Title of Invention

METHOD FOR PROCESSING A MINERAL FILLER WITH A PHOSPHATE, MINERAL FILLERS TREATED IN THIS MANNER, POLYURETHANE FOAMS AND COMPOSITE POLYURETHANES

Abstract A treated mineral filler mixed with a polyol, characterized in that it is Produced by a process wherein a mineral filler a) is treated with least one compound of the general formula (1): with R1 =either H or alkyl with C8 to C40 or aryl or alkylaryl or arylalkyl with C6 to C40, with R2 =either alkyl with C8 to C40 or aryl or alkylaryl or arylalkyl with C6 to C40, X=--CH2 -CH2 - or -CH(CH3)-CH2 --or -CH2 -CH(CH3)- or ~(CH2)5 ~ CO-, Y=-CH2 -CH2 - or -CH(CH3)-CH2 -or -CH2 ~CH(CH3)~ or -(CH2)5~ CO-, X and Y being identical or different, (m+n) ranges from 0 to 60 (including limits) as well as (p+q) with 0<=m+n<=60 and 0<=p+q<=60 when X=Y=-CH2-CH2- and with (K=m<=10 and K=p<=10) and (0<=n<=59 and 0<=q<=59) when X is different from Y; b) undergoes a deagglomeration stage; c) optionally undergoes a selection stage; and d) is mixed with a palyol.
Full Text FORM 2
THE PATENTS ACT, 1970 (39 Of 1970)
COMPLETE SPECIFICATION
(See Section 10 rule 13)




METHOD FOR PROCESSING A MINERAL FILLER WITH A PHOSPHATE, MINERAL FILLERS! TREATED IN THIS MANNER, POLYURETHANE FOAMS AND COMPOSITE POLYURETHANES

OMYA SA Of 35 QUAI ANDRE CITROEN 75725 PARIS CEDEX 15, FRANCE, FRENCH Company
The following specification particularly describes the nature of (the invention and the manner in which it is to be performed




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.
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.

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 hand 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.).
The reaction of the water on the isocyanate, catalysed by the amine, generates C02 which forms the foam.
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

2
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.
These days, there are several methods of incorporating the mineral fillers with these polyurethane compounds.

In a first type of method (FR 2651236), \/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.
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.
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.
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.
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).
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.
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.
According to this document] the mineral fillers are treated with a view to placing hem 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):
O
HO - P - 0 - (X-0)m - (Y-0)n - R,
O - (X-O) - (Y-0)q - R2
where Rj = either H or alkyl with 8 to 40 carbon atoms or aryl or alkylaryl or arylalkyl with 6 to 40 carbon atoms
where R2 = either alkyl with 8 to 40 carbon atoms or aryl or alkylaryl or arylalkyl with
6 to 40 carbon atoms
X = -CH2-CH2-
Y = CH(CH3)-CH2- or -CH2-CH(CH3)-
(m+n) varies from 0 to 30 where m s 30 and n s (p+q) varies from 0 to 30 where p s 30 and q 1 ' I
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.

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 C02 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...
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 C02 is injected into the mixing
head directly or through the polyol flow in the liquid state. The C02 is therefore used
as an auxiliary blowing agent. '.;/:
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 fluturc.
However, this new method does have technical problems in addition to those inherent
■ i
in manufacturing PUR foam.
In order to implement a method of this type correctly, known as PUR foam with C02 or "C02 method", it seems to be necessary to reduce significantly the time neededjo mix the filler with the polyol and to improve the mixing quality.
i.s proposed by this invention, it has been found that the probjejnjjf the_jnixing time land the difficulties inherent in the new C02 method can be resolved by treating a
ineral filler in a manner comparable to the techniques described in EP 0 726 298, but with significant improvements.
Surprisingly, it was also discovered whilst conducting research into the C02 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.
S '

Accordingly, the problem to be resolved,
invention is not limited to the C02 processes, which was the original but on the contrary is applicable in a general manner.

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: CaC03, 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.
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

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 C02 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 C02 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.
More specifically, the invention relates to a method of treating mineral fillers, characterised in that the filler:
a) is treated using at least one compound of the general formula (1):
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where R, = either H or alkyl with 8 to 40 carbon atoms or aryl or alkylaryl or arylalkyl
with 6 to 40 carbon atoms
where R2 = either alkyl with 8 to 40 carbon atoms or aryl or alkylaryl or arylalkyl with
6 to 40 carbon atoms
X = -CH2-CH2- or-CH(CH3)-CH2-
or-CH2-CH(CH3) or-(CH2)5-CO-
Y = CH2-CH2- or-CH(CH3)-CH2-
or -CH2-CH(CH3)- or -(CH2)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 ^ m+n 60 when X=|Y= -CH2-CH2-and
where (1 s m <: and n q if x is different from y.> b) undergoes a de-agglomeration step and
c) optionally undergoes a selection step.
Said filler is of a specific grain size as described below.
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 accordant with the North gauge procedure, which is governed by a standard (ISO 1524).
'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



7


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.
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.
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 C02 or others, or composite PURs, and more specifically mineral fillers of the carbonate type treated by this method and for this purpose.
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 C02 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 C02 or others and for the manufacture of composite polyurethanes.
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
8

blowing agent such as methylene chloride, acetone or C02 or others, or composite polyurethanes, cellular or not, containing the fillers treated by the method of the invention in a mixture with polyol.
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.
The invention also relates to the preliminary mixtures with a polyol of the fillers

the manufacture of polyurethanes and more specifically polyurethane foams or
treated by the method 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.!
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-

The treatment proposed by the invention is implemented dry or wet_

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,
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magnesia, barium sulphate, calcium sulphates, magnesium hydroxides, aluminium hydroxides, silica, wollaslonite, 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.
■ -
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.
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.
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 lOOg or 100 ml of filler substance under the test measurement conditions stipulated by a method based on the ISO 787/5 standard.
The polyols used belong to the family of polyethers and polyesters polyethers and the
polyesters.
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 i 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.
10

Amongst the polyol polyesters, mentioned may be made, for example, of those resulting from the polycondcnsation of polyalcohols on polyacids or their anhydrides, such as the diacids, sup 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).
Other polyols which may also be mentioned are various hydroxyl compounds such as, for example, hydroxylatep 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.
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 antioxidants 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 clecantation 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. haying 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).
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.
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
11

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.
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.
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.
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.
Other features and advantages of the invention will become clear from the description given below.
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:
A. Tests for preparing various treated fillers
To this end, tests No. 1 to lO 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.
12

Tests No. 1 to 4:
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).
Test No. 1:
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.
Test No. 2:
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.
Test No. 3:
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.
Test No. 4:
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.
Tests No. 5 to 7:
These tests illustrate the inversion 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).
13

Test No. 5:
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.
Test No. 6:
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.
Test No. 7:
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.
Test No. 8:
1
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.
To this end, 3kg of product C (chalk) and 30 g of AGT are introduced into a laboratory ball mill having a 15 1 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
Test No. 9:
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.
To this end, 3kg 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 1 capacity and containing 9 kg of crushing medium, followed by crushing for 8 hours to obtain the desired grain
15
size, followed by drying, de-agglomeration and selection using a 24-dynamic laboratory classifier.
Test No. 10:
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 diaeter of 1.8 micrometres (product B).
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.
The results of tests 1 to 4 land 5 to 7 are set out in Table I and those of tests 8 to 10 in Table II.
15

TABLE!

CHARACTERISTICS Invention Invention Invention Invention
TEST No. 1 • 2 3 4
FILLER PRODUCT Product A Product A Product A Product A
FEED RATE . , 700 kg/h 700 kg/h 700 kg/h 700 kg/h
TREATMENT RATE 1% 1% \% 1%
SEPARATOR/FINS- —— 2~4 24 16 No selector
De-agglomerationsimultaneouswith injectionof AGT agent +Selection AGT agent injected prior to de-agglomeration + Selection Reducedefficiency ofthe selector ascompared withtest No. 2 De-agglomeration without selection

TABLE I (CONTINUED)

CHARACTERISTICS Invention Invention Invention
TEST No. 5 6 7
FILLER PRODUCT Product B Product B ' Product B
FEED RATE 700 kg/h 700 kg/h 700 kg/h
TREATMENT RATE 1% __1%——
T70
__SEPARATOR/FINS without selector 24 24
De-agglomeration without selection AGT agent injected prior to de-agglomeration + selection De-agglomerationsimultaneous withinjection of AGTagent + selection

TABLE II

CHARACTERISTICS Prior art Invention Invention
TEST No. 8 9 10
FILLER PRODUCT Product C Dry method Product C Wet method Product B Dry method
FEED RATE -
TREATMENT RATE-- 1% 1%
r%
SEPARATOR/FINS without selector 24 24
Treatment and crushing without de-agglomeration nor selection Treatment and crushing by wet method with de-agglomeration and selection De-agglomerationsimultaneous withinjection of AGTagent + selection

TABLE III-l

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 + 0.5114% AGT Product A + 0.4742% AGT Product A Product D
Filler quantity 25g 25g 25g 25g 25g 25g 25g
Polyol type IOH48 Visco 750 IOH48 [ Visco 750 IOH 48 Visco 750 IOH 48 Visco 750 IOH 48 Visco 750 IOH 48 Visco 750 IOH 48 Visco 750
Polyol quantity 250g 250g 250g 250g 250g
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 mn / / / 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 / / / /

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 + GUEDU Product B + GUEDU Product Test 1 Product Test 2 Product Test 3 Product Test 4 Product Test 5 Product Test 8
Filler quantity 25g 25g 25g 259 25g 25g 25g 25g
Polyol type IOH 48 Visco 750 IOH 48 Visco 750 IOH 48Visco 750 IOH 48 Visco 750 IOH 48 Visco 750 IOH 48 Visco 750 IOH 48___VjscoJ!50 IOH 48
Polyol quantity 250g 250g 2509 __250g___— 250g 250g 250g
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.
--G^ng^afteTTrnin 0 0 0.5 / / / / /
Gauge after 5 min 0 0 4.5 1.5 4 1.5 2.5 0
Gauge after 8 min 0 0 2 / / / / /
Gauge after 10 min 0 0 2 3.5 5 3 4 0
Gauge after 12 min 0 0 3 / / / / /
Gauge after 15 min 0 6 4 3.5 3.5 4 0
Gauge after 18 min / / / / / / /
Gauge after 20 min 0 3 2 4 3.5 3 0
Gauge after 22 min / / / / /
Gauge after 24 min / / / / /
Gauge after 25 min 5.5 3 4 3.5 2.5 0
Gauge after 26 min / / / / /
Gauge after 28 min / / / / /
Gauge after 30 min 6 2 4.5 3.5 2.5 0
Gauge after 32 min / / / / /
Gauge after 35 min / / / / /

TABLE III-3

Test 26 Test 27 Test 28
INVENTION INVENTION INVENTION
Filler type Product Test 9 Product Test 10 Product B + 1 % AGT
Filler quantity 25g 25g 25g
Polyol type IOH48 Visco 750 IOH 48 Visco 750 IOH 48 Visco 750
Polyol quantity 250g 250g 250g______
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 / / /

In these tables, AGT refers to the agent of the phosphate type proposed by the invention, GUEDU the known mixer and 10H the hydroxyl index.
Test No. 11:
This test illustrates the dispersion of a Champagne chalk of an average diameter of 2
micrometres, not treated,, in the above-mentioned polyol.
There is no gauge reading and therefore none of the mixing performed is homogeneous and without agglomerates.
The result is poor; this is a reference test.
Test No. 12:
This test represents an example of the invention using Product A from test No. 1. The
gauge reading is 4.5 after 8 minutes.
Accordingly, mixing is good after 8 minutes.
Test No. 13: i
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).
The result is poor.
Test No. 14:
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.
The results are poor and confirm the importance of performing the treatment proposed by one of the steps of the invention.
22
Test No. 15:
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.
The result is also poor.

Test No. 16:
shows that more than 20 minutes are needed in order to produce a good mixture (gauge = 3), hence requiring much more mechanical energy.
This test is identical to the . 11 except for the agitation speed used to form the mixture
(almost double), which
Test No. 17:
This test is identical to N6. 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.


Tests No. 18 and 19:
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.
Test No. 18:
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.
Test No. 19:
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-jester of acid phosphate of decyl alcohol type containing 5 ethylene oxide chains.

Tests No. 20 to 23:
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,
Test No. 24:
This test illustrating the invention is conducted using calcite instead of chalk (the
product of test No. 5 is used).
The result (gauge = 4 after 0.0 minutes) can be regarded as good.
Test No. 25:
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.
Test No. 26:
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.
Test No. 27:
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.
Test No. 28:
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.
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:
This example relates to the use of different fillers, all treated using the method of test No. 1.
The following are the different fillers that were used:

Product R: Product S:
Product T: Product U: Product V:
Product G: Product W:

marble with an average diameter of 8 micrometres,
commercial magnesium hydroxide with an average diameter of
1.4-1.8 micrometres,
talc with an average diameter of 2.5 micrometres,
dolomite with an average diameter of 3 micrometres,
aluminium hydroxide with an average diameter of 0.8
micrometres,
kaolin with an average diameter of 0.50 micrometres,
precipitated calcium carbonate with an average diameter of 0.3
micrometres.

Test No. 29:
This test is a reference test representing an untreated kaolin with an average diameter
of 0.50 micrometres, dispersed in the above-mentioned polyol.
There was no gauge reading and therefore no mixture was formed that was homogeneous and without agglomerates.
The result was poor.
Test No. 30:
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.
The gauge reading is good compared with the reference test.

Test No. 31:
This is a reference test conducted with product U. There was no gauge reading.
Test No. 32:
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 re

erence test.

Test No. 33:
This test is a reference test with product W. There is no gauge reading.
Test No. 34:
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.
Test No. 35:
This test is a reference test conducted on product R. There is no gauge reading.
Test No. 36:
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.
Test No. 37:
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.
26
Test No. 38:
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.

Test No. 39:
This test is a reference test

conducted on product V. There is no gauge reading.

Test No. 40:
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.
Test No. 41:
This is a reference test on product S. There is no gauge reading.

Test No. 42:
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.
The results are set out in Tables IV-1 and IV-2 below

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 + 1.5% AGT Product U Product U + 1.5% AGT Product W Product W + 2.5% AGT
Filler quantity 25g 259 25g 25g 25g 25g
Polyol type IOH48 Visco 750 IOH48 Visco 750 IOH48 Visco 750 - IOH48 Visco 750 IOH48 Visco 750 IOH48 Visco 750
Polyol quantity 250g 250g 250g 250g- 250g 250g
Mixing speed 690r./min. 690 r./min. 690 r./min. 690 r./min. 1 69J)j\/rmn^ n A
uauge aiier z. mm —Gwge-afteT^TlrTlrP" u 0 1 0 i2 u 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 L_ 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 / / / / /

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 + 1 % NP1OP04 Product A + Product T Product-Test 37 +0.5% AGT Product V Product V + 1.2% AGT Product S Product S + 1,5% AGT
Filler quantity 25g 25g 25g 25g 25g 25g 25g 25g
Polyol type IOH48 Visco 750 IOH48 Visco 750 IOH48 Visco 750 IOH4S Visco 750 IOH48 Visco 750 IOH 48 . Visco 750 IOH 48Visco 750 IOH 48Visco 750
Polyol quantity 250g£QO r /min 250g^QO r /min 250g£QA r /min 250g Gauge after 2 min 0 3 0-?u r./min0 —u-'U r./ruin. 4 OVU l./lluu.0 ovu r./min. 5 0 U7u r./rniu. 5
Gauge after 5 min 0 3 0 4.5 0 5 0 /
Gauge after 8 min 0 3.5 0 / 0 6 0 5
Gauge after 10 min 0 3.5 0 / 0 6 0 /
Gauge after 12 min 0 3.5 0 / 0 0 6
Gauge after 15 min 0 3 0 6.5 0 0 /
Gauge after 18 min „ 3.5 0 7 0 0 7
Gauge after 20 min 3 0 / 0 0 7
Gauge after 22 min / / 6.5
Gauge after 24 min / /
Gauge after 25 min / /
Gauge after 26 min / ' /
Gauge after 28 min / /
Gauge after 30 min / /
Gauge after 32 min / /
Gauge after 35 min / / /


A review of Tables IV suspensions of various homogeneous and contain
shows that the method proposed by the invention enables .mineral fillers in a polyol to be obtained which are particles of less than 70 micrometres after 15 minutes.

EXAMPLE 3:

This example relates to a polyol using different

trie manufacture of preliminary mixtures of mineral fillers with quantities of filler.

Test No. 43:
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°C in a ratio by weight of 60% polyol - 40% calcium carbonate.
Test No. 44:
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°C in a ratio by weight of 50% polyol - 50% calcium carbonate.
Test No. 45:
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°C in a ratio by weight of 40% polyol - 60% calcium carbonate.
Test No. 46:
This test illustrates the indention and uses product A as a filler treated as in test No. t and, as a polyol, a polycl with a hydroxyl index of 48 mg/g and a viscosity of 700 mPa.s at 200°C in a ratio py weight of 90% polyol -10 % calcium carbonate.
Test No. 47:
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°C in a ratio by weight of 50% polyol - 50% kaolin.
30

The results are set out in Table V below.

31

TABLE V

INVENTION INVENTION INVENTION INVENTION INVENTION .
Test 43 Test 44 Test 45 Test 46 Test 47
PolyolQuantity (% weight) IOH = 48Viscosity =700 IOH = 48 Viscosity = 700 IOH = 48 Viscosity = 700 IOH = 48 Viscosity = 700 IOH = 56Viscosity = 300 -
60 50 40 90 50
Filler Treated product Test No. 1 Treated product h_^T_esU4£LJ_ Treated product( Test Nc^4 Treated product Test-Norf Treated product Test No. 30
-Quantity (% of dry weight ot filler) 40 50 60 10 50
Dispersant typeQuantity (% of dry weight of filler) Agent Test No. 1 Agent Test No. 1 Agent Test No. 1 Agent Test No. 1 Agent Test No. 1
1 1 1 1 1
Brookfieid viscosities after 2 hours (mPa.s) at 23°C 10 r/min 5250 6500 29800 750 44160
100 r/min 2430 3450 9600 720 17630
Brookfieid viscosities after 24 hours (mPa.s) at 23°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

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.
EXAMPLE4
This example illustrates how a PUR foam containing the fillers treated in accordance with the
invention are obtained.
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.
Test No. 48:
For this test, the anticipated density is 25 kg/m3 and the quantity of filler is 10 parts relative to
the polyol.
Test No. 49:
For this test, the anticipated density is 35 kg/m3 and the quantity of filler is 20 parts relative to the polyol.
Test No. 50:
For this test, the anticipated density is 40 kg/m3 and the quantity of filler is 5 parts relative to
the polyol.
The results are set out in Table yl below.
33

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
number of NCO functions

Isocyanate index =

x 100

number of OH functions
Slurry time = Onset of foam formation = appearance time
* Rise time = Total time from the reaction whereby the foam is manufactured to stabilisation

A review of Table VI shows the improvement proposed by
that it is possible to obtain PUR foams by a method incorporating the present invention.
35
975/MUMNP/2003
8983

We Claim:
1.A treated mineral filler mixed with a polyol, characterized in that it is Produced by a process wherein a mineral filler
a) is treated with least one compound of the general formula (1):




with R1 =either H or alkyl with C8 to C40 or aryl or alkylaryl or arylalkyl
with C6 to C40,
with R2 =either alkyl with C8 to C40 or aryl or alkylaryl or arylalkyl with C6
to C40,
X=--CH2 -CH2 - or -CH(CH3)-CH2 --or -CH2 -CH(CH3)- or ~(CH2)5 ~
CO-,
Y=-CH2 -CH2 - or -CH(CH3)-CH2 -or -CH2 ~CH(CH3)~ or -(CH2)5~
CO-,
X and Y being identical or different,
(m+n) ranges from 0 to 60 (including limits) as well as (p+q) with
0 (K=m different from Y;
b) undergoes a deagglomeration stage;
c) optionally undergoes a selection stage; and
d) is mixed with a palyol.
2. A treated mineral filler as claimed in claim 1, wherein said treatment agent is a mixture of mono-ester and di-ester of acid phosphate of decyl alcohol with 5 mols of ethylene oxide.
36

3. A treated mineral filler as claimed in claim 1, wherein said treatment agent is the mono-ester of acid phosphate of tristyrylphenol containing 60 mols of ethylene oxide.
4. A treated mineral filler as claimed in claim 1, wherein said treatment agent is a mixture of mono-ester and di-ester of acid phosphate of ketostearyl alcohol.


5. A treated mineral filler as claimed in claim 1, wherein that said treatment agent is a mixture of mono-ester and di-ester of acid phosphate of nonylphenol containing 10 mols of ethylene oxide.

6. Mineral fillers as claimed in any one of claims 1 to 5, wherein the treated mineral filler selected from among 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 i 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.

7. Mineral fillers as claimed in any one of claims 1 to 6, wherein the treated
mineral filler selected from among natural calcium carbonate selected from
chalk, calcite and marble, precipitated calcium carbonate, dolomite,
aluminum or magnesium hydroxides, kaolin, talc, wollastonite and mixtures thereof.

8. Minerals fillers as claimed in anyone of claims 1 to 7, wherein treated mineral filler consist of products having an average diameter of between 0.1 and 15 micrometers, preferably between 0.1 and 10 micrometers.
37


9. Mineral fillers as claimed in any one of claims 1 to 7, wherein treated mineral filler consist of products having an average diameter of between 0.3
and 8 micrometers.
10. Minerals fillers as claimed in any one of claims 1 to 9 wherein treated mineral filler are selected from amongst the following: a marble with an average diameter of 8 micrometers, a magnesium hydroxide with an average diameter of between 1.4 and 1.8 micrometers, a talc with an average diameter of 2.5 micrometers, a dolomite with an average diameter of 3 micrometers, an aluminium hydroxide with an average diameter of 0.8 micrometers, a kaolin with an average diameter of 0.5 micrometers, a precipitated calcium carbonate with an average diameter of 0.30 micrometers.
11. Mineral fillers as claimed in any one of claims 1 to 10 wherein treated mineral filler 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.
Dated this 24th of November, 2000

HIRAL CHANDRAKANT JOSHI AGENT FOR OMYA SA.
38

Documents:

975-MUMNP-2003-ABSTRACT(20-10-2003).pdf

975-MUMNP-2003-ABSTRACT(GRANTED)-(5-3-2008).pdf

975-MUMNP-2003-CANCELLED PAGES(25-1-2005).pdf

975-MUMNP-2003-CLAIMS(20-10-2003).pdf

975-MUMNP-2003-CLAIMS(AMENDED)-(21-9-2004).pdf

975-MUMNP-2003-CLAIMS(AMENDED)-(22-7-2004).pdf

975-MUMNP-2003-CLAIMS(AMENDED)-(25-1-2005).pdf

975-MUMNP-2003-CLAIMS(GRANTED)-(5-3-2008).pdf

975-mumnp-2003-claims.doc

975-mumnp-2003-claims.pdf

975-MUMNP-2003-CORRESPONDENCE(21-9-2004).pdf

975-MUMNP-2003-CORRESPONDENCE(IPO)-(4-4-2008).pdf

975-mumnp-2003-correspondence-others.pdf

975-mumnp-2003-correspondence-received-ver-140904.pdf

975-mumnp-2003-correspondence-received-ver-201003.pdf

975-mumnp-2003-correspondence-received-ver-220704.pdf

975-mumnp-2003-correspondence-received-ver-250105.pdf

975-mumnp-2003-descripiton (complete).pdf

975-MUMNP-2003-DESCRIPTION(COMPLETE)-(20-10-2003).pdf

975-MUMNP-2003-DESCRIPTION(GRANTED)-(5-3-2008).pdf

975-MUMNP-2003-FORM 19(15-12-2003).pdf

975-MUMNP-2003-FORM 2(COMPLETE)-(20-10-2003).pdf

975-MUMNP-2003-FORM 2(GRANTED)-(5-3-2008).pdf

975-MUMNP-2003-FORM 2(TITLE PAGE)-(20-10-2003).pdf

975-MUMNP-2003-FORM 2(TITLE PAGE)-(GRANTED)-(5-3-2008).pdf

975-mumnp-2003-form-1.pdf

975-mumnp-2003-form-19.pdf

975-mumnp-2003-form-2.doc

975-mumnp-2003-form-2.pdf

975-mumnp-2003-form-26.pdf

975-mumnp-2003-form-3.pdf

975-mumnp-2003-form-5.pdf

975-mumnp-2003-granted.pdf

975-mumnp-2003-pct-search report.pdf

975-MUMNP-2003-WO INTERNATIONAL PUBLICATION REPORT(20-10-2003).pdf


Patent Number 216010
Indian Patent Application Number 975/MUMNP/2003
PG Journal Number 13/2008
Publication Date 31-Mar-2008
Grant Date 05-Mar-2008
Date of Filing 20-Oct-2003
Name of Patentee OMYA SA
Applicant Address 35 QUAI ANDRE CITROEN 75725 PARIS CEDEX 15, FRANCE
Inventors:
# Inventor's Name Inventor's Address
1 FICHOU, JEAN PIERRE 17, RUE JULES GUESDE, 92300 LEVALLOIS PERRET, FRANCE
2 HUSSON, MAURICE 4, rue Jean Moulin F-51000 Chalons en Champagne (FR).
3 RAVET GEORGES Route Louis Pradel F-69290 Saint Genis les Ollières (FR).
4 BLANCHARD PIERRE Route de Veissieux le Bas 63, chemin de Budron F-01600 Reyrieux
PCT International Classification Number C09C 3/08
PCT International Application Number PCT/FR99/01456
PCT International Filing date 1999-06-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 98/08483 1998-06-30 France