Title of Invention	GLASSY TYPE FILLER FOR PLASTICS AND RESINS AND PROCESS FOR OBTAINING IT
Abstract	A filler (1) is envisioned which comprises glass-based granules (2) provided with a sizing composition, in which filler each of the granules (2) consists of a multiplicity of milled glass fragments (3) agglomerated together by the agency of a sizing composition (4) containing especially a compound chosen from esters of alkylsilicic acids, particularly an aminosilane. The process comprises a milling step (6) during which the glassy material is comminuted into fragments by this milling, a metering step (7) during which a mixture including the fragments (3) and the sizing composition (4) is formed and an agglomeration step (8) during which the mixture is dried so as to form granules each including a multiplicity of fragments {3} and dried parts of the sizing composition (4).

Title of Invention

GLASSY TYPE FILLER FOR PLASTICS AND RESINS AND PROCESS FOR OBTAINING IT

Abstract

A filler (1) is envisioned which comprises glass-based granules (2) provided with a sizing composition, in which filler each of the granules (2) consists of a multiplicity of milled glass fragments (3) agglomerated together by the agency of a sizing composition (4) containing especially a compound chosen from esters of alkylsilicic acids, particularly an aminosilane. The process comprises a milling step (6) during which the glassy material is comminuted into fragments by this milling, a metering step (7) during which a mixture including the fragments (3) and the sizing composition (4) is formed and an agglomeration step (8) during which the mixture is dried so as to form granules each including a multiplicity of fragments {3} and dried parts of the sizing composition (4).

Full Text	GLASSY-TYPE FILLER FOR PLASTICS AND RESIHS AND PROCESS FOR OBTAINING IT The subject of the invention is a filler of the 5 glassy type for plastics and resins and a process for obtaining it. As known, -wf illersjr are of great importance in the overall composition of articles and products based on resins, especially phenolic resins, and on plastics, 10 especially when these articles and products are produced by a molding operation. Fillers are an additive material which is normally incorporated into the polymers and can fulfil, depending on the situation, the function of simply 15 filling the polymer or that of significantly reinforcing it. As a percentage by weight, the amount of fillers may even be very high, for example 40%, and they can have a key influence on the physicochemical 20 characteristics of the articles produced. Among the various existing fillers, those of the glassy type are very important and very widely used, and one well-known type of glassy filler consists of minute, approximately spherical, glass elements 25 hereafter called microspheres or granules, the maximum diameter of which is very small, for example, about one tenth or one hundredth of a millimeter. The polymers or -aftnatrices7 which surround these glass microspheres or granules result in articles whose 30 abrasion resistance, impact strength, compressive strength and flexural strength are improved and which exhibit impermeability and enhanced acid and solvent resistance. Further advantages resulting from the use of 35 said glass microspheres or granules as fillers are the overall improvement in the electrical and thermal properties. The molding operations are markedly improved because of the reduction in the in-mold shrinkage and a - 2 - smoother and better finished molding surface is obtained. There is also as a result a cost reduction in proportion to the cost and amount of microspheres 5 added. Unfortunately, these glass microspheres cannot be simply added to said materials or matrices made of plastic or phenolic resins. This is because they require to be pretreated 10 on the surface with substances, called ^sizing compositions^, which act as a binder between the glass and the matrices in order to guarantee perfect and lasting adhesion to the glass- Among sizing compositions recognized as .being the most effective are 15 those commonly called "fsilanes. These particular sizing compositions consist of molecules having one part provided with affinity for the glass of the microspheres and another part capable of copolymerizing with the matrices. 20 In practice, said microspheres or granules are basically made of glass coated with an appropriate-type sizing composition. The abovementioned known technique obviously has advantages and disadvantages. As already mentioned, 25 the advantages relate to the qualitative improvement to the end-products which contain said microspheres. The drawbacks stem from a certain difficulty in the production of said microspheres and from their cost. This is because they must have well-defined 30 dimensions. In particular, the glass particles which form them must have small dimensions, between one tenth and one hundredth of a millimeter. In order to produce such f&EfJjrJ&s. ue^y expensive -systems- """£ equipment must be used. 35 Furthermore^ th_e sji&aexmmt ,aepli£a£ion of the sizing compositions introduces an additional pjuase -whircn adds to the production .phase of t.he gl as.s. .part, with a substantial cost increase. - 3 - The high production cost and application cost of sizing compositions consequently mean an increase in the cost of the end-products and considerably reduce the use of the fillers described. 5 in fact, it should not be forgotten that the fillers used in plastics are often regarded as a filling which makes it possible to reduce, in a simple and effective manner, the overall costs of the materials employed in the molding operations. 10 Another disadvantage stems from the fact that, despite the use of sizing compositions, the bonding of the microspheres or qranules to the matrices is not always optimal. From this standpoint, it is certainly desirable to obtain better adhesion between the glass 15 and the polymer. The technical objective of the invention is therefore to substantially reduce the abovementioned disadvantages, particularly those associated with the cost and the process for manufacturing satu Utter o-20 spn'eres or granules, and with the bondability of these microspheres or granules to the matrices which surround rnem. This objective is achieved by means of a glassy-type filler fefr plastics and cesinnsv espec-ially 25 phenolic resins, of ths type including granules of glassy material which are provided with a sizing. Composition, characterized in that each. ,of. sai-d granules comprises a multiplicity of fraaments o.f glassy material agglomerated together by said sizing 30 composition. According to advantageous characteristics: o said sizing composition comprises a compound chosen from esters of alkylsilicic acids; o said sizing is an aminosilane, in particular of 35 formula NH2-~R'-Si (OR) 3, in which: - R' denotes an optionally substituted, saturated or unsaturated, linear or branched hydrocarbon chain advantageously containing from 1 to 20 carbon - 4 - atoms, especially from 2 to 8 carbon atoms, preferably an alkylene chain; - R denotes an alkyl group, preferably having from 1 to 5 carbon atoms. 5 One particularly preferred silane is amino-propyltriethoxysilane NH2(CH2)3Si (OC2H5)3; o said granules have a maximum mean size of between twenty and sixty micrometers and comprise at least two of said fragments; 10 o said fragments have on average a maximum linear dimension of between five and fifteen micrometers; o said fragments are made of glass, especially "E"-type glass; o said fragments are made of milled glass; 15 o said fragments are portions of glass yarns; o the amount of said sizing composition is substantially between five and fifty parts per thousand parts, especially between five and twenty- five parts per thousand parts, by weight of the dry 20 glassy material; o the sizing composition furthermore contains a mineral binder, such as a clay or a mixture of clays. The subject of the invention is also a process for obtaining this filler, characterized in that it 25 comprises: a milling step in which the glassy material is reduced to fragments; a metering step in which a mixture including said fragments and a sizing composition is formed; and an agglomeration step in which said mixture of fragments and sizing composition 30 is dried so as to form compact granules each including a multiplicity of said fragments and of the portions of said dried sizing composition. According to advantageous characteristics: o said milling step is preceded by a selection step in 35 which glass yarns coming from production waste and scrap are chosen for said milling step; o said milling step is extended until fragments are obtained which have on average a maximum linear dimension of between five and fifteen micrometers; - 5 - o during said milling step, water and a plasticizer and/or a mineral binder such as a clay, for example bentonite, are added to the glassy material; o during said metering step, said fragments are mixed with a sizing chosen from esters of alkylsilicic acids, especially an aminosilane; o during said metering step, said sizing composition is metered in an amount of between five and fifty parts per thousand parts by weight of dry glassy material; o during said agglomeration step, said mixture of fragments and sizing composition is heated to a drying temperature of between one hundred and twenty- five and one hundred and forty-five degrees Celsius; o said agglomeration step is carried out in a heated vessel and said mixture of fragments and sizing composition is injected into said vessel by means of compressed air so as to form granules having on average a maximum size of between twenty and sixty micrometers. We will now describe, by way of nonlimiting' example, a preferred embodiment of a glassy-type filler illustrated by the appended drawings in which: - figure 1 shows, highly schematically and on a very enlarged scale, the structure of a granule constituting the filler according to the invention; and - figure 2 shows the sequence of the main steps of the process for manufacturing the granules of figure 1. Referring to these figures, the filler according to the invention is indicated, overall and schematically, in its entirety by the reference number 1 within the context of figure 2. The filler 1 is generally of the type formed from particles which may be termed approximately spherical elements or microspheres or granules of very small diameter, consisting here of glass provided with a sizing composition. These granules are intended to be embedded in plastics and phenolic resins in order to - 6 - improve the many characteristics thereof, as indicated above. In particular, as may be seen in figure 1, the filler 1 advantageously consists of granules 2 whose 5 structure is of the composite type. This is because each granule 2 essentially consists of a multiplicity of glass fragments 3 agglomerated together by means of a sizing composition 4 which comprises a sizing preferably chosen from 10 particular silanes, the great effectiveness of which has been demonstrated experimentally: alkoxysilanes or esters of alkylsilicic acids. Among esters of alkylsilicic acids, an amino- silane NH2-R'-Si(OR)3 is preferred in which R' denotes 15 an alkyl group and R an organic group, and more particularly the aminosilane of formula NH2-(CH2)- Si{OC2H5)3. The silane contained in the sizing composition 4 which joins together the fragments 3 is present in an 20 amount of approximately between five and twenty-five parts per thousand parts by weight of the dry glass. The granules 2 have, on average, a maximum size of between twenty and sixty micrometers and contain at least two fragments '3. The term "maximum size" of the 25 granules 2, which have a compact structure because of the tendency of the sizing composition to form drops, is understood to mean the maximum diameter taken in the most greatly developed direction of the granules. In contrast, the fragments 3 have a 30 particularly irregular profile and have, on average, a maximum linear dimension of between five and fifteen micrometers, and preferably equal to ten micrometers. Another aspect of the invention resides in the fact that the fragments 3 are made of milled glass. For 35 example, without excluding other types of glass, they may be portions of >6eE/-type glass yarns obtained by milling. As known, jfeE-type glass is a glass having optimum strength properties and a high elastic modulus. - 7 - together with a high melting point. It may be defined as a calcium aluminum borosilicate, characterized by a very low alkali metal content. Glass yarns of different diameters can be used, 5 by mixing them, the diameters preferably being less than 10 micrometers. Overall, purely by way of an example given of a preferred composition of the milled glass, the filler 1 may have the following composition: 10 - aminosilane NH2 (CH2) sSi (OC2H5) 3: 1.95% by weight silica SiO2: 71.5% by weight sodium oxide Na2O: 13.43% by weight calcium carbonate CaO: 9.6% by weight magnesium oxide MgO: 3.23% by weight 15 - alumina A12O3: 0.39% by weight iron oxides FeO/Fe2O3: 0.2% by weight potassium oxide K2O: 0.1% by weight. The granules 2 thus produced have a minimal cost since they consist simply of milled glass and have 20 a rough structure suitable for guaranteeing maximum bonding to the polymer matrices, without however introducing excessive irregularities. This is because the fragments 3 are partly coated with sizing composition 4 and are' associated with other fragments 25 so as overall to define a compact shape. One advantageous characteristic of the granules 2 is that, once they have been produced, they do not need to be treated with a sizing composition: the latter is still present in the binder which 30 agglomerates the fragments 3. The invention also comprises a novel process for obtaining a glassy-type filler. The process is composed of several steps. In the first place, there is a selection step, denoted by 35 the reference number 5, in which the type of glass that has to undergo the successive operations is chosen. w / P For . example, rE#-type glass and preferably glass yarns coming from production waste and scrap, such as those of the $Borosil£ brand, consisting of wet - 8 - glass waste obtained during the operation of fiberizing wet filaments, indicated schematically by the reference number 5a, is chosen. Next, the chosen glass is subjected to a 5 milling step 6 in which it is reduced to fragments. The milling is carried out for example in wet mills of the Allubit type, that is to say mills known for milling' ceramics and comprising rotating rolls lined with Allubit or sintered alumina, inside which 10 there is a milling charge composed of Allubit spheres of various diameters. The glass yarn is introduced with water and bentonite into these mills, which are shown simply by two rolls labeled 6a. 15 Bentonite is a well-known natural mixture essentially consisting of clayey minerals and has the property of being a plasticizer in the wet state and a tackifier in the dry state. In the mills, the milled mass is composed 20 approximately of one percent by weight of bentonite, the rest consisting of glass and water in equal parts. The bentonite and water facilitate the milling of the glass, the bentonite helping to keep the glass in suspension in th£' water. This milling is carried 25 out, for example, for twenty hours if ten tons of glass are milled, until glass fragments having on average a maximum linear dimension of between five and fifteen micrometers are obtained. Preferably, this dimension is approximately 30 equal to ten microns. After milling, the process continues with auxiliary steps such as filtration, de-ironing and storage in containers - If the milled material is collected in 35 specialized containers, it is important to keep it agitated and to take into account any loss of water in order to prevent it forming a relatively compact glassy mass difficult to process. - 9 - Next, a metering step 7 is carried out, during which a mixture is produced which includes the fragments 3 possibly carrying some of the bentonite and a sizing compound preferably chosen from esters of 5 alkylsilicic acids, in particular an aminosilane. The amount of this sizing agent (silane) is between five and twenty-five parts per thousand parts by weight of the dry glass. The combination formed by the bentonite present with the fragments and the silane constitutes 10 the sizing composition for the fragments within the meaning of the present invention. If the glass is collected in a container, the metering is preferably carried out by removing from the container the defined amounts, for example one cubic 15 meter, and simply adding said amounts of additives. The mixture is treated very carefully in order to prevent the components from separating, particularly by keeping them rapidly stirred, for example by blades rotating at between eighty and one hundred and sixty 20 revolutions per minute. Next, an agglomeration step 8 is carried out during which said mixture of fragments and sizing composition is dried, preferably by spray drying, so as to form compact ^granules 2 each including a 25 multiplicity of fragments and of dried portions of the sizing composition. To carry out this step 8, the mixture of fragments and sizing composition is heated to a drying temperature of between one hundred and twenty-five and 30 one hundred and forty-five degrees Celsius, preferably one hundred and forty degrees Celsius. This temperature is obtained in a heated vessel into which the mixture is injected by compressed air, so as to form granules 2 having on average a maximum 35 size of between twenty and sixty micrometers, as already mentioned. In detail, provision is made, for example, for the mixture to be sucked up and then injected by - 10 - compressed-air sprayers into a drier provided with methane burners. The preferred temperature of one hundred and forty degrees removes the residual water and, above 5 all, causes the reaction of the si lane of the sizing composition which, by solidifying, results in the agglomeration of the fragments 3 into granules 2 and also solidifies the bentonite residues which contribute to the agglomeration. 10 The filler 1 thus produced, indicated in the box showing the agglomeration step 8, may be conveyed to a packing step 9. In particular, it may be envisioned to pack the filler into bags 10 or to pack it into large sacks 11 15 of one thousand kilograms. The process thus allows the filler 1 to be produced in various steps which are not particularly complex and do not require complex and very expensive equipment. 20 The invention has significant advantages. The original structure of the granules, formed from milled glass fragments agglomerated by the same sizing composition as that used to promote bonding between the glass and the plastic or the phenolic 25 resin, eliminates the final step of applying the sizing composition to the microspheres. Furthermore, the cost of the granules is reduced, both because of the raw materials used, which are mostly simple glass fragments, and because of the 30 manufacturing process which does not include preparation steps requiring large equipment. The granules produced are compact but rough and thus allow optimum bonding to the plastic without conferring excessive roughness on the latter. 35 The invention described above in a preferred embodiment is capable of numerous modifications and variants, all falling within the field of the inventive concept. In particular, it is envisioned according to the invention for silane alone to be used to form the - 11 - sizing composition which agglomerates the fragments 3, the milling possibly being able to be assisted by a plasticizer which does not have a tackifying property in the dry state. Moreover, further details may be replaced by equivalent elements. -12-We CLAIM: 1. A gfassy-type filler (1) for plastics and resins, of the type including granules (2) of glassy material which are provided with a sfzlng composition, such as herein described, the amount of said sizing composition being between five and fifty parts per thousand parts by weight of the dry glassy material, characterized In that each of said granules comprises a multiplicity of fragments (3) of glassy material agglomerated together by said sizing composition (4). 2. The glassy-type filler as claimed in claim 1, in which said sizing composition comprises a compound chosen from esters of alkylsilicic acids. 3. The glassy-type filler as claimed in one or both of the preceding claims, in which said sizing is an amfnosflane, in particular of formula NH2 (CHfeh Si (OC2H5)3. 4. The glassy-type fitter as claimed in one or more of the preceding claims, in which said granules (2) have a maximum mean size of between twenty and sixty micrometers and comprise at least two of said fragments (3). 5. The glassy-type filler as claimed in one or more of the preceding claims, in which said fragments (3) have on average a maximum linear dimension of between five and fifteen micrometers. 6. The glassy-type filler as claimed in one or more of the preceding claims, particularly claim 1, in which said fragments (3) are made of glass, especially "E" type glass. 7. The glassy-type filler as claimed in one or more of the preceding claims, In which said fragments (3) are made of milled glass. 8. The gfassy-type filler as claimed in one or more of the preceding claims, in which said fragments (3) are portions of glass yarns (5a). - 13 - 9- . A process for manufacturing a glassy-type filler for plastics and resins, characterized in that it comprises; a milling step in which the glassy material is ; reduced to fragments; a metering step in 5 which a mixture including said fragments and a sizing composition is formed; and an agglomeration step ir which said mixture of fragments and sizing composition is dried so as to form compact granules each including a multiplicity of said fragments and of the portions of 10 said dried sizing composition. * 10.. The process as claimed ¦ in claim 10, in which said milling step is preceded by a selection step in which glass yarns coming from production waste and scrap are chosen for said milling step. 15 11. The process as claimed in one or both of claims 10 and 11, in which said milling step is extended until fragments are obtained which have on average a maximum linear dimension of between five and fifteen micrometers. 20 1%. The process as claimed in one or more of claims 10 to 12, in which, during said milling step, water and a plasticizer and/or a mineral binder such as bentonite are added to the glassy material. 13. The process as claimed in one or more of 25 claims 10 to 13, in which, during said metering step, said fragments are mixed with a siring chosen from esters of alkyls-iiicic ' 'acids, especially an aminosilane. 1*1. The process as claimed in one or more of 30 claims 10 to' 14, in which, during said metering step, said sizing composition is metered in an amount of between five and fifty parts per thousand parts by weight of dry glassy material. 15"- The process as claimed in one or more of 35 claims 10 to 15, in which, during said agglomeration step, said mixture of fragments and sizing compositi.cn is heated to a drying temperature of between one hundred and twenty-five and one hundred and forty-five degrees Celsius. - 14 - 16. The process as claimed in one or more of claims 10 to 16, in which said agglomeration step is carried out in a heated vessel and in which said mixture of fragments and sizing composition is injected into said vessel by means of compressed air so as to form granules having on average a maximum size of between twenty and sixty micrometers. A filler (1) is envisioned which comprises glass-based granules (2) provided with a sizing composition, in which filler each of the granules (2) consists of a multiplicity of milled glass fragments (3) agglomerated together by the agency of a sizing composition (4) containing especially a compound chosen from esters of alkylsilicic acids, particularly an aminosilane. The process comprises a milling step (6) during which the glassy material is comminuted into fragments by this milling, a metering step (7) during which a mixture including the fragments (3) and the sizing composition (4) is formed and an agglomeration step (8) during which the mixture is dried so as to form granules each including a multiplicity of fragments {3} and dried parts of the sizing composition (4).

Full Text

GLASSY-TYPE FILLER FOR PLASTICS AND RESIHS AND PROCESS FOR OBTAINING IT
The subject of the invention is a filler of the 5 glassy type for plastics and resins and a process for obtaining it.
As known, -wf illersjr are of great importance in
the overall composition of articles and products based
on resins, especially phenolic resins, and on plastics,
10 especially when these articles and products are
produced by a molding operation.
Fillers are an additive material which is
normally incorporated into the polymers and can fulfil,
depending on the situation, the function of simply
15 filling the polymer or that of significantly
reinforcing it.
As a percentage by weight, the amount of fillers may even be very high, for example 40%, and they can have a key influence on the physicochemical 20 characteristics of the articles produced.
Among the various existing fillers, those of
the glassy type are very important and very widely
used, and one well-known type of glassy filler consists
of minute, approximately spherical, glass elements 25 hereafter called microspheres or granules, the maximum
diameter of which is very small, for example, about one
tenth or one hundredth of a millimeter.
The polymers or -aftnatrices*7 which surround these
glass microspheres or granules result in articles whose 30 abrasion resistance, impact strength, compressive
strength and flexural strength are improved and which
exhibit impermeability and enhanced acid and solvent
resistance.
Further advantages resulting from the use of 35 said glass microspheres or granules as fillers are the
overall improvement in the electrical and thermal
properties.
The molding operations are markedly improved
because of the reduction in the in-mold shrinkage and a

- 2 -
smoother and better finished molding surface is obtained.
There is also as a result a cost reduction in proportion to the cost and amount of microspheres 5 added.
Unfortunately, these glass microspheres cannot be simply added to said materials or matrices made of plastic or phenolic resins.
This is because they require to be pretreated 10 on the surface with substances, called ^sizing compositions^, which act as a binder between the glass and the matrices in order to guarantee perfect and lasting adhesion to the glass- Among sizing compositions recognized as .being the most effective are 15 those commonly called "fsilanes*. These particular sizing compositions consist of molecules having one part provided with affinity for the glass of the microspheres and another part capable of copolymerizing with the matrices.
20 In practice, said microspheres or granules are basically made of glass coated with an appropriate-type sizing composition.
The abovementioned known technique obviously has advantages and disadvantages. As already mentioned, 25 the advantages relate to the qualitative improvement to the end-products which contain said microspheres. The drawbacks stem from a certain difficulty in the production of said microspheres and from their cost.
This is because they must have well-defined 30 dimensions. In particular, the glass particles which form them must have small dimensions, between one tenth and one hundredth of a millimeter. In order to produce such f&EfJjrJ&s*. ue^y expensive -systems- """£ equipment must be used.
35 Furthermore^ th_e sji&aexmmt ,aepli£a£ion of the
sizing compositions introduces an additional pjuase -whircn adds to the production .phase of t.he gl as.s. .part, with a substantial cost increase.

- 3 -
The high production cost and application cost of sizing compositions consequently mean an increase in the cost of the end-products and considerably reduce the use of the fillers described.
5 in fact, it should not be forgotten that the
fillers used in plastics are often regarded as a
filling which makes it possible to reduce, in a simple
and effective manner, the overall costs of the
materials employed in the molding operations.
10 Another disadvantage stems from the fact that,
despite the use of sizing compositions, the bonding of the microspheres or qranules to the matrices is not always optimal. From this standpoint, it is certainly desirable to obtain better adhesion between the glass 15 and the polymer.
The technical objective of the invention is therefore to substantially reduce the abovementioned disadvantages, particularly those associated with the cost and the process for manufacturing satu Utter o-20 spn'eres or granules, and with the bondability of these microspheres or granules to the matrices which surround
rnem.
This objective is achieved by means of a
glassy-type filler fefr plastics and cesinnsv espec-ially
25 phenolic resins, of ths type including granules of
glassy material which are provided with a sizing.
Composition, characterized in that each. ,of. sai-d
granules comprises a multiplicity of fraaments o.f
glassy material agglomerated together by said sizing
30 composition.
According to advantageous characteristics:
o said sizing composition comprises a compound chosen
from esters of alkylsilicic acids;
o said sizing is an aminosilane, in particular of
35 formula NH2-~R'-Si (OR) 3, in which:
- R' denotes an optionally substituted, saturated or unsaturated, linear or branched hydrocarbon chain advantageously containing from 1 to 20 carbon

- 4 -
atoms, especially from 2 to 8 carbon atoms, preferably an alkylene chain; - R denotes an alkyl group, preferably having from 1
to 5 carbon atoms.
5 One particularly preferred silane is amino-propyltriethoxysilane NH2(CH2)3Si (OC2H5)3;
o said granules have a maximum mean size of between
twenty and sixty micrometers and comprise at least
two of said fragments;
10 o said fragments have on average a maximum linear dimension of between five and fifteen micrometers;
o said fragments are made of glass, especially "E"-type
glass;
o said fragments are made of milled glass;
15 o said fragments are portions of glass yarns;
o the amount of said sizing composition is
substantially between five and fifty parts per
thousand parts, especially between five and twenty-
five parts per thousand parts, by weight of the dry
20 glassy material;
o the sizing composition furthermore contains a mineral
binder, such as a clay or a mixture of clays.
The subject of the invention is also a process for obtaining this filler, characterized in that it
25 comprises: a milling step in which the glassy material is reduced to fragments; a metering step in which a mixture including said fragments and a sizing composition is formed; and an agglomeration step in which said mixture of fragments and sizing composition
30 is dried so as to form compact granules each including a multiplicity of said fragments and of the portions of said dried sizing composition.
According to advantageous characteristics:
o said milling step is preceded by a selection step in
35 which glass yarns coming from production waste and
scrap are chosen for said milling step;
o said milling step is extended until fragments are
obtained which have on average a maximum linear
dimension of between five and fifteen micrometers;

- 5 -
o during said milling step, water and a plasticizer
and/or a mineral binder such as a clay, for example
bentonite, are added to the glassy material;
o during said metering step, said fragments are mixed
with a sizing chosen from esters of alkylsilicic
acids, especially an aminosilane;
o during said metering step, said sizing composition is
metered in an amount of between five and fifty parts
per thousand parts by weight of dry glassy material;
o during said agglomeration step, said mixture of
fragments and sizing composition is heated to a
drying temperature of between one hundred and twenty-
five and one hundred and forty-five degrees Celsius;
o said agglomeration step is carried out in a heated
vessel and said mixture of fragments and sizing
composition is injected into said vessel by means of
compressed air so as to form granules having on
average a maximum size of between twenty and sixty
micrometers.
We will now describe, by way of nonlimiting' example, a preferred embodiment of a glassy-type filler illustrated by the appended drawings in which:
- figure 1 shows, highly schematically and on a
very enlarged scale*, the structure of a granule
constituting the filler according to the invention; and
- figure 2 shows the sequence of the main steps
of the process for manufacturing the granules of
figure 1.
Referring to these figures, the filler according to the invention is indicated, overall and schematically, in its entirety by the reference number 1 within the context of figure 2.
The filler 1 is generally of the type formed from particles which may be termed approximately spherical elements or microspheres or granules of very small diameter, consisting here of glass provided with a sizing composition. These granules are intended to be embedded in plastics and phenolic resins in order to

- 6 -
improve the many characteristics thereof, as indicated above.
In particular, as may be seen in figure 1, the filler 1 advantageously consists of granules 2 whose 5 structure is of the composite type.
This is because each granule 2 essentially consists of a multiplicity of glass fragments 3 agglomerated together by means of a sizing composition 4 which comprises a sizing preferably chosen from 10 particular silanes, the great effectiveness of which has been demonstrated experimentally: alkoxysilanes or esters of alkylsilicic acids.
Among esters of alkylsilicic acids, an amino-
silane NH2-R'-Si(OR)3 is preferred in which R' denotes
15 an alkyl group and R an organic group, and more
particularly the aminosilane of formula NH2-(CH2)-
Si{OC2H5)3.
The silane contained in the sizing composition 4 which joins together the fragments 3 is present in an 20 amount of approximately between five and twenty-five parts per thousand parts by weight of the dry glass.
The granules 2 have, on average, a maximum size of between twenty and sixty micrometers and contain at least two fragments '3. The term "maximum size" of the 25 granules 2, which have a compact structure because of the tendency of the sizing composition to form drops, is understood to mean the maximum diameter taken in the most greatly developed direction of the granules.
In contrast, the fragments 3 have a 30 particularly irregular profile and have, on average, a maximum linear dimension of between five and fifteen micrometers, and preferably equal to ten micrometers.
Another aspect of the invention resides in the
fact that the fragments 3 are made of milled glass. For
35 example, without excluding other types of glass, they
may be portions of >6eE/-type glass yarns obtained by
milling.
As known, jfeE*-type glass is a glass having optimum strength properties and a high elastic modulus.

- 7 -
together with a high melting point. It may be defined as a calcium aluminum borosilicate, characterized by a very low alkali metal content.
Glass yarns of different diameters can be used, 5 by mixing them, the diameters preferably being less than 10 micrometers.
Overall, purely by way of an example given of a preferred composition of the milled glass, the filler 1 may have the following composition:
10 - aminosilane NH2 (CH2) sSi (OC2H5) 3: 1.95% by weight
silica SiO2: 71.5% by weight
sodium oxide Na2O: 13.43% by weight
calcium carbonate CaO: 9.6% by weight
magnesium oxide MgO: 3.23% by weight
15 - alumina A12O3: 0.39% by weight
iron oxides FeO/Fe2O3: 0.2% by weight
potassium oxide K2O: 0.1% by weight.
The granules 2 thus produced have a minimal cost since they consist simply of milled glass and have 20 a rough structure suitable for guaranteeing maximum bonding to the polymer matrices, without however introducing excessive irregularities. This is because the fragments 3 are partly coated with sizing composition 4 and are*' associated with other fragments 25 so as overall to define a compact shape.
One advantageous characteristic of the granules
2 is that, once they have been produced, they do not
need to be treated with a sizing composition: the
latter is still present in the binder which
30 agglomerates the fragments 3.
The invention also comprises a novel process for obtaining a glassy-type filler.
The process is composed of several steps. In
the first place, there is a selection step, denoted by
35 the reference number 5, in which the type of glass that
has to undergo the successive operations is chosen.
w / P
For . example, *rE#-type glass and preferably
glass yarns coming from production waste and scrap,
such as those of the *$Borosil£ brand, consisting of wet

- 8 -
glass waste obtained during the operation of fiberizing wet filaments, indicated schematically by the reference number 5a, is chosen.
Next, the chosen glass is subjected to a 5 milling step 6 in which it is reduced to fragments.
The milling is carried out for example in wet
mills of the Allubit type, that is to say mills known
for milling' ceramics and comprising rotating rolls lined with Allubit or sintered alumina, inside which 10 there is a milling charge composed of Allubit spheres of various diameters.
The glass yarn is introduced with water and bentonite into these mills, which are shown simply by two rolls labeled 6a.
15 Bentonite is a well-known natural mixture
essentially consisting of clayey minerals and has the property of being a plasticizer in the wet state and a tackifier in the dry state.
In the mills, the milled mass is composed 20 approximately of one percent by weight of bentonite, the rest consisting of glass and water in equal parts.
The bentonite and water facilitate the milling of the glass, the bentonite helping to keep the glass in suspension in th£' water. This milling is carried 25 out, for example, for twenty hours if ten tons of glass are milled, until glass fragments having on average a maximum linear dimension of between five and fifteen micrometers are obtained.
Preferably, this dimension is approximately 30 equal to ten microns.
After milling, the process continues with auxiliary steps such as filtration, de-ironing and storage in containers -
If the milled material is collected in
35 specialized containers, it is important to keep it
agitated and to take into account any loss of water in
order to prevent it forming a relatively compact glassy
mass difficult to process.

- 9 -
Next, a metering step 7 is carried out, during
which a mixture is produced which includes the
fragments 3 possibly carrying some of the bentonite and
a sizing compound preferably chosen from esters of
5 alkylsilicic acids, in particular an aminosilane. The
amount of this sizing agent (silane) is between five
and twenty-five parts per thousand parts by weight of
the dry glass. The combination formed by the bentonite
present with the fragments and the silane constitutes
10 the sizing composition for the fragments within the
meaning of the present invention.
If the glass is collected in a container, the metering is preferably carried out by removing from the container the defined amounts, for example one cubic 15 meter, and simply adding said amounts of additives.
The mixture is treated very carefully in order
to prevent the components from separating, particularly
by keeping them rapidly stirred, for example by blades
rotating at between eighty and one hundred and sixty
20 revolutions per minute.
Next, an agglomeration step 8 is carried out during which said mixture of fragments and sizing composition is dried, preferably by spray drying, so as to form compact ^granules 2 each including a 25 multiplicity of fragments and of dried portions of the sizing composition.
To carry out this step 8, the mixture of
fragments and sizing composition is heated to a drying
temperature of between one hundred and twenty-five and
30 one hundred and forty-five degrees Celsius, preferably
one hundred and forty degrees Celsius.
This temperature is obtained in a heated vessel
into which the mixture is injected by compressed air,
so as to form granules 2 having on average a maximum
35 size of between twenty and sixty micrometers, as
already mentioned.
In detail, provision is made, for example, for the mixture to be sucked up and then injected by

- 10 -
compressed-air sprayers into a drier provided with methane burners.
The preferred temperature of one hundred and forty degrees removes the residual water and, above 5 all, causes the reaction of the si lane of the sizing composition which, by solidifying, results in the agglomeration of the fragments 3 into granules 2 and also solidifies the bentonite residues which contribute to the agglomeration.
10 The filler 1 thus produced, indicated in the
box showing the agglomeration step 8, may be conveyed to a packing step 9.
In particular, it may be envisioned to pack the filler into bags 10 or to pack it into large sacks 11 15 of one thousand kilograms.
The process thus allows the filler 1 to be
produced in various steps which are not particularly
complex and do not require complex and very expensive
equipment.
20 The invention has significant advantages.
The original structure of the granules, formed from milled glass fragments agglomerated by the same sizing composition as that used to promote bonding between the glass and the plastic or the phenolic 25 resin, eliminates the final step of applying the sizing composition to the microspheres.
Furthermore, the cost of the granules is
reduced, both because of the raw materials used, which
are mostly simple glass fragments, and because of the
30 manufacturing process which does not include
preparation steps requiring large equipment.
The granules produced are compact but rough and thus allow optimum bonding to the plastic without conferring excessive roughness on the latter.
35 The invention described above in a preferred
embodiment is capable of numerous modifications and variants, all falling within the field of the inventive concept. In particular, it is envisioned according to the invention for silane alone to be used to form the

- 11 -
sizing composition which agglomerates the fragments 3, the milling possibly being able to be assisted by a plasticizer which does not have a tackifying property in the dry state.
Moreover, further details may be replaced by equivalent elements.

-12-We CLAIM:
1. A gfassy-type filler (1) for plastics and resins, of the type including
granules (2) of glassy material which are provided with a sfzlng
composition, such as herein described, the amount of said sizing
composition being between five and fifty parts per thousand parts by
weight of the dry glassy material, characterized In that each of said
granules comprises a multiplicity of fragments (3) of glassy material
agglomerated together by said sizing composition (4).
2. The glassy-type filler as claimed in claim 1, in which said sizing
composition comprises a compound chosen from esters of alkylsilicic
acids.
3. The glassy-type filler as claimed in one or both of the preceding claims, in
which said sizing is an amfnosflane, in particular of formula NH2 (CHfeh Si
(OC2H5)3.
4. The glassy-type fitter as claimed in one or more of the preceding claims, in
which said granules (2) have a maximum mean size of between twenty
and sixty micrometers and comprise at least two of said fragments (3).
5. The glassy-type filler as claimed in one or more of the preceding claims, in
which said fragments (3) have on average a maximum linear dimension of
between five and fifteen micrometers.
6. The glassy-type filler as claimed in one or more of the preceding claims,
particularly claim 1, in which said fragments (3) are made of glass,
especially "E" type glass.

7. The glassy-type filler as claimed in one or more of the preceding claims, In
which said fragments (3) are made of milled glass.
8. The gfassy-type filler as claimed in one or more of the preceding claims, in
which said fragments (3) are portions of glass yarns (5a).

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9- . A process for manufacturing a glassy-type
filler for plastics and resins, characterized in that
it comprises; a milling step in which the glassy
material is ; reduced to fragments; a metering step in
5 which a mixture including said fragments and a sizing
composition is formed; and an agglomeration step ir
which said mixture of fragments and sizing composition
is dried so as to form compact granules each including
a multiplicity of said fragments and of the portions of
10 said dried sizing composition. *
10.. The process as claimed ¦ in claim 10, in which said milling step is preceded by a selection step in which glass yarns coming from production waste and scrap are chosen for said milling step.
15 11. The process as claimed in one or both of claims 10 and 11, in which said milling step is extended until fragments are obtained which have on average a maximum linear dimension of between five and fifteen micrometers.
20 1%. The process as claimed in one or more of claims 10 to 12, in which, during said milling step, water and a plasticizer and/or a mineral binder such as bentonite are added to the glassy material. 13. The process as claimed in one or more of 25 claims 10 to 13, in which, during said metering step, said fragments are mixed with a siring chosen from esters of alkyls-iiicic ' 'acids, especially an aminosilane.
1*1. The process as claimed in one or more of 30 claims 10 to' 14, in which, during said metering step, said sizing composition is metered in an amount of between five and fifty parts per thousand parts by weight of dry glassy material.
15"- The process as claimed in one or more of 35 claims 10 to 15, in which, during said agglomeration step, said mixture of fragments and sizing compositi.cn is heated to a drying temperature of between one hundred and twenty-five and one hundred and forty-five degrees Celsius.

- 14 -
16. The process as claimed in one or more of claims 10 to 16, in which said agglomeration step is carried out in a heated vessel and in which said mixture of fragments and sizing composition is injected into said vessel by means of compressed air so as to form granules having on average a maximum size of between twenty and sixty micrometers.
A filler (1) is envisioned which comprises glass-based granules (2) provided with a sizing composition, in which filler each of the granules (2) consists of a multiplicity of milled glass fragments (3) agglomerated together by the agency of a sizing composition (4) containing especially a compound chosen from esters of alkylsilicic acids, particularly an aminosilane. The process comprises a milling step (6) during which the glassy material is comminuted into fragments by this milling, a metering step (7) during which a mixture including the fragments (3) and the sizing composition (4) is formed and an agglomeration step (8) during which the mixture is dried so as to form granules each including a multiplicity of fragments {3} and dried parts of the sizing composition (4).

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Patent Number

201713

Indian Patent Application Number

IN/PCT/2001/01058/KOL

PG Journal Number

08/2007

Publication Date

23-Feb-2007

Grant Date

23-Feb-2007

Date of Filing

10-Oct-2001

Name of Patentee

SAINT GOBAIN VETRO TEX FRANCE SA

Applicant Address

130 AVENUE DES FOLLAZ,F 73000 CHAMBERY,

Inventors:

#	Inventor's Name	Inventor's Address
1	ROSSI ,FRANCESCO	VIALE EUROPA 44/2, I-17028 SPOTORNO, ITALY
2	FERRANTE,ANTONIO,	VIA IPPOLITO NIEVO,9,I-20145 MILAN,

PCT International Classification Number

C 03 C 25/10

PCT International Application Number

PCT/FR00/00961

PCT International Filing date

2000-04-13

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	MI99A000768	1999-04-14	Italy