U.S. patent application number 10/694799 was filed with the patent office on 2004-06-03 for method for processing a mineral filler with a phosphate, mineral fillers treated in this manner, polyurethane foams and composite polyurethanes using this filler, objects containing them which may or may not be moulded.
This patent application is currently assigned to Omya S.A.. Invention is credited to Blanchard, Pierre, Fichou, Jean Pierre, Husson, Maurice, Ravet, Georges.
Application Number | 20040106701 10/694799 |
Document ID | / |
Family ID | 9528188 |
Filed Date | 2004-06-03 |
United States Patent
Application |
20040106701 |
Kind Code |
A1 |
Fichou, Jean Pierre ; et
al. |
June 3, 2004 |
Method for processing a mineral filler with a phosphate, mineral
fillers treated in this manner, polyurethane foams and composite
polyurethanes using this filler, objects containing them which may
or may not be moulded
Abstract
The invention relates to the technological sector of mineral
fillers used in the sector which manufactures polyurethane foams
and in particular fillers of the carbonate, hydroxide, silicate,
sulphate type and similar mineral fillers. The invention relates in
particular to a method of treating mineral fillers of a specific
grain size with the aid of treatment agents of the organic
phosphate type, incorporating a de-agglomeration step, and
optionally a selection step, with a view to improving the
techniques used to manufacture polyurethane foams either by foaming
without an auxiliary blowing agent or with a blowing agent such as
CO.sub.2, and composite polyurethane, whilst reducing the time
needed to mix this treated filler treated with the polyol and other
reagents. Numerous applications for block foams or moulded foams,
for mattresses and similar, the automotive industry, various
industrial components, etc . . .
Inventors: |
Fichou, Jean Pierre;
(Levallois Perret, FR) ; Husson, Maurice; (Chalons
En Champagne, FR) ; Ravet, Georges; (Saint Genis Les
Ollieres, FR) ; Blanchard, Pierre; (Reyrieux,
FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Omya S.A.
Paris Cedex
FR
|
Family ID: |
9528188 |
Appl. No.: |
10/694799 |
Filed: |
October 29, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10694799 |
Oct 29, 2003 |
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09719574 |
May 14, 2001 |
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09719574 |
May 14, 2001 |
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PCT/FR99/01456 |
Jun 17, 1999 |
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Current U.S.
Class: |
523/200 ;
106/416; 106/419; 521/107 |
Current CPC
Class: |
C09C 3/08 20130101; C08G
65/2639 20130101; C01P 2004/61 20130101; C08G 2110/0083 20210101;
C08K 9/04 20130101; C01P 2006/22 20130101; C01P 2004/50 20130101;
C08G 65/3355 20130101; C01P 2006/10 20130101; C01P 2004/62
20130101; C08K 9/04 20130101; C08L 75/04 20130101 |
Class at
Publication: |
523/200 ;
521/107; 106/416; 106/419 |
International
Class: |
C08K 009/00; C09C
001/04; C04B 002/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 30, 1998 |
FR |
98/08483 |
Claims
1. A method of treating mineral fillers, characterised in that said
filler a) is treated using at least one compound of the general
formula (1): 3where R.sub.1=either H or alkyl with 8 to 40 carbon
atoms or aryl or alkylaryl or arylalkyl with 6 to 40 carbon atoms
where R.sub.2=either alkyl with 8 to 40 carbon atoms or aryl or
alkylaryl or arylalkyl with 6 to 40 carbon atoms
X=--CH.sub.2--CH.sub.2-- or --CH(CH.sub.3)--CH.sub.2--- or
--CH.sub.2--CH(CH.sub.3) or
--(CH.sub.2).sub.5--CO--Y=--CH.sub.2--CH.su- b.2-- or
--CH(CH.sub.3)--CH.sub.2--or --CH.sub.2--CH(CH.sub.3)-- or
--(CH.sub.2).sub.5--CO--X and Y being the same or different, (m+n)
varies from 0 to 60 (boundaries included) as well as (p+q) where
0.ltoreq.m+n.ltoreq.60 and 0.ltoreq.p+q.ltoreq.60 when
X=Y=--CH.sub.2--CH.sub.2-- and where (1.ltoreq.m.ltoreq.10 and
1.ltoreq.p.ltoreq.10) and (0.ltoreq.n.ltoreq.59 and
0.ltoreq.q.ltoreq.59) if X is different from Y: b) undergoes a
de-agglomeration step and c) optionally undergoes a selection
step.
2. A method of treating mineral fillers as claimed in claim 1,
characterised in that said treatment agent is an acid phosphate of
aliphatic alcohol, branched or not with 8 to 20 carbon atoms, on
which from 0 to 12 ethylene oxide chains are condensed and
optionally containing a mixture of mono-esters and di-esters.
3. A method of treating mineral fillers as claimed in claim 1 or 2,
characterised in that said treatment agent is a mixture of
mono-ester and di-ester of acid phosphate of decyl alcohol with 5
mols of ethylene oxide.
4. A method of treating mineral fillers as claimed in claim 1,
characterised in that said treatment agent is the mono-ester of
acid phosphate of tristyrylphenol containing 60 mols of ethylene
oxide.
5. A method of treating mineral fillers as claimed in claim 1 or 2,
characterised in that said treatment agent is a mixture of
mono-ester and di-ester of acid phosphate of ketostearyl
alcohol.
6. A method of treating mineral fillers as claimed in claim 1 or 2,
characterised in that said treatment agent is a mixture of
mono-ester and di-ester of acid phosphate of nonylphenol containing
10 mols of ethylene oxide.
7. A method of treating mineral fillers as claimed in claim 1,
characterised in that said treatment is applied by a dry method or
by a wet method.
8. A method of treating mineral fillers as claimed in any one of
claims 1 to 7, characterised in that said filler is selected from
amongst: the carbonates, phosphates and sulphates of natural or
synthetic alkaline earths, zinc carbonate, the combined salts of
magnesium and calcium such as dolomites, lime, magnesia, barium
sulphate, calcium sulphates, magnesium hydroxides, aluminium
hydroxide, silica, wollastonite, the clays and other silico-alumina
such as the kaolins, silica-magnesia such as talc, mica, solid or
hollow glass beads, the metal oxides such as zinc oxide, the iron
oxides, titanium oxide and mixtures thereof.
9. A method of treating mineral fillers as claimed in any one of
claims 1 to 7, characterised in that said filler is selected from
amongst: the natural calcium carbonates selected from chalk,
calcite and marble, precipitated calcium carbonate, dolomite, the
aluminum or magnesium hydroxides, kaolin, talc, wollastonite and
mixtures thereof.
10. A treated mineral filler of a specific grain size for the
manufacture of polyurethane foams by a method whereby said filler
is mixed with at least some of the polyol in the reaction forming
the polyurethane and having a shorter mixing time with the polyol
and the other reagents, characterised in that it a) is treated
using at least one compound of the general formula (1): 4where
R.sub.1=either H or alkyl with 8 to 40 carbon atoms or aryl or
alkylaryl or arylalkyl with 6 to 40 carbon atoms where
R.sub.2=either alkyl with 8 to 40 carbon atoms or aryl or alkylaryl
or arylalkyl with 6 to 40 carbon atoms X=--CH.sub.2--CH.sub.2-- or
--CH(CH.sub.3)--CH.sub.2-- or --CH.sub.2--CH(CH.sub.3) or
--(CH.sub.2).sub.5--CO--Y=--CH.sub.2--CH.sub.2-- or
--CH(CH.sub.3)--CH.sub.2--or --CH.sub.2--CH(CH.sub.3)-- or
--(CH.sub.2).sub.5--CO--X and Y being the same or different, (m+n)
varies from 0 to 60 (boundaries included) as well as (p+q) where
0.ltoreq.m+n.ltoreq.60 and 0.ltoreq.p+q.ltoreq.60 when
X=Y=--CH.sub.2--CH.sub.2-- and where (1.ltoreq.m.ltoreq.10 and
1.ltoreq.p.ltoreq.10) and (0.ltoreq.n.ltoreq.59 and
0.ltoreq.q.ltoreq.59) if X is different from Y. b) undergoes a
de-agglomeration step and c) optionally undergoes a selection
step.
11. A treated mineral filler as claimed in claim 10, characterised
in that said treatment agent is a mixture of mono-ester and
di-ester of acid phosphate of decyl alcohol with 5 mols of ethylene
oxide.
12. A treated mineral filler as claimed in claim 10, characterised
in that said treatment agent is the mono-ester of acid phosphate of
tristyrylphenol containing 60 mols of ethylene oxide.
13. A treated mineral filler as claimed in claim 10, characterised
in that said treatment agent is a mixture of mono-ester and
di-ester of acid phosphate of ketostearyl alcohol.
14. A treated mineral filler as claimed in claim 10, characterised
in that said treatment agent is a mixture of mono-ester and
di-ester of acid phosphate of nonylphenol containing 10 mols of
ethylene oxide.
15. Mineral fillers as claimed in any one of claims 10 to 14,
characterised in that they consist of carbonates, phosphates and
sulphates of natural or synthetic alkaline earths, zinc carbonate,
the combined salts of magnesium and calcium such as dolomites,
lime, magnesia, barium sulphate, calcium sulphates, magnesium
hydroxides, aluminium hydroxide, silica, wollastonite, the clays
and other silico-alumina such as the kaolins, silica-magnesia such
as talc, mica, solid or hollow glass beads, the metal oxides such
as zinc oxide, the iron oxides, titanium oxide and mixtures
thereof.
16. Mineral fillers as claimed in any one of claims 10 to 14,
characterised in that they consist of natural calcium carbonates
selected from chalk, calcite and marble, precipitated calcium
carbonate, dolomite, aluminum or magnesium hydroxides, kaolin,
talc, wollastonite and mixtures thereof.
17. Mineral fillers as claimed in anyone of claims 10 to 16,
characterised in that they consist of products having an average
diameter of between 0.1 and 15 micrometres, preferably between 0.1
and 10 micrometres.
18. Mineral fillers as claimed in any one of claims 10 to 16,
characterised in that they consist of products having an average
diameter of between 0.3 and 8 micrometres.
19. Mineral fillers as claimed in any one of claims 10 to 18,
characterised in that they are selected from amongst the following:
a marble with an average diameter of 8 micrometres, a magnesium
hydroxide with an average diameter of between 1.4 and 1.8
micrometres, a talc with an average diameter of 2.5 micrometres, a
dolomite with an average diameter of 3 micrometres, an aluminium
hydroxide with an average diameter of 0.8 micrometres, a kaolin
with an average diameter of 0.5 micrometres, a precipitated calcium
carbonate with an average diameter of 0.30 micrometres.
20. Mineral fillers as claimed in any one of claims 10 to 19,
characterised in that they conserve their hydrophilic nature whilst
exhibiting an up-take of polyol reduced by at least 15% and
preferably at least 20% relative to the untreated mineral
filler.
21. Suspensions of mineral fillers in polyols, characterised in
that the filler is a filler as claimed in any one of claims 10 to
20.
22. Suspensions of mineral fillers in polyols, as claimed in claim
21, characterised in that the polyols used belong to the families
of the polyethers and polyesters-polyethers and the polyesters, in
particular, among the polyol polyethers the addition products of
propylene oxide on a simple polyol such as glycol, glycerol,
trimethylolpropane, sorbitol, in the presence of ethylene oxide or
not, or the special polyol polyethers such as the amine-based
polyethers obtained by the addition of propylene oxide or
optionally ethylene oxide on amines, halogen polyethers, grafted
polyethers resulting from the copolymerisation of styrene and
acrylonitrile in suspension in a polyether, or alternatively
polytetramethylene glycol, in particular among the polyol
polyesters those resulting from the polycondensation of
polyalcohols on polyacids or their anhydrides, such as the diacids,
such as adipic, phthalic or other diacids, reacting with diols such
as ethylene glycol, propylene glycol, butylene glycol or others,
triols such as glycerol, trimethylolpropane or others and tetrols
such as pentaerythritol or others, alone or in a mixture, or
various hydroxyl compounds such as hydroxylated polybutadienes, the
prepolymers with hydroxyl terminations resulting from the reaction
of excess polyol on a diisocyanate or the simple polyols such as
glycerol, amino alcohols used in a small quantity with the polyol
polyethers or the polyol polyesters.
23. Suspensions of mineral fillers in polyols as claimed in claim
21 or claim 22, characterised in that they contain other mineral
and/or organic products such as catalysts and/or anti-oxidants
and/or others.
24. Suspensions of mineral fillers in polyols as claimed in any one
of claims 21 to 23, characterised in that the concentration of dry
substance of the treated mineral substances may be as high as 80%
by weight, and in that they are not susceptible either to
decantation or sedimentation or damning thickening after storage
for 7 days in readiness for the manufacture of flexible, semi-rigid
or rigid polyurethane foams, i.e. having a stable apparent
Brookfield viscosity which is lower than that of suspensions of
mineral fillers which have not been treated and in that they
contain 0.5% to 3% by weight, relative to the weight of the mineral
filler, of at least one treatment agent having the general formula
(1).
25. Pre-mixtures of mineral fillers with a polyol and in particular
in proportions appropriate for the manufacture of polyurethanes and
more specifically polyurethane foams either by foaming without an
auxiliary blowing agent or by foaming with an auxiliary blowing
agent such as methylene chloride, acetone or CO.sub.2 or others, or
composite polyurethanes, characterised in that the fillers are
pre-treated by a method as claimed in any one of claims 1 to 9.
26. Pre-mixtures of mineral fillers with a polyol as claimed in
claim 25, characterised in that the filler consists of a filler
such as described in any one of claims 15 to 19, in particular
natural calcium carbonates selected from among chalk, calcite and
marble, precipitated calcium carbonate, aluminium or magnesium
hydroxides, kaolin, talc, wollastonite and mixtures thereof.
27. Use of the pre-mixtures of mineral filler and polyol as claimed
in claims 25 or 26 for the manufacture of flexible, semi-rigid or
rigid polyurethane foams by the method, either by foaming without
an auxiliary blowing agent or by foaming with an auxiliary blowing
agent such as methylene chloride, acetone or CO.sub.2 or others,
and for the manufacture of composite polyurethanes.
28. Use of pre-mixtures of mineral filler and polyol as claimed in
claim 25 or 26 for the manufacture of composite materials with a
polyurethane matrix, cellular or not, such as polyurethanes
reinforced with vegetable fibres or glass or quartz or synthetic
fibres, cut fibres in general, or similar, in particular in the
field of accessories for the automotive industry, for the transport
sector, in particular road or rail, and industrial accessories used
in a variety of applications.
29. Flexible, semi-rigid or rigid polyurethane foams obtained by
the method either by foaming without an auxiliary blowing agent or
by foaming with an auxiliary blowing agent such as methylene
chloride, acetone or CO.sub.2 or others, characterised in that they
incorporate a filler pre-treated as claimed in any one of claims 10
to 20.
30. Composite polyurethanes, cellular or not, characterised in that
they incorporate a filler pre-treated as claimed in any one of
claims 10 to 20.
31. Objects, moulded or not, characterised in that they are
obtained from foams and composite polyurethanes obtained as claimed
in claim 29 or 30.
Description
[0001] The present invention relates to the technological sector
which manufactures polyurethane foams and more specifically to the
mineral fillers used in this sector, in particular fillers of the
carbonate, hydroxide, silicate and sulphate type and similar
mineral fillers.
[0002] It is known that polyurethane foam (or PUR) is obtained by
the reaction of a polyol on an isocyanate such as toluene
diisocyanate or TDI, concurrently with a reaction of the isocyanate
on water.
[0003] To produce block foam, the "mixing head" is charged either
with a master batch of polyol and mineral additive on the one hand
and on the other band the remaining polyol, the catalyst system
such as an amine catalyst, tin catalyst or any other catalyst, one
or more surface active agents, generally of the silicon type,
water, toluene diisocyanate, optionally an auxiliary foaming agent
which may be methylene chloride, acetone and various additives such
as heat stabilising agents or, alternatively, with the polyol in
which the master batch has been diluted to the desired
concentration beforehand and on the other the above-mentioned
additives (catalyst, surface active agent, etc . . . ).
[0004] The reaction of the water on the isocyanate, catalysed by
the amine, generates CO.sub.2 which forms the foam.
[0005] In order to reduce the cost price per litre and per kilogram
of objects made from flexible, semi-rigid or rigid polyurethane
foam, which may or may not be moulded, it has become increasingly
necessary to increase the quantity of filler contained in the
flexible, semi-rigid or rigid polyurethane foams whilst conserving
or improving their physical-chemical properties, such as
compression modulus or tear strength, or improve their aesthetic or
other qualities such as their fireproof qualities, a required by
the different fields of industry such as the automotive, furniture,
building and other industries.
[0006] These days, there are several methods of incorporating the
mineral fillers with these polyurethane compounds.
[0007] In a first type of method (FR 2 651 236), calcium carbonate
is introduced into a polyurethane plasticiser. This method of
producing a suspension of filler in a plasticiser, which allows the
proportion of filler in the polyurethane compound to be increased,
has proved to be expensive and too awkward to implement when
manufacturing flexible, semi-rigid or rigid polyurethane foams
because of the accompanying deterioration in the physical and
chemical properties of the foams obtained using this filler
suspension.
[0008] Attempts were then made to introduce the mineral fillers to
the flexible, semi-rigid or rigid polyurethane foams in a simpler,
less costly manner, eliminating the inherent problem which causes a
significant reduction in the reaction capacity of the polyurethane
foams.
[0009] To this end, various methods of introducing the filler into
a polyol, one of the ingredients of polyurethane, have become known
to those skilled in the art.
[0010] A first type of method is based on a teaching of grafting
methacrylic acid (DE 2 654 746, DE 2 714 291, DE 2 739 620) or
another vinyl compound such as styrene onto the polyol. However,
with this type of method the calcium carbonate suspension in the
polyol becomes unworkable, being too difficult to handle due to a
very high viscosity and a poor distribution of the filler in the
medium in conjunction with problems caused by sedimentation of the
suspension.
[0011] Another type of method consists in treating the surface of
the filler before it is introduced into the polyol using an agent,
which might be an alcohol with 8 to 14 carbon atoms for example (FR
2 531 971) or a phosphate of hydroxycarboxylic acid (EP 0 202
394).
[0012] However, these methods produce the same type of
disadvantages as those outlined above because the user is faced
with problems caused by the poor capacity of the mineral filler
treated in this way to disperse in the polyol.
[0013] Another method of treating a mineral filler has been
developed (EP 0 726 298) using at least one agent of the organic
phosphate type for treatment purposes, in conjunction with a
treated mineral filler, producing a suspension of mineral filler in
the polyols which has a high filler content and a low viscosity,
i.e. a homogeneous suspension which is not susceptible to
sedimentation or to decantation, nor does it inherently thicken
when manufacturing flexible, semi-rigid or rigid polyurethane
foam.
[0014] According to this document, the mineral fillers are treated
with a view to placing them in suspension in the polyols with the
aid of at least one agent of the organic phosphate type for
treatment purposes, having the general formula (1): 1
[0015] where R.sub.1=either H or alkyl with 8 to 40 carbon atoms or
aryl or alkylaryl or arylalkyl with 6 to 40 carbon atoms
[0016] where R.sub.2=either alkyl with 8 to 40 carbon atoms or aryl
or alkylaryl or arylalkyl with 6 to 40 carbon atoms
[0017] X=--CH.sub.2--CH.sub.2--
[0018] Y=CH(CH.sub.3)--CH.sub.2-- or --CH.sub.2--CH(CH.sub.3)--
[0019] (m+n) varies from 0 to 30 where m.ltoreq.30 and
n.ltoreq.30
[0020] (p+q) varies from 0 to 30 where p.ltoreq.30 and
q.ltoreq.30.
[0021] This latter technique is satisfactory but a new problem has
been encountered in connection with a specific and more recent
technique of manufacture of PUR foams.
[0022] According to the conventional method, the mixer head is
charged with a mixture of polyol and mineral filler on the one hand
and the remaining polyol, TDI, an auxiliary foaming agent such as
methylene chloride and various additives such as a tin salt and a
surfactant, generally of the silicon type, on the other. The
reaction generates CO.sub.2 in situ, as mentioned above, which
forms the foam. Formation of the foam passes through two main
stages, the first occurring at the onset of foaming and the second
when the foam block is being stabilised, after which a mass of PUR
foam is produced which is then cut into blocks of the desired
dimension in order to make mattresses, seat coverings, etc...
[0023] A new method has been developed in recent years and is
described in particular in patents EP 0 645 226 and WO 96/00644,
whereby the CO.sub.2 is injected into the mixing head directly or
through the polyol flow in the liquid state. The CO.sub.2 is
therefore used as an auxiliary blowing agent.
[0024] This method has advantages, particularly. in terms of
reducing in quite a remarkable way the use and formation of toxic
or inflammable products and is likely to take on increasing
importance in the future.
[0025] However, this new method does have technical problems in
addition to those inherent in manufacturing PUR foam.
[0026] In order to implement a method of this type correctly, known
as PUR foam with CO.sub.2 or "CO.sub.2 method", it seems to be
necessary to reduce significantly the time needed to mix the filler
with the polyol and to improve the mixing quality.
[0027] As proposed by this invention, it has been found that the
problem of the mixing time and the difficulties inherent in the new
CO.sub.2 method can be resolved by treating a mineral filler in a
manner comparable to the techniques described in EP 0 726 298, but
with significant improvements.
[0028] Surprisingly, it was also discovered whilst conducting
research into the CO.sub.2 method that the method used to treat the
mineral fillers as proposed by the invention also improves the
conventional processes used to manufacture PUR foams.
[0029] Accordingly, the invention is not limited to the CO.sub.2
processes, which was the original problem to be resolved, but on
the contrary is applicable in a general manner.
[0030] It has also been found that the method proposed by the
invention for treating mineral fillers can be applied to the
methods used to manufacture composite materials with a PUR matrix,
whether or not they are cellular, and that whatever the filler
used: CaCO.sub.3, talcs, kaolins, aluminium hydroxide, magnesium
hydroxide, etc... in numerous applications in the field of
accessories for the automotive industry, for the transport sector,
in particular road or rail and for industrial objects used in a
variety of applications.
[0031] By the terms "composite materials" or "composite PUR" used
here is meant polyurethanes reinforced with vegetable fibres, glass
or quartz or synthetic fibres, cut fibres in general, or similar.
By the expression "cellular PUR" used here is meant polyurethanes,
whether they are expanded or not.
[0032] The invention relates to a method of treating mineral
fillers of a specific grain size with the aid of processing agents
of the organic phosphate type, incorporating a de-agglomeration
stage and optionally a selection stage, with a view to improving
the techniques applied to manufacturing PUR foams either by foaming
without an auxiliary blowing agent or foaming with an auxiliary
blowing agent such as methylene chloride, acetone or CO.sub.2 or
others, and composite PURs, whilst reducing the time taken to mix
the filler treated in this way, with the polyol and other reagents
and overcoming the specific difficulties encountered with regard to
the filler agglomerates which clog the static dispersing equipments
provided for the CO.sub.2 and which tend to detract from the
mechanical properties of PUR foams and. composites, cellular or
not, such as the tear strength of PUR foams, for example.
[0033] More specifically, the invention relates to a method of
treating mineral fillers, characterised in that the filler:
[0034] a) is treated using at least one compound of the general
formula (1): 2
[0035] where R.sub.1=either H or alkyl with 8 to 40 carbon atoms or
aryl or alkylaryl or arylalkyl with 6 to 40 carbon atoms
[0036] where R.sub.2=either alkyl with 8 to 40 carbon atoms or aryl
or alkylaryl or arylalkyl with 6 to 40 carbon atoms
[0037] X=--CH.sub.2--CH.sub.2-- or --CH(CH.sub.3)--CH.sub.2--
[0038] or --CH.sub.2--CH(CH.sub.3) or --(CH.sub.2).sub.5--CO--
[0039] Y=--CH.sub.2--CH.sub.2-- or --CH(CH.sub.3)--CH.sub.2--or
--CH.sub.2--CH(CH.sub.3)-- or --(CH.sub.2).sub.5--CO--
[0040] X and Y being the same or different,
[0041] (m+n) varies from 0 to 60 (boundaries included) as well as
(p+q) where 0.ltoreq.m+n.ltoreq.60 and 0.ltoreq.p+q.ltoreq.60 when
X=Y=--CH.sub.2--CH.sub.2--and
[0042] where (1.ltoreq.m.ltoreq.10 and 1.ltoreq.p.ltoreq.10) and
(0.ltoreq.n.ltoreq.59 and 0.ltoreq.q.ltoreq.59) if X is different
from Y.
[0043] b) undergoes a de-agglomeration step and
[0044] c) optionally undergoes a selection step.
[0045] Said filler is of a specific grain size as described
below.
[0046] By the term "de-agglomeration" is meant a step whereby the
number of agglomerates are reduced using an appropriate apparatus,
of the crusher type, more specifically a crusher of the pin type or
known "attritor" type. The agglomerates can be evaluated by a known
method in accordance with the North gauge procedure, which is
governed by a standard (ISO 1524).
[0047] By "selection" is meant the operation whereby a certain
range within the grain size is separated by passage through
"separators" (screens, dynamic classifiers, etc . . . which are
known). An operation of this type does not affect the quality of
the product but the skilled person will be able to decide whether
to apply it or not as a means of optimising the product, depending
on the anticipated end use.
[0048] By "specific grain size" for the purposes of the invention
is meant that the grain size must be neither too fine nor too
coarse and should be produced directly by crushing or by mixing
fillers. In one illustrative but not restrictive example, given in
order to provide an understanding of this criterion, the filler may
substantially have a mean diameter of d50 in terms of grain size.
This mean diameter for the mineral fillers proposed by the
invention will be between 0.1 micrometres and 15 micrometres,
preferably between 0.1 micrometres and 10 micrometres and most
preferably between 0.3 and 8 micrometres. Furthermore, the person
skilled in the art will know how to make up fillers which comply
with this requirement.
[0049] The invention also relates to mineral fillers of a specific
grain size treated with this treatment agent by a de-agglomeration
step, and optionally a selection step, requiring a shorter time to
mix the filler thus treated with the polyol and other reagents and
intended to be placed in suspension in a polyol with a view to use
in the manufacture of polyurethane foams either by foaming without
an auxiliary blowing agent or foaming with an auxiliary blowing
agent such as methylene chloride, acetone or CO.sub.2 or others, or
composite PURs, and more specifically mineral fillers of the
carbonate type treated by this method and for this purpose.
[0050] The invention also relates to suspensions in the polyols of
the mineral fillers so treated, prepared so that they can be
incorporated in a method of manufacturing PUR foams either by
foaming without an auxiliary blowing agent or foaming with an
auxiliary blowing agent such as methylene chloride, acetone or
CO.sub.2 or others, as well as their use in the manufacture of
flexible, semi-rigid or rigid polyurethane foams by the method
either by foaming without an auxiliary blowing agent or foaming
with an auxiliary blowing agent such as methylene chloride, acetone
or CO.sub.2 or others and for the manufacture of composite
polyurethanes.
[0051] In addition, the invention relates to the actual foams
obtained by a method involving either by foaming without an
auxiliary blowing agent or foaming with an auxiliary blowing agent
such as methylene chloride, acetone or CO.sub.2 or others, or
composite polyurethanes, cellular or not, containing the fillers
treated by the method of the invention in a mixture with
polyol.
[0052] Furthermore, the invention relates to the use of flexible,
semi-rigid or rigid polyurethane foams or composites, cellular or
not, thus obtained for the manufacture of moulded or non-moulded
objects.
[0053] The invention also relates to the preliminary mixtures with
a polyol of the fillers treated by the method of the invention and
in particular in proportions appropriate to the manufacture of
polyurethanes and more specifically polyurethane foams or composite
PURs.
[0054] In a preferred embodiment of the invention, the filler will
be used immediately it leaves the manufacturing equipment, the
moisture content of which will be compatible with its
application.
[0055] Most preferably, the mineral filler will be treated with an
acid phosphate of aliphatic alcohol, branched or not, with 8 to 20
carbon atoms, onto which 0 to 12 ethylene oxide chains are
condensed, and may optionally contain a mixture of mono-esters and
di-esters.
[0056] The treatment proposed by the invention is implemented dry
or wet.
[0057] The mineral fillers treated as proposed by the invention and
which enable stable and homogeneous suspensions to be obtained in
the polyols are selected from among the mineral fillers which
impart to polyurethane foams and PURs used to make up composites
with a PUR matrix, cellular or not, physical and chemical
properties that are compatible with the use to which these products
will be put when manufacturing objects, moulded or not, and are
selected in particular from among the carbonates, phosphates and
sulphates of natural or synthetic alkaline earths such as, in
particular, calcium carbonates of natural or synthetic origin,
magnesium carbonate, zinc carbonate, the combined salts of
magnesium and calcium such as dolomites, lime, magnesia, barium
sulphate, calcium sulphates, magnesium hydroxides, aluminium
hydroxides, silica, wollastonite, the clays and other
silico-alumina such as the kaolins, silica-magnesia such as talc,
mica, solid or hollow glass beads, the metal oxides such as zinc
oxide, the iron oxides, titanium oxide and more specifically
selected from among the natural or precipitated calcium carbonates
such as chalk, calcite, marble, the dolomites, aluminum hydroxide,
magnesium hydroxide, talc or mixtures thereof.
[0058] The mineral fillers proposed by the invention are
distinctive compared with those of the prior art due to the fact
that they retain their hydrophilic properties and exhibit an
up-take of polyol which is reduced by at least 15% and preferably
at least 20% as compared with an untreated mineral filler and more
specifically the fact that they are obtained by the method of the
invention.
[0059] By "preferably" is meant that the invention also covers the
values of between 15% and 20% although the effectiveness of the
results is better the greater the decrease in polyol take-up.
[0060] By definition, the polyol take-up, which represents the
absorption capacity of the fillers, is the number of milligrams or
grams of polyol used for 100 g or 100 ml of filler substance under
the test measurement conditions stipulated by a method based on the
ISO 787/5 standard.
[0061] The polyols used belong to the family of polyethers and
polyesters-polyethers and the polyesters.
[0062] Amongst the common polyol polyethers, mention may be made,
for example, of the addition products of propylene oxide on a
simple polyol such as, for example, glycol, glycerol,
trimethylolpropane, sorbitol, in the presence of ethylene oxide or
not. However, mention may also be made of the special polyol
polyethers such as, for example, the amine-based polyethers
obtained by the addition of propylene oxide or optionally ethylene
oxide on amines, halogen polyethers, grafted polyethers resulting
from the copolymerisation of styrene and acrylonitrile in
suspension in a polyether, or alternatively polytetramethylene
glycol.
[0063] Amongst the polyol polyesters, mentioned may be made, for
example, of those resulting from the polycondensation of
polyalcohols on polyacids or their anhydrides, such as the diacids,
such as, for example, adipic, phthalic or other diacids, reacting
with diols (for example ethylene glycol, propylene glycol, butylene
glycol or others), triols (for example glycerol, trimethylolpropane
or others) and tetrols (for example pentaerythritol or others,
alone or in a mixture).
[0064] Other polyols which may also be mentioned are various
hydroxyl compounds such as, for example, hydroxylated
polybutadienes, the prepolymers with hydroxyl terminations
(resulting from the reaction of excess polyol on a diisocyanate) or
the simple polyols such as, for example, glycerol, amino alcohols
used in a small quantity with the polyol polyethers or the polyol
polyesters in order to increase cross-linking.
[0065] The suspensions of mineral fillers in the polyols, as
proposed by the invention, which may also contain other mineral
and/or organic products such as catalysts and/or anti-oxidants
and/or others, are characterised in that the concentration of dry
substance of the treated mineral substances may be as high as 80%
by weight, and in that they are not susceptible either to
decantation or sedimentation or damning thickening after storage
for 7 days in readiness for the manufacture of flexible, semi-rigid
or rigid polyurethane foams, i.e. having a stable apparent
Brookfield viscosity which is lower than that of suspensions of
mineral fillers which have not been treated and in that they
contain 0.5% to 3% by weight, relative to the weight of the mineral
filler, of at least one treatment agent having the general formula
(1).
[0066] An additional objective of the invention is to produce
homogenous, stable and low-viscosity suspensions of these treated
mineral fillers in the polyols, characterised by a concentration by
weight of mineral fillers which may be as high as 80% and a content
of treatment agent which may range from 0.5% to 3% by weight
relative to the dry weight of the filler and containing no
agglomerates.
[0067] These homogeneous, stable, low-viscosity suspensions
proposed by the invention are easy to handle because they do not
exhibit, under the normal conditions in which they are used by the
skilled person, any occurrence of decantation, i.e. the separation
in two phases, of sedimentation, i.e. the presence of a hard
deposit at the bottom of the tank in which the suspension is
stored, nor is there any damning thickening, which means that it
will be possible to produce flexible, semi-rigid or rigid
polyurethane foams or composite PURs, cellular or not, with
excellent physical and chemical properties.
[0068] Finally, another objective of the invention is the use of
these homogeneous, stable and low-viscosity dispersions of mineral
fillers for the manufacture of flexible, semi-rigid or rigid
polyurethane foams or cellular or non-cellular composites as well
as the use of these foams or these composites for the manufacture
of objects which may or may not be moulded.
[0069] The homogeneous, stable and low-viscosity suspensions filled
in this manner, as proposed by the invention, exhibit a specific
feature in that they can be used for the manufacture of
polyurethane foams, regardless of whether they are flexible,
semi-rigid or rigid, or for the manufacture of polyurethane
composites, which may be cellular or not.
[0070] Furthermore, the flexible, semi-rigid or rigid polyurethane
foams, cellular or not, obtained by using the suspensions of
mineral fillers, treated as proposed by the invention, in polyols
are used to make objects which may or may not be moulded.
[0071] Other features and advantages of the invention will become
clear from the description given below.
[0072] The scope and interest of the invention will be more readily
appreciated from the examples given below, although these are not
intended to be restrictive in any respect.
EXAMPLE 1
[0073] A. Tests for Preparing Various Treated Fillers
[0074] To this end, tests No. 1 to 10 were conducted using three
different filler bases and a treatment agent of the phosphate type,
referred to as "AGT" hereafter, as set out in the various
tables.
[0075] Tests No. 1 to 4:
[0076] These tests illustrate the invention and are conducted using
a treatment agent which is a mixture of mono-ester and di-ester of
acid phosphate of decyl alcohol having 5 mols of ethylene oxide,
using as the filler a Champagne chalk having an average diameter of
2 micrometres (product A).
[0077] Test No. 1:
[0078] For this test, the treated filler was made in accordance
with the method proposed by the invention by introducing the agent
proposed by the invention (AGT) simultaneously with the
de-agglomeration operation into a pin mill, followed by a fine
selection process using a 24-dynamic classifier.
[0079] Test No. 2:
[0080] For this test, the treated filler was made using the method
proposed by the invention by introducing the agent proposed by the
invention (AGT) prior to the de-agglomeration and selection
operation described in test No. 1.
[0081] Test No. 3:
[0082] For this test, the treated filler was made in accordance
with the method proposed by the invention by introducing the agent
proposed by the invention (AGT) prior to the de-agglomeration
operation into a pin mill, followed by a fine selection process
using a 16-dynamic classifier.
[0083] Test No. 4:
[0084] For this test, the treated filler was made using the method
proposed by the invention by introducing the agent proposed by the
invention (AGT) into a pin mill prior to the de-agglomeration
operation, dispensing with the selection operation.
[0085] Tests No. 5 to 7:
[0086] These tests illustrate the invention and are conducted using
as a treatment agent a mixture of mono-ester and di-ester of acid
phosphate of decyl alcohol with 5 mols of ethylene oxide and, as
the filler, a calcite with an average diameter of 1.8 micrometres
(product B).
[0087] Test No. 5:
[0088] For this test of the invention, the same method was used to
make the treated filler of the invention as that used for test No.
4.
[0089] Test No. 6:
[0090] For this test of the invention, the same method was used to
make the treated filler of the invention as that used for test No.
2.
[0091] Test No. 7:
[0092] For this test of the invention, the same method was used to
make the treated filler of the invention as that used for test No.
1.
[0093] Test No. 8:
[0094] This test illustrates the prior art and the treatment agent
used is a mixture of mono-ester and di-ester of acid phosphate of
decyl alcohol with 5 mols of ethylene oxide and a Champagne chalk
with an average diameter of 2.4 micrometres (product C) as the
filler.
[0095] To this end, 3 kg of product C (chalk) and 30 g of AGT are
introduced into a laboratory ball mill having a 15 l capacity and
containing 9 kg of crushing medium and the mixture is crushed for 4
hours to obtain the grain size of product A, without carrying out
the de-agglomeration step.
[0096] Test No. 9:
[0097] This test illustrates the invention and the treatment agent
used is a mixture of mono-ester and di-ester of acid phosphate of
decyl alcohol with 5 mols of ethylene oxide and a Champagne chalk
with an average diameter of 2.4 micrometres (product C) as the
filler.
[0098] To this end, 3 kg of product C are mixed with 1.6 kg of
water and 30 g of AGT and this "slurry" is introduced into a
laboratory ball mill having a 15 l capacity and containing 9 kg of
crushing medium, followed by crushing for 8 hours to obtain the
desired grain size, followed by drying, de-agglomeration and
selection using a 24-dynamic laboratory classifier.
[0099] Test No. 10:
[0100] This test illustrates the invention and the agent used is a
mono-ester of acid phosphate of tristyrylphenol containing 60 mols
of ethylene oxide and the filler used is a calcite with an average
diameter of 1.8 micrometres (product B).
[0101] For this test of the invention, the same method was used to
make the treated filler of the invention as that used for test No.
1.
[0102] The results of tests 1 to 4 and 5 to 7 are set out in Table
I and those of tests 8 to 10 in Table II.
1TABLE I CHARACTER- Invention Invention Invention Invention
Invention Invention Invention ISTICS TEST No. 1 2 3 4 5 6 7 FILLER
Product A Product A Product A Product A Product B Product B Product
B PRODUCT FEED RATE 700 kg/h 700 kg/h 700 kg/h 700 kg/h 700 kg/h
700 kg/h 700 kg/h TREATMENT 1% 1% 1% 1% 1% 1% 1% RATE SEPARATOR/ 24
24 16 No selector without selector 24 24 FINS De-agglomeration AGT
agent Reduced De-agglomeration De-agglomeration AGT agent injected
De-agglomeration simultaneous injected prior efficiency of without
without selection prior to de- simultaneous with with injection to
de- the selector as selection agglomeration + injection of AGT of
AGT agent + agglomeration + compared with selection agent +
selection Selection Selection test No. 2
[0103]
2TABLE II CHARACTER- Prior art Invention Invention ISTICS TEST No.
8 9 10 FILLER Product C Product C Product B PRODUCT Dry method Wet
method Dry method FEED RATE -- 1 kg/h 400 kg/h TREATMENT 1% 1% 1%
RATE SEPARATOR/ without selector 24 24 FINS Treatment and Treatment
and De-agglomeration crushing without crushing by wet simultaneous
with deagglomeration method with de- injection of AGT nor selection
agglomeration agent + selection and selection
[0104] The fillers treated in this manner, as well as the other
fillers, whether treated or not, are used for the tests described
below, which illustrate how they are dispersed in a polyol in order
to simulate the speed and ease with which the filler is dispersed
in this polyol.
[0105] B. Tests Showing Dispersion in a polyol:
[0106] To this end, 250 g of a triol with a hydroxyl index equal to
48 mg/g and a viscosity of 750 mPa.s are weighed out and placed in
a metal container of a height of 105 mm and a diameter of 90 mm and
are then placed under agitation using an agitator of the Pendraulik
brand fitted with a de-flocculating blade having a diameter of 50
mm and a speed regulator. The rotation speed of the agitation shaft
was checked with a tachymeter (380 or 690 r/min.) 25 g of mineral
were introduced into the polyol and the timer started immediately
all the powder is introduced. Samples of 2 or 3 g of dispersion are
taken at regular intervals using a Pasteur pipette . The sample is
applied to the North gauge (0 to 100 .mu.m) and the measurement
taken as described in ISO standard 1524. The gauge reading used is
the value on the scale at which the first point of non-dispersed
mineral appears. The North gauge is cleaned with isopropyl alcohol
and dried between each test.
[0107] In each of tests No. 11 to 28, the polyol used is described
in Tables III-I, III-2 and III-3 below, which set out the
results.
3 TABLE III-1 Test 11 Test 12 Test 13 Test 14 Test 15 Test 16 Test
17 REFERENCE INVENTION PRIOR ART PRIOR ART PRIOR ART REFERENCE
PRIOR ART Filler type Product A Product A Product D Product A +
Product A + Product A Product D 0.5114% AGT 0.4742% AGT Filler
quantity 25 g 25 g 25 g 25 g 25 g 25 g 25 g Polyol type IOH 48 IOH
48 IOH 48 IOH 48 IOH 48 IOH 48 IOH 48 Visco 750 Visco 750 Visco 750
Visco 750 Visco 750 Visco 750 Visco 750 Polyol quantity 250 g 250 g
250 g 250 g 250 g 250 g 250 g Mixing speed 380 r./min. 380 r./min.
380 r./min. 380 r./min. 690 r./min. 690 r./min. 690 r./min. Gauge
after 2 min 0 0 0 0 0 0 / Gauge after 5 min 0 0.5 0 0 0 0 1 Gauge
after 8 min 0 4.5 0 0 0 1 1 Gauge after 10 min 0 / 0 0 0 1 1.5
Gauge after 12 min / 7 0 0 0 1 2 Gauge after 15 min / / / / / 1 1.5
Gauge after 18 min / / / / / 2 1 Gauge after 20 min / / / / / 2.5 2
Gauge after 22 min / / / / / 3 3 Gauge after 24 min / / / / / 3.5 /
Gauge after 25 min / / / / / / 3 Gauge after 26 min / / / / / 3.5 /
Gauge after 28 min / / / / / 4.5 2 Gauge after 30 min / / / / / 4.5
2 Gauge after 32 min / / / / / 5 / Gauge after 35 min / / / / / /
/
[0108]
4 TABLE III-2 Test 18 Test 19 Test 20 Test 21 Test 22 Test 23 Test
24 Test 25 PRIOR ART PRIOR ART INVENTION INVENTION INVENTION
INVENTION INVENTION PRIOR ART Filler type Product A + Product B +
Product Product Product Product Product Product GUEDU GUEDU Test 1
Test 2 Test 3 Test 4 Test 5 Test 8 Filler quantity 25 g 25 g 25 g
259 25 g 25 g 25 g 25 g Polyol type IOH 48 IOH 48 IOH 48 IOH 48 IOH
48 IOH 48 IOH 48 IOH 48 Visco 750 Visco 750 Visco 750 Visco 750
Visco 750 Visco 750 Visco 750 Visco 750 Polyol quantity 250 g 250 g
2509 250 g 250 g 250 g 250 g 250 g Mixing speed 380 r./min. 380
r./min. 690 r./min. 690 r./min. 690 r./min. 690 r./min. 690 r./min.
690 r./min. Gauge after 0 0 0.5 / / / / / 2 min Gauge after 0 0 4.5
1.5 4 1.5 2.5 0 5 min Gauge after 0 0 2 / / / / / 8 min Gauge after
0 0 2 3.5 5 3 4 0 10 min Gauge after 0 0 3 / / / / / 12 min Gauge
after 0 0 6 4 3.5 3.5 4 0 15 min Gauge after / / / / / / / / 18 min
Gauge after / 0 3 2 4 3.5 3 0 20 min Gauge after / / / / / / / / 22
min Gauge after / / / / / / / / 24 min Gauge after / / 5.5 3 4 3.5
2.5 0 25 min Gauge after / / / / / / / / 26 min Gauge after / / / /
/ / / / 28 min Gauge after / / 6 2 4.5 3.5 2.5 0 30 min Gauge after
/ / / / / / / / 32 min Gauge after / / / / / / / / 35 min
[0109]
5 TABLE III-3 Test 26 Test 27 Test 28 INVENTION INVENTION INVENTION
Filler type Product Product Product B + Test 9 Test 10 1% AGT
Filler quantity 25 g 25 g 25 g Polyol type IOH 48 IOH 48 IOH 48
Visco 750 Visco 750 Visco 750 Polyol quantity 250 g 250 g 250 g
Mixing speed 690 r./min. 690 r./min. 690 r./min. Gauge after 2 min
/ 2.5 4 Gauge after 5 min 0 3 4.5 Gauge after 8 min / / / Gauge
after 10 min 2 / 5 Gauge after 12 min / / / Gauge after 15 min 3 /
5 Gauge after 18 min / 3.5 / Gauge after 20 min 2 / 5 Gauge after
22 min / / / Gauge after 24 min / / / Gauge after 25 min 3 / /
Gauge after 26 min / / / Gauge after 28 min / / / Gauge after 30
min 2 / / Gauge after 32 min / / / Gauge after 35 min / / /
[0110] In these tables, AGT refers to the agent of the phosphate
type proposed by the invention, GUEDU the known mixer and IOH the
hydroxyl index.
[0111] Test No. 11:
[0112] This test illustrates the dispersion of a Champagne chalk of
an average diameter of 2 micrometres, not treated, in the
above-mentioned polyol.
[0113] There is no gauge reading and therefore none of the mixing
performed is homogeneous and without agglomerates.
[0114] The result is poor; this is a reference test.
[0115] Test No. 12:
[0116] This test represents an example of the invention using
Product A from test No. 1. The gauge reading is 4.5 after 8
minutes.
[0117] Accordingly, mixing is good after 8 minutes.
[0118] Test No. 13:
[0119] This test represents the prior art and a Champagne chalk is
used, simply treated with stearic acid and having an average
diameter of 2 micrometres and commercially available (Product
D).
[0120] The result is poor.
[0121] Test No. 14:
[0122] This test illustrates the addition of the treatment agent
used for tests 1 to 9, not for treating the filler as in tests No.
1 to 9 but as a dispersing agent, since it is added to the
filler-polyol mixture.
[0123] The results are poor and confirm the importance of
performing the treatment proposed by one of the steps of the
invention.
[0124] Test No. 15:
[0125] This test is identical to test No. 14 except for the
quantity of agent (very little) and the agitation speed used to
form the mixture (almost double) in order to supply greater
dispersion energy.
[0126] The result is also poor.
[0127] Test No. 16:
[0128] This test is identical to No. 11 except for the agitation
speed used to form the mixture (almost double), which shows that
more than 20 minutes are needed in order to produce a good mixture
(gauge=3), hence requiring much more mechanical energy.
[0129] Test No. 17:
[0130] This test is identical to No. 13 except for the agitation
speed used to form the mixture (almost double), which shows that
more than 20 minutes are needed in order to produce a good mixture
(gauge=3), hence requiring much more mechanical energy.
[0131] Tests No. 18 and 19:
[0132] These tests use a simple mixer of the Guedu type and produce
poor results, proving that the treatment performed in accordance
with the steps of the invention is not one of simple mixing.
[0133] Test No. 18:
[0134] This test is conducted with an untreated Champagne chalk of
an average diameter of 2 micrometres. The mixing process in the
Guedu mixer is performed using a treatment agent of the mono-ester
and di-ester of nonylphenol phosphate type containing 30 ethylene
oxide chains.
[0135] Test No. 19:
[0136] This test is conducted with an untreated calcite of an
average diameter of 1.8 micrometres. The mixing process in the
Guedu mixer is performed using a treatment agent of the mono-ester
and di-ester of acid phosphate of decyl alcohol type containing 5
ethylene oxide chains.
[0137] Tests No. 20 to 23:
[0138] These tests respectively show the use of the test products
No. 1 to 4 and are variations of the method proposed by the
invention, demonstrating that de-agglomeration is sufficient and
selection is not compulsory.
[0139] Test No. 24:
[0140] This test illustrating the invention is conducted using
calcite instead of chalk (the product of test No. 5 is used).
[0141] The result (gauge=4 after 10 minutes) can be regarded as
good.
[0142] Test No. 25:
[0143] This test uses the product of test No. 8 of the prior art
and shows that crushing in the ball mill without de-agglomeration
does not produce satisfactory results.
[0144] Test No. 26:
[0145] This test uses the product of test No. 9 and gives suitable
results (gauge=3 after 15 minutes); this test demonstrates the
possibility of using a treatment proposed by the invention with the
wet method.
[0146] Test No. 27:
[0147] This test uses the product of test No. 10 and gives suitable
results (gauge=3 after 5 minutes); this test is an example of what
happens when an agent of a different type proposed by the invention
is used.
[0148] Test No. 28:
[0149] This tests uses a calcite (product B) treated by the method
proposed by the invention for test No. 1, using 1% by weight of a
mixture of acid phosphate mono-ester and di-ester of ketostearylic
alcohol.
[0150] This test produces suitable results (gauge=4 after 2
minutes) and is an example showing the use of an agent of a
different type proposed by the invention.
EXAMPLE 2
[0151] This example relates to the use of different fillers, all
treated using the method of test No. 1.
[0152] The following are the different fillers that were used:
6 Product R: marble with an average diameter of 8 micrometres,
Product S: commercial magnesium hydroxide with an average diameter
of 1.4-1.8 micrometres, Product T: talc with an average diameter of
2.5 micrometres, Product U: dolomite with an average diameter of 3
micrometers, Product V: aluminium hydroxide with an average
diameter of 0.8 micrometres, Product G: kaolin with an average
diameter of 0.50 micrometres, Product W: precipitated calcium
carbonate with an average diameter of 0.3 micrometres.
[0153] Test No. 29:
[0154] This test is a reference test representing an untreated
kaolin with an average diameter of 0.50 micrometres, dispersed in
the above-mentioned polyol.
[0155] There was no gauge reading and therefore no mixture was
formed that was homogeneous and without agglomerates.
[0156] The result was poor.
[0157] Test No. 30:
[0158] This test is a test of the invention, based on the method of
test No. 1, using a kaolin of an average diameter of 0.50
micrometres treated with 1.5% by weight of the agent used in test
No. 1.
[0159] The gauge reading is good compared with the reference
test.
[0160] Test No. 31:
[0161] This is a reference test conducted with product U. There was
no gauge reading.
[0162] Test No. 32:
[0163] This is a test of the invention, conducted on treated
product U, using the method of test No. 1, with 1.5% by weight of
the agent used in test No. 1. The gauge reading was good compared
with the reference test.
[0164] Test No. 33:
[0165] This test is a reference test with product W. There is no
gauge reading.
[0166] Test No. 34:
[0167] This is a test of the invention, conducted on treated
product W, using the method of test No. 1, with 2.5% by weight of
the agent used in test No. 1. The gauge reading was good compared
with the reference test.
[0168] Test No. 35:
[0169] This test is a reference test conducted on product R. There
is no gauge reading.
[0170] Test No. 36:
[0171] This is a test of the invention, conducted on treated
product R, using the method of test No. 1, with 1% by weight of the
agent which is an acid phosphate mono-ester and di-ester of
nonylphenol containing 10 mols of ethylene oxide. The gauge reading
was good compared with the reference test.
[0172] Test No. 37:
[0173] This test is a reference test conducted on a mixture
(product A+product T) with an average diameter of 2.5 micrometres
in a ratio of 50/50 by weight. There is no gauge reading.
[0174] Test No. 38:
[0175] This is a test of the invention, conducted on the treated
product used in test No. 37, using the method of test No. 1, with
0.5% of the agent used in test No. 1. The gauge reading was good
compared with the reference test.
[0176] Test No. 39:
[0177] This test is a reference test conducted on product V. There
is no gauge reading.
[0178] Test No. 40:
[0179] This is a test of the invention, conducted on treated
product V, using the method of test No. 1, with 1.2% of the agent
used in test No. 1. The gauge reading was good compared with the
reference test.
[0180] Test No. 41:
[0181] This is a reference test on product S. There is no gauge
reading.
[0182] Test No. 42:
[0183] This is a test of the invention, conducted on treated
product S, using the method of test No. 1, with 1.5% of the agent
used in test No. 1. The gauge reading was good compared with the
reference test.
[0184] The results are set out in Tables IV-1 and IV-2 below.
7 TABLE IV-1 Test 29 Test 30 Test 31 Test 32 Test 33 Test 34
REFERENCE INVENTION REFERENCE INVENTION REFERENCE INVENTION Filler
type Product G Product G + Product U Product U + Product W Product
W + 1.5% AGT 1.5% AGT 2.5% AGT Filler quantity 25 g 259 25 g 25 g
25 g 25 g Polyol type IOH 48 IOH 48 IOH 48 IOH 48 IOH 48 IOH 48
Visco 750 Visco 750 Visco 750 Visco 750 Visco 750 Visco 750 Polyol
quantity 250 g 250 g 250 g 250 g 250 g 250 g Mixing speed 690
r./min. 690 r./min. 690 r./min. 690 r./min. 690 r./min. 690 r./min.
Gauge after 2 min 0 0 0 1 0 4 Gauge after 5 min 0 1 0 2 0 4 Gauge
after 8 min 0 2 0 / 0 4.5 Gauge after 10 min 0 2 0 3 0 5 Gauge
after 12 min 0 2 0 / 0 6 Gauge after 15 min 0 3 0 3 0 6 Gauge after
18 min 0 3.5 0 / 0 6 Gauge after 20 min 0 3 0 4 0 7 Gauge after 22
min / 3.5 / / / / Gauge after 24 min / 3 / / / / Gauge after 25 min
/ 3 / 4 / 7 Gauge after 26 min / / / / / / Gauge after 28 min / / /
/ / / Gauge after 30 min / / / / / / Gauge after 32 min / / / / / /
Gauge after 35 min / / / / / /
[0185]
8 TABLE IV-2 Test 35 Test 36 Test 37 Test 38 Test 39 Test 40 Test
41 Test 42 REFERENCE INVENTION REFERENCE INVENTION REFERENCE
INVENTION REFERENCE INVENTION Filler type Product R Product R +
Product A + Product Test Product V Product V + Product S Product S
+ 1% NP1OP04 Product T 37 + 1.2% AGT 1.5% AGT 0.5% AGT Filler
quantity 25 g 25 g 25 g 25 g 25 g 25 g 25 g 25 g Polyol type IOH 48
IOH 48 IOH 48 IOH 48 IOH 48 IOH 48 IOH 48 IOH 48 Visco 750 Visco
750 Visco 750 Visco 750 Visco 750 Visco 750 Visco 750 Visco 750
Polyol quantity 250 g 250 g 250 g 250 g 250 g 250 g 250 g 250 g
Mixing speed 690 r./min. 690 r./min. 690 r./min. 690 r./min. 690
r./min. 690 r./min. 690 r./min. 690 r./min. Gauge after 0 3 0 4 0 5
0 5 2 min Gauge after 0 3 0 4.5 0 5 0 / 5 min Gauge after 0 3.5 0 /
0 6 0 5 8 min Gauge after 0 3.5 0 / 0 6 0 / 10 min Gauge after 0
3.5 0 / 0 / 0 6 12 min Gauge after 0 3 0 6.5 0 / 0 / 15 min Gauge
after 1 3.5 0 7 0 / 0 7 18 min Gauge after 1 3 0 / 0 6 0 7 20 min
Gauge after 1 / / / / / / 6.5 22 min Gauge after 1 / / / / / / / 24
min Gauge after 1 / / / / / / / 25 min Gauge after / / / / / / / /
26 min Gauge after / / / / / / / / 28 min Gauge after / / / / / / /
/ 30 min Gauge after / / / / / / / / 32 min Gauge after / / / / / /
/ / 35 min
[0186] A review of Tables IV shows that the method proposed by the
invention enables suspensions of various mineral fillers in a
polyol to be obtained which are homogeneous and contain particles
of less than 70 micrometres after 15 minutes.
EXAMPLE 3
[0187] This example relates to the manufacture of preliminary
mixtures of mineral fillers with a polyol using different
quantities of filler.
[0188] Test No. 43:
[0189] This test illustrates the invention and uses product A as a
filler treated as in test No. 1 and, as a polyol, a polyol with a
hydroxyl index of 48 mg/g and a viscosity of 700 mPa.s at
200.degree. C. in a ratio by weight of 60% polyol-40% calcium
carbonate.
[0190] Test No. 44:
[0191] This test illustrates the invention and uses product A as a
filler treated as in test No. 1 and, as a polyol, a polyol with a
hydroxyl index of 48 mg/g and a viscosity of 700 mPa.s at
200.degree. C. in a ratio by weight of 50% polyol-50% calcium
carbonate.
[0192] Test No. 45:
[0193] This test illustrates the invention and uses product A as a
filler treated as in test No. 1 and, as a polyol, a polyol with a
hydroxyl index of 48 mg/g and a viscosity of 700 mPa.s at
200.degree. C. in a ratio by weight of 40% polyol-60% calcium
carbonate.
[0194] Test No. 46:
[0195] This test illustrates the invention and uses product A as a
filler treated as in test No. 1 and, as a polyol, a polyol with a
hydroxyl index of 48 mg/g and a viscosity of 700 mPa.s at
200.degree. C. in a ratio by weight of 90% polyol-10% calcium
carbonate.
[0196] Test No. 47:
[0197] This test illustrates the invention and uses kaolin as a
filler treated as in test No. 30 and, as a polyol, a polyol with a
hydroxyl index of 56 mg/g and a viscosity of 300 mPa.s at
250.degree. C. in a ratio by weight of 50% polyol-50% kaolin.
[0198] The results are set out in Table V below.
9 TABLE V INVENTION INVENTION INVENTION INVENTION INVENTION Test 43
Test 44 Test 45 Test 46 Test 47 Polyol IOH = 48 IOH = 48 IOH = 48
IOH = 48 IOH = 56 Viscosity = 700 Viscosity = 700 Viscosity = 700
Viscosity = 700 Viscosity = 300 Quantity (% weight) 60 50 40 90 50
Filler Treated product Treated product Treated product Treated
product Treated product Test No. 1 Test No. 1 Test No. 1 Test No. 1
Test No. 30 Quantity (% of dry weight of filler) 40 50 60 10 50
Dispersant type Agent Agent Agent Agent Agent Test No. 1 Test No. 1
Test No. 1 Test No. 1 Test No. 1 Quantity (% of dry weight of
filler) 1 1 1 1 1 Brookfield viscosities after 2 hours (mPa
.multidot. s) at 23.degree. C. 10 r/min 5250 6500 29800 750 44160
100 r/min 2430 3450 9600 720 17630 Brookfield viscosities after 24
hours (mPa .multidot. s) at 23.degree. C. 10 r/min 5000 6350 28700
750 40000 100 r/min 2350 3500 9900 720 22170 Stability 7 days NO
DECANTATION, NO SEDIMENTATION, NO THICKENING
[0199] A review of Table V shows that it is possible to obtain
suspensions of mineral fillers in polyols which are not susceptible
to decantation or sedimentation or to damning thickening.
EXAMPLE 4
[0200] This example illustrates how a PUR foam containing the
fillers treated in accordance with the invention are obtained.
[0201] A known process is used to make PUR foam, using a
preliminary mixture of filler treated as described in example 3
(test No. 44 with 50% calcium carbonate) in differing PUR foam
densities and differing proportions of filler proposed by the
invention.
[0202] Test No. 48:
[0203] For this test, the anticipated density is 25 kg/m.sup.3 and
the quantity of filler is 10 parts relative to the polyol.
[0204] Test No. 49:
[0205] For this test, the anticipated density is 35 kg/m.sup.3 and
the quantity of filler is 20 parts relative to the polyol.
[0206] Test No. 50:
[0207] For this test, the anticipated density is 40 kg/m.sup.3 and
the quantity of filler is 5 parts relative to the polyol.
[0208] The results are set out in Table VI below.
10 TABLE VI TEST No. 48 49 50 Polyol (IOH = 48) 100 100 100 Treated
filler of test No. 1 10 20 5 Amine catalyst 0.15 0.18 0.39 Tin
octoate 0.22 0.24 0.19 Silicon-based surfactant 0.8 0.8 0.8 Water
4.6 4.1 2.5 TDI (isomer 80 ortho-20 para) 56.2 51 34.5 * Isocyanate
index 108 108 108 * Slurry time 17.3 18 22 * Rise time 92 100 140
Density 26 29.8 40 1 * Isocyanate index = number of NCO functions
number of OH functions .times. 100 * Slurry time = Onset of foam
formation = appearance time * Rise time = Total time from the
reaction whereby the foam is manufactured to stabilisation
[0209] A review of Table VI shows that it is possible to obtain PUR
foams by a method incorporating the improvement proposed by the
present invention.
* * * * *