as they maintain the swelling properties by absorbing water.

The invention will now be explained further with the aid of the following examples.

3 g of a commercially available phthalic acid derivative of gelatin (Gelatin No. 2567, manufactured by Liner Co., Great Britain; it is believed that 98% of the F-amino groups of the original gelatin are substituted with phthalic acid) and 4 g of ordinary photographic gelatin in 60 ml Dissolved water and the pH of the solution was adjusted to 6.0. To this solution 1.5 g Polymethacryldimethylaminoäthanolester-benzyl chloride was gradually added at 5O ⁰ C (said in the preceding compound VII) in 300 ml water in the form of a fine stream added to give a stable suspension was formed, which coacervate particles having a diameter of less than 1 / u included. The suspension was 6 ml

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a 1O? £ Fonnaldehydlösung strength and then stirred for one hour at 5O ⁰ C.

The coacervate dispersion thus obtained (about 100 ml) was washed thoroughly with 50 ml of a 4% solution of a purple colored coupler of the following formula (this solution was obtained by dissolving the Coupler in water using the smallest possible amount of n-NaOH solution).

W ~ V "C-CH,

C.

L-as obtained mixture became 500 ml of a green sensitized Silver chloride emulsion added which using of 10 g of silver nitrate and 30 g of gelatin. A preferred emulsion for preparation was thereby formed a green-sensitive emulsion layer of ordinary Color paper. The mixture was applied from a baryta paper in a coating amount of about 100 g / m ", whereby a monochrome color paper was obtained giving a purple image. This colored paper can be completely identical Develop like a multilayer colored paper (see Example 3).

. '■' ■■ - 20 -

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- Here ».

So

The coacervate dispersion prepared according to Example 1 (about 100 ml) was thoroughly mixed with 60 ml of a 3% solution of a cyan coupler represented by the formula shown below (this solution was prepared by dissolving of the coupler in water using as little as possible Amount of n-NaOH and a small amount of methanol).

OH WH - NH-C ^ A-co- U - ' S0 _z H

The resulting mixture was added to 300 ml of a red-sensitive safe Silver chloride emulsion was added, which was prepared using 10 g of silver nitrate and 30 g of gelatin. As a result, a preferred emulsion for making a red-sensitive emulsion layer for color paper was obtained. The mixture was applied to a baryta paper as in Example 1, whereby a cyan color forming monochrome color paper was obtained. .

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Z09C 2 Ή 0903- BADQR ₁ G ₁ NAL Example 3

The coacervate dispersion prepared according to Example 1 (about 100 ml) was washed thoroughly with 40 ml of an "! Oxygenated solution of a yellow color coupler of the general types listed below Formula mixed (this solution was made by dissolving the coupler in methanol using a minimal Amount of MaOH and water produced).

COOH

- The resulting mixture was added to 300 ml of a silver chlorobromide emulsion which g using 10 silver nitrate and 35 g of gelatin was prepared. These

"...- ■■ 2

Emulsion was applied in a coating amount of about 100 g / m on the surface of a so-called RG (resin-coated) photographic paper, which was made by applying a thin film of white opaque polyethylene on the surface side and a thin film of colorless polyethylene on the back of a photographic base paper was produced. A blauemp-L'irid emulsion layer was obtained on the photographic paper. Separately, 100 ml of the coacervate dispersion of yauii'S example. 1 with a solution of 1.5 g of a rinse aid

O • c

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the formula shown below mixed in 50 ml of methanol, making the detergent diffusion-proof on the Coacervate particles were adsorbed as in the case of the coupler.

The resulting mixture was applied to the above-described emulsion layer in a coating amount of about
60 g / m 2 and then dried to obtain an intermediate layer. On the intermediate layer formed in this way, about 100 g / m 2 of the green-sensitive emulsion layer forming a purple color, as in FIG

2
Example 1 and about 60 g / m 2 of the same intermediate layer as

2
applied above. About 100 g / m 2 of the cyan-forming red-sensitive emulsion was then applied. Furthermore, 100 ml of the coacervate dispersion according to Example 1 were mixed with a dispersion of 2 g of a brightener of the following formula in 50 ml of water;

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«3

SO ₅ Ia

/ | -M Q-M = CH - ^ - M- ^ A-

The brightener was adsorbed onto the coacervate particles; then was with 500 ml of a 10 $ gelatin solution mixed. The resulting mixture was finally applied to the above-described multilayer emulsion layer in one Coating weight of about 100 g / m applied and such a Overlayer produced. In this way, a multi-layer color paper was obtained.

The color paper is preferably used for making a color print from a color negative. After the exposure, by a suitable color negative color paper is developed (25 ⁰ C, 4 minutes), placed in a Unterbrechungsfixierbad '(25 ⁰ C, 4 Hinuten), washed with water (Zimmertemparatur,' 1 Mnute) bleach-fixed, (25 C , 4 minutes), washed with water (1 minute) and stabilized (25 ° C, 5 minutes) using the solutions listed below. The paper was then dried.

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ti

Color forming developer:

Hydroxyethylethylaminoaniline sulfate Hydroxylamine sulfate Sodium carbonate (monohydrate) Potassium bromide Anhydrous sodium sulfite Sodium hexamethaphosphate Water up to 7.5 g 4.0 g 70.0 g 1.0 g 3.0 g 2.0 g 1 liter

Interrupt f ixing bath:

Sodium thiosulfate (pentahydrate) Potassium methabisulfite Boric acid anhydrous sodium acetate

Potassium alum water except for g
15.0 g 23.0 g 9.0 g 15.0 g 1 liter

Bleach-fix bath

Ethylenediaminetetraacetic acid sodium hydroxide ferric chloride (hexahydrate) Sodium Thiosulfate (Pentahydrate) Anhydrous sodium sulfite Water up to 42.0 g 20.0 g.-26.0 g 200.0 g 10.0 g 1 liter

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StaMlizer:

Sodium acetate (trilhydrate) 90 g

Potassium alum 30 g

Formalin ($ 35-40) 50 g

Water Ms to 1 liter

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100 g of polyvinyl alcohol with a degree of polymerization of about 500 were dispersed in 1 liter of glacial acetic acid in a three-necked flask fitted with a silica tube. 250 g of phthalic anhydride, 100 g of maleic anhydride and 75 g of anhydrous sodium acetate were added to the dispersion obtained, and the mixture obtained was ^{reacted at 95 °} C. for 10 hours while drilling. Then the reaction liquid was poured into 8 liters of acetone. The precipitate which separated out was filtered off, washed with Icetone and dried. 450 g of a pure white powder were obtained. Although the exact measurement of the degree of esterification is difficult, it can be assumed that about 50% of the hydroxy groups in the molecules were converted into phthalic acid monoesters and about 10% of the hydroxy groups were converted into maleic acid monoesters.

The powder obtained in this way is in at acidic pH Insoluble in water, but becomes water-soluble when one is with Alkali neutralized.

5 g of the powder obtained was therefore dissolved in 100 ml of weakly alkaline water, and then the pH of the solution was adjusted to 6.5. The solution thus obtained was then mixed with 100 ml of a separately prepared 0.5 solution of polyvinyl alcohol (degree of polymerisation 1000, degree of saponification 95%). Into the mixture was added with stirring and heating at 5O ⁰ C 100 ml of a separately prepared 5 ^ aqueous solution (room temperature) of poly-2-vinylpyridine (I) which had been acidified with acetic acid (pH = 3.0) poured. A dispersion of KoacervatteilGhen with a partial

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size from 2 to 3 / u. The dispersion was heated 10 hours at 5O ⁰ C, so as to achieve crosslinking in the coacervate particles due to the Maleinsäurereste and harden the particles sufficiently. To the liquid (total amount 300 ml) was added 15 g of gelatin, and the obtained coacervate dispersion was cooled and stored in a refrigerator. The dispersion stored in this way can then be used at any point in time, since the crosslinking is limited only to the coacervate particles and does not extend to the entire dispersion.

If the procedure of Example 3 is repeated, wherein but 100 ml of the coacervate dispersion prepared in the above manner instead of 100 ml of the coacervate dispersion used in Examples 1, 2 and 3, see above a similar colored paper as in Example 3 is obtained.

To 100 ml of the coacervate dispersion according to Example 4 were 100 ml of a 2 # strength solution of a cyan color forming Orange coupler of the following formula (this Solution was made by dissolving the coupler in a 1: 1 mixture of methanol and water using a minimal amount of IaOH) added, with the coupler on adsorbed to the coacervate particles by complex formation.

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2?

The yellow liquid obtained was diluted with an equal amount (200 ml) of a 5% gelatin solution and coated over a clear film base layer in an amount of about 150 g / m 2 and then dried to obtain a paint film. This film is not made of a photosensitive material, but can be used to produce a two-color image, namely cyan and orange, which is useful for advertising and similar purposes in combination with a silver halide sensitized material suitable.

First, the color-forming film thus prepared is immersed in the color developer according to Example 3 to obtain a adsorb sufficient amount of developer into the film. Then a commercially available low-sensitivity one is placed in a darkroom Paper or direct positive paper exposed by reflex copying and thus a latent image of a letter or a drawing (in the present case a black and white template). The photosensitive paper with the latent image of the original is immersed in the color developer described above and applied to the one described above the color-forming film with the absorbed developer is applied. The composite obtained in this way is gently squeezed out

and then pressed for 3 minutes on a plate heated to 30 ° C. During the treatment, a part of the oxidation product of the developer diffuses, which is usually on the exposed Places the photosensitive material arises locally from the photosensitive material in the opposite color forming film. According to the following equation, a cyan image is formed on the Eüd area compared to the exposed area, with unreacted

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«■

. Orange coupler on the non-image area versus the non-exposed area The surface of the usual photosensitive materials remains:

-CO-KH-

OCII ₅

SO ₅ Well

Cyan color forming Orange coupler

CO-IlH-

SOjNa

■ \

_; ... O ₂ H ₅ O ₂ H ₄ OH

Cyan image

Therefore, if an ordinary photosensitive paper is used, a cyan-colored letter or letter is formed cyan line with an orange background. If, on the other hand, one uses a direct positive paper, then one imagines orange letter or line with a cyan background. The copy thus obtained can be dried after a short soak and there are no time-consuming and cumbersome treatment processes, such as fixing, Bleach or wash required. In addition, the

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Copy has a clear hue and is therefore suitable as a Advertising board or the like, which can be illuminated from the back.

Example 6

A mixture of 50 g of commercially available soluble starch and 68 g of phthalic anhydride was at a slightly elevated temperature below 6O ⁰ C for 1 hour in 200 ml of formamide in counter-

"Was converted from 37.5 g of anhydrous sodium acetate and so on obtained a phthalic acid monoester of starch. The monoester thus obtained was precipitated by pouring it into 1.2 liters of acetone and then washed with a mixture of methanol and acetone. 87 g of monoester were obtained as a white powder (about 70% of the Carboxylic acid groups were in the form of the sodium salt). The degree of substitution was $ 35 (average 1.05 phthalic acid residues per glucose unit). 3 g of this monoester and 0.4 g of gelatin were dissolved in 100 ml of water and the pH of the solution thus obtained was adjusted to 6.5

k provided, and then the solution heated to 5O ⁰ C.

Separately, an aqueous solution of aminoguanidized aldehyde starch was prepared. Since commercially available aminoguanidized dialdehyde starch has a low degree of aminoguanidization (about $ 5), the aqueous solution of this starch was prepared by dispersing a commercially available dialdehyde starch (SUMSTAB-150, 'manufactured by Miles Laboratories Inc., degree of oxidation about $ 50) in 300 ml of water, adding a Solution of 45 g of aminoguanidine hydrochloride in 450 ml of water (pH 2) to the obtained dis- ^; persion, and subsequent reaction of the mixture obtained for 20 hours at room temperature. the

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solution thus obtained was filtered off and the cake obtained was then washed with water and with methanol and then dried at a temperature below 4O ⁰ C. In this way, an aminoguanidized dialdehyde starch was obtained in the form of a white powder in which about 50% of the total aldehyde groups were aminoguanidized. This starch derivative has particularly good properties for achieving a coacervate with anionic substances. 2.5 g of this starch were dissolved in one hundred ml of water at an elevated temperature and then the solution, after adjusting the pH to 6.5, was cooled to room temperature. The aminoguanidisierte dialdehyde starch (total 200 ml) thus obtained was poured into the previously prepared Phthalsäuremonoesterlösung in gelatin with vigorous stirring at 4O ⁰ C, said coacervate formed. After the formation of the coacervate particles using a microscope had been detected, the Koazervatdispersion was heated for 2 hours at 8O ⁰ C, to cure the coacervate particles by reaction with the aldehyde groups in the coacervate. Then 10 g of gelatin was added to the dispersion, and the finished coacervate dispersion thus obtained was stored after cooling and gelling.

This coacervate dispersion is also capable of a complex with an anionic color coupler or detergent, as in the case of the coacervate dispersion according to Example 1 or 4. The dispersion thus obtained can be used in light-sensitive silver halide emulsion layers or intermediate layers are introduced, resulting in a multilayer color photograph Forms material similar to that described in Example 3

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2 09827/0903 BAD OR | Q _JNAL

Material is identical or similar to this material. The dispersion can also be used to prepare a non-sensitive color material according to Example 5.

Example 7

This example describes a reversal material which is for the so-called silver complex diffusion transmission system on a multi-layer color film. According to this system, / color slide can be exposed in a camera.

A detergent stock solution is prepared by adding 500 ml of the coacervate dispersion obtained according to Example 6 with 250 ml of a 4% solution of 2,5-dioctylhydroquinone-3-sulfonic acid (latrium salt) mixed and thus causes a complex formation. Is on a clear film layer first applied a layer of a multi-layer color composite film in a coating weight of about 100 g / m 2. This Mixture consists of 300 ml of a red-sensitive 'highly sensitive' Silver iodobromide emulsion and 150 ml of the above called detergent stock solution, which are applied as the first layer. On top of this layer was the second layer

2 in a coating amount of about 80 g / m, consisting of one Mixture of 160 ml of the coacervate dispersion according to Example 2, in which a cyan coupler was previously applied in the form of a complex, as in Example 1, and 300 ml of a reduction nucleus solution the composition listed below is applied:

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Heduction kernel solution:

Gelatin x 20 g

Polyvinyl alcohol 20 g

Vinyl methyl ether-maleic anhydride copolymer . 10 g

Colloidal dispersion of

Cadmium Sulphide ($ 1) 15 ml

Water up to 1 liter

(The pH of the solution was adjusted to 6.0 by adding a small amount of NaOH)

The third layer was applied to the second layer by applying about 60 g / m 2 of a mixture 300 ml of the above-mentioned heduction nuclei solution with 150 ml of the above-mentioned detergent stock solution are applied. A fourth layer of about 100 g / m 2 of a mixture of a green-sensitive layer was then applied to this third layer highly sensitive silver iodobromide emulsion and the detergent stock solution. On the fourth shift was then added a fifth layer by applying

about 80 g / m 2 of a mixture of 300 ml of the heduction nuclei solution and 160 ml of the coacervate dispersion mixed with 2 g of a yellow color coupler which forms a purple-red color of the following structural formula was complexed.

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BATH ORIGINAL

<> ^S0 3 ^H

C ₁₅ H ₃₁

This yellow coupler works as a filter layer and not only limits the intrinsic sensitivity of the lower two layers to ultraviolet radiation, that is of the red and green sensitive emulsion layers, but also acts as a coupler to form a magenta colored one Image. However, unreacted yellow coupler tends to lose the yellow color during treatment after To develop. On the fifth layer, a sixth layer is applied by applying about 60 g / m 2 of the same mixture as applied to form the third layer. On the sixth layer, a seventh layer is applied by applying about 100 g / m of a mixture of 150 ml of the detergent stock solution and 300 ml of a blue-sensitive, non-sensitizing th highly sensitive silver iodobromide solution applied. on the seventh layer finally becomes the top (eighth layer) by applying a mixture of 300 ml of the Reduction kerosene solution and 150 ml of the coacervate dispersion according to Example 6, which had been converted into a complex with 4 g of the yellow color coupler according to Example 3, applied. After drying, a multiple

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BATH

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aar

layered color film obtained.

After exposure, the color film was 5 minutes at 25 ° G with the following developer behancS-t:

Development transfer solution:

Water 750 ml

Ethylenediaminetetraacetic acid disodium salt 2.0 g

Sodium sulfite -2.0 g Sodium thiosulfate (pentahydrate) 5.0 g

Potassium carbonate (monohydrate) 50.0 g

Hydroxylamine hydrochloride 1.5 g

Potassium bromide 0.5 g

i-phenyl-3-pyrazolidone 1, above

p-diethylaminoaniline sulfate 5.0 g

Water up to 1 liter

Thereafter, in the same manner as in Example 3, the developed film was cut into one and one Treated and stabilized bleach-fix bath. To this In this way, you can immediately get a transparent positive paper for color slides.

2 0 9 8 2 7/0303

Claims (3)

Patent claims: . 1. Color photographic material consisting of Silver halide emulsion layers, intermediate layers, an overcoat or other layers, and anionic color couplers for color-forming development, finely dispersed and diffusion-resistant protective colloid binder of emulsion layers or adjacent layers through complex formation this coupler with finely divided particles of a coacervate, which .zusor by reacting at least one polymeric organic hydrophilic cationic compound with katio- ™ Niche nitrogen-containing groups in the molecule, with at least one phthalic acid derivative of gelatin, polyvinyl alcohol or Starch was produced in an aqueous medium. 2. A color photographic material, consisting of silver halide emulsion layers, intermediate layers, an overcoat layer or other layers as well as anionic detergents for color development, a finely dispersed and diffusion-resistant protective colloid binder of the intermediate layers or emulsion layers by complex formation this washing-up liquid \ tel with finely divided particles of a coacervate, which had previously been prepared by reacting at least one polymeric organic hydrophilic cationic compound with cationic nitrogen-containing groups in the molecule, with at least one phthalic acid derivative of gelatin, polyvinyl alcohol and starch in an aqueous medium. - 36 - ' 209 8 27/09 0 3 3. Color photographic "material consisting of Silver halide emulsion layers, intermediate layers, an overlay or other layers, and anionic layers Couplers or anionic rinsing agents for color-forming development, finely dispersed and diffusion-resistant protective colloid binders of emulsion layers or intermediate layers by complexing these couplers or scavenging agents with finely divided particles of a coacervate, which previously by reacting at least one polymeric organic hydrophilic cationic bond with cationic Nitrogen groups in the molecule, with at least one Phthalic acid derivative of gelatin, or polyvinyl alcohol Starch was produced in an aqueous medium. 209827/0903