NZ232533A - Cement compositions containing an organic polyisocyanate and a terpineol - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £32533 / t* 23253 \ r% © priority Oate(s)'* ;i.

P,c citication PUecl -cr: Spe cq:&fc-.«••••• 2, V ,Vi I :*. >>s: (&>.•••—" , ' Cfc.^-si,"f I ".bilcatlon 0*« -££2 No.': Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION RAPIDLY CURING CEMENT COMPOSITION COMPRISING TERPINEOL CORE RETARDANT o XI We, IMPERIAL CHEMICAL INDUSTRIES PLC, a British company, of Imperial Chemical House, Millbank, London SW1P 3JF, United Kingdom, hereby declare the invention for whichxI^ we pray that a patent may be granted to fS£/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page 1A) 7 C j^5 -lA- S 35142 RAPIDLY CURING CEMENT COMPOSTION COMPRISING TERPINEOL CURE RETARDANT Cement compositions which are capable of rapid curing such that they may be applied and used as flooring within a short period of time (typically of less than one day) have been described in the prior art. Thus UK Patent 1,192,864 describes rapidly curing cement compositions containing as essential elements an hydraulic cement, a silica filler, water and an organic compound containing a plurality of isocyanate groups. Such compositions generally further comprise an isocyanate-reactive organic compound which is typically a polyhydroxy-substituted compound. These cement compositions set very quickly and make it possible to provide a new flooring or wall surface with only a minimum of delay between the laying of the surface and the bringing of it into use.

Unfortunately, while such compositions set very rapidly and make it possible to obtain floors which are sufficiently stable to walk upon within 1 or 2 hours after laying, as noted in UK Patent 1,346,300 (at page 4, column 10) such very rapid setting can be disadvantageous. Specifically, these compositions may set so rapidly after being mixed that there may not be sufficient time to spread such composition after the mixing of the components thereof is complete. Moreover, the reaction of the isocyanate with water will liberate carbon dioxide gas. If such gas cannot be properly released or absorbed due to premature setting, the resulting cement may become pitted or cracked.

UK Patent 1,346,300 proposes to cure this problem by adding an effective amount of a cure retardant which is a monocarboxylic acid, a monohydric alcohol or an epoxy compound. However, the use of the monocarboxylic acids described (e.g., linoleic acid, oleic acid, stearic acid and the like) is undesirable because such compounds will preferably react with lime (which is generally present in the cement component) and will thus not be able to effectively perform their chain termination function. Moreover, the use of the monohydric alcohols disclosed in such specification is undesirable as such aliphatic alcohols are in general either highly S 35142 volatile (such as methanol, propanol, butanol and the like) and could thus present hazards during application; possess undesirable aesthetic qualities (such as octanol, nonanol and the like); or are so highly viscous (such as decanol, dodecanol and the like) that they can adversely interfere with the pourability and spreadability of the cement composition. The use of the epoxy compounds described is not always desirable as such epoxy compounds frequently contain some amounts of impurities which may create a potential health hazard unless strict precautions are observed.

Consequently, it would be desirable to possess an effective cure retardant for such rapidly curing cement compositions, which retardant which would not present a health hazard, had a pleasant aesthetic effect, and which would not adversely interfere with the pourability or spreadability of the cement composition.

It has now been unexpectedly found that terpineols, such as that contained in pine oil, exhibit admirable properties in rapidly curing cement compositions such as those described in UK Patent 1,192,864. In addition to possessing the above-desired qualities, terpineols have the added effect that they possess antimicrobial activity -- an advantage for laying floors in areas such as pharmaceutical or food production facilities where a germ-free environment is necessary.

Accordingly, in one aspect, the present invention is directed to a rapidly curing cement compostion comprising: (a) an hydraulic cement; (b) a filler; (c) an organic polyisocyanate ; (d) a terpineol; and (e) water.

In another aspect, this invention relates to a process for rapidly producing a cement surface, said process comprising the steps Of: (A) forming a cement composition by blending: (a) an hydraulic cement; (b) a filler; N.2. PATEMTCFF'C? ' -3- S 35142 (c) an organic polyisocyanate; (d) terpineol; and (e) water; (B) applying the blend of step (A) to form a surface; and (C) allowing said surface to harden.

The terpineol component may be added in a pure form or in the form of a mixed terpineol/hydrocarbon blend, such as pine oil. The terpineol is present in a cure-retardant effective amount, i.e., an amount sufficient to slow down the curing of the composition such that any damage resulting from entrapped gas (such as pitting or cracking) due to premature setting is reduced. This amount can be easily determined by one of ordinary skill in the art.

The effect of adding terpineol can be determined by comparison of the working life of the composition containing terpineol relative to the working life of a similar composition which is free from added terpineol. The working life can be determined as described in Note (a) to Table One or by any other suitable method. The cure-retardant effective amount of terpineol should be sufficient to increase the working life of the composition by at least 252 relative to the working life in the absence of terpineol. Preferably, the cure-retardant effective amount is sufficient to increase the working life of the composition by at least 50Z and especially by at least 100Z.

To achieve the desired increase in the working life of the composition, the weight ratio of the organic polyisocyanate to terpineol is preferably not greater than about 30:1, for example in the range 30:1 to 3:1.

Because of the desirable properties of terpineol (which include low volatility, good flow characteristics, biocidal activity and a pleasing aesthetic effect), the compositions of this invention are unexpectedly superior to known compositions, for example those containing aliphatic alcohols or epoxy compounds.

As is employed herein, the term "hydraulic cement" is used in its usual sense to denote the class of structural materials which are applied in admixture with water and thereafter harden or set as a result of physical or chemical changes which consume the water present. As well as Portland cement, this term includes: S 35142 1. Rapid hardening cements, as characterised by those with high alumina contents. 2. Low-heat cements, as characterised by high percentages of dicalcium silicate and tetracalcium alumino ferrite and low percentages of tricalcium silicate and tricalcium aluminate. 3. Sulphate-resisting cements as characterised by unusually high percentages of tricalcium silicate and dicalcium silicate and unusually low percentages of tricalcium aluminate and tetracalcium alumino ferrite. 4. Portland blast-furnace cement as characterised by a mixture of Portland cement clinker and granulated slag.

. Masonry cements as characterised by mixtures of Portland cement and one or more of the followings: hydrated lime, granulated slag, pulverised limestone, colloidal clay, diatomaceous earth or other finely divided forms of silica, calcium stearate and paraffin. 6. Natural cements as characterised by material obtained from deposits in the Lehigh Vally, USA. 7. Lime cements as characterised by oxide of calcium in its pure or impure forms and whether containing or not some argillaceous materials. 8. Selenitic cement as characterised by the addition of 5 102 of plaster of Paris to lime. 9. Pozzolanic cement as characterised by the mixture of pozzolana, trass kieselguhr, pumice, tufa, santorin earth or granulated slag with lime mortar.

. Calcium sulphate cements as characterised by those depending on the hydration of calcium sulphate and including plaster of Paris, Keene's cement and Parian cement.

The preferred hydraulic cement is Portland cement. There may also be used white Portland cement which is a cement of low iron and carbon content manufactured from specially selected ingredients.

As examples of fillers which may be used as component (b) of the compositions of this invention there may be mentioned siliceous fillers such as sand and gravel having a low clay content, preferably washed and having a particle size in the range of from 0.076 mm to 4 cm in diameter. r, -? r • • J <l 5 j -5- S 35142 These materials may be in their natural state or they may be artificially coloured, for example, by application of a dyestuff or pigment. Fragments of glass, which may be clear, translucent or opaque, colourless or coloured, are also suitable. Other fillers which may be used are materials which have a low density compared with the siliceous fillers mentioned above, for example, fragments of colourless or mass-pigmented plastic in the form of chips, turningss tape or granules, conveniently the plastic waste resulting from the trimming of injection moulded articles or from other moulding processes. Suitable plastic materials are thermoplastic or thermosetting polymers and copolymers, for example, nylon polymers, polyvinyl chloride, vinyl chloride/vinyl acetate copolymers, urea/formaldehyde polymers, phenol/formaldehyde polymers, melamine/formaldehyde polymers, acetal polymers and copolymers, acrylic polymers and copolymers, acrylonitrile/butadiene/styrene terpolymers, cellulose acetate, cellulose acetate butyrate, polycarbonates, polyethylene terephthalates, polystyrenes, polyurethanes, polyethylenes, and polypropylenes.

There may also be used foamed plastics such as polystyrene foam and polyurethane foam, sawdust, wood chips, pumice, vermiculite and fibrous materials of natural or synthetic origin, for example, glass fibre, cotton, wool, polyamide fibre, polyester fibre, and polyacrylonitrile fibre.

By the use of low density fillers the overall density of the cured products resulting from the compositions of the present invention may be greatly reduced. Fillers having a fine particle size, by which is meant in the range from 75 microns to 1 micron, may also be used, and as examples of such materials there may be mentioned power station fly ash, expanded clay, foamed slag, mica, chalk, talc, clays such as china clay, barytes, silica, and powdered slate, reduced to the required degree of subdivision where necessary by grinding, milling , micronising or other suitable means.

S 35142 Other suitable fillers include an aluminium silicate refractory aggregate made by high temperature calcination of a china clay specially selected for low alkali content, and obtainable commercially under the name "Molochite" (Registered Trade Mark); also crushed mineral aggregates manufactured from blue flints obtained from deposits in the Thames Valley and available commercially under the name "Flintag" (Registered Trade Mark) and multicoloured calcined flints.

The organic polyisocyanate, component (c), may comprise a simple polyisocyanate or it may comprise an isocyanate-terminated prepolymer obtained by the reaction of an excess of a simple polyisocyanate with a hydroxyl-terminated polyether, polyester or polyesteramide.

As examples of polyisocyanates there may be mentioned aliphatic diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl hexamethylene diisocyanates; aromatic diisocyanates such as tolylene- 2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4, 4'-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, and 4,4'-diisocyanato -3,3'-dimethydiphenyl; diphenylether diisocyanates; and cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanates, methylcyclohexylene diisocyanates and 3-isocyanatomethyl -3,5,5-trimethylcyclohexyl isocyanate. Triisocyanates which may be used include aromatic triisocyanates such as 2,4,6-triisocyanato-toluene and triisocyanatodiphenyl ether. Examples of other suitable organic polyisocyanates include the reaction products of an excess of a diisocyanate with simple polyhydric alcohols such as ethylene glycol, 1.4-, 1,3-, and 2,3,- butanediolS, diethylene glycol, dipropylene glycol, pentamethylene glycol, hexamethylene glycol, neopentylene glycol, propylene glycol, glycerol, hexanetriols, trimethylol-propane, pentaerythritol and low molecular weight reaction products of the above polyols with ethylene oxide or propylene oxide. 232533 -7- S 35142 There may also be used uretedione dimers and isocyanurate polymers of diisocyanates, for example, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate and mixtures thereof, and the biuret polyisocyanates obtained by the reaction of polyisocyanates with water.

Mixtures of polyisocyanates may be used, including the mixtures obtained by the phosgenation of the mixed polyamines prepared by the reaction of formaldehyde with aromatic amines such as aniline and ortho-toluidine under acidic conditions. An example of the latter polyisocyanate mixture is that known as crude MDI, which is obtained by phosgenation of the mixed polyamines prepared by the reaction of formaldehyde with aniline in the presence of hydrochloric acid and which consists of diphenylmethane-4,U'-diisocyanate in admixture with isomers thereof and with methylene-linked polypheny1 polyisocyanates containing more than two isocyanate groups.

Examples of suitable hydroxyl terminated polyesters and polyesteramides of use in the preparation of prepolymers (mixtures of polyesters and polyesteramides may be used if desired) are those obtained by known methods from carboxylic acids, glycols and, as necessary, minor proportions of diamines or aminoalcohols. Suitable dicarboxylic acids include succinic, glutaric, adipic, suberic, azelaic, sebacic, phthalic, isophthalic and terephthalic acids and mixtures of these. Examples of dihydric alcohols include ethylene glycol, 1:2-propylene glycol, l:3-butylene glycol, hexamethylene glycol, decamethylene glycol and 2:2-dimethyltrimethylene glycol. Suitable diamines or amino-alcohols include hexamethylene diamine, ethylene diamine, mono-ethanolamine and phenylenediamines. Small proportions of polyhydric alcohols such as glycerol or trimethylolpropane may also be used, in which case branched polyesters and polyesteramides are obtained.

S 35142 As examples of hydroxyl—terminated polyethers which may be reacted with an excess of an organic polyisocyanate as defined above to form a prepolymer there may be mentioned polymers and copolymers of cyclic oxides, for example l:2-alkylene oxides such as ethylene oxide, epichlorohydrin, 1:2-propylene oxide, l:2-butylene oxide and 2:3-butylene oxide, oxacyclobutane and substituted oxacyclobutanes and tetrahydrofuran. There may be mentioned polyethers obtained by the polymerisation of an alkylene oxide in the presence of a basic catalyst and water, glycol or a primary monoamine. Mixtures of such polyethers may be used.

Other prepolymers which may be used in the compositions of the present invention are those obtained by reacting a coal tar pitch which contains isocyanate-reactive groups with an excess of an organic polyisocyanate, for example, one or more of the organic polyisocyanates defined above, optionally together with an organic compound containing isocyanate-reactive groups such as the polyesters, polyesteramides and polyethers defined above.

In addition to the hydraulic cement, filler, organic polyisocyanate, terpineol and water, the compositions of this invention preferably further comprise an isocyanate-reactive organic compound.

Such isocyanate-reactive organic compounds include any of the hydroxyl-terminated polyethers, polyesters or polyesteramides disclosed above as being suitable for the preparation of isocyanate-terminated prepolymers and also the simple polyhydric alcohols containing from 2 to 6 carbon atoms and from 2 to 4 hydroxyl groups and the low molecular weight reaction products thereof with ethylene oxide or propylene oxide.

Further, other isocyanate-reactive organic compounds which may be used include aminoalcohols such as monoethanolamine, polyamines, such as ethylene diamine, hexamethylene diamine, m- and p-phenylene diamines and 2,4- and 2,6-diaminotoluenes, epoxy resins which also contain isocyanate-reactive groups, for example, the f ! i ■ ; S 35142 hydroxyl group-containing products obtained by reaction between diphenylolpropane and epichlorohydrin, drying oil and non-drying oil modified alkyd resins, castor oil, hydrogenated castor oil, urethane oils, which are the reaction products of diisocyanates with the alcoholysis products of the drying oil, for example, mono- or di-glycerides from linseed oil, and urethane alkyds, which are alkyd resins in the manufacture of which a part of the phthalic anhydride has been replaced by diisocyanate.

A further isocyanate-reactive resin which may be present in the compositions of this invention is that obtained by the high temperature reaction of castor oil with a complex resin obtained by reacting together natural rosin, glycerol and a resol resin at a high temperature. The castor oil and complex resin may be reacted in the proportions from 95:5 to 20:80 parts by weight, preferably at a temperature from 230° to 250°C for a time of from % to 2 hours. Typically, castor oil and the complex resin in the proportion of 4:1 by weight are heated together at a temperature of approximately 240°C for about 45 minutes. Most preferably to prepare a complex resin, natural rosin (colophony), glycerol and the resol (which is preferably prepared by the condensation of 1 mole of diphenylolpropane with approximately 4 moles of formaldehyde under aqueous alkaline conditions at moderate temperatures) in the proportions of about 8.2:1.1:1.0 by weight are heated at a temperature of up to 275°C in an inert atmosphere until the acid value is less than 20 mg KOH/g. The use of such a castor oil rosinate or castor oil is beneficial as the resultant compositions may be organic solvent free without the necessity of adding water soluble polymeric isocyanate-reactive organic compounds and the large amount of additional cure retardants required thereby.

In addition, the isocyanate-reactive compound component of the composition of this invention, may comprise a water-soluble, isocyanate-reactive polymer such as a derivative of cellulose, for example, alkyl, hydroxyalkyl, carboxyal kyl and alkyl hydroxy a 1 kyl ethers of cellulose such as methyl cellulose, ethyl cellulose, hydroxy ethyl cellulose, sodium carboxymethyl cellulose, methyl -7 O <: d l j -10- S 35142 hydroxypropyl cellulose, ethyl-hydroxypropy 1 cellulose, ethyl-hydroxyechyl cellulose, methyl — hydroxyethyl cellulose and sodium methyl-carboxymethyl cellulose. There may also be used polyvinyl alcohols, polyoxyethylene glycols, the water-soluble polyoxyethylene/oxypropylene glycol block copolymers obtained by the addition of ethylene oxide to polyoxypropylene glycols (obtainable commercially under the name "Pluronic" (Registered Trade Mark)), low molecular weight initial stage condensation products or prepolymers of formaldehyde with melamine, urea, amides, carbamate, urons, ureins, ureides, imidazolidinones, pyrimidinones and triazinones and the lower alkyl ethers of such initial stage condensation products in which the alkyl groups contain from 1 to 3 carbon atoms, for example, methylated polymethylol melamine/urea, dimethylol and diethylol ethylene urea and dihydroxy dimethylol and diethylol ethylene urea resin precondensates. There may also be used polyvinyl pyrrolidone and water-soluble addition products of ethylene oxide with fatty alcohols and alkyl phenols such as cetyl alcohol, oleyl alcohol and mixtures thereof, octyl phenol and nonyl phenol.

While a terpineol should comprise the major proportion (that is at least 50 percent by weight) of the chain-terminating component, monohydric alcohols, monocarboxylic acids, or compounds containing at least one epoxy group may additionally be employed.

As examples of monohydric alcohols which may be used in the compositions there may be mentioned methanol, ethanol, propanol, butanol, hexanol, isooctanol, nonanol, decanol, dodecanol, cetanol, unsaturated alcohols such as allyl alcohol and propargyl alcohol and the polyether alcohols obtained by the interaction of alkylene oxides, for example, ethylene oxide and/or propylene oxide, with monohydric alcohols.

Monocarboxylic acids which may be used in the compositions include, for example, the acids obtainable by oxidation of any of the above-mentioned monohydric alcohols which contain two or more carbon atoms, the mixed fatty acids derived from any of the oils mentioned below and also elaeostearic, linolenic, linoleic, oleic and stearic acids. 23253 -11- S 35142 As examples of compounds which contain at least one epoxy group per molecule there may be mentioned epoxidised oils, such as those derived from rape seed, tobacco seed, soya bean, safflower, sunflower seed, grape seed, niger seed, poppy seed, hemp seed, candle nut, rubber seed, linseed, perilla, stillingia, chia, corophor, tung, oiticica, Japanese wood, poyok, soft lumbang, castor, dehydrated castor, tall and fish oil. There may be used the products obtained by first esterifying the mixed fatty acids, obtainable from the above-mentioned oils by saponification, with monohydric alcohols, diols or polyols of higher functionality and then epoxidising the mixed esters so obtained. As further examples of compounds containing epoxy groups which may be used in the compositions of the present invention there may be mentioned the bisepoxy compounds derived from diphenylolpropane and epichlorohydrin, as well as those which contain at least one epoxycyclohexane or epoxycyclopentane group. A further epoxy-compound which may be used is the product available commercially as "Cardura E", which is the glycidyl ester of the synthetic resin "Versatic 911" ("Cardura" and "Versatic" are Registered Trade Marks).

The compositions of this invention may also comprise effective amounts of a plasticiser such as dibutyl phthalate, dinonyl phthalate, butyl benzyl phthalate, tricresyl phosphate, tritolyl phosphate, tri-(2-chloroethyl) phosphate and chlorinated hydrocarbons such as those sold under the name "Cereclor" (Registered Trade Mark).

If desired, the compositions according to the present invention may also contain bitumen (by which is meant the residue from the distillation of crude petroleum and which is essentially aliphatic in nature and substantially free from isocyanate-reactive groups), which in general improves flexibility and water resistance. Coal tar pitches may also be added to the compositions. 2&Z5 33 In general, although polyisocyanate and water are present together in the compositions of this invention, foaming does not occur because the cement is present in sufficient amount and is basic enough to absorb the carbon dioxide which is liberated when isocyanates react with water. Should the composition be such that it has a tendency to foam, then this tendency can be minimised by incorporating into the composition an effective amount of an antifoaming agent, such as a basic compound of a metal selected from Groups I to IV inclusive of the Periodic Table (as set out on the inside back cover of the book "Advanced Inorganic Chemistry" by Cotton and Wilkinson, 2nd Edition, published 1966 by Interscience Publishers.) Such basic compounds may be oxides, hydroxides, basic salts, complex salts or double salts of metals and as examples there may be mentioned calcium oxide, magnesium oxide, barium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, cadmium hydroxide, calcium silicate, barium silicate, sodium silicate, lead hydroxide and basic lead acetate. Other antifoaming agents which may be employed include siloxanes such as poly (siloxane), poly (alkylsiloxanes) and poly (dialkylsiloxanes).

The compositions may also contain, if appropriate, an effective amount of a cure accelerator which is known to increase the rate of reaction between isocyanate groups and hydroxyl groups. Suitable accelerators include, for example, organometallic compounds, metal salts and tertiary amines, specific examples of which are dibutyl tin dilaurate, tetrabutyl titanate, zinc octoate, zinc naphthenate, stannous octoate, stannic chloride, ferric chloride, lead octoate, potassium oleate, cobalt 2-ethylhexoate, N,N-dimethylcyclohexy-lamine, N,N-dimethylbenzylamine, N-ethylmorpholine, 1,4-diazabicyclo-2,2,2-octane, 4-dimethylaminopyridine, oxypropylated triethanolamines, beta-diethylaminoethanol and N,N,N',N*,-tetrakis (2-hydroxypropyl)ethylenediamine. 2325 33 -13- S 35142 Moreover, the composition of this invention may be formed into elements having a Terrazzo-like decorative effect by either (1) incorporating any filler (whether silica or otherwise) which is in the form of coarse particles into the above-mentioned compositions and, after spreading the composition, grinding or otherwise treating the surface to expose the particles of filler; or (2) by first bonding coarse particles of plastics or other material to the substrate, filling in between the bonded particles with the above-mentioned composition, and grinding the surface to expose the particles of material.

The particles employed for such Terrazzo-effeet uses may be in the form of mass-pigmented plastic fragments of thermoplastic or thermosetting polymers or copolymers, for example, nylon polymers, polyvinyl chloride, vinyl chloride/vinyl acetate copolymers, urea/formaldehyde polymers, phenol/formaldehyde polymers, melamine/formaldehyde polymers, acetal polymers and copolymers, acrylic polymers and copolymers, acrylonitrile/butadiene/styrene terpolymers, cellulose acetate, cellulose acetate butyrate, polycarbonates, polyethylene terephthalates, polystyrene, polyurethanes , polyethylenes and polypropylenes.

The mass-pigmented plastics may be in the form of chips or turnings and are conveniently the plastic waste resulting from the trimming of injection moulded articles or from other moulding processes.

Other particles which may be used include materials selected from glass and stone fragments and stone aggregate. The glas9 fragments may be colourless or coloured. The stone, either in the form of fragments or aggregate, may be used in its natural colour or it may be artificially coloured, for example, by the application of a dyestuff or pigment to the surface. Provided that the compositions which are obtained by using these artificially coloured materials are only lightly ground, the surface colouring remains essentially intact. 232533 S 35142 Colourless plastics fragments may also be used as the filler. By fragments or particles is meant those materials having a particle size not less than about 250 microns.

There may also be used in any of the formulations of this invention any of the volatile organic solvents of the kind which are conventionally employed in the formulation of polyurethane products, such solvents being inert towards isocyanate and isocyanate-reactive (e.g., hydroxyl) groups. Suitable solvents include esters, ketones, hydrocarbons and halogenated hydrocarbons. Specific solvents which may be used are methyl ethyl ketone, methyl isobutyl ketone, 4 methyl - 4 - methoxypentan - 2 - one, ethyl acetate, butyl acetate, ethoxyethyl acetate, cyclohexanone, toluene and xylene. It is preferred not to use such volatile solvents because they add to the cost of the compositions, cause pollution of the atmosphere and may give rise to a flammability hazard.

A wide variation in the proportions of the different ingredients of the compositions is possible. Thus, per 100 parts by weight of hydraulic cement there may be used from 10 to 10,000 parts by weight of filler, from 5 to 500 parts by weight of water and from 5 to 5000 parts by weight of organic polyisocyanate. The isocyanate-reactive organic compound, if employed, may be present in amounts ranging between 5 and 5,000 parts by weight per 100 parts by weight of cement while the terpineol may be present at between 1 and 70 parts per 100 parts by weight of cement. Preferably, there are employed between 10 and 100 parts by weight of water, between 25 and 5,000 parts by weight of filler, between 1.5 and 20 parts by weight of terpineol, between 10 and 250 parts by weight of isocyanate-reactive organic compound, and between 10 and 500 parts by weight of polyisocyanate per 100 parts by weight of cement. If desired, a minor amount, i.e., less than 50 percent, of the terpineol may be replaced with another chain - terminating compound as described above. ?325i; -15- S 35142 The weight ratio of isocyanate-reactive organic compound to terpineol typically employed in the compositions of the present invention will generally range between 25:1 and 1:5. Preferably, such ratio will range between 15:1 and 1:1 and especially between 10:1 and 1:1. In such preferred amounts the benefits of the addition of terpineol discussed above are even more pronounced.

The compositions of this invention are typically applied by first mixing all of the ingredients, utilizing means well known to those of skill in the art such as cement mixers, forced paddling mixers and the like until a satisfactory blend is obtained. The blended composition may then be applied to form a surface any means typically employed for the application of cement compositions such as troweling, pouring, spraying and the like, as appropriate.

The invention is illustrated by the following Examples which are presented for illustrative purpose only and are not intended to limit the scope of the invention in any manner whatsoever. In such Examples all parts listed are presented in parts by weight.

Example 1 100 parts of Portland cement and 300 parts of sand (30 200 BS sieve-size; 0.05 - 0.0076 cm in diameter) are blended together and added to a mixture of 75 parts crude MDI (containing approximately 50 2 by weight of diphenylmethane-4,4*-diisocyanate, the remainder being isomers thereof and methylene-linked polypheny! polyisocyanates containing more than two isocyanate groups); 30 parts of a polyester obtained by condensing together 1,3-butylene glycol, hexanetriol and adipic acid in the molar ratio 3:1:3 and having an acid value below 3 mg KOH/g.; 10.5 parts terpineol (in the form of 15 parts of pine oil); and 20 parts of water. This blend is further mixed until an even dispersion is obtained. The resultant mixture remains in a spreadable un-set state for a sufficient period of time to apply an even coating, but still cures such that it can be walked on within one day. 232 5 j S 35142 Example 2 100 parts of Portland cement and 300 parts of sand (0.05 0.0076 cm in diameter) are blended and added to a mixture of 75 parts crude MDI, 20 parts of an oxypropylated glycerol of hydroxyl value 160 mg/KOH/g., 10.5 parts terpineol (in the form of 15 parts of pine oil) and 20 parts of water. The mixture is further blended until an even dispersion is obtained. Such dispersion possesses excellent flow properties and is easily spread prior to setting. The resultant surface is capable of being walked upon in less than 24 hours after being laid.

Examples 3 to 5 The process of Example 1 is repeated using 100 parts of Portland cement, 300 parts of sand, 75 parts of crude MDI, 37.5 parts of castor oil rosinate (obtained as hereinafter described), various proportions of terpineol (in the form of pine oil) and 20 parts of water. The working life of each mixture was determined.

The castor oil/rosin based product used in these examples is obtainable by heating 320 parts of first pressings castor oil together with 80 parts of an esterified resin modified phenol formaldehyde resol resin at 240°C for 45 minutes. The latter component is obtained by heating together natural rosin, glycerol and the condensation products of diphenylolpropane with approximately 4 moles of formaldehyde in the proportions 8.2:1.1:1.0 by weight at 275°C until the acid value of the material is less than 20mg KOH/kg.

The proportion of terpineol and the working life of the composition are set out in Table One.

Claims (20)

i' -17- 23253 S 35142 Table One | Ex or Comp Terpineol Working life | | Ex (parts by wt) (a) | A 0 100 | B 1.4 117 | 3 3.5 150 | 4 7 167 | 5 10.5 200 | Note to Table One (a) Working life is determined by spreading out a sample of the mixture and, at one minute intervals, putting a scratch mark with a spatula, into the laid-out mixture and noting whether or not the mixture flows back and causes the scratch mark to disappear. For any composition, the working life is the time at which the mixture fails to flow. In all cases the working life is given relative to the working life of the mixture which contains no terpineol, as follows Working life = (Time to no flow of mixture )x 100 (Time to no flow of mixture without terpineol) -18- ? 3 2 5 S 35142 WHAT^WE CLAIM IS: camis

1. A curable composition comprising; (a) an hydraulic cement; (b) a filler; (c) an organic polyisocyanate; (d) a terpineol, and (e) water

2. A curable composition as claimed in Claim 1 wherein the terpineol is present in a cure-retardant effective amount.

3. A curable composition as claimed in Claim 1 or Claim 2 wherein the weight ratio of the organic polyisocyanate to terpineol is not greater than 30:1.

4. A curable composition as claimed in any one of Claims 1 to 3 wherein said terpineol is added in the form of pine oil.

5. A curable composition as claimed in any one of Claims 1 to 4 wherein said composition further comprises an isocyanate-reactive organic compound.

6. A curable composition as claimed in any one of Claims 1 to 5 wherein the hydraulic cement is selected from Portland cement, rapid hardening cements, low-heat cements, sulphate-resisting cements, Portland blast furnace cement, masonry cements, natural cements, lime cements, selenitic cements, Pozzolanic cement and calcium sulphate cements.

7. A curable composition as claimed in any one of Claims 1 to 6 wherein the filler is a siliceous filler having a particle size in the range 0.0076 cm - 4 cm. y 7}p ^ -19- S 35142 U

8. A curable composition as claimed in any one of Claims 1 to 7 wherein said composition further comprises bitumen.

9. A curable composition as claimed in any one of Claims 1 to 8 wherein said composition further comprises a plasticiser.

10. A curable composition as claimed in any one of Claims 1 to 9 wherein said composition further comprises a cure accelerator.

11. A curable composition as claimed in any one of Claims 1 to 10 wherein the terpineol comprises the major proportion, by weight, of the chain terminating component.

12. A curable composition as claimed in any one of Claims 5 to 11 wherein the weight ratio of the isocyanate-reactive organic compound to terpineol is in the range from 10:1 to 1:1.

13. A curable composition as claimed in any one of Claims 5 to 12 wherein there are used 5 - 500 parts by weight of water, 10 10,000 parts by weight of filler, 1 - 70 parts by weight of terpineol, 5 - 500 parts by weight of isocyanate-reactive organic compound and 5-5,000 parts by weight of polyisocyanate per 100 parts by weight of cement.

14. A curable composition as claimed in Claim 13 wherein there are used 10 - 100 parts by weight of water, 25 - 5,000 parts by weight of filler, 1.5 - 20 parts by weight of terpineol, 10 - 250 parts by weight of isocyanate-reactive organic compound and 10 - 500 parts by weight of polyisocyanate per 100 parts by weight of cement.

15. A method for producing a cement surface comprising the steps of : -20- ?325j S 35142 A) forming a cement composition by blending (a) an hydraulic cement; (b) a filler; (c) an organic polyisocyanate; (d) terpineol; and (e) water; B) applying the blend of step (A) to form a surface; and C) allowing said surface to harden.

16. A method as claimed in Claim 15 wherein said composition further comprises an isocyanate-reactive organic compound.

17. A method as claimed in either Claim 15 or Claim 16 wherein the terpineol is added in the form of pine oil.

18. A surface produced in accordance with the method of any one of Claims 15 to 17.

19. A curable composition as claimed in any one of claims 1 to 14 substantially as herein described with reference to any example thereof.

20. A method for producing a cement surface as claimed in any one of claims 15 to 17 substantially as herein described with reference to any example thereof. DATED THIS \{T DAY Of A. J. P^RK & SON ,jlU AGENTS FOR THE APPLICANTS