DE2442166A1 - CROSS-LINKABLE POLYMER WITH ACTIVE METHYLENE RESIDUES - Google Patents

Description

. »Crosslinkable polymer with active methylene residues

The invention relates to a crosslinkable polymer with active ■ -! Etaylenresten. ·.

It is known to use gelatin as a binder for the production of photographic recording materials, because of the unique properties of gelatin, in particular its good dispersion properties and its excellent protective colloid properties. However, the disadvantage of using gelatin for the production of photographic recording materials is that it is subject to a change in dimension when it is subjected to different temperatures and different humidities. He has therefore tried many times to replace the gelatin with naturally occurring and synthetic substances in one or more layers of a photographic recording material in order to improve the dimensional stability of the material.

From US-PS 3,062,674 and 3,142,568 it is known, for example, as a binder in layers of photographic recording materials to improve physical properties including dimensional stability vinyl polymers or addition polymers to use. It has been found, however, that when such polymers are used in layers of photographic recording materials often the hardness of the layers, their resistance to abrasion and their adhesion to the film support be adversely affected.

From JA-PS 7 002 726 there are also copolymers prepared from a monomer of the following general formula

R.
CH ₂ = C-COCII ₂ R ⁴

wherein R and R ^{4 represent} hydrogen atoms or short-chain alkyl, hydroxy, acetyl or acetoxy groups or halogen atoms and

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at least one vinyl monomer consisting of styrene, acrylonitrile, Vinyl acetate, vinyl chloride, ethyl methacrylate and acrylamide

known.

From US Pat. Nos. 3,459,790, 3,488,708, 3,554,987 and 3,658,878, polymers with active methylene radicals are also known which serve as cross-linking centers capable of reacting with common gelatin hardeners. With these.n polymers the active methylene residue is arranged in a side chain and attached to the main polymer chain through an ester group. Disadvantageous The thing about the use of these polymers is that when they are used in larger amounts, the hardness of the layer, the toughness against abrasion and the adhesion to the substrate are adversely affected. Exists under certain conditions furthermore the tendency of the ester group to hydrolyze, whereby the cross-linking center is lost.

The object of the invention was a polymer which can be used as a binder indicate which can be used to make photographic materials and which are free from the drawbacks the well-known substitute for gelatin. In particular, a crosslinkable polymer which can be used as a gelatin substitute should be specified which has active crosslinkable centers in part of the side chains, but with the remainder representing the Side chain binds to the main polymer chain has an increased resistance to hydrolysis.

The invention was based on the knowledge that such polymers can be obtained by polymerizing a certain ethylenically unsaturated Monomers with an active methylene radical, optionally with at least one further monomer, which is preferably is free of active methylene residues.

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The invention relates to a crosslinkable polymer with active methylene radicals, which is characterized in that it is built up to

A) 1 to 100% by weight of at least one polymerized monomer Λ with at least one active methylene radical of the formula:

0 0

C-CHi -C-R

in which:

η = 0 or 1 ;

R is a hydrogen atom, a methyl radical or a radical of Formula: 0

-C-O-R,

in which R is an alkyl, cycloalkyl or aryl radical, R is an arylene ethylene radical and

R is an alkoxy or amino radical when η = 0 or a Alkyl, alkoxy, amino, cycloalkyl or aryl radical when η = 1, and

B) 0 to 99 wt .- $ of at least one with the monomer A copolymerized ethylenically unsaturated monomers.

The polymers according to the invention are outstandingly suitable, alone or in admixture with gelatin, as binders for photographic layers, for example for the production of photographic emulsion layers. The polymers can be further provided with conventionally known gelatin hardeners cure, for example, compounds with aldehydes and bis (vinylsulfonyl). The polymers are therefore suitable as gelatin substitutes and as modifiers which can be crosslinked with the customary known gelatin hardeners.

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It has been found that monomers A of the formula given with active methylene radicals both homopolymers with excellent Provide properties as well as mixed polymers with excellent properties with other ethylenically unsaturated monomers. The polymers according to the invention are characterized by active methylene residues in the side chains, i.e. methylene residues between two activating residues or groups, e.g. electronegative residues, e.g. carbonyl residues. Such methylene residues have unusual chemical activity and are therefore referred to as "active".

The molecular weight of the polymers according to the invention can vary widely. Polymers with a molecular weight of about 5,000 to about 500,000 have proven to be particularly advantageous. The polymers according to the invention, which are generally soluble in water, have inherent viscosities of 0.75 to 2.0, in particular about 0.9 to about 1.25, measured using 0.25 g of polymer in 100 ml of a 1N sodium chloride solution at 25 ⁰ C.

Particularly advantageous polymers are built up from residues of monomers of the given formula A) with at least one active Methylene radical and up to 50% by weight of radicals at least one second Monomers which can be polymerized with the monomer of the formula given.

The arylenethylene radical represented by R in the formula given corresponds to the formula:

-Ar-CH ₇ -CH ₀ -

in which Ar is an aryl radical, preferably an aryl radical with 6 to 12 carbon atoms, in particular a phenyl or naphthyl radical, which can optionally be substituted, for example by alkyl and / or alkoxy radicals, preferably with 1 to 10 carbon

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atoms, for example by methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl, nonyl or dedyl residues or Methoxy, ethoxy, propoxy, butoxy or pentyloxy radicals. In the Cases in which the aryl radical Ar is substituted, it is preferably by short-chain alkyl and / or alkoxy radicals with 1 to 5 carbon atoms substituted. The aryl radical represented by Ar can, however, also be substituted by amino radicals, in particular by amino residues of the formula:

-N

wherein R and R are hydrogen atoms and alkyl radicals, preferably with 1 to 10 carbon atoms, substituted or unsubstituted Cycloalkyl radicals, preferably with 5 to 7 carbon atoms, e.g. cyclopentyl, cyclohexyl or cycloheptyl radicals or optionally substituted aryl radicals, preferably having 6 to 12 carbon atoms of the type described. The aryl radical represented by Ar can furthermore be substituted by cycloalkyl radicals be, preferably by cycloalkyl radicals having 5 to 7 carbon atoms, as indicated, and / or cyano radicals and / or halogen atoms, e.g. bromine, chlorine, fluorine and iodine atoms and / or nitro radicals or other common radicals. Since the aryl radical Ar can be substituted in different positions, different isomers can exist.

If η has the meaning of 0, then R can be an alkoxy radical, preferably with 1 to 10 carbon atoms, in particular with 1 to 5 carbon atoms, for example an alkoxy radical as indicated for the substituents of Ar. If η ^{3 is} 0, R can furthermore be an amino radical, in particular an amino radical of the following formula:

R ⁴

-N

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wherein R and R represent hydrogen atoms or alkyl, cycloalkyl or aryl radicals, as they are for the amino substituents des Remainder Ar were given.

If η = 1 in the formula given, R can be an alkyl or Be alkoxy, preferably with 1 to 10 carbon atoms, for example a methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, nonyl or decyl radical or a methoxy, Ethoxy, propoxy, butoxy or pentyloxy radical.

2
If R has the meaning of an alkyl or alkoxy radical, the radical preferably has 1 to 5 carbon atoms.

2
If η = 1, then R can also be an amino radical, in particular of the formula:

-N

\ _R 5

be, in which R and R ^{5 have} the meaning already given.

2
If R has the meaning of a cycloalkyl radical, this preferably consists of an optionally substituted cycloalkyl radical having 5 to 7 carbon atoms, for example an optionally substituted cyclopentyl, cyclohexyl or cycloheptyl radical. If R has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or naphthyl series, d.ii, an optionally substituted phenyl or naphthyl radical, it being possible for the substituents to consist, for example, of alkyl, carboxyl or alkoxycarbonyl radicals, ie in this Case R is, for example, a tolyl, XyIyI or benzoyl radical.

Particularly advantageous monomers for the preparation of the inventive Polymers with active methylene groups are:

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Ethyl acrolylacetate,

Ethyl 5- (m- and p-vinylphenyl) -3-oxopentanoate and 6- (m- and p-vinylphenyl) -2,4-hexanedione.

In the case of the last-mentioned compounds, there are generally mixtures of 60% by weight of the meta-isomer and 40 wt. I consist of the para isomer, since the isomers are not are easy to separate. It has been shown that only slight differences in the polymerization behavior between the mixture and the pure isomers can be observed.

The monomers mentioned can, like the other monomers mentioned under the given formula can be homopolymerized or, advantageously, copolymerized with one or more other monomers will.

Particularly advantageous polymers according to the invention are:

Copolymers of ethyl acrylol acetate (20 to 5% by weight ) and acrylamide (80 to 95% by weight!);

Copolymers of Athylacryloylacetat (50 parts by weight I) and methacrylic acid (50 wt ⁰ O;

Terpolymers of ethyl acrylol acetate (5 to 20 percent by weight) and N-alkyl acrylamide with a short-chain alkyl radical, e.g. N-isopropyl acrylamide (5 to 20% by weight) and a salt of a sulfoacrylate, e.g., sodium 3-methacryloyloxypropane-i-sulfonate (50 to 90% by weight);

Copolymers of 6- (m- and p-vinylphenyl) -2,4-hexanedione (20 bis Wt .- *) and sodium 3-methacryloyloxypropane-i-sulfonate (80 to 20% by weight!);

Copolymers of 6- (m- and p-vinylphenyl) -2,4-hexanedione (20 bis % By weight) and sodium p-styrenesulfonate (80 to 20% by weight) and

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Copolymers of 6- (m- and p-vinylphenyl-2,4-hexanedione (20 to 80 Weight I) and 2-acrylamido-2-methylpropane-1-sulfonate (80 to 20 weight I)

Homopolymers of ethyl 5- (m- and p-vinylphenyl) -3-oxopentanoate;

Homopolymers of 6- (m- and p-vinylphenyl) -2,4-hexanedione;

Copolymers of acrylamide (80% by weight) and ethyl 5- (m- and p-vinylphenyl) -3-oxopentanoate (20% by weight);

Copolymers of acrylamide (80 to 95% by weight) and 6- (m- and p-vinylphenyl) -2,4-hexanedione (20 to 5% by weight) and

Copolymers of N, N-dimethyl-m-2-hydroxypropylamine methacrylimide (85 to 90% by weight) and 6- (m- and p-vinylphenyl) -2,4-hexanedione (15 to 10% by weight).

The monomers required for the preparation of the polymers according to the invention can be prepared by customary known methods. For example, ethylacryloylacetate can be produced by methods such as those described by N.Nazarov and S.I. Zavyalov in the magazine Zh. Obshch. Khim., £ 2> 1953, page 1793 and by E. Wenkert, A. Alfonso, J. B-Son Bredenberg, C. Kaneko and A. Tahara in the journal J. Am. Chem. Soc., Jto, 1964, p 2038 and by G. Stork and R. Natix Guthikonda, in the journal Tetrahedron Letters, 2_7, 1972, pages 2755 to 58 described in more detail will.

The production of 6- (m- and p-vinylphenyl) -2,4-hexanedione and Ethyl 5- (m- and p-vinylphenyl) -3-oxopentanoate can be made by methods described by C. R. Hauser and T. M. Harris in the journal J. Amer. Chera. Soc, J50, 1958, pages 6360 and by L. Weller in the journal J. Amer. Chem. Soc, 9-2, 1970, p. 6702 are described in more detail.

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Suitable for the production of copolymers according to the invention Ethylenically unsaturated monomers are for example:

Vinyl esters, amides, nitriles, ketones, halides, ethers, a, ß-unsaturated Acids or esters thereof as well as olefins and diolefins.

Typical examples of suitable ethylenically unsaturated monomers are:

Acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, sodium pstyrenesulfonate, Acrylamide, methacrylamide, vinyl chloride, methyl vinyl ketone, fumaric acid ^, maleic and itaconic acid esters, 2-chloroethyl vinyl ether, Acrylic acid, sodium methacryloyloxyethyl sulfate, sodium Z-acrylamido-Z-methylpropane-i-sulfonate, methacrylic acid, üimethylaminoäthylmethacrylat, 4,4,9-Trimethyl-8-oxo-7-oxa-4-azonia-9-decen-1-sulfonat, N-vinylsuccinamide, N, N-dimethyl-N-2-hydroxypropylamine acrylimide, N-vinylphthalimide, N-vinylpyrazolidone, Butadiene, isoprene, vinylidene chloride, ewdc ethylene, and vinylimidazole.

Sulfone acrylate salts have proven to be particularly advantageous comonomers proven. Typical examples of such salts are:

Sodium 3-methacryloyl oxypropane-i-sulfonate; Sodium 3-acryloyloxypropane-1-sulfonate and Sodium 4-acryloyloxybutane-2-sulfonate.

Such sulfoacrylate salts are described, for example, in US Pat. No. 3,411,911.

The production of polymers up to 30 Gew.-i from units of one or more monomers A) of the specified formula with active methylene residues are built up can be carried out, for example, by solution polymerization in a suitable medium, for example in water or in mixtures of water with water-miscible solvents, for example methanol, ethanol, Propanol or isopropanol.

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- ίο -

If the polymers consist of more than 30% by weight of units one or more monomers of the formula given with active methylene radicals, the polymerization can be carried out in an advantageous manner by solution polymerization in a suitable organic solvent, for example acetone, benzene, cyclohexanone, dimethylformamide, Dimethyl sulfoxide or tetrahydrofuran take place or by polymerization in aqueous emulsion or by suspension polymerization according to customary known methods.

The temperature used during the polymerization can be very different. The most favorable temperature in the individual case depends on various factors, for example the monomers used in the individual case or the monomers used in the individual case, the heating time, the pressure used and the like. As appropriate, it has proven in general, when the polymerization temperature is not above 110 ^0C. Often it has been found advantageous to polymerize at temperatures of about 50 to about 100 ⁰ C.

The pressure used in the polymerization, if any is used, is usually only so high that the reaction mixture is in liquid form, although quite generally it is possible to work not only with normal prints but also with superatmospheric or subatmospheric prints.

The concentration of the polymerizable monomers in the polymerization mixture can also be very different. It is expedient to work with concentrations of up to 40% by weight, in particular at concentrations of about 20 to 40 percent by weight based on the weight of the polymerization mixture.

Customary known polymerization catalysts can be used to carry out the polymerization may be used, for example, free radical generating catalysts such as hydrogen peroxide and

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Cumene hydroperoxide and also water-soluble initiators of the azo type. In the case of redox polymerization systems, the usual System components are applied. Optionally, the polymers can be isolated from the reaction medium, namely for example by freezing out, by salting out, by precipitation or by other customary known methods.

It can optionally be advantageous for the production of the polymers to use a surface-active compound or a compatible mixture of such compounds, such as, for example from US-PS 3,142,568 for the production of vinyl or addition polymers are known. The surface-active compounds genes can consist of non-ionic, ionic or amphoteric compounds consist, for example, of polyoxyalkylene derivatives, amphoteric amino acid dispersants including sulfobetaines and the like. Such surface-active Compounds or wetting agents are disclosed, for example, in US Pat. Nos. 600,831, 2,271,623, 2,275,727, 2,787,604, 2,816,920 and 2 7 39 891 known.

Silver halide photographic dispersions containing an addition homopolymer or a mixed polymer with active Methylene residues in combination with conventional photographic binders, e.g., gelatin, can be prepared in various ways will. For example, an aqueous gelatin dispersion of a photographic silver halide with an aqueous Dispersion or solution of one of the Ilomopolymers or copolymers according to the invention are mixed. on the other hand photographic silver halide can also be used in an aqueous dispersion or solution of one of the substances according to the invention Homopolymers or copolymers with or without another colloid, depending on the dispersion characteristics of the homopolymer used or copolymers precipitate. In this case, a water-soluble salt such as silver nitrate is mixed with a water-soluble salt Halide, e.g., potassium bromide, mixed in the presence of the mixture. On the other hand, the photographic silver halide can also be used in one aqueous gelatin solution and precipitated in the usual known manner

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be digested. After digestion, before the emulsion is applied to a layer support, the emulsion can then have a Aqueous dispersion of one of the homopolymers or copolymers according to the invention with active methylene radicals in the side chains can be added. The mass of the resulting dispersion can be increased by adding more Homopolymers or copolymers and / or naturally occurring or synthetic colloids or other binders that are suitable for the preparation of photographic silver halide emulsions. Typical suitable colloids are, for example Gelatin, protein derivatives such as carboxymethylated proteins, colloidal albumin, cellulose derivatives, synthetic resins such as e.g., polyvinyl compounds, e.g., polyacrylamide.

The homopolymers and copolymers that can be used as gelatin substitutes of the invention can be used as binders in one or more layers of a photographic recording material can be used with at least one silver halide emulsion layer.

The photographic silver halides are particularly advantageous however, in the presence of binders such as gelatin or other colloids, which have a very good peptizing effect have failed. As a result, silver halide emulsion layers contain of a photographic recording material containing one of the homopolymers according to the invention or Mixed polymers advantageously have a proportion of a binder with a very good peptizing effect, such as, for example Gelatin. In these cases, the concentration of the homopolymers and copolymers according to the invention is advantageous 20 to 85 wt .-%, preferably 50 to 85 wt .-%, based on the total binder weight when dry. Preferably the remainder consists of 100% by weight gelatin, although instead other colloids can also be present from gelatin.

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Are the polymers according to the invention for the production of other Layers used as emulsion layers, for example to produce filter layers, antihalation layers, abrasion-resistant Layers, antistatic layers, release layers, image receiving layers for the diffusion transfer process and the like, they can be used as the sole binder or in a mixture with conventional known naturally occurring or synthetic columbs can be used.

The use of polymers and copolymers according to the invention in gelatin emulsions leads to emulsions with improved hardness properties. The achievable hardness of the emulsions depends on this quite obviously from the ratio of the gelatin in the Emulsion and the absolute concentration of the active methylene units in the homopolymer or copolymer used.

Emulsions containing a homopolymer according to the invention or copolymers can be chemically sensitized in a conventional manner.

In a particularly advantageous manner, the invention Use polymers to produce hardened emulsion layers with silver halides, which are chemical and gold compounds were sensitized. It has been found that the fogging problems that often were sensitized in the case of emulsions, for example with gold Emulsions occur which have been hardened with reducing hardeners, e.g. with formaldehyde or Mucochloric acid, are greatly reduced when gelatin emulsions are used with polymers according to the invention, which are used to achieve a hardened emulsion does not require the use of reducing hardeners.

The homopolymers and copolymers according to the invention can be used for the preparation of the customary known photographic emulsions be used. For example, they can be used to produce

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direct-positive silver halide emulsions are used, also for the production of X-ray emulsions and X-ray emulsions and other non-spectrally sensitized emulsions, as well as for the preparation of orthochromatically sensitized, panchromatic sensitized and infrared-sensitive emulsions, especially for the production of emulsions containing merocyanine dyes, Cyanine dyes and carbocyanine dyes have been sensitized. Furthermore, the polymers can be used for production of emulsions intended for the production of color photographic materials, for example for the production of emulsions with color-producing color couplers or for the production of emulsions necessary for development are determined with solutions which contain color couplers or other dye-producing compounds. After all, they can Polymers can also be used to make photographic emulsions containing developer compounds such as polyhydroxybenzenes.

The polymers can also be used for the production of recording materials which are intended to carry out the diffusion transfer process, such as for example are known from U.S. Patents 2,352,014, 2,543,181 and 3,020,155.

The polymers according to the invention can also be used for production photographic materials can be used for the color diffusion transfer process disclosed, for example, in U.S. Pat 2,856,142, 2,983,606 and 3,227,552 as well as GB-PS 904 364 and 840 731 is known.

The polymers according to the invention are also suitable for production Photographic recording materials having at least one produced using a polymer according to the invention uncured colloid layer, especially used for developing are determined by means of so-called hardening developers, as they are known, for example, from GB-PS 825 544. Under use

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the photograph produced by the polymers according to the invention Recording materials can also be developed in single baths as they are known, for example, from US Pat. No. 2,875,048 or in the context of so-called stabilizing development processes.

The photographic recording materials produced using polymers according to the invention can furthermore contain bleachable dyes, preferably non-diffusing dyes of the known type. To the "bleachable dyes" also include compounds which are so-called dye precursor compounds, i.e. compounds which during become colored during the development process of the photographic material. Under "non-diffusing" dyes are to be understood as meaning bleachable dyes which do not diffuse even in the emulsion layer, or dyes which non-diffusing by using a suitable mordant such as a mordant of the type disclosed in U.S. Patent 2,882,156 be made.

Those made using polymers of the invention Photographic recording materials can also be made from those having a simple emulsion layer for formation monochrome dye images are made up of either an azo dye or a mixture of azo dyes can be generated, whereby the generated dye images can either be colored or consist of so-called neutral images, i.e. black and white images. Azo dyes are mainly used in so-called silver dye bleaching systems, whereby the -N = N double bond is split on bleaching producing two aromatic fragments which are used to produce color. Typical azo dyes, which for the production of photographic recording materials of the invention can be used, for example from GB-PS 923 265, 999 996, 1042 300 and 1077628 as well as the U.S. Patents 3,178,290, 3,178,291, 3,183,225 and 3,211,556 are known.

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It has been shown that azo dyes are able to react with the polymers of the invention when the polymers are more than 30 wt .-% consist of units with active methylene residues. This azo dye-polymer reaction causes the polymer binder coated on the support to form small spheres or Forms particles as in the case of a latex. The reaction between azo dye and polymer does the advantageous binding properties the curable polymers used according to the invention, however, do not cause any interruption.

The following examples describe the preparation of some polymers according to the invention.

example 1

Production of a polymer from acrylamide and ethyl acryloylacetate in a weight ratio of 90.0: 10.0% by weight

To a mixture of 180 g of acrylamide and 20 g of ethylacryloylacetate in 1600 ml of water and 125 ml of absolute ethanol, which was stored under a nitrogen atmosphere, 1.0 g of 2,2'-azobis (2-methylpropionitrile) admitted. The solution was then heated to 65 ° C. for 4 hours. The mixture then became 1 liter Water was added, whereupon the reaction product was precipitated from the solution by adding 37.85 liters of isopropyl alcohol. The precipitated reaction product was filtered off, washed and dried. There was a total of 170 g of a flaky white get solid mass.

The elemental analysis showed:

C: 47.4t;
H: 7.6%;
N: 1 7.3t;

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The polymer consisted of 94 wt -.% Of acrylamide units and 6 parts by weight of ⁹ ₀ Athylacry loy lace tateinheiten. The inherent viscosity of the polymer, measured using a 1N NaCl solution, was 0.95.

Example 2

Production of a polymer from ethyl acetate, N-isopropyl acrylamide and 5-methacryloyloxypropane-i-sulfonate, sodium salt with a weight ratio of the units of 8.8: 6.9; 84 »3 wt. -%

To a mixture of 20.2 g of N-isopropyl acrylamide and 26.0 g of ethylacryloylacetate and 248 grams of sodium 3-methacryloyloxypropane isulfonate in 2250 ml of water and 180 ml of absolute ethanol was 1.0 g of 2,2'-azobis (2-methylpropionitrile) under a nitrogen atmosphere added as initiator. The solution was warmed to 65 ° C. overnight. The reaction product was obtained from the biscous solution in water precipitated by adding 37.85 liters of isopropyl alcohol. It was filtered off, washed and dried. The obtained polymer had an inherent viscosity when measured by means of a 1N NaCl solution of 0.97.

Example 3

Production of a polymer from methacrylic acid and ethylacryloylacetate in a weight ratio of 50.0: 50.0% by weight

To an i> liscaung of 10 g methacrylic acid and 10 ethyl acryloylacetate in 40 ml of acetone was 0.1 g of 2,2'-azobis (2-methylpropionitrile) added as initiator. The solution was warmed to 65 ° C overnight. The polymer obtained was precipitated in Ether, filter off and dry isolated. The polymer was Inherent viscosity measured in methanol of 0.58.

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- 18 Example 4 Production of poly (ethylacryloylacetate)

50 ml of 2,2'-azobis (2-methylpropionitrile) were added to 10.0 g of ethylacryloylacetate in 5 ml of benzene. The mixture was heated ^{to 65 °} C. overnight under a nitrogen atmosphere. The viscous mass obtained was dissolved in acetone and precipitated using isopropyl alcohol. The polymer obtained was filtered off immediately after the precipitation and dissolved in acetone for further use. The yield of polymer was 7.0 g.

Example 5

Manufacture of poly ^ ~ 6- (m- and p-vinylphenyl) -2,4-hexanedione J

50 ml of 2,2'-azobis (2-methylpropionitrile) were added to 10.0 g of 6- (m- and p-vinylphenyl) -2,4-hexanedione in 5 ml of benzene. The mixture was heated ^{to 60 °} C. overnight under a nitrogen atmosphere. The resulting viscous mass was dissolved in acetone, whereupon the polymer was precipitated by isopropyl alcohol. The polymer obtained was filtered off immediately after the precipitation and dissolved in acetone for further use. The yield of polymer was 8.0 g.

Example 6 Production of poly / "6- (m- and p-vinylphynyl) -2,4-hexanedione_7

To 13 g of 6- (m- and p-vinylphenyl) -2,4-hexanedione in 60 ml of water with one milliliter of a surface-active compound (Triton 770 with 401 active substance) were added 100 mg of potassium persulfate and 33 mg of sodium bisulfite. ^{The emulsion system was heated to 80 °} C. for 2 hours under a nitrogen atmosphere. The resulting emulsion was then dialyzed into a bath of distilled water overnight. The yield of polymer was 10.0 g.

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- 19 Example 7

Production of a polymer from acrylamide and 6- (m- and p-vinylphenyl) -2,4-hexanedione in a weight ratio of 10.0: 90.0% by weight

To 12Ü ml of water, 200 mg of potassium persulfate and 20 mg of sodium bisulfite were added simultaneously at 80 ⁰ C under a nitrogen atmosphere 18 g 6- (m- and p-vinylphenyl) -2,4-hexanedione and 2 g of acrylamide from a dropping funnel and 20 mg of sodium added in 20 ml of water from another dropping funnel. ^{The emulsion system was heated to 8U 0} C for 2 hours under a nitrogen atmosphere. The resulting emulsion was then dialyzed into a bath of distilled water overnight. The yield was 20 g,

Example 8

Production of a polymer from 6- (m- and p-vinylphenyl) -2,4-hexanedione and 3-methacryloyloxypropane-i-sulfonic acid, sodium salt in a weight ratio of 48.5 to 51.5% by weight

To a mixture of 130 g of 6- (m- and p-vinylphenyl) -2,4-hexanedione and 138 g of sodium 3-methacryloyloxypropane-1-sulfonate in 80 ml of dimethyl sulfoxide, which was stored under a nitrogen atmosphere, were 2.0 g of 2,2'-azobis (2-methylpropionitrile) were added. The solution was heated to 60-65 ° C for 20 hours. The polymer obtained was precipitated from the solution by adding 15.1 liters of isopropyl alcohol, filtered and washed. The resulting white solid polymer was immediately dissolved in water to give a 15.7 % solids solution. The yield of polymer was $ 100.

Example 9

Production of a polymer from 6- (m- and p-Viny! Phenyl) -2,4-hexanedione and 2-acrylamido-2-inethy! Propane-1-sulfonic acid, sodium salt in a weight ratio of 48.5: 51.5 wt. -%

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To a mixture of 6.5 g of 6- (m- and p-vinylphenyl) -2, 4-hexanedione and 6.9 g of sodium ^ -acrylamido ^ -methylpropanesulfonate in 40 ml of dimethyl sulfoxide, which was stored under a nitrogen atmosphere, was 0 , 1 g of 2, 2 ^f -azobis (2-methylpropioniiril was added. The solution was ^{heated for 20 hours to a temperature of 60 to 65 °} C. The polymer obtained was precipitated from the solution using 3.785 liters of isopropyl alcohol. It was filtered off and washed The resulting white polymer was dissolved in water immediately after washing to prepare a solution of 11.1 wt% solids, and the yield of the polymer was 551%.

Example 10

Preparation of a polymer from 6- (m- and p-vinylphenyl) -2,4-hexanedione and p-styrenesulfonic acid, sodium salt in a weight ratio of 51.2: 48.8% by weight

To a mixture of 13.0 g of 6- (m- and p-vinylphenyl) -2,4-hexanedione and 12.4 g of sodium p-styrene sulfonate in 60 ml of dimethyl sulfoxide, which was stored under a nitrogen atmosphere, 0.2 g of 2,2'-AzobLs (2-methylpropionitrile) were added. The solution was heated to a temperature of 60 to 65 ^° C. for 20 hours. The polymer obtained was precipitated from the solution using 3.786 liters of isopropyl alcohol. The precipitated polymer was filtered off and washed. The washed polymer was then immediately dissolved in water to make a 13.3% solids solution. The yield of polymer was 801.

Example 11

Production of a polymer from acrylamide and 6- (m- and p-Viny! Phenyl) -2,4-hexanedione in a weight ratio of 90:10 percent by weight

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To a mixture of 18.0 g of acrylamide and 2 g of 6- (m- and p-vinylphenyl) -2,4-hexanedione in 160 ml of water and 20 ml of absolute ethanol stored under a nitrogen atmosphere 0.1 g of 2,2'-azobis (2-methylpropionitrile) was added. The solution was heated to 65 ° C. for 6 hours. The polymer obtained became from the resulting viscous solution by means of 4 liters Precipitated isopropyl alcohol, filtered off, washed and immediately plunged into water to produce a 5.51 solids solution solved. The polymer obtained had an inherent viscosity of 1.21, determined in a 1N sodium chloride solution.

Following the procedure described in Example 4, the following were made other polymers:

Poly / ethyl 5- (m- and p-vinylphenyl) -3-ketopentanoate 7;

_ ivjj ^r oxopentaTioesäureaniid

Poly / N, N-diethyl-5- (m- and p-vinylphenyl) -3-άαϋοβ6οΦβηαθ (1χ_ / and Poly / ~ t-butyl-5- (m- and p-vinylphenyl) -3-ketopentanoate_7.

Following the procedure described in Example 5, the following were made produced further polymers, the weight ratios of the first polymerize monomer polymerize to the second Polymers at about 1: 9 to about 4: 1 were:

Polymer of methacrylic acid and ethyl acetate at a weight ratio of 85:15 and 90:10;

Polymer of methacrylic acid and 6- (m- and p-vinylphenyl) -2,4-hexanedione at a weight ratio of 85:15 and 90:10; .

Polymer made from methacrylic acid and ethyl 5- (m- and p-vinylphenyl) -3-ketopentanoate in a weight ratio of 85:15 and 90:10;

Polymer of methacrylic acid and N, N-diethyl-5- (m- and p-vinyl-

phenyl) -3-li »dW (paxodöm * fc in a weight ratio of 85:15; oxopentanoic acid amide

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2U2166

Polymer of methacrylic acid and t-butyl 5- (m- and p-vinylphenyl) -3-ketopentanoate in a weight ratio of 85:15;

Polymer made from n-butyl acrylate, methacrylic acid and ethylacroyloylacetate in a weight ratio of 10:10:80;

Polymer of n-butyl acrylate, methacrylic acid and 6- (m- and p-vinylphenyl) -2,4-hexanedione in a weight ratio of 10:15:75;

Polymer of n-butyl acrylate and ethyl acrylate in a weight ratio of 50:50;

Polymer of n-butyl acrylate and 6- (m- and p-vinylphenyl) -2,4-hexanedione in a weight ratio of 50:50;

Polymer of N, N-dimethyl-N-2-hydroxypropylamine acrylamide and 6- (m- and p-vinylphenyl) -2,4-hexanedione in weight ratio 85:15 and 90:10.

The following polymers which can be used according to the invention were prepared by solution polymerization in benzene:

Polymer of 2-hydroxyethyl methacrylate and ethyl acryloylacetate in the molar ratio of 1.0: 4.0 and

Polymer made from 2-hydroxyethyl methacrylate and 6- (m- and p-vinylphenyl) 2,4-hexanedione in a molar ratio of 1.0: 3.0.

The following examples illustrate the use of polymers according to the invention as binders for the production of photographic recording materials.

Example 12 (usage example)

This example illustrates that a polymer made of acrylamide and ethyl acetate with a weight ratio of the monomers of 90:10, similar to a copolymer with a weight ratio

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ratio of 94.6, as described under A, can be used as a binder for a photographic recording material which, after exposure and development, provides sensitometric results that correspond to the results, which are obtained when grains of the same emulsion are dispersed in gelatin.

First, a highly sensitive silver bromide iodide negative emulsion was made (Ratio of bromide to iodide = 94: 6) that described by Trivelli and Smith in the journal PSA J., volume 79, page 330 Type produced, namely using a polymer of 3-thiapentyl acetate and 3-acryloyloxypropane-1-sulfonic acid, Sodium salt in a molar ratio of 1: 6 as a peptizing agent. The polymeric peptizer contained a thioether residue. That Polymer is known from U.S. Patent 3,615,624. The removal of soluble salts and the concentration of the emulsion were carried out Ultrafiltration. After digesting for optimum speed, the emulsion was divided into several portions.

A portion was made in a polymer of acrylamide and ethyl acetate (Weight ratio 90:10) dispersed, 160 g of polymer being accounted for 1 mol of silver. A second part of the emulsion was made dispersed in 160 g of gelatin per mole of silver.

After admixing the usual additives and a cross-linking agent (2 g formaldehyde on 100 g polymer or gelatin) both emulsions were applied to transparent substrates and in such a way that on a dm 53.82 mg of silver and 79.85 mg of binder, i.e. polymer or gelatin were omitted.

The exposure took place at 500 W, 540O ⁰ K.

The development took place in a developer with the following composition:

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Water, about 5O ⁰ C 500 ml

p-methylaminophenol sulfate 2.5 g

Sodium sulfite, dehydrated 30.0 g, hydroquinone 2.5 g

Balancing alkali 10.0 g potassium bromide 0.5 g

Made up to 1 liter with water.

The developer ^{temperature was 20 °} C. and the development time was 5 minutes. The sensitometric data compiled in the following table were obtained. The polymer "A" is the polymer made from acrylamide and ethyl acetate with a weight ratio of 90:10.

Binding Relative Gamma of the real haze (total mean sensation haze minus density of the ability of the layer carrier)

Polymer "A" 155 1.00 0.10

Gelatin 100 0.82 0.06

The polymers of the invention are as already dargelegr in an excellent manner customary to replace the binder or carrier gelatin emulsions, in particular replacement of the binder of photographic recording materials intended for the silver dye Ausbleichverfahren.

Improved s ensitometric results are obtained due to the presence of crosslinkable centers in the polymer which, when crosslinked, are more stable to the acidic conditions of the bleaching process.

The following example illustrates the use of inventive polymers for the production of recording materials of this type.

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- 25 Example 13 (usage example)

Several polyester film-based recording materials were used produced by the fact that layers were applied to the support, which consist of a dispersion of an azo dye of the structure given below in a binder as given in Table I below.

CONH (CH ₂ ) ₄ -0

CH ₂ CH ₃

.

Table I.

Sample binding no. middle

Conc.
(mg / dm

Formaldehyde hardener G ^ / dm ^z )

(Ver gelatin
equal)

(Ver gelatin
equal)

XY-90
XY-90

26.9

26.9

26.9 26.9

0.269

2.69

2.269 2.69

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Table I continued

5 XZ'-80 26.9 0.269 6th XZ ^f -80 26.9 2.69 7th XZ-90 26.9 0.269 8th XZ-90 26.9 2.69 9 XZ-90 26.9 2.69 10 XZ- 80 26.9 2.69

In the table, the letters X, Y, Z and Z ^{1 have} the following meanings:

- (CH ₇ -CH) CO

Z = i CH ₂ -CH>

0

CH ₂ -CH ₂ -C-CH ₂ -C-CH ₃

{CH - CH)

«Ι

CO CH ₇

ι * ·

CO OCH ₇ -CH,

CH ₇ -CH ₀

CO CH ₇

I *

c «o

OCH ₇ -CH,

The numerical data used in connection with the letters X, Y, Z and Z ¹ relate to the weight of the units X, based on the total weight of the polymers, when the polymerization resulted in a 100,000 degree of conversion.

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Furthermore, an acidic activator sheet was prepared by placing a mixture of the following on a polyester support Components was applied:

sulfonated polystyrene 26.9 mg / dnr

p-toluenesulfonic acid 53.8 mg / dm

Thiourea 53.8 mg / dm

1,6-hexanediol. 53.8 mg / dm ²

To examine the polymeric binders, sections of the activator sheet were ^{heated to 100 °} C. for 10 seconds. The heated sections were then laminated with sections of the recording materials described at 100 ° C. for 10 seconds. While still in the molten state, the recording materials were separated off, allowed to cool and washed in water. The crosslinking and adhesion of the dye layers on the support was determined.

The following results were obtained:

In the case of specimen 1, there was no adhesion of the dye layer found against the substrate of the material. Rather, there was complete degradation of the gelatin binder he follows. In the case of sample 2 using gelatin and a higher concentration of formaldehyde, some degradation occurred the gelatin, but the results were improved over Sample 1. In the case of samples 3 to 10, the colored ones remained Layers intact and no degradation of the binder was evident.

Example 14 (usage example)

Further test specimens were produced as described in Example 13, but this time 13.5 mg gelatin per dm and 13.5 mg of the polymers of Samples 3 to 8 of Table I.

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The results of the investigation showed that a partial degradation of the binder was done. In each case, however, the results obtained were better than the results obtained with comparison samples were obtained using only gelatin for their production.

Example 15 (usage example)

A variety of other silver halide photographic recording materials have become available as described in Example 13, but which contains a silver chlorobromide emulsion in the

the same layer in a layer thickness of 4.31 mg Ag / dm.

Sections of the recording materials were then exposed for 1 minute at 23 ° C with e:
specified composition:

For 1 minute at 23 ° C with a developer of the following

Water, about 50 ^° C. 500 ml

p-methylaminophenol sulfate 2.0 g

Sodium sulfite, dehydrated 90.0 g

Hydroquinone 8.0 g

Sodium carbonate, monohydrate 52.5 g Make up to 1 liter with water

developed, fixed, washed and dried. The silver images and total dye densities were the same in all cases.

Portions of the recording materials were then mixed with portions of the Aktivatorblattes described in Example 13 is laminated, namely 10 to 60 seconds at temperatures of 100 to 150 ⁰ C. Further samples were left after heating in the laminated state, u * consider the quality of the bleached dye images to be able to.

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From the results obtained, it was found that longer periods of time and elevated temperatures were required to obtain dye images in the recording materials embodying the invention Polymers contained. However, it was found that the images obtained were significantly superior to those obtained when used of comparative materials containing gelatin.

Example 16 (usage example)

Various exposed sections of recording materials, produced as described in Example 15, were developed at 23 ^° C. with an aqueous viscous developing solution instead of with an activator sheet of the type described in Example 13. The viscous developing liquid used had the following composition:

g / l H ₂ O

3,6-dithiaoctane-1,8-diol 10

p-toluenesulfonic acid 10 phenazine 0.02

Hydroxyethyl cellulose 40

Within 24 hours, the images of comparison samples with gelatin as a binder were no longer recognizable, due to the hydrolysis of gelatin. Images and binders of the other recording materials made using the not hydrolyzable polymers according to the invention are produced, in contrast, remain intact.

Example 17 (usage example)

There were other recording materials with dye-binding. middle layers as described in Example 13, prepared, wherein however this time the formaldehyde hardener by the same Amounts by weight of bisvinylsulfonylmethyl ether was replaced.

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The recording materials were then tested according to the procedure given in Example 13, whereupon the results obtained with those of Example 13 were compared. There was little difference, but it was found that the bisvinylsulfone methyl ether curing agent had more favorable properties in the case of the use of gelatin as a binder, whereas formaldehyde somewhat more suitable as a hardening agent for the recording materials were made using polymers of the present invention.

Example 18 (usage example)

The binders listed below were used with different Concentrations of curable entities were tested according to the procedure described in Example 15.

The composition of the polymers tested and the percentages by weight hardenable units are summarized in the following table:

Polymer weight percent curable units

XZ-95 5

XZ-90 10

XZ-85 15

XZ-80 20

where X and Z are as given in Example 13, defined.

The results obtained became with increasing amounts of curable Units always better. There were no adverse effects on silver development or silver dye fading observed.

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- 31 Example 19 (comparative example)

Further dye-binder coating compositions were prepared and tested according to the procedure described in Example 13. One set of specimens consisted of specimens 1 and 2 of Example 13 with gelatin as a binder, and a second set The set of test items contained a polymer of N-isopropyl acrylamide as a binder, 3-methacryloyloxypropane-i-sulfonic acid, sodium salt and acetoacetoxyethyl methacrylate in a weight ratio of 53: 31.5: 14.5 weight percent. This polymer is none of the polymers according to the invention. Although the polymer was a good emulsion binder, it performed well on the dye fade tests like the gelatin reference material and degradation of the binder was found in all cases.

509813/1005

Claims (8)

PATENT CLAIMS 1. Crosslinkable polymer with active methylene residues, characterized in that it is built up to: A) 1 to 100% by weight of at least one polymerize Monomers with at least one active methylene radical of the formula: R 0 0 CH ₉ -C-f-R ¹ -4-C-CH ₉ -CR ²
z ^v 'n L in which: η «0 or 1; R is a hydrogen atom or a methyl radical or a radical of the formula 0 -COR ⁰ in which R ^{3 is} an alkyl, cycloalkyl or aryl radical, R is an arylene ethylene radical and R is an alkoxy or amino radical when η ■ is 0 or a Alkyl, alkoxy, amino, cycloalkyl or aryl radical, when η is 1, and B) 0 to 99 wt. I from at least one with the monomer A) mixed-polymerized ethylenically unsaturated monomers. 2. Polymer according to claim 1, characterized in that it is built up is to: A) 1 to 100% by weight of at least one polymerized monomer with at least one active methylene radical of the formula : RO 0 CH ₂ -CC-CH ₂ -C-R ' 509813/1005 in which: R is an IV hydrogen atom or a methyl radical and R ^{1 is} an alkoxy or amino radical, and B) 0 to 99% by weight! of at least one ethylenically unsaturated monomer copolymerized with the monomer A). 3. Polymer according to claims 1 and 2, characterized in that it has an inherent viscosity of 0.10 to 2.0. 4. Polymer according to claims 1 to 3, characterized in that it consists of a film-forming Addtionsmischpolymer, from 0 to 99 wt.! consists of slfoacrylate salt units. 5. Polymer according to claim 1, characterized in that it consists of an addition copolymer which is built up to 0 to 99 wt .-% from units of at least one of the following monomers: Acrylamide; n-butyl acrylate ; 2-hydroxyethyl methacrylate; N-isopropyl acrylamide; N, N-dimethyl-N-2-hydroxypropylaroin acrylamide; Methacrylamide; Methacrylic acid; Sodium 2-acrylamido-2-methyl-propane-1-sulfonate; Sodium 4-acryloyloxybutane-2-sulfonate; Sodium 3-acryloyloxypropan -1-sulfonate; Sodium 3-methacryloyloxypropane-1-sulfonate and / or sodium o-styrene sulfonate. 6. Polymer according to claim 2, characterized in that it is composed of 1 to 100 wt. -I from ethyl acryloylacetate units. 7. Polymer according to claim 1, characterized in that it is built on to 1 to 50 wt.! from units A and from 50 to 99 % by weight! from units B. 8. Polymer according to claim 1, characterized in that it is built up to 509813/1005 . A) 1 to 100 weight -% of at least one polymerized monomer having at least one active methylene group of the following formula: 0 0
CH ₂ -CH ₂ -C-CH ₂ -CR ¹ where mean: R is a hydrogen atom or a methyl radical and R ^{1 is} an alkyl, alkoxy, amino, cycloalkyl or aryl radical, where the aromatic radical can optionally be substituted by at least one alkyl, alkoxy, cyano and / or cycloalkyl radical and / or at least one halogen atom and B) 0 to 99% by weight of at least one with the monomer A copolymerized ethylenically unsaturated monomers, 9t polymer according to claim 8, characterized in that it is built up to 1 to 30 wt -. \ Comprising units of the component A) and 70 to 99 parts by weight of units of at least one component I B) 509813/1005