WO2003004555A1 - Use of cyanogen acetylureas for stabilising antistatic organic plastics containing halogen - Google Patents

Abstract

The invention relates to cyanogen acetylurea of formula (I), NC-CH2-CO-N(R1)-CO-NH-R2 (I), wherein the radicals R1 and R2 independently represent hydrogen or an unbranched or branched, linear or cyclic alkyl radical having 1 -18 C-atoms or an aryl radical having 6 -18 C-atoms, which can be optionally substituted by one or more alkyl radicals having respectively 1 - 6 C-atoms. According to the invention, said cyanogen acetylureas are suitable for stabilising antistatic organic plastics containing halogen, especially PVC, against thermal and/or photochemical decomposition.

Description

 "Use of cyanoacetylureas to stabilize antistatically treated halogen-containing organic plastics"

Field of the Invention

The invention relates to the use of cyanoacetylureas for the stabilization of antistatically treated halogen-containing organic plastics.

State of the art

Halogen-containing plastics or molding materials made from them are known to tend to decomposition or decomposition reactions when they are exposed to thermal stress or come into contact with high-energy radiation, for example ultraviolet light.

Metal-containing stabilizers based on Pb, Ba, Cd, Sn, Ca and Zn are mostly used to stabilize PVC during processing. Urea derivatives such as e.g. Diphenylthiourea proposed for stabilizing PVC (compare: Gächter / MüUer, "Plastic Additives", Carl Hanser Verlag 1989, p. 312). These compounds are mostly used in combination with metal-containing stabilizers, since they generally do not result in adequate long-term stabilization.

It is also known that plastics, and thus also PVC, are pronounced non-conductors, that is to say high-quality electrical insulators. This property causes the surface to be electrically charged and, due to the dust attraction associated therewith, moldings quickly become dirty and unsightly. These disadvantageous properties can largely be prevented by antistatic agents. In the case of antistatic agents, a distinction is made between external and internal antistatic agents. External antistatic agents are products that are applied to PVC moldings as a thin layer on the surface. The disadvantage of this surface application is the low resistance of the antistatic effect, so that the protective effect wears off over time and aftertreatment is necessary, especially after rinsing and washing. Internal antistatic agents are part of the PVC compound and are mixed with the PVC together with other additives. The decisive advantage of internal antistatic agents is the permanent effect they can achieve.

Solutions of quaternary ammonium salts, amine derivatives and special phosphoric acid esters are used as external antistatic agents. Hygroscopic substances such as glycerin, glycol and other polyols are also suitable. While the application of the external antistatic is not problematic, several criteria have to be considered for the internal antistatic. It is known to the person skilled in the art that the internal antistatics greatly deteriorate the thermostability of PVC compounds, the quaternary ammonium compounds, which are particularly antistatic in particular, showing the greatest negative effect, as a result of which these products are not suitable as internal antistatics for PVC, in particular hard PVC (See also: Kunststoff-Handbuch, Volume 2/1: Polyvinylchlorid, Hans K. Felger (Editor), Munich 1985, page 730). The same applies to amine derivatives, such as ethoxylated fatty amines.

Description of the invention

It was an object of the present invention to provide substances which are notable for the stabilization of halogen-containing organic plastics which have antistatic properties, in particular PVC with antistatic properties, against thermal and / or photochemical degradation. In particular, these substances should be able to ensure the thermal stability of PVC equipped with internal antistatic agents, in particular quaternary ammonium compounds and amine derivatives.

The present invention relates to the use of

Cyanoacetylureas for stabilizing antistatically treated halogen-containing organic plastics against thermal and / or photochemical degradation.

In one embodiment, the compounds (I) are used to stabilize antistatic PVC against thermal and / or photochemical degradation. The stabilization of PVC equipped with internal antistatic agents, in particular quaternary ammonium compounds and amine derivatives, is particularly preferred.

Cyanoacetylureas are substances known to the person skilled in the art and are characterized by the formula (I)

NC-CH2-CO-N (R CO-NH-R ² (I)

wherein the radicals R and R independently of one another each have an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which may be one or more alkyl radicals can each be substituted with 1 to 6 carbon atoms. In the context of the present invention, N, N'-dimethyl-N-cyanoacetylurea is particularly preferred; in this compound, the radicals R ¹ and R ² in the formula (I) each represent a methyl group.

Another subject of the invention are stabilizer compositions for stabilizing antistatic halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation, characterized in that these compositions contain one or more cyanoacetylureas (I). In one embodiment, the stabilizer compositions contain one or more perchlorates in addition to the compounds (I).

Perchlorates in the sense of the invention are understood to mean metal salts and ammonium salts of perchloric acid. Examples of perchlorates suitable according to the invention are those of the formula M (C10 ₄ ) _n , where M in particular represents ammonium, Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. The index n corresponds to the valence of the cation M 1, 2 or 3.

The perchlorate salts can be complexed with alcohols, for example polyols, cyclodextrins, or ether alcohols or ester alcohols, or be dissolved therein. The polyol partial esters are also to be counted among the ester alcohols. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization are also suitable. With regard to perchlorate-alcohol complexes, the types known to the person skilled in the art from EP-B-394 547, page 3, lines 37 to 56 are expressly included. The perchlorate salts can be used in various common dosage forms, for example as a salt or solution in water or an organic solvent as such, or mounted on a carrier material such as PVC, calcium silicate, zeolites or hydrotalcites, or incorporated by chemical reaction in a hydrotalcite or another layered lattice compound. Are as polyol partial ethers

Glycerol monoether and glycerol monothioether preferred.

The perchlorates can be used both individually and in a mixture with one another.

Another subject matter of the invention is a method for stabilizing antistatic halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation, one or more cyanoacetylureas (I) being added to the plastics, which in particular contain internal (internal) antistatic agents. The components, that is to say the antistatic PVC and the compounds (I) are preferably mixed intimately in suitable apparatus.

The stabilizer compositions according to the invention can expediently be incorporated by the following methods:

• As an emulsion or dispersion (one possibility is, for example, the form of a pasty mixture. An advantage of the combination according to the invention in this dosage form is the stability of the paste.);

• As a dry mix while mixing additional components or polymer blends;

• by direct addition to the processing apparatus (e.g. calender, mixer, kneader, extruder and the like) or

• as a solution or melt.

The invention further relates to a stabilized PVC which on the one hand contains one or more antistatic agents, in particular internal (internal) antistatic agents, and on the other hand contains one or more of the compounds (I). Such a stabilized and antistatic PVC can be known Be prepared by using compounds known per se, such as the processing apparatus mentioned above, to mix the compounds (I) or a stabilizer combination according to the invention and antistatic agents and, if desired, other conventional plastic additives with PVC. In a preferred embodiment, the PVC additionally contains one or more perchlorates.

The stabilized PVC containing antistatic agents preferably contains the compounds (I) in an amount of 0.01 to 2.0 phr and in particular 0.01 to 0.5 phr. The term phr ("parts per hundred resin") familiar to the person skilled in the art indicates how many parts by weight of the component are present in PVC, based on 100 parts by weight of PVC.

The stabilized PVC containing antistatic agents preferably contains the perchlorates in an amount of 0.01 to 2.0 phr and in particular 0.01 to 0.5 phr.

The PVC stabilized according to the present invention can be brought into the desired shape in known ways. Such processes are, for example, calendering, extruding, injection molding, sintering or spinning, furthermore extrusion blowing or processing according to the plastisol process.

Plastisol processing, extrusion and calendering are particularly preferred as processes for processing the PVC stabilized according to the invention.

The PVC stabilized according to the invention is suitable for hard, semi-hard and soft formulations.

Halogen-containing organic plastics In the case of antistatically treated halogen-containing organic plastics, the compounds (I) or the compositions according to the invention are used Stabilize applies, it is in particular chlorine-containing polymers or their recyclates. Examples of such chlorine-containing polymers or their recyclates to be stabilized are: polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile Copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, such as acrolein , Vinyl methyl ether, vinyl isobutyl ether and the like; Polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; Polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride; and mixtures of the polymers mentioned with one another or with other polymerizable compounds.

Also included are the graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the homopolymers and copolymers mentioned above, in particular vinyl chloride homopolymers, with other thermoplastic and / or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Suspension and bulk polymers and emulsion polymers are also preferred. Polyvinyl chloride is particularly preferred as the chlorine-containing polymer, in particular suspension polymer and bulk polymer.

In the context of this invention, PVC is also understood to mean copolymers or graft polymers of PVC with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. PVC homopolymer is also preferred in combination with polyacrylates.

Recyclates of chlorine-containing polymers are also suitable, these being the polymers described in more detail above, which have been damaged by processing, use or storage. PVC recyclate is particularly preferred. The recyclates may also contain small amounts of foreign substances, such as paper, pigments, adhesives, which are often difficult to remove. These foreign substances can also come from contact with various substances during use or refurbishment, such as fuel residues, paint components, metal traces and initiator residues.

B e i s p i e l e

About the substances used

Norvinyl S 6260 = S-PVC (K-value = 62) (Hydro Polymers AB)

Vestolith E 6007 = E-PVC (K value = 60) (Degussa)

Vestinol AH = dioctyl phthalate (from BASF)

Kronoss 2220 = titanium dioxide (Kronos Titan)

PEG 200 monolaurate (Cognis / DE)

N, N'-dimethyl-N-cyanoacetylurea (commercial product)

Examples 1 and 2

In Table 1 below, the individual recipe components of the examined test recipes were given, on the one hand, and the determined test results, on the other hand. The respective numbers of the examples are given in the first line of the table. The proportions of the individual components are given in phr; phr means "part per hundred resin" and indicates how many parts by weight of the respective component are present in PVC after adding the composition - based on 100 parts by weight of PVC. Accordingly, the recipes each contain 100 parts of PVC (sum of Norvinyl S 6260 and Vestolith E 6007).

Example 2 is according to the invention. Examples 1 are used for comparison.

The test recipes were. - partially or completely - the following measurements were carried out:

• Stability test under thermal stress: Rolled skins were produced in accordance with the recipes and the static thermal stability at 170 ° C was determined. The rolled skins were produced by homogenizing and plasticizing the PVC powder mixture and the recipe components mentioned on a laboratory rolling mill for 5 minutes at 170 ° C. Test pieces (test specimens) measuring 17 x 17 mm were cut out from the approximately 0.5 mm thick rolled skins thus produced. The test specimens were opened at 170 ° C in the heating cabinet Glass plates placed on rotating trays and removed again at 15-minute intervals until all samples were "burnt" (ie had turned black) • Color measurement on the rolled skin: In addition, the L *, a * known to the person skilled in the art was used for further characterization. , b * method (see DIN 6174). The L value indicates the brightness. A commercially available device with the designation "Micro Color" (company Dr. Lange) was used for the measurements.

Table 1:

Claims

Patent claims 1. Use of cyanoacetylureas (I), NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (I) wherein the radicals R and R each independently of one another are hydrogen or an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 C atoms or an aryl radical having 6 to 18 C atoms, which may optionally be substituted by one or more alkyl radicals each having 1 to 6 C atoms, for the stabilization of antistatic halogen-containing organic Plastics against thermal and / or photochemical degradation. 2. Use according to claim 1, wherein the compound (I) chosen is N, N'-dimethyl-N-cyanoacetylurea. 3. Use according to claim 1 or 2, wherein the halogen-containing organic plastic is PVC. 4. Use according to one of claims 1 to 3, wherein the halogen-containing organic plastic is equipped with an internal antistatic. 5. Stabilizer compositions for stabilizing antistatic halogen-containing organic plastics against thermal and / or photochemical degradation, characterized in that these compositions contain one or more cyanoacetylureas (I) NC-CH2-CO-N (R ¹ ) -CO-NH-R ² (I) in which the radicals R and R each independently of one another are an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or is an aryl radical having 6 to 18 carbon atoms, which can optionally be substituted by one or more alkyl radicals each having 1 to 6 carbon atoms, contain. 6. Compositions according to claim 5, wherein the compositions contain one or more perchlorates in addition to the compounds (I). 7. A method for stabilizing antistatic halogen-containing organic plastics against thermal and / or photochemical degradation, characterized in that these plastics have a stabilizer composition containing one or more cyanoacetylureas (I) NC-CH ₂ -CO-N (R ^I ) -CO-NH-R ² (I) 1 in which the radicals R and R independently of one another each have an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which may be replaced by one or more alkyl radicals each having 1 to 6 carbon atoms Atoms can be substituted mean adds and the components are thoroughly mixed 8. Stabilized PVC which on the one hand contains one or more antistatic agents and on the other hand contains one or more cyanoacetylureas (I) NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (I) 1 ^* in which the radicals R and R independently of one another each have an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which may be replaced by one or more alkyl radicals each having 1 to 6 C atoms can be substituted. 9. Stabilized PVC according to claim 8, wherein the antistatic is an internal antistatic. Stabilized PVC according to claim 9, wherein the PVC additionally contains one or more perchlorates.