Patent GB-723580-A (GB)
Title: Improvements relating to the treatment of vinyl resin articles to reduce their tendency to accumulate charges of static electricity
IPC: D06M13/46
Filed: 1952-07-02
Abstract: The tendency of a vinyl resin fibre, fabric or film to accumulate charges of static electricity is reduced by depositing upon the article from 0.2-10 per cent by weight (based on the dry untreated article) of a compound of the formula: RCONH(CH2)3N(R1)(R11)(R111)Y from a solution or dispersion in a volatile liquid.  R may be an aliphatic or an alicyclic radical, R1 and R11 an alkyl or hydroxyalkyl radical and R111 an alkyl, hydroxyalkyl, alkenyl or aralkyl radical, and Y may be a halide, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, thiosulphate, isocyanate, sulphite, bisulphite, nitrite, nitrate, oxalate, silicate, sulphide, cyanate or acetate anion.  Many examples of compounds of the formula above are given in which R has 7 and more carbon atoms and includes saturated and unsaturated radicals, R1 and R11 have 1 to 5 carbon atoms and R111 includes the alkyl radicals up to octadecyl, the alkenyl radicals up to octadecenyl, including allyl, methallyl, ethallyl, 2-butenyl, 3-butenyl, 3 - methyl - 2 - butenyl, 3 - pentenyl, 4 - pentenyl, 2,3-pentadienyl and 3-methyl-3-butenyl, and, as aralkyl radicals, benzyl, phenylethyl, phenylpropyl, phenylisopropyl, phenylbutyl and a -naphthylmethyl. Among the examples given is abietamidopropyl dimethyl beta1-hydroxyethylammonium chloride.  The liquid phase of the treating solution or dispersion may be water, ethyl alcohol, propyl alcohol or mixtures of water and alcohols, and the solid phase may include mixtures of the quaternary ammonium compounds. Other antistatic agents or blown or unblown neatsfoot oil, sperm oil, olive oil, teaseed oil, peanut oil, soya bean oil, cottonseed oil or sulphonated olive oil, or methyl, ethyl, propyl, amyl or hexyl stearate, palmitate or oleate may be included in the treating liquid. The vinyl resins from which the fibres, films or fabrics are made include vinyl chloride-vinyl acetate copolymers, copolymers of vinyl chloride with acrylonitrile or methacrylonitrile, copolymers of vinyl chloride and other vinylhalides and resins produced by the chlorination of such p  compounds, resins produced by the chlorination of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, copolymers of vinyl chloride with N-butylmaleimide, and resins produced by the conjoint polymerization of a vinyl halide, a vinyl ester of an aliphatic acid and maleic acid.  The treating liquid may be applied by spraying, padding or brushing and at temperatures up to 100 DEG  C., and may be applied to the finished fibre, yarn, film, or fabric, or at any stage in the production of yarns, including the stage when the resin is in gelled form.  U.S.A. Specification 2,404,713 is referred to.ALSO:A composition comprising a compound of the formula RCONH(CH2)3N(R1)(R11)(R111)Y in solution or dispersion in water, ethyl or propyl alcohol or mixtures of alcohols and water is applied to vinyl resin fibres or films at any stage in the production thereof, including the stage when the articles are in the gelled condition or during the stretching of a wet spun fibre to orientate the molecules thereof or between any of the guides or godets employed in the spinning process or between the guide and the point of winding or twisting. In the above formula R may be an aliphatic or an alicyclic radical, R1 and R11 alkyl or hydroxyalkyl radicals, R111 an alkyl, hydroxyalkyl, alkenyl or aralkyl radical and Y a halide, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, thiosulphate, isocyanate, sulphite, bisulphite, nitrite, nitrate, oxalate, silicate, sulphide, cyanate or acetate anion.  The composition may be applied at temperatures up to 100 DEG  C. by spraying or brushing or during the spinning process by roll, wick or felt, and the composition may also include a blown, unblown or sulphonated animal, vegetable or mineral oil or methyl, ethyl, propyl, butyl, amyl or hexyl stearate, palmitate or oleate or other textile adjuvant.  The fibres or films may be made from copolymers of vinyl chloride with vinyl acetate, acrylonitrile, methacrylonitrile or other vinyl halides and resins produced by the chlorination of such compounds or by the chlorination of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid, copolymers of vinyl chloride with N-butylmaleimide and copolymers of a vinyl halide, a vinyl ester of an aliphatic acid and maleic acid.  In example 7 a solution of acrylonitrile and methyl acrylate in an aqueous solution of calcium thiocyanate, the pH of which is adjusted to 6.8 with hydrochloric acid, is extruded from a steam-heated spinneret into a coagulating solution of calcium thiocyanate in water at -1 DEG  C. and the spun yarn looped over a pair of converging stainless steel rolls, during the passage over which the yarn is washed and from which the yarn is passed through a trough of heated water to a pair of converging, electrically heated drying rolls rotating at a higher speed than the wash rolls, so stretching the yarn in the hot water trough. At either or both of the drying rolls an aqueous solution of gamma-stearamidopropyldimethyl - beta1 - hydroxyethyl ammonium chloride or gamma-stearamidopropyl-dimethylbenzyl ammonium chloride is applied by means of a jet to the yarn.  Many examples of compounds of the above formula are given in which R has 7 and more carbon atoms and includes saturated and unsaturated radicals, R1 and R11 have 1 to 5 carbon atoms and R111 includes the alkyl radicals up to octadecyl, the alkenyl radicals up to octadecenyl, including allyl, methallyl, ethallyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 3-pentenyl, 4-pentenyl, 2,3-pentadienyl and 3-methyl-3-butenyl, and, as aralkyl radicals, benzyl, phenylethyl, phenylpropyl, phenylisopropyl, phenylbutyl and a -naphthylmethyl.ALSO:Compounds of the general formula RCONH(CH2)3N(R1)(R2)(R3)Y are obtained by a process which comprises reacting acrylonitrile with a secondary amine R1R2NH to obtain a product (R1)(R2)N(CH2)2CN, which is catalytically reduced to give (R1)(R2)N(CH2)3NH, the resulting diamine being acylated with an acid R.COOH to obtain the amide RCONH(CH2)3N(R1)(R2), which is reacted with an alkylating agent such as an alkyl halide, a halohydrin, ethylene oxide or a dialkyl sulphate, or with an aralkyl chloride.  In an example of this last step, gamma-myristamidopropyl dimethyl amine is reacted with benzyl chloride.  Numerous examples are given of substances obtainable in this way.  R may be an aliphatic or an alicyclic radical, R1 and R2 an alkyl or hydroxyalkyl radical, R3 an alkyl, hydroxyalkyl, alkenyl or aralkyl radical, a Y is a chloride, bromide, fluoride, iodide, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, thiosulphate, isocyanate, sulphite, bisulphite, nitrate, nitrite, oxalate, silicate, sulphide, cyanate or acetate anion.  R may have 7 or more carbon atoms and may include saturated and unsaturated radicals, e.g. tetradecyl or tetradecenyl, R1 and R2 may contain 1 to 5 carbon atoms, e.g. propyl or isopropyl, and R3 includes the alkyl radicals given for R1 and R2 and higher alkyl radicals, e.g. from hexyl to octadecyl, the alkenyl radicals up to octadecenyl, e.g. allyl, methallyl, ethallyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 3-pentenyl, 4-pentenyl, 2,3-pentadienyl or 3-methyl-3-butenyl and, as aralkyl radicals, benzyl, phenylethyl, phenylpropyl, phenylisopropyl, phenylbutyl and a -naphthylmethyl. Included in a long list of examples is abietamidopropyl dimethyl beta1-hydroxyethyl ammonium chloride.  U.S.A. Specification 2,404,713 is referred to.ALSO:Vinyl resin fibres, fabrics or films are treated, to reduce their tendency to accumulate static charges of electricity (see Group IV(c)), with a composition which comprises a compound of the general formula:  RCONH (CH2)3 N(R1) (R2) (R3) Y in solution or dispersion in a volatile liquid such as water, ethyl or propyl alcohol or mixtures of alcohols and water and which may also comprise a lubricant such as butyl stearate, or mineral vegetable or animal oils, particularly blown or unblown neatsfoot oil, sperm oil, olive oil, teaseed oil, peanut oil, soya bean oil, cottonseed oil or sulphonated olive oil.  R in the formula is aliphatic or alicyclic, R1 and R2 are alkyl or hydrooxyalkyl, R3 is alkyl, hydroxyalkyl, alkenyl or aralkyl and Y is a halide, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, thiosulphate, isocyanate, sulphite, bisulphite, nitrite, nitrate, oxalate, silicate, sulphide, cyanate, or acetate anion. Many examples of compounds of the formula above are given in which R has 7 or more carbon atoms including saturated and unsaturated radicals, R1 and R2 have 1 to 5 carbon atoms and R3 includes alkyl radicals up to octadecyl, alkenyl radicals up to octadecenyl, including alkyl, methallyl, ethallyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 3-pentenyl, 4-pentenyl, 2-3-pentadienyl and 3 methyl 3 butenyl, and, as aralkyl radicals, benzyl, phenylethyl, phenylpropryl, phenylisopropyl, phenylbutyl and a -naphthylmethyl. In some cases, a composition consisting solely of the volatile liquid and the compound of the above formula may be employed, particularly when the compound of the above formula contains long-chain aliphatic grouping, specifically an alkyl grouping, of such length that the compound is capable of functioning both as a lubricating agent and as an anti-static agent.  U.S.A. Specification 2,404,713 is referred to.