Patent GB-878362-A (GB)
Title: Improvements relating to benztriazole derivatives non-actinic agents and their use
IPC: C09K15/30
Filed: 1957-12-13
Abstract: Triazole derivatives of general formula:  <FORM:0878362/IV (a)/1> in which A and B represent aromatic radicals consisting of not more than 2 fused rings which may be further substituted by halogen and by groups not having dyeing characteristics, such groups being bound to the aromatic rings by means of carbon, oxygen or sulphur atoms, and in which any further aromatic radicals or a further triazole structure of the above formula are linked direct, or by means of saturated bridging members, to A or B, are incorporated in synthetic polymers and cellulose derivatives to protect them from ultra-violet light.  The polymer may be an unsaturated poylester, a terephthalic acid polyester, a superpolyamide, a superpolyurethane, polyvinyl chloride, a polyhydrocarbon such as polyethylene or polystyrene, polymethyl methacrylate, a polymer of a drying oil, or a cellulose ether or ester.  In Examples (a) films are produced from acetyl cellulose, dibutyl phthalate and a small amount of 2-(21-hydroxy- 51-methylphenyl)- benztriazole, 2-(21-hydroxy- 51- methylphenyl) - benztriazole- 5-carboxylic acid butyl ester, 2-(21-hydroxy-51-tert.-butyl phenyl)-5-chlorobenztriazole, 2-(21-hydroxy-51-phenyl)-benztriazole or 2-(21-hydroxy-51-tert.-butylphenyl)-benztriazole; (b) foils are produced from a cellulose ester containing benzoyl and acetyl groups, dibutyl phthalate and small amounts of 2-(21-hydroxy-31, 51-dimethylphenyl)-benztriazole, 2-(21-hydroxy-31, 51-dimethylphenyl)- 5-methoxybenztriazole, 2- (21-hydroxy-31, 51-dimethylphenyl)- 5-methylbenztriazole or 2-(21-hydroxy-51-carboxylic acidphenyl)-benztriazole ethyl ester; (c) a polyester is polymerized with benzoyl peroxide after incorporation of a small amount of 2-(21-hydroxy- 51-methylphenyl)-benztriazole, 2-(21-hydroxy-51-tert.-butylphenyl)-benztriazole, 2-(21-hydroxy- 51-tert.-butylphenyl) - 5-chloro-benztriazole, 2-(21-hydroxy- 31-methyl- 51-tert. butylphenyl)-benztriazole, or similar compounds covered by the general formula given above; (d) a polyester resin containing chlorendic acid is polymerized by means of a peroxide after the addition of a small amount of 2-(21-hydroxy-51-methylphenyl)- benztriazole, 2-(21-hydroxy-51- amylphenyl)-benztriazole or 2-(21-hydroxy-51-methylphenyl) -benztriazole- 5- carboxylic acid butyl ester; (e) polyester resin plates are produced as in (d) but incorporating glass fibres and using 2-(21-hydroxy- 51-tert.-butylphenyl) -5-chlorobenz-triazole or 2-(21-hydroxy- 51- methylphenyl)-benztriazole as non-actinic agent; (f) methacrylic acid methyl ester is polymerized by lauroyl peroxide after the addition of 2-(21-hydroxy- 51-methylphenyl)-benztriazole or 2-(21-hydroxy-31, 51-dimethylphenyl)-benztriazole; (g) foils are made from a mixture of polyvinyl chloride, dioctyl phthalate and a minor amount of 2-(21-hydroxy- 51-methylphenyl)-benztriazole, 2-(21-hydroxy- 51-methylphenyl) -benztriazole- 5-carboxylic acid hexyl ester, 2-(21-hydroxy- 51-tert.-butylphenyl)- benztriazole or 2-(21-hydroxy-51- tert.- butylphenyl) - 5-chlorbenztriazole; (h) foils are produced as in (g) but with the addition of varying amounts of dibutyl tin dilaurate and 2-(21-hydroxy- 51-methylphenyl)- benztriazole; (j) a mixture of caprolactam, water, sebacic acid and TiO2 is polymerized after the addition of 2-(21-hydroxy- 51-methylphenyl)-benztriazole, 2-(21-hydroxy-31, 51-dimethylphenyl)-benztriazole or 2-(21-hydroxy- 51-tert.-butylphenyl) -5-chloro-benztriazole; (k) granulated nylon and 2-(21-hydroxy- 51-tert.- buthylphenyl)-benztriazole or 2-(21-hydroxy-31, 51-dimethylphenyl)- 5-methyl-benztriazole are melted together; and (1) granulated polyethylene is mixed with a minor proportion of 2-(21-hydroxy- 51-tert.- butylphenyl) - 5-chloro-benztriazole or 2-(21-hydroxy- 51-amylphenyl)-benztriazole and the product is extruded into foils.  In all cases the products are protected from the injurious effects of ultra-violet light.ALSO:The invention comprises 2-(monohydroxy-phenyl)-1.2.3-benzotriazole compounds of the general formula <FORM:0878362/IV (b)/1> in which the benzene nuclei A and B can be further substituted by halogen and groups not imparting dyestuff characteristics, the groups being bound to the aromatic rings by means of a carbon, oxygen or sulphur atom, and in which any further aromatic radicals are linked direct or by means of saturated bridging members to A and B.  In general, compounds of the formula <FORM:0878362/IV (b)/2> in which A and B represent aromatic radicals consisting of at most 2 fused rings which can be further substituted by halogen and by groups not having dyeing characteristics, such groups being bound to the aromatic rings by means of a carbon, oxygen or sulphur atom, and in which any further aromatic radical or a further triazole structure of the above general formula, if present, are linked direct or by means of saturated bridging members to A and B, are produced by methods known per se.  For example, they can be produced by coupling aryl diazonium compounds with azo compounds of the benzene and naphthalene series which couple in the o-position to a primary amine group and oxidising the o-amino-azo dyestuffs thus formed to the 1.2.3-triazole compound.  The azo components may be further substituted as defined.  Alternatively they can be produced by coupling o-nitro aryl diazonium compounds of the benzene or naphthalene series with phenols or naphthols coupling in the o- or p-positions, or with amines of the benzene and naphthalene series coupling in the p-positions to a primary amino group, and then reducing the o-nitro-azo dyestuffs by the usual methods, e.g. with ammonium sulphide or with zinc in an alkaline medium, to form the 1.2.3-triazole compounds.  In these processes the aromatic rings can be further substituted as defined and hydroxyl groups in the products may be alkylated or acylated. Primary amino groups must be removed by diazotising them and replacing the diazo group by the usual methods, by for example, hydrogen, halogen, cyano or hydroxyl groups.  If desired, dinuclear diphenols may be used as azo components or dinuclear bis-o-nitroaryl amines used as diazo components, e.g. bis-p-hydroxy phenyl ethers or thioethers, bis - p - amino - m - nitrophenyl ketones, sulphoxides, sulphones or disulphimides, and the products will then contain more than one thiazole nucleus.  The triazole compounds are incorporated in synthetic polymers, cellulose derivatives, fats and oils to protect them from ultra-violet light (see Groups III and IV(a)).  Specification 878,363 is referred to.ALSO:Fats and oils are protected from the injurious effects of ultra-violet light by incorporating therein a compound of formula <FORM:0878362/III/1> in which A and B represent aromatic radicals consisting of at most 2 fused rings which can further be substituted by halogen and by groups not having dyeing characteristics such groups being bound to the aromatic rings by means of a carbon, oxygen or sulphur atom, any further aromatic radicals present being linked direct or by means of saturated bridging members to A and B, and in which A is bound to the nitrogen atoms at two adjacent carbon atoms. Preferably the fats and oils contain 0.01-2.0% of the active ingredient.  The preferred compounds used as the active ingredient are 2-(21-hydroxy-51-alkylphenyl)-benztriazoles which may have additional substituents in the benzene rings.  Specification 878,363 is referred to.