MouldreleasecompositionsWO 2002016096 A1ABSTRACTA mouldreleasecomposition for moulded silicaceous products, comprising anaqueousmixtureofamine soapsoforganic acids.CLAIMS(OCR text may contain errors)CLAIMS:1. A mouldreleasecomposition for moulded silicaceous products, comprising anaqueousmixtureofamine soapsoforganic acids.2.Themouldreleasecompositionofclaim 1 whereinthecomposition includes silicaceous solids.3.Themouldreleasecompositionofclaim 2 whereinthesilicaceous solids comprise talcand/or attapulgite.4.Themouldreleasecompositionofany oneofclaims 1 to 3 whereinthecomposition includes insoluble nucleation agents for calcium soaps.5.Themouldreleasecompositionofclaim 1 whereintheacidic portionoftheorganic acid soaps is comprisedofa compound or mixtureofcompounds each withthegeneral formula:-R - COOH (I)where R is any moiety containing from 8 to 50 C atoms.6.Themouldreleasecompositionofclaim 1 or claim 5 whereinthebasic portionoftheorganic acid soaps is comprisedofan amine or mixtureofamines chosen from:-(i) primaryand/or secondaryand/or tertiary amines chosen from:- (a) those amines containingthemoiety II:-> N - CR1R2- CR3R4- 0 - (II) where Riand/or R2and/or R3and/or R4is H or any alkyl or aryl group,and/or(b) those amines containingthemoiety III:-> N - CR1R2- CR3R4- N < (III)where R-iand/or R2and/or R3and/or R4is H or any alkyl or aryl group,and/or(c) those amines withthegeneral formula IV:-HO - NRR!(IV)where R or R., is H or any alkyl or aryl group,and/or(d) any amine salt which might produce anyoftheabove amines by simple neutralization,and/or(ii)thecationic portionofany quaternary amine or amines.7.Themouldreleasecompositionofclaim 2 whereinthesilicaceous solids comprise smectite clays.8.Themouldreleasecompositionofclaim 1 whereinthecomposition further includes one or more membersofthegroup consistingofmagnesium silicates,aluminiumsilicatesandmagnesiumaluminiumsilicates.DESCRIPTION(OCR text may contain errors)MOULDRELEASECOMPOSITIONS TECHNICAL FIELDThepresent invention relates to compositions foruseas mouldreleaseagents, particularlyinthemanufactureofmoulded silicaceous products. Forthepurposesofthepresent invention, moulded silicaceous products are defined as cementitious products produced from fluid composites being allowed to set solid within a mould,andclay bricksandother clay based products formed by extrusionofpliable composites.Theinvention also relates to processes forthepreparationofsuch compositionsandto methodsofimprovingthesurface qualityofmoulded products bytheuseofsuch compositions. BACKGROUND ARTWet cement tends to stick tenaciously to steel or timber moulds used to contain concrete until it sets. Mouldreleaseagents comprising a large varietyofcompositions have been produced overthepast century to assistinreducing or eliminating this sticking. Their primary action is to provide a waterproof barrier betweentheconcreteandthemould, but a secondary action is lubricationofthemould so that setting concrete may slide rather than adhere tothemould as it passes through expansionandcontraction phases. Oleic acid, gum rosin, mineralandvegetable oilsandother naturalandsynthetic oleiferous products have been used for many yearsindiverse preparations designed forreleaseofmoulded silicaceous products.Thecommon formofthese oleiferous products has been either neat or as solutionsinpetroleum derived solvents, such as distillate, turpentine,andother fractions. Concernsinrecent years about environmentalandhealth effectsofpetroleum based products have led to increasing demand to replace petroleum derived solvents with water-based systems,andmany such systems have been described.Incritical applications, water-based systems have failed to provide performance equal to thatofcomparably priced petroleum based products.Petroleuminone form or another has been used for 80 years as a mouldreleaseagentwith both film-formingandlubricating functions. Standard "offtheshelf" products used for many decades to preventthestickingofwet cement to steel or timber moulds have been solutionsofeither gum rosin or oleic acid with concentrations between 2%and30%ina cheap, petroleum derived solvent, such as distillate or mineral turpentine. As mentioned earlier, recent concerns abouttheenvironmentalandhealth effectsofthese solvents are reflectedintighter regulatory attention from health, safetyandenvironmental authorities. Several water-based systems designed to replace petroleum derived solvents have been describedintheprior art, but these are uneconomicalandcannot replace petroleum derived solventsinall applications.Thepresent invention seeks to address these shortcomings. Another approach which has been taken bytheprior art over a long time has been to prepare dry mouldreleasefilms from water or other solvent solutions. However, for manufactureofpipes, concrete slabsandthevast majorityofconcretemouldings, films preformed on moulds are far too weak to withstandtheaggressive conditionsofconcrete pouring, vibration, centrifugation, heatingandother treatments normally usedinthese applications,andso permanent or semi-permanent preformed films have very limited applicability.Theoverwhelming industrial demand is for a liquid mouldreleasecomposition which can be applied to a mould by brushing or spraying, then overlaid with wet concrete immediately or not much later.Thepresent invention directly addresses this demand.Water isthecomponentofwet concrete which tends to bond cement to uncoated moulds. Conventional wisdom is that gum rosinandoleic acidinpetroleum derived solvents perform as mouldreleaseagents by reacting quickly with calcium ions dissolvedinthewateroffreshly mixed concrete to form calcium soaps which are insolubleinwater. These soaps precipitateandcongregateintheinterface betweenthewet concreteandthemould, where they form a film, thus excluding water fromtheinterfaceandso preventing bonding or stickingofwet cement tothemould. Petroleum derived solvents are themselves repelled by waterandso tend to congregateinthesame region, helping to lubricatetheinterfaceandto keeptheactive mouldreleaseagents attheinterface. However,thesame results have not occurred when those same agents have been appliedina water-based system. Instead, mouldreleaseagentsinwater based systems tend to be greatly dilutedanddispersed bytheoverwhelming amountofwaterinwet concrete. This dilution tends to make mouldreleaseagentsinwater based systems very inefficient unless some counter-measure is taken. Conventionally,theliquid mouldreleasecompositionsoftheprior art seem to provide a high enough concentrationofsolubilized water-repellent components, i.e. hydrocarbons, fatty materialsinmany forms, silicones, waxes, rosin,andother materials, to perform their required mouldreleasefunction either from solution or emulsion or by being precipitated attheinterface bythemassive influxofwater when wet concrete is poured intothemould.Incontrast, it is a preferred objectofthepresent invention to create a water repellent interface by another mechanism, namely, bytherapid formationofcalcium soaps by reactionofcalcium ions dissolvedinthewateroffreshly mixed concrete with amine soapsoforganic acids. Those calcium soaps immediately precipitateandso become independentoftheir water carrierand, being highly water repellent, remain at or close totheinterface at a concentration sufficient to form an effective film. Thus, this mechanismofcalcium soapandfilm formation is unaffected by dilution with water added viathewet concrete mix totheregionoftheapplied mouldrelease,andprovidesinthat region a water repellent filmofthesame kind as that formed by gum rosinandoleic acidinpetroleum derived solvents. Sodium, potassiumandammonium soaps are too stable to react with dissolved calciuminthis typeofsystem,andso they are unable to form a water repellent film. Prior art mouldreleasecompositions containing those stable soaps seem to rely for their mouldreleasefunction upon, either,thesoap being presentinsufficient concentration to act as a lubricant withinthediluted water phase, orthesoap being present primarily to solubilize esters, hydrocarbons or other oily agents which become destabilisedandprecipitated when diluted with water added intotheconcrete mix.Reaction productsofcarboxylic acids with water soluble amines to form soapsandamides have been described for many applications, includingreleaseofconcrete moulded products, but their usefulnessinthepresenceofhigh water content as foundinwet concrete has depended upon compounding with hydrocarbons, organosilicon compounds or other petroleum based compounds whose presence is generally regarded as undesirable for reasonsofcost, health, safety or environmental concern. SUMMARYOFINVENTIONTherefore, it is an objectofthis invention to provide practicalandinexpensive mouldreleasecompositions with performance equal to or exceeding thatofcommonly used petroleum based products, together with environmentalandhealth impacts substantially lower than thatofthose petroleum based products.It is another objectofthis invention to provide mouldreleasecompositions comprisedofstable,aqueousmixturesofamine soapsoforganic acids which retain a high levelofefficacyinconditionsofhigh water content normally experienced when performing as a mouldreleaseagent, while reducing or eliminating components generally regarded to be undesirable.It is still another preferred objectofthepresent invention to form mouldreleasecompositionsofa highly active kind that utilizeaqueoussolutionsofgum rosinandfatty soaps prepared with water-soluble amines.Theformationofsuch compositions is readily facilitatedinthepresent invention becausetheaqueousmixturesofamine soaps presentinthemouldreleasecompositionsoftheinvention behave quite differently from those made with conventional inorganic alkalis.It is yet another preferred object tousethecalcium ionsinwet concrete to precipitate active mouldreleaseagents from anaqueouscarrier.It is a still further preferred objectoftheinvention to provide a mouldreleasecomposition that is freeofsilicones, hydrocarbons, alcohols, estersandmetal soaps, which have beenthebasis fortheaqueousconcrete mouldreleaseagentsoftheprior art.According totheinvention, there is provided a mouldreleasecomposition for moulded silicaceous products, comprising anaqueousmixtureofamine soapsoforganic acids. Preferably,thecomposition includes silicaceous solids, together with other compounds which provide surfactancy, dispersion, suspensionandstorage stability.Preferably,thesilicaceous solids comprise talcand/or attapulgite.Preferably,thecomposition includes insoluble nucleation agents for calcium soaps.It is preferred that boththesilicaceous solidsandinsoluble nucleation agents assistinforming a film attheinterface by acting as nucleation agents for calcium soaps as they are created, forming physical composites with those soaps whose relatively high density tends to concentrate them attheinterface. Preferably,theacidic portionoftheorganic acid soaps is comprisedofa compound or mixtureofcompounds each withthegeneral formula:-R - COOH (I)where R is any moiety containing from 8 to 50 C atomsandwhich may also contain any combinationofnon-metallic elements, provided thattheoverall activityofthemolecule remains acidic with respect to anaqueousbase.Preferably,thebasic portionoftheorganic acid soaps is comprisedofan amine or mixtureofamines chosen from:- (i) primaryand/or secondaryand/or tertiary amines chosen from:-(a) those amines containingthemoiety II:-> N - CRR - CR 3Ra4 -'O - (II)where ^and/or R2and/or R3and/or R4is H or any alkyl or aryl group,and/or (b) those amines containingthemoiety II I:-> N - CR1R2- CR3R4- N < (III)where Rand/or R2and/or R3and/or R4is H or any alkyl or aryl group,and/or(c) those amines withthegeneral formula IV:-HO - NRRT (IV)where R or R1is H or any alkyl or aryl group,and/or(d) any amine salt which might produce anyoftheabove amines by simple neutralization,and/or (ii)thecationic portionofany quaternary amine or amines.Preferably,thecompositionoftheinvention includes silicaceous solids which improvetheusefulnessofthecompositionincertain applications. Preferably, such silicaceous solids are chosen fromthegroup consistingoftalc, palygorskite (attapulgite),andsmectite clays,andmay be both crudeandrefined. Preferably,thecompositionoftheinvention includes one or more membersofthegroup consistingofmagnesium silicates,aluminiumsilicatesandmagnesiumaluminiumsilicates. Preferably,thecompositionoftheinvention includes auxiliary ingredients which assistthedesired functionoftheaforementioned componentsand/or which stabilizethecomposition by controlling homogeneity, rheology, viscosity, foaming, wetting, anticorrosivityandbiological degradation. Such auxiliary ingredients are chosen from:- (a) carboxylic acid estersofpolyols with optional polyoxyethylene sidechains, such polyols being chosen from ethylene glycolanditsdimersandhigher condensates, propylene glycolanditsdimersandhigher condensates, sorbitans, glycerol, pentaerythritol,and/or trimethylol alkanesandarylalkanes;(b) polyoxyethylene-polyoxypropylene (EO-PO) block polymersofthegeneral formula V: -HO(CH2CH20)x(CHCH20)y(CH2CH20)zH (V)CH3wherethesumofx + z is from 5 to 160andy is from 15 to 60;(c) esterand/or phosphatide emulsifying agents chosen from wool grease, egg yolk, soybeansandtheir extracted components including lanolin, lanolin alcoholsandtheir esters,andlecithin, all being presentinsmaller amounts thantheamine soaps; (d) polysaccharide-based rheological modifying agents chosen from hydroxyethylcellulose, methylhydroxyethylcellulose, sodium carboxymethylcellulose, xanthan gum, guar gum, tragacanth, pectin, acacia gum, carrageeninand/or saltsofalginic acid; (e) antifoam agents being chosen from commercial siloxane-based products designed for such functions;and(f) preservative agents with anticorrosive, antioxidantandantimicrobial functions chosen from commercial products designed for such functions. DETAILED DESCRIPTIONOFTHEPREFERRED EMBODIMENTSInorder thattheinvention may be readily understoodandput into practical effect, reference will now be made tothefollowing Examples.Example 1Part A- Gum rosin was crushed to pass through a 2.5mm screen. To 74gofdemineralized water were added 60gofsorbitan monooleate (Ecoteric S80), 10gofpolyoxyethylene (15) oleylamine (Teric 16M15), 10gofpolyoxyethylene (5) stearylamine (Teric 18M5), then 26gofmorpholine. This mixture was heatedandstirred untilitstemperature reached 80C, then 10Ogofcrushed gum rosin was addedinsmall aliquots, allowing time for each aliquot to be dissolved before addingthenext aliquot. When alltherosin was addedandthemixture had become homogeneous, this mixture was set aside to cool.Part B - 2.4gofxanthan gum (Kelzan D) was dispersed with high speed shearingin117.6gofdemineralized water. This mixture was set aside overnight, then blended again shortly beforeuse.Part C - 70goftalc (Commercial Minerals T38B, 98% < 38m) was dispersedin130gofdemineralized water together with 40gofan EO-PO block polymer dispersant (Teric PE68),thetalcanddispersant being added tothewaterinsmall lots, alternating betweenthetwo additives.To 400gofdemineralized water was added allofPart C, then allofPart B, thenthemixture was stirred for 20 minutes at moderate speed. A further 958gofdemineralized water was added together with 2gof37%aqueousoraqueous/ methanolic formaldehyde (37% formalin). This mixture was stirred for 3 to 5 minutes, then allofPart A was added. Stirring was resumedandcontinued for 30 minutes.This product remained homogeneous for at least two months at all temperatures between 0Cand40C. This product was useful forreleaseofconcrete pipes produced by conventional spinningandheat-cure processes. Pipes thus produced had a rateofoccurrenceofdefectsandgeneral surface appearances similar to thatofpipes produced using a conventional petroleum- based mouldreleaseagent.Example 2Part A - Gum rosin was crushed to pass through a 2.5mm screen. To 14.8gofdemineralized water were added 12gofsorbitan monooleate (Ecoteric S80), 2gofpolyoxyethylene (15) oleylamine (Teric 16M15), 2gofpolyoxyethylene (2) stearylamine (Teric 18M2), then 5.2gofmorpholine. This mixture was heatedandstirred untilitstemperature reached 80C, then 20gofcrushed gum rosin was addedinsmall aliquots, allowing time for each aliquot to be dissolved before addingthenext aliquot. When alltherosin was addedandthemixture had become homogeneous, this mixture was set aside to cool. Part B - 1.2gofxanthan gum (Kelzan D) together with 1.2g guar gum(Guar Gum NP3500FG, Germantown International) was dispersed with high speed shearingin296.4gofdemineralized water. 1.2gof37% formalin was added, then blended slowly intothemixture which was set aside overnight, then blended again shortly beforeuse.40gofEO-PO block polymer dispersant (Teric PE68) was dissolvedin73.2gofdemineralized water. To this mixture was added 30goftalc (WMC Westmin 8, 98% < 8m) with stirring at medium speed for 30 minutes to form a thin paste, then 0.8gofformalinandallofPart B were added tothemixture with stirring for 3 to 5 minutes. 1500gofdemineralized water was added,themixture was stirred for 3 to 5 minutes, then allofPart A was added. Stirring was resumedandcontinued for 30 minutes. This product remained homogeneous for at least two months at all temperatures between 0Cand40C. This product was useful forreleaseofconcrete roofing tiles cast onaluminiumtemplatesandconcrete blocks castinvibrated or static moulds without heating.Thesurfaceofconcrete produced using this product was less sandy than controls produced with a conventional petroleum-based mouldreleaseagent. Residues remaining on uncleaned, recycled templates after six cycles were similar to control samples produced by conventional processes.Example 3 Part A - 56g produced bytheprocess describedinExample 2.Part B - 40gofattapulgite (Attagel 50) was dispersed with high speed shearingin460gofdemineralized water. This was ready for immediateuse. 40gofEO-PO block polymer dispersant (Teric PE68) was dissolvedin21 Ogofdemineralized water. To this mixture was added 30goftalc (Westmin 8) with stirring at medium speed for 30 minutes to form a thin paste, then 2gofformalinandallofPart B were added tothemixture with stirring for 3 to 5 minutes. 1160gofdemineralized waterand2g Antifoam S (Castrol) were added,themixture was stirred for 3 to 5 minutes, then allofPart A was added. Stirring was resumedandcontinued for 30 minutes.This product remained homogeneous for at least one month at all temperatures between 0Cand60C. This product was useful forreleaseofconcrete roofing tiles cast onaluminiumtemplatesandconcrete blocks castinstatic moulds with or without heating. This product better withstood prolonged hot storage conditions than Examples 1and2.It is an advantageofthemouldreleasecompositionsofthepresent invention that they: (a) avoidthedangers to health, safetyandtheenvironment associated with petroleum based products;and(b) enable easy separationofmoulds from theirmouldingswith low incidenceofsurface defects, including chalky or tacky residues, adhesionofmoulding material tothemould, pitting,andcolour variations.Various modifications may be madeindetailsofcomponentsandprocesses forthepreparationofthecompositionofthepresent invention without departing fromthescopeandambitoftheinvention.PATENT CITATIONSCited PatentFiling datePublication dateApplicantTitle

DE3535255A1*Oct 3, 1985Jul 10, 1986Haertol WerkProcess for producing non-porous surface of construction elements

JP60013508A*Title not available

SU1030174A1*Title not available

* Cited by examinerNON-PATENT CITATIONSReference

1*DATABASE WPI Derwent Publications Ltd., London, GB; Class P64, AN 1984-100065/17 & SU 1 030 174 A (KIEV ENG CONS INST) 23 July 1983

2*DATABASE WPI Derwent Publications Ltd., London, GB; Class P64, AN 1985-058314/10 & JP 60 013 508 A (NIPPON MINING KK) 24 January 1985

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