Patent GB-822861-A (GB)
Title: Process for the production of light-sensitive compounds
IPC: C08F8/30
Filed: 1957-01-11
Abstract: In a process for the production of compounds which are soluble in organic solvents and insolubilized by the action of light, b -aryl acrylic acid derivatives which contain at least one isocyanate group are reacted, at a temperature of up to 150 DEG  C., with compounds having groups which contain active hydrogen atoms, or b -aryl acrylic acid derivatives which contain at least one reactive hydrogen atom are reacted at a temperature of up to 150 DEG  C. with polyfunctional isocyanates, the reactants being so chosen that the products contain the b -aryl acrylic acid grouping at least three times in the molecule, the reaction in each case being terminated when all the isocyanate groups have reacted.  The term "b -aryl acrylic acid derivative" means a b -aryl acrylic acid in which the aryl radical, the carbon to carbon double bond and/or the carboxylic acid group can be substituted and also includes unsubstituted b -aryl acrylic acids. Examples of suitable b -aryl acrylic acid derivatives containing at least one isocyanate group are those of the formula <FORM:0822861/IV (a)/1> in which X is a CN, COOR, or CON(R1)2 group in which R1 is an alkyl or aryl radical which may contain one or more isocyanate groups, R2 is hydrogen, alkyl, aryl, alkoxy or halogen and R3 is hydrogen or one or more alkyl, alkoxy, halogen, nitro or isocyanate groups.  The isocyanate groups can also be present in a substituent on the benzene nucleus or in the alcohol component of the ester or the amine component of the acid amide.  Examples of such compounds are m- and p-isocyanatocinnamic acid alkyl esters, m-isocyanato-a -chlorocinnamic acid alkyl esters, o-methylcinnamic acid o -isocyanatoethyl ester, 3,31-diisocyanato-a -phenyl-cinnamic acid alkyl esters, b -(a -naphthyl)-acrylic acid o -isocyanatoethyl ester, p-isocyanatocinnamic acid nitrile, 3-nitro-4-isocyanatocinnamic acid dimethyl amide, and 3 - ethoxy - 4 - isocyanato - cinnamic acid dimethyl amide.  Also included are b -arylacrylic acid esters of polyhydric alcohols, e.g. the bis - (p - isocyanatocinnamic acid) glycol ester or the p-isocyanato-cinnamic acid ester of trimethylol propane and polyamides obtainable from cinnamic acid and polyamines, e.g. the compound obtained by reacting 2 mols. of p-nitrocinnamic acid chloride with 1 mol. of N,N1-dimethyl hexamethylene diamine, reducing the product and phosgenating to give the diisocyanate. Suitable b -aryl acrylic acid derivatives containing at least one active hydrogen are the esters, amides, hydrazides or nitriles of cinnamic acid such as compounds of the above formula in which X may additionally represent CONH or (R1)2, R1 is hydrogen or an alkyl or aryl radical which may contain substituents having active hydrogen, R2 is as above defined and R3 represents hydrogen or one or more alkyl, aryl, or alkoxy groups which have substituents with active hydrogen or halogen atoms or nitro, hydroxyl, amino, mercapto, carboxyl, carbonamido or sulphonamide groups.  The term "b -aryl acrylic acid derivatives" also includes: b -aryl acrylic acid esters of polyhydric alcohols provided the benzene nucleus has a substituent with active hydrogen; polyhydric alcohols partially esterified with a b -aryl acrylic acid; amides from b -aryl acrylic acid and polyamines; polyesters containing the b -aryl acrylic acid group; compounds of the above formula where R2 is -CR2=CR2-X.  The compound containing active hydrogen, and the polyisocyanate can be compounds of high molecular weight such as cellulose, starch, gelatine, partially esterified or etherified cellulose, polyesters, polyacrylic or methacrylic acid, polyvinyl ester saponification products, maleic anhydride/styrene copolymers.  High molecular weight compounds with isocyanate groups include reaction products of excess diisocyanates with trimethylol propane, polyesters, polyester amides, polyethers or thioethers, hydrogenated carbon monoxide/ethylene copolymers and also polymerized acrylic acid ethyl ester isocyanate and copolymers thereof.  Any groups with active hydrogen, especially OH groups in the product are preferably acylated or may be reacted with isocyanates, e.g. cyclohexyl or anthracene-2-isocyanate.  The products can be dissolved in formamide, dimethyl formamide, cyclohexanone, acetone, butyl acetate or hydrocarbons, or their halogen or nitro derivatives.  Dyes may be incorporated to increase their light sensitivity.  Examples describe the formation of photosensitive products by reacting (1) polyvinyl alcohol and p-isocyanotocinnamic acid ethyl ester; (2) starch and p-isocyanatocinnamic acid ethyl ester; (3) polyvinyl alcohol and cinnamic acid o -isocyanatoethyl ester; (4) pentaerythritol and cinnamic acid o -isocyanatoethyl ester; (5) p,p1-diisocyanatocinnamic acid glycol ester and glycol (or a diamine such as hexamethylene diamine); (6) m - isocyanatocinnamic acid methyl ester and a polyester from adipic acid, phthalic anhydride, trimethylol propane and butane diol; (7) trimethylolpropane monocinnamate and hexamethylene diisocyanate; (8) m-aminocinnamic acid ethyl ester and the reaction product of 1 mol. of trimethylol propane with 3 mols. of toluylene diisocyanate; (9) p-oxycinnamic acid ethyl ester and the copolymer of b -isocyanatoethyl methacrylate and vinyl acetate; (10) m-aminocinnamic acid ethyl ester and a copolymer of b -isocyanatoethyl methacrylate, styrene and maleic anhydride; (11) poly - b  - isocyanatoethyl methacrylate and cinnamic acid hydroxyethyl ester; (12) 1,4 - phenylene - bis-acrylic acid oxyethyl ester and 1,3-phenylene diisocyanate; (13) cinnamic acid-p-carboxylic acid bis-oxyethyl ester; (14) 1,3-phenylene diisocyanate and a mixture of cinnamic acid bis-oxyethyl ester and 1,4-phenylene bis-acrylic acid oxyethyl ester; (15) 1,3 - phenylene diisocyanate and a mixture of 1,4-phenylene bis-acrylic acid oxyethyl ester and terephthalic acid bis-oxyethyl ester; (16) 1,4-phenylene bis-acrylic acid oxypropylamide and 1,3-phenylene diisocyanate.  The products are used in the production of printing plates and printed circuits.ALSO:In a process for the production of compounds which are soluble in organic solvents and insolubilized by the action of light, b -aryl acrylic acid derivatives which contain at least one isocyanate group are reacted, at a temperature of up to 150 DEG  C., with compounds having groups which contain active hydrogen atoms, or b -aryl acrylic acid derivatives which contain at least one reactive hydrogen atom are reacted at a temperature of up to 150 DEG  C. with polyfunctional isocyanates, the reactants being so chosen that the products contain the b -aryl acrylic acid grouping at least three times in the molecule.  Typical b -aryl acrylic acid derivatives containing at least one isocyanate group are those of the formula <FORM:0822861/IV (a)/1> in which X is a CN, COOR1 or CON(R1)2 group, R1 is an alkyl or aryl group which may contain isocyanate substituents, R2 is hydrogen, alkyl, aryl, alkoxy or halogen and R3 is hydrogen or one or more alkyl, alkoxy, halogen, nitro or isocyanate groups.  Isocyanate groups can also be present in the benzene nucleus, in the alcohol portion of the ester or in the amine component of the acid amide.  Suitable b -aryl acrylic acid derivatives containing at least one active hydrogen are the esters, amides, hydrazides, or nitriles of cinnamic acid, such as compounds of the above formula in which X may also represent CONH.N(R1)2, R1 is H or an alkyl or aryl radical which may contain substituents having active hydrogen, R2 is as defined above and R3 represents one or more alkyl, aryl or alkoxy groups which have substituents containing active hydrogen or halogen atoms or nitro, hydroxyl, amino, mercapto, carboxyl, carbonamido or sulphonamido groups. "b -aryl acrylic acid derivatives" also includes b -aryl acrylic acid esters of polyhydric alcohols, amides from b -aryl acrylic acid and polyamines and compounds of the above formula where R3 is -CR2 = CR2-X.  In an Example (4) pentarerythritol is reacted with cinnamic acid o -isocyanato-ethyl ester.