Patent GB-898065-A (GB)
Title: New monomeric, polymerisable, ultra-violet light-screening esters and amides, their polymerisation and use
IPC: C08F20/52
Filed: 1959-03-13
Abstract: Ultra-violet light-screening polymers are obtained by the polymerization of a monomeric U.V.-absorbing ester or amide which has been prepared by reacting an acid halide of a polymerizable aliphatic mono- or dicarboxylic acid with a U.V.-absorbing compound containing at least one benzene ring and a grouping attached thereto which together form a conjugated system; the said compound containing at least one hydroxyl or amino group capable of reacting with an acid halide without losing its U.V.-absorbing properties; said compound, and said monomeric ester or amide, having a molecular extinction coefficient (measured in ethanol) of at least 10,000 in the range 240-400 mm .  Specified polymerizable acids for the preparation of the monomers are acrylic, crotonic, methacrylic, chloroacrylic, itaconic, fumaric and maleic acids; specified U.V.-absorbing hydroxy- and amino-compounds are those of the formul  <FORM:0898065/IV (a)/1> where R8 is a benzene, diphenyl or pyridine residue; <FORM:0898065/IV (a)/2> where A is an aliphatic hydrocarbon radical; R9-R10-NH2, where R9 is a benzthiazole, benzoxazole or benzimidazole residue bound in 2-position to R10, which is a benzene residue bound in 4-position to the amino group; A-O-COR10NH2, where A is an alkyl group and R10 is a benzene residue bound in 1-position to the -OCO- group and in 4-position to the amino group; and 7-aminocoumarins (see Group IV(b)).  The monomers may be homopolymerized or copolymerized, in bulk, in organic solution or in emulsion.  Suitable monomers for copolymerization contain the group CH2=C<, such as vinyl esters of organic acids (e.g. the acetate, formate, butyrate or benzoate); vinyl alkyl ketones; vinyl halides such as vinyl and vinylidene chloride; styrene and substituted styrenes; acrylic acid esters; acrylonitrile; acrylamide; substituted amides of acrylic, methacrylic, chloroacrylic, maleic and fumaric acids; olefines, such as isobutylene, butadiene; 2-chlorobutadiene; heterocyclic compounds such as N-vinylcarbazole, N-vinylimidazole, vinylpyrrolidone and vinylpyridine; unsaturated ethers such as vinyl and isobutylvinyl ethers; acids such as acrylic and methacrylic acids.  One or more such polymerizable compounds may be used to prepare copolymers with the U.V.-absorbing ester or amide.  The polymers are used for impregnating or coating, e.g. coating wood surfaces, paper, textiles and laminates.  Specifications 880,549 and 893,236 are referred to.ALSO:The invention comprises monomeric polymerizable ultra-violet light-screening esters or amides which retain their light-screening properties on polymerization, and which have been obtained by reacting an acid halide of a polymerizable aliphatic mono- or dicarboxylic acid with an ultra-violet light-absorbing compound containing at least one benzene ring and a grouping attached thereto which together form a conjugated system, the said compound containing at least one hydroxyl or amino group capable of reacting with an acid halide without losing its ultra-violet light-screening properties; said compound, and also the ester or amide derived therefrom by reaction with the polymerizable acid halide, having a molecular extinction coefficient (measured in ethanol) of at least 10,000 in the range 240-400 mm .  Specified polymerizable acids are acrylic, crotonic, methacrylic, chloroacrylic, itaconic, fumaric and maleic acids.  Specified types of ultra-violet screening hydroxy-and amino-compounds are those of the formulae <FORM:0898065/IV (b)/1> where R8 is a benzene, diphenyl or pyridine residue; <FORM:0898065/IV (b)/2> where A is an aliphatic hydrocarbon residue; R9-R10-NH2, where R9 is a benzthiazole, benzoxazole or benzimidazole residue bound in 2-position to R10 and R10 is a benzene residue bound in 4-position to the amino group; A-O-CO-R10-NH2, where A is an alkyl group and R10 is a benzene residue bound in 1-position to the -OCO-group and in 4-position to the amino group; and 7-aminocoumarins.  Examples prepare the compounds of the formulae <FORM:0898065/IV (b)/3> Specifications 880,549 and 893,236 are referred to.ALSO:Textiles are protected against ultra-violet light by treatment with a polymerisable u.v.-absorbing ester or amide (see Group IV (b)) or with a homopolymer or copolymer thereof (see Group IV (a); or dyed textiles can be similarly protected by a screen of such a polymer.  In Examples (33) a polyamide fabric is treated with the ester <FORM:0898065/IV (c)/1> in ethanol in the presence of a reaction product from octadecyl alcohol and ethylene oxide; (34) as in (33) in the presence of formic acid also; (35) polyamide fibre yarn is similarly treated; (36) wool gaberdine dyed with a commercial acid wool dye is protected against u.v-light by an acetylcellulose film containing the ester <FORM:0898065/IV (c)/2> (38) bleached jute is coated with an emulsion obtained by polymerising the ester <FORM:0898065/IV (c)/3> and dried; (41) a polyamide fabric dyed with the dyestuff <FORM:0898065/IV (c)/4> is coated with the emulsion used in (38) and dried; (42) wool serge dyed with the above dyestuff is protected against u.v. light by a glass plate coated with the emulsion used in (38). Specifications 880,549 and 893,236 are referred to.