CURING COMPOSITIONS

Abstract: Two component curing compositions comprise a) a binder component comprising a polymerisable vinyl monomer, an organic acid, a peroxy polymerisation initiator and a high molecular weight polymer, and b) a hardener component comprising a polymerisable vinyl monomer, a thione polymerisation accelerator and a high molecular weight polymer.

Description: CURING COMPOSITIONS The present invention relates to two-component compositions having impmaeed curing properties. Conventional two-component adhesive compositions generally consist of a binder component comprising monomer and an initiator of polymerisation and a hardener component comprising a polymerisation accelerator. Each compenent is stable and has a mong shelf-life, but when mixed the combined effect of initiator and accelerator is to cause the polymerisation of the monomer. Such adhesive compositions have been successfully used where inlay a thin film of adhesive is required between the substrates to be joined, but have been unsatisfactory when applied to wide gaps. It has now been found that certain formulations have improved curing properties such that wide gaps may be bridged by adhesive. These formulations are also suitable for use as casting resins and fillers. Moreover the cured adhesive is colourless or only slightly coloured. Accordingly the present invention provides a twocomponent composition comprising: a binder component comprising: a polymerisable vinyl monomer, an organic acid, a peroxy polymerisation initiator, and a high molecular weight polymer; and a hardener component comprising: a polymerisable vinyl monomer, a thione polymerisation accelerator, and a high molecular weight polymer. The two component compositions may be formulated for use as, for instance, an adhesive, filler or casting material. Preferably it is formulated for use as an adhesive. The polymerisable vinyl monomer may be any vinylic compound capable of polymerisation in the presence of a peroxy initiator and a thione accelerator of polymerisation or a mixture of such vinylic compounds. Preferably the polymerisable:vinyl monomer is a mixture comprising a major proportion of a monofunctional vinyl monomer and a minor proportion of a di-,tri- or polyfunctional vinyl monomer. Suitable vinyl monomers include various acrylate esters, for example: methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, methyl acrylate1 ethyl acrylate, butyl methacrylate, cyclorhexyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, butyl acrylate1 cyclehexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate and itaconic acid; ethylene glycol and higher glycol acrylate and methacrylate esters; acrylamide and methacrylamide; halogenated monomers, such as vinylidene chloride, ortst} chlorostyrene, 2, 3-dichloro-l,3-butadiene and 2-chloro 1,3-butadiene; styrene and mono and polyalkylstyrenes such as methyl styrene, dimethyl styrene, ethyl styrene and t-butyl styrene. Preferred vinyl monomers include lower alkyl acrylates and lower alkyl methacrylates, and tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Suitable mixtures of vinyl monomers comprise at least 30% of a monofunctional vinyl monomer, preferably about 60 to 80% of a monofunctional vinyl monomer. Suitable di-, tri- and polyfunctional vinyl monomers include ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, tetramethyleneglycol diacrylate, di {pentamethyleneglycol7 dimethacrylate tetraethyleneglycol diacrylate, tetraethyleneglycol di(chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, butyleneglycol dimethacrylate, neopentylglycol diacrylate and trihydromethylpropyl triacrylate. Preferred di-, tri-and polyfunctional vinyl monomers include ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, 1,3- and 1,4-butanediol methacrylate. Suitable organic acids include, for example, methacrylic acid, acrylic acid, crotonic acid, maleic acid, itaconic acid, p-toluenesuiphonic acid and ascorbic acid. Preferred organic acids include methacrylic and acrylic acids. Suitable peroxy polymerisation initiators include organic peroxides, hydroperoxides, peresters and peracids, such as cumene hydroperoxide, benzoyl peroxide, acetyl peroxide, t-butyThydropervxide.,., lauroylperoxide, methylethyl ketone peroxide, t-butylperbenzoate, di-t-butylperoxide, di-t-butyldiperphthalate and t-butylperacetate. Preferred peroXy initiators of polymerisation include cumene hydroperoxide, Suitable thione polymerisation accelerators include thiourea and derivatives thereof such as ethylene thiourea, diphenyl thiourea, trimethyl thiourea, tetramethyl thiourea, and tributyl thiourea and thioketones such as tetrahydro-3,5-dimethyl-4-H-1,3,5-oxadiazin-4-thione. Preferred thione polymerisation accelerators include tetramethyl thiourea, tetrahydro-3,5-dimethyl-4-H-1,3,5- oxadiazine-4-thione and tributyl thiourea. Suitable high molecular weight polymers include, for example, acrylonitrile-butadiene rubber, polychloroprene rubber acrylonitrile-butadiene-styrene resin and polymethyl methacrylate. These may be used singly or admixed as desired to achieve the required properties of hardness, resilience etc in the cured adhesive. The high molecular weight polymer or mixture of such polymers is conveniently the same in both the binder and hardener components, but this is not essential and the high molecular weight polymer or polymer mixture may be different in the two components. Suitably the binder component comprises from 50 to 90fi0 W/W, preferably 55 to 65% W/W of the polymerisable vinyl monomer, from I to 12% W/W,cpreferably 5 to 8; W/w of the organic acid, from 0.5 to 10% w/w, preferably 2 to 6% W/W of the peroxy polymerisation initiator and from 5 to 40 fiO W/W, preferably 10 to 25% W/W of the high molecular weight polymer. Suitably the hardener component comprises from 50 to 80% w/w, preferably 60 to 75% W/w of polymerisable vinyl monomer, from 1 to 10% W/W, preferably 3 to 6% W/W, of the thione polymerisation accelerator and from 5 to 40 /0 W/W, preferably 10 to 250/d W/W of the high molecular weight polymer. Either dr both components may additionally comprise non-essential accesory ingredients such as thickeners, pigments, fillers, perfumes and shelf-life stabilisers, A suitable shelf-life stabiliser is hydroquinone. Advantageously a redox indicator, having EO from above + 0.01 to below + 0.76 volts and g from 13.5 to 28, may be included in either or both components, such indicators display a change from one colour to another, or from coloured to colourless when the admixed components have polymerised to the extent that the composition is no longer workable, thus affording an objective assessment of the processing time of the composition. Suitable indicators include thionine, 2,6-dichloro-N (4-hydroxyphenyl) - 1 , 4-benzoquinonimine, m-cresolindophenol and thymolindophenol and alkali metal salts, especially the sodium salts thereof. Suitably the, or each component comprises from 0.005 to Q.1% W/W, preferably about 0.01 to 0.02% W/W of such an indicator. Each component may be produced by conventional methods known in the adhesives art, for instance by mixing with high or low shear mixers or in kneters. Suitably the binder component is produced by dissclving the high molecular weight polymer in the vinyl monomer. The other ingredients except the initiator are then added and mixed thoroughly. The mixture is cooled to 25 C or below and, finally, the initiator is added and mixed in thoroughly. The product can be filled into conventional containers such as tubes or cans. The same procedure is recommended for producing the hardener component except that the cooling and addition of initiator is, of course, omitted. In use the two components may be admixed and then applied to one or both substrates to be joined. Alternatively, when both substrates are to be joined one component may be applied to the first substrate; and the other component to the second substrate. The two substrates are then brought into contact and maintained in the necessary relative positions whilst the adhesive cures. The present invention further provides a process for joining two substrates which process comprises applying a two component composition as hereinbefore defined, to one or both substrates and bringing the substrates into contact. Suitably the process comprises admixing the two components and applying the mixture to one or both substrates. Alternatively the process comprises applying one component to a first substrate and the other component to a second substrate, then bringing1 the substrates into contact. The present invention also provides a process for filling spaces or casting in a mould which comprises admixing the two components of a two component composition as hereinbefore defined and applying the mixture to the space to be filled or packing the mould with the mixture. The present invention will now be illustrated in the following examples, which are not intended to limit the scope of invention in any way. Examples Twn-component adhesives were prepared by conventional methods according to the following table: Component A (Binder) Ex.l 2 3 Methyl methacrylate 50,00 64,75 43,5 Ethyleneglycol dimethacrylate 3,45 - 5,0 Methacrylic acid 7,76 3,00 2,0 Cumene hydroperoxide 6,90 3,00 3,0 Luperox 101 - 4,50 7,0 Plexigum M 286 30,17 Degalan LP 87/09 - 6,75 4,5 Hycar 1072 - 7,50 7,0 Toyolac 900/110 - 8,00 5,5 Experimental Resin QM 657 - - 20,0 Wacker HDK V15 1,29 1,50 1,5 Jonol 0.43 1,00 1,0 Component B (Hardener) Methyl methacrylate 68,00 63,5 33,0 2-Hydroxyethyl methacrylate 8,00 Tetrahydrofurfuryl methacrylate - 7,5 7,0 Ethyleneglycol diethacrylate - - 5,0 N-Vinylpyr rolidone - - 32,0 Tetramethylthiourea - 2,5 Tetrahydro-3,5-dimethyl-4-H-1,3, 7,00 - - 5-oxadiazine-4-thione Ethylenethiourea - - 1,0 Hycar 1072 8,00 - - Degalan LP 87/09 7,00 13,5 20,0 Heyplast AC 3452 - 5,0 Experimental Resin QM 657 - 5,0 Jonol - 2,0 1,0 Wacker HDK V15 2,0 1,0 1,0 Plexigum M 286 = Rohm Gmbh (a trade name for an acrylic resin) Jonol = Shell (2,6-Di-tert.-butyl-4- methylphenol) Wacker HDK V 15 = Wacker (silicic acid) Hycar 1072 = Goodrich ((acrylonitrile rubber) Degalan LP 87/09 = Degussa (acrylic resin) Exp.Resin QM 657 = Rohm & Haas (methacrylicallylic-resin) Toyolac 900/110 = Nordmann & Rapmann (ABS-resin) Luperox 101 = Luperox Gmbh (2,5-dimethyl-2,5-bis (t-butylperoxy)-hexan) Heyplast AC 3452 = Goodrich (acrylonitrile rubber)

Claims: CLAIMS 1. A two component curing composition comprising a) a binder component comprising a polymerisable vinyl monomer, an organic acid, a peroxy polymerisation initiator and a high molecular weight polymer, and b) a hardener component comprising a polymerisable vinyl monomer, a thione polymerisation accelerator and a high molecular weight polymer. 2. A two component adhesive composition as claimed in claim 1. 3. A composition as claimed in claim 1 or claim 2 wherein one or both of the binder and hardener components comprise a mixture of a major proportion of a mono functional vinyl monomer and a minor proportion of a di-, tri- or polyfuntional vinyl monomer. 4. A composition as claimed in any one of claims 1 to 3 wherein the vinyl monomer is selected from methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, butyl methacrylate, cyclohexyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate and itaconic acid, ethylene glycol, higher glycol acrylate and methacrylate esters, acrylamide, methacrylamide, vinylidene chloride, chlorostryrene, 2, 3-d ichloro-l, 3-butadiene, 2-chloro-1,3-butadiene, methyl styrene, dimethyl styrene, ethyl styrene and t-butyl styrene, ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, tetramethyleneglycol diacrylate, di (pentamethyleneglycol) dimethacrylate, tetraethyleneglycol diacrylate, tetraethyleneglycol di (chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, butyleneglycol dimethacrylate, neopentylglycol diacrylate and trihydromethylpropyl triacrylate. 5. A composition as claimed in any one of claims 1 to 4 wherein the organic acid is selected from methacrylic acid, acrylic acid, crotonic acid, maleic acid, itaconic acid, p-toluenesulphonic acid and ascorbic acid. 6. A composition as claimed in any one of claims 1 to 5 wherein the peroxy polymerisation initiator is selected from cumene hydroperoxide, benzoyl peroxide, acetyl peroxide, t-butylhydroperoxide, lauroylperoxide, methylethyl ketone peroxide, t-butylperbenzoate, di-t butylperoxide, di-t-butyldiperphthalate and t-butylperacetate. 7. A composition as claimed in any one of claims 1 to 6 wherein the thione polymerisation accelerator is selected from ethylene thiourea, diphenyl thiourea, trimethyl thiourea, tetramethyl thiourea, and tributyl thiourea and tetrahydro-3,5-dimethyl-4-H 1,3,5-oxadiazin-4-thione. 8. A composition as claimed in any one or claims I to 7 wherein the high molecular weight polymer is selected from acrylonitrile-butadiene rubber, polychloroprene rubber acrylonitrile-butadiene-styrene resin and polymethyl methacrylate. 9. A composition as claimed in any one ot claims I to 8 wherein the binder component comprises trom 5U to 908 w/w of polymerisable vinyl monomer, from 1 to 12% w/w of the organic acid, from 0.5 to 10% w/w ot the peroxy polymerisation initiator and from 5 to 40% w/w of the high molecular weight polymer and the hardener component comprises trom 3U to 80% w/w of polymerisable vinyl monomer, from 1 to 10% w/w of the thione polymerisation accelerator and trom 5 to 40% w/w of the high molecular weight polymer. LO. A process tor producing a composition as claimed in claim I which process comprises bringing into association the ingredients of each component.

Inventors: GOLLUB, HANS JUERGEN, HECHENBERGER, DIETER ANTON
Applicants: LINGNER AND FISCHER GMBH
Application year: 1982
Main classification: C09J3
IPC codes: C08L51, C08L33, C09J4, C08L7, C08F246, C08L21