Mould release compositions

WO 2002016096 A1
ABSTRACT
A mould release composition for moulded silicaceous products, comprising anaqueous mixture of amine
soaps of organic acids.

CLAIMS (OCR text may contain errors)

CLAIMS:
1. A mould release composition for moulded silicaceous products, comprising
an aqueous mixture of amine soaps of organic acids.
2. The mould release composition of claim 1 wherein the composition includes silicaceous solids.
3. The mould release composition of claim 2 wherein the silicaceous solids comprise talc and/or
attapulgite.
4. The mould release composition of any one of claims 1 to 3 wherein thecomposition includes insoluble
nucleation agents for calcium soaps.
5. The mould release composition of claim 1 wherein the acidic portion ofthe organic acid soaps is
comprised of a compound or mixture ofcompounds each with the general formula:R - COOH (I)
where R is any moiety containing from 8 to 50 C atoms.
6. The mould release composition of claim 1 or claim 5 wherein the basic portion of the organic acid
soaps is comprised of an amine or mixture ofamines chosen from:(i) primary and/or secondary and/or tertiary amines chosen from:- (a) those amines containing the moiety
II:> N - CR1R2 - CR3R4 - 0 - (II) where Ri and/or R2 and/or R3 and/or R4 is H or any alkyl or aryl group, and/or
(b) those amines containing the moiety III:> N - CR1R2 - CR3R4 - N < (III)
where R-i and/or R2 and/or R3 and/or R4 is H or any alkyl or aryl group,and/or
(c) those amines with the general 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 any of the above amines by simple neutralization, and/or
(ii) the cationic portion of any quaternary amine or amines.
7. The mould release composition of claim 2 wherein the silicaceous solids comprise smectite clays.
8. The mould release composition of claim 1 wherein the composition further includes one or more
members of the group consisting of magnesium
silicates, aluminium silicates and magnesium aluminium silicates.

DESCRIPTION (OCR text may contain errors)

MOULD RELEASE COMPOSITIONS TECHNICAL FIELD
The present invention relates to compositions for use as mould release agents,
particularly in the manufacture of moulded silicaceous products. For thepurposes of the present invention,
moulded silicaceous products are defined as cementitious products produced from fluid composites being
allowed to set solid within a mould, and clay bricks and other clay based products formed by
extrusion of pliable composites.
The invention also relates to processes for the preparation of such compositionsand to
methods of improving the surface quality of moulded products by the useof such compositions.
BACKGROUND ART
Wet cement tends to stick tenaciously to steel or timber moulds used to contain concrete until it sets.
Mould release agents comprising a large variety ofcompositions have been produced over the past
century to assist in reducing or eliminating this sticking. Their primary action is to provide a waterproof
barrier between the concrete and the mould, but a secondary action is lubrication of themould so that
setting concrete may slide rather than adhere to the mould as it passes through
expansion and contraction phases. Oleic acid, gum rosin, mineral and vegetable oils and other
natural and synthetic oleiferous products have been used for many years in diverse preparations
designed for release ofmoulded silicaceous products. The common form of these oleiferous products has
been either neat or as solutions in petroleum derived solvents, such as distillate, turpentine, and other
fractions. Concerns in recent years about environmental and health effects of petroleum based products
have led to increasing demand to replace petroleum derived solvents with water-based
systems, and many such systems have been described. In critical applications, water-based systems
have failed to provide performance equal to that ofcomparably priced petroleum based products.
Petroleum in one form or another has been used for 80 years as a mould releaseagent with both filmforming and lubricating functions. Standard "off the shelf" products used for many decades to

prevent the sticking of wet cement to steel or timber moulds have been solutions of either gum rosin or
oleic acid with concentrations between 2% and 30% in a cheap, petroleum derived solvent, such as
distillate or mineral turpentine. As mentioned earlier, recent concerns about the environmental and health
effects of these solvents are reflected intighter regulatory attention from health, safety and environmental
authorities. Several water-based systems designed to replace petroleum derived solvents have been
described in the prior art, but these are uneconomical and cannot replace petroleum derived
solvents in all applications. The present invention seeks to address these shortcomings. Another
approach which has been taken by the prior art over a long time has been to prepare dry
mould release films from water or other solvent solutions. However, for manufacture of pipes, concrete
slabs and the vast majority of concrete mouldings, films preformed on moulds are far too weak to
withstand the aggressive conditions of concrete pouring, vibration, centrifugation, heating and other
treatments normally used inthese applications, and so permanent or semi-permanent preformed films
have very limited applicability. The overwhelming industrial demand is for a liquid
mould release composition 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 is the component of wet concrete which tends to bond cement to uncoated moulds. Conventional
wisdom is that gum rosin and oleic acid in petroleum derived solvents perform as mould release agents
by reacting quickly with calcium ions dissolved in the water of freshly mixed concrete to form calcium
soaps which are insoluble in water. These soaps precipitate and congregate in the interface
between the wet concrete and the mould, where they form a film, thus excluding water
from the interface and so preventing bonding or sticking of wet cement to the mould. Petroleum derived
solvents are themselves repelled by water and so tend to congregate in the same region, helping to
lubricate the interfaceand to keep the active mould release agents at the interface. However, the same
results have not occurred when those same agents have been applied in a water-based system. Instead,
mould release agents in water based systems tend to be greatly diluted and dispersed
by the overwhelming amount of water in wet concrete. This dilution tends to make
mould releaseagents in water based systems very inefficient unless some counter-measure is taken.
Conventionally, the liquid mouldrelease compositions of the prior art seem to provide a high enough
concentration of solubilized water-repellent components, i.e. hydrocarbons, fatty materials in many forms,
silicones, waxes, rosin, and other materials, to perform their required mould release function either from
solution or emulsion or by being precipitated at the interface by the massive influx ofwater when wet
concrete is poured into the mould.
In contrast, it is a preferred object of the present invention to create a water repellent interface by another
mechanism, namely, by the rapid formation of calcium soaps by reaction of calcium ions
dissolved in the water of freshly mixed concrete with amine soaps of organic acids. Those calcium soaps
immediately precipitate and so become independent of their water carrier and, being highly water
repellent, remain at or close to the interface at a concentration sufficient to form an effective film. Thus,
this mechanism of calcium soap and film formation is unaffected by dilution with water added via the wet

concrete mix to the region of the applied mould release, and provides in that region a water repellent
film of the same kind as that formed by gum rosin and oleic acid in petroleum derived solvents. Sodium,
potassium and ammonium soaps are too stable to react with dissolved calcium in this
type of system, and so they are unable to form a water repellent film. Prior art mouldrelease compositions
containing those stable soaps seem to rely for their mould release function upon, either, the soap being
present in sufficient concentration to act as a lubricant within the diluted water phase, or the soap being
present primarily to solubilize esters, hydrocarbons or other oily agents which become
destabilised and precipitated when diluted with water added into the concrete mix.
Reaction products of carboxylic acids with water soluble amines to form soaps and amides have been
described for many applications, including release of concrete moulded products, but their
usefulness in the presence of high water content as found in wet concrete has depended upon
compounding with hydrocarbons, organosilicon compounds or other petroleum based compounds whose
presence is generally regarded as undesirable for reasons of cost, health, safety or environmental
concern. SUMMARY OF INVENTION
Therefore, it is an object of this invention to provide practical and inexpensive
mould release compositions with performance equal to or exceeding that of commonly used petroleum
based products, together with environmental and health impacts substantially lower than that of those
petroleum based products.
It is another object of this invention to provide mould release compositions
comprised of stable, aqueous mixtures of amine soaps of organic acids which retain a high
level of efficacy in conditions of high water content normally experienced when performing as a
mould release agent, while reducing or eliminating components generally regarded to be undesirable.
It is still another preferred object of the present invention to form mould release compositions of a highly
active kind that utilize aqueous solutions of gum rosin and fatty soaps prepared with water-soluble
amines. The formation of such compositions is readily facilitated in the present invention
because the aqueous mixtures of amine soaps present in themould release compositions of the invention
behave quite differently from those made with conventional inorganic alkalis.
It is yet another preferred object to use the calcium ions in wet concrete to precipitate active
mould release agents from anaqueous carrier.
It is a still further preferred object of the invention to provide a mould release composition that is
free of silicones, hydrocarbons, alcohols, esters and metal soaps, which have been the basis
for the aqueous concrete mould release agentsof the prior art.
According to the invention, there is provided a mould release composition for moulded silicaceous
products, comprising anaqueous mixture of amine soaps of organic acids. Preferably, the composition

includes silicaceous solids, together with other compounds which provide surfactancy, dispersion,
suspension and storage stability.
Preferably, the silicaceous solids comprise talc and/or attapulgite.
Preferably, the composition includes insoluble nucleation agents for calcium soaps.
It is preferred that both the silicaceous solids and insoluble nucleation agents assist in forming a film
at the interface 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 at the interface.
Preferably, the acidic portion of the organic acid soaps is comprised of a compound or
mixture of compounds each with the general formula:R - COOH (I)
where R is any moiety containing from 8 to 50 C atoms and which may also contain any
combination of non-metallic elements, provided that the overall activity of the molecule remains acidic
with respect to an aqueous base.
Preferably, the basic portion of the organic acid soaps is comprised of an amine or mixture of amines
chosen from:- (i) primary and/or secondary and/or tertiary amines chosen from:(a) those amines containing the moiety II:> N - CRR - CR 3Ra4 -' O - (II)
where ^ and/or R2 and/or R3 and/or R4 is H or any alkyl or aryl group, and/or (b) those amines
containing the moiety II I:> N - CR1R2 - CR3R4 - N < (III)
where R and/or R2 and/or R3 and/or R4 is H or any alkyl or aryl group, and/or
(c) those amines with the general formula IV:HO - NRRT (IV)
where R or R1 is H or any alkyl or aryl group, and/or
(d) any amine salt which might produce any of the above amines by simple neutralization, and/or
(ii) the cationic portion ofany quaternary amine or amines.

Preferably, the composition of the invention includes silicaceous solids which

improve the usefulness of the composition incertain applications. Preferably, such silicaceous solids are
chosen from the group consisting of talc, palygorskite (attapulgite), and smectite clays, and may be both
crude and refined. Preferably, the composition of the invention includes one or more
members of the group consisting of magnesium
silicates, aluminium silicates and magnesium aluminiumsilicates.
Preferably, the composition of the invention includes auxiliary ingredients which assist the desired
function of theaforementioned components and/or which stabilize the composition by controlling
homogeneity, rheology, viscosity, foaming, wetting, anticorrosivity and biological degradation. Such
auxiliary ingredients are chosen from:- (a) carboxylic acid esters of polyols with optional polyoxyethylene
sidechains, such polyols being chosen from ethylene glycol and its dimersand higher condensates,
propylene glycol and its dimers and higher condensates, sorbitans, glycerol, pentaerythritol,and/or
trimethylol alkanes and arylalkanes;
(b) polyoxyethylene-polyoxypropylene (EO-PO) block polymers of the general formula V: HO(CH2CH20)x(CHCH20)y(CH2CH20)zH (V)
CH3
where the sum of x + z is from 5 to 160 and y is from 15 to 60;
(c) ester and/or phosphatide emulsifying agents chosen from wool grease, egg yolk, soybeans and their
extracted components including lanolin, lanolin alcohols and their esters, and lecithin, all being
present in smaller amounts than theamine soaps; (d) polysaccharide-based rheological modifying agents
chosen from hydroxyethylcellulose, methylhydroxyethylcellulose, sodium carboxymethylcellulose, xanthan
gum, guar gum, tragacanth, pectin, acacia gum, carrageenin and/or salts of alginic acid; (e) antifoam
agents being chosen from commercial siloxane-based products designed for such functions; and
(f) preservative agents with anticorrosive, antioxidant and antimicrobial functions chosen from commercial
products designed for such functions. DETAILED DESCRIPTION OF THE PREFERRED
EMBODIMENTS In order that the invention may be readily understood and put into practical effect,
reference will now be made to the following Examples.
Example 1
Part A- Gum rosin was crushed to pass through a 2.5mm screen. To 74g of demineralized water were
added 60g of sorbitan monooleate (Ecoteric S80), 10g of polyoxyethylene (15) oleylamine (Teric 16M15),
10g of polyoxyethylene (5) stearylamine (Teric 18M5), then 26g of morpholine. This mixture was
heated and stirred until its temperature reached 80C, then 10Og ofcrushed gum rosin was
added in small aliquots, allowing time for each aliquot to be dissolved before adding the next aliquot.

When all the rosin was added and the mixture had become homogeneous, this mixture was set aside to
cool.
Part B - 2.4g of xanthan gum (Kelzan D) was dispersed with high speed
shearing in 117.6g of demineralized water. This mixture was set aside overnight, then blended again
shortly before use.
Part C - 70g of talc (Commercial Minerals T38B, 98% < 38m) was dispersed in 130g of demineralized
water together with 40g of an EO-PO block polymer dispersant (Teric PE68), the talc and dispersant
being added to the water in small lots, alternating between the two additives.
To 400g of demineralized water was added all of Part C, then all of Part B, then the mixture was stirred for
20 minutes at moderate speed. A further 958g of demineralized water was added together with
2g of 37% aqueous or aqueous/ methanolic formaldehyde (37% formalin). This mixture was stirred for 3
to 5 minutes, then all of Part A was added. Stirring was resumedand continued for 30 minutes.
This product remained homogeneous for at least two months at all temperatures between 0C and 40C.
This product was useful for release of concrete pipes produced by conventional spinning and heat-cure
processes. Pipes thus produced had a rate of occurrence of defects and general surface appearances
similar to that of pipes produced using a conventional petroleum- based mould release agent.
Example 2
Part A - Gum rosin was crushed to pass through a 2.5mm screen. To 14.8g of demineralized water were
added 12g ofsorbitan monooleate (Ecoteric S80), 2g of polyoxyethylene (15) oleylamine (Teric 16M15),
2g of polyoxyethylene (2) stearylamine (Teric 18M2), then 5.2g of morpholine. This mixture was
heated and stirred until its temperature reached 80C, then 20g of crushed gum rosin was added in small
aliquots, allowing time for each aliquot to be dissolved before adding thenext aliquot. When all the rosin
was added and the mixture had become homogeneous, this mixture was set aside to cool. Part B 1.2g of xanthan gum (Kelzan D) together with 1.2g guar gum
(Guar Gum NP3500FG, Germantown International) was dispersed with high speed
shearing in 296.4g of demineralized water. 1.2g of 37% formalin was added, then blended slowly
into the mixture which was set aside overnight, then blended again shortly before use.
40g of EO-PO block polymer dispersant (Teric PE68) was dissolved in 73.2g of demineralized water. To
this mixture was added 30g of talc (WMC Westmin 8, 98% < 8m) with stirring at medium speed for 30
minutes to form a thin paste, then 0.8g of formalin and all of Part B were added to the mixture with stirring
for 3 to 5 minutes. 1500g of demineralized water was added, the mixture was stirred for 3 to 5 minutes,
then all of Part A was added. Stirring was resumed and continued for 30 minutes. This product remained
homogeneous for at least two months at all temperatures between 0C and 40C. This product was useful

for release of concrete roofing tiles cast on aluminium templates and concrete blocks cast in vibrated or
static moulds without heating. The surface of concrete produced using this product was less sandy than
controls produced with a conventional petroleum-based mould release agent. Residues remaining on
uncleaned, recycled templates after six cycles were similar to control samples produced by conventional
processes.
Example 3 Part A - 56g produced by the process described in Example 2.
Part B - 40g of attapulgite (Attagel 50) was dispersed with high speed shearing in 460g of demineralized
water. This was ready for immediate use. 40g of EO-PO block polymer dispersant (Teric PE68) was
dissolved in 21 Og of demineralized water. To this mixture was added 30g of talc (Westmin 8) with stirring
at medium speed for 30 minutes to form a thin paste, then 2g of formalin and all of Part B were added
to the mixture with stirring for 3 to 5 minutes. 1160g of demineralized waterand 2g Antifoam S (Castrol)
were added, the mixture was stirred for 3 to 5 minutes, then all of Part A was added. Stirring was
resumed and continued for 30 minutes.
This product remained homogeneous for at least one month at all temperatures between 0C and 60C.
This product was useful for release of concrete roofing tiles cast on aluminium templates and concrete
blocks cast in static moulds with or without heating. This product better withstood prolonged hot storage
conditions than Examples 1 and 2.
It is an advantage of the mould release compositions of the present invention that they: (a)
avoid the dangers to health, safety and the environment associated with petroleum based
products; and (b) enable easy separation of moulds from theirmouldings with low incidence of surface
defects, including chalky or tacky residues, adhesion of moulding material to themould, pitting, and colour
variations.
Various modifications may be made in details of components and processes
for the preparation of the composition of thepresent invention without departing
from the scope and ambit of the invention.

PATENT CITATIONS
Cited Patent

DE3535255A1
*
JP60013508A *

Filing
date

Oct 3, 1985

Publication
date

Jul 10, 1986

Applicant

Haertol
Werk

Title

Process for
producing nonporous surface of
construction
elements
Title not available

Cited Patent

Filing
date

Publication
date

Applicant

SU1030174A1
*

Title

Title not available

* Cited by examiner
NON-PATENT CITATIONS
Reference

DATABASE WPI Derwent Publications Ltd., London, GB; Class P64, AN 1984100065/17 & SU 1 030 174 A (KIEV ENG CONS INST) 23 July 1983

DATABASE WPI Derwent Publications Ltd., London, GB; Class P64, AN 1985058314/10 & JP 60 013 508 A (NIPPON MINING KK) 24 January 1985

* Cited by examiner
REFERENCED BY
Citing Patent

WO2007104319A1
*

EP2181820A1

US8044014

Filing date

Mar 13,
2007

Oct 28, 2009

Oct 30, 2009

Publication
date

Sep 20, 2007

May 5, 2010

Oct 25, 2011

Applicant

Title

Mati Alles

Cold-pressing
and low
temperature
firing method
for producing
clay targets
from clay

Mexel
Industries

Stable liquid
oil-in-water or
water-in-oil
emulsions
based on
vegetal or
mineral oils

Mexel
Industries

Liquid and
stable oil-inwater or waterin-oil emulsion
with a
vegetable oil or
mineral oil base