Patent GB-949919-A (GB)
Title: Novel light-sensitive polymers
IPC: C08B3/10
Filed: 1962-10-23
Abstract: Cinnamylideneacetic acid may be prepared by reacting malonic acid and cinnamaldehyde in pyridine in the presence of piperidine. 7-Phenyl-2, 4, 6-heptatrienoic acid may be prepared by refluxing a solution of 5-phenyl-2, 4-pentadienol and O, O-diethyl carbethoxymethyl phosphonate in methanol in the presence of sodium methoxide. The acids may be converted to the corresponding acid chlorides by conventional means.ALSO:Film-forming, light-sensitive organic polymers containing alkapolyenoate side chains of formula <FORM:0949919/C3/1> where R is an aromatic or heterocyclic group and n is 2 or 3, attached to carbon atoms therein may be prepared by reacting hydroxyl-containing polymers with the corresponding alkapolyenoic acid chlorides in an organic solvent such as pyridine. Specified polymers are polyvinyl alcohol and copolymers of vinyl alcohol with olefins, vinyl esters, vinyl halides and acrylic esters, many suitable monomers being listed; cellulose and cellulose derivatives such as cellulose acetates, propionates and butyrates, hydroxyethyl cellulose and ethyl cellulose; and starch, guar and alginic acid and their partial esters and ethers.  Many suitable acid halides are specified.  Preferred light-sensitive polymers include poly(vinyl cinnamylidene-acetate), poly(vinyl benzoate cinnamylideneacetate), poly(vinyl cinnamate cinnamylideneacetate), poly(vinyl carbethoxymethyl carbamate cinnamylideneacetate), poly(vinyl acetate benzoate cinnamylideneacetate), poly(vinyl acetate cinnamylideneacetate), poly(vinyl acetate benzoate 7-phenyl-2,4,6-heptatrienoate), poly(ethylene vinyl cinnamylideneacetate), poly(vinyl butyral cinnamylideneacetate), cellulose acetate cinnamylideneacetate and cinnamylideneacetate of hydroxyethyl cellulose. Examples describe the preparation of lightsensitive polymers by reacting polyvinyl alcohol with (IV) cinnamylideneacetyl chloride, (V) cinnamylideneacetyl chloride and benzoyl chloride, (VI) cinnamylideneacetyl chloride and carbethoxymethyl isocyanate, and (VII) cinnamylideneacetyl chloride and cinnamoyl chloride; partially hydrolysed polyvinyl alcohol with (VIII) cinnamylideneacetyl chloride and benzoyl chloride, (IX) cinnamylideneacetyl chloride and acetic anhydride, and (X) 7-phenyl-2,4,6-heptatrienoyl chloride and benzoyl chloride; hydrolysed ethylene-vinyl acetate copolymer with (XI) cinnamylideneacetyl chloride; partial polyvinyl butyral with (XII) cinnamylideneacetyl chloride; cellulose acetate with (XIII) cinnamylideneacetyl chloride; and hydroxyethyl cellulose with (XIV) cinnamylideneacetyl chloride.  In XIII and XIV, acetone is added to the solution of the product in pyridene, and the mixture poured into water to precipitate the product.  The polymers may be dissolved in solvents, e.g. methoxyethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, 2-butanone, 2,5-hexane-dione, cyclohexanone, benzene, toluene, chlorobenzene, chlorotoluene, methyl chloride and tetrachlorethane; together with antioxidants, e.g. hydroquinone and butylated hydroxyanisole; and sensitizers, e.g. Nphenylthioacridone, methyl(3-methyl-2-benzothiazolinylidene)-dithioacetate, 2,6-bis(p-anisyl)4-(p-n-amyloxyphenyl) thiapyrylium perchlorate, 2-benzoylmethylene-1-methyl-b -naphthothiazoline, 2,6-bis(p-ethyl-phenyl)-4-phenyl-thiapyrylium perchlorate, 2,6-bis(p-ethyl-phenyl)-4-(p-n-amyloxyphenyl)-thiapyrylium perchlorate and 2,6-bis(p-ethylphenyl)-4-(p-n-amyloxyphenyl)pyrylium perchlorate. The solutions may be used for coating substrates, e.g. aluminium, silicated grained aluminium, copper and polyethylene terephthalate sheets, to produce photoresist elements. Specifications 713,947, 717,708, 717,710, 717,711, 717,712 and 743,455 are referred to.