Patent GB-827512-A (GB)
Title: Photopolymerisable compositions, ingredients therefor and processes for their production and use
IPC: G03F7/032
Filed: 1957-02-07
Abstract: A solid, transparent, photopolymerizable composition comprises (A) a polychelate of a polyvalent metal with a polyligand which polychelate may contain one or more vinylidene or vinylene groups; (B) optionally when the polychelate contains a vinylidene and of necessity when it does not, an addition polymerizable compound containing such a group; and (C) an addition polymerization initiator, actuatable by actinic light, the vinylidene group constituting at least 0.5% by weight of the composition.  The polychelates specified are of four main types: (a) linear saturated polychelates, e.g. the polymeric beryllium chelates of 4.4-bis (acetoacetyl) diphenyl ether and 1 : 8-bis (benzoylacetyl) octane; (b) cross-linked saturated polyesters, e.g. those described or whose precursors are described in Specifications 791,325 and 791,326 for instance polyvinyl alcohol acetoacetates chelated with aluminium or nickel and polyglycerol phthalate benzoyl acetates chelated with chromium or manganese; (c) vinylene containing polychelates, preferably chelate cross-linked, e.g. nickel or iron chelated with glycerol maleate benzoyl acetates and pentaerythritol citraconate phthalate acetoacetate; (d) vinylidene substituted polychelates preferably chelate cross-linked, e.g. polyvinyl acrylate acetoacetates chelated with aluminium, copper, iron and or chromium. Specified polymerizable compounds are unsaturated carboxylic acids, amides, sulphonic acids, carboxyaldehydes and ethers, vinyl esters and aldehydes of which many are specified, examples being acrylic and methacrylic acid, ethylene, diethylene glycol and glycerol diacrylates, vinyl benzoate, divinyl adipate, acrylamide acetaldehyde, a -phenyl acrolein and p-2(2-methoxyacryloyloxyethoxy) benzaldehyde.  Specified polymerization initiators are diacetyl, benzil, benzoin, pivaloin, benzoin methyl or ethyl ether, a -methyl benzoin, -alkyl benzoin and a -phenyl benzoin.  The Specification describes the making of polychelates and the polymerization of the unsaturated components on exposure to actinic light in the examples: (I) an unsaturated polyester is made from tetraethylene glycol, maleic anhydride and pentaerythritol and reacted with ethyl acetoacetate and dioxan to produce a polyester polyacetoacetate ligand which is mixed with dioxan, dimethylacrylate esters of a mixture of polyethylene glycols, tris (ethylacetoacetato) aluminium and benzoin methyl ether, cast on a glass plate and polymerized by exposure to actinic light; (II) methyl methacrylate, polymethyl methacrylate and benzoin are photopolymerized in a layer on polyvinyl butyral coated steel plates, and a film of the photo polymerizable composition of (I) cast thereon and photopolymerized; (III) a mixture of the unsaturated polyester polyacetoacetate ligand of (I), dialkyl phthalate, benzoin methyl ether, dioxan and tris (ethyl acetoacetato) aluminium is cast as a gel on glass and polymerized by actinic light; (IV) an unsaturated modified polyester prepared from diethylene glycol, glycerol, maleic acid and ethyl acetatoacetate is mixed with triallyl cyanurate, benzoin methyl ether, dioxan and tris (ethyl aceto acetato) aluminium, cast on to glass plates and photopolymerized; (V) a modified unsaturated polyester ligand as in (IV) is mixed with the dimethacrylate of mixed polyethylene glycols, dioxan, benzoin methyl ether and tris (ethyl aceto acetate) aluminium cast on to glass plates and photopolymerized with actinic light; (VI) the modified unsaturated polyester ligand as in (IV) is mixed with diallyl phthalate, benzoin methyl ether, dioxan and bis (butyl acetoacetato) nickel, cast on to glass plates and photopolymerized; (VII) dimethacrylate esters of polyethylene glycols, dioxan, benzoin methyl ether and tris (ethylacetoacetato) aluminium are mixed with ligands made from maleic acid, ethyl acetoacetate and (a) tetraethylene glycol and pentaerythritol; (b) and (c) diethylene glycol and glycerol; (d) diethylene glycol and pentaerythritol; and (e) and (f) propylene glycol, glycerol and phthalic acid, are cast into films and photopolymerized; (VIII) a saturated polyester from pentaerythritol, ethylene glycol and phthalic anhydride and containing free hydroxyl groups is modified with ethyl acetoacetate, reacted with methacryloyl chloride, mixed with benzoin methyl ether and tris (ethylacetoacetato) aluminium, cast on to glass plates and photopolymerized; (IX) an unsaturated polyester made from glycerol and maleic anhydride is modified with ethylacetoacetate, reacted with methacryloyl chloride, mixed with benzoin methyl ether, ethyl acetate and tris (ethylacetoacetato) aluminium, cast on to glass plates and photopolymerized; (X) pentarerythritol acetoacetate is mixed with a monomeric dimethacrylate of a mixture of polyethylene glycols, benzoin, methyl ether, dioxan and tris (ethyl aceto acetate) aluminium, cast on to a glass plate and photopolymerized; (XI) a polyester made from diethylene glycol, glycerol and maleic acid is mixed with diallyl phthalate, benzoin methyl ether, dioxan and tris (ethyl acetoacetato) aluminium, cast on to a glass plate and photopolymerized; (XII) the polyester of (XI) is mixed with a dioxan solution of 2 : 3-dihydroxy propyl methacrylate, tris (ethyl acetoacetato) aluminium and benzoin methyl ether, the mixture cast on to glass and photopolymerized.  Parts of the compositions not exposed to light may be dissolved out by suitable solvents leaving relief images.  In the examples, the solvents used are (I) acetyl acetone, (II) an ethyl acetate/ethanol/ethyl acetoacetate mixture, (III) to (IX) and (XI) and (XII) a mixture of ethyl acetate, ethanol and hydrochloric acid, and in (X) an ethyl acetate/ethanol/2 : 4-pentadione mixture.  The compositions which may contain transparent filters and reinforcing agents, e.g. silicas, bentonites and powdered glass and may be coated on suitable support materials, e.g. steel and aluminium plates, and polymer films, e.g. vinyl chloride polymers, copolymers of vinyl chloride or vinylidene, chloride with vinyl maleate, styrene, isobutylene and acrylonitrile and polyesters and polyamides, may be used in the production of relief images for printing. Specifications 741,294, 741,441, 741,470, 786,119, 802,853 and 815,277 also are referred to.