Patent GB-746046-A (GB)
Title: Process for treating materials which are susceptible to ultra-violet rays or responsive to optical brightening and preparations therefor
Filed: 1953-05-20
Abstract: For the treatment of materials which are susceptible to ultra-violet rays or are responsive to optical brightening, use is made of compounds containing at least one 1,3,4-oxdiazole ring, i.e. compounds of the formula <FORM:0746046/IV(a)/1> where R and R1 are any organic residues, in cluding residues containing another 1,3,4-oxdiazole ring.  The compounds must not contain substituents imparting the character of a dyestuff to the molecule, and at least one of the residues should contain conjugated double bonds in conjugated relation with the double bonds of at least one oxdiazole ring.  All the compounds defined above are useful for rendering materials impermeable or less permeable to ultra-violet rays, but only some of them are useful as optical brightening agents.  For the latter purpose the residues R and R1 in the formula should each contain at least four double bonds in conjugated relation with the double bonds of an oxdiazole ring, except that the necessary number of double bonds may be reduced by one when the residues R and R1 contain aromatically bound amino groups, which may be alkylated or aralkylated.  The compounds may be applied as aqueous solutions, suitably in the form of their salts with acids or bases, as may be appropriate.  They may also be applied as solutions in organic solvents or as dispersions prepared with the aid of dispersing agents, such as soaps, polyglycol ethers of fatty alcohols, sulphitewaste liquor or condensation products of formaldehyde with naphthalene sulphonic acids, which may be alkylated.  The preferred compounds contain water-solubilizing or salt-forming groups, e.g. sulphonic, carboxylic or quaternary ammonium grops, polyglycol residues, or amino groups, which may be alkylated or aralkylated, specified groups being mono- or di-ethylamino, dimethylamino, mono- or di-hydroxyethylamino and benzylamino groups.  Specified compounds are those of the following formul , where X denotes the 1,3,4-ozdiazolyl-2,5 residue : (1) <FORM:0746046/IV(a)/2> sulphonated <FORM:0746046/IV(a)/3> preparation of these compounds is described in Specification 746,047, [Group IV (b)].  Specified materials which may be treated with the compounds include plastics, which may be in film form. The compounds may also be added to compositions for making filaments or films, e.g. viscose, cellulose-acetate solutions or synthetic polyamides.  In example (11) a film is made from an acetone solution of cellulose acetate containing compound 12 above.ALSO:For the treatment of materials which are susceptible to ultra-violet rays or are responsive to optical brightening, use is made of compounds containing at least one 1, 3, 4-oxdiazole ring, i.e. compounds of the formula:- <FORM:0746046/IV(c)/1> where R and R1 are organic residues, including residues containing another 1, 3, 4-oxdiazole ring.  The components must not contain substituents imparting the character of a dyestuff to the molecule, and at least one of the residues should contain conjugated double bonds in conjugated relation with the double bonds of at least one oxdiazole ring.  All the compounds defined above are useful for rendering materials impermeable or less permeable to ultra-violet rays, but only some of them are useful as optical brightening agents.  For the latter purpose the residues R and R1 in the formula should each contain at least four double bonds in conjugated relation with the double bonds of an oxdiazole ring, except that the necessary number of double bonds may be reduced by one when the residues R and R1 contain aromatically bound amino groups, which may be alkylated or aralkylated.  The compounds may be applied as aqueous solutions, suitably in the form of their salts with acids or bases, as may be appropriate.  They may also be applied as solutions in organic solvents or as dispersions prepared with the aid of dispersing agents, such as soaps, polyglycol ethers of fatty alcohols, sulphite waste liquor or condensation products of formaldehyde with naphthalene sulphonic acids, which may be alkylated.  The preferred compounds contain water-solubilizing or salt-forming groups, e.g. sulphonic, carboxylic or quaternary ammonium groups, polyglycol residues, or amino groups, which may be alkylated or aralkylated, specified groups being mono- or di-ethylamino, di-methylamino, mono- or di-hydroxyethylamino and benzylamino groups.  Specified compounds are those of the following formulae, where X denotes the 1, 3, 4-oxdiazolyl-2, 5 residue:- <FORM:0746046/IV(c)/2> (8) sulphonated C10H7XC10H7, <FORM:0746046/IV(c)/3> The preparation of these compounds is described in Specification 746,047, [Group IV(b)].  Specified materials which may be treated with the compounds include textile materials of animal, vegetable or synthetic origin and in any form, a number being specified, and non-textile fibrous materials, e.g. feathers, hair, fur, skins, leather, straw, paper cardboard or pressed wood.  The compounds may also be added to dyestuffs or to dyebaths, printing pastes or discharge or resist pastes, to baths for after-treating dyeings, prints or discharge prints, to bleaching baths, e.g. baths containing sodium hypochlorite, to textile dressing agents, e.g. starch, or to textile anti-creasing baths.  In the examples.  (1) bleached cotton is treated with an aqueous solution of compound 1 above: (2) undyed cotton yarn is treated with an aqueous solution of compound 7 above: (3) cotton is washed in a bath containing soap, soda, sodium pyrophosphate, sodium perborate, magnesium silicate and compound 5 above; (4) the sodium salt of 2 - heptadecyl - N - benzylbenzimidazole disulphonic acid is mixed with compound 5 above and the composition is used for washing cotton; (5) compound 2 above is added to a sodium hypochlorite bleaching bath for cellulose; (6) a composition containing the sodium salt of 2-heptadecyl - N - benzylbenzimidazole disulphonic acid, primary sodium phosphate and compound 1 above is used for washing nylon or perlon; (7) nylon or perlon is treated in a bath containing formic acid and compound 1 above; (8) nylon or perlon is dyed in a bath containing formic acid, compound 1 above and the dye obtainable from diazotized p-nitranilino and N-ethyl-N-hydroxyethylaniline; (9) wool is treated in a bath containing sulphuric acid and compound 11 above; (10) bleached cotton is treated with a finishing liquor containing starch and compound 1 above.ALSO:For the treatment of materials which are susceptible to ultra-violet rays or are responsive to optical brightening, use is made of compounds containing at least one 1, 3, 4-oxdiazole ring, i.e. compounds of the formula <FORM:0746046/III/1> where R and R1 are any organic residues, including residues containing another 1, 3, 4-oxdiazole ring.  The compounds must not contain substituents imparting the character of a dyestuff to the molecule, and at least one of the residues should contain conjugated double bonds in conjugated relation with the double bonds of at least one oxdiazole ring.  All the compounds defined above are useful for rendering materials impermeable or less permeable to ultra-violet rays, but only some of them are useful as optical brightening agents. For the latter purpose the residues R and R1 in the formula should each contain at least four double bonds in conjugated relation with the double bonds of an oxdiazole ring, except that the necessary number of double bonds may be reduced by one when the residues R and R1 contain aromatically bound amino groups, which may be alkylated or aralkylated.  The compounds may be applied as aqueous solutions, suitably in the form of their salts with acids or bases, as may be appropriate.  They may also be applied as solutions in organic solvents or as dispersions prepared with the aid of dispersing agents, such as soaps, polyglycol ethers of fatty alcohols, sulphite waste liquor or condensation products of formaldehyde with naphthalene sulphonic acids, which may be alkylated.  The preferred compounds contain watersolubilizing or salt-forming groups, e.g. sulphonic, carboxylic or quaternary ammonium groups, polyglycol residues, or amino groups, which may be alkylated or aralkylated, specified groups being mono- or di-ethylamino, dimethylamino, mono- or di-hydroxyethylamino and benzylamino groups.  Specified compounds are those of the following formulae, where X denotes the 1, 3, 4-oxdiazolyl-2, 5 residue:- <FORM:0746046/III/2>  The preparation of these compounds is described in Specification 746,047, [Group IV(b)]. Specified materials which may be treated with the compounds or to which they may be added include edible oils or fats, lacquers, resins or inorganic pigments, e.g. plaster of Paris or whitewash.  The compounds may be included also in detergent compositions, which may contain (1) soaps or (2) salts of sulphonated detergents, e.g. sulphonated benzimidazoles substituted in the 2 - position with a higher alkyl radical, monocarboxylic esters of 4 - sulphophthalic acid with higher fatty alcohols, fatty alcohol sulphonates, alkyl-aryl sulphonic acids or condensation products of higher fatty acids with oxy- or amino-sulphonic acids, or (3) non-ionic detergents, e.g. condensation products of ethylene oxide with higher fatty alcohols or amines or alkylphenols.  Such detergent compositions may also contain other customary ingredients, e.g. alkali carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates.  In examples, (3) cotton is washed in a bath containing soap, soda, sodium pyrophosphate, sodium perborate, magnesium silicate and compound 5 above; (4) the sodium salt of 2 - heptadecyl - N - benzylbenzimidazole disulphonic acid is mixed with compound 5 above and the composition is used for washing cotton; (6) a composition containing the sodium salt of 2 - heptadecyl - N - benzylbenzimidazole disulphonic acid, primary sodium