NZ232534A - Organic solvent-free cement compositions containing a polyisocyanate, pine oil and castor oil or castor oil rosinate - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £32534 2 32534 I I 4 fp';r.riiy Daie^s): ).7..r...^ I .^A.r..i:>...-..^^ SpociticaUcn Filed: J..4t.."..^r. jO-. , (5)*.Q1 «lvi■ !»!••/lj.«2HY• • •' ;2-»nAR"B9Z ;.-.I.-. >sr Vc-f rv^i?: ;;'-.0. .«.*..."-r ....i;3..^.W_ w™.— 'ALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION ORGANIC SOLVENT-FREE RAPID SETTING CEMENT COMPOSITION 7 \ 4PEB1990 'j K/We, IMPERIAL CHEMICAL INDUSTRIES PLC, a British company, of Imperial Chemical House, Millbank, London SWIP 3JF, United Kingdom, hereby declare the invention for which >1X^ we pray that a patent may be granted to ncxe/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) 232534 -l/\~ S 35141 ORGANIC SOLVENT-FREE RAPID SETTING CEMENT COMPOSITION 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, U.K. 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.

However, as is noted in U.K. Patent 1,413,121, the compositions of U.K. Patent 1,192,864 have the drawback that it is generally necessary to incorporate an organic solvent into such compositions in order to obtain a satisfactory blend of the various ingredients. The use of such organic solvents (such as toluene, xylene and the like) is undesirable for several reasons. Not only do such solvents add considerable cost to the formulations and present a fire hazard, but, in addition, many are volatile chemicals exposure to which can be harmful to workers' health unless strict safety precautions are observed. Moreover, tools and other equipment used in the preparing and laying of such compositions have to be cleaned with organic solvents, with the associated difficulties referred to above.

U.K. Patent 1,413,121 proposes to overcome these difficulties by the further addition of an isocyanate- reactive water-soluble polymer. The addition of such water-soluble polymer, which must be present in significant amounts, allows the compositions to be thinned with water and permits the aqueous washing of the equipment used to apply such compositions. >325 J S 35141 Unfortunately, the use of such isocyanate-reactive water-soluble polymers has an unforeseen drawback in that the presence of such water-soluble polymers increases the rate of contact between water and the polyisocyanate compound, thereby causing the composition to set much more rapidly. In commercial scale operations the cement composition may set before it can be properly spread. Moreover, the reaction of the isocyanate groups with water during the setting of the composition will liberate gaseous carbon dioxide. If such gas cannot be properly released or absorbed (by lime which is generally present in the cement component) due to premature setting, the resulting cement may become pitted or cracked.

In order to reduce the rate with which these water-soluble polymer-containing cement compositions cure (as is evident from the Examples of U.K. Patent 1,413,121), considerable amounts of chain-terminating compounds, which typically contain a single isocyanate-reactive group, must be employed. Not only does the requirement of the presence of these additional compounds impose an economic penalty, but many of the compounds which are preferably so employed (such as epoxy-substituted compounds) may themselves contain impurities which could present a potential health hazard.

Consequently, it would be extremely desirable to possess an organic solvent-free rapidly curing cement composition which could be economically and safely formulated and applied.

It has now been unexpectedly found that when a castor oil rosinate or castor oil is employed as the isocyanate-reactive organic compound in combination with pine oil, which functions as a plasticising cure retardant, a rapidly curing organic solvent-free cement composition is produced. This composition, unlike those containing large amounts of water-soluble polymer, will not set too rapidly, and is therefore practically applicable and will dry without evidencing the pitting or cracking associated with premature setting. Moreover, the use of pine oil as a cure retardant, whether or not solvent is present, provides many improvements over prior art cure retardants including low volatility, good spreadability, biocidal activity and beneficial aesthetic effect. 23253 -3- S 35141 Accordingly, in one aspect, the present invention is directed to a solvent-free rapidly setting cement composition comprising: (a) an hydraulic cement; (b) a filler; (c) an organic polyisocyanate; (d) a castor oil rosinate or castor oil; (e) pine oil, and (f) water.

In another aspect this invention is directed to a method of preparing a cement surface comprising the steps of: A) blending a mixture comprising an hydraulic cement; a filler; an organic polyisocyanate; a castor oil rosinate or castor oil; pine oil; and water to produce a cement composition; B) forming said cement composition into a surface; and C) allowing said surface to harden.

In yet another aspect, this invention relates to a surface produced in accordance with the method of this invention.

As is employed herein the term "organic solvent-free" means that the addition of those volatile organic solvents of the kind which are conventionally used in the formulation of polyurethane products (which are typically esters such as ethyl acetate, butyl acetate, ethoxyethyl acetate and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, 4-methyl - 4 - methoxypentan -2 - one and the like; aromatic hydrocarbons such as toluene, xylene and the like; or chlorinated hydrocarbons) is not necessary to formulate the composition into a spreadable state. It is to be noted, however, that the compositions of this invention may contain minor amounts of those hydrocarbons which are typically associated with naturally occuring terpineols, i.e., the hydrocarbon component of pine oil. In general, these hydrocarbons do not present any of the drawbacks associated with the use of the volatile polyurethane solvents described above. / 3 2 5 j 4 S 35141 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: 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 following: 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. ?325j4 -5- S 35141 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 hereof 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.

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, turnings, 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. ^ 2325 -6- S 35141 \ By the use of such 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 of 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.

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 simple polyisocyanates or isocyanate- terminated prepolymers obtained by the reaction of an excess of a simple polyisocyanate with an 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-methyldiphenyl methane-4,4'-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato -3,3'-dimethyldiphenyl; diphenylether diisocyanates; and cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanates, methylcyclohexylene diisocyanates and 3-isocyanatomethyl -3,5,5-trimethylcyclohexyl isocyanate. Triisocyanates which may be 232 5 -7- S 35141 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.

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 comprises diphenylmethane-4,4'-diisocyanate in admixture with isomers thereof and with methylene-linked polyphenyl polyisocyanates containing more than two isocyanate groups.

Examples of suitable hydroxy1—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, 1:3- 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 2325 -8- S 35141 proportions of polyhydric alcohols such as glycerol or trimethylolpropane may also be used, in which case branched polyesters and polyesteramides are obtained.

As examples of hydroxy1—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, 1:2- butylene oxide and 2:3-butylene oxide; oxd cyclobutane 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 reaction 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.

The castor oil rosinate which may be employed in the present invention may be obtained by heating castor oil with a resin which is either a rosinate of a metal of Group Ila of the Periodic Table; or a condensation product: of rosin with: (i) at least one polyhydric alcohol; or (ii) at least one polyhydric alcohol and at least one optionally substituted phenol/formaldehyde resol resin; or (iii) at least one polyhydric alcohol and at least one unsaturated dicarboxylic acid or the anhydride thereof. 23 2 -9- S 35141 Examples of rosinates which may be reacted with castor oil are calcium rosinate and barium rosinate.

Examples of polyhydric alcohols which may be condensed with rosin, either alone or together with an optionally substituted phenol I formaldehyde resol resin or an a,|3 - unsaturated dicarboxylic acid or the anhydride thereof, are glycerol, pentaerythritol, trimethylolpropane and sorbitol.

By resol resins is meant the alkaline catalysed reaction products of one mole of a phenol with at least one mole of formaldehyde. The most commonly used and preferrred phenol for use in the preparation of resol resins is phenol itself, but other phenols and alkyl substituted phenols, for example, p - butylphenol, p -octylphenol and p - alkyl substituted phenols generally may also be used.

Examples of alpha, beta-unsaturated dicarboxylic acids and anhydrides thereof which may be condensed with rosin together with a polyhydric alcohol as defined above are maleic acid, fumaric acid and maleic anhydride.

The castor oil and resin may be used in the proportion of from 99:1 to 1:99 parts by weight, the preferred range being from 95:5 to 20:80 parts by weight. Typically, the reaction of the castor oil with the resin as defined above is carried out at high temperature, for example, at 235- 240°C for a time of from ^ to 2 hours.

The weight ratio of castor oil rosinate and/or castor oil to pine oil typically employed in the compositions of the present invention will generally range between 25:1 and 1:5. Preferably, such ratio will range between 10:1 and 1:1. The pine oil is present in a cure-retardant effective amount.

The cure-retardant effective amount can be easily determined by one of ordinary skill in the art. More specifically, the effect of adding pine oil can be determined by comparison of the working life of the composition containing pine oil relative to the working life of a similar composition which is free from added pine oil. 232 534 S 35141 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 pine oil should be sufficient to increase the working life of the composition by at least 252 relative to the working life in the absence of pine oil. 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 be achieve the desired increase in the working life of the composition, the weight ratio of the organic polyisocyanate to pine oil is preferably not greater than about 20:1, for example in the range 20:1 to 2:1.

In addition to the hydraulic cement; filler; water; polyisocyanate; castor oil rosinate or castor oil; and pine oil, which are necessary components of the organic solvent-free cement composition of this invention, the compositions of this invention may further comprise one or more isocyanate-reactive organic compounds other than the castor oil rosinate or castor oil, for example, 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 contain!nq from 2 to 6 carbon atoms and from 2 to 4 hydroxy1 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 including 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 hydroxyl group-containing products obtained by reaction between diphenylolpropane and epichlorohydrin, drying oil and non-drying oil modified alkyd resins, urethane oils, which are the reacton products of diisocyanates with the alcoholysis products of the drying oil, for example, mono- or di-glycerides from linseed oil, and 2325 urethane alkyds, which are alkyd resins in the manufacture of which a part of the phthalic anhydride has been replaced by diisocyanate.

The above defined other isocyanate reactive organic compounds may in part replace the castor oil rosinate or castor oil, but a major proportion, by weight, of the isocyanate reactive component should comprise castor oil rosinate and/or castor oil.

Similarly, while pine oil should comprise the major proportion, by weight, of the chain-terminating component, monohydric alcohols, monocarboxylic acids, and components 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.

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.

S 35141 r , r J <L 5 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, 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.

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 in 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 ?32554 -13- S 35141 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 an accelerator compound which is knov/n to increase the rate of the reaction between isocyanate groups and hydroxyl groups. Suitable accelerator compounds 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-dimethylcyclohexylamine, 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.

Moreover, the composition of this invention may be formed into elements having a Terrazzo-like decorative effect by either (1) incorporating a 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 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-described composition, and grinding the surface to expose the particles of material. 232534 -14- S 35141 The particles employed for such Terrazzo-effeet uses may be in the form of mass-pigmented plastics 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. Such 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 glass 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.

Colourless plastics fragments may also be used as the particles. By coarse particles is meant those materials having a particle size not less than about 250 microns.

The proportions of the different components comprising the compositions of this invention may vary over a wide range, depending upon the specific ingredients (and additives) selected. In general, per 100 parts by weight of hydraulic cement there will be included from 5 to 500 parts by weight of water, from 10 to 10000 parts by weight of filler, from 1 to 100 parts by weight of pine oil, from 5 to 5000 parts by weight of castor oil rosinate or castor oil, and from 5 to 5000 parts by weight of polyisocyanate. Preferably, for most combinations and applications, per 100 parts by weight of cement ? 3 2 5 3 4 -15- S 35141 there will be employed from 10 to 100 parts by weight of water, from 25 to 5000 parts by weight of filler, from 2 to 25 parts by weight of pine oil, from 10 to 250 parts by weight of castor oil rosinate and/or castor oil, and from 10 to 500 parts by weight of isocyanate.

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 by any means typically employed for the application of cement compositions, such as troweling, pouring, spraying and the like, as appropriate.

The present 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 reference to "parts" refers to 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,A'-diisocyanate, the remainder being isomers thereof and methylene-linked polyphenyl polyisocyanates containing more than two isocyanate groups), 37.5 parts of castor oil rosinate (provided as described below), 15 parts of pine oil and 20 parts of water. This blend is further mixed until an even dispersion is obtained. This 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.

The castor oil/rosin based product used in this Example is obtained by heating 320 parts of 1st pressings castor oil together with 80 parts of an esterified rosin 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 20 mg KOH/kg. ? 3 2 5 o -16- S 35141 Example 1 The process of Example 1 is repeated except that the castor oil rosinate is replaced with 40 parts of castor oil. The resultant composition can be readily spread to form a floor which is sufficiently cured to be used within 24 hours of being applied.

Examples 3 and 4 The process of Example 1 was repeated using either no pine oil or different proportions of pine oil, other components and the proportions thereof being as in Example 1.

The working life of each mixture was determined. The proportion of pine oil and the working life of the composition are set out in Table One.

Table One | Ex or 1 1 | Pine Oil | Working Life | | Camp Ez |(parts by wt) | 1 1 (a) I 1 A 1 1 I 0 1 100 | 1 B 1 2 1 117 | I 3 1 5 1 150 | 1 ^ 1 io 1 167 | | 1 1 15 1 200 |

Claims (16)

23253 -17- S 35141 Notes 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 pine oil, as follows Working life = (Time to no flow of mixture ) x 100 (Time to no flow of mixture without pine oil) -18- /32534 S 35141 WKATJr/WE CLAIM IS:

1. An organic solvent-free curable composition comprising; (a) an hydraulic cement; (b) a filler; (c) an organic polyisocyanate; (d) a castor oil rosinate or castor oil; (e) pine oil, and (f) water.

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

3. A curable composition as claimed in Claim 1 or Claim 2 wherein the hydraulic cement is selected from Portland cement, rapid hardening cements, low-heat cements, sulphate-resisting cements, natural cements, lime cements, selenitic cements, Pozzolanic cement, and calcium sulphate cements.

4. A curable composition as claimed in any one of Claims 1 to 3 wherein the filler is a siliceous filler having a particle size in the range 0.0076 cm - 4 cm.

5. A curable composition as claimed in any one of Claims 1 to 4 wherein said composition further comprises a plasticiser.

6. A curable composition as claimed in any one of Claims 1 to 5 wherein said composition further comprises bitumen.

7. A curable composition as claimed in any one of Claims 1 to 6 wherein said composition further comprises an accelerator compound.

8. A curable composition as claimed in any one of Claims 2 to 7 wherein the weight ratio of organic polyisocyanate to pine oil is not greater than 20:1. -19- S 35141 23253

9. A curable composition as claimed in any one of Claims 1 to 8 wherein the pine oil comprises the major proportion, by weight, of the chain terminating component.

10. A curable composition as claimed in any one of Claims 2 to 9 wherein the weight ratio of organic polyisocyanate to pine oil is not greater than 20:1.

11. A curable composition as claimed in Claim 1 wherein there are used 5 - 500 parts by weight water, 10 - 10000 parts by weight of filler, 1 - 100 parts by weight of pine oil, 5 - 5000 parts by weight of castor oil rosinate or castor oil and 5 - 5000 parts by weight of polyisocyanate per 100 parts by weight of cement.

12. A curable composition as claimed in Claim 11 wherein there are used 10 - 100 parts by weight of water, 2-5 - 5000 parts by weight of filler, 2-25 parts by weight of pine oil, 10 - 250 parts by weight of castor oil rosinate or castor oil and 10 - 500 parts by weight of polyisocyanate per 100 parts by weight of cement.

13. A method for preparing a cement surface comprising the steps of: A) blending a mixture comprising an hydraulic cement; a filler; an organic polyisocyanate; a castor oil rosinate or castor oil; pine oil; and water to form a cement composition; B) forming said cement composition into a surface; and C) allowing said surface to harden.

14. A cement surface produced in accordance with the method of claim 13.

15. An organic solvent-free curable composition as claimed in any one of claims 1 to 12 substantially as herein described with reference to any example thereof.

16. A method for preparing a cement surface as claimed in claim 13 substantially as herein described with reference to any example thereof. oated this p* day of Febaoxj A. J. PARK * SON / ]/"N I