DE2905260A1 - METHOD OF PRODUCING A HYDROPHOBIC SUBSTANCE LOADED POLYMERIC LATEX COMPOUND AND A PHOTOGRAPHIC RECORDING MATERIAL CONTAINING SUCH - Google Patents

Description

Henkel, Kern, Feiler & Hänzel Patent attorneys

Registered Representatives before the

European Patent Office

Möhlstrasse 37 D-8000 Munich 80

Tel .: 089 / 982085-87 Telex: 0529802 hnkl d Telegrams: ellipsoid

.12. Feb

CDR 334 G Dr.F / rm

KONISHIROKU PHOTO INDUSTRY CO., LTD. Tokyo, Japan

Process for the production of a polymeric latex composition loaded with a hydrophobic substance and containing one photographic recording material

909833/0779

S- 2S05260

Description

The invention relates to a method for loading in an aqueous polymeric latex dispersed polymer particles with a hydrophobic substance, in particular a process for the preparation of a polymeric latex composition loaded with a hydrophobic photographic additive is.

In the manufacture of silver halide photographic light-sensitive recording materials were used to evenly distribute the most varied of hydrophobic compounds, in particular of compounds such as color formers, UV-absorbing substances and the like, in a gelatin solution or another hydrophilic colloid solution made the most diverse attempts. In one of these attempts will have a solid or liquid hydrophobic compound mixed with a hydrophobic colloid solution, whereupon the mixture obtained several times through a working with high shear force Grinder, e.g. a colloid mill, is run. Here, the mixture is converted mechanically into a dispersion, which in turn is converted into a hydrophilic one Colloid solution is dispersed. In this method, however, there may be only a poor state of dispersion is achieved so that the poor dispersion formed is often unstable a greater expenditure of energy is required to pulverize the solid hydrophobic compound as much as necessary and the to sufficiently disperse powdered compound in the hydrophilic colloid solution «the consumption of a such a large amount of energy is often from excessive heat generation or undesirable local heating accompanied, xiras to undesirable chemical changes in the in components contained in a system.

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From US Patents 2,304,940 and 2,322,027 there is another method for dispersing hydrophobic compounds in hydrophilic ones Known colloid solutions. In this process, the hydrophobic compound is first in an oil or in a high-boiling solvent to prepare an oily solution, whereupon the oily solution obtained is dissolved in a hydrophilic Colloid solution is dispersed. A modification of this process is disclosed, for example, in US Pat. No. 2,801,171 known. The latter method is often used to facilitate the dissolution of a hydrophobic substance in the oily solvents use a low molecular weight solvent, e.g. ethyl acetate, or a low molecular weight ketone, as an auxiliary or cosolvent used. In the production of ballast groups containing color formers or couplers Silver halide color photographic emulsions often employ a method in which the ballast groups containing coupler is dissolved in an oily high-boiling solvent known as a coupler solvent whereupon the resulting solution in a hydrophilic colloid solution, e.g. a gelatin-silver halide emulsion, is dispersed. In this dispersing process, too, an energy-consuming pulverization must be carried out in order to achieve the to ensure the desired state of dispersion and the required particle size of the coupler. Often there are certain Components contained in a mass to be pulverized against impairments, e.g. thermal decomposition and the like, prone. In addition, such pulverization takes quite a long and increased time to cease the prime cost. In view of this, there is a considerable need for an improved dispersion process, in which hydrophobic compounds, e.g. containing ballast groups Couplers and the like, uniformly in photographic

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see emulsions as well as other hydrophilic colloid solutions can be dispersed. In such an improved method, however, should be based on the use of a Grinders with high energy requirements, as they were previously used to disperse the hydrophobic compounds in hydrophilic ones Colloid solutions were used can be dispensed with.

From the JA patent application 30 494/1973 it is known in Water-insoluble polymers, on the other hand, soluble in organic solvents for dispersing hydrophobic couplers with respect to an improvement in photographic properties, for example image durability. In this case, however, it is also necessary to emulsify the with the couplers added polymers to use a grinder which has a high energy requirement. The teachings of the JA patent applications 59 942/1976 and 19 943/1976 aim to have a high energy requirement in such processes To avoid grinding mills and the disadvantages associated with them and to further improve photographic emulsions. According to the teachings of the aforementioned JA patent applications, a method is used in which a polymer latex with dispersed polymer particles which are individually loaded with hydrophobic substances, in such a way in a hydrophilic one Colloid solution is dispersed that the hydrophobic substances are dispersed in the hydrophilic colloid solution, while the dispersed polymer particles are still loaded with the hydrophobic substances in question. Using of such a polymer latex, some desirable properties can be imparted to the obtained silver halide emulsions. In comparison with the photographic emulsions obtained when conventional dispersing measures are observed, the. Particles of the coupler-containing dispersion formed of small size, so that the image ultimately obtained in terms of

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lent sharpness and responsiveness between the developer and coupler is improved. Furthermore, it has become possible to use hydrophobic compounds in hydrophilic colloid solutions should be dispersed, but could not because they are susceptible to oxidation by air, now with the help of the method described last to be introduced into hydrophilic colloid solutions, since they are sufficient in the latter case are protected against oxidation. Furthermore, hydrophobic compounds that are excessively highly reactive and in undesirably with other constituents present in a layer containing the hydrophobic compounds in question react, are incorporated into hydrophilic colloid solutions with the help of the polymer latex. The usage of polymer latices as dispersion carriers for photographic Additives is a technique that can be used without the use of grinders that have a high energy requirement photographic emulsions excellent photographic Can confer properties. However, as will be shown, this technique also leaves much to be desired.

First of all, the amounts of hydrophobic substances with which the dispersed polymer particles of polymer latices can be loaded according to the teachings of the two last-mentioned JA patent applications are not sufficient. For example, if the dispersed particles in the polymer latex are to be loaded with couplers, ie typical photographic hydrophobic additives, it is necessary to use the dispersed particles in a larger amount than the coupler, in certain cases even in an amount more than twice the amount of the coupler . As a result, the photographic material ultimately obtained has a large film thickness and is impaired in its developability and resolution. Disadvantageous

909033/0779

Another aspect of the process described is that because of the low concentration of the polymer latex used dispersed particles large amounts of liquid polymer latex are required and therefore when drying the coated recording materials encounter difficulties. Another disadvantage is that when loading the dispersed particles with hydrophobic substances relatively large amounts of water-miscible organic solvents must be used. As a result, there is a large-sized device and a lot of time for removal this solvent is required. In addition, the number of polymer latices that can be used is limited and the polymer latex compositions loaded with hydrophobic substances are not always sufficiently stable. As already mentioned, completely satisfactory results are not achieved with any of the known processes.

The invention was therefore based on the object of a method for production free of the disadvantages outlined of polymer latex masses loaded with hydrophobic substances, which does not require a high expenditure of energy and in carrying it out, loading the dispersed polymer particles contained in the polymer latex with large ones Amounts of hydrophobic substances is possible, polymer latex with dispersed therein contained in high concentration Polymer particles can be used, the loading of the dispersed particles of the polymer latex with hydrophobic Substances is easy to carry out and the removal of the respective solvent after loading no difficulties and the number of polymer latexes that can be used is not so limited.

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According to the invention, it has now surprisingly been found that the problems set can be achieved if one disperses Polymer particles with hydrophobic substances in the presence of three media, i.e. water, one miscible with water organic solvent and a water-immiscible organic solvent.

When carrying out the method according to the invention, the following advantages are achieved:

(1) Since there is no dispersing device requiring a large amount of energy is required, there is also no risk that the mass obtained is due to a heating Undergoes change in their properties.

(2) Since the polymer particles dispersed in the mass can be loaded with large amounts of hydrophobic substances, when this composition is used in the production of photographic recording materials Keep film thickness thinner, which improves both developability and resolving power has the consequence.

(3) Since one can use an aqueous polymer latex of high latex concentration, the drying of the Lessen mass-related difficulties.

(4) Since the amount of organic solvent required for loading can be kept to a minimum, the solvent can be removed in a short time without the need for a large-scale drying device remove without difficulty.

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(5) The aqueous polymer latexes which can be used according to the invention are not so narrowly limited in terms of their type, so that even hydrophobic substances, which were previously not present Constituents contained in aqueous polymer latices could be made to adhere, can be used. In addition, the loaded polymer latex compositions are very stable.

In the various embodiments of the method according to the invention, in which in an aqueous polymer latex dispersed polymer particles contained in the presence of three media, i. e. Water, an organic one that is miscible with water Solvent and a water-immiscible organic solvent, loaded with hydrophobic substances the order of mixing these components, as will be explained in more detail later, can be very different and consequently cannot be determined in an unambiguous manner. In short, is an indispensable requirement the presence of the three components water, a water-miscible organic solvent and one with water immiscible organic solvent, but the order of mixing these ingredients is not critical.

In principle, all water-miscible solvents in any amount can be used as water-miscible organic solvents Solvents can be used. Those whose miscibility with water is 20% by weight or more are preferred. With Water-immiscible organic solvents are those whose miscibility with water is not more than 20, preferably is less than 10% by weight. For the sake of an easy Removability after loading, both types of organic solvents should not have too high boiling points, expedient-

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wise boiling points below 200 ⁰ C, preferably below 100 ⁰ C, have.

Organic water-miscible organic compounds which can be used according to the invention Solvents are for example acetone, methyl ethyl ketone, Ethanol, methanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, Dimethylformamide and dimethyl sulfoxide.

Water-immiscible organic which can be used according to the invention Solvents are, for example, ethyl acetate, n-butanol, chloroform, carbon tetrachloride, ethyl chloride, ethylene chloride, Dibromoethane, n-propyl acetate, n-butyl acetate, sec-butyl acetate, Cyclohexanone, cyclohexanol, ethylene glycol monomethyl ether, isobutanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, Diethyl ether, diisopropyl ether, methyl-n-propyl ketone, Methyl n-butyl ketone, benzene, toluene, xylene and benzyl alcohol.

Part of the water-immiscible organic solvent can also be achieved by a high-boiling organic solvent that was previously used for the production of so-called protective dispersions was used and is practically immiscible with water. With the help of such high boilers The photographic recording materials can be solvents with regard to their color properties and others improve photographic properties. Examples of usable high-boiling organic solvents are Dibutyl phthalate, tricresyl phosphate, triphenyl phosphate, diethyl lauryl amide and dioctyl phthalate.

The amounts of an aqueous polymer latex to be added under optimal conditions, miscible with water and with water Immiscible organic solvents may vary depending on

909833/0779

the nature of those contained in a particular aqueous polymer latex polymeric substance or the hydrophobic substance used can be very different. Usually the ratio is Aqueous polymer latex: water-miscible organic solvent 1 0.1 to 10, preferably 1: 0.5 to 3. The ratio of water-miscible organic solvent: water-immiscible organic solvent is about 1: 0.01 to 1, preferably about 1: 0.03 to 0.5% The water-miscible organic solvent and the water-immiscible organic solvent can be used individually in combination with others with water Miscible and water-immiscible organic solvents in the form of mixtures of two or more solvents get used.

According to the invention, hydrophobic substances are to be understood as meaning those whose solubility in water is about Λ% .

Examples of such hydrophobic substances are agricultural chemicals _for drugs, dyes and the like, and photographic hydrophobic additives.

Typical photographic hydrophobic substances with which the Processes according to the invention can be carried out are couplers, UV absorbers, development inhibitors-releasing Substances «, agents releasing dyes through cross-oxidation and photographic dyes, as well as fluorescent ones Brighteners, antihalation agents or against exposure to light protective agents, developers and the like «,

Couplers are, for example, open-chain methylene yellow couplers, 5-pyrazolone magenta coupler, phenol or naphthol cyan coupler and the same. These couplers can be

act so-called 2-equivalent or 4-equivalent couplers. They can also be used in combination with couplers for car masking, e.g. colored azo couplers, osazone compounds, diffusible Dye-releasing couplers and the like, are used. To improve the photographic The hydrophobic couplers mentioned can also have properties in combination with other couplers, for example so-called competing couplers, DIR couplers (development inhibitors Release Couplers) and BAR Couplers (Fading Accelerating Compound Release Couplers) are used will.

Usable yellow couplers are those known and already used open-chain ketomethylene compounds, such as fivaloylacetanilide yellow couplers known from US Pat. No. 3,265,505 Benzoylacetanilide yellow couplers known from GB-PS 1,240,600 and US-PS 2,875,051. Further yellow couplers known as so-called 2-equivalent couplers are those from US Pat. No. 3,408 known couplers which are O-aryl-substituted at the active site, the couplers known from US Pat. No. 3,447,928, O-acyl-substituted couplers in the active site, those from British Pat 1,351,424 known at the active site with a hydantoin compound substituted couplers known from GB-PS 1,331,179 at the active site by a urazole compound or substituted a succinic imide compound Couplers known from GB-PS 944 490 substituted at the active site by a monooxoimide compound or fluorine substituted couplers known from GB-PS 780 507 which are chlorine or bromine substituted at the active site Couplers and the couplers known from GB-PS 1,092,506 which are O-sulfonyl-substituted at the active site.

Magenta couplers which can be used according to the invention are those from the pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole and In-

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dazolon type. Pyrazolone magenta couplers are disclosed in U.S. Patents 3,127,269, 2,600,788, 3,519,429, 3,419,391, 3,062,653 and 3,684,514 and GB-PS 1,342,553 and 1,399,306. Pyrazolotriazole magenta couplers are known from GB-PS 1,247. Pyrazolinobenzimidazole magenta couplers are from the U.S. Patent 3,061,432 is known. Indazolone magenta couplers are known from GB-PS 1,335,603. Particularly good according to the invention Magenta couplers which can be used are known from US Pat. Nos. 3,684,514 and 3,127,269.

Cyan couplers which can be used according to the invention are phenolic compounds of the types known from U.S. Patents 2,423,730, 2,801,171 and 2,895, from U.S. Pat. No. 2,474,293 and British Pat

1,084,480 known 0-aryl-substituted at the active site Naphtho! Compounds and those from CA-PS 913 082 and phenolic and naphtholic compounds known in U.S. Patent No. 3,737,316.

Colored magenta couplers are, for example, compounds which, at the active site, colorless magenta couplers of the described Art are arylazo or heteroarylazo substituted. Examples of this can be found in US Pat. No. 3,005,712,

2 983 608, 2 801 171 and 3 684 514 as well as GB-PS 937 621.

Colored cyan couplers are compounds that are arylazo-substituted at the active site. Find examples of this U.S. Patents 3,034,892, 2,521,908 and 3,811,892 and GB-PS 1,255,111. Furthermore, these can be masking Couplers of the type which, when reacted with an oxidized developing agent, form a dye in a treatment bath submit (see GB-PS 1 084 480), act.

Suitable competing couplers are those disclosed in US Pat

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2,742,832 (e.g. citrazinic acid and the like) and from Compounds known in U.S. Patent No. 2,998,314.

Substances which release development inhibitors are preferably those from US Pat. Nos. 3,632,345, 3,928,041 and 3,958 and 3,961,959 known compounds are used.

Compounds which can be used as UV absorbers are triazoles, triazines or benzophenones (cf. US Pat. No. 3,004,896,

3 253 921, 3 533 794, 3 292 525, 3 705 805, 3 738 837 and

3 754 919, GB-PS 1 321 355 and JA patent application 25 237/1975), also acrylonitrile compounds (see US Pat. Nos. 3,052,636 and 3,707,535). The preferred UV absorbers are Commercial products from Ciba-Geigy Tinuvin S-320, 326, and 328 are used either alone or in combination. Further suitable UV absorbers are those from azoles disclosed in U.S. Patents 2,537,877, 2,739,971, 2,739,888, 2,784,087, and 3,250,687; and those disclosed in U.S. Patent 3,512,984 and 3,549,374 known high molecular weight triazine compounds.

In the context of the process according to the invention, in addition to the hydrophobic photographic additives mentioned, for example also photographic dyes (see US Pat

2,751,298 and 3,506,443), DDR couplers (diffusible dyes releasing couplers) (see U.S. Patents 3,443,939, 3,443,940,

3,343,941 and 3,725,062), indicator dyes (see US Pat

3,647,437), sulfonamidophenols, reducing agents (see US Pat 3,810,321), reductones (see U.S. Patents 3,572,896 and 3,679,426), bisnaphthol reducing agents (see U.S. Patents 3,672,904 and 3,751,294), hydrophobic developers (see U.S. Patents 3,672,896, 3,672,904, 3,679,426 and 3,751,249) and so-called through Cross-oxidation dye-releasing agents, also called DRR substances (dye-releasing redox compounds)

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are known (see U.S. Patents 3,628,952, 3,698,897 and 3,725,062 and BE-PS 788 268, 796 040, 796 041 and 796 042) can be used.

In the case of the aqueous polymer latexes which can be used according to the invention with polymer particles dispersed therein, it should be those after adding one with water miscible organic solvent and a water-immiscible organic solvent neither aggregation precipitation of the dispersed particles still takes place and the dispersed particles are stably dispersed in the latex remain »In general, the aqueous polymer latexes should be those which, after addition to a hydrophilic colloid solution such as gelatin does not cause aggregation or precipitation of the dispersed particles and after application and drying on a substrate, provide transparent films.

Aqueous polymer latices of the type mentioned are obtained by emulsion copolymerization of free-radically polymerizable Ethene Monomers »The polymer contained in such latices contains as at least one component a compound with a hydrophilic group, e.g. a sulfonate, sulfonate, Sulfonyl, carboxy ,, carboxylate, hydroxy, amido, sulfonamido-j, quaternary ammonium, polyalkylene oxide and / or suI-fat group » The amount of the compound with the hydrophilic group contained in the polymer is generally up to 50%, a monomeric compound with a hydroxyl group as However, the hydrophilic group can be up to an amount of 70? i> are present. According to the invention, highly concentrated aqueous polymer latexes with up to 60 Gew "-? O of dispersed particles can be used.

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As already mentioned, the aqueous polymer latexes which can be used according to the invention are obtained by emulsion copolymerization radically polymerizable ethene monomers. Examples of usable monomers are:

1) Acrylic acid ester compounds, such as methyl, ethyl, butyl, dodecyl, glycidyl or 2-acetoacetoxyethyl acrylate;

2) methacrylic acid ester compounds, such as methyl, ethyl, butyl, dodecyl, glycidyl or 2-acetoxyethyl methacrylate;

3) Acrylamides, such as butyl, Ν, Ν-diethyl, N, N-diisopropyl or dodecylacrylamide;

4) methacrylamides, such as butyl, Ν, Ν-diethyl, dodecyl or N, N-diisopropy! Methacrylamide;

5) vinyl ester compounds such as vinyl acetate and vinyl butyrate;

6) halogenated vinyl compounds such as vinyl chloride;

7) halogenated vinylidene compounds such as vinylidene chloride;

8) vinyl ether compounds, such as vinyl methyl ether, vinyl ethyl ether, Vinylhexylather or Vinylglycidylä-Öieri

9) styrene compounds such as styrene, α-methylstyrene, hydroxystyrene, Chlorostyrene or methylstyrenej

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- aar -

2905280

10) other compounds such as ethylene, propylene, butylene, butadiene, isoprene or acrylonitrile;

11) Compounds with hydrophilic groups:

(1) CH ₂ = C - R

COO (CH ₂ ) ₃ SO 3 M

909833/0779

(2) R.

CHp - C

(3) R ι

CH ₀ «C CH _x ² I.

CONH - C - CH ₂ SO _x M

CH,

CII ₂ «C

(5) CH ₂ -

CH

SO _x M

(6) CH ₂

CH

SO _x M

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- «Γ - ■

2305260

CH ₂ - G

O C-O

SOYM

(8) CH _D m CH

CQM - / "~ \ -OCH, 0OM

(9) R.

CH ₂ . C? ° 3 ^M

CH,

(10) CH ₂ • GH

Googh ₂ SO ₅ M

(11) p

CHp - σ

OH

909833/0771

2S0526Ö

CIL

CH ₃ COO (CH ₀ ).

, 2 2.

C?,

I /

COO (CH ₂ ) ₂ -N

CH,

C>

CH,

C CH,

II ⁵

CONH- C - CH

II CHj OH

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²³ 2305260

I ₂ -Q

OH

(18) H.

CH ₂ «C

CONH ₂

CH - CI CONHO (OH _x ) -

(20) p

CH ₀ «C CH,

² II

COWHC - CH ₀ COCH ²

(21) · HI CH ₂ «C

COOCH ₀ CHCH ₀ N (CH,) ^d \ ^d Gl $ OH θ

909833/07

- -ST -

CH ₂ - (23) CH ₂ - (24) CH ₂ - O CH,
I Ιφ ⁵ θ
COOCH ₂ N - CH ₂ SO ₅
^ H - H
I. B.
ι I.
C.
j C CH,
GOOCH ₂ CH ₂ N - CH ₂ CH ₂ SO ₅ C00 (GH _{2) 2} 0H CH,

(25) R.

CH ₂ - C.
j GH ₀
J <- COOCH ₂ OH (26) B.
I. CH ₂ « I.
C. GOO (CH , CH - OH ₂ ) ₃ 0H

909833/0779

₅ , «= α

² I.

COOCH ₂ CH ₂ OCH ₂ Ch ₂ OH

CH ₂ µ G
COQCi I ²
I ₂ Q - CH ₂ OH CH ₂ OH R.
ι CH ₂ - I.
C.
ι GOOM CH ₂ - CH ₀ GOOM
I ^d
C.
f

COOM

(31) CH ₀ - CH

C00 (0H ₂ ) ₂ QCQ- / ™ \ -C00ri

(32) H.

CHj-J * 5 C CH

- CH ₂ COO

(33) R.

ΛΤΤ __ Λ WÜq "V

^d I

COO (CH ₂ CH ₂ O) ₂ SO ₃ M

CONHCH ₂ CH ₂ N -

(CH ₃ ) ₂

(35) CH ₂ • CH

SO ₂ NH ₂

(36) CHCOO (CHp), S0, M.

II * * CHCOO (CH ₂ ) 3SO ₃ M, etc.

In the formulas given, R stands for a hydrogen atom or a short-chain alkyl group and M for an alkali metal, a hydrogen atom or -

Examples of aqueous poly which can be used in accordance with the invention The copolymers contained in merenlatices are (indicated by their monomer units):

1) -4 CH ₂ - CH - ^ ₀ -f CH ₂ - CH

COOC ₂ H ₅ COOCH ₂ CH ₂ CH ₂ SO ₅ Na

MW: 12O ₁ OOO

2) -t CH ₂ -CH- ^ g -t CH ₂ - CH ^

COOCH ₂ CHCH, CONHG ₂ H ₅ SO ₅ Na

OH, MW: 105,000

3) -ir CH ₂ - CH -) q ₅ · -ir CH ₂ COOCH ₂ CH ₂ CH ₂ Ch ₅

-f CH ₂ - CH- ^ ₀

MW: 75,000

4) -e CH ₂ -CH- ^ ₀ -ir CH ₂ -

COOCH ₅ CONH ₂ MW: 98,000

5) CH,

CH ₂ - CH ^ ₀ -eCH ₂ - C -hf _{# 5}

COOC ₂ H ₅ COOCH ₂ CHCH ₂

COOCH ₀ CH - CH ₀ MW: 110,000

OH OH

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-fßf ₂ - CH ^ ₀ - ^ GH ₂ -GE

OCOCH ₂ COCH ₃

GH ₀ - CH
² f

8} -i CH ₂ - CH - ^ ₅ -6 CH ₂ - CH

CH ₂ Ch ₂ CH ₃ OCOCH ₃

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MW: 68,000

CH ₂ - CH ^ g ₅ -6 CH ₂ - C

GOOCHCH ₂ CH ₃ "COOH

| _H MW: 87,000

^ Z "^ ^ tO

GOOCH ₂ CH ₂ CH ₂ SO ₃ Na MVf: 75,000

9} -t CH ₂ - CH ^ _& -t CH ₂ - CH

t GH,

COO - C - CH _x

CH ₃

- <- CH ₂ - CH - ^ j ₀ MW: 66,000

COOH

10) -f CHg - CH

COOC ₂ H ₅

CHg - CH - ^ ₅ 2905260 CH- ^ g ₅ SO _x Na "
* - - OCOCH, W: 75, 000

11) -f CHg I. - £ CH ₂ - CH-kj ₀ MW: 120,000 COOCgH ₅ CONH - ^ SO _{x well} 12) CHg COOCH ₂ CHgCH ₃ MW: 91,000 CH _x

13) -f CHp - CH -hjt- -f-CIU - CH
^ I ^nd \,
COOCH, COOH

OH,
I. CH ₀ "- CH -> 5
^, 2.
COOCHg CHCH
W. C00CHgCHCHgS0, Na OH COOGHgCH - CH ₃ CHg CHg

, 000

CH ₃ 0

( / in / irr \

-f OWg - ^Ο11 ^ Ϊ9.5

COuCH ₀ CH - CH ₀ MW: 140,000

OH OH

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3ο

15) - (- CH ₂ - CH ^ ₅ -ir GH, COOCH,

5 coo -f \

, 000

CH-> 8 ₅ -fCH ₂ -

COO (CH ₂ ), CH,

CH,

GONH - C - CH ^ SO _x Na

CH

3- ^ν -

MW: 136,000

-f CH ₂ - CH -> g ₀

COO (CH ₂ ), CH;

-e Ch ₂ -

CH

SO _{x well}

CH ₅

ch ₂ .c-) 3

OCOCH ₂ CN

MW: 102,000

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18) CH ₃ ,

-f CH ₂ - CE

COOCH, GOOCH ₀ CJ

OCOCH _x GOCH,

/ rvtr

COONa

19) - (- CH ₀ - CH -> 5c -f- CH ₀ - CH

J ₁ UUt Ol

CH ₀ -

COONa KVF: 156,000

2G) - ^ CH ₂ - CH- ^ ₀ -f-CH ₂ - CH

COOC ₀ Ht- COOCH ₁₁ CHCH ₀ SO ^ Na

2 5 ² f ² *

- <- CH ₂ -'CH ^ ₀ -e CH -C

COO (CH _2), CH, C00 _{(CH2> 2} 0H

MWi102,000

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2 & 0526Q '

COOCHCK ₀ CH f ²

GH, 5

COOM

MW: 94,000

-f CHp -

CH
COOC ₂ H ₅

COOCHo - N t CH,

MW: 72,000

-f CH ₂ -

CII
COOCH

-eCH ₂ -

MWι87,000

25) - - (- CII ₂ - CH COO

CH

-ir OH ₂ -.

CH ₅

C - CH ₅

^CH 5

I "Φ

COOCII ₀ CHCH ₀ N (CH _x ). ^ά \ ^d Eq 1 ■ OH θ

CH ₂ -

MW: 88,000

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26) -f CH ₂ -

27) - (■ CH ₂ - CH-) ß

ß ₅ COOC ₂ H ₅

-ir CHp - CH -> ος? ^Η 2 ^0Η

COOCH ₀ G - CH ₀ OH

■ * Ί * CH ₂ OH

-CH ₂ -

MW: 88,000

MW: TO?, 000

CH

GOOH

GH

PH

CH

^C 36.5
COOCH ₀ CHCH

OH OH

3.5

COOCH ₀ CHCH ² \ /

MW; 65,000

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30) CH ₃

₂ ^ ₀

COOCH, COOCH ₀ CHCH ₀ CH ₃ 0

COOCH ₀ CH - CH ₀

OH OH MW: 78,000

3D CH ₅

- ^ ₀ -fCH ₂ - (

^CH 3 COOCH ₂ CHCh ₂ SO;

COO - C - CH, .. '. '

ι 5 -: .-- ■ "■ - Un

CH ₃

CH ₃ -ir ch _o - ι

. 5

COOCH ₂ Ch ₂ OCOCH ₂ COCH ₃ MW: 83,000

32) CH ₃

COOCH ₂ CII ₂ CH ₂ OO ₃ Na

MW: 79, OOO

909833/0770

COOCH ₂ CH ₂

CH,

t ⁵

COOCH ₂ CH ₂ CH ₂ SO ₅ Na MW; 82,000

- CH

-f CH ₂ - CH ^

COOCH ₂ Ch ₂ OCOCH ₂ COCH,

CH _x

-t CH ₂ -C

COOCH ₂ CH ₂ CH ₂ SO ₅ Na

MW:? 8,000

Under FM is the molecular weight of the polymer in question to understand.

The aqueous polymer latexes which can be used according to the invention are obtained by emulsion polymerization which is known per se. For example, the aqueous polymer latex can be prepared in such a way that 10 to 60% by weight of the respective monomers are introduced into deaerated distilled water, which optionally contains an emulsifier, a polymerization initiator, a polymerization accelerator and a polymerization control agent, and then the mixture obtained is added to a temperature heated from 40 ° to 90 ⁰ C and finally the whole is stirred for several hours.

909833/077 ©

2305260

Emulsifiers which can be used here are, for example, anionic ones surfactants, such as sodium alkylbenzenesulfonate, Polyethylene oxide alkyl ether sulfate, sodium and the like. chen, nonionic surfactants such as polyethylene oxide alkyl ethers and the like, amphoteric surfactants Agents such as those of the betaine or sulfobetaine type, and cationic surfactants such as quaternary ammonium salts and the like. These surfactants can be used either alone or in combination. Suitable polymerization initiators are ammonium persulfate, Potassium persulfate, hydrogen peroxide and the like. Sodium hydrogen sulfite, sodium hydrogen carbonate and the like are suitable as the polymerization accelerator. Suitable polymerization control substances are, for example, mercaptan compounds, isopropanol, tert-butanol and the like. In addition to the additives mentioned, other additives that relate to the synthesis of the Aqueous polymer latex have a beneficial effect, can also be used. Those contained in the obtained aqueous polymer latex dispersed polymer particles should preferably have a particle diameter of about 0.01 to about 1 µm. However, the particle diameter may vary depending on the kind and amount of the emulsifier used, the kind and amount of the emulsifier used Monomers, the type and amount of the polymerization initiator added and the synthesis conditions (temperature, Duration, stirring speed and the like) can be very different. The concentration of polymeric material in the Aqueous polymer latex used according to the invention expediently ranges from 5 to 60, preferably from 30 to 50 Weight .-? Ό.

The following preparation examples describe the synthesis typical aqueous polymer latices that can be used according to the invention.

909833/0779

-, 36 -

Production example 1

(Aqueous dispersion with the copolymer 1)

A 2 liter four-necked flask with a thermometer, a reflux condenser, a 300 ml dropping funnel A and a 300 ml dropping funnel B and a stirrer is charged with 2 g of a commercially available anionic wetting agent (sodium dodecylbenzenesulfonate) and 600 g of distilled water, whereupon the flask is charged 30 minutes introduced gaseous nitrogen and then the flask contents are heated to a temperature of 80 ⁰ C. Then 0.5 g of ammonium persulfate and 0.2 g of sodium hydrogen sulfite are introduced into the flask. Immediately thereafter, 161.7 g of ethyl acrylate are added dropwise from dropping funnel A and 200 ml of an aqueous solution of 38.7 g of sodium 3-acroyloxypropane-i-sulfonate from dropping funnel B over a period of 30 minutes. After the completion of the dropping, the contents of the flask are stirred for 1 hour, after which the temperature of the contents of the flask is allowed to drop to room temperature to complete the reaction. The concentration of polymeric material in the aqueous polymer latex obtained is 20% by weight. The dispersed polymer particles contained in the polymer latex have a particle diameter of about 0.07 µm. The measured molecular weight of the latex is 120,000. '

Production example 2

(Aqueous dispersion with the copolymer 6}

A 1 liter four-necked flask with a thermometer, a Reflux cooler Pj, a 300 ml dropping funnel A and a 300 ml dropping funnel B and a stirrer is mixed with 2 g of a commercially available anionic wetting agent

5a

fed by means of (sodium lauryl sulfate) and 266 g of distilled water, and then introduced into the flask for 30 minutes, nitrogen gas and then the temperature of the flask contents is raised to 80 ⁰ C. Thereafter, a mixture of 169.1 g of n-butyl acrylate and 8.8 g of 2-acetoacetoxyethyl acrylate and from the dropping funnel B 200 ml of an aqueous solution of 22.1 g of sodium are simultaneously in the flask within 30 minutes from the dropping funnel A -i-sulfopropyl-3-acrylamide allowed to drop in. After the completion of the dropping, the contents of the flask are stirred for 1 hour, after which the temperature of the contents of the flask is allowed to drop to room temperature to complete the reaction. The concentration of polymeric material in the aqueous polymer latex obtained is 30% by weight . The particle diameter of the polymer particles dispersed in the polymer latex is about 0.09 µm. The determined molecular weight of the polymer is 68,000.

Production example 3

(Aqueous dispersion with the copolymer 14)

A 2 l four-necked flask with a thermometer, a reflux condenser, a 300 ml dropping funnel and a stirrer is charged with 10 g of a commercially available anionic wetting agent (sodium lauryl sulfate) and 600 g of distilled water, whereupon gaseous nitrogen is introduced into the flask for 30 minutes and thereafter the temperature of the flask contents is raised to 85 ⁰ C. The flask is then charged with 0.5 g of potassium persulfate and 0.2 g of sodium bisulfite and 0.5 g of p-toluenesulfonic acid. Immediately after the addition has ended, a mixture of 160 g of isobutyl acrylate and 40 g of glycidyl acrylate is allowed to drip into the flask through the dropping funnel over the course of 30 minutes. After the end of the dropping in, the contents of the flask are stirred for 15%, whereupon the temperature is increased

909833/0779

2305260

the contents of the flask are allowed to drop to room temperature to terminate the reaction. The concentration of the obtained aqueous polymer latex of polymeric material is 20 wt .- 6. The particle diameter of the polymer latex dispersed polymer particles is about 0.1 µm. the Nuclear magnetic resonance spectral analysis and elemental analysis show that the polymer contained in the latex is from the copolymer 14 exists. The polymer obtained has a molecular weight of 140,000.

Production example 4

(Aqueous dispersion with the copolymer 15)

A 2 liter four-necked flask with a thermometer, a reflux condenser, a 300 ml dropping funnel A, a 200 ml dropping funnel B and a stirrer is charged with 2 g of sodium triisopropylnaphthalene sulfonate, an anionic surfactant and 200 g of distilled water, whereupon the flask 30 initiated min nitrogen gas and then the temperature of the flask contents is increased to 75 ⁰ C. After the addition of 0.5 g of ammonium persulfate and 0.1 g of sodium hydrogen sulfite, 173.5 g of methyl acrylate through the dropping funnel A and 100 ml of an aqueous solution with 26.5 g of sodium 3-acroyloxyphenyl are immediately added over the course of 30 minutes -1-sulfonate and 0.2 g sodium bisulfite allowed to drop in. After the end of the dropping in, the contents of the flask are stirred further, whereupon the temperature of the contents of the flask is allowed to drop to room temperature to complete the reaction. The concentration of polymeric material in the aqueous polymer latex obtained is 40% by weight . The particle diameter of the polymer particles dispersed in the polymer latex

909833/0779

is 0.08 µm. The polymer obtained has a molecular weight from 84000.

Production example 5

(Aqueous dispersion with the copolymer 20)

A 2 liter four-necked flask with a thermometer, a reflux condenser, a 300 ml dropping funnel A, a 300 ml dropping funnel B and a stirrer is charged with 1 g of a commercially available anionic wetting agent (sodium dodecylbenzenesulfonate) and 271 g of distilled water, whereupon the flask is charged 30 minutes introduced nitrogen gas and then the temperature of the flask contents is raised to 80 ⁰ C. After adding 0.5 g of azobiscyanovaleric acid, 159 g of ethyl acrylate are immediately added dropwise over the course of 30 minutes through the dropping funnel A and 100 ml of an aqueous solution of 41 g of sodium 3-acroyloxypropane-2-hydroxy-1-sulfonate through the dropping funnel B . After the end of the dropping, the contents of the flask are stirred for a further 1 hour, after which the temperature of the contents of the flask is allowed to drop to room temperature to complete the reaction. The concentration of polymeric material in the aqueous polymer latex obtained is 35% by weight . The polymer particles dispersed in the polymer latex are about 0.09 µm in size. The molecular weight of the polymer obtained is 117,000.

Production example 6

(Aqueous dispersion with the copolymer 2)

A 3 liter four-necked flask with a thermometer, a Reflux condenser, two 300 ml dropping funnels

909833/0779

-XT-

and a stirrer is charged with 2 g of a commercially available anionic surfactant (sodium dodecylbenzenesulfonate) and 1.2 1 of distilled water were charged, followed by 30 ^minu-1 -tigem introducing gaseous nitrogen, the temperature of the flask contents at 85 ° C is increased. 5 min after the addition of 2 g of potassium persulfate and 0.4 g of sodium hydrogen sulfite, 490 g of isobutyl acrylate and a solution of a mixture of 40.6 g of Jf-sulfoethyl acrylate, sodium salt and 0.6 g of sodium hydrogen sulfite are simultaneously added over a period of 30 minutes with the introduction of gaseous nitrogen Dripped in 400 ml of pure water. After the contents of the flask have been stirred for 4 hours at a temperature (of the contents of the flask) of 85 ^° C., the temperature of the contents of the flask is allowed to drop to room temperature to end the reaction. The concentration of polymeric material in the aqueous polymer latex obtained is 25.3% by weight . The particle diameter of the polymer particles dispersed in the polymer latex is 0.07 µm. The molecular weight of the polymer obtained is found to be 105,000.

Other aqueous polymer latexes can be produced in a corresponding manner with the other specified copolymers.

Polymer latex compositions loaded with photographic hydrophobic additives can be used in all fields of application, including those by conventional known processes obtained polymer latex can be used.

For example, one with a photographic hydrophobic Addition loaded polymer latex mass to form a Layer with or without a photographic binder on one photographic support can be applied.

9098337077t

The photographic recording material contains at least one light-sensitive layer. The latex polymer compound The layer containing the layer may be composed of a photosensitive layer or a non-photosensitive layer, e.g. Protective layer or intermediate layer. A preferred example of a photosensitive layer is a photosensitive one Silver halide layer.

Since the inventively loaded with hydrophobic substances, polymer particles dispersed in an aqueous polymer latex are excellent in particle diameter Have uniformity, obtained coupler-containing color photographic Recording materials (which are produced using the polymer latex composition loaded according to the invention were) excellent chromogenic properties in color development. These are far better than the corresponding ones Properties of conventionally produced color photographic images Recording materials. Those with the former color photographic Color images produced from recording materials show excellent color purity and stability.

Since far more polymers can be used according to the invention compared to known processes, they can be used in polymer latex compositions dispersed polymer particles are also loaded with substances that have hitherto been considered for this purpose not considered usable.

The following examples are intended to illustrate the invention in more detail. in particular, the order of mixing water, i.e. the dispersion medium to obtain a aqueous polymer latex, an organic solvent which is miscible with water, an organic solvent which is immiscible with water Solvent and the respective hydrophobic substances is modified.

909839/0779

- (ar -

example 1

Using a 5% aqueous polymer latex with the Copolymer 2 is made according to the following five process variants (of the mixing process) each produced a polymer latex composition loaded with a hydrophobic substance.

a) A mixture of 100 ml of the aqueous polymer latex, 150 ml of a water-miscible organic solvent in the form of a 1: 1 mixture of tetrahydrofuran and acetone and 20 ml of ethyl acetate as the water-immiscible organic solvent are 10 g of 2-octafluoropentylamido-5- [2- (2,4-di-tert-amylphenoxy) hexylamido] phenol incorporated as a blue-green coupler. The resulting mixture is stirred, the dispersed polymer particles are loaded with all of the coupler. A uniform dispersion is obtained in 1 to 2 minutes. Using a rotary evaporator, then in a conventional manner under reduced pressure removes the organic solvents from the rest of the liquid. The mass obtained becomes 100 ml of a 6% gelatin solution incorporated, a dispersion a) being obtained.

b) A mixture of 100 ml of the aqueous polymer latex and 150 ml of the acetone / tetrahydrofuran mixed solvent are mixed with TO g of the blue-green coupler mentioned. While stirring, 20 ml of ethyl acetate are incorporated into the dispersion, whereupon the stirring continues. Here, the dispersed polymer particles are loaded with all of the coupler, whereby one A uniform dispersion is obtained in 1 to 2 minutes. The organic Solvents are removed in the manner described, whereupon the remaining mass 100 ml of a 6 ounce gelatin solution be incorporated. This gives a dispersion b).

909833/0779

c) A mixture of 10 g of said cyan coupler and 100 ml of the aqueous polymer latex is added with stirring 150 ml of the tetrahydrofuran / acetone solvent mixture and further mixed with 20 ml of ethyl acetate. Here are the dispersed polymer particles loaded with the entire coupler, with a uniform dispersion in 1 to 2 minutes receives. After removing the organic solvent in the manner described, the remaining mass is 100 ml of a 6% gelatin solution incorporated, with a dispersion

c) receives.

d) In a mixture of 150 ml of the tetrahydrofuran / acetone solvent mixture and 20 ml of ethyl acetate, 10 g of said blue-green coupler are dissolved beforehand. The received Coupler solution is then in. With stirring within 2 min 100 ml of the aqueous polymer latex entered. After removing the organic solvents in the manner described the remaining mass is incorporated into 100 ml of a 6% gelatin solution, a dispersion d) being obtained.

e) 100 ml of the aqueous polymer latex are incorporated into a solution of 10 g of said cyan coupler in 150 ml of the tetrahydrofuran / acetone solvent mixture with stirring over the course of 2 minutes. Although parts of the coupler settle, after the addition of 20 ml of ethyl acetate the dispersed polymer particles are loaded with all of the coupler, a uniform dispersion being obtained within a short time. After removing the organic solvents in the manner described, the remaining mass is incorporated into 100 ml of a 6% gelatin solution, a dispersion e) being obtained.

909833/0779

For comparison purposes, the measures a) to e) are repeated, but with the use of the ethyl acetate

is waived. This gives five dispersions f) to j). When visually examining the In the state of the dispersions, it was found that the dispersions a) to e) were excellent without the formation of precipitates Condition. An examination of the dispersions f) to j) shows that the coupler has settled in these and that the dispersions are of poor quality.

The results of the visual inspection show that if the measures according to the invention are complied with, one is independent a high quality dispersion is obtained in each case from the order in which the individual constituents are mixed. This is obviously due to the use of the water-immiscible organic solvent.

Example 2

Using an aqueous polymer latex above with Mixtures A and B are prepared for the copolymer 33 after addition of the solvents mentioned below.

Mixture A: aqueous polymer latex 50 ml

Tetrahydrofuran / acetone (ratio:

1: 1) 75 ml

Ethyl acetate 10 ml

Mixture B: aqueous polymer latex 50 ml

Tetrahydrofuran / acetone (ratio:

1: 1) 75 ml

The resulting mixtures A and B are mixed with varying amounts of 2- [α- (2,4-di-tert-amylphenoxy) butyryl-

909833/0779

amido] -4,6-dichloro-5-methylphenol added as a blue-green coupler. The organic solvents are then reduced in a conventional manner using a rotary evaporator Pressure evaporated, whereupon the mass obtained is incorporated 100 ml of a 10% gelatin solution. The respectively The dispersion obtained is examined microscopically to determine whether precipitates and aggregates have formed. Here the following results are obtained.

T a b e Coupler quantity lie Mixture B 5 g Mixture A good ^i; 10 g Well bad 12.5 g Well at distance
of the solution with
tels are formed
No blows 15 g Well It 20 g Well Il Footnote 1): The terms "ta some
bad and something it "," bad "

bad "of the table are determined individually on the basis of the visual inspection. You has the following meaning: "good": It is neither a precipitation nor a

Determine aggregate formation, "somewhat bad": There is slight precipitation and determine aggregate formations.

"Bad": There are noticeable precipitates and a noticeable formation of aggregates.

909833/0779

The results in the table show that according to the invention the dispersed polymer particles can be loaded with up to three times their own weight by weight. In the absence of the water-immiscible organic solvent, on the other hand, the loading limit is through given identical amounts of polymer particles and coupler.

Example 3

1) A mixture of 100 ml of a 15% strength aqueous polymer latex, 150 ml of a 1: 1 mixed solvent of tetrahydrofuran and acetone and 20 ml of ethyl acetate is stirred with 30 g of a yellow coupler oc- (3-benzyl-2,4-dioxoimidazolidin-3-yl) -a-pivaloyl-5-α '- (2,4-di-tert -amylphenoxy) butyrylamido-2-chloroacetanilide offset. About 1 minute after the addition is complete, the dispersed polymer particles are also present loaded all of the coupler with a uniform dispersion being obtained. Using a rotary evaporator the solvents are evaporated from the rest of the liquid under reduced pressure in a conventional manner. The resulting mass becomes 100 ml of a gelatin solution above incorporated, a uniform dispersion C being obtained.

2) In a mixture of 150 ml of the tetrahydrofuran / acetone solvent mixture and 20 ml of ethyl acetate, 30 g of said yellow coupler are dissolved. The obtained coupler solution 100 ml of said aqueous polymer latex are added with stirring over the course of 2 minutes, whereupon the solvent can be removed using a rotary evaporator. The resulting mass becomes 100 ml of a 1Obigen Gelatin solution incorporated, a uniform dispersion D being obtained.

909833/0779

3) The measures described under 1) and 2) are implemented repeated, but omitting the use of ethyl acetate. It should be noted that the dispersed polymer particles are not fully loaded with the coupler and that considerable amounts to form precipitates.

Example 4

20 g of the yellow coupler used in Example 3 are in a mixture of 10 g of dibutyl phthalate and 50 ml of ethyl acetate solved. The solution obtained is 200 ml of a 5% gelatin solution with a commercially available alkylbenzenesulfonic acid incorporated, whereupon the resulting mixture is dispersed to a dispersion E by means of a colloid mill. The dispersion obtained and the dispersions prepared according to Example 3 are then individually treated with a silver bromide emulsion mixed for color papers. Thereafter, the mixtures obtained are individually in the table in the following table collated manner applied to a cellulose triacetate film support, with various specimens obtained will.

Tabel

Test item no.

Dispersion

Coupler amount (mg / dm ^{2 support area} )

Amount of emulsion, based on ₀ silver (mg / dnr)

1 (comparison)

E C D

9.3 8.9 9.2

6.2

5.9 6.1

After image-appropriate exposure, the various test specimens are 3 min and 30 s at a temperature of 31 ⁰ C with a

909853/0779

Developer of the following composition:

2-methyl-4- (N-ethyl-H-ß-methanesulfonamidoethylamino) aniline-1,5-sulfate 4.5 g

Sodium carbonate, monohydrate 20 g

Potassium bromide 2.0 g

Sodium sulfite 3.0 g

Hydroxylamine sulfate 2.0 g

Sodium hexametaphosphate 2.0 g

Benzyl alcohol 10 ml

topped up with water to 11

the pH of the developer is adjusted to 10.1,

developed and then bleached and in the usual known manner fixed, watered and dried.

The test specimens treated in the manner described are examined sensitometrically, with those in the table below Values listed in the compilation.

Table .

DUT No. Sensitivity

1 100

2 103

3 105

The sensitivity is a relative value based on a sensitivity of test item 1 out of 100 (using comparative test specimen produced by dibutyl phthalate).

min 2, 18th ^υ ι Max 0.08 2, 32 1 , 95 0.06 2, 29 2 , 10 0.07 2 , 18

909833/077 $

From the tabular compilation it can be seen that using a colloid mill without using a colloid mill prepared polymer latex mass produced test specimens are not affected by the coupler and Comparative Sample 1 in all photographic properties are superior.

Example 5

A mixture of 100 ml of a 15% strength aqueous polymer latex, 160 ml of acetone and 40 ml of ethyl acetate are stirred with 30 g of the magenta coupler 1- (2,4,6-trichlorophenyl-3- (2-chloro-5-octadecylsuccinimidoanilino) pyrazolino-5-one offset. When stirring is continued, the dispersed polymer particles are loaded with the coupler, a homogeneous one in 1 to 2 minutes Liquid is obtained. After removing the organic solvents from the remaining liquid under reduced Pressure is the obtained mass 100 ml of a gelatin solution above incorporated, a uniform dispersion F being obtained.

For comparison purposes, a solution of 20 g of the said Magenta coupler in a mixture of 10 g of dibutyl phthalate and 60 ml of ethyl acetate in 200 ml of a 5% gelatin solution with a commercially available alkylbenzenesulfonic acid as a dispersant registered. The mixture obtained is dispersed into a dispersion G by means of a colloid mill.

The two dispersions obtained are individually incorporated into a silver chlorobromide emulsion for color papers, whereupon the emulsions are coated individually on a cellulose triacetate film support for the preparation of test specimens.

909833/0779

- scr -

Tabel

Test item Mr. Dispersion amount of coupler amount of emulsion,

(mg / dm ² trays on silver surface) (mg / dm ² )

4 F 5.7 4.4

5 G 6.5 5.0

After exposure through a step wedge, the individual test specimens are treated in the manner described in Example 4, iv where the following results are obtained.

Tabel

Test item Wr. sensitivity ^D min 2
2 JT Max 4th
5 104
100 0.05
0.08 , 10
, 03 2.03
1.86

The table shows that the polymer latex dispersion prepared according to the invention is used Sample No. 4 produced in all photographic properties to the same sample 5 is superior.

Example 6

Example 1 is repeated, but with the exception that instead of the water-immiscible organic solvent Ethyl acetate five different water-immiscible organic solvents, namely cyclohexanone, Cyclohexanol, benzyl alcohol, chloroform and toluene can be used. In any case, one obtains a uniform one Dispersion in which neither precipitation nor aggregation

909833/0779

gate formation is to be determined. Will be the most varied of dispersions individually incorporated into a photographic emulsion and its photographic properties determined, correspondingly good results are obtained as in example 1.

Example 7

A mixture of 100 ml of an aqueous polymer latex above with the copolymer 28, 150 ml of a 1: 1 solvent mixture from tetrahydrofuran and acetone and 20 ml of ethyl acetate, while stirring with 20 g of the blue-green coupler, 2- [ct- (2,4-di-tert-amylphenoxy) butyrylamidoJ-4,6-dichloro-5-methylphenol offset. The dispersed polymer particles are loaded with the entire coupler in 1 to 2 minutes, whereby a homogeneous liquid is obtained. Using a rotary evaporator, remove the organic solvents evaporated from the remaining liquid under reduced pressure, whereupon the remaining liquid obtained 100 ml of a gelatin solution above is incorporated. This gives a dispersion H.

Dispersions I and J are prepared in a corresponding manner, with the organic solvent mixture prior to addition of the coupler 3 g of dibutyl phthalate or 3 g of tricresyl phosphate are added. The cyan coupler is also used for comparison dissolved in a mixture of 5 g of dibutyl phthalate and 30 ml of ethyl acetate, whereupon the resulting solution with 100 ml a 5% gelatin solution with the commercially available alkylbenzenesulfonic acid is mixed. Then the whole thing is dispersed in a colloid mill and 100 ml of a 5-6 gelatin solution incorporated. This gives a dispersion K.

909833/0779

After mixing with a red sensitive silver chlorobromide emulsion for color papers, the dispersions obtained for the production of test specimens are individually on a CeI applied.

Tabel

Test item Wr. Dispersion amount of coupler amount of emulsion,

(mg / dm ² trays on silver surface) (mg / dm ² )

(Comparative test item)

7th
3

K
H
I.
J

8.1 7.8 7.6 7.8

4.5
4.3
4.2
4.3

After exposure through a step wedge, the test specimens obtained are individually treated for 4 minutes at a temperature of 31 ^° C. with a developer of the following composition

2 ~ Amino-5- (N, N-diethylamino) toluene

Hydroxylamine sulfate sodium carbonate, monohydrate Sodium sulfate

Potassium bromide

topped up with water

2.2 g

3.0 g

31.2 g

1.5 g

0.6 g 1 1

the pH of the developer is set to 10.3,

developed and then bleached and fixed, soaked and dried in the usual known manner «

The sensitometric results of the treated test specimens can be found in the following table:

909833/07 7.9

T a ' 1 e t 2905 Test item no. 5 *
at min 2.48
2.58 Max 6th
(Comparative
test)
7th State of mind 0.14
0.11 1.88
2.01 100
110

8 108 0.13 2.57 2.08

9 101 0.13 2.65 2.11

From the results of the tabular compilation it can be seen that, according to the invention, ultimately excellent can achieve photographic properties and that the use high-boiling organic solvents in the preparation of the coupler-laden aqueous polymer latices is possible.

Example 8

10 g of the ultraviolet absorber 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole are added to a mixture of 10 g of dibutyl phthalate and 50 ml of ethyl acetate dissolved, whereupon the resulting solution with 250 ml of a 1Obigen gelatin solution with the commercial alkylbenzenesulfonic acid is mixed. The mixture obtained is then used to prepare a dispersion treated by means of a colloid mill. Using a rotary evaporator, remove the organic solvents evaporated from the dispersion under reduced pressure to give a dispersion L. After that, be in a mixture of Example 7 with 100 ml of the aqueous polymer latex, 150 ml of the 1: 1 solvent mixture of tetrahydrofuran and Acetone and 20 ml of ethyl acetate incorporated with stirring 10 g of said UV absorber, the dispersed

909833/0779

Polymer particles can be loaded with all of the absorbent in 1 to 2 minutes. Here you get a uniform Dispersion. Using a rotary evaporator, the organic solvents are evaporated under reduced pressure removed from the dispersion, whereupon the remaining mass 250 ml of a gelatin solution above are incorporated. Here receives a dispersion M.

The two dispersions obtained are individually applied to a cellulose triacetate film support for the production of test specimens applied and dried. With the help of a spectrophotometer, the optical density values are obtained Test specimens determined at 370 nm and 415 nm. Here are the results listed in the following table were obtained.

tab Hurry optical
at
370 nm density
at
415 nm Dispersion Amount of
gelatin
(g / m ² ) Amount of Ab
sorption with
tel (g / m2) 1.6
2.9 0.43
0.10 L (comparative
test)
M. 0.55
0.55 0.2
0.2

The table shows that the dispersion prepared according to the invention is used of the UV absorber obtained test pieces have a very high density in the UV range and a low density in the have visible area. This shows that they have sharp separating properties, which in turn indicates that that the UV absorber was dispersed extremely uniformly.

909833 / 077§

SC

example 9

Example S is made with the stain inhibiting agent 2,5-dioctylhydroquinone instead of the UV absorber repeated. This gives a comparison dispersion M and a polymer latex composition or a dispersion 0 according to the invention.

The two dispersions obtained are examined microscopically in accordance with Example 2 to determine the formation of precipitates and aggregates to be determined. Do two hours of standing after dispersing the stain inhibiting Each dispersion is diluted ten times its volume with water by means of and then using white Examines light for its density. Here are the listed in the following table Get results.

Tabel

Dispersion Dispersibility * Density

Ii (comparison dispersion) bad 70§ä

O well 40? £

* The dispersibility is determined according to Example 2 .

From the tabular compilation shows that the _r inventively prepared dispersion provides better results.

909833/0779

Claims (12)

Claims 1. Method of making one with a hydrophobic Substance-laden polymeric latex composition, characterized in that it is dispersed in an aqueous polymeric latex Polymer particles, a hydrophobic substance, a water-miscible organic solvent, and a water-immiscible organic solvent mixed together. 2. The method according to claim 1, characterized in that polymer particles in the form of at least one compound with at least one hydrophilic sulfonate, sulfonate, Sulfonyl, carboxy, carboxylate, hydroxy, amido, sulfonamido, quaternary ammonium, polyalkylene oxide and / or sulfate group used. 3. The method according to claim 1, characterized in that one polymer particles with 1 to 50 wt .-% of a monomer unit, consisting of carboxy-, carboxylate-, sulfo-, sulfonate-. Sulfonyl or sulfate groups are used. 4. The method according to claim 3, characterized in that one polymer particles with 2 to 50 wt .-% of a monomer unit, consisting of carboxy-, carboxylate-, sulfo-, sulfonate-, Sulfate or sulfonyl groups, and 0.2 to 10 % By weight of a monomer unit having an active methylene group used. 5. The method according to claim 1, characterized in that polymer particles with 10 to 70 wt .-? - o a monomer unit used with a hydroxyl group. 909033/077 « _ 2 - 6. The method according to claim 1, characterized in that the concentration of in an aqueous polymer latex dispersed polymer particles below 60 wt. Jo selects. 7. The method according to claim 1, characterized in that there is a photographic additive as the hydrophobic substance used. 8. The method according to claim 7, characterized in that a coupler, a UV absorber, a development inhibitor releasing one Material, a cross oxidation dye releasing agent or a photographic dye is used. 9. The method according to claim 1, characterized in that a water-miscible organic solvent, a miscibility of more than 20 wt -.% In water and a water-immiscible organic solvent miscibility of not more than 20 wt .-% used in water. 10. The method according to claim 1, characterized in that the water-miscible organic solvent and the water-immiscible organic solvent is used in a ratio of 1: 1 to 1: 0.01. 11. The method according to claim 1, characterized in that there is used as the water-miscible organic solvent Ethyl acetate, n-butanol, chloroform, ethyl chloride, ethylene chloride, Dibromoethane, n-propyl acetate, n-butyl acetate, sec-butyl acetate, cyclohexanone, cyclohexanol, isobutanol, n-amyl alcohol, isoamyl alcohol, sea-amyl alcohol, diisopropyl ether and / or benzyl alcohol is used. 9O9833 / Ö770 2305260 12. A photographic recording material comprising an impregnated polymeric latex composition prepared according to claim 7. 909833/0770