WO2008141952A1 - Siliconized vinyl chloride copolymer - Google Patents

Abstract

The subject of the invention is vinyl chloride copolymers obtainable by the free radical initiated polymerization of a mixture containing a) 50 to 99.99% by weight of vinyl chloride; b) 1 to 50% by weight of one or more monomers from the group of vinyl esters and methacrylate esters; c) 0.01 to <5% by weight of one or more copolymerizable silicones; and d) 0 to 10% by weight of one or more additional comonomers, capable of copolymerizing with a), b), and c), from the group comprising epoxide-functional comonomers, acrylate esters, ethylenically unsaturated mono- and dicarboxylic acids, the anhydrides thereof, and alkyl esters of ethylenically unsaturated dicarboxylic acids, wherein the percentages by weight add up to 100% by weight and, in each case, are relative to the total weight of the vinyl chloride copolymer.

Description

 Siliconized vinyl chloride copolymers

The invention relates to siliconized vinyl chloride copolymers, processes for their preparation, and their use in particular in paint resin compositions.

A major problem in the use of vinyl chloride-vinyl acetate copolymers is their insufficient solubility at room temperature in organic solvents, especially in ketones and also esters. Commercially available products must therefore be dissolved at higher temperatures of about 50 ⁰ C, which requires a temperature-controlled release device. WO 07/025847 A1 discloses a process in which vinyl chloride and vinyl acetate are copolymerized in aqueous suspension in the presence of a vinyl chloride-vinyl acetate mixed polymer which is soluble in ethyl acetate in order to improve solubility.

The object was to provide a vinyl chloride copolymer which has improved solubility at room temperature in organic solvents such as ketones or esters. This problem was solved by means of siliconization of the vinyl chloride polymers.

A number of processes are known in the literature in which organopolymers are modified with silicones in such a way that the organomonomers are polymerized in the presence of a silicone to give silicone organocopolymers, thus providing a more stable attachment of the silicone building block in the finished coating enable. This is particularly important if you want to use the products in food-grade applications and avoid migration from the coating.

From DE 102005034121 Al coating compositions are known which contain 0.1 to 20 wt.% Of a silicone organocopolymer, which by free radical polymerization of a mixture containing 1 to 50 wt.% Of one or more silicones with or is available without polymerizable groups. Siliconized vinyl chloride copolymers are not described therein.

In EP 1354900 A1, a mixture of low molecular weight polysiloxane (n <30) having a terminal polymerizable group and of relatively high molecular weight polysiloxane (n> 55) having one or two terminal polymerizable groups in the presence of ethylenic is used to prepare extrudable, low migration silicone organocopolymers polymerized unsaturated monomers.

EP 0131911 A1 discloses vinyl chloride copolymers, grafted copolymers or blends of different polymers or copolymers, the polymers or copolymers comprising vinyl chloride units and / or organosilicon units, such as organosilane, polymerizable organopolysiloxane or nonpolymerizable organopolysiloxane units, and, optionally, units of further ethylenically unsaturated monomers, such as acrylic acid esters. With regard to the solubility properties, EP 0131911 A1 only discloses that the polymers or copolymers described therein are insoluble in organic solvents.

WO 05/087827 A1 discloses a process for preparing silicone-containing copolymers of ethylenically unsaturated organomonomer and 5 to 50% by weight of silicone macromer in the form of their aqueous polymer dispersions or water-redispersible polymer powders, wherein the polymerization in the presence of water-soluble initiator and oil-soluble initiator to reduce the amount of migratable free silicone.

JP-A 61-061825 discloses heat-shrinkable casting resins based on vinyl chloride copolymers which contain from 1 to 50% by weight of polymerizable unsaturated silicone components and which can be prepared by suspension polymerization, wherein the elasticity is introduced by the silicone part. The invention provides vinyl chloride copolymers obtainable by free-radically initiated polymerization of a mixture comprising a) from 50 to 99.99% by weight of vinyl chloride, b) from 1 to 50% by weight of one or more monomers from the group consisting of vinyl esters and methacrylates, c ) 0.01 to <5% by weight of one or more copolymerizable silicones, and d) 0 to 10% by weight of one or more further comonomers copolymerizable with a), b) and c) from the group comprising epoxide functional comonomers, acrylic esters, ethylenically unsaturated monocarboxylic and dicarboxylic acids and their anhydrides, and also dialkyl esters of ethylenically unsaturated dicarboxylic acids, the data being added in% by weight to 100% by weight and based on the total weight of the vinyl chloride Copolymers are obtained.

Preferably, the siliconized vinyl chloride copolymers contain from 55 to 90% by weight of vinyl chloride, more preferably from 60 to 85% by weight of vinyl chloride.

Suitable comonomers b) are one or more ethylenically unsaturated monomers from the group comprising vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms or methacrylic acid esters of unbranched or branched alcohols having 1 to 18 carbon atoms. Preferred vinyl esters are those of carboxylic acids having 1 to 12 carbon atoms. Particular preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of C-C-branched monocarboxylic acids having 9 to 13 carbon atoms, for example VeoVa9 or VeoValO (trade names of Company Hexion). Most preferred is vinyl acetate.

The siliconized vinyl chloride copolymers which contain as comonomer units b) those which are derived from vinyl esters can also be saponified so that comonomer units b) as well as vinyl ester units also contain vinyl alcohol units. Preferably, it is saponified such that up to 10% by weight of vinyl alcohol units in the copolymer, based on the total weight of the siliconized vinyl chloride copolymer.

Suitable comonomers b) from the group of methacrylic esters are esters of unbranched or branched alcohols having 1 to 15 C atoms. Preferred methacrylic acid esters are methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate. Particularly preferred is methyl methacrylate. Suitable comonomers b) are also hydroxyalkyl

(meth) acrylates having C 1 to C 4 -alkyl radicals, preferably hydroxyethyl acrylate and hydroxypropyl acrylate.

In a preferred embodiment, the vinyl chloride copolymers contain 10 to 50 wt .-% of comonomers b), more preferably, the vinyl chloride copolymers contain 15 to 40 wt .-% of comonomers b).

Suitable copolymerizable silicones c) are diorganopolysiloxanes having at least 5 diorganosiloxane units and one or two polymerisable groups. Suitable polymerizable groups are ethylenically unsaturated groups. The copolymerizable groups can be arranged in the chain or terminal. In general, the copolymerizable silicones c) are linear or branched diorganopolysiloxanes having a chain length n (= number of diorganosiloxane units) of 5 to 2000, preferably n of 5 to 1000, particularly preferably n of 50 to 500. Preferably, 0, 01 to 3 wt .-%, particularly preferably 0.1 to 3 wt .-%, in particular 0.1 to 2 wt.%, Copolymerizable silicones used.

(SiR2θ) _nSiR3-_aR¹ _a besteht, wobei R gleich oder verschieden ist, und einen einwer- tigen, gegebenenfalls substituierten, Alkylrest, Alkenylrest oder Alkoxyrest mit jeweils 1 bis 18 C-Atomen bedeutet, oder einen gegebenenfalls substituierten Arylrest, bedeutet, R¹ eine polymerisierbare Gruppe bedeutet, a gleich oder verschieden ist und 0 oder 1 bedeutet, wobei mindestens ein a gleich 1 ist, und n eine ganze Zahl von 5 bis 2000 ist.Preference is given as copolymerizable silicones c) diorganopolysiloxanes having the general formula

(SiR2θ) _n SiR3- _a R ¹ _a, where R is the same or different, and a monohydric term, optionally substituted alkyl, alkenyl or alkoxy group each having 1 to 18 carbon atoms, or an optionally substituted aryl radical, , R ^{1 represents} a polymerisable group, a is the same or different and 0 or 1, wherein at least one a is 1, and n is an integer of 5 to 2,000.

(SiR₂O)

sind Beispie- Ie für Reste R Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, 1-n- Butyl-, 2-n-Butyl-, iso-Butyl-, tert . -Butyl-, n-Pentyl-, iso- Pentyl-, neo-Pentyl-, tert . -Pentylrest, Hexylreste wie der n- Hexylrest, Heptylreste wie der n-Heptylrest, Octylreste wie der n-Octylrest und iso-Octylreste wie der 2, 2, 4-Trimethylpentyl- rest, Nonylreste wie der n-Nonylrest, Decylreste wie der n-De- cylrest, Dodecylreste wie der n-Dodecylrest, und Octadecylreste wie der n-Octadecylrest, Alkenylreste, wie der Vinyl- und der Allylrest; Cycloalkylreste wie Cyclopentyl-, Cyclohexyl-, Cyc- loheptyl- und Methylcyclohexylreste, Arylreste, wie der Phenyl- , Naphthyl- und Anthryl- und Phenanthrylrest ; Alkarylreste, wie o-, m-, p-Tolylreste, Xylylreste und Ethylphenylreste; Aralkyl- reste, wie der Benzylrest, der alpha- und der ß-Phenylethyl- rest. Bevorzugt handelt es sich bei dem Rest R um einen einwertigen Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen, wie Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, sec-Butyl-, tert-Butyl-, Amyl-, Hexyl und Phenyl-Rest, wobei der Methyl- bis Propylrest und der Phenylrest besonders bevorzugt sind.In the general formula

(SiR ₂ O)

Examples of radicals R are methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as n -De- cylrest, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical, alkenyl radicals, such as the vinyl and the allyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals such as the phenyl, naphthyl and anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the alpha- and the β-phenylethyl radical. Preferably, the radical R is a monovalent hydrocarbon radical having 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl , Hexyl and phenyl radical, with the methyl to propyl radical and the phenyl radical being particularly preferred.

Preferred alkoxy radicals R are those having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and n-butoxy radicals, which may optionally be substituted by oxyalkylene radicals, such as oxyethylene or oxymethylene radicals. Particularly preferred are the methoxy and ethoxy. If appropriate, the radicals R mentioned can also be substituted, for example with halogen, mercapto groups, epoxy-functional groups, carboxyl groups, keto groups, enamine groups, amino groups, aminoethylamino groups, isocyanate groups, aryloxy groups, alkoxysilyl groups and hydroxyl groups.

Suitable polymerizable groups R ¹ are alkenyl radicals having 2 to 8 C atoms. Examples of such polymerizable groups are the vinyl, allyl, butenyl, as well as acryloxyalkyl and methacryloxyalkyl group, wherein the alkyl radicals 1 to 4 carbon atoms contain. Preference is given to the vinyl group, acryloxymethyl, methacryloxymethyl, 3-acryloxypropyl and 3-methacryloxypropyl group.

Preferred copolymerizable silicones are c) OC, CO-di-vinyl-polydimethylsiloxanes, CC, G) -di- (3-acryloxypropyl) -poly-dimethylsiloxanes, OC, G) -di- (3-methacryloxypropyl) -polydimethylsiloxanes , CC, G) -di (acryloxymethyl) -polydimethylsiloxanes, CC-monovinyl-polydimethylsiloxanes, CC-mono- (3-acryloxypropyl) -polydimethylsiloxanes, α-mono- (3-methacryloxypropyl) -polydimethylsiloxanes, CC- Mono (acryloxymethyl) -polydimethylsiloxanes, CC-mono- (methacryloxymethyl) -polydimethylsiloxanes.

The preparation of the copolymerizable silicone c) is known in the art, it can, for example, by ring-opening

Polymerization of D3 or D4 cycles (low molecular weight cyclic dialkylsiloxanes) with suitable catalysts, with a terminal functionalization with low molecular weight compounds having a polymerizable group, followed. With the selection of a suitable catalyst for the ring opening of the cyclic dialkylsiloxanes, it is also possible to introduce a further functional group as described above into the polymerizable silicone component. Appropriate methods for the preparation of copolymers are given in HG Elias, Macromolecules, Volume 2, Technology, Hüthig & Wepf Verlag, Basel, Heidelberg, New York, 5th edition, 1992, pp 68-116 and HG Elias, Macromolecules, Volume 1 , Chemical Structure and Synthesis, Wiley VCH, Weinheim, New York, Chichester, Brisbane, Toronto, Singapore, 6th Edition, 1999, Ch.6, pp. 148-184, Chap. 10, pp. 299-350 and chap. 12, pp. 376-414.

Suitable epoxide-functional comonomers d) are, for example, methyl glycidyl acrylate, methyl glycidyl methacrylate, allyl glycidyl ether, allyl phenol glycidyl ether, glycidyl acrylate, glycidyl methacrylate. Preference is given to glycidyl methacrylate (GMA). Examples of acrylic acid esters suitable as comonomer component d) are esters of unbranched or branched alcohols having 1 to 18 C atoms, in particular having 1 to 15 C atoms. preferred Acrylic acid esters are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate. Particularly preferred are methyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate. Examples of suitable comonomer component d) ethylenically unsaturated mono- and di-carboxylic acids and their anhydrides are acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride. Also suitable as comonomers d) are the mono- and dialkyl esters of dicarboxylic acids with C 1 - to C 6 -alkyl groups, for example ethyl fumarate and dibutyl maleate.

The epoxide-functional comonomers d) are preferably copolymerized in an amount of 0.01 to 5.0% by weight, particularly preferably 0.1 to 0.5% by weight. The acrylic esters or the alkyl esters of ethylenically unsaturated dicarboxylic acids are preferably copolymerized in an amount of from 0.1 to 10.0% by weight, particularly preferably from 2 to 9% by weight.

The free-radically initiated polymerization can be carried out by means of solution polymerization, suspension polymerization and emulsion polymerization. The suspension polymerization and the emulsion polymerization are preferred. The polymerization temperature is generally from 20 ⁰ C to 80 ⁰ C. The initiation of the polymerization can be carried out with the customary water-soluble or monomer-soluble initiators or redox initiator combinations. Examples of water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid. Examples of monomer-soluble initiators are dicetyl peroxydi- carbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, di- lauryl peroxide and tert. Butyl peroxypivalate. The initiators mentioned are generally used in an amount of 0.01 to 1.0 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the total weight of the monomers.

In the solution polymerization are organic solvents such as Ci- to C ₅ -alkanols such as methanol, ethanol or isopropanol, Ci- to C ₅ alkyl esters of Ci- to C ₅ -carboxylic acids such as methyl acetate tat, ethyl acetate or ketones such as acetone and methyl ethyl ketone used.

In the processes of suspension and emulsion polymerization mentioned as preferred, polymerization is carried out in water in the presence of surface-active substances such as protective colloids and / or emulsifiers. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units. Suitable protective colloids are, for example, partially hydrolyzed and fully hydrolyzed polyvinyl alcohols, celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives. In general, the surface-active substances are used in an amount of from 0.01 to 5% by weight, based on the total weight of the comonomers.

For controlling the molecular weight, regulating substances can be used during the polymerization. If regulators are used, they are usually used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered in separately or else premixed with reaction components. Examples of such substances are halogenated alkanes and halogenated alkenes such as carbon tetrachloride, chloroform, methyl chloride, trichlorethylene and aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.

Preferably, polymerization is carried out in the presence of propionaldehyde. Propionaldehyde has over other regulators such as trichlorethylene the advantage that with smaller amounts already a regulatory effect is achieved. It is therefore preferably, depending on the desired molecular weight, in an amount of 0.02 to 5 wt .-%, based on monomer added. The monomers can be added in total or be introduced in portions and the remainder be added after the initiation of the polymerization. The dosages can be carried out separately (spatially and temporally) or the components to be metered can be metered in all or in part pre-emulsified. In a preferred embodiment, the optionally epoxy-containing vinyl monomers as a whole are metered in continuously or more preferably continuously.

After completion of the polymerization, residual monomer removal can be postpolymerized using known methods, for example by postpolymerization initiated with the redox catalyst. Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing or passing inert inert gases, such as air, nitrogen or steam.

In a preferred embodiment, during or after the polymerization, from 0.001 to 0.1% by weight of one or more carboxylic acids from the group comprising aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxy-mono-, hydroxy-di-, hydroxy-tri-carboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxy groups are added. The addition preferably takes place after completion of the monomer metering and before, during or after the removal of residual monomer. Examples of dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and also maleic acid and fumaric acid. Particularly preferred are the hydroxycarboxylic acids mentioned, for example tartronic acid, malic acid, tartaric acid, citric acid, iso-citric acid, ascorbic acid, iso-ascorbic acid.

Most preferred are ascorbic acid and iso-ascorbic acid, in particular combinations of ascorbic acid or iso-ascorbic acid with citric acid. The amount of (iso) ascorbic acid and citric acid is preferably in each case from 0.005 to 0.05 wt .-%, each based on the total weight of the monomers.

The siliconized vinyl chloride copolymer obtained according to this process can be isolated by conventional methods by precipitation, filtration and subsequent drying

The siliconized vinyl chloride copolymers are suitable, for example, as binders for paints, especially in heat seal coatings, for example for aluminum coating. They are characterized by their excellent solubility in all common solvents for paints. It should be emphasized that the products not only dissolve in the frequently used as solvent ketones, but even at room temperature (23 ° C) are also readily soluble in vinyl chloride-vinyl acetate copolymers critical solvents such as aliphatic esters without heating.

The siliconized vinyl chloride copolymers are also suitable for use as a primer, as an adhesive, as a binder in printing inks and as a coating agent.

The following examples serve to further explain the invention:

Comparative Example 1

In a 15 liter reactor, 7 liters of water, 8 g of methylcellulose,

420 g of vinyl chloride, 45 g of fumaric acid and 9 g of lauryl peroxide are provided. Subsequently, 890 g of α-mono- (3-methacryloxypropyl) -CO-n-butyl-polydimethylsiloxane (n = 63) (Chisso FM 721) were metered in together with 170 g of vinyl acetate and heated to 70 ° C. after 60 minutes. Thereafter, a mixture of 2350 g of vinyl chloride and 590 g of vinyl acetate was added over 7 hours. Immediately after the end of the monomer feed, the batch was depressurized to atmospheric pressure. The mixture was then demonomerized, the mixture was neutralized by adding 10.0% strength by weight sodium hydroxide solution, the copolymer was filtered, washed and dried. A copolymer was obtained with 62% by weight of vinyl chloride, 20% by weight of silicone, 17% by weight of vinyl acetate and 1% by weight of fumaric acid.

To test the solubility, a 20% strength by weight solution of the copolymer in ethyl acetate or methyl ethyl ketone was prepared at room temperature and the solubility was evaluated. The results of the evaluation of the solution properties are summarized in Table 1.

Comparative Example 2:

Analogously to the procedure of Comparative Example 1, a copolymer of 72 wt .-% vinyl chloride, 10 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in ethyl acetate showed even after heating to 50 ⁰ C many undissolved particles, a milky appearance and painful liges splits after 2 days in an upper and a lower phase.

Comparative Example 3 Analogously to the procedure of Comparative Example 1, a copolymer of 77% by weight of vinyl chloride, 5% by weight of silicone fraction, 17% by weight of vinyl acetate, 1% by weight of fumaric acid was prepared. A 20 wt .-% solution of the copolymer in ethyl acetate showed after heating to 50 ⁰ C many undissolved particles and a milky, quale appearance.

Example 4:

Analogously to the procedure of Comparative Example 1, a copolymer of 81 wt .-% vinyl chloride, 1 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared.

A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed no undissolved content, only a slight haze and remained homogeneous after 2 days.

Comparative Example 5:

Analogous to the procedure of Comparative Example 1 was a copolymer of 72 wt .-% vinyl chloride, 10 wt .-% CC, CO-divinyl-polydimethylsiloxane (having a viscosity at 25 ° C of 300 mPa.s, n = 133), 17% by weight of vinyl acetate, 1% by weight of fumaric acid.

A 20% by weight solution of the copolymer in methyl ethyl ketone showed a gel-like consistency.

Comparative Example 6:

Analogously to the procedure of Comparative Example 5, a copolymer of 77 wt .-% vinyl chloride, 5 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20% by weight solution of the copolymer in methyl ethyl ketone showed a gel-like consistency.

Example 7:

Analogous to the procedure of Comparative Example 5, a copolymer of 79 wt .-% vinyl chloride, 3 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20% strength by weight solution of the copolymer in methyl ethyl ketone occasionally showed undissolved particles and was slightly cloudy.

Example 8:

Analogously to the procedure of Comparative Example 5, a copolymer of 81 wt .-% vinyl chloride, 1 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% solution of the copolymer in methyl ethyl ketone was completely dissolved, showed only a slight haze and remained homogeneous after 2 days. The solution in ethyl acetate was completely dissolved at 23 ° C and was only slightly cloudy.

Example 9:

Analogously to the procedure of Comparative Example 5, a copolymer of 81.5 wt .-% vinyl chloride, 0.5 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone, or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days. Example 10:

Analogously to the procedure of Comparative Example 5, a copolymer of 81.75 wt .-% vinyl chloride, 0.25 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days.

Example 11 Analogously to the procedure of Comparative Example 5, a copolymer of 81.9% by weight of vinyl chloride, 0.1% by weight of silicone fraction, 17% by weight of vinyl acetate, 1% by weight of fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed even after heating to 50 ⁰ C no turbidity and remained homogeneous after 2 days.

Example 12:

Analogously to the procedure of Example 1, a copolymer of 81 wt .-% vinyl chloride, 1 wt .-% CC, CO-divinyl-polydimethyl siloxane (having a viscosity at 25 ° C of 1000 mPa-s, n = 219), 17% by weight of vinyl acetate, 1% by weight of fumaric acid. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days.

Example 13:

Analogously to the procedure of Example 12, a copolymer of 81.5 wt .-% vinyl chloride, 0.5 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days.

Example 14 Analogously to the procedure of Example 12, a copolymer of 81.75 wt .-% vinyl chloride, 0.25 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days.

Example 15:

Analogously to the procedure of Example 12, a copolymer of 81.9 wt .-% vinyl chloride, 0.1 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 ⁰ C and remained homogeneous after 2 days.

Comparative Example 16:

Analogously to Comparative Example 1, a copolymer of 82% by weight of vinyl chloride, 17% by weight of vinyl acetate, 1% by weight of fumaric acid was prepared, but the addition of the silicone oil was omitted. A 20% solution of the copolymer in ethyl acetate could not be prepared at room temperature. After warming to 50 ⁰ C, a solution was obtained in ethyl acetate, but had a clear turbidity and was still homogeneous after 2 days. A 20% solution in methyl ethyl ketone could be obtained only after much longer dissolution time.

Assessment of the solution properties:

The polymers prepared in Examples and Comparative Examples were evaluated for their solubility in various solvents as well as the clarity and consistency of the solution as follows. The solvent (methyl ethyl ketone => MEK, ethyl acetate => EtAc) was placed in a 250 ml glass bottle and the material to be dissolved was added slowly (within approximately 30 seconds) with rapid stirring (stirrer disk of 35 mm diameter and 1000 rpm) that a solution with 20 wt .-% solids content was obtained.

After the sample had dissolved, the solution was allowed to stand briefly without stirring to allow air bubbles to separate, and then the solution was evaluated as follows: Release time [min]:

Time to complete dissolution

Solubility:

1 (solved), 2 (occasionally undissolved particles),

3 (some unresolved particles), 4 (many unresolved particles), 5 (unresolved)

Clarity:

1 (clear), 2 (iridescent), 3 (slightly hazy),

4 (turbid), 5 (very murky), 6 (milky - quallig)

Table 1: Evaluation of the solution properties X / Y / Z means with the evaluations as given above: X = dissolution time [min] / Y = solubility / Z = clarity * = product separated into two phases

Ex.% Si MEK - 23 ° C EtAc - 50 ° C EtAc - 23 ° C

Vl 20,00 - / 3/6 * - / 4/6 * -

V2 10, 00 - / 3/5 * - / 4/6 * -

V3 5.00 - / 2/4 * - / 4/6 -

4 1, 00 - / 1/3 - / 3/3 -

V5 10.00 - / 5/6 - -

V6 5.00 - / 5/6 - -

7 3, 00 30/2/3 6/2/4 60/2/4

8 1.00 20/1/3 6/1/3 60/1/3

9 0.50 20/1/2 6/1/2 60/1/2

10 0.25 20/1/2 6/1/2 60/1/2

11 0, 10 20/1/1 6/1/2 60/1/2

12 1,00 20/1/1 3/1/2 30/1/2

13 0,50 20/1/1 3/1/2 30/1/2

14 0.25 20/1/1 3/1/2 30/1/2

15 0, 10 20/1/1 3/1/1 30/1/2

V16 - 30/1/1 10/1/4 - / 4/5 Comparing the comparative examples 1 to 3 listed in Table 1 with Example 4, it can be seen that when used from 5% by weight of the monovinyl-functional silicone oil, no good properties of the polymer solution can be obtained, neither in MEK nor in EtAc. Only when using 1 wt .-% was a soluble and only slightly cloudy product obtained.

The comparison of Comparative Examples 5 and 6 with Examples 7 to 11 with respect to their solubility in MEK shows that with a silicone content of <3% by weight, readily soluble products are obtained. In this case, the chain length of the divinyl-functional silicone oil used can be increased (Examples 12 to 15), without a phase separation is observed. The dissolution properties of the products are even more improved by the incorporation of the longer-chain divinyl-functional silicone oil and a clear solution is obtained. Compared to Comparative Example 16, the solubility in MEK shows that the incorporation of up to 3% by weight of silicone can positively influence the dissolution rate of the products.

The solubility in the less polar ethyl acetate shows a clear improvement not only in the dissolution rate but also in the solution quality. Thus, comparative example 16 dissolves only cloudily in ethyl acetate, whereas the product modified with vinyl-functional silicone oils results in clearer solutions up to an amount of <3% by weight of silicone oil. However, the decisive advantage of the products modified with vinyl-functional silicone oils is their solubility in ethyl acetate at room temperature. Under these conditions, the unmodified product no longer dissolves and gives only a very quallige gel-like mass.

Another property of the vinyl chloride copolymers modified by the copolymerization with the copolymerizable silicones is the surface friction of vinyl chloride-polymer coated surfaces which overlay the surface of the vinyl chloride copolymers Sliding friction coefficients (GRK, kinematic value, force in motion) and static friction coefficients (HRK, static value, force from standstill) are described.

To determine these parameters, the sample was dissolved in ethyl acetate at 20% strength by weight and applied to soft aluminum foil with a 24 μm spiral doctor blade. Subsequently, the sample was dried at 150 ^° C. for 10 seconds.

The measurement of the coefficient of sliding friction (GRK) and the static friction coefficient (HRK) was carried out in accordance with DIN 53375 with the friction tester Model 225/1 from Hermann Klemmt Mess- und Prüftechnik.

Furthermore, the contact angle for the evaluation of surface properties, such as e.g. hydrophobicity. The measurement of the static contact angle was carried out with the method of the lying drop with the contact angle measuring device DSA10 from. Krüss / Hamburg. For this purpose, a drop of liquid (in this case water) of a certain volume was applied to the sample by means of a syringe (sessile drop). After a defined time, a digital image analysis of the drop was performed by video camera.

Table 2 shows the coefficient of sliding friction (GRK), the static friction coefficient (HRK) and the contact angle of coatings which were produced with the VC copolymers of the corresponding (comparative) examples.

Considering the contact angle, which is accessible by the use of the comparative example 16, this is about 80 °. Through the use of siliconized vinyl chloride copolymers, the contact angle can be increased and thus the hydrophobicity of the surface can be permanently increased. It turns out that even with the use of 1% by weight of copolymerizable silicone, a maximum level is achieved which corresponds to the usual of siliconized surfaces. In parallel, the GRK and HRK lowered and reaches ^¬ be already in use of 0.25 wt .-% of silicone copolymerizable an approximate minimum. By further increasing the amount of copolymerizable silicone used, the GRK and HRK can no longer be significantly reduced.

Table 2:

Assessment of surface friction and contact angle

Furthermore, can be achieved by the incorporation of the copolymerizable silicones and the metal adhesion of the VC copolymers, wherein ^¬ play increase a coating on aluminum foil. The adhesion properties of the siliconized vinyl chloride copolymers were determined by the determination of the Tesa tear and the seal seam strength. Determination of the adhesion of paints by Tesa demolition

From the sample to be examined, a bubble-free film was drawn on a film with a film applicator from Erichsen with a doctor blade and dried (drying conditions for aluminum foil are 10 sec. At 150 ⁰ C in a drying oven).

In order to test the adhesive strength was applied to the dried and 16 hours at room temperature (23 ° C) supported film, a sufficiently long strip of adhesive tape glued ^® (Beiersdorf AG having a width of 15 mm). By even, vigorous stroking with the fingernail, with one end of the strip is held to obtain a trigger tab, now the pressure was fixed. The film to be tested should be on a hard surface. The Tesafilm ^® was then pulled off abruptly at the flap at an angle of approx. 45 °.

The tested site was examined to determine whether and how much the film has come off the substrate and adheres to the adhesive tape ^®. The test was carried out in several places under the same condition.

The rating is in grades from 1 to 4, with 1 being the best and 4 being the worst rating:

1 = good adhesion (no detached parts) 2 = coating has separated in isolated places

3 = coating has detached at several points

4 = no adhesion of the coating (completely detached)

Determination of the seal seam strength of paints

From the 20% strength by weight coating solution to be examined, a bubble-free film is drawn on two aluminum foils using a 24 μm wire bar and, after about 10 minutes. Flash off at room temperature for 10 sec. At 150 ⁰ C dried in a drying oven. Now the coated film is sealed paint against paint by means of heat contact heat sealer. Sealing conditions: 0.5 sec, 180 ⁰ C, 30 N / cm ² , baking: 15 x 1 cm. From each sealed film 5 strips (1.5 cm wide) are cut and without pretreatment by means of tensile tester (Instron) at a take-off angle of 180 ° and a speed of 100 mm / min, measured. The 5 test pieces of a seal are averaged, the measured value is given in N / 15mm.

Determination of the block point of paints

The method described here is used to determine the blocking point of adjacent coatings above a certain temperature.

From the sample to be examined, a bubble-free film is drawn on a soft, cleaned aluminum foil and dried at 150 ^° C. for 10 sec. The applied weight should be 3 to 5 g / m ² . The coated aluminum foil is now laid one on top of the other. With the sealing jaws (1 x 4 cm) of the sealing device (for description, see "Determination of the seal seam strength of paints"), the film is loaded with 2.5 kp / cm ² (= 100 N total) in the sealing device for 30 sec

Block point, the sealing jaws are heated to 30 ⁰ C. If the sample does not block, the determination is repeated, increasing the temperature in 5 ° C increments. After loading, the sealed piece of foil is cut off with scissors and smoothed by hand. By pulling apart the sample placed against each other, the sticking, sticking or total blocking of the sample is visually evaluated. To assess the blocking point, the temperature at which the specimens adhere to one another is given in ⁰ C.

Considering the adhesive properties shown in Table 3, it can be seen that the adhesion of the coating is not deteriorated compared to Comparative Example 16 by the incorporation of copolymerizable silicones. The tesa tear is in all cases rated 1, which corresponds to a good adhesion without detached areas. Table 3: Assessment of adhesion and seal strength

With regard to the seal seam strength, it should be noted that these are due to the incorporation of the silicones in comparison to the unmodified Vbsp. 16 is significantly improved. This is also an indication that the silicones are covalently attached to the polymer matrix, as free silicones can migrate to the interface and thus lead to a reduction in the Sieglenahtfestigkeit. It is also noteworthy in this connection that the incorporation of the silicones does not reduce the block point of the polymer, even though low-glass transition temperatures have been incorporated into the polymer via the silicones, which usually leads to higher tack and reduced blocking resistance of the polymers ,

The incorporation of small amounts of copolymerizable silicones thus has several positive effects. It improves the solubility of the products in nonpolar solvents such as ethyl acetate, allowing faster production of clearer solutions. It reduces surface friction (GRK and HRK => faster machinability + productivity when coating surfaces) and increases surface hydrophobicity (contact angle increased => easy cleaning, protection-repellent). It also improves the adhesion to aluminum surfaces and thus increases the bond strength. As a result, the use of material can be reduced with the same composite adhesion.

Claims

Claims: 1. vinyl chloride copolymers obtainable by means of free-radical containing lisch initiated polymerization of a mixture of a) 50 to 99.99 wt .-% of vinyl chloride, b) from 1 to 50 wt .-% of one or more monomers from the Grup ^¬ pe of Vinylester and methacrylic acid , c) 0.01 to <5% by weight of one or more copolymerizable silicones, and d) 0 to 10% by weight of one or more further comonomers copolymerizable with a), b) and c) from the group comprising epoxide-functional comonomers , Acrylic acid esters, ethylenically unsaturated mono- and dicarboxylic acids and their Anhydrides, and alkyl esters of ethylenically unsaturated dicarboxylic acids, wherein the information in wt .-% to 100 wt .-% and add in each case based on the total weight of the vinyl chloride copolymers. 2. Vinyl chloride copolymers according to claim 1, characterized in that as comonomers b) 10 to 50 wt .-% vinyl ester of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms are used. 3. vinyl chloride copolymers according to claim 1 or 2, as ^¬ characterized in that are used as copolymerizable silicones c) diorganopolysiloxanes having at least 5 diorganosiloxane units and one or two polymerizable groups selected from ethylenically unsaturated. 4. vinyl chloride copolymers according to claim 3, characterized in that as copolymerizable silicones c) diorganopolysiloxanes having the general formula

(SiR2θ) _n SiR3- _a R ¹ _a are employed, where R is the same or different and is a monovalent, optionally substituted, alkyl, alkylene or alkoxy each having 1 to 18 carbon atoms, or an optionally substituted aryl radical, R ^{1 represents} a polymerizable group, a is the same or different and 0 or 1, wherein at least one a is 1, and n is an integer from 5 to 2000. 5. Vinyl chloride copolymers according to claim 1 to 4, characterized in that 0.01 to 5.0 wt .-% epoxy-functional comonomers d) are used. 6. vinyl chloride copolymers according to claim 1 to 5, characterized in that 0.1 to 10.0 wt .-% mono- or dialkyl esters of ethylenically unsaturated dicarboxylic acids are used. 7. A process for the preparation of vinyl chloride copolymers according to claim 1 to 6 by means of free-radically initiated solution polymerization, suspension or emulsion polymerization. 8. The method according to claim 7, characterized in that during or after the polymerization from 0.001 to 0.1 wt .-% of one or more carboxylic acids from the group comprising aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxy mono-, hydroxy di, hydroxy tri-carboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxy groups are added. 9. The method according to claim 7 or 8, characterized in that the vinyl chloride copolymers containing as comonomer units b) contain those derived from vinyl esters are saponified so that as comonomer units b) in addition to vinyl ester units still contain vinyl alcohol units. 10. Use of the vinyl chloride copolymers according to claim 1 to 6 as a binder for paints. 11. Use of the vinyl chloride copolymers according to claim 1 to 6 as a binder in heat sealing lacquers. 12. Use of the vinyl chloride copolymers according to claim 1 to 6 as a primer. 13. Use of the vinyl chloride copolymers according to claim 1 to 6 as an adhesive. 14. Use of the vinyl chloride copolymers according to claim 1 to 6 as a binder in printing inks. 15. Use of the vinyl chloride copolymers according to claim 1 to 6 as a coating agent.