DE2905260C2 - Process for the production of a polymeric latex composition loaded with a hydrophobic substance - Google Patents

Description

The invention relates to a method for producing a loaded with a hydrophobic substance polymeric Laiex mass.

In the manufacture of silver halide photographic light-sensitive materials for evenly distributing the most varied of hydrophobic compounds, especially compounds, such as color images, UV absorbing substances and the like, in a gelatin solution or a other hydrophilic colloid solution made the most diverse attempts. In one of these attempts a solid or liquid hydrophobic compound is mixed with a hydrophobic colloid solution, whereupon the mixture obtained several times through a grinder working with high shear force, e.g. a colloid mill, is run. The mixture is converted into a dispersion by mechanical means, which in turn is dispersed in a hydrophilic colloid solution. With this procedure it can however, it happens that only a bad state of dispersion is obtained, so that the bad one is formed

ίο Dispersion is often unstable this process required a large amount of energy to make the solid hydrophobic compound as far as necessary to pulverize and the pulverized compound in the hydrophilic colloid solution in sufficient Disperse dimensions. The consumption of such a large amount of energy is often excessive Heat generation or a ujk. -Wished accompanied by local warming, leading to undesirable chemical changes contained in a system May lead to constituents.

From US-PS 23 04 940 and 23 22 027 another method for dispersing is more hydrophobic Compounds in hydrophilic colloid solutions known In this process, first the hydrophobic

Compound in an oil or in a high-boiling solvent for the preparation of an oily solution dissolved, whereupon the oily solution obtained is dispersed in a hydrophilic colloid solution. One Modification of this process is known, for example, from US Pat. No. 2,801,171. In the latter case is often used to facilitate the dissolution of a hydrophobic substance in the oily solvent a low molecular weight solvent, e.g. B. ethyl acetate, or a low molecular weight ketone, as an auxiliary or cosolvent used. In the preparation of of color photographic silver halide emulsions containing ballast groups or couplers one often uses a method in which the ballast groups have-

■ »0 the coupler in one as a coupler solvent known oily and high-boiling solvents are dissolved, whereupon the resulting solution in a hydrophilic colloid solution, e.g. B. a gelatin-silver halide emulsion, is dispersed. In this dispersing process, too, energy-consuming pulverization must be carried out to the desired state of dispersion and the required particle size of the coupler. Often certain ingredients contained in a mass to be pulverized are

äo le against impairments, e.g. B. thermal decomposition and the like, prone. In addition, such pulverization takes a long time to complete long and increases the prime costs. In view of this, there is a significant need for one improved dispersing process in which hydrophobic compounds, e.g. B. having ballast groups Couplers and the like, uniformly in photographic emulsions as well as in other hydrophilic ones Colloid solutions can be dispersed. In such an improved method, however, should be based on the Use of grinders, which have a high energy requirement, as previously used for dispersing the hydrophobic compounds used in hydrophilic colloid solutions can be dispensed with.

From the JA patent application 30 494/1973 it is known, insoluble in water, in organic solvents on the other hand, soluble polymers for dispersing hydrophobic couplers with a view to improving

tion of photographic properties such as image durability to use. In this case it is however, it is also necessary to emulsify the polymers mixed with the couplers at a high level To use grinder exhibiting energy requirements. The teachings of the JA patent applications 59 942/1976 and 19 943/1976 aim at such processes having a high energy requirement Avoid grinding mills and the associated disadvantages and continue to use photographic emulsions to enhance. According to the teachings of the aforementioned JA patent applications a method is used in which a polymer latex is dispersed Polymer particles which are individually loaded with hydrophobic substances, in such a way as to be hydrophilic Colloid solution is dispersed that the hydrophobic substances dispersed in the hydrophilic colloid solution while the dispersed polymer particles are still with the respective hydrophobic substances loaded. When such a polymer latex is used, the silver halide emulsions obtained can be used impart some desirable properties. Compared to the usual when adhered to The photographic emulsions obtained by dispersing are the particles of the coupler-containing ones formed Dispersion of a small size, so that the ultimately obtained image in terms of sharpness and Reactivity between the developer and coupler is improved. Furthermore, it is possible hydrophobic compounds that should be dispersed in hydrophilic colloid solutions do this however, because they are susceptible to oxidation by air, nunmthr mk could not help the last to introduce the described method in hydrophilic colloid solutions, as they are sufficient against in the latter case Oxidation are protected. Furthermore, hydrophobic compounds that are overly reactive can also be used are and in an undesirable manner with others in one of the hydrophobic compounds in question The constituents present in the layer react with the aid of the polymer latex in hydrophilicity Colluid solutions are incorporated. The usage of polymer latices as a dispersion carrier for photographic additives is a technique with the help of which one can use photographic grinders without the use of grinders which have a high energy requirement Emulsions can impart excellent photographic properties. However, this also leaves Technology, as will be shown, leaves a lot to be desired.

First are the amounts of hydrophobic substances with which, according to the teachings of the two, last said JA patent applications, the dispersed polymer particles are loaded by polymer latices can, not enough. If, for example, in the polymer latex, the dispersed particles with Couplers, d. H. typical photographic hydrophobic additives to be loaded, it is necessary the dispersed particles in a larger amount than the coupler, in certain cases even in the more than double the amount of coupler to use. This leads to the fact that the ultimately obtained photographic Recording material has a large film thickness and thereby in its developability and its resolution is impaired. Another disadvantage of the method described is that that because of the low concentration of contained in 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 in relatively large amounts with water Miscible organic solvents must be used. As a result, one Large-scale device and a lot of time needed to remove these solvents In addition, the number of polymer latices that can be used are limited, and those with hydrophobic ones Substances loaded polymer latex compositions are not always sufficiently stable. As already mentioned, achieved now with none of the known methods completely satisfactory results.

The invention was therefore based on the object of providing a method free of the disadvantages outlined to create for the production of loaded with hydrophobic substances polymer latex, the does not require a high expenditure of energy and when it is carried out the loading of the polymer latex contained dispersed polymer particles with large amounts of hydrophobic substances is possible, Polymerenlaiexmassen used with dispersed polymer particles contained therein in a high concentration 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 is not necessary Difficulties and the number of polymer latices that can be used is not so limited

The subject matter of the invention is explained in more detail in the claims

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

(1) Since no dispersing device requiring a high expenditure of energy is required, there is also there is no risk that the mass obtained will undergo a change in its that can be attributed to heating Properties experiences.

(2) Since you have the polymer particles dispersed in the mass with large amounts of hydrophobic

■ »5 substances can be loaded when using the film thickness of this mass in the context of the production of photographic recording materials keep thinner, improving both developability and resolution capacity.

(3) Since an aqueous polymer latex of high latex concentration can be used, it can be used reduce the difficulties associated with drying the mass.

(4) Since the amount of organic solvent required for loading is kept to a minimum can hold, the solvent can be used in a short time without the need for a large one Remove the drying device without difficulty.

(5) The aqueous polymer latexes which can be used in the process according to the invention are in terms of their nature is not so narrowly limited, so that even hydrophobic substances that have not previously participated in in Aqueous polymer latices contained constituents could be made to adhere, used can get. In addition, the loaded polymer latex compositions are very stable.

In the various embodiments of the method according to the invention, in which in one dispersed polymer particles containing aqueous polymer latex in the presence of three media, i. Water, a water-miscible organic solvent, and a water-immiscible solvent organic solvent, loaded with hydrophobic substances, the order of the Mixing these components, as will be explained later will be very different and consequently cannot be determined in an unambiguous manner. In short, an indispensable requirement is that Presence of the three components water, a water-miscible organic solvent and of a water-immiscible organic solvent, the order of mixing them Components, on the other hand, is not critical.

As a matter of principle, all water-miscible solvents in any amount can be used as organic solvents which are miscible with water. Preferred are those whose miscibility with water is 20% by weight or more. Water-immiscible organic solvents are those whose miscibility with water is not more than 20, preferably less than 10% by weight loading should both kinds of organic solvents not too high boiling points, suitably boiling points below 200 ° C, preferably below 100 C ³ having.

Water-miscible organic solvents which can be used in the process according to the invention are for example acetone, methyl ethyl ketone, ethanol, methanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, Dimethylformamide and dimethyl sulfoxide.

Water-immiscible organic solvents which can be used in the process according to the invention are for example ethyl acetate, n-butanol, chloroform, Carbon tetrachloride, ethyl chloride, ethylene chloride, dibromoethine, n-propyl acetate, n-butyl acetate, sec-butyl acetate, Cyclohexanone, cyclohexanol, ethylene glycol monomethyl ether, isobutanol, η-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 organic, non-miscible with water Solvent can also be produced by a high-boiling organic solvent that was previously used So-called protective dispersions was used and is practically immiscible with water, for Use. The photographic recording materials can be processed with the aid of such high-boiling solvents with regard to their color properties and other photographic properties to enhance. Examples of high-boiling organic solvents that can be used 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, with Water-miscible and water-immiscible organic solvents can vary depending on the nature of the in a specific aqueous polymer latex contained polymeric substance or the used hydrophobic substance can be very different. As a rule, the ratio of aqueous polymer latex is to water-miscible organic solvent 1: 0, 1 to 10, preferably 1: 0.5 to 3. The ratio from water-miscible organic solvents to water-immiscible organic solvents! is about 1: 0.01 to 1, preferably about 1: 0.03 to 0.5. The organic, miscible with water Solvent and the water-immiscible organic solvent can be used individually in combination with other water-miscible and water-immiscible organic solvents used in the form of mixtures of two or more solvents

Hydrophobic substances are to be understood as meaning those whose solubility in water is about 1% amounts to

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

Typical photographic hydrophobic substances with which the method according to the invention can be performed are couplers, UV absorbers, Substances releasing development inhibitors, cross-oxidation dye-releasing agents and photographic dyes, and also fluorescent ones Brighteners, antihalation agents bz · //. light protection agents, developers and like that.

Couplers are, for example, open-chain methylene yellow couplers, 5-pyrazolone magenta couplers, phenol or Naphthol cyan couplers and the like. at

these couplers can be so-called 2-equivalent or act 4-equivalents. They can also be used in combination with couplers for car masking, z. B. colored azo couplers, osazone compounds, diffusible dyes-releasing couplers and the like, are used. To improve the photographic properties, the named hydrophobic coupler also in combination with other couplers, e.g. B. so-called competing Couplers, DIR couplers (development inhibitors couplers releasing) and BAR couplers (compounds that accelerate fading Couplers) can be used.

Usable yellow couplers are the known and already used open-chain ketomethylene compounds, such as pivaloylacetanilide yellow couplers known from US Pat. No. 3,265,505, from British Pat

12 40 600 and US-PS 28 75 051 known benzoylacetanilide yellow couplers. Further yellow couplers known as so-called 2-equivalent couplers are those from US-PS 34 08 194 known, at the active site O-aryl-substituted couplers, which from US-PS 34 47 928 known O-acyl-substituted at the active site Couplers known from GB-PS 13 51424 at the active site with a hydantoin compound substituted couplers known from GB-PS

13 31 179 known couplers substituted at the active site by a urazole compound or a succinic acid imide compound, the couplers known from GB-PS 9 44 490, ^{substituted at J} .er active site by a monooxoimide compound or fluorine-substituted couplers, which are known from GB-PS 7 80,507 known couplers which are chlorine- or bromine-substituted at the active site and those which are known from GB-PS 10 92 506 and which are O-sulfonyl-substituted at the active site.

Usable! - "primeval red couplers are those from Pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole and indazolone type. Pyrazolone magenta couplers are off U.S. Patent 3,127,269, 2,600,788, 35 19 429, 3419391.

30 62 653 and 36 84 514 as well as GB-PS 13 42 553 and 13 99 306 known. Pyrazolotriazole magenta couplers are known from GB-PS 12 47 493. Pyrazolinobenzimidazole Crimson Cups are known from US-PS 30 61 432. Indazolone magenta couplers are known from GB-PS 13 35 603. Particularly according to the invention Well-usable magenta couplers are known from US Pat. Nos. 3,684,514 and 3,127,269.

Cyan couplers which can be used are phenolic compounds from US Pat. No. 2,423,730, 2,801,171 and 28 95 826 known types, from US-PS 24 74 293 and GB-PS 10 84 480 known, at the active site O-aryl-substituted naphthol compounds and those from the CA-PS 9 13 082 and the US-PS 37 37 316 known phenol and naphthol compounds.

Colored magenta couplers are, for example, compounds which, at the active site, have colorless magenta couplers of the type described arylazo or heteroaryla- »r» 5tjKctjtjtnigrt CmH ₁ Examples of this can be found in US Pat. Nos. 3005 712, 29 83 608, 28 01 171 and 36 84 514 as well asGB-PS9 37 621.

Colored cyan couplers are compounds that are arylazo-substituted at the active site. Examples this can be found in US-PS 30 34 892.25 21 908 and

38 11 892 and GB-PS 12 55 111. It can also masking couplers of the type which react with an oxidized developing agent release a dye into a treatment bath (cf. GB-PS 10 84 480), act.

Competing couplers are those from jo U.S. Pat. No. 2,742,832 (e.g. citrazinic acid and the like) and compounds known from U.S. Pat. No. 2,998,314.

Substances which release development inhibitors are preferably those from US Pat. No. 3,632,345,

39 28 041, 39 58 993 and 39 61 959 known connec- J5 fertilizing used.

Compounds which can be used as UV absorbers are triazoles, triazines or benzophenones (see US-PS 30 04 896. 32 53 921, 35 33 794, 32 92 525, 37 05 805, 37 38 837 and 37 54 919, GB-PS * or similar 13 21 355 and JA patent application 25 237/1975), furthermore Acrylic nitrile compounds (see U.S. Patents 3,052,636 and 3,7 07,535). As UV absorbers are preferred Commercially available benzene triazole derivatives are used either alone or in combination. - »5 Further suitable UV absorbers are those from US Pat. No. 25 37 877.27 39 971.27 39 888.27 84 087 and 32 50 687 known azoles and those from US-PS

35 12 984 and 35 49 374 known high molecular weight triazine compounds.

In the context of the method according to the invention, in addition to the hydrophobic photographic Additions, for example, also photographic dyes (cf. US Pat. No. 2,751,298 and 3,506,443), DDR couplers (diffusible dye-releasing couplers) (cf. US Pat. No. 34 43 939.34 43 940.33 43 941 and 37 25 062), indicator dyes (see. US-PS 36 47 437), Sulfonamidophenols, reducing agents (see US Pat. No. 3,810,321), reductones (cf. US Pat. No. 3,572,896 and

36 79 426), bisnaphthol reducing agents (see US Pat 36 72 904 and 37 51 294), hydrophobic developers (see US Pat. No. 36 72 896.36 72 904.36 79 426 and 37 51 249) and so-called cross-oxidation dye-releasing agents, also known as DRR substances (dyes releasing redox compounds) are known (vgL &?

US-PS 36 28 952, 36 98 897 and 37 25 062 as well as BE-PS 788 268, 7 96 040, 7 96 041 and 7 96 042) are used will.

In the case of the aqueous polymer latexes which can be used in the process according to the invention and which have dispersed therein Polymer particles should be those which, after adding one with water miscible organic solvent and a water-immiscible organic solvent neither aggregation nor precipitation of the dispersed particles takes place and the dispersed ones Particles remain stably dispersed in the latex. It should preferably be the case with the aqueous polymer latexes are those which after addition to a hydrophilic colloid solution such as gelatin, neither an aggregation still cause precipitation of the dispersed particles and after application and drying on provide transparent films on a substrate.

Aqueous polymers of the said alloys are produced by emulsion copolymerization of radically polymerizable ethene monomers. The polymer contained in such latices contains as at least one component one having a hydrophilic group, e.g. B. a sulfo, sulfonate, sulfonyl, carboxy, carboxylate, hydroxy, amido, sulfonamido, quaternary ammonium, polyalkylene oxide and / or sulfate group. The amount of the contained in the Polymerij · Λ monomer component having the hydrophilic group generally ranges up to 50%, however, a monomer having a hydroxy group as a hydrophilic group can be up to an amount of 70% are present. According to the invention, highly concentrated aqueous polymer latexes with up to 60% by weight of dispersed particles can be used.

As already mentioned, the aqueous polymer latexes which can be used in the process according to the invention are obtained Ethane monomers which can be radically polymerized by emulsion copolymerization. examples for 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 Ν, Ν-diisopropyl 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, Vinyl hexyl ether or vinyl glycidyl ether;

9) styrene compounds, such as styrene, «-methylstyrene, Hydroxystyrene, chlorostyrene, or methylstyrene;

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

11) Compounds with hydrophilic groups:

CONH-C-CHjSO ₃ M

CONH ^ f V-OCH ₃

SO ₃ M

R.
CH ₂ = C

COOCH— jf

CH ₃
CH ₂ = CH

COOCH ₂ SO ₃ M

SO ₃ M

(D

(2)

(3)

(4)

(5)

(6)

IO

15th

20th

25th

(7)

(8th)

(9)

(10)

J5

40

45

50

55

60

65

10

R CH ₂ = C

COOCH ₂ CHCh ₂ SO ₃ M OH

CH ₂ COO (CH ₂ ), SOjM CH ₂ = C COO (CH ₃ ) JSO ₃ M

R CH ₂ = C

R CH ₂ = C COCHCHj) ₂ -N

R CH ₂ = C

C =

CH ₂

(11)

(12)

(13)

(14)

(15)

R (16)

CH ₂ = C CH ₃

I I χ

CONH-C CH ₂ CHCH ₂ -N

CH ₃ OH

CH ₂ = C COOCH ₂ CHCH ₂ -N

OH

CH ₂ = C CONH ₂

(18)

ο ι

(17) I.

11th

CH ₂ = C (19)

CONHC (CHj) ₉

R CH ₂ = C CH ₃ (20)

I I

CONHC - CH ₂ COCH ₃

CH ₃ R CH ₂ = C (21)

COOCH ₂ CHCHjN (CH ₃ ),

I ci

OH ^θ R CH ₂ = C CH ₃ (22)

I U

COOCH ₂ N-CH ₂ SOf CH ₃

R CH ₂ = C CH ₃ (23)

I I *

COOCH ₂ CH ₂ N - CH ₂ CH ₂ SOf CH ₃ 15

20th

25th

30th

R CH ₂ = C

R CH ₂ = C

COOCH ₂ CH-CH ₂ OH OH

R CH ₂ = C COOiCHjiOH

R CH ₂ = C

COOCH ₂ CH ₂ OCH ₂ Ch ₂ OH

40

45

50

CH ₂ = C CH ₂ OH

COOCH ₂ C-CH ₂ OH CH ₂ OH

R.
CH ₂ = C

COOM

CH ₂ COOM

CH ₂ = C

COOM
CH ₂ = CH

(30)

(31)

CH ₂ = C

CH ₃

(32)

I L

COO (CHj) ₂ N-CH ₂ COO ⁹ CH ₃

R.
CH ₂ = C (33)

COO (CH ₂ CH ₂ O) ₂ SOjM

R.
CH ₂ = C (34)

CONHCH ₂ CH ₂ N- (CH ₂ ), SOf

(CH ₃ ), CH ₂ = CH (35)

SO ₂ NH ₂
CHCOO (CH ₂ ) JSOjM (36)

Il

CHCOOCCH ^ SOjM

60

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 -NH ₄ . Examples of copolymers contained in the small polymer latices that can be used in the process (27) according to the invention are (indicated by their monomer units):

13th 14th

1) - (CH ₂ -CH) ₅₅ - - ^ CH ₂ -CH) ₁ J- MW: 120,000

COOC ₂ H ₅ COOCH ₂ CH ₂ CH ₂ SO ₃ Na

2) - (CH ₂ -CH ^ ₅ - - (CH ₂ -CH) ₅ - MW: 105,000

COOCH ₂ CHCH ₃ CONHC ₂ H ₅ SO ₃ Na

CH ₃

3) - ^ CH ₂ -CH) _n - -4CH ₂ -CH), - - ^ CH ₂ -01% - MW: 75,000

COOCH ₂ CH ₂ CH ₂ Ch ₃ SO ₃ Na

4) - (CH ₂ -CH) ₅₅ - - (CH ₂ -CH) ₅₅ - -CH ₂ COOCH ₃ CONH ₂ OH CH ₃ 5) - ^ CH ₂ -CH) ₅₅ - - (CH ₂ - Qr 5-
I ■ COOC ₂ H ₅
CH ₃
ι COOCH ₂ CHCH ₂
0 I.
—R <- H ₂ - C Μήβ— COOCH ₂ CH
I. OH

MW: 98,000

6) - (CH ₂ -CH) ₅₅ -

COCKCH ^ CHj

- (CH ₂ -CH) ₅ -

CONHC ₃ H ₆ SO ₃ Na

7) - (CH ₂ -CH) U-

COOCHCH ₂ CH ₃ CH ₃

COOCH ₂ CH ₂

OCOCH ₂ COCH ₃

CH ₃

- (CH ₂ -C) _n -COOH MW: 110,000

MW: 68,000

MW: 87,000

8) - (CH ₂ - CH) ₅₅ -

COOCH ₂ CH ₂ Ch ₂ CH ₃ CH ₃

- (CH ₂ - CH) ₀ -

OCOCH ₃

OOCH ₂ CH ₂ CH ₂ SO ₃ Na MW: 73,000

9) - (CH ₂ -

COOH

15th

CH ₃

COO-C-CH ₃ CH ₃

10) - (CH ₂ - CH) ₅₅ - - (CH ₂ -CH) ₅ - - (CH ₂ -CH) ₅ -

16

COOC ₂ H,

OCOCH ₃ SO ₃ Na

MW: 66,000

MW: 75,000

11) - (CH ₂ -CH) -

COOC ₂ H ₅ MW: 120,000

12)

AoOCH.CH.CH, CH ₃

- (CH ₂ -CH) J ₅ -

O ₃ Na

13) - (CH ₂ - CH) ₅₅ - - (CH ₂ -CH) ₅ - - (CH ₂ -

CH ₃ C

COOCHj

14) - (CH ₂ -CH) ₅ -

MW: 91,000

COOH

- (CH ₂ -CH) ₀ -

COOCH ₂ CHCH ₂ SOjNa

MW: 113,000

OH

COOCH ₂ CH-CHj CH ₃ COOCH ₂ CHCH ₂

^χ ο ^κ

- (CH ₂ -

COOCH ₂ CH-CH ₂

I I

OH OH MW: 140,000

15) - (CH ₂ -CH) = - - (CH ₂ -CH) ₅ -

I I

COOCH3 COO

SO ₃ Na

16) - (CH ₂ -CH) _n -

COO (CHj) ₃ CHj

- (CH ₂ -

CH ₃ CONH-C-CH ₂ SO ₃ Na

MW: 84,000

MW: 136,000

308 139/186

17th 17) - (CH ₂ - CH) ₈₅ - - (CH ₂ 29 05
CH ₃
τ COO (CH ₂ ) JCH ₃ , -Q ₅ - - (CH ₂ -CH) ₅ - COOCH ΓΙ SO ₃ Na CF
I. 260 ₂ CH ₂ OCOCH ₂ CN

18th

18) - (CH ₂ -CH) ₅₅ - - (CH ₂ -C) ₅ -

COOCH ₃ COOCH ₂ CH ₂

OCOCH ₃ COCH ₃ - (CH ₂ -CH) ₅ -

COONa
-CH) J ₅ - - (CH ₂ -CH) ₅₅ -

COO (CHj) jCH ₃ Cl

19)

.? 0) - (CH ₂ - CH) ₅₅ - - (CH ₂ -

COOC ₂ H ₅ COOCH ₂ CHCH ₂ SO ₃ Na

OH COONa

21)

COO (CH ₂ ) JCH ₃

CH ₃ - (CH ₂ - CJjj-

COO (CHj) ₂ OH CH ₂ COOM

22) - (CH ₂ -CH) ₅₅ - - (CH ₂ -

COOCHCH ₂ CH ₃ COOM

CH ₃

CH ₃

23) - {CHj - CH) J ₅ - - (CH ₂ -C) J ₅ - CH ₃

COOC ₂ H ₅ COOCH ₂ -N * -CH ₂ CH ₂ SOf

CH ₃

24) ^ CH ₂ -CH ^ ₅ - - (CH ₂ -CH) ₅₅ -

COOCH ₃ N

MW: 102,000

MW: 98,000

MW: 156,000

MW: 117,000

MW: 102,000

MW: 94,000 I. 1 I. I. MW: 72,000 5-
!
; '■'. ; MW: 87,000

25)

CH ₃

COO-C-CH ₃

CH ₃ CH ₃

- (CH ₂ - CH) ₅ -

- (CH ₂ -C) ₁ J-

COOCH ₂ CHCh ₂ N (CH ₃ ^

I ?

OH ^θ 20th

MW: 88,000

26) - (CH ₂ - CH) = - - (CHj-CHW- CH ₂ OH

I I I

COOCH ₃ COOCH ₂ C-CH ₂ OH

CH ₂ OH MW: 88,000

27) - (CH ₂ --CHW- - (CH ₂ - CHW-

COOC ₂ H ₅ SO ₂ NH ₂

MW: 107,000

28) - (CH ₂ - CHW-

COOiCHjiCHj

29) - (CH ₂ -CHW-

COO (CHj) ₃ CH ₃

CH ₃
- (CH-Oj ₀ -

COOCH ₂ CHCH ₂ HO OH

CH ₃

- (CH ₂ -CW-COOH

CH ₃ - (CH ₃ -C) _5x -

COOCHjCHCHj \ κ O MW: 81,000

MW: 65,000

30) - (CH ₂ -CHW-

COOCHj

CHj

- (CH ₂ -CW-

CHj

- (CH ₂ -CW-

COOCHjCHCHj \ / O

COOCHjCH-CH ₂

I I

OH OH MW: 78,000

21 22

CH ₃

31) - (CH ₂ -CiQ ₅₅ - - <CH ₂ -CJ ₅ - MW: 83,000

CH ₃ I.

I COOCH ₂ CHCh ₂ SO ₃

COÜ - C - CH ₃ I.

I OH

CH ₃

CH ₃
- (CH ₂ -C) ₅ -

COOCH ₂ CH ₂ OCOCH ₂ COCh ₃

CH ₃

32) - (CH ₂ -CH ^ ₅ - - (CH ₂ - C) ₁ - MW: 79,300 |

COOCH ₂ CH ₂ CH ₂ Ch ₃ COOCK ₂ CK ₂ CH ₂ SO ₃ Na ■

CH ₃

33) - (CH ₂ -CH) Jj- - (CH ₂ -C) ₅ - MW: 82,000

COOCH ₂ CH ₂ COOCH ₂ CH ₂ CH ₂ SO ₃ Na

34) - (CH ₂ -CH) ₅₅ - - (CH _{2 -CH) 5} - MW: 78,000

COOCH ₂ CH ₂ CH ₂ Ch ₃ COOCH ₂ CH ₂ OCOCh ₂ COCH ₃

CH ₃

- (CH ₂ -C) ₅ -

COOCH ₂ CH ₂ CH ₂ SO ₃ Na

Under MW is the molecular weight of the respective tan compounds, isopropanol, tert-butanol and the

Understanding Polymtrs. 40 same. In addition to the additives mentioned,

In the process according to the invention, if necessary, other additives that relate to the

Ren aqueous polymer latex is obtained by synthesis of the aqueous polymer latex in a favorable way.

known emulsion copolymerization. So can be ken, be used. The received in the

the aqueous polymer latex, for example, such aqueous polymer latex contained dispersed

produce that one in deaerated distilled water, 45 polymer particles should preferably a particle

which optionally have an emulsifier, a polymerisation diameter of about 0.01 to about 1 μm ,

The particle diameter can, however, depend on the

ger and contains a polymerization control agent, 10 to type and amount of the emulsifier used, the type

60% by weight of the respective monomers enters, then and amount of the monomers used, the type and

the resulting mixture to a temperature of 40 ° to 50 ° amount of the polymerization initiator added

90 "C and finally the whole thing for several hours and the synthesis conditions (temperature, duration,

stirs. Rührgeschwindigksit and the like) very different

Emulsifiers that can be used here are, for example, the concentration of polymeric material in the

se anionic surface-active agents, such as sodium al- according to the invention used aqueous Pohmerenla-

Kylbenzenesulfonat, Polyäthylenoxidalkyläthersulfat, Na- 55 tex expediently ranges from 5 to 60, preferably

trium and the like, non-ionic surfactants from 30 to 50% by weight.

Agents such as polyethylene oxide alkyl ethers and the like. The following preparation examples describe the

amphoteric surfactants, e.g. B. those from the synthesis of typical usable aqueous Polymerla-

Betaine or suifobetaine type and cationic surfaces.

chemically active agents, e.g. B, quaternary ammonium salts and 60

like that. These surfactants can be used in Preparation Example 1

either alone or in combination with the application “wn r> · · ·. j »* · u 1 ·. _f \

reach. Suitable polymerization initiators ( ^{water length Dls} P ^{erslon mlt the} M.schpolymensat 1)

are ammonium persulphate, potassium persulphate, water - A 2 l four-necked flask with a thermo

substance peroxide and the like. As a polymerization rod 65 meters, a reflux condenser, a 300 ml

Sodium hydrogen sulfite, sodium dropping funnel A and a 300 ml dropping funnel are more suitable.

jmhydrogencarbonut and the like. Suitable Po- ter B and a stirrer is 2 g of one

Polymerization control substances are, for example, mercap commercially available anionic wetting agents in sodium

dodecylbenzenesulfonate) and 600 g of distilled water were charged, whereupon introduced into the flask for 30 minutes, gaseous nitrogen and then the flask contents siuf a temperature of 8O ⁰ C is heated. Then 0.5 g of ammonium persulfate and 02 g of sodium hydrogen sulfite are introduced into the flask. Immediately thereafter, 161.7 g of ethyl acrylate are dripped into the flask from dropping funnel A and 200 ml of an aqueous solution of 38.7 g of sodium 3-acroyloxypropane-1-sulfonate from dropping funnel B over a period of 30 minutes. After the end 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! A 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 are charged with 2 g of a customary anionic wetting agent (sodium lauryl sulfate) and 266 g of distilled water introduced into the flask for 30 minutes gaseous .Stickstoff and thereafter the temperature of the flask contents is raised to 8O ⁰ C. Thereafter, a mixture of 169.1 g of n-butylacry-IiLi üfiu 8.8 g of 2-AcciuäCciöXyüiiiyiäCryiäi and from the dropping funnel B 200 ml of an aqueous solution of 22.1 g of sodium oil are simultaneously in the flask within 30 min -sulfopropyl-3-acrylamide allowed to drop in. After the end of the dropping in, the contents of the flask are stirred for 1 hour, whereupon the temperature of the contents of the internal flask is allowed to drop to room temperature to end 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 thermoireter, a reflux condenser, a 300 ml dropping funnel and a stirrer is charged with 10 g a commercially available anionic wetting agent (Natri-U tilauryl sulfate) and 600 g of distilled water are charged whereupon gaseous nitrogen passed into the flask for 30 minutes and then the temperature of the IC oil content is increased to 85 ° C. After that, the Flask with 0.5 g potassium persulfate and 0.2 g sodium bisulfite and 03 g of p-toluene sulfonic acid are charged. Direct When the addition is complete, 30 microns of iraierhaib are placed in the flask. a mixture of 150 g of isobutyl acrylate and 40 g of glycidyl acrylate through the dropping funnel dropped in. After the end of the dropping in, the contents of the flask are stirred for 15 hours, whereupon the 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 particle diameter of the polymer particles dispersed in the polymer latex is about 0.1 μΐπ. Nuclear magnetic resonance spectral analysis and elemental analysis show that that contained in the latex Polymers from the copolymer 14 consists. That

ίο obtained polymers has a molecular weight of 14,000.

Production example 4
'' (Aqueous dispersion with 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 min long gaseous nitrogen and then the temperature of the flask contents is increased to 75 ⁵ C. After adding 0.5 g of ammonium persulfate and 0.1 g of sodium hydrogen sulfite, 173.5 g of methyl acrylate and 100 ml of an aqueous solution through the dropping funnel B immediately within 30 minutes

jo solution with 26.5 g of sodium 3-acroyIoxyphenyl-1-sulfonate and allowed to drop in 0.2 g of sodium bisulfite. After the dropping in, the contents of the flask are stirred further, whereupon the temperature of the contents of the flask rose to room temperature to complete the reaction is lowered. The concentration of polymeric material in the aqueous polymer latex obtained is 40% by weight. The diameter of the in the polymer particles dispersed in the polymer latex is 0.08 μm. The polymer obtained has a Molecular weight of 84,000.

Production example 5
(Aqueous dispersion with the copolymer 20)

A 2 l 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 dodecylbePTolsulfonate) 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 within 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. 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 the resulting aqueous polymer latex in polymer! Maieria! is 35% by weight. The polymer particles dispersed in the polymer latex have a size of about 0.09 μm. The molecular weight of the polymer obtained is 117,000.

Production example 6

(Aqueous dispersion with the copolymer 2)

A 3 l four-necked flask with a thermometer, a reflux condenser, two 300 ml each dropping funnels with a capacity of 2 g of a commercially available anionic wetting agent (Sodium dodecylbenzenesulfonate) and 1.2 L of distilled water are charged, whereupon under 30 minutes Introducing gaseous nitrogen, the temperature of the flask contents is increased to 85 ° C. 5 min after Addition of 2 g of potassium persulfate and 0.4 g of sodium hydrogen sulfite are carried out simultaneously within 30 min while passing in gaseous nitrogen, 490 g of isobutyl acrylate and a solution of a mixture of 40.6 g of γ-sulfoethyl acrylate. Sodium salt and 0.6 g sodium hydrogen sulfite dropped into 400 ml of pure water. After stirring the inside of the flask for 4 hours a) at a temperature (of the contents of the flask) of 85 ° C, the temperature of the contents of the flask is used to terminate the Reaction allowed to drop to room temperature. The concentration of the obtained aqueous polymer latex of polymeric material is 25.3% by weight. The particle diameter of the polymer latex dispersed polymer particles is 0.07 μπι. The molecular weight of the polymer obtained is with 105,000 determined.

In a corresponding manner, other aqueous polymer latexes can be mixed with the other specified copolymers produce.

Polymer latex compositions loaded with photographic hydrophobic additives can be applied to all Bring application areas to use, on which also obtained by customary known methods Polymer latex can be used.

For example, a polymeric material loaded with a photograph! - b) see hydrophobic additive to form a layer with or without a photographic binder on a photographic Layer support are applied.

The photographic recording material contains at least one light-sensitive layer. The those The layer containing polymeric latex composition may consist of a photosensitive layer or a non-photosensitive layer Layer, e.g. B. a protective layer or intermediate layer exist. A preferred example for a photosensitive layer is a photosensitive silver halide layer.

Since the substances prepared according to the invention are loaded with hydrophobic c) ben substances, in an aqueous polymer Renlatex dispersed polymer particles have excellent uniformity in terms of their particle diameter have obtained coupler-containing color photographic recording materials (using of the polymer latex composition loaded according to the invention) during color development excellent chromogenic properties. These are far better than the corresponding properties of in conventionally produced color photographic recording materials. Those with the former color photographic D) Color images produced from recording materials show excellent color purity and Stability.

Since the method according to the invention uses far more polymers compared to known methods The polymer particles dispersed in polymer latex compositions can also be mixed with substances are loaded that were previously not considered to be usable for this purpose.

The following examples are intended to illustrate the invention in greater detail, with particular reference to the sequence mixing water, d. H. the dispersion medium for obtaining an aqueous polymer latex, a water-miscible organic solvent, a water-immiscible organic solvent Solvent and the respective hydrophobic substances is modified.

example 1

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

10 g of 2-octafluoropentylamido-5- [2- (2,4-di-tert-amylphenoxy) hexylamidojphenol incorporated as a cyan coupler. The resulting mixture is stirred, whereby 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, the organic solvents are then removed from the remainder of the liquid in a conventional manner under reduced pressure. The mass obtained is incorporated into 100 ml of a 6% gelatin solution, a dispersion a) being obtained.
10 g of the cyan coupler mentioned are added to a mixture of 100 ml of the aqueous Polymereniatex and 150 ml of the acetone / tetrahydrofuran solvent mixture. While stirring, 20 ml of ethyl acetate are incorporated into the dispersion, whereupon stirring is continued. In this case, the dispersed polymer particles are loaded with all of the coupler, a uniform dispersion being obtained in 1 to 2 minutes. The organic solvents are removed in the manner described, whereupon the remaining mass 100 ml of a 6% gelatin solution are incorporated. This gives a dispersion b).
A mixture of 10 g of said cyan coupler and 100 ml of the aqueous polymer latex is admixed with stirring with 150 ml of the tetrahydrofuran / acetone solvent mixture and further with 20 ml of ethyl acetate. In this case, the dispersed polymer particles are loaded with all of the coupler, a uniform dispersion being obtained in 1 to 2 minutes. After removing the organic solvents in the manner described, the remaining mass is incorporated into 100 ml of a 6% gelatin solution, a dispersion c) being obtained

In a mixture of 150 ml of the tetrahydrofuran / acetone solvent mixture and 20 ml of ethyl acetate 10 g of said cyan coupler are previously dissolved. The coupler solution obtained is then introduced into 100 ml of the aqueous polymer latex over the course of 2 minutes with stirring. To Removal of the organic solvent in the manner described, the remaining mass

100 ml of a 6% gelatin solution incorporated, table

a dispersion d) being obtained.

e) A solution of 10 g of said cyan coupler in 150 ml of the tetrahydrofuran / acetone solvent mixture 100 ml of the aqueous polymer latex are incorporated with stirring within 2 minutes. Although parts of the coupler settle, after adding 20 ml of ethyl acetate, the dispersed polymer particles with the load the entire coupler, giving a uniform dispersion within a short time receives. After removing the organic solvent in the manner described, the remaining Mass incorporated 100 ml of a 6% gelatin solution, a dispersion e) being obtained.

Amount of coupler mixture A

Mixture B

5g Well good ¹ ) 10 g Well bad 12.5 g Well when removing the Solvent form down blows 15 g Well the same 20 g something bad the same

For comparison purposes, measures a) to e) are repeated, although the use of the Ai'nyiaceiais is forgone. Five dispersions f) to j) are used here. When the state of the dispersions was visually examined by means of a microscope, it was found that the dispersions a) to e) were in an excellent state without the formation of precipitates. An examination of the dispersions f) to j) shows that the coupler has settled in them and that the dispersions are of poor quality.

The results of the visual inspection show that if the values according to the invention are adhered to, one can see that Measures regardless of the order of mixing the individual components in each Trap receives a high quality dispersion. This is obviously due to the use of the water non-miscible organic solvent.

35

Example 2

Using a 10% strength aqueous polymer latex with the copolymer 33, according to Addition of the following solvent mixtures A and B prepared.

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- [a- (2,4-di-tertamylphenoxyJbutyrylamidoj- ^ e-dichloro-S-methylphenol offset as blue-green coupler. Now in the usual way using a rotary evaporator the organic solvents evaporated under reduced pressure, whereupon the mass obtained 100 ml of a 10% gelatin solution is incorporated. The dispersion obtained in each case is examined microscopically to determine whether there are precipitates and Have formed aggregates. The following results are obtained.

Footnote 1):

The expressions "good", "bad" and "somewhat bad" of the table are determined individually on the basis of the visual inspection. They have the following meaning:

"Well":

Neither precipitation nor aggregate formation can be observed.

"A little bad":

There is slight precipitation and aggregate formations

ascertain.

"bad":

There are noticeable precipitates and a noticeable formation of aggregates.

It can be seen from the results in the table that, according to the invention, the dispersed polymer particles can be loaded with up to three times the weight of their own weight. In absence of the water-immiscible organic solvent, on the other hand, the loading limit is identical Amounts of polymer particles and couplers added.

Example 3

1) A mixture of 100 ml of a 15% strength aqueous polymer latex, 150 ml of a 1: 1 solvent mixture from tetrahydrofuran and acetone and 20 ml of ethyl acetate is stirred with 30 g of one Yellow coupler <x- (3-Benzyl-2,4-dioxoimidazolidin-3-yl) -a-pivaloyI-5-oc '- (2,4-di-tert-amyIphenoxy) butyrylamido-2-chloroacetanilide offset. About 1 minute after the addition is complete, the dispersed polymer particles are with all of the coupler

so loaded, obtaining a uniform dispersion. Using a rotary evaporator, in conventional manner the solvent is evaporated from the rest of the liquid under reduced pressure The mass obtained is incorporated 100 ml of a 10% gelatin solution, whereby a uniform Dispersion C is 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 coupler solution obtained is under 100 ml of the aqueous polymer latex mentioned are added to the mixture over the course of 2 minutes, whereupon the solvents are removed using a rotary evaporator. The The mass is incorporated 100 ml of a 10% gelatin solution, a uniform dispersion D is obtained.

3) The measures described under 1) and 2) are repeated, but with the inclusion of wounding of the ethyl acetate is dispensed with. It should be noted that the dispersed polymer particles are not completely loaded with the coupler and that considerable amounts of 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 dissolved. The solution obtained is 200 ml of a 5% gelatin solution with a commercially available Incorporated alkylbenzenesulfonic acid, whereupon the mixture obtained by means of a colloid mill to a Dispersion E is dispersed. The dispersion obtained and the dispersions prepared according to Example 3 are now mixed individually with a silver bromide emulsion for color papers. After that, the obtained Mixtures individually on a cellulose triacetate film support as set out in the table below applied, whereby various specimens are obtained.

Tabel

Test item no. Dispersion Coupler Emulsions lot amount, related (mg / dm ² on silver Carrier- (mg / dm ² ) area) 1 (comparison) E. 9.3 6.2 2 C. 8.9 5.9 3 D. 9.2 6.1

Test object sensitivity D _niK γ D _m

No possibility

100 0.08

103 0.06

105 0.07

2.18 2.32 23

1.95 2.10 2.18

After proper exposure, the various Samples for 3 minutes and 30 seconds at a temperature of 31 ° C. with a developer of the following Composition:

2-methyl-4- (N-ethyl-N-j3-methane

sulfonamidoethylaminojaniline-

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 1 1

the pH of the developer is adjusted to 10.1,

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

The test specimens treated in the manner described are examined sensitometrically, with those in the The values listed in the following table can be obtained.

Tabel

The sensitivity is a relative value, based on a sensitivity of the test item 1 of 100 (under Use of comparative test specimen made from dibutyl phthalate).

The table shows that the using a without With the use of a colloid mill prepared polymer latex mass produced by the Couplers are not affected and Comparative Test Item 1 in all photographic Properties are superior.

Example 5

A mixture of 100 ml of a 15% aqueous

Polymer latex, 160 ml of acetone and 40 ml of ethyl acetate is added with 30 g of the magenta coupler while stirring 1- (2,4,6-Trichlorophenyl-3- (2-chloro-5-octadecylsuccinimidoanilino) pyrazolino-5-one offset. If you continue to stir the dispersed polymer particles with the Load coupler, a homogeneous liquid is obtained in 1 to 2 minutes. After removing the organic Solvent from the remaining liquid under reduced pressure, the resulting mass IDOmI incorporated into a 10% gelatin solution, a uniform dispersion F being obtained.

For comparison purposes, a solution of 20 g of 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 registered as a dispersant. The mixture obtained is by means of a Colloid mill dispersed to form a dispersion G.

The two dispersions obtained are individually incorporated into a silver chlorobromide emulsion for color papers, whereupon the emulsions are individually applied to a cellulose triacetate film base for the preparation of specimens be applied.

Tabel

Test item no.

Dispersion amount of coupler (mg / dm ² support surface)

Amount of emulsion, based on ai ·· "silver

F.
G

5.7
6.5

4.4 5.0

After exposure through a step wedge, the individual test specimens are shown in the example! 4 described Manner treated with the following results.

Tabel

Test item
No.

Sensitivity D _min
opportunity

104
100

0.05
0.08

2.10 2.03

It can be seen from the tabular summary that the using a according to the invention Prepared polymer latex dispersion prepared Sample No. 4 in all photographic properties is superior to comparative test 5

Example 6

Example 1 is repeated, but with the exception that instead of the water-immiscible organic solvent ethyl acetate five different, with Water-immiscible organic solvents, namely cyclohexanone, cyclohexanol, benzyl alcohol, Chloroform and toluene can be used. In every FaU you get a uniform dispersion in which neither precipitation nor aggregate formation can be determined. Will be the most varied of dispersions individually incorporated into a photographic emulsion and their photographic properties determined, one gets correspondingly good results like in example 1.

Example 7

A mixture of 100 ml of a 10% strength aqueous polymer latex with the copolymer 28, 150 ml a 2: 1 solvent mixture of tetrahydrofuran and acetone and 20 ml of ethyl acetate is added with stirring with 20 g of the cyan coupler 2 - [«- (2,4-di-tert-amylphenoxy) butyrylamidoJ-4,6-dichloro-5-methylphenol added Here, 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, the organic solvent was evaporated from the remaining liquid under reduced pressure, whereupon the remaining liquid obtained is incorporated 100 ml of a 10% gelatin solution. Here you get a Dispersion H.

Dispersions I and J are prepared in a corresponding manner, using the organic solvent mixture before adding the coupler, 3 g of dibutyl phthalate or 3 g of tricresyl phosphate are added. Also, for comparison, the cyan coupler is presented in one Dissolved mixture of 5 g of dibutyl phthalate and 30 ml of ethyl acetate, whereupon the resulting solution with 100 ml of a 59% gelatin solution with the commercially available alkylbenzenesulfonic acid is mixed. After that, the whole is dispersed in a colloid mill and 100 ml incorporated into a 5% gelatin solution. This gives a dispersion K.

After mixing with a red-sensitive silver chlorobromide emulsion for color papers, the obtained dispersions for the production of test specimens individually on a cellulose triacetate film support applied.

Tabel

Test item no. Dispersion Coupler
lot
(mg / dm ²
Carrier-
area) Emulsions
amount, related
on silver
(mg / dm ² ) 6th
(Comparative
prijfling) K 8.1 4.5 7th H 7.8 4.3 8th I. 7.6 4a 9 J 7.8 4.3

Temperature of 31 ° C with a developer of the following composition:

2-Amino-5- (NjNl-diethylamino) toluene
Hydroxylamine sulfate 3.0 g

Sodium carbonate, monohydrate 31.2 g
Sodium sulfite 1.5 g

Potassium bromide 0.6 g

topped up with water to 11

the pH of the developer is adjusted to 103,

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

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

Tabel

Test item No.

sensitivity

6th
(Ver
equal
examinee) 100 0.14 2.48 1.88 7th 110 0.11 2.58 2.01 8th 108 0.13 2.57 2.08 9 101 0.13 2.65 2.11

After exposure through a step wedge, the specimens obtained are individually for 4 minutes at a

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

Example 8

In a mixture of 10 g of dibutyl phthalate and 50 ml of ethyl acetate, 10 g of the ultraviolet absorber 2- (2'-hydroxy-5'-tert.-butylphenyl) benzotriazole dissolved, whereupon the resulting solution with 250 ml of a 10% gelatin solution with the commercially available Alkylbenzenesulfonic acid is mixed. The mixture obtained is then used to prepare a dispersion treated by means of a colloid mill. Organize using a rotary evaporator The solvent is evaporated from the dispersion under reduced pressure, a dispersion L receives. Thereafter, in a mixture of Example 7 with 100 ml of the aqueous polymer latex, 150 ml of the 1: l solvent mixture of tetrahydrofuran and acetone and 20 ml of ethyl acetate while stirring 10 g of des mentioned UV absorber incorporated, wherein the dispersed polymer particles with the entire Absorbent can be loaded in 1 to 2 min. A uniform dispersion is obtained here. Under Using a rotary evaporator, the organic solvents are removed at reduced pressure removed from the dispersion, whereupon 250 ml of a 10% gelatin solution were incorporated into the remaining mass will. This gives 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 of the test specimens obtained were determined at 370 nm and 415 nm results listed in a table.

Tabel

Dispersion

Amount amount of optical density

to GeIa- to Ab-

tine

(g / m ² ) (g / m ² )

_at

415n _m

L (comparative
checking)

0.55 0.2 1.6 0.43

0.55 0.2

2.9

0.10

From the tabular compilation it can be seen that using a according to the invention prepared dispersion of the UV absorber test specimens obtained a very high density in UV range and a low density in the visible range. This shows that they have sharp release properties which in turn indicates that the UV absorber is extremely uniform was dispersed.

Example 9

Example 8 is substituted with the stain inhibiting agent 2 ^ -dioctylhydroquinone of the UV absorber repeated. This gives a comparison dispersion N and a polymer latex composition or a dispersion 0 according to the invention. The two dispersions obtained are accordingly Example 2 examined microscopically to determine the -

to determine the formation of precipitates and aggregates. After standing for two hours after dispersing the stain inhibitor Each dispersion is diluted to ten times its volume with water and then under The density of the use of white light is examined results listed in a table.

Tabel

Dispersion

N {comparative dispersion)
O

*) The dispersibility
certainly

bad
Well

70% 40%

The table shows that the dispersion prepared according to the invention gives better results.

Dispersibility *) Density IjJ

is according to example 2 f |

Claims (7)

Patent claims: 1. A method for producing a loaded with a hydrophobic substance polymeric latex composition, characterized in that in an aqueous latex of a polymer containing units having a hydrophilic group dispersed polymer, a hydrophobic substance, a water-miscible organic solvent having a boiling point below 200 ⁰ C. and a miscibility of more than 20 wt .-% in water and a water-immiscible organic solvent with a boiling point below 200 ° C and a miscibility of not more than 20 wt .-% in water, optionally partially by a with water The immiscible high-boiling organic solvent is replaced, mixed with one another and that the two organic solvents are removed from the mixture obtained 2. The method according to claim 1, characterized in that that one polymer particles with at least one monomer component with at least a hydrophilic sulfo, sulfonate, sulfonyl, carboxy, carboxylate hydroxy, amido, sulfonamido, quaternary ammonium, polyalkenylene oxide and / or sulfate group used. 3. The method according to claim 1, characterized in that polymer particles rait I to 50 % By weight of a monomer unit with carboxy, carboxylate, sulfo, sulfonate, sulfonyl or sulfate groups, used 4. The method according to claim 3, characterized in that polymer particles with 2 to 50 % By weight of a monomer unit with carboxy, carboxylate, sulfo, sulfonate, sulfate or sulfonyl groups and 0.2 to 10% by weight of a monomer unit having an active methylene group is used 5. The method according to claim 1, characterized in that polymer particles with 10 to 70 % By weight of a monomer unit having a hydroxyl group is used. 6. The method according to claim 1, characterized in that the concentration of in one Aqueous polymer latex dispersing polymer particles below 60 wt .-% selects. 7. The method according to claim 1, characterized in that the miscible with water organic solvents and the water-immiscible organic solvent in the ratio 1: 1 to 1: 0.01 used