Patent GB-983232-A (GB)
Title: Coated articles
IPC: D06N3/06
Filed: 1961-03-10
Abstract: A coating composition comprises a mixture of water-insoluble emulsion copolymer molecules containing polymerized vinylidene chloride and whose average composition corresponds to a polymerized mixture of:- (A) vinylidene chloride in an amount which is at least 35%, but not more than 65%, by weight of the total monomer mixture; (B) a second monomeric component constituted by (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate or (d) an acrylic ester-containing mixture of (1) at least one monomer having a hardening effect and which is styrene, vinyl toluene, or a C1-C3 alkyl methacrylate with (2) at least one monomer having a softening effect and which is an ester of acrylic acid with a C1-C18 saturated aliphatic alcohol or an ester of methacrylic acid with a C4-C18 saturated aliphatic alcohol, the second monomeric component defined under (B) providing at least 35% by weight of ester monomer based on the total monomer mixture, the hardening monomer(s) in the acrylic ester-containing mixture (d), together with any hardening monomer in the third monomeric component (C) specified hereinafter, being present in an amount from 10 to 50% by weight of the total monomer mixture, and the softening monomer(s) in the acrylic ester-containing mixture (d), together with any softening monomer present in the third monomeric component (C) being present in an amount from 15-55% by weight of the total monomer mixture; and, optionally, (C) a third monomeric component present in an amount up to 5% by weight of the total monomer mixture and which is constituted by at least one monomer imparting hydrophilic characteristics to the copolymers, e.g. acrylic, methacrylic or itaconic acid, b -hydroxyethyl acrylate, b -hydroxyethyl vinyl ether or allyl glycidyl ether.  The composition may comprise a blend of at least two water-insoluble emulsion copolymers each containing between 35 and 65% by weight of polymerized vinylidene chloride, the balance of each copolymer being such that the average composition of the blend corresponds to the polymerized monomer mixture defined.  At least one copolymer in the blend may be a copolymer of vinylidene chloride, 35 to 65% by weight of one or more of the hardening monomers listed as a component of the acrylic ester-containing mixture (d) and 0 to 20% by weight of one or more softening monomers listed as a component of acrylic ester-containing mixture (d) and wherein at least one other copolymer is a copolymer of vinylidene chloride, 10 to 30% by weight of one or more of the aforesaid hardening monomers and 20 to 55% by weight of one or more of the aforesaid softening monomers. The composition may comprise a single water-insoluble emulsion copolymer, as opposed to a blend, of the monomer mixture set out above. The copolymer may be a copolymer of 35 to 65% by weight vinylidene chloride and (1) 35 to 65% by weight of methyl acrylate or butyl methacrylate; (ii) 10 to 45% by weight of methyl methacrylate vinyl toluene or styrene and 20 to 55% by weight of at least one ester of acrylic acid with a saturated aliphatic alcohol having 1 to 18 carbon atoms; (iii) 10 to 45% by weight of methyl methacrylate and 20 to 55% by weight of at least one ester of methacrylic acid with a saturated aliphatic alcohol having 3 to 18 carbon atoms, e.g. butyl methacrylate.  The polymeric material may have a viscosity average molecular weight from 500,000 to 10,000,000.  The copolymer latex may be obtained by conventional emulsion polymerization techniques using any conventional free-radical initiator, e.g. organic peroxides and hydroperoxides such as acetyl peroxide; cumene, t-butyl or phenyl cyclohexane hydroperoxide, hydrogen peroxide; and inorganic persulphates such as ammonium of potassium persulphate; activators such as ascorbic or isoascorbic acid, sodium-formaldehyde sulphoxylate, alkali metal hydrosulphites and metabisulphites, and anionic, nonionic or cationic emulsifiers. Thickening agents, e.g. polyvinyl alcohol, sodium polyacrylate, sodium salts of copolymers of methacrylic acid and methyl methacrylate, sodium alginate, carboxymethyl cellulose, methyl cellulose, casein, and hydroxyethyl cellulose, methyl cellulose, casein, and hydroxyethyl cellulose, and sequestering agents e.g. sodium citrate and pyrophosphate, and the sodium salt of ethylene diamine tetra-acetic acid, may also be present.ALSO:Flooring material, or felt-base or woven fabric wall-surfacing material has, as an outer coating, a film comprising a mixture of water-insoluble emulsion copolymer molecules containing polymerized vinylidene chloride and whose average composition corresponds to a polymerized monomer mixture of: (A) vinylidene chloride in an amount which is at least 35%, but not more than 65%, by weight of the total monomer mixture; (B) a second monomeric component constituted by (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate or (d) an acrylic ester-containing mixture of (1) at least one monomer having a hardening effect and which is styrene, vinyl toluene, or a C1-C3 alkyl methacrylate with (2) at least one monomer having a softening effect and which is an ester of acrylic acid with a C1-C18 saturated aliphatic alcohol or an ester of methacrylic acid with a C4-C18 saturated aliphatic alcohol, the second monomeric component defined under (B) providing at least 35% by weight of ester monomer based on the total monomer mixture, the hardening monomer(s) in the acrylic ester-containing mixture (d), together with any hardening monomer in the third monomeric component (C) specified hereinafter, being present in an amount from 10-50% by weight of the total monomer mixture, and the softening monomer(s) in the acrylic ester-containing mixture (d), together with any softening monomer present in the third monomeric component (C) being present in an amount from 15-55% by weight of the total monomer mixture; and, optionally, (C) a third monomeric component present in an amount up to 5% by weight of the total monomer mixture and which is constituted by at least one monomer imparting hydrophilic characteristics to the copolymers, e.g. acrylic, methacrylic or itaconic acid, b -hydroxyethyl acrylate, b -hydroxyethyl vinyl ether or allyl glycidyl ether.  The film may comprise a blend of at least two water-insoluble emulsion copolymers each containing between 35% and 65% by weight of polymerized vinylidene chloride, the balance of each copolymer being such that the average composition of the blend corresponds to the polymerized monomer mixture defined.  At least one copolymer in the blend may be a copolymer of vinylidene chloride, 35-65% by weight of one or more of the hardening monomers listed as a component of the acrylic ester-containing mixture (d) and 0-20% by weight of one or more softening monomers listed as a component of acrylic ester-containing mixture (d) and wherein at least one other copolymer is a copolymer of vinylidene chloride, 10-30% by weight of one or more of the aforesaid hardening monomers and 20-55% by weight of one or more of the aforesaid softening monomers.  The film may comprise a single water-insoluble emulsion copolymer, as opposed to a blend, of the monomer mixture set out above.  The copolymer may be a copolymer of 35-65% by weight vinylidene chloride and (i) 35-65% by weight of methyl acrylate or butyl methacrylate; (ii) 10-45% by weight of methyl methacrylate, vinyl toluene or styrene, and 20-55% by weight of at least one ester of acrylic acid with a saturated aliphatic alcohol having 1-18 carbon atoms; (iii) 10-45% by weight of methyl methacrylate and 20-55% by weight of at least one ester of methacrylic acid with a saturated aliphatic alcohol having 3-18 carbon atoms, e.g. butyl methacrylate.  The polymeric material in the film may have a viscosity average molecular weight from 500,000 to 10,000,000.  The flooring material is characterized in that it has a felt, or woven fabric base, as in linoleum, asphalt-saturated felt, rubber or vinyl resin tile.  The film may be applied by coating the material with an aqueous copolymer dispersion and drying the coating to form a continuous film.  The copolymer latex may be obtained by conventional emulsion polymerization techniques using any conventional free-radical initiator, e.g. organic peroxides and hydroperoxides such as acetyl peroxide; cumene, t-butyl or phenyl cyclohexane hydroperoxide, hydrogen peroxide; and inorganic persulphates such as ammonium or potassium persulphate; activators such as ascorbic acid, sodium-formaldehyde sulphoxylate, alkali metal hydrosulphites and metabisulphites, and anionic, nonionic or cationioc emulsifiers.  Thickening agents, e.g. polyvinyl alcohol, sodium polyacrylate, sodium salts of copolymers of methacrylic acid and methyl methacrylate, sodium alginate, carboxymethyl cellulose, methyl cellulose, casein, and hyroxyethyl cellulose, and sequestering agents, e.g. sodium citrate and pyrophosphate, and the sodium salt of ethylene diamine tetra acetic acid, may also be present.