Patent GB-1070299-A (GB)
Title: Antistatic coatings
IPC: C08J7/044
Filed: 1964-10-09
Abstract: An antistatic film-forming composition comprises a polymer or copolymer of a quaternized derivative of a base of formula <FORM:1070299/C3/1> wherein R represents a hydrogen atom or a methyl group and R1 and R2 each represents a methyl or ethyl group, or R1 and R2 together with the adjacent nitrogen atom represents a heterocyclic group, e.g. morpholino, piperidino or piperazino, the composition including groups, either bonded to the polymer or contained in a second chemical compound forming part of the composition, capable of reacting, to effect cross-linking of the polymer or copolymer at a temperature of 40 DEG  C.  The quaternized derivative is b -dimethyl aminoethyl methacrylate quaternized with methyl chloride.  The composition may comprise a copolymer of the quaternized derivative together with a further monomer which is a free base of formula <FORM:1070299/C3/2> wherein R, R1 and R2 are as defined above, the molar ratio of quaternized derivatives to free base monomer in the copolymer being at least 1:1.  The free base monomer may provide at least 0.5% by weight of the copolymer, and the copolymer may be cross-linked by the reaction of the free basic groups of formula -NR1R2, provided by the free base monomer, with halogen-containing quaternizing groups. The halogen-containing quaternizing groups may be of formula <FORM:1070299/C3/3> wherein R4 is a hydrogen atom or an alkyl or aryl group, Hal is a chlorine or bromine atom, and X is an oxygen atom or a carbonyl, carboxy, carbamide, dicarboxyalkylene, dicarbamido alkylene, carboxy carbamidoalkylene or aryl group.  The copolymer may be cross-linked by reaction with a polymer or copolymer of a monomer of formula <FORM:1070299/C3/4> where R3 represents a hydrogen atom or a methyl group and R4, Hal and X are as defined for Formula (3), e.g. a polymer or copolymer of chloromethyl or b -chloroacetoxy ethyl acrylate or methacrylate.  The copolymer may be cross-linked by reaction with a low molecular bi- or polyfunctional quaternizing agent, i.e. having a molecular weight below 500, such as compounds of formula <FORM:1070299/C3/5> wherein R represents a hydrogen atom, or an alkyl or aryl group, Hal represents a chlorine or bromite atom, X is as defined for Formula (3). A represents a group having a valency equal to the integer n, e.g. the chloroacetate of a polyhydric alcohol, examples of which are given.  The composition may comprise a copolymer of (A) a quaternized derivative of Formula (1), (B) a free base monomer of Formula (2), and (C) a monomer having a halogen-containing quaternizing groups which may be of Formula (3), the copolymer being cross-linked by reaction between the subsstituted amino groups of monomer (B) and the halogen-containing quaternizing groups of monomer (C).  Monomer (C) may be of Formula (4). The composition may comprise a copolymer of a quaternized derivative as defined in Formula (1) together with a further monomer which is a halogen-containing compound of Formula (4), and the copolymer may be cross-linked by reaction with a di- or poly-functional amine, e.g. ethylene diamine or an N-alkylated derivative thereof.  The polymer or copolymer may be cross-linked by reaction between formaldehyde or a compound splitting off formaldehyde, and reactive groups, e.g. carboxy, carbamido, or alkoxy methyl carbamido groups, in the polymer or copolymer.  The composition may comprise a copolymer of the quaternized derivative and a monomer which is an ester, amide or nitrile of acrylic or methacrylic acid. The -NR1R2 groups of the copolymer may be in salt form and the pH of the solution is greater than 3.  The composition may contain water and/or an organic solvent, e.g. an alcohol or ketone.  Examples illustrate the preparation of copolymers by polymerizing the corresponding monomers in water and/or alcohol using ammonium persulphate or azobisisobutyronitrile as initiator.ALSO:Fibres of polyamide, polyacrylonitrile, polypropylene and polyester are provided with an antistatic polymeric coating by applying to the fibre a coating of a film forming composition comprising a polymer or copolymer of a quaternised derivative of a base of formula:  <FORM:1070299/D1-D2/1> wherein R represents a hydrogen atom or a methyl group and R1 and R2 each represents a methyl or ethyl group, or R1 and R2 together with the adjacent nitrogen atom represents a heterocyclic group, the composition including groups, either bonded to the polymer or contained in a second chemical compound forming part of the composition, capable of reacting, when the composition has been applied as a coating, to effect cross-linking of the polymer or copolymer at a temperature of 40 DEG C. and the polymer or copolymer after application is cross-linked to form an antistatic water-insoluble polymer coating. The quaternised derivative is b -dimethyl aminoethyl methacrylate quaternised with methyl chloride.  The composition may comprise a copolymer of the quaternised derivative together with a further monomer which is a free base of formula:  <FORM:1070299/D1-D2/2> wherein R, R1 and R2 are as defined above, the molar ratio of quaternised derivatives to free base monomer in the copolymer being at least 1:1.  The free base monomer may provide at least 0.5% by weight of the copolymer, and the copolymer may be crosslinked by the reaction of the free basic groups of formula -NR1 R2, provided by the free base monomer, with halogen - containing quaternising groups. The halogen containing quaternising groups may be of formula: <FORM:1070299/D1-D2/3> wherein R4 is a hydrogen atom or an alkyl or aryl group, Hal is a chlorine or bromide atom, and X is an oxygen atom or a carbonyl, carboxy, carbamido dicarboxyalkylene, dicarbamido, alkylene carboxy carbamidoalkylene or aryl group.  The copolymer may be cross-linked by reaction with a polymer or copolymer of a monomer of formula:  <FORM:1070299/D1-D2/4> where R3 represents a hydrogen atom or a methyl group and R4, Hal and X are as defined for formula 3 e.g. a polymer or copolymer of chloromethyl or b -chloroacetoxy ethyl acrylate or methacrylate.  The copolymer may be crosslinked by reaction with a low molecular bi-or polyfunctional quaternising agent i.e. having a molecular weight below 500, such as compounds of formula:  <FORM:1070299/D1-D2/5> wherein R represents a hydrogen atom, or an alkyl or aryl group, Hal represents a chlorine or bromite atom, X is as defined for formula 3.  A represents a group having a valency equal to the integer n e.g. the chloroacetate of a polyhydric alcohol, examples of which are given.  The composition may comprises a copolymer of (A) a quaternised derivative of formula 1, (B) a free base monomer of formula 2, and (C) a monomer having a halogen - containing quaternising groups which may of formula 3, the copolymer being crosslinked by reaction between the substituted amino groups of monomer (B) and the halogen-containing quaternising groups of monomer (C).  Monomer (C) may be of formula 4.  The composition may comprise a copolymer of a quaternised derivative as defined in formula 1 together with a further monomer which is a halogen - containing compound of formula 4, and the copolymer may be crosslinked by reaction with a di - or poly-functional amine e.g. ethylene diamine or an N-alkylated derivative thereof.  The polymer or copolymer may be crosslinked by reaction between formaldehyde or a compound splitting off p  formaldehyde, and reactive groups e.g. carboxy, carbamido, or alkoxy methyl carbamido groups, in the polymer or copolymer.  The composition may comprise a copolymer of the quaternised derivative and a monomer which is an ester, amide or nitrile of acrylic or methacrylic acid.  The -NR1R2 groups of the copolymer may be in salt form and the pH of the solution is greater than 3. The composition may contain water and/or an organic solvent e.g. an alcohol or ketone.  The coating may be applied by spraying, brushing, padding or dipping.ALSO:Articles are provided with an antistatic polymeric coating by applying to the article a coating of a film forming composition comprising a polymer or copolymer of a quaternised derivative of a base of formula <FORM:1070299/B1-B2/1> wherein R represents a hydrogen atom or a methyl group and R1 and R2 each represents a methyl or ethyl group, or R1 and R2 together with the adjacent nitrogen atom represents a heterocyclic group, the composition including groups, either bonded to the polymer or contained in a second chemical compound forming part of the composition, capable of reacting, when the composition has been applied as a coating, to effect cross-linking of the polymer or copolymer at a temperature of 40 DEG C, and the polymer or copolymer after application is crosslinked to form an anti-static water-insoluble polymer coating.  The quaternised derivative is b -dimethyl aminoethyl methacrylate quaternised with methyl chloride. The composition may comprise a copolymer of the quaternised derivative together with a further monomer which is a free base of formula <FORM:1070299/B1-B2/2> wherein R, R1 and R2 are as defined above, the molar ratio of quaternised derivatives to free base monomer in the copolymer being at least 1:1.  The free base monomer may provide at least 0.5% by weight of the copolymer, and the copolymer may be crosslinked by the reaction of the free basic groups of formula -NR1 R2, provided by the free base monomer, with halogen-containing quaternising groups.  The halogen-containing quaternising groups may be of formula <FORM:1070299/B1-B2/3> wherein R4 is a hydrogen atom or an alkyl or aryl group, Hal is a chlorine or bromine atom, and X is an oxygen atom or a carbonyl, carboxy, carbamido dicarboxyalkylene, dicarbamido alkylene, carboxy carbamidoalkylene or aryl group.  The copolymer may be cross-linked by reaction with a polymer or copolymer of a monomer of formula <FORM:1070299/B1-B2/4> where R